JP2005115361A - Hologram recording material and hologram recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hologram recording material which is applicable to a high density optical recording medium, a three-dimensional display, a holographic optical element, etc. and in which reconcilement between high sensitivity, high diffraction efficiency, good storage stability and adaptivity to dry processing are realized, and to provide a hologram recording method. <P>SOLUTION: In the hologram recording method, a change in the orientation of a compound having an intrinsic index of double refraction is caused by hologram exposure and the orientation is fixed as it is by a chemical reaction, whereby recording is performed as refractive index modulation by an unrewritable system. The hologram recording material comprises at least a low molecular liquid-crystalline compound having a polymerizable group, a photoreactive compound and a polymerization initiator and employs an unrewritable system. <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.

  The general principles for hologram production are described in several documents and technical books, for example, Chapter 2 of [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, [Patent Document 1]. In addition, the reflection hologram can be created by a known method disclosed in, for example, [Patent Document 2] and [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 recording image information of 100 GB or more inexpensively and easily for consumer use.
In addition, 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, a volume phase hologram recording material has 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 speed reaching 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 diffraction efficiency of hologram (4) Processing at the time of recording is dry and quick (5) Multiple recording is possible (Wide dynamic range)
(6) Small shrinkage after recording (7) Good hologram storage stability

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.
Moreover, although the dry photopolymer method using radical polymerization described in Patent Documents 1 to 3 described above has relatively high sensitivity among the photopolymer methods, it has a very high shrinkage rate and cannot be used as a holographic memory. Absent. 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 [Patent Document 4], [Patent Document 5] and the like, a cationically polymerizable compound (monomer or oligomer) is used instead of a binder, and further, a sensitizing dye, a radical polymerization initiator, a cationic polymerization initiator, a radical polymerizable property. Hologram recording materials combining compounds are disclosed.
[Patent Document 6], [Patent Document 7] and the like disclose hologram recording materials using only a sensitizing dye, a cationic polymerization initiator, a cationic polymerizable compound and a binder without using radical polymerization. .
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 practical use.

  On the other hand, [Patent Document 8] presents a rewritable hologram recording material using refractive index anisotropy and orientation control of an azobenzene polymer (photochromic polymer). In addition to the low rate, this method is accompanied by a change in orientation, so the sensitivity is extremely low, and there is a problem that the record storability is poor due to the contradiction of being rewritable, which is far from practical use. In addition, rewritable and undesired uses in that the records are accidentally deleted. In [Patent Document 9], a partially cured material sandwiched between a binder polymer, a liquid crystal monomer having a refractive index anisotropy and a polymerization property, and a photopolymerization initiator between transparent conductive films is used. Although a method for reversibly controlling the presence / absence of reflection by applying electricity is disclosed, this method also has the drawbacks that it requires application of an electric field and recording stability is poor and records arbitrary information at an arbitrary location. In principle, it is difficult to apply to optical recording media and display hologram (3D imaging) applications that need to be performed.

  The above problems of high sensitivity, good storage stability, low shrinkage dilemma, and multiple recording characteristics are unavoidable in terms of physical laws as long as a photopolymer system with mass transfer is used. Further, the existing system using the alignment control of the liquid crystal compound does not satisfy the requirements required for the optical recording medium in terms of sensitivity and storage stability.

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 Takiuchi, Industrial Books JP-A-6-43634 JP-A-2-3082 Japanese Patent Laid-Open No. 3-50588 Japanese Patent Laid-Open No. 5-107999 JP-A-8-16078 Special table 2001-523842 Special table 11-512847 specification International Publication No. 9744365A1 Pamphlet Japanese Patent Laid-Open No. 5-80309

  Accordingly, an object of the present invention is to provide a hologram recording material capable of achieving both high sensitivity and high diffraction efficiency, good storage stability, and dry processing applicable to high-density optical recording media, three-dimensional displays, holographic optical elements, and the like. It is to provide a hologram recording method.

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 recording method, wherein a change in orientation of a compound having an intrinsic birefringence is caused by hologram exposure, and the compound is recorded as a refractive index modulation by a non-rewritable method by fixing it by a chemical reaction.
(2) The hologram recording method as described in (1) above, wherein the compound having an intrinsic birefringence has a polymerizable group and is fixed by polymerization.
(3) The hologram recording method according to (1) or (2) above, wherein the compound having an intrinsic birefringence is a liquid crystalline compound.
(4) A hologram recording material comprising at least a low-molecular liquid crystalline compound having a polymerizable group, a photoreactive compound, and a polymerization initiator, and a non-rewritable method.
(5) The hologram recording material according to (4), further comprising a sensitizing dye.
(6) The sensitizing dye reacts with a photoreactive compound by electron transfer or energy transfer from an excited state generated by absorbing light at the time of hologram exposure. Hologram recording material.
(7) The hologram recording material according to any one of (4) to (6) above, wherein the photoreactive compound is a photoisomerizable compound.
(8) The photoreactive compound is an azobenzene compound, stilbene compound, spiropyran compound, spirooxazine compound, diarylethene compound, fulgide compound, fulgimide compound, cinnamic acid compound, coumarin compound or chalcone compound. The hologram recording material according to any one of (4) to (7) above, which is any one of the above.
(9) The hologram recording material as described in (8) above, wherein the photoreactive compound is an azobenzene compound.
(10) The method of (4) to (9) above, wherein the system has at least a low-molecular liquid crystalline compound having a polymerizable group, a photoreactive compound, a polymerization initiator, and a binder, and cannot be rewritten. The hologram recording material according to any one of claims.
(11) The above (5), which has at least a low molecular liquid crystalline compound having a polymerizable group, a photoreactive compound, a polymerization initiator, a sensitizing dye, and a binder and is a system that cannot be rewritten. (6) The hologram recording material according to any one of (10) above.
(12) The hologram recording material according to any one of (4) to (11) above, wherein the photoreactive compound is a low molecular compound.
(13) The hologram recording material according to any one of (4) to (11) above, wherein the photoreactive compound is a polymer compound.
(14) The hologram recording material as described in (13) above, wherein the photoreactive compound is a polymer compound in which a photoreactive site is pendant.
(15) The hologram recording material as described in (10) or (11) above, wherein the binder is a polymer compound in which a photoreactive compound is pendant.
(16) The low-molecular liquid crystalline compound having a polymerizable group is any one of a nematic liquid crystalline compound, a smectic liquid crystalline compound, a discotic nematic liquid crystalline compound, a discotic liquid crystalline compound, and a cholesteric liquid crystalline compound. The hologram recording material according to any one of (4) to (15) above.
(17) The hologram recording material as described in (16) above, wherein the low molecular liquid crystalline compound having a polymerizable group is any one of a nematic liquid crystalline compound, a discotic nematic liquid crystalline compound, and a cholesteric liquid crystalline compound.
(18) The hologram recording material as described in (17) above, wherein the low molecular liquid crystalline compound having a polymerizable group is a nematic liquid crystalline compound.
(19) Any of (4) to (18) above, wherein the polymerizable group in (4) is an acryl group, a methacryl group, a styryl group, a vinyl group, an oxirane group, an oxolane group, or a vinyl ether group. The hologram recording material according to claim 1.
(20) Any one of (4) to (19) above, wherein the polymerization initiator of (4) is any one of a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator. The hologram recording material described in 1.
(21) Polymerization initiator is ketone, organic peroxide, bisimidazole, trihalomethyl-substituted triazine, diazonium salt, diaryl iodonium salt, sulfonium salt, organic borate, diaryl iodonium organic boron complex, sulfonium organic boron complex, metal arene The hologram recording material as described in (20) above, which is a radical polymerization initiator of any one of the complexes.
(22) The polymerization initiator is a cationic polymerization initiator (acid generator) of any of trihalomethyl-substituted triazine, diazonium salt, diaryliodonium salt, sulfonium salt, metal arene complex, and sulfonate ester. The hologram recording material according to the above (21).
(23) The above description (20), wherein the polymerization initiator is an anionic polymerization initiator (base generator) represented by at least one of general formulas (1-1) to (1-4). Hologram recording material.

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.
(24) The hologram recording material as described in (23) above, wherein N1 is 1 in the general formulas (1-1) and (1-2).
(25) In the general formula (1-1), R ₃ is any one of a nitro group substituted at the 2-position, 2, 6-position, or an alkoxy group substituted at the 3, 5-position. (23) or the hologram recording material according to (24) above.
(26) The hologram recording material as described in (23) or (24) above, wherein in formula (1-2), R ₆ is an alkoxy group substituted at the 3,5-position.
(27) When performing hologram recording on the hologram recording material having the liquid crystalline compound according to any one of (4) to (26) above, hologram recording is performed at a temperature at which the liquid crystalline compound takes a liquid crystal state. The hologram recording method according to any one of (1) to (3) above, characterized in that:
(28) A hologram recording method comprising performing hologram recording while heating the hologram recording material according to any one of (4) to (26).
(29) When performing hologram recording using the hologram recording material according to any one of (4) to (26) above, the whole surface exposure, heat treatment, or both are performed after hologram exposure. The hologram recording method according to any one of (1) to (3) to (27) to (28) above.
(30) A hologram recording method, wherein volume hologram recording is performed using the hologram recording material according to any one of (1) to (3) and (27) to (28).
(31) In the hologram recording method, multiplex recording is performed ten times or more.
(32) A hologram recording method comprising performing multiple recording 10 times or more using the hologram recording material.
(33) In the above (29), any one of the above (29) to (32) is characterized in that the multiple exposure can be performed with the exposure amount at the time of multiple recording being constant throughout the multiple recording. 2. The hologram recording method according to 1.
(34) An optical recording method using the hologram recording method according to any one of (1) to (3) and (27) to (33).
(35) An optical recording medium using the hologram recording material according to any one of (4) to (26).
(36) An optical recording medium, wherein the hologram recording material according to any one of (4) to (26) is stored in a light-shielding cartridge at the time of storage.
(37) A three-dimensional display hologram recording method using the hologram recording method according to any one of (1) to (3) and (27) to (33).
(38) A three-dimensional display hologram using the hologram recording material according to any one of (4) to (26).
(39) A holographic optical element manufacturing method using the hologram recording method according to any one of (1) to (3) and (27) to (33).
(40) A holographic optical element using the hologram recording material according to any one of (4) to (26).

  By using the hologram recording material of the present invention, hologram recording based on the orientation change can be performed in a non-rewritable manner, and application to a holographic memory or the like having good storage stability is expected.

The best mode for carrying out the hologram recording method and hologram recording material of the present invention will be described below in detail with reference to the drawings.
The hologram recording method of the present invention is characterized in that interference fringe recording by refractive index modulation is performed in a non-rewritable manner by causing an orientation change of a compound having an intrinsic birefringence by hologram exposure and fixing it by a chemical reaction as it is. This is a hologram recording method.

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

Here, the compound having an intrinsic birefringence preferably represents a compound having a different refractive index (N _e ) in the major axis direction and a refractive index (N _o ) in the minor axis direction inherent to the molecule. Here, the intrinsic birefringence represents the intrinsic birefringence of a molecule, and can be obtained from a bulk birefringence such as a solid or liquid crystal state, but can also be obtained by molecular orbital calculation. The hologram recording method of the present invention is a method of recording by refractive index modulation by controlling the orientation of a compound having an intrinsic birefringence by hologram exposure, so that the refractive index anisotropy of the compound having an intrinsic birefringence ΔN = | N _e −N _o | is preferably as large as possible, preferably 0.01 or more, more preferably 0.05 or more, and most preferably 0.1 or more.
Therefore, the compound having an intrinsic birefringence of the present invention is preferably a rod-like compound having a long conjugation in the long axis direction of the molecule.

  The compound having an intrinsic birefringence of the present invention is preferably a so-called dichroic compound (pigment) or a liquid crystal compound, more preferably a liquid crystal compound, still more preferably a low molecular liquid crystal compound, and most preferably. Is a low-molecular liquid crystalline compound having at least two or more rings in the core.

The compound having an intrinsic birefringence of the present invention, preferably a liquid crystal compound, is preferably fixed as it is after the orientation change by hologram exposure. Therefore, it is preferable that the compound having an intrinsic birefringence of the present invention, preferably a liquid crystal compound, has a reactive group and can be fixed in its orientation upon reaction during hologram exposure or by subsequent treatment. As the chemical reaction, an irreversible reaction is preferable, and an addition reaction, a ring-opening addition reaction, a condensation reaction, a ring-opening condensation reaction, a cyclization reaction, a nucleophilic reaction, an electrophilic reaction, a radical reaction, a complexing reaction, and the like are preferable.
In the present invention, the chemical reaction is more preferably a polymerization reaction. Examples of the polymerization reaction include an addition polymerization reaction, a ring-opening addition polymerization reaction, a condensation polymerization reaction, a ring-opening condensation polymerization reaction, a complexing reaction, and the like, more preferably an addition polymerization reaction or a ring-opening addition polymerization reaction. At that time, it is preferable that any one of radical polymerization reaction, cationic polymerization reaction and anionic polymerization reaction occurs.
Accordingly, the compound having an intrinsic birefringence of the present invention, preferably a liquid crystal compound, more preferably a low molecular liquid crystal compound, more preferably has a polymerizable group, and more preferably is immobilized by a polymerization reaction. In this case, the polymerizable group is preferably an acryl group, a methacryl group, a styryl group, a vinyl group, an oxirane group, an oxolane group, or a vinyl ether group.

The liquid crystalline compound of the present invention is preferably a nematic liquid crystalline compound, a smectic liquid crystalline compound, a discotic nematic liquid crystalline compound, a discotic liquid crystalline compound, or a cholesteric liquid crystalline compound. More preferably, it is either a discotic nematic liquid crystalline compound or a cholesteric liquid crystalline compound, and more preferably a nematic liquid crystalline compound.
Therefore, the liquid crystalline compound of the present invention is more preferably a low molecular liquid crystalline compound having a polymerizable group and having the above phase.

  When performing hologram recording on the hologram recording material having the liquid crystalline compound of the present invention, it is preferable to perform hologram recording at a temperature at which the liquid crystalline compound takes a liquid crystal state, and when it is higher than room temperature, the hologram recording material It is also preferable to perform hologram recording while heating the film.

The hologram recording material of the present invention preferably has at least a low-molecular liquid crystalline compound having a polymerizable group, a photoreactive compound, and a polymerization initiator.
Here, the photoreactive compound of the present invention can change its structure by absorbing light and passing through an excited state. As a result, the orientation of a liquid crystal compound, preferably a low molecular liquid crystal compound having a polymerizable group, is aligned. Represents a compound that can change its state to modulate the refractive index. Preferably, the photoreaction caused by the photoreactive compound is an isomerization reaction, bimolecular cyclization reaction, ring closure reaction, ring opening reaction, addition reaction, elimination reaction, condensation reaction, solvent addition reaction, nucleophilic reaction, electrophilic reaction. , Radical reaction, complexing reaction, etc., preferably isomerization reaction, bimolecular cyclization reaction, ring closure reaction, ring opening reaction.
Preferred examples of the photoreactive compound that undergoes isomerization reaction include azobenzene compounds and stilbene compounds, and preferred examples of the compound that undergoes bimolecular cyclization reaction include cinnamic acid compounds, coumarin compounds, and chalcone compounds. Preferred compounds that undergo a ring-opening reaction include spiropyran compounds and spirooxazine compounds, and preferred compounds that undergo a ring-closing reaction include diarylethene compounds, fulgide compounds, and fulgimide compounds.
As the photoreactive compound of the present invention, a photoisomerizable compound is more preferable, and an azobenzene compound is more preferable.
The photoisomerization compound may be a low molecular compound or a high molecular compound, but in the case of a high molecular compound, a high molecular compound in which a photoreactive site is pendant is more preferable.

The hologram recording material of the present invention preferably further contains a sensitizing dye in addition to the photoreactive compound. At that time, it is preferable to react the photoreactive compound by electron transfer or energy transfer from an excited state generated by absorption of light at the time of hologram exposure by the sensitizing dye. When the hologram recording material of the present invention contains a sensitizing dye, it preferably contains an electron donating compound capable of reducing the radical cation of the sensitizing dye or an electron accepting compound capable of oxidizing the radical anion of the sensitizing dye.
The hologram recording material of the present invention preferably contains a polymerization initiator. The polymerization initiator is preferably a radical polymerization initiator that generates radicals, a cationic polymerization initiator that generates acids, or an anionic polymerization initiator that generates bases.
The polymerization initiator of the present invention preferably generates a radical, an acid or a base from an excited state of a sensitizing dye or a photoreactive compound by energy transfer or electron transfer, or by direct excitation.

The hologram recording material of the present invention preferably uses a binder (polymer matrix compound) in addition to a low-molecular liquid crystalline compound, a photoreactive compound, a polymerization initiator, and a sensitizing dye. The binder is used for the purpose of increasing the film strength and improving the film forming property. In addition, when the photoreactive compound is a polymer compound, particularly when the photoreactive compound is a polymer compound pendant with a photoreactive site, it is preferable that the photoreactive compound also serves as a binder.
Furthermore, 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 are used as necessary.
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. This is because of the purposes such as improvement, storage stability improvement, shrinkage reduction.

  The hologram recording material of the present invention is preferably not subjected to wet processing after hologram exposure.

  The hologram recording material of the present invention is preferably a recording material for performing volume phase type 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 to the recording material (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, after the hologram exposure, a fixing step may be performed by light, heat, or both.
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). Preferred examples of the light source used include 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, and an organic EL.
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.

  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 light used in the present invention is preferably ultraviolet light, visible light, or 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 further preferably 400 to 700 Nm. Of visible light.
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, but preferable laser light is, for example, a 532 Nm YAG laser double wave, a 355 Nm YAG laser triple wave, and around 405 to 415 Nm. GaN laser, 488 or 515 Nm Ar ion laser, 632 Nm 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.

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 this 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, according to 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, a CCD or CMOS is 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 preferable to perform multiplex recording 10 times or more, more preferably 50 times or more, and still more preferably 100 times or more. Further, it is more preferable from the viewpoints of simplifying the recording system, improving the S / N ratio, etc. that the exposure amount during multiple recording can be kept constant throughout the multiple recording.

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

  First, the liquid crystal compound of the present invention will be described.

As described above, the liquid crystalline compound of the present invention is preferably a low molecular liquid crystalline compound, more preferably a low molecular liquid crystalline compound having at least two or more rings in the core portion.
Furthermore, the liquid crystalline compound of the present invention preferably has a reactive group, and more preferably has a polymerizable group. Therefore, the liquid crystalline compound of the present invention is more preferably a low molecular liquid crystalline compound having a polymerizable group.

  The low molecular liquid crystalline compound having a polymerizable group of the present invention is preferably represented by the following general formula (2).

In the general formula (2), L ₁₀₁ represents a liquid crystalline core part, and examples of the liquid crystalline core part include: Koji Okano and Keisuke Kobayashi, “Liquid Crystal Fundamentals”, Baifukan, 1985, “Chemical Review No. 22 , Liquid Crystal Chemistry ", 1994, etc., but in the present invention, it is preferably represented by any of the following. In the figure, a line extending from the liquid crystalline core portion represents a substitution position. However, a substituent may be substituted at a place other than the line indicated.

  The liquid crystalline core portion has an alkyl group that promotes the appearance of liquid crystalline properties (preferably 1 to 20 carbon atoms (hereinafter referred to as C number), for example, methyl, ethyl, N-propyl, N-butyl, N-pentyl. , N-hexyl, benzyl), alkenyl group (preferably C 2-20, such as vinyl, allyl, 2-butenyl, 1,3-butadienyl), alkynyl group (preferably C 2-20, such as ethynyl, 2 -Propynyl, 1,3-butadiynyl, 2-phenylethynyl), cyano group, nitro group, halogen atom (for example, F, Cl, Br, I), alkoxy group (preferably having 1 to 20 carbon atoms, for example, methoxy, ethoxy ), An acylamino group (preferably having 1 to 20 carbon atoms, such as acetylamino, benzoylamino), an amino group (preferably having 1 to 20 carbon atoms, such as dimethyl group). Arylamino, diethylamino, dibutylamino), etc. may also be one or more substituents.

  The liquid crystalline core of the present invention is preferably one of nematic liquid crystalline, smectic liquid crystalline, discotic nematic liquid crystalline, discotic liquid crystalline, cholesteric liquid crystalline, nematic liquid crystalline, discotic nematic liquid crystalline. Or cholesteric liquid crystallinity, more preferably nematic liquid crystallinity.

In the general formula (2), R ₁₀₁ represents a polymerizable group or a hydrogen atom, preferably an acryl group, a methacryl group, a styryl group, a vinyl group, an oxirane group, an oxolane group, a vinyl ether group, or a hydrogen atom, more preferably Represents an acryl group, a methacryl group, an oxirane group, and an oxolane group.

In the general formula (2), L ₁₀₂ represents a linking group, preferably L ₁₀₂ represents an alkylene group (preferably having a C number of 1 to 20, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene), an alkenylene group ( Preferably C number 2-20, such as ethenylene, propenylene, butenylene, butadienylene), alkynylene group (preferably C number 2-20, such as ethynylene, butadienylene), arylene group (preferably C number 6-26, such as 1,4 -Phenylene, 1,4-naphthylene, 2,6-naphthylene), a heterylene group (preferably having 1 to 20 carbon atoms, such as 2,5-thienylene, 2,5-pyrrolylene, 2,5-pyridinylene, 2,5 - pyrimidinylene), - O -, - S -, - NR 102 -, - COO -, - CONR 103 - , alone or in multiple It is a connecting group formed by connecting several. R ₁₀₂ and R ₁₀₃ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms, such as methyl, ethyl, benzyl), an alkenyl group (preferably having 2 to 20 carbon atoms, such as vinyl or allyl), A cycloalkyl group (preferably having 3 to 20 carbon atoms, such as cyclohexyl, cyclopentyl), an aryl group (preferably having 6 to 20 carbon atoms, such as phenyl, 2-naphthyl), a heterocyclic group (preferably having 1 to 20 carbon atoms, for example, 2-thienyl, 2-pyridinyl, 2-pyrimidinyl).

In the general formula (2), N101 represents an integer of 1 to 8, L ₁₀₁ is a nematic liquid crystal core part, a smectic liquid crystal core part, the N101 is preferably 1 or 2 when the cholesteric liquid crystal core part, L ₁₀₁ Is a discotic nematic liquid crystalline core part or a discotic liquid crystalline core part, N101 is preferably an integer of 3 to 8.
N102 represents 0 or 1.

  The compound represented by the general formula (2) has at least one polymerizable group.

  Although the specific example of the liquid crystalline compound which has a polymeric group of this invention represented by General formula (2) below is shown, this invention is not necessarily limited to this.

  The liquid crystalline compounds of the present invention are described in the methods described in Kouji Okano and Keisuke Kobayashi, “Liquid Crystal Fundamentals”, Bakukan, 1985, “Chemical Review No. 22, Liquid Crystal Chemistry”, 1994, etc. Can be synthesized.

  Next, the photoreactive compound of the present invention will be described in detail.

The photoreactive compound for isomerization reaction of the present invention is preferably an azobenzene (azobenzene derivative) compound or a stilbene compound, and the compound for bimolecular cyclization reaction is preferably a cinnamic acid compound, a coumarin compound, Examples of the compound that undergoes a ring opening reaction include a spiropyran compound and a spirooxazine compound, and examples of the compound that undergoes a ring closure reaction include a diarylethene compound, a fulgide compound, and a fulgimide compound.
As the photoreactive compound of the present invention, a photoisomerizable compound is more preferable, and an azobenzene compound is more preferable.
The photoisomerization compound may be a low molecular compound or a high molecular compound, but in the case of a high molecular compound, a high molecular compound in which a photoreactive site is pendant is more preferable.

  Specific examples of the photoreactive compound of the present invention are shown below, but the present invention is not limited thereto.

  All of the photoreactive compounds of the present invention are commercially available products or can be synthesized by known methods.

  Next, the sensitizing dye of the present invention will be described in detail.

  When a sensitizing dye is used separately from the photoreactive compound in the present invention, the photoreactive compound is transferred by transferring electrons or energy from an excited state generated by absorption of light at the time of hologram exposure by the sensitizing dye. Is preferably reacted.

In the case of the energy transfer mechanism from the excited state of the sensitizing dye, either the Forster mechanism in which energy transfer occurs from the singlet excited state of the sensitizing dye or the Dexter mechanism in which energy transfer occurs from the triplet excited state. good.
In that case, in order for energy transfer to occur efficiently, the excitation energy of the sensitizing dye is preferably larger than the excitation energy of the photoreactive compound.

On the other hand, in the case of an electron transfer mechanism from a sensitizing dye excited state, either a mechanism in which electron transfer occurs from a singlet excited state of a sensitizing dye or a mechanism in which electron transfer occurs from a triplet excited state may be used.
Further, the excited state of the sensitizing dye may give electrons to the photoreactive compound or may receive electrons. When electrons are supplied from the sensitizing dye excited state, in order for the electron transfer to occur efficiently, the orbital (LUMO) energy of the excited electron in the excited state of the sensitizing dye is higher than the LUMO orbital energy of the photoreactive compound. Is preferably high.
When the sensitizing dye excited state receives electrons, in order for electron transfer to occur efficiently, the orbital (HOMO) energy of holes in the excited state of the sensitizing dye is higher than the energy of the HOMO orbital of the photoreactive compound. Preferably it is low.

  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 400 to 700 Nm of visible light 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. Pyran dyes, xanthene dyes, thioxanthene dyes, condensed aromatic dyes, metal complex dyes, metallocene dyes and the like, more preferred are cyanine dyes, merocyanine dyes, oxonol dyes, metal complex dyes, metallocene dyes. The metal complex dye is particularly preferably a Ru complex dye, and the metallocene dye is preferably a ferrocene.

  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 sensitizing dyes can be selected in accordance with the wavelength of the laser serving as a light source according to the purpose of use, and two or more kinds of sensitizing dyes may be used in combination depending on the application.

  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 commercial product, or can be synthesized by a known method.

  Here, in the hologram recording method of the present invention, when a sensitizing dye is not used, the photoreactive compound is used. When a sensitizing dye is used, the sensitizing dye or the sensitizing dye and the photoreactive compound are used in the hologram recording wavelength. Hologram recording is performed by absorbing light.

At that time, since the hologram recording material is used in a thick film and most of the recording light needs to pass through the film, it is possible to increase the sensitivity by reducing the molar extinction coefficient of the sensitizing dye and the photoreactive compound at the hologram exposure wavelength. It is preferable for increasing the sensitivity to increase the addition amount of the dye-sensitive and photoreactive compound as much as possible.
The molar extinction coefficient of the sensitizing dye at the hologram exposure wavelength is preferably from 1 to 10,000, more preferably from 1 to 5000, further preferably from 5 to 2500, and more preferably from 10 to 1000. Most preferred.
Similarly, the molar extinction coefficient of the photoreactive compound at the hologram exposure wavelength is preferably from 0 to 10,000, more preferably from 0 to 5000, still more preferably from 0 to 2500, and more preferably from 0 to 1000. Most preferably:

  The recording wavelength light transmittance of the hologram recording material is preferably 10 to 99%, more preferably 20 to 95%, further preferably 30 to 90%, and 40 to 85%. It is most preferable in terms of diffraction efficiency, sensitivity, and recording density (multiplicity). Therefore, it is preferable to adjust the molar extinction coefficient and the added molar concentration at the recording wavelength of the sensitizing dye and the photoreactive compound in accordance with the film thickness of the hologram recording material so as to be like that.

Further, λmax of the sensitizing dye is preferably shorter than the hologram recording wavelength, and more preferably within the range from the same as the hologram recording wavelength to a wavelength shorter than 100 Nm.
The λmax of the photoreactive compound is also preferably shorter than the hologram recording wavelength, and more preferably in the range from the same as the hologram recording wavelength to a wavelength shorter than 200 Nm.

Furthermore, the molar extinction coefficient at the recording wavelength of the sensitizing dye is preferably 1/5 or less, more preferably 1/10 or less of the molar extinction coefficient of λmax.
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. Is most preferred.

  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 ferrocenes. 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 polymerization initiator in the hologram recording material of the present invention will be described in detail.
The polymerization initiator of the present invention is a radical or acid by performing energy transfer or electron transfer (giving or receiving electrons) from the excited state of a sensitizing dye or photoreactive compound, or by being directly excited. (Bronsted acid or Lewis acid), a compound capable of generating a base (Bronsted base or Lewis base) and initiating polymerization of a polymerizable compound.
The polymerization initiator of the present invention is preferably a radical polymerization initiator capable of generating radicals to initiate radical polymerization of polymerizable compounds, and cationic polymerization of polymerizable compounds by generating only acids without generating radicals. A cationic polymerization initiator capable of initiating only a radical, a polymerization initiator capable of initiating both radicals and acids to initiate both radical and cationic polymerization, an anionic polymerization initiating capable of initiating anion polymerization by generating a base One of the agents.

First, a radical polymerization initiator, a cationic polymerization initiator, and an initiator capable of initiating both will be described.
The polymerization initiator of the present invention preferably includes the following 12 systems. In addition, you may use these polymerization initiators as 2 or more types of mixtures by arbitrary ratios as needed.

1) Ketone polymerization initiator 2) Organic peroxide polymerization initiator 3) Bisimidazole polymerization initiator 4) Trihalomethyl-substituted triazine polymerization initiator 5) Diazonium salt polymerization initiator 6) Diaryliodonium salt polymerization Initiator 7) Sulfonium salt polymerization initiator 8) Borate polymerization initiator 9) Diaryliodonium organic boron complex polymerization initiator 10) Sulfonium organic boron complex polymerization initiator 11) Metal arene complex polymerization initiator 12 ) Sulphonic acid ester polymerization initiator

  1) Ketone-based polymerization initiator

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

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

  Preferred examples include quinone polymerization initiators (for example, 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone. Quinone, octamethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-methyl-1,4-naphthoquinone, 2, 3-dichloronaphthoquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 2-phenylanthraquinone, 2,3-dimethylanthraquinone, sodium salt of anthraquinone alpha-sulfonic acid, 3-chloro-2 -Methylanthraquinone, Rethenequinone, 7,8,9,10-tetra Mud naphthacene quinone, and 1,2,3,4-tetrahydrobenz (a) anthracene-7,12-dione) can be mentioned.

  2) Organic peroxide polymerization initiator

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

  3) Bisimidazole polymerization initiator

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

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

  4) Trihalomethyl-substituted triazine polymerization initiator

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

In 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 represents a hydrogen atom, —CR ₂₁ R ₂₂ R ₂₃ , or a substituent.
Preferred examples of the substituent include, for example, an alkyl group (preferably having a C number of 1 to 20, for example, methyl, ethyl, N-propyl, isopropyl, N-butyl, N-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, Carboxymethyl, 5-carboxypentyl), alkenyl group (preferably C 2-20, for example, vinyl, allyl, 2-butenyl, 1,3-butadienyl), cycloalkyl group (preferably C 3-20, for example, Cyclopentyl, cyclohexyl), an aryl group (preferably having 6 to 20 carbon atoms, for example, phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), a heterocyclic group (preferably having 1 to 20 carbon atoms). For example, pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyro Dino, piperidino, morpholino), alkynyl groups (preferably C 2-20, eg ethynyl, 2-propynyl, 1,3-butadiynyl, 2-phenylethynyl), halogen atoms (eg F, Cl, Br, I ), Amino group (preferably C 0-20, such as amino, dimethylamino, diethylamino, dibutylamino, anilino), cyano group, nitro group, hydroxyl group, mercapto group, carboxyl group, sulfo group, phosphonic acid group, An acyl group (preferably having 1 to 20 carbon atoms, such as acetyl, benzoyl, salicyloyl, pivaloyl), an alkoxy group (preferably having 1 to 20 carbon atoms, such as methoxy, butoxy, cyclohexyloxy), an aryloxy group (preferably having C number) Formula 6-26, for example, phenoxy, 1-naphthoxy), alkyl O group (preferably C number 1-20, for example, methylthio, ethylthio), arylthio group (preferably C number 6-20, for example, phenylthio, 4-chlorophenylthio), alkylsulfonyl group (preferably C number 1-20) , For example, methanesulfonyl, butanesulfonyl), arylsulfonyl group (preferably C number 6-20, such as benzenesulfonyl, paratoluenesulfonyl), sulfamoyl group (preferably C number 0-20, such as sulfamoyl, N-methyl) Sulfamoyl, N-phenylsulfamoyl), carbamoyl group (preferably having 1 to 20 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-phenylcarbamoyl), acylamino group (preferably C number 1-20, for example, acetyla Mino, benzoylamino), imino group (preferably C 2-20, eg phthalimino), acyloxy group (preferably C 1-20, eg acetyloxy, benzoyloxy), alkoxycarbonyl group (preferably C 2 20, for example, methoxycarbonyl, phenoxycarbonyl), a carbamoylamino group (preferably having a C number of 1-20, such as carbamoylamino, N-methylcarbamoylamino, N-phenylcarbamoylamino), more preferably an alkyl group, An aryl group, a heterocyclic group, a halogen atom, a cyano group, a carboxyl group, a sulfo group, an alkoxy group, a sulfamoyl group, a carbamoyl group, and an alkoxycarbonyl group.
R ₂₄ preferably represents —CR ₂₁ R ₂₂ R ₂₃ , more preferably —OCl 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 polymerization initiator include 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (trichloromethyl) -1, 3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4′-methoxyphenyl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- (4′-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (p -Methoxyphenylvinyl) -1,3,5-triazine, 2- (4′-methoxy-1′-naphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like are exemplified. . Preferable examples also include compounds described in British Patent No. 1388492 and JP-A No. 53-133428.

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

R ₂₆ represents an aryl group or a heterocyclic group, 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, and 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 polymerization initiator such as benzene diazonium, 4-methoxy diazonium, 4-methyl aforementioned X ₂₁ of diazonium ^- such salts.

  6) Diaryliodonium salt polymerization initiator

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

In general formula (13), X ₂₁ ^- has the same meaning as in general formula (12). R ₂₈ and R ₂₉ each independently represents a substituent (preferably the same as the 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 represent 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-based 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-dimethoxy anthracene-2-sulfonate, methanesulfonate, benzenesulfonate, 4-trifluoromethylbenzenesulfonate, tosylate, tetra (pentafluorophenyl) borate, perfluorobutanesulfonate and pentafluorobenzenesulfonate sulfonates.
Further, compounds described in “Macromolecules”, Vol. 10, p1307 (1977), Japanese Patent Application Laid-Open Nos. 58-29803, 1-287105, and Japanese Patent Application No. 3-5569. And diaryliodonium salts as described in 1).

  7) Sulfonium salt polymerization initiator

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

In general formula (14), X ₂₁ ^- has the same meaning as in general formula (12). R _30, R _31, R ₃₂ each independently represent an alkyl group, an aryl group, a Hajime Tamaki (preferred examples above same as those for R _24), preferably an alkyl group, a phenacyl group, an aryl group.

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

  8) Borate polymerization initiator

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

In the general formula (15), R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ each independently represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group or an aryl group (preferred examples are the same as those for R ₂₄ ). And preferably an alkyl group or an aryl group. However, not all of R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ become an aryl group at the same time. X ₂₂ ⁺ represents a cation.
More preferably, R ₃₃ , R ₃₄ and R ₃₅ are aryl groups, R ₃₆ is an alkyl group, most preferably R ₃₃ , R ₃₄ and R ₃₅ are phenyl groups, and R ₃₆ is an N-butyl group. is there.

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

  9) Diaryliodonium organoboron complex polymerization initiator

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

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

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

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

  10) Sulfonium organoboron complex polymerization initiator

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

In general formula (17), R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ have the same _{meaning as} in general formula (15). R ₃₇ , R ₃₈ and R ₃₉ are each independently an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group or an amino group (and more preferred examples). Is the same as R ₂₄ ), more preferably an alkyl group, a phenacyl group, an aryl group or an alkenyl group. R ₃₇ , R ₃₈ and R ₃₉ may be connected to each other to form a ring. R ₄₀ represents an oxygen atom or a lone electron pair.

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

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

  11) Metal arene complex polymerization initiator

As the metal arene complex polymerization initiator, the metal is preferably iron or titanium.
Specifically, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712 and “Journal of Imaging Science (J. Imag. Sci.)”, 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.

  12) Sulfonic acid ester polymerization initiator

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

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

  13) Other polymerization initiators

Examples of the polymerization initiator other than the above 1) to 14) include organic azide compounds such as 4,4′-diazidochalcone, aromatic carboxylic acids such as N-phenylglycine, polyhalogen compounds (CI ₄ , CHI ₃ , CBrCI _3), 1- benzyl-2-cyano-pyridinium salt pyridinium salts such as hexafluoroantimonate, phenyl iso oxazolone, silanol-aluminum complex, such as aluminate complexes described in JP-a-3-209477 and the like.

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

a) A polymerization initiator capable of activating radical polymerization performs energy transfer or electron transfer from the excited state of the sensitizing dye or photoreactive compound (giving electrons to the sensitizing dye or receiving electrons from the sensitizing dye) Alternatively, it is a polymerization initiator capable of generating radicals by direct excitation and initiating radical polymerization of a polymerizable compound.
Among the above, the following systems are polymerization initiator systems that can activate radical polymerization.
1) Ketone polymerization initiator 2) Organic peroxide polymerization initiator 3) Bisimidazole polymerization initiator 4) Trihalomethyl-substituted triazine polymerization initiator 5) Diazonium salt polymerization initiator 6) Diaryliodonium salt polymerization Initiator 7) Sulfonium salt polymerization initiator 8) Borate polymerization initiator 9) Diaryliodonium organic boron complex polymerization initiator 10) Sulfonium organic boron complex polymerization initiator 11) Metal arene complex polymerization initiator

More preferably as a polymerization initiator capable of activating radical polymerization,
1) ketone polymerization initiator 3) bisimidazole polymerization initiator 4) trihalomethyl-substituted triazine polymerization initiator 6) diaryliodonium salt polymerization initiator 7) sulfonium salt polymerization initiator, more preferably
3) Bisimidazole polymerization initiator 6) Diaryliodonium salt polymerization initiator 7) Sulfonium salt polymerization initiator.

  A polymerization initiator that can activate only cationic polymerization is an energy transfer or electron transfer from the excited state of a sensitizing dye or photoreactive compound, or an acid (Bronsted acid or Lewis acid without generating a radical by direct excitation). It is a polymerization initiator capable of generating an acid) and initiating cationic polymerization of the polymerizable compound with the acid.

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

  Examples of the cationic polymerization initiator include “UV curing; science and technology (UV CURING; SCIENCE AND TECHNOLOGY)” [p. 23-76, S.M. Edited by S. PETER PAPPAS, A TECHNOLOGY MARKING PUBLICATION] and “Comments Inorg. Chem.” [B. Klingelt, M.M. Reedy Car and A. Rolov (B. KLINGERT, M. RIEDICER aNd A. ROLOFF), Vol. 3, p109-138 (1988)] and the like can also be used.

  A polymerization initiator capable of simultaneously activating radical polymerization and cationic polymerization is a radical or acid (Bronsted acid or Lewis acid) that undergoes energy transfer or electron transfer from the excited state of a sensitizing dye or photoreactive compound, or by direct excitation. Acid) is a polymerization initiator capable of simultaneously generating radical polymerization of the polymerizable compound by the generated radical, and cationic polymerization of the polymerizable compound by the generated acid.

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

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

Next, the anionic polymerization initiator of the present invention will be described. The anionic polymerization initiator of the present invention is preferably a base generator capable of initiating anionic polymerization by generating a base (Bronsted base or Lewis base).
In this case, the base generator is a compound that can generate a base by energy transfer or electron transfer from an excited state of a sensitizing dye or a photoreactive compound, or by direct excitation. 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 an excited state of a sensitizing dye or a photoreactive compound.
The base generator of the present invention preferably generates a Bronsted base by light, more preferably generates an organic base, and particularly preferably generates an amine as the organic base.

  The anionic polymerization initiator of the present invention, that is, the base generator 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), an alkenyl group (preferably having 2 to 20 carbon atoms) , For example, vinyl, allyl, 2-butenyl, 1,3-butadienyl), a cycloalkyl group (preferably C 3-20, such as cyclopentyl, cyclohexyl), an aryl group (preferably C 6-20, such as phenyl , 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl, 2-naphthyl), heterocyclic group (preferably Or C 1-20, for example, pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino), more preferably a hydrogen atom, an alkyl group, a cycloalkyl group, Preferably, it represents a hydrogen atom, a methyl group, an ethyl group, a cyclohexyl group, or a cyclopentyl group.
R ₁ and R ₂ may be connected to each other to form a ring, and the heterocyclic ring to be formed is preferably a piperidine ring, a pyrrolidine ring, a piperazine ring, a morpholine ring, a pyridine ring, a quinoline ring, or an imidazole ring, and more A piperidine ring, a pyrrolidine ring and an imidazole ring are preferable, and a piperidine ring is most preferable.
As a more preferable combination of R 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 general formula (1-1) or (1-2), N1 is 0 or 1, preferably 1.

In the general formula (1-1), R ₃ each independently represents a substituent, and examples of preferable substituents include an alkyl group (preferably an alkyl group (preferably having 1 to 20 carbon atoms, for example, methyl, ethyl, N-propyl, Isopropyl, N-butyl, N-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), alkenyl group (preferably having 2 to 20 carbon atoms, for example, vinyl, allyl, 2-butenyl 1,3-butadienyl), a cycloalkyl group (preferably having 3 to 20 carbon atoms, such as cyclopentyl, cyclohexyl), an aryl group (preferably having 6 to 20 carbon atoms, such as phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), heterocyclic group (preferably having 1 to 20 carbon atoms, such as pyridyl, thie , Furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino), alkynyl group (preferably having 2 to 20 carbon atoms, such as ethynyl, 2-propynyl, 1,3-butadiynyl, 2-phenylethynyl), halogen atom (For example, F, Cl, Br, I), an amino group (preferably C 0-20, for example, amino, dimethylamino, diethylamino, dibutylamino, anilino), a cyano group, a nitro group, a hydroxyl group, a mercapto group, Carboxyl group, sulfo group, phosphonic acid group, acyl group (preferably C 1-20, for example, acetyl, benzoyl, salicyloyl, pivaloyl), alkoxy group (preferably C 1-20, for example, methoxy, butoxy, cyclohexyl) Oxy), an aryloxy group (preferably C6) To 26, for example, phenoxy, 1-naphthoxy), alkylthio group (preferably having 1 to 20 carbon atoms, for example, methylthio, ethylthio), arylthio group (preferably having 6 to 20 carbon atoms, for example, phenylthio, 4-chlorophenylthio) , Alkylsulfonyl groups (preferably having 1 to 20 carbon atoms, such as methanesulfonyl and butanesulfonyl), arylsulfonyl groups (preferably having 6 to 20 carbon atoms, such as benzenesulfonyl and paratoluenesulfonyl), sulfamoyl groups (preferably C number 0-20, for example, sulfamoyl, N-methylsulfamoyl, N-phenylsulfamoyl), carbamoyl group (preferably C number 1-20, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl) N-phenylcarbamoyl), Silamino group (preferably having 1 to 20 carbon atoms, such as acetylamino, benzoylamino), imino group (preferably having 2 to 20 carbon atoms, such as phthalimino), acyloxy group (preferably having 1 to 20 carbon atoms, such as acetyloxy, benzoyl) Oxy), alkoxycarbonyl group (preferably C 2-20, such as methoxycarbonyl, phenoxycarbonyl), carbamoylamino group (preferably C 1-20, such as carbamoylamino, N-methylcarbamoylamino, N-phenylcarbamoyl) Amino), and more preferably an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an amino group, a cyano group, a nitro group, a carboxyl group, a sulfo group, an alkoxy group, an alkylthio group, an arylsulfonyl group, a sulfamoyl group. , Carbamoy Group, an 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 to 5, preferably an integer of 0 to 3, and more preferably 1 or 2. N2 is 2 or more, plural R ₃ may be the same or different and may be bonded to form a ring, a ring to be formed is preferably a benzene ring, a naphthalene ring and the like.
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 general formula (1-1), R ₄ and R ₅ each independently represents a hydrogen atom or a substituent (preferably the same as the substituents mentioned in R ₃ as the substituent). Preferred examples are 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 represent a substituent (preferably the same as the substituents exemplified in R ₃ as the substituent), preferably an alkoxy group, an alkylthio group, nitro Group and an alkyl group, and more preferably a methoxy group.
In General Formula (1-2), N3 and N4 each independently represent an integer of 0 to 5, preferably an integer of 0 to 2. When N3 and N4 are 2 or more, a plurality of R ₆ and R ₇ may be the same or different, and may be linked to form a ring. Preferred examples of the ring formed include a benzene ring and a naphthalene ring. .
In general formula (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 substituents exemplified for R ₃ as a substituent), preferably an alkyl group, an aryl group, a benzyl group, an amino group. And more preferably an alkyl group which may be substituted, a t-butyl group, a phenyl group, a benzyl group, an anilino group which may be substituted, or a cyclohexylamino group.
The compound represented by the general formula (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, and 2-naphthyl group are 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 morpholine ring, a pyridine ring, a quinoline ring, an imidazole. A ring, more preferably a piperidine ring, a pyrrolidine ring, and an imidazole ring.

In the general formula (1-4), R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ each independently represents an alkyl group or an aryl group, R ₁₆ , R ₁₇ and R ₁₈ are phenyl groups, and R ₁₉ is It is more preferably an N-butyl group or a phenyl group.

  The base generator of the present invention is preferably represented by the general formula (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.

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 liquid crystal compounds, polymerization initiators, photoreactive compounds, sensitizing dyes and the like 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, acrylates 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 having acrylate or methacrylate groups) Poxy compounds), polyamides (eg N-methoxymethyl polyhexamethylene adipamide), cellulose esters (eg cellulose acetate, cellulose acetate succinate and cellulose acetate butyrate), cellulose ethers (eg 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 U.S. Pat. No. 3,458,311 and U.S. Pat. 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 (e.g., formula HO (CH ₂₎ NOH (wherein N is an integer of 2 to 10) polymethylene glycol, and (1) hexahydroterephthalic acid, sebacic 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 such as those disclosed in Kamogawa et al. In Journal Nal of Polymer Science Nce, Polymer Chemistry Edito N, 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 mass.

  As the fluoroolefin in the fluorine atom-containing polymer, tetrafluoroethylene, chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride, or the like is used. In addition, as alkyl vinyl ether which is another copolymer component, ethyl vinyl ether, isobutyl vinyl ether, N-butyl vinyl ether, etc., alicyclic vinyl ether as cyclohexyl vinyl ether and its derivatives, hydroxy vinyl ether as hydroxybutyl vinyl ether, olefin and halo Ethylene, propylene, isobutylene, vinyl chloride, vinylidene chloride, etc. as olefins, vinyl acetate, N-vinyl butyrate, etc. as carboxylic acid vinyl esters, and (meth) acrylic acid, crotonic acid, etc. as unsaturated carboxylic acids and their esters 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 propyl, (meth) acrylate butyl, 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.

In addition, when the photoreactive compound mentioned above is a high molecular compound, it is also preferable to serve as a binder, and in that case, it is particularly preferable that the photoreactive compound is a pendant high molecular compound.
In that case, the binder is preferably used for controlling the orientation of the low-molecular liquid crystal.

  In the hologram recording material of the present invention, additives such as an electron donating compound, an electron accepting compound, a polymerizable monomer, a polymerizable oligomer, a crosslinking agent, a heat stabilizer, a plasticizer, and a solvent can be used as necessary.

  When a sensitizing dye is used in the hologram recording material of the present invention, an electron donating compound having the ability to reduce the radical cation of the sensitizing dye, or an electron accepting compound having the ability to oxidize the radical anion of the sensitizing dye 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, -Tetrachlorobenzoquinone, 2,6-dichloro-3,5-dicyanobenzoquinone, 2,3-dichloro-5,6-dicyanobenzoquinone, naphthoquinone, anthraquinone), imides (preferably, for example, N, N'-dioctylpyro Meritimide, 4-nitro-N-octylphthalimide), metal complexes (preferably, for example, Ru trisbipyridine complexes, Ru bisbipyridine complexes, Co trisbipyridine complexes, CR trisbipyridine complexes, PtCl ₆ complexes, Additional 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 the excitation potential of the sensitizing dye, and the reduction potential of the electron-accepting compound is that of the sensitizing dye. It is preferably noble (plus side) from the reduction potential or the oxidation potential in the excited state of the sensitizing dye.

  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.

It may be preferable to use a chain transfer agent for the hologram recording material of the present invention. Preferred chain transfer agents are thiols such as 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 2-mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol, 4 , 4-thiobisbenzenethiol, p-bromobenzenethiol, thiocyanuric acid, 1,4-bis (mercaptomethyl) benzene, p-toluenethiol, etc., as described in USP No. 4414312 and JP-A No. 64-13144 Thiols, disulfides described in JP-A-2-291561, thiones described in USP 3,558,322 and JP-A 64-17048, O-acylthiohydroxamates and N-alkoxy described in JP-A-2-291560 Also included are pyridinethiones.
In particular, when the polymerization initiator is 2,4,5-triphenylimidazolyl dimer, it is preferable to use a chain transfer agent.
As for the usage-amount of a chain transfer agent, 1.0-30 mass% is preferable with respect to the whole composition.

  A heat stabilizer 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. Also useful are dinitroso dimers described in US Pat. No. 4,168,982 to Pazos.

  The plasticizer is used to change the adhesiveness, flexibility, hardness, 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, dibutyl phthalate, alcohols, and phenols.

In general, the ratio of each component in the hologram recording material and the composition of the present invention is preferably in the following% range based on the total mass of the composition.
Binder: preferably 0 to 95% by mass, more preferably 0 to 70% by mass,
Liquid crystalline compound: preferably 10 to 99% by mass, more preferably 30 to 99% by mass,
Photoreactive compound: preferably 0.1 to 30% by mass, more preferably 1 to 10% by mass
Polymerization initiator: preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass
Sensitizing dye: preferably 0 to 10% by mass, more preferably 0.1 to 5% 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.

  In the present invention, an alignment film may be used for the substrate in order to align the liquid crystalline compound. The alignment film may be rubbed or photo-aligned. Examples of the alignment film by rubbing include polyvinyl alcohol and polyimide. Examples of the alignment film by photo-alignment include those described in “Liquid Crystal” 1999, Vol. 3, page 3. Also, the so-called “command surface” described in “Applied Physics” 1993, 62, 998 and “Polymer Processing” 2000, 49, 50 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.

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. Displays, color filters for liquid crystals, reflective liquid crystal reflectors, lenses, diffraction gratings, interference filters, couplers for optical fibers, optical polarizers for facsimiles, architectural windows), 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.

  2 to 4 times the sensitizing dye, electron donating compound, photoreactive compound, polymerization initiator (+ chain transfer agent), liquid crystalline compound having a polymerizable group, and binder shown in Table 1 under a red light Dissolved in a weight of methylene chloride (when used, acetonitrile, acetone, and methanol were also used in combination) to prepare hologram recording material compositions 101-106. In Table 1, “%” represents mass%.

  The composition for hologram recording material 101 to 106 is applied to a glass substrate with a blade so that the thickness is about 80 μm (overcoat if necessary) to form a photosensitive layer, and then dried by heating at 40 ° C. for 3 minutes. The solvent was distilled off. Furthermore, hologram recording materials 101 to 106 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 400 seconds (irradiation energy ranges from 0.8 to 3200 mJ / cm ² ). And exposed. While exposing the hologram, a He—Ne laser 632 Nm beam was passed through the center of the exposure area at a black angle, and the ratio of the diffracted light to the incident light (absolute diffraction efficiency) was measured in real time.

  As a result, the diffraction of the He—Ne laser was observed with high efficiency in any of the hologram recording material samples 101 to 106 of the present invention, and it was confirmed that hologram recording could be performed by this method. Furthermore, it was also confirmed that when the entire surface was irradiated with visible light to ultraviolet light with a xenon lamp at room temperature, the recording could be fixed by entire polymerization while being preserved. It was also confirmed that the recording could be satisfactorily preserved because the recording could not be performed even if further rewriting recording was performed thereafter, and the recorded hologram was not erased even when the recorded hologram was heated or exposed to the entire surface.

  The hologram recording material of the present invention is a system capable of performing hologram recording by refractive index modulation by in-situ orientation change of a liquid crystalline compound without mass transfer as in the current photopolymer system, and the orientation change Since it is a system that can be fixed and cannot be rewritten by being hardened by polymerization, it is a recording system that is completely different from known hologram recording materials, and is particularly suitable for write-once holographic memory applications. .

Furthermore, the hologram recording material of the present invention increases ΔN (calculated based on Kugelnick's formula from refractive index modulation amount, diffraction efficiency and film thickness in interference fringes) almost linearly according to the exposure amount (mJ / cm ² ). However, this is advantageous for multiple recording.

  Actually, using the hologram recording material of the present invention, 10 times of multiple hologram recordings were performed 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 giving the maximum diffraction efficiency. After that, fixing by full exposure was performed, and then it was confirmed that each object light could be reproduced by changing the angle of the reproduction light by 2 degrees and irradiating. 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. As described above, since the hologram recording material of the present invention can perform multiple multiplex recording, high-density (capacity) recording is possible.

  On the other hand, known photopolymer hologram recording materials such as Japanese Patent Laid-Open No. 6-43634 perform the same recording in the latter stage of multiple recording because the polymerization of the photopolymer progresses and the movement of monomers 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 Samples 101 to 103, sensitizing dyes were D-1, D-22, D-31, D-49, D-53, D-55, D-74, D-87, D-91, D. The same effect was obtained even when changed to -97, D-107, D-115, D-116, D-117, D-119 or the like. In the samples 101, 102, 104, and 105, the photoreactive compounds are R-1, R-3, R-9, R-10, R-13, R-15, R-18, R-19, R The same effect was obtained even when changed to -23, R-24, R-32, R-34, R-35, R-38, R-40.
In addition, the same effect was obtained even when the photoreactive compound was changed to R-41 or R-49 in the samples 103 and 106.
Moreover, even if it changed the liquid crystalline compound which has a radically polymerizable group in sample 102,104 to LC-2, LC-4, LC-10, LC-14, LC-25, LC-28, LC-33. Similar effects were obtained.
Moreover, LC-3, LC-5, LC-7, LC-11, LC-15, LC-17, LC-20, and the liquid crystalline compounds having a cationic polymerizable group in Samples 101, 103, 105, and 106, The same effect was obtained even if it changed to LC-26 and LC-35.
Moreover, the same effect was obtained even when the radical polymerization initiator was changed to Irgacure 907, Irgacure 184, or Irgacure 651 of the ketone polymerization initiator in Samples 102 and 104.
In samples 101, 103, 105, and 106, the cationic polymerization initiator (acid generator) is tris (4-methylphenyl) sulfonium tetra (pentafluorophenyl) borate, triphenylsulfonium perfluoropentanoate, bis (1 The same effect was obtained even when it was changed to-(4-diphenylsulfonium) phenyl sulfide ditriflate, dimethylphenacylsulfonium perfluorobutane sulfonate, diphenyliodonium triflate, 4-octyloxyphenylphenyliodonium hexafluoroantimonate.
In Samples 102 and 105, the binder was changed to polymethyl methacrylate (Mw 996000, 350,000), poly (methyl methacrylate-butyl acrylate copolymer (Mw 75000), polyvinyl acetal (Mw 83000), polycarbonate, cellulose acetate butyrate, etc. The same effect was obtained.

  In advanced information society, it is expected to be used as a three-dimensional optical recording medium that is one step ahead.

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 (17)

  A hologram recording method characterized by causing a change in orientation of a compound having an intrinsic birefringence by hologram exposure, and recording it as a refractive index modulation by a non-rewritable method by fixing it by a chemical reaction as it is.   2. The hologram recording method according to claim 1, wherein the compound having an intrinsic birefringence has a polymerizable group and is fixed by polymerization.   The hologram recording method according to claim 1, wherein the compound having an intrinsic birefringence is a liquid crystal compound.   A hologram recording material comprising at least a low-molecular liquid crystalline compound having a polymerizable group, a photoreactive compound, and a polymerization initiator, and a non-rewritable method.   5. The hologram recording material according to claim 4, further comprising a sensitizing dye.   6. The hologram recording material according to claim 5, wherein the sensitizing dye reacts with a photoreactive compound by electron transfer or energy transfer from an excited state generated by absorbing light during hologram exposure.   The hologram recording material according to claim 4, wherein the photoreactive compound is a photoisomerizable compound.   The photoreactive compound is an azobenzene compound, stilbene compound, spiropyran compound, spirooxazine compound, diarylethene compound, fulgide compound, fulgimide compound, cinnamic acid compound, coumarin compound, or chalcone compound. The hologram recording material according to any one of claims 4 to 7, wherein the hologram recording material is provided.   The hologram recording material according to any one of claims 4 to 8, wherein the photoreactive compound is a polymer compound in which a photoreactive site is pendant. The low-molecular liquid crystalline compound having a polymerizable group is any one of a nematic liquid crystalline compound, a smectic liquid crystalline compound, a discotic nematic liquid crystalline compound, a discotic liquid crystalline compound, and a cholesteric liquid crystalline compound. The hologram recording material according to any one of claims 4 to 9.   4. The hologram recording method according to claim 3, wherein hologram recording is performed at a temperature at which the liquid crystalline compound takes a liquid crystal state.   A hologram recording method using the hologram recording material according to any one of claims 4 to 10, wherein hologram recording is performed at a temperature at which the liquid crystalline compound takes a liquid crystal state.   The hologram recording method according to any one of claims 1 to 3, 11, or 12, wherein volume hologram recording is performed.   14. The hologram recording method according to claim 13, wherein multiplex recording is performed ten times or more.   15. The hologram recording method according to claim 14, wherein the multiple recording can be performed while the exposure amount at the time of multiple recording remains constant throughout the multiple recording.   A three-dimensional display hologram using the hologram recording material according to claim 4.   A holographic optical element using the hologram recording material according to claim 4.

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