TW200804968A - Photoreactive composition, optical material, optical recording material, volume hologram recording material, optical recording medium, and optical recording method therefor - Google Patents

Abstract

This invention provides a photoreactive composition which, when used in hologram recording, can realize reading of record without reducing a residual record capacity. The photoreactive composition comprises a sensitizer (A), which is exited upon photon absorption, and a polymer (B) containing a chemically convertible reactive group (C). In this case, the sensitizer (A) takes a reduced electron configuration relative to the reactive group (C).

Description

200804968 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a photoreactive composition, an optical material, and a body. μ 丨"1竹九έ己录,王像圮录材料, optical recording media, and complex, [previous technology] /, first 5 recorded methods.

The site can be used for high-density recording or multiple recording, so the activity is recorded. It is known that such a holographic image is used and that a phase hologram is used, and the amplitude hologram system uses a recording material, a transmittance change, a phase hologram, a recording material ratio, and a change in unevenness. In the % singular type hologram recording material, as a one-time writing method that does not require wet-free ε::, generally, a photopolymer method in which a group is polymerized in a sensitizer. The polymer-free mode can be simply a simple way to change the monomer or combination of substrates. - In particular, in the conventional photopolymer method using a sensitizer, it is difficult to suppress the volume shrinkage which occurs during recording. Therefore, the improvement of the volume shrinkage is improved by the following holographic recording technique, and the isomerization reaction is caused by the combination of the rearrangement reaction without combining the polymerization reaction (see Patent Documents 1 and 2). - In addition, a two-photon absorption type optical material (refer to Document 3) or a two-stage absorption type optical material (see Non-Patent Document 〇 for use in hologram recording) is also proposed. [Patent Document Π Japanese Patent Laid-Open 2002 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 94916 Non-Patent Document 1] The J〇urnal 〇f physical 1981, 85, 123. [Summary of the Invention] (The problem to be solved by the invention) However, by the patent document 丨~3, non-specialized When the holographic recording is performed by the technique disclosed in the 丨 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The object of the above-mentioned problems is to provide a photoreactive composition, an optical material using the same, an optical recording material, a volume hologram recording material, an optical recording medium, and an optical recording method thereof. Gate function In the case of holographic recording, recording and reading can be performed without destroying the recorded content. φ (Means for Solving the Problem) The inventor of the wood researched the above problems and found that by using a sensitizer and The photoreactive compound of the polymer having a reactive group can be used as a material for the recording medium of the king image, and a person having a reduced electron configuration with respect to the above reaction group can be used as the sensitizer. The holographic recording medium having a function (that is, a function of performing recording and reading without destroying the recorded content) has been completed. The present invention relates to a photoreactive composition characterized in that it contains a sensitizer (4) excited by absorption of photons, and a polymer (B) having a reactive group (C) which can be chemically converted by a 312XP/invention specification (supplement) scratching (4) 6114965 200804968, and the sensitizer ( a) having a reduced electron arrangement with respect to the reactive group (C) (part 1 of the patent application). w In this case, it is preferred that the sensitizer (A) is excited by absorbing two or more photons ( In addition, it is preferable that the sensitizer (excited by absorbing two or more photons of different wavelengths (Patent No. 3). Further, preferably, the sensitizer (A) is a multi-stage excited type sensitizer which is excited to a singlet excited state by absorbing photons of the first excitation light, and then transferred to the lowest triplet excited state by inter-system conversion, and then by A photon of a second excitation light having a different wavelength from the first excitation light is absorbed, and the excitation is a triplet excitation state higher than the lowest triplet excited state (the fourth application of the patent application). Further, preferably, the sensitization In the case where the substance (A) is excited, the reaction group (C) undergoes chemical 10 conversion due to the action of the excited sensitizer (A). The optical characteristics of the photoreactive composition change (application patent scope) Item 5). Further, it is preferred that the above chemical conversion is an isomerization reaction (item 6 of the patent application). - Other gist of the present invention relates to an optical material characterized by comprising the above-mentioned photoreactive composition (Application No. 7 of the patent application). Still another object of the present invention relates to an optical recording material characterized by comprising the above optical material (Application No. 8 of the patent application). Another object of the present invention relates to a volumetric holographic recording material, the special 312XP/invention specification (supplement) grabbing 8/96114965 7 200804968: in the above optical recording material of the package 3 (application for another patent of the invention) Having the above-mentioned recording medium, which is characterized by the layer of the recording material (the other patent of the patent application scope is related to the optical recording medium of the optical recording medium), is characterized by the above-mentioned optical recording medium. Lu/Xinguang (Application No. 11). (3) The above excitation is preferably to irradiate the reference light while illuminating the excitation light, and to record the image on the layer by the interference of the excitation light and the reference light. (Applicant's Patent Item No. 12) S. "Wang (Effect of Invention) According to the present invention, a photoreactive composition can be provided, using the same: two =: material, volume hologram recording material, optical recording medium, Two::= and the hologram recording method; the photoreactive composition can be performed without destroying the recorded content when the two images are recorded by the HDR [Embodiment] Hereinafter, the embodiment is not disclosed. The present invention will be described with respect to the present invention, and the present invention is not limited to the following embodiments, and may be arbitrarily changed without departing from the gist of the present invention. [I·Photoreactive Composition] The present invention The photoreactive composition contains a sensitizer (Α) excited by photons (hereinafter referred to as "excitation light" by appropriately including photons of an excitable sensitizer (Α)), and a polymer (Β) In addition, the polymer has a reactive group (C) which can produce chemical conversion. Furthermore, the so-called "(A)", r(B)" and r(c)" 312XP appear here. /Invention specification (supplement)/96-08/96114965 8 200804968 is a symbol for distinguishing a sensitizer, a polymer, and a reactive group. Further, the photoreactivity of the present invention is provided as long as the effect of the present invention is not significantly impaired. The composition may contain other components. ▲ Among them, in the photoreactive composition of the present invention, the sensitizing substance (A) phase • has a reduced electron arrangement for the reactive group (c). Here, the sensitizer (A) relative to the reactive group (〇 has a reduced electron configuration, refers to increase The substance (A) can provide an electronic configuration of electrons to the reactive group (C). Specifically, the sensitizer 10 (A) is higher than the reactive group (jjighest 〇CCUpied Molecular Orbital, HOMO). c) the highest occupied orbital energy ° [I - 1 · sensitizer (A)] sensitizer (A) is a substance that absorbs photons and is excited by excitation light (贞b cloud whole Or in the light-reactive composition of the present invention, in the case of appropriately stimulating the sensitizer, due to the action of the excited sensitizer (Α) The electron or energy is transferred to the like, and the reaction group (C) is chemically converted. Among them, as the sensitizer, those having a reproducible electron arrangement with respect to the reactive group are used. Here, the sensitizer w)i reactive group ((:) electron arrangement can be confirmed by oxidation-reduction potential measurement. ' As the sensitizer (A), for example, a well-known sensitizer can be used. Further, _ The term "sensitizer" is used to mean a molecule. The term "sensitizer (A)" means the whole or a part of a molecule. If an example of a compound which can be used as a sensitizer (A) is mentioned, Examples of synthetic dyes, natural colors, aromatic compounds, heterocyclic compounds, etc. 312XP/Invention Manual (supplement)/96-08/96114965 200804968 As a specific example of synthetic dyes, it can be used as a pigment, Dyes, scattered dyes? Azo dyes, materials, 噎 染料 dyes, 腼 imine dyes;:: benzene; two: dyes, dyed "wood, triphenylmethane dyes, nitrate ^ π than salina, dyes, times Methyl dyes, sulphur dyes, etc.

Further, as a specific example of the natural pigment, carotenoids, yellow S, township, r cyanine (factory cy Jbe), chlorophyll, cultivating, and browning may be mentioned. The non- morphine, ketone (deal) derivative 1 may be a polycondensation aromatic, and further, as a specific example of the aromatic compound, an oligomeric phenyl group, a copolydiene or the like. Specific examples of the heterocyclic compound include coumarin, aza: (4), aza, anthracene, benzo, anthracene, af bismuth, bismuth, pyrazoline, pyrene Yttrium imine, naphthyl imine, acridine, ruthenium sigma, heterocyclic salt, and the like.

7 is another sensitizer (1), and a pigment such as cyanine, phthalocyanine, phthalocyanine, purpurin, di-arylene, azopropion, D morphine, chlorophyll or the like may also be used. Among the X and the like, in particular, benzophenone, oligosporin, tetramorph, sulphur, and purpurin are preferred because they can function as multistage sensitized sensitizers (described below). Further, for example, a portion of the exemplified compound which exhibits a sensitizing action can be used as the sensitizer (A). Further, the sensitizer (A) may be used singly or in combination of two or more kinds in any combination and ratio. 3 Inventive specification (supplement)/96-08/96114965 200804968 In addition, 'in the sensitizer (A)' is preferably excited by absorbing two or more photons (multiphoton absorption) (for example, a multiphoton absorbing compound) Or part thereof). The reason for this is that, as described below, the photoreactive composition of the present invention achieves a non-destructive readout function by combining the redox properties of the sensitizer (A) and the reactive group (c), if used by When a person who absorbs two or more photons and excites (for example, a 'multiphoton absorption compound or a part thereof) as a sensitizer, the non-destructive readout function as a property of the sensitizer (A) can be more stably achieved. The following is a detailed description of the multiphoton absorption. The term "multiphoton absorption" means that the sensitizer absorbs a plurality of photons simultaneously or in stages until the energy required to start the reaction (chemical conversion) is supplied to the reaction body (in the present invention, the reaction group (c)). Fully orbital energy level U, hunting for mandatory excitation Q multiphoton absorption has (a) light emitted from a single wavelength source (see Figures i and 2), and absorbed from a number of different wavelengths The light emitted by the light source (refer to Figure 3). • (a) The photon absorption of light emitted from a single-wavelength source absorbs the multiphoton absorption of light emitted from a single-wavelength source, with (i) self-single-excited state (S1) supplying energy to the reactive group. ((:), and (ii) from the single-rehabilitation evil (S1) to the triplet excited state by inter-system conversion, (T1), from which energy is supplied to the reactive group (C). In the case of 1), the sum of the minimum required amount of photon energy is the amount of energy ΔΕ from the state of the substrate (SO) to the singlet excited state (S1). On the other hand, in the case of (ii) Next, the amount of energy required to reach the ego level of the single-shot sorrow (S1) from the basal state (so), the single-excitation 312XP/invention specification (supplement)/96-08/96114965 11 200804968 state (si It is possible to provide the triplet excited state (T1) even if energy is lost during the inter-system conversion, and needs to be higher than the energy. The case of absorbing the two photons and exciting the sensitizer (A) is exemplified in detail. Explain this feature. • Figure 1 is a diagram showing the state of electron transfer accompanied by photon absorption. In addition, in Fig. 基底, the base state (so) and the singlet excited state (S1) represent the actual energy state. In addition, the hypothetical state (Sx) represents the energy state of only one photon higher than the base state (so). Among them, the hypothetical state (Sx) assumes that the person 'is not the actual energy state. Therefore, the electron cannot be transferred under the imaginary state. (i) The absorption system is called simultaneous multiphoton absorption (in this case, At the same time, the absorption of 2 photons is absorbed. As shown in Fig. ,, when the excitation is performed, the sensitizing material (A) is irradiated with light (excitation light), and two photons are absorbed, thereby being in the basal state of the sensitizing substance (A). The electrons of (so) are transferred to the singlet excited state (S1), whereby the sensitizer (A) can be excited to activate the reactive group (c). Thus, in the simultaneous 2-photon absorption, the excitation is used. The energy level of 2 times the photon can be in the real excitation state, so that the wavelength of the absorption region (non-resonant region) in the absorption spectrum can be used to excite the molecule. Further, the non-resonant region will be used in this way. Wave of light causes a non-linear shape The case of absorption is called non-resonance 2 photon absorption. - The efficiency of this non-resonant 2 photon absorption is proportional to the power of 2 times of the optical electric field applied to the sensitizer (A) (2 power factor of photon absorption). Therefore, in the 3-dimensional space, only 2 photons are absorbed in the region where the applied light intensity is large, and 2 photon absorption is not caused in the region where the light intensity is weak. Since 312χρ/invention specification (supplement)/96- 08/96114965 12 200804968 This is compared with the linear absorption which is proportional to the intensity of the applied electric field and causes excitation at all positions. In the non-resonant 2 photon absorption, it is only inside the space due to the 2nd power characteristic. The specific area causes excitation, so the space division-solution energy is significantly improved. Further, in general, when non-resonant two-photon absorption is induced, a wavelength region having a wavelength higher than linear absorption (i.e., a wavelength region where photon absorption is present) is often used and wavelength laser light having no absorption is present. Therefore, a laser that transmits a transparent region (i.e., a laser that emits laser light in a wavelength region where i-photon absorption does not exist) is used as a light source for excitation light, and the laser light can be absorbed or scattered without reaching the photoreactive composition. internal. Further, in the above example, the case of absorbing two photons of two photons is exemplified, but the same advantage can be obtained by absorbing more photon absorption of three or more photons. In addition, in the case of inducing non-resonant two-photon absorption, the photon absorption cross-sectional area indicating the ease of absorption of two photons is not particularly limited, but preferably _ is usually 100 GM or more, preferably iooogm or more, more preferably Sensitizer (A) of 1 0000 GM or more. Furthermore, the evaluation method of the 2-photon absorption sectional area is as follows. The evaluation of the photon absorption cross-sectional area of the reference compound is carried out by the open-cell z-scan method disclosed in I (IEEE J. Quant. Electron 26 (1990) ~ 760). Two-photon absorption cross-sectional area • The light source used for the measurement is a T i · sapphire pulsed laser and an optical parametric oscillator laser excited by its laser. The pulse using the pulse as the light source has a width of 110 femtoseconds to 130 femtoseconds, a pulse repetition frequency of 76 Hz, and an average power of 10 to l 〇〇 mW. The wavelength range is from 570 nm to 1200 nm and is measured in 312 XP/invention specification (supplement)/96-08/96114965 13 200804968. The measurement system is disclosed in document i, using a lens to condense a pulsed laser beam from a light source to scan the sample to be measured in the forward direction (z-axis) of the laser beam, and to measure the transmittance at each sample position on the z-axis. rate. The root, the curve of the transmittance of each sample position obtained, the incident average power, the *incident wavelength, the incident pulse width, the sample concentration, and the thickness of the sample, etc., using the literature (Chem· Phys· Lett· 372, 386 (2003) The method disclosed in )) obtains a two-photon absorption cross-sectional area. Further, the so-called GM system indicates that each molecule and photon is 1>< 10, cm, and seconds (1 GM = lxl (r5. cm4.s / (molecule 'photon, molecule · photon)). Fig. 2 is a view schematically showing the state of electron transfer accompanying photon absorption. In Fig. 2, the same reference numerals as in Fig. 1 denote the same as Fig. 1. (ii) In the case of sensitization - (A) illuminating the excitation light; absorbing the i of the photons, whereby the electrons in the substrate state (s〇) are transferred to the single-excitation core Ui). Wherein, in the case of (lf), the electrons in the singlet excited state (Μ) are transferred to the triplet excited state (T1) by inter-system switching. Further, by this, the sensitizer (Α) can be excited to activate the reactive group (c). In the case of (U), the absorption phenomenon generated is simultaneous multiphoton absorption, and non-resonant two-photon absorption can be performed in the same manner as in the above (i), and the same advantages as in the case of (i) can be obtained. • At, in the case of (ii), the energy is lost from the single-excited state (S1) to the triple-excitation~IJDf-to-system conversion, so it is higher than (i) in order to excite the sensitizer (A). The energy of the situation. Furthermore, in the above example, the 2 photon absorption 312 XP absorbing instructions of 2 photons are exemplified (replacement V96働6114965 200804968), and the same advantages can be obtained in absorbing more photon absorption of more than 3 photons. In any of the above (i) and (ii), a plurality of photons are used to forcibly supply a quantity equivalent to the energy from the base state (S0) to the desired excitation state (phantom or T1). Therefore, in the case of a compound having absorption and a part thereof (a portion which exhibits a sensitizing effect), the sensitizer (A) can be used without particular limitation. However, in reality, if a large ultraviolet region is used, In the case of photon absorption, the energy is too high, and the sensitizer (A), the reactive group (c), other components, etc. may be destroyed. In addition, 'in the case of producing an optical recording medium using the photoreactive composition of the present invention', it may be damaged. The configuration of the optical recording medium such as a support body is another energy. In the case where the infrared region light is used as the excitation light, the energy is too low, and in order to supply the energy required for the excitation of the sensitizer (A) to the sensitizer, a large amount of the sensitizer is required. Photon, It is possible to significantly reduce the efficiency. Therefore, as a sensitizer (A) suitable for multiphoton absorption of light emitted from a light source of a single wavelength, for example, a compound having absorption in a visible region can be preferably used. Cyanine, phthalocyanine, ugly phthalocyanine, purple two stars: triarylmethyl 6, aziridine, morphine, chlorophyll and other pigments, or polycondensed aromatic rings, oligomeric phenyl groups, a total of two women and other aromatic compounds, or not Bean: aza coumarin, quinoline, azaquinoline, benzopyrene: oxadiazole, furan, benzofuran, pyrazoline, quinone imine, quinone imine, 0, miscellaneous a heterocyclic compound such as a cyclic salt, etc. Further, a compound which is sensitized as a sensitizer can be used as a sensitizer 312 ΧΡ / invention specification (supplement) / 96-〇8/96114965 15 200804968 (A) 〇(b) multiphoton absorption of light emitted from light sources of a plurality of different wavelengths as multiphoton absorption of light emitted from light sources of a plurality of different wavelengths, which may be multi-stage absorption. By absorbing the first light emitted from the first source (first excitation) Light photons cause the sensitizer (A) to be excited from the substrate state (SO) to a singlet excited state (S1), after which it is transferred to the lowest triplet excited state (T1) by inter-system conversion, and then by The photon of the second light (second excitation light) emitted from the second light source is excited to be a triplet excited state (Τη) which is south of the lowest triplet excited state (Π). Furthermore, the first light and the second light system are called Refers to the difference in wavelength. In this case, the triplet excited state (Τη) is the energy level with sufficient energy at the beginning of the reaction, and is supplied from the doublet excited state (Τη) to the reactive group (c). The energy of the initial reaction is described in detail by taking the case of absorbing two photons and exciting the sensitizer (A) as an example. Fig. 3 is a diagram showing the state of electron transfer accompanying photon absorption. In FIG. 3, the same reference numerals as in FIGS. 1 and 2 denote the same as those in FIGS. 1 and 2. This multistage absorption is referred to as the absorption of periodic multiphoton absorption (in this case, stage 2 photon absorption). As shown in FIG. 3, when the excitation is performed, the sensitizer (A) absorbs one photon of the first light, thereby causing the electron in the substrate state (so) of the sensitizer (a) to be single-excited (S1). Transfer. Thereafter, the electric-excited state (T1) existing in the single-excited state (S1) is transferred by the inter-system conversion. Mm-312XP/Invention Manual (Supplement)/96-〇8/96114965 16 200804968 Thereafter, the sensitizer (A) absorbs one photon of the second light. By absorbing the photon (second photon), the electron in the lowest triplet excited state (T1) of the sensitizer (A) is transferred to the triplet excited state (?n) at a higher energy level. By ▲ this can excite the sensitizer (A) and activate the reactive group (C). • In a system of staged multiphoton absorption, the wavelength of the first light that causes the first phase of excitation is preferably shorter than (which is high energy) the wavelength of the second light that is excited by the second stage. Further, when the sensitizer (A) is excited from the substrate state (s?) to the singlet excited state (S1), it is preferred to absorb light of the second wavelength only weakly, or not absorb at all. In addition, the 'single-excited state of the first stage (S1) and/or the lowest triplet excited state (T1) from which it passes through the inter-system transition is preferably an orbital level, ie, at the reactive group ( C) When the chemical conversion is started, there is not enough energy, and after the second stage of excitation, the triplet excited state (Tn) is excited to start chemical conversion. By selecting such a system, the so-called "light gate April b" can be given, that is, only light of any one of the first light and the second light can be used to supply sufficient energy to the reactive group (C). The chemical conversion of the reactive group (c) can be initiated by the irradiation of both wavelengths. That is, as described above, the phasic multiphoton absorption system is produced by the sum of the actual excitations. Therefore, the excitation wavelength of the first photon (that is, the first wavelength of light) does not occur if there is a region (resonance region) where absorption is not necessarily present. Therefore, in the case of using the sensitizer (4) which generates the phase 2 photon absorption, the optical recording medium hologram recording medium formed of the photoreactive composition of the present invention is irradiated only after the recording. Two wavelengths of luminescence (ie, first-light and second light) (ie, 312XP/invention specification (supplement)/96_〇8/96114965 200804968 first to Ψ彳-T) Does not stimulate the sensitizer (A). . Furthermore, in the above example, two photons of two photons are taken as an example, but the same advantages can be obtained in the phase multiphoton absorption of absorbing three or more photons. As a sensitizer (A) suitable for such a staged multiphoton absorption, a compound having at least one condition under fit is mentioned. (1) The 7 p of the singlet excited state (S1) is longer (2) The singlet excited state (S1) has less fluorescence, that is, the inter-system conversion efficiency is good; and (3) the lowest triplet excited state (τι) has a longer lifetime. In addition, the more the right meets the above-mentioned necessary conditions, the better. Specific examples of the preferred sensitizer (Α) which satisfy such a ', and the 'parts' may be exemplified by purple, poly sigma, koushankou, g too: it, mining-main ^,乃 ^ 酞月香素, oral azole, benzophenone, low-concentration base, Blessing, etc. In addition, you can also use 兮望-vj" to use 忒 and other compounds to play The two parts are used as the sensitizer (A). Further, regarding the sensitizer (A) suitable for the stage multiphoton absorption, the quantum yield (φτ) of the triplet excited state is not particularly limited, preferably 0.5 or more, more preferably 0.7 or more, and even more. Jia is more than 9 years old. In addition, there is no special system for the triplet doublet Mohs absorption (ετ) in the wavelength region of the excitation light of the second stage of the money (1), preferably iq, _: above, more preferably 50,000 or more, further It is preferably 1 inch or more. The quantum yield (Φτ) and the triplet state of the triplet excited state—the absorptivity coefficient (the method of evaluation of (1) is the method disclosed in the document niU:e:tc ear Faraday Trans·(3)(10)川(10)). This ^, using the 3rd spectral wave or m skin of the Q-switch YAG laser as the light source. ',,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The excitation of the stage, the excitation of the second stage, etc.) are independent, such as r(a) is absorbed from a single wavelength source. As illustrated by the photon absorption of light, it can be caused by absorbing a plurality of photons of each wavelength. Further, when an exciter (for example, a multiphoton absorption compound or a portion thereof) is used as a sensitizer by (multiphoton absorption), when an optical recording medium is produced using the photoreactive composition of the present invention, The optical recording medium can be recorded or reproduced using excitation light of a relatively long wavelength. Therefore, the following advantages can be obtained: • The short-wavelength laser which is generally expensive and difficult to obtain can be used, and the long-wavelength laser which is inexpensive and easily available can be used for recording and reproduction, and the reaction originally caused by the ultraviolet laser is caused by the visible light laser. Therefore, it is possible to suppress a side reaction which is easily generated by ultraviolet light, and it is possible to record a good recording quality. Further, in the above multiphoton absorption, the shutter function can also be realized, so that it is better to phase multiphoton absorption than Φ. Therefore, as the sensitizer (A), a multi-photon absorbing compound or a portion thereof, it is preferred to use a multi-stage excited type multiphoton absorbing compound (multi-stage excited type sensitizer) which produces phase multiphoton absorption or a part thereof As a sensitizer (A). Further, as described above, in the case where the sensitizer (A) absorbs two or more photons, it is preferable to excite by absorbing two or more photons of different wavelengths. Here, the type of the photon wavelength means a case where the wavelengths are each other 3 〇 nm or more, more preferably 50 nm or more. By making the wavelength of the photons absorbed by the sensitizer (A) into two or more types, it is possible to obtain the advantage that the step 312XP/invention specification (supplement)/96·08/96114965 19 200804968, multiphoton absorption can be performed. When the photoreactive composition of the present invention is used to achieve the above-mentioned periodic photon absorption, the first excitation first and the second excitation light are used, and the wavelength of the photon is two. Further, the content of the sensitizing substance contained in the photoreactive composition of the present invention is arbitrary as long as the effect of the present invention is not significantly impaired, but the photoreactive composition is usually 〇·001 weight. More than %, preferably 〇· 01. More than or equal to 5% by weight, and more preferably 重量·i by weight or more, and usually it is weight = /g or less, preferably 4% by weight or less, more preferably 3% by weight or less. If the amount of the sensitizing material (A) is too small, the sensitivity may be lowered. If the amount of the sensitizing material (A) is too large, the absorption of light for recording or reproduction may become large, and it may be difficult for the light to reach the depth direction. Further, in the case where the sensitizing substance (A) is a part of a compound (for example, a functional group or the like), the sensitizing 狯(a)f may be contained in the polymer as long as the effect of the present invention is not impaired. )in. In the case where the sensitizing substance (A) is contained in the polymer (B), the sensitizing substance (A) may be contained in the polymer (B) as a side chain, or 10 may be contained in the polymer (B). One part of the main chain. Further, the ratio of the sensitizing substance (A) to the reactive group (〇 is not limited. [I 2· polymer (B) and the reactive group polymer (B) are reactive groups capable of generating a specific chemical conversion (c) Any polymer can be used. Here, the reverse group, the base (c) will be described first, and then the polymer (B) will be described. The reactive group (C) can actually participate. The atomic group for chemical conversion may use any group which produces a chemical conversion. The chemical conversion produced by the reactive group (c) is not limited, and the 312 edge/invention specification may be arbitrarily used according to the use of the photoreactive composition of the present invention ( Supplement)/96-08/96114965 20 200804968 Conversion with an appropriate chemical, wherein the reactive group (¢) is preferably chemically converted when the sensitizer (A) is suitably excited. Therefore, the reactive group (C) The chemical conversion is preferably produced by the action of the excited sensitizer (A). If a preferred embodiment is given in the chemical conversion of the reactive group (C), an organic reaction may be mentioned. For photoreaction, polymerization, polymer reaction, etc. Examples of the reaction include an isomerization reaction, a rearrangement reaction, a cyclization reaction, a dimerization reaction, a dehydrogenation reaction, an addition reaction, and the like. Specific examples of preferred chemical conversion are given below. Further, the exemplified chemistry is as follows. In the conversion, it is exemplified that the compounds react with each other, but it is understood that one of the exemplified compounds reacts as a reactive group (c) in the chemical conversion. Therefore, the chemical conversion exemplified herein is applied to the reactive group. In the case of (C), the chemical conversion of the exemplified compound (this portion corresponds to the reactive group (c)) is replaced by the chemical conversion using the compound. • As an example of the isomerization reaction, an olefin, An isomerization reaction of an azo compound or a carbonyl compound, etc. As a specific example of the earth, as an isomerization reaction of an olefin, a cis-trans isomerization reaction (for example, stilbene, anthracene, 3-pentane) a diene, a cyclic olefin, a cis-trans isomerization reaction of an olefin conjugated with a carbonyl group, a nitrogen compound, etc. - In addition, as an isomerization reaction of an azo compound, cis-trans isomerism Examples of the rearrangement reaction include a rearrangement reaction of an olefin, a polyene, an alkene with a compound, a light rearrangement reaction of a compound, and the like. 312XP/Invention Manual (Supplement)/96-08/ 96114965 21 200804968 As a specific example, a rearrangement reaction of an olefin and a polyene may be carried out by a cyclization reaction and an isomerization reaction by intramolecular rearrangement of protons, and -7Γ - a rearrangement reaction of a methane compound (for example, a rearrangement reaction generated by an ethylenecyclopropane-forming reaction using a 1,4-pentadiene derivative, and utilizing a cyclic bis-7Γ- A rearrangement reaction (for example, a rearrangement reaction of norbornadiene-tetracycloalkane), etc., which occurs during the formation reaction of cyclopropane by methane light rearrangement. Further, for example, as a rearrangement reaction of the ketene compound, a rearrangement reaction of 1,2-aryl group and photoketone rearrangement in α, Cyclohexenone, and cyclopentenone may be mentioned. Light rearrangement reaction, stone, light rearrangement reaction of r-fluorenone, rearrangement reaction of dienone compound (formation reaction of dicyclohexene or hydroxyketone by 2, 5-cyclohexadienone) Rearrangement reaction during production; rearrangement of hetero-2, cyclohexadienone, 2,4-cyclohexadienone, and rearrangement reaction during ring-opening reaction; indophenol ketone (cycloheptatriene) a rearrangement reaction produced by a photochemical reaction of a ketone). Further, for example, as a photoreaction reaction of a carbonyl compound, a light rearrangement reaction which occurs when a ketene and an aldehyde are formed by decomposition of a cyclic ketone, and a decarburization reaction of a carbon oxide by a carbonyl compound The light rearrangement reaction by Rizhao, the ring-extension reaction by a cyclic ketone, and the light rearrangement reaction produced by the formation reaction of a cyclic ether. Examples of the cyclization reaction include a cyclization reaction of a diene and a triene, a photocyclization reaction of stilbene and a derivative thereof, and an intermolecular photocyclization reaction of an olefin. As a specific example on the right, the cyclization reaction of an alkene and a triene can be exemplified by the intramolecular cyclization reaction of a non-conjugated diene by 3 UXP/invention specification (supplement)/96-08/96114965 22 200804968 The cyclization reaction produced during the formation reaction of cyclobutane, the cyclization reaction produced by the formation reaction of cyclobutene by the cyclization of the molecule of the conjugated diene, and the cyclic conjugated diene The cyclization reaction, the ring formation reaction with a diene by ring opening of dicyclohexadiene, the cyclization reaction of a heterocyclic diene and a triene, and the like. Further, examples of the photocyclization reaction of stilbene and a derivative thereof include a photocyclization reaction during synthesis reaction of phenanthrene, a photocyclization reaction of azobenzene or an aniline derivative, an anthrone and a heterocyclic ring. The cyclization reaction of styrene and the like. Further, as the intermolecular photocyclization reaction of an olefin, an intermolecular photocyclization reaction of a conjugated dilute hydrocarbon and an olefin, an intermolecular photocyclization reaction when a photoaddition reaction to an enone compound, and an acetylene to an olefin are mentioned. The intermolecular photocyclization reaction which occurs during the addition reaction, and the intermolecular photocyclization reaction which occurs when an aromatic ring of an olefin is subjected to an addition reaction. Examples of the dimerization reaction include a photodimerization reaction of an ene cigarette. In the photodimerization reaction of the olefin, a photodimerization reaction occurring during the formation reaction of cyclobutane by dimerization of an alkyl olefin, and dimerization by an aromatic olefin is carried out. Photodimerization reaction in the formation reaction of cyclobutane, dimerization by a dimerization of a common olefin, photodimerization reaction in the formation reaction of divinylcyclobutane, and use of an enone compound Photodimerization reaction (for example, photodimerization reaction of a chain ketene compound; photodimerization reaction of a cyclopentenone, a cyclohexenone, a heterocyclic ring, etc.) during the formation reaction of cyclobutane by dimerization; Photodimerization of lanthanide compounds, fumaric acid and maleic acid and its derivatives 312XP/invention specification (supplement)/96-08/96114965 23 200804968 Photodimerization reaction of the substance. Examples of the deoximation reaction include a dehydrogenation reaction of a carbonyl compound. Specific examples of the dehydrogenation reaction of the carbonyl compound include an intramolecular dehydrogenation reaction of an aromatic ketone, a depurination reaction generated by a cycloalkyl ketone to form a cyclobutanol reaction, and a cyclic ketone formation. Dehydrogenation reaction during the reaction of bicyclic alcohol, dehydrogenation reaction in the molecule of diketone, α, depurination reaction in the knife of non-unsaturated ketone, cyclization of ortho-substituted aromatic ketone and enolization reaction The dehydrogenation reaction which occurs, the dehydrogenation reaction which occurs during the intramolecular cyclization reaction of quinone imine, the dehydrogenation reaction which occurs when the carbonyl group is reduced, and the like. As an example of the addition reaction, an addition reaction of an olefin of a carbonyl compound or the like can be given. When a specific example is given, an addition reaction to an olefin of a carbonyl compound may be carried out by an addition reaction of an oxetane which is carried out by reacting an olefin with an electron-rich olefin; An oxirane produced by the reaction of an oxetane with an electron-deficient olefin, and an oxetane produced by an intramolecular addition reaction of an unsaturated ketone; An addition reaction generated when a reaction is formed; an addition reaction generated by an oxetane formation reaction by an addition reaction of an olefin having an electron attracting group; benzoquinone, fluorination _ Addition reaction of olefins such as benzene and the like. Further, as another chemical conversion, a photoreaction of an aromatic compound or the like can be given. Examples of the photoreaction of the aromatic compound include an isomerization reaction of benzene and a derivative thereof, an isomerization reaction of pyridine and a derivative thereof, an addition reaction to an aromatic ring, and photo-baking (Ph〇). T〇_fries) rearrangement ^ 312XP / invention manual (supplement) / 96-08/96114965 24 200804968 Substituting benzene age and aniline synthesis reaction, photoreaction reaction of aromatic compounds (nucleophilic reaction of xiaojifang g private compound, benzene A photo-substitution reaction of methyl ether or a halogenated benzene or the like, a photo-substitution reaction of a polysubstituted benzene, a 'photoaddition or substitution reaction of benzonitrile, and the like. Further, examples of the polymerization reaction include an addition polymerization reaction, a transition metal catalyst polymerization reaction, a ring-opening polymerization reaction, a cyclization polymerization reaction, a polycondensation reaction, and a polyaddition/addition condensation reaction. • /乍 is an addition polymerization', for example, a radical polymerization reaction (for example, ethyl hydrazine, vinyl chloride, vinyl acetate, vinylidene chloride, styrene, butadiene, methacrylic acid monomer, acrylic monomer, propylene) Radical polymerization of nitrile or the like), cationic polymerization (for example, cation polymerization of styrene, isobutylene, ethyl bond, N: B: ί: azole, etc.), anionic polymerization (example ': Q~butene) , an anionic polymerization reaction of a τ-based acrylic monomer, an acrylic monomer, or a nitroethylene), a plasma polymerization reaction, or the like. In addition, examples of the transition metal catalyst polymerization reaction include a polymerization reaction using a φ medium (for example, a catalyst polymerization reaction of an olefin, a styrene, an ethylene block, or a diene), and a polymerization reaction using a metathesis catalyst ( For example, a catalyst polymerization reaction of a cyclic olefin, a lump tobacco, a diene or the like) is additionally carried out as a ring-opening polymerization reaction or the like. For example, a ring-opening of a cyclic monomer can be cited as a "molecular reaction, and for example, a crosslinking reaction (for example, a lactam-amine reaction, an epoxy-sulfur reaction, a residue, and a g|_amine reaction) should be mentioned. Unsaturated ester-thiol reaction, hydrazine hydrogenation reaction, urethane ethylation reverse 312XP/invention specification (supplement)/96-08/96114965 25 200804968, etc.; synthesis of dendrimer, etc. Preferably, the isomerization reaction and the rearrangement reaction are used. As the reactive group (C), by using an isomerization reaction or a rearrangement reaction, the advantage of being small in free volume and not easily depending on the surrounding environment can be obtained. Further, as the chemical conversion, it is preferred to use the chemical conversion to cause the optical characteristics of the photoreactive composition of the present invention to be changed. That is, in the case of exciting the sensitizer (A), it is preferred. In order to use the reactive group (c), the optical properties of the photoreactive composition of the present invention are changed by chemical conversion by the action of the sensitizer (0). As the optical characteristics of the change here, Refractive index, Abbe number (inverse dispersion rate) Preferably, the refractive index is preferably used. Thereby, the photoreactive composition of the present invention can be preferably used as the hologram recording material. As described above, the optical characteristics of the photoreactive composition field are changed. Examples of the conversion include an addition reaction, an isomerization reaction, a rearrangement reaction, a cyclization reaction, etc. Among them, in order to cause a large change in the refractive index, it is preferable to be an isomerization reaction, a rearrangement reaction, The cyclization reaction is exemplified as a cis-trans isomerization reaction, and a more preferable reaction is exemplified by an azo compound cis-trans isomerization reaction. In the specific examples of the particularly preferred rearrangement reaction, an intramolecular rearrangement reaction of an olefin or a polyene can be mentioned. Among them, a better reaction can be carried out by a rearrangement reaction from a woman to a tetracyclic ring. Further, examples of the particularly preferable cyclization reaction include an intermolecular photocyclization reaction. Among them, a more preferable reaction is a molecule of ruthenium 312 χ ρ / invention specification (supplement) / 96-08 / 96114965 26 200804968 Photocyclization reaction Furthermore, in the chemical conversion towel, it is not necessary to use (4) which part of the photoreaction as the reactive group (C): the F of the product is used, but it is presumed that at least part of the chemical deuteration reaction of the disc is used as the reactive group (c) In addition, in the case of /, f, when the refractive index change is changed as the optical characteristic, the refraction is not limited, but it is preferable that the 〇.001 is usually 0.01 or more, more preferably 〇〇5 or more. The reason is that the change in refractive index is the result of the change in the refractive index, and the degree of repetition of the S record can be increased as the value of α is reduced from the I. The more the recording capacity per unit volume can be expanded. Examples of the chemical conversions include halo-diluted bases, etc. J's eight-body j is 'the best use of purple as the yang (Α), and the lower blessing base is used as the reactive group ( C). The reaction group (C) may be used singly or in combination of two or more kinds in any combination and in any ratio. Therefore, the polymer (8) may have two or more kinds of reactive groups (C). Further, the molecular weight of the reactive group (C) is not limited. The number of reactive groups (c) having T and having a polymer (8) is also not limited. /, 'The polymer' (B) will be described. κ & (B) is a polymer having a reactive group (c). In this case, the reactive group (^) may be contained in the polymer (8) as a side chain 'and may be contained in the polymer (8) as a part of the main chain. Further, in addition to this, a reactive group (c) which is not contained in the polymer (B) may be contained. The polymer (B) may be a polymer obtained by polymerizing only a monomer, or may be a copolymer of 312XP/invention duck (supplement) grab 08/96114965 27 200804968 monomer copolymerized in any combination and ratio. Things. The type of σ is not limited, and a polymer using any type of polymerization such as block polymerization, random addition, or graft polymerization can be used. Further, the polymer (8) may be linear and the village is branched. In the case of the right 歹1 kk ** compound (8), it can be exemplified by a reactive group (C) t polymethacrylic acid vinegar, polyacrylic acid vinegar, polystyrene (tetra) vinegar, poly brewing

Makeup, polyurethane, polycarbonate, polyether, cellulose ester, polyvinyl ester, polyvinyl ether, polyoxyalkylene, polyolefin derivative, and the like. In addition, the polymer (8) may be used singly or in combination of two or more kinds in any combination and in any ratio. According to the viewpoint of improving the sensitivity at the time of photoexcitation, the polymer (B) is an optically transparent n-polymer (B) in the spectral region (ie, in the wavelength region) which is absorbed in the sensitizing material (A). It is preferred that there is no meaningful absorption within the wavelength (excitation wavelength) of the excitation light. Specifically, the haze of the polymer (B) having a thickness of 1 _ is usually 3% or less, preferably 10% or less, more preferably 5% or less. Further, the smaller the haze, the better, and the lower limit is 0%. Further, as the polymer (B), it is preferred that the chemical conversion of the reactive group (c) is not hindered. Namely, it is preferred that the chemical conversion of the reactive group (c) is not hindered by a portion other than the reactive group (C) in the molecular structure of the polymer (B). Further, the polymer (B) may have a substituent in addition to the reactive group (C) as long as the effect of the present invention is not significantly impaired. Further, the substituent may be used singly or in combination of two or more kinds in any combination and in any ratio. Further, the weight average molecular weight of the polymer (B) is not limited as long as it does not significantly impair the effects of the present invention, and is usually just above, preferably not more than 312XP/invention specification (supplement)/96-08/96114965 28 200804968. It is 3,000 or more, more preferably 5 〇〇〇 or more, and even more preferably 1 〇 or more. Furthermore, there is no (four) upper limit. If the molecular weight is , (4) f (four) life is shortened. Further, the weight average molecular weight of the polymer (8) can be measured by Gpc (gel permeation chromatography). Among them, from the viewpoint of prolonging the storage life of the photoreactive composition of the present invention as a recording material, a material or a volume hologram recording material, it is preferred to reduce the micro-Brown movement of the polymer (B) at the time of use. In order to achieve the object, the glass transition temperature Tg of the polymer (B) is usually 2 〇 t: or more, preferably 30 C or more, more preferably 50 c or more, and usually 3 〇〇 t > c or less. Preferably, it is 290 ° C or less, more preferably 28 ° ° C or less. The effect of the present invention is not significantly impaired. The content of the polymer (B) contained in the photoreactive composition of the present invention is arbitrary.

Further, the synthesis method of the polymer (B) is not limited. For example, the reactive group (C) may be bonded to any polymer (the polymer before the reactive group (c) is bonded) to produce a polymer (Bh is a reaction carried out during the synthesis, and for example, an aminocarboxylic acid may be mentioned. g, s, sulphide, sulfide, oxo-epoxy reaction, amine-epoxy reaction, thiol-epoxy reaction, hydrazide reaction, anhydride-amine reaction, etc. [I (3) Other components] The photoreactive composition of the present invention may contain other components (additives) in addition to the sensitizer (A) and the polymer (B). For the purpose of (A) excitation (controlling the excitation wavelength or excitation energy, etc.), controlling the reaction, improving the characteristics, etc., the 312XP/invention specification (supplement)/96-08/96114965 29 200804968 can be used as a control. The additive to be excited by the sensitizer (A) may, for example, be a sensitizing aid. Further, as an additive for controlling the reaction, for example, an initiator, a chain transfer agent, a polymerization stopper, and a compatibilizing agent may be mentioned. Reaction aid, etc. Further, as a characteristic change The additive may be a dispersant, an antifoaming agent, a plasticizer, a preservative, a stabilizer, etc. In order not to impair the effect of the present invention, the amount of the additive used is Rens. Among them, the photoreactivity of the present invention The concentration in the composition is usually _0·001% by weight or more, preferably 〇·〇1% by weight or more, and usually 30% by weight or less, preferably 10% by weight or less. Since the sensitizer (A) has a reduced electron arrangement with respect to the reaction group (c), when the photoreactive composition of the present invention is used for an optical recording medium such as a hologram recording medium, the recorded content can be prevented from being destroyed. Recording and reading are performed. The reason for obtaining such excellent advantages is presumed as follows. Fig. 4 is a view showing the sensitizing substance at the time of reading when the sensitizer has an oxidized electron pairing with respect to the reactive group. Fig. 5(a) to Fig. 5(c) show the sensitizer and reaction at the time of reading when the sensitizer has an oxidized electron arrangement with respect to the reactive group. A diagram of an example of the electronic configuration of the base. Further Fig. 6 is a view showing an example of the change of the sensitizing substance (A) and the reactive group (c) in the photoreactive composition of the present invention, and Fig. 7(a) to Fig. 7(c) is a view showing an example of the electronic arrangement of the sensitizing substance (A) and the reactive group (c) in the photoreactive composition of the present invention, as an example of the optical recording medium. Including sensitizer (sensitizer 312XP / invention specification (supplement) / 96-08/96114965 30 200804968 (A), etc.), and a substance having a reactive group (reactive group (c), etc.) The composition of the composition forms a volume holographic recording medium. First, the case where the sensitizer has an oxidized electron arrangement with respect to the reactive group will be described. The readout light (reproduced light) is irradiated to the volume hologram recording medium in order to read the information recorded in the volume hologram recording medium. When the readout light is irradiated, the sensitizer is excited (refer to step 1 of Fig. 4). At this time, the electrons in the occupied orbit A0 of the sensitizer are transferred to the intermediate space 对应 corresponding to the intensity of the illuminating light (see Fig. 5(a)). Thus, a vacancy occurs in the occupied orbit Α0 of the sensitizer, and electrons can enter (see Fig. 5(b)). In this example, since the sensitizer has an oxidized electron configuration with respect to the reactive group, the energy level of the occupied orbital Α0 of the sensitizer is lower than the occupied axis of the reactive group. Therefore, as indicated by the solid arrows in Fig. 5(b), electrons are transferred from the occupied channel C0 of the reactive group to the occupied orbit A0 of the sensitizing substance which generates the above-mentioned void. The reactive group is oxidized by the transfer of the electrons (refer to _steP2 in Fig. 4). As shown in Fig. 5(c), the oxidized reactive group is in an excited state in which only one electron is present in the occupied channel C0, so that it is in an active state in which chemical variability can occur. The reactive group of the activated state may cause chemical conversion. If the reactive group is converted into a chemical conversion, it sometimes causes damage to the recorded content. That is, the chemical conversion is caused by the fact that the information is generated when the information is written, and the chemical conversion is caused when the information is read, which causes the hologram of the recording unit to change and destroys the recorded content. Further, in Figs. 5(a) to 5(c), A1 and C1 respectively indicate the stagnation of the sensitizer and the reactive group. 312XP/Invention Manual (Supplement)/96-08/96114965 31 200804968 In contrast, the case of forming a volume hologram recording medium using the photoreactive composition of the present invention is as follows. That is, when the reading light is applied to the volume hologram recording medium at the time of information reading, the sensitizing material (A) is excited (see step 1 of Fig. 6 -). At this time, the electrons on the occupied orbit A0 of the sensitizer (A) are transferred to the intermediate space 对应 corresponding to the intensity of the read light (see Fig. 7(a)). Thus, a vacancy occurs in the occupied orbit Α0 of the sensitizer (Α), and electrons can enter (see Fig. 7(b)). However, in the photoreactive composition of the present invention, since the sensitizer (Α) has a reduced electron arrangement with respect to the reactive group (C), the energy level of the occupied orbital Α0 of the sensitizer (Α) is higher than The occupied orbital (C) occupied orbital c〇. Therefore, electrons are not transferred from the occupied orbit C0 of the reactive group (C) to the occupied enthalpy of the sensitizer (A) which causes the above-mentioned void. Further, by controlling the energy of the read light within an appropriate range or the like, if the intermediate air enthalpy is lower than the empty channel C1 of the reaction group (C) (that is, if it is not located in the sensitizer (Α) If the electrons on the Α0 提供 提供 提供 提供 提供 提供 提供 提供 提供 提供 电子 电子 电子 电子 电子 电子 电子 电子 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ). Therefore, as indicated by the solid arrows in Fig. 7(b), the electrons transferred on the intermediate track ^ will be transferred to the occupied track A of the sensitizer (A). Thus, the sensitizing substance (A) is relaxed and returned to the state before the excitation (refer to Fig. 7 (c)), and the reaction group (c) is still inactive (refer to Fig. 6).

SteP2). Therefore, the reactive group (C) does not cause chemical conversion and does not damage the recorded content. Further, in Fig. 7(a) to Fig. 7(c), A1 indicates the sensation of the sensitizer (1) 312XP/invention specification (supplement)/96-08/96114965 32 200804968 orbit. In the above manner, it is presumed that the photoreactive composition of the present invention can be recorded and read without destroying the recorded content. Further, as described below, if appropriate excitation light is irradiated, the reaction group (C) undergoes chemical conversion. That is, in the photoreactive composition of the present invention, the following function (i.e., the shutter function) can be realized, that is, if the light of a specific condition is used, the reaction group (c) can be chemically converted. Under the condition light, the reaction group does not undergo chemical conversion. Specifically, the energy supplied to the sensitizer according to the illuminating light is controlled to be a chemical conversion in the intermediate space orbit 高于 which is higher or lower than the empty orbit C1 of the reactive group (C). Further, when the photoreactive composition of the present invention is used for hologram recording, 'the sensitizer (A) is excited, and the reactive group (C) is caused by the action of the excited sensitizer (a). Chemical conversion, by which you can read and write information ^ below, to illustrate its mechanism. As a mechanism for chemically converting the reactive group (c) by the action of the excited sensitizer (A), for example, a case where the reactive group (c) is activated by reduction, and The case where the reaction group (C) is activated by energy transfer. First, the reaction group is described by reduction (Fig. 8(a) to Fig. 8(c) are respectively shown in the photoreactive composition of the present invention, and the reaction is carried out by reduction. In the case of activation of the group (C), an example of the electronic arrangement of the sensitizer (A) and the reaction group (C) at the time of writing. In addition, in FIGS. 8(a) to 8(c), A0 and A1 respectively indicate the electronic arrangement of the occupied and empty orbits of the sensitizing substance (A), and co and C1 respectively represent the electronic arrangement of the occupied circuit and the airway of the reactive group (c). 312XP/Invention Manual (Supplement) /96-08/96114965 33 200804968 In the present example, when information is written, the photoreactive composition of the present invention is irradiated with recording light, and the sensitizer (A) absorbs photons of the recording light. As shown in Fig. 8(a), the energy of the photon is used to transfer the electrons on the occupied ridge A0 of the sensitizer (A) to the empty track A1 (refer to the arrow head of the figure). As shown in Fig. 8(b), the electrons on the occupied channel A0 of the sensitizer (A) are transferred to the airway A1. The electrons transferred to the empty track μ of the sensitizer (A) are followed by , as shown in Figure 8(b) _ As shown in the foregoing, it is transferred to the empty channel C1 of the reactive group (C). That is, the reactive group (C) is reduced by receiving electrons from the sensitizing substance (A). As a result, as shown in Fig. 8(c) It is shown that the reactive group (having an electron in the empty channel C1 is in an active state. Therefore, thereafter, the reactive group (C) in the living state is chemically converted. Thus, if the chemical conversion is used for information writing, The volume hologram recording medium can be formed using the photoreactive composition of the present invention. That is, the volume hologram recording medium can write information by absorbing the photons by the sensitizer (A). _ Secondly, by energy transfer The reaction group (the case of hydrazine activation will be described. Fig. 9(a) to 9(c) are respectively shown in the photoreactive composition of the present invention, and the reactive group (c) is activated by energy transfer. In the case of the sensitizer (A) and the reaction group ((:), an example of the electronic arrangement of the case of writing. In addition, in Fig. _ to Fig. 9 (AUA1 indicates that the sensitizer (1) is occupied, respectively. The electronic configuration of the executive, (3) and C1 respectively indicate the electronic configuration of the reactive base (c) In this example, when the information is written, the photoreactive composition of the present invention 312XP/invention specification (supplement)/96-08/96114965 200804968 is irradiated with recording light 'sensitizing matter (A) absorption As shown in Fig. 9(a)f, the energy of the photon is the same as that of the above-mentioned Fig. 8(^) and is the same as that of the case of reduction, which is used to make the sensitizer (A) - The electrons are transferred to the air-passing lane Al (refer to the arrow of Fig. 9(a)). Thereby, as shown in Fig. 9(b), the electrons on the occupied orbit A0 of the sensitizer (A) are transferred to Empty track A1. In addition, there is a vacancy in the possession of the sensitizer (A). φ = electrons transferred on the empty channel A1 of the sensitizer (A), and then transferred to the empty channel C1 of the reaction group (C) as indicated by the solid arrow in Fig. 9(b). Further, at this time, since there is an energy difference between the empty orbit A1 of the sensitizer (A) and the empty carrier C1 of the reactive group (c), energy (+ ΔΕ) is generated due to the transfer of the electrons. This energy (+ Δ£) is used as the energy (-ΔΕ') for the electron self-reactive group (the transfer of C0 to the sensitized soft (A). As shown by the dotted arrow in Fig. 9(b), electrons are transferred from the occupied orbit C0 of the reactive group (C) to the sensitizer (A) by the ancient obedience A. The soil is as shown in Fig. 9(c). By the transfer of the above-mentioned electrons, there are two electrons in the occupied orbit A0 in the sensitizing material (A), and no electrons are present in the empty orbit A1. On the other hand, the state is as follows. In the reaction group (C), one electron is present in each of the occupied orbital C0 and the empty orbital C1. The reactive group (c) having electrons in the empty orbital C1 is in an active state. Therefore, it becomes a reactive group (C). Further, in this example, the amount of electrons in the sensitizing substance (A) and the reactive group (C) does not change, and no oxidation or reduction occurs. However, self-sensitizing substances (a) may occur. Energy transfer of the reactive group (C), as a result of which the energy is excited by the energy transferred by the 312 ΧΡ/invention specification (supplement)/96·〇8/96114965 200804968 The reaction group (c) is activated by the transfer of the base (c). The reason is that in this example, by using the energy, if the chemical conversion of the reactive group (6) activated by the energy transfer is used, the information is used. The photoreactive composition of the invention forms a volumetric holographic recording medium that can be written into a beryllium. That is, by absorbing the photons by the sensitizer (A), the volume holographic recording medium can also write information.

Further, according to the photoreactive composition of the present invention, the storage life in the case of a volume hologram recording medium can be prolonged. Specifically, the storage life of the film is determined depending on the composition of the photoreactive composition or the use environment of the volume hologram recording medium. Here, the capital A' written in the volume hologram recording medium using the photoreactive composition of the present invention has a temperature of usually 3 years or more, preferably 1 year or more, and more preferably at a temperature (25 ° C). The storage life of more than 3 years is the reason for achieving such a long shelf life. However, according to the research of this month, it is speculated that the reaction group (c) is bonded to the polymer (Β) ^ That is, it is presumed that since the polymer (Β) has a reactive group (c), the interaction acts in coordination, thereby achieving a long storage life. [Π. Use] The photoreactive composition of the present invention can be used as a material in the industrial two-member domain. If it is used as an optical material, the characteristics of the photoreactive composition of the present invention can be effectively utilized, so that it is preferable. . In the case where the photoreactive composition of the present invention is used as an optical material, the photoreactive composition of the present invention can be used alone as an optical material, or can be used as a photo-reactive composition. Optical material. Other 312XP/Invention Manual (Supplement 200804968 Ingredients are not limited to 'For example, 'Dispersing agents, color materials, etc.' can be used. In addition, the amount of other components used is also arbitrary. The use of optical materials is also arbitrary, especially for use. Further, the optical recording material is preferably a # volume hologram recording material, whereby the advantages of the above-described photoreactive composition of the present invention can be effectively utilized. [m · Optical recording medium] Optical recording of the present invention The medium uses the photoreactive composition of the present invention as an optical recording medium or a volume hologram recording material to form a part of the material information recording. If the photoreactive group of the present invention is included, the composition is not limited and is arbitrary. Hereinafter, an embodiment of an optical recording medium of the present invention will be described in detail. The optical recording medium of the present embodiment includes a recording layer formed of an optical recording material, and the optical recording material contains at least the photoreactive composition of the present invention. In addition, the optical recording medium has a support and other layers as needed.

Composition. [Guayi 1 · Recording Layer] The recording layer is the layer of information recorded. Information is usually recorded as a hologram. In the optical recording medium of the present invention, the recording layer is formed of an optical recording material containing the photoreactive composition of the present invention. The optical recording material can be formed separately from the photoreactive composition of the present invention, and it can be seen that it is necessary to contain other components. Further, as long as the effects of the present invention are not significantly impaired, the extent to which other components are contained is arbitrary. Specific examples of the other components include acrylic acid, poly (terephthalic acid) 312 ΧΡ / invention specification (supplement) / 96_〇 8/96114965 37 200804968 ethylene vinegar, polycarbonate, polyethylene, polypropylene, Polystyrene, cellulose acetate, polyamine vinegar, etc. These may be used alone or in combination of two or more kinds in any combination. Furthermore, the present invention is not limited to the above-mentioned ones. In addition, the thickness of the recording layer is not limited. Usually, the thickness of the recording layer differs depending on the method of recording 5 or the like. In the optical recording medium, the degree of the recording layer is usually 1 _ or more, preferably 10 / ζιη or more, and is usually less than 1 cm, and the age of Du Yan 9nnn _ Hua Wei is 2000 // m or less. If the recording layer is too thick 7 to perform multiple recording in an optical recording medium, the selectivity of each hologram may be lowered and the degree of repeated recording may be lowered. Further, if the recording layer = the entire recording layer μ is formed, it may be difficult to perform multiplex recording in which the hologram is uniform in efficiency and the S/N ratio is high. [Dish 1 2 support] ::: An optical recording medium consists of a support, a recording layer or another layer, etc., which is formed on an edge support to constitute an optical recording medium. The support is generally capable of having the required strength and durability. The shape is not limited and is usually formed into a flat shape or a film shape. There is no restriction on the material that constitutes the support body. 'It can be transparent or not. If the material of the support is transparent, it can be exemplified by propylene glycol, poly Γ i 7 ί vinegar film, and poly Cai Er f acid ethyl vinegar, polycarbonate, quartz, ethylene, cellulose acetate and other organic materials; glass, enamel, glass: Γ =. Among them, preferred are polycarbonate, propylene glycol, polyester, and glassy 4, and particularly preferably acrylic, polycarbonate, and glass. 3] 2ΧΡ/inventive manual (supplement)/96-0 dust 14965 38 200804968 All the genus is in the genus. Yu Γ If you list opaque, you can, ^^, the transparent support is coated with gold, silver, aluminum Such as a metal, or coating a dielectric such as fluorine tilting or zirconium oxide. The thickness of the branch is not _. Its towel, the money is better to be called. If the right support is too thin, the mechanical strength of the optical recording medium may be insufficient, and if it is too thick, the cost may be increased.疋 Surface treatment can also be applied to the surface of the support. The surface treatment is generally used to improve the adhesion of the support layer to the recording layer. 0 = may be subjected to corona discharge treatment, or formed for S: Here, as a layer for surface treatment, it may be exemplified by halogenated benzene or Partially hydrolyzed vinyl chloride-vinyl acetate vinegar copolymer coating, undercoat, etc.). a _ Further, the surface treatment may be carried out for purposes other than adhesion enhancement. As an example, for example, a reflective coating process for forming a reflective coating material using a metal such as gold, ruthenium or ruthenium; a dielectric coating treatment of a magnesium oxide or an oxide dielectric layer; Further, the layers may be formed in a single layer or may be formed in two or more layers. Further, the support may be provided only on either the upper side and the lower side of the recording layer of the optical recording medium of the present invention, or may be provided on both sides. Here, in the case where the support is provided on the upper and lower sides of the recording layer, either side of the support is made transparent to transmit the active energy rays (excitation light, reference light, regenerated light, etc.). In the case where the optical recording medium of the "transparent support" is provided on both sides of the recording layer, a transmissive type or a reflection type hologram can be recorded. Further, in the case of using a support having a reflection characteristic on one side, a reflection type hologram can be recorded. 3 UXP/Invention Manual (supplement)/96-08/96114965 39 200804968 Method and can set the pattern for data address. The pattern η of the pattern is as follows L', such that the support can form irregularities on the crucible, and can also be reversed. (4) The upper case may also be a form in which the method of combining the methods is not essential, and the recording layer or the other layer may have no necessary support if it has the necessary strength or durability. [m — 3· Other layers] = In addition to the recording layer and the support, the recording medium may be provided with, for example, a protective layer, a reflective layer, and an anti-reflection layer (the anti-protection layer is used to prevent the sensitivity caused by oxygen from decreasing). The layer of the bad influence. The specific composition of the protective layer is not limited = '"It is known that the water-soluble poly layer can be used as a protective layer." In addition, the reflective layer is formed when the reflective optical recording medium is formed. In the case of a reflective optical recording medium, the reflective layer may be formed between the support and the recording layer 'may also be formed on the outer side of the support, usually between the recording layer and the recording layer. Any of the transmissive and reflective optical recording media may be provided with an anti-reflection film on the side where the recording light and the read light are incident and emitted, or between the recording layer and the support. The anti-reflection film exhibits enhanced light utilization efficiency and suppresses generation. The function of the ghost image. [Dish 1 4. Manufacturing method] There is no limitation on the manufacturing method of the optical recording medium. 312ΧΡ/Invention Manual (Repair)/96-08/96114965 200804968 Sex 2 You can use the solvent instead of the support. The photoreaction of the present invention is produced by forming a recording layer. (4) The coating method may be any:: For example, a spray method, a spin coating method, a wire rod 1 method, and a dipping may be used. Crushing method, air knife coating method, light coating method, doctor roll coating method, etc. Main, ^成"History layer, especially in the village where a thick film thickness is formed, which is formed by using a mold a method, or a method of applying a stamping die on a release film. The photoreactive composition of the present invention and a solvent or an additive=coating: coating liquid can also be applied to a support and dried. Forming > Ύ k k. In this case, the coating method can also use any method 'for example, the same method as above can be employed. :: 峨 no limitation 'but usually it is preferred to use two components = Reading degree, providing good film-coating property, and supporting body of non-corrosion substrate. For example, examples of the agent include acetone, methyl ethyl _, methyl isobutyl territate, and 曱Ketoyl ketone solvent; aromatic solvent such as toluene or xylene; methanol, ethanol, propanol, positive Alcohol, heptanol, hexanol, di(tetra)ol, mercapto alcohol and other alcohol-based solvents; diacetone alcohol, 3-cysyl-3-methylbutanone and the like - alcohol solvent; tetrahydrofuran, diammonium, etc. It is a solution of chloroform, chloroethene, chloroform, etc.; methyl oxime chain, ethyl celecoxib, butyl hydrazine, such as Lu, ·, Wo, methyl acetate, acetic acid Ethyl celescens and other celluloid solvents; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monotop, propylene glycol monomethyl ether acetate vinegar, propylene glycol monoethyl ether 312XP / invention manual (supplement) / 96-08/96114965 41 200804968 propylene glycol solvent such as ethyl hydrazine, propanol saponin _ acetic acid vinegar, dipropylene glycol dimethyl ether, ethyl acetate, butyl acetate, amyl acetate, butyl acetate, ethylene glycol diacetate, two Ethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate ethyl acetonitrile acetate, methyl lactate, ethyl lactate, 2-hydroxyisobutyrate decyl ester, 3-decyloxy An ester solvent such as methyl propionate; a perfluoroalkyl alcohol solvent such as tetrafluoropropanol, 2 fluoropentanol or hexafluorobutanol; dimethylformamide: "methyl ethyl hydrazine" , N- Yue yl bite unitary with pyrrole, dimethylmethylene stone very high wind, A j, n-hexyl burning, n-octyl special burn-chain hydrocarbon-based solvents; cyclohexyl burn: cyclohexyl? a cyclic hydrocarbon-based solvent such as ethylcyclohexane, dimethylcyclohexane, n-butylcyclohexane, di-butyl hexane or cyclooctane; or a mixed solvent. In addition, the solvent may be used singly or in combination of two or more kinds in any combination and in any ratio. There is no limit to the amount of solvent used. Among them, in view of coating and enthalpy, it is preferred to prepare a coating liquid having a solid content concentration of 1%. Υυυ重里%左右= and 'the light-reactive composition of the present invention is a light-reactive composition in the case of thermoplasticity, and the photo-formation y-producing knives of the present invention; the (first) thermosetting property In the case, for example, the glow forming method and the liquid injection molding method are used to make a target, and the first reaction group is charged with 5 layers. In this case, if the degree of formation, rigidity, strength, and the like are formed, the molded body can be made thick and thick, and as a method of manufacturing the optical recording medium, for example, == Table 312ΧΡ/@0@___^/96· 〇狮1 Touch $ 42 ' 200804968 A method in which a thermally soluble photoreactive composition is applied to a support, cooled and solidified to form a recording layer, and a liquid emollient composition is applied to a method in which a recording layer is formed by curing by thermal polymerization, and a liquid photoreactive composition is applied onto a support, and is cured by photopolymerization to form a recording layer. Method and so on. The optical recording medium manufactured in this manner can be used in a three-dimensional image display device or a diffractive optical element, a large-capacity memory, or other devices. [ΠΙ - 5 • Recording and reproducing method] Information written (recorded) and read (reproduced) on an optical recording medium can be performed by irradiation of light. 9 When recording, the recording layer is irradiated with the excitation light of the sensitizing material (4), that is, the light corresponding to the excitation wavelength of the sensitization (A) is used as the recording light, and the reaction group (C) is converted by the recording light. Make information records. On the other hand, in the case of information reproduction, the regenerated light is irradiated to the recording layer, if it is transmitted ^

The optical recording medium reads the transmitted light, and if it is a reflective optical recording medium, it reads the reflected light and performs information reproduction. Further, in the case where the information is recorded on the optical recording medium as a hologram of a volume hologram or the like, the reference layer is irradiated with the recording light (also referred to as object light). The right δ recorded light interferes with the reference light in the recording layer, and the dry ♦ stripes are recorded as chemical conversion of the reactive groups in the recording layer. For example, the photoreactive composition of the present invention is recorded in a case where a refractive index change occurs in a reaction group ((:) chemical conversion, and the interference fringe is recorded as a refractive index difference in the recording layer. The hologram is recorded in the recording layer by the interference fringes recorded in the recording layer of the above-mentioned 312XP/invention specification (supplement)/96-08/96114965 43 200804968. Furthermore, it is excited by the stage multiphoton absorption. The sensitizer is subjected to f-signaling, m, and for the excitation light, for example, the recording light can be used as the first-and second-lights, and the reference light can be used as the first and second lights, or the recording light and the reference light can be used. One is used as the first light, and the other is used as the first light. When the recording layer is used to reproduce the full image, the recording layer is ::::: usually reference light). The irradiated regenerated light is diffracted corresponding to the L y m produced. The diffracted light contains reproduction of information in the same manner as the recording layer described above. Recording on the recording layer « : I Gan: test, the regenerative light system is set to be independent and does not produce the wavelength and intensity of the sensitizer (A) / eight ~ Saki, excitation. The non-destructive reading of the recording medium during the reproduction is performed. X仟/, the light having the first gate function: the wavelength region of the reproducing light and the reference light is arbitrary for each purpose, and may be an infrared region. It can also be in the ultraviolet region. As the number in the 箄弁 “ “ 4 见 见 见 见 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ), Nd_YV0 shell oxide) and other solid lasers; GaAS, in YV04 (Convergence - Ji Yan Si, Argon, Helium, quasi-eight early, one 4-diode laser; 氦-laser and other monochromatic : Excellent to the sex: = Ray: The dye with pigment can be pulsed laser or continuous (the laser shot used by C '. US Wave, continuous wave) Ray 312XP / invention manual (supplement) / 96 Confucian 611 side 44 200804968 In addition, in the recording light, the regenerative light, and the reference light, the amount of irradiation is unlimited. 'If it is the range of recordable and reproducible, it is arbitrary. In rare cases, the chemical conversion of the reactive group (c) may not be completely excessive, and the richness and mechanical properties of the recording layer may not be sufficiently exhibited. Conversely, in the case of extreme immersion, the photoreactive composition of the recording layer may be Therefore, the recording light, the regenerated light, and the reference light are usually composed of 0·1 to 20 J depending on the composition of the composition of the recording layer, the type of the polymerization initiator (C), and the amount of the polymerization initiator. The present invention will be specifically described with reference to the embodiments. However, the present invention is not limited to the following examples, and the invention can be carried out arbitrarily without departing from the gist of the invention. Μη represents a number average molecular weight, and Mw represents a weight average molecular weight. [Synthesis Example 1: Synthesis of Polymer (B)] Hereinafter, by the equivalent of "Synthesis and Photochemical Property of Polymers with Pendant Donor-Acceptor-Type Norbornadiene Moieties N Kawashima; A. Kameyama; T. Nishikubo; T. Nagai: Photoresponsive Polymers, 1764, 2001, page 2, the synthesis of the reaction (C) Polymer (B) (Synthesis Stage 1: MTMPN (mercapto 1,4,5,6-tetramethyl-3-phenyl-2, 5-normidine dihalide-2-buffer) ,Methyl l,4,5,6-Tetramethyl-3-pheny 1-2, 5-norbornadiene-2-carboxyl ate) Synthesis of methyl 3-phenylpropene in a 50 ml flask with a cooling tube 2-Acid 312XP/Invention Manual (supplement)/96-08/96114965 45 200804968 Ester (MPP, Methy 1 3-phenyIprop-2-ynolate) (8 g, 50 mmol) with 1, 2, 3, 4- 4 Methyl-1,3-cyclopentadiene (12 g, 100 mmol) was reacted at 1 ° C for 8 hours while stirring with a magnetic stirrer. - If the crude product is purified by hydrazine column chromatography and the solvent is removed, "MTMPN of the intended product is obtained in the form of a pale yellow oil. The yield is 13 g (yield 92%). 2 : Ding ^0^(:(1,4,5,6-tetradecyl-3-phenyl-2,5-norpredene-2-redecic acid, 1,4,5,6-butyl 61 :^11161:1171-311161^1-2,5- Synthesis of norbornadiene-2-carboxyl ic acid) Dissolve hydrazine (3·36 g, 12 mmol) with potassium hydroxide (2.4 g, 36 mmol) The mixture was stirred at room temperature for 48 hours in a mixed solvent of methanol/water = 25/5 (m 1 ). After the reaction was completed, it was diluted with water, transferred to a separatory funnel and washed twice with dichloromethane. Transfer to an Erlenmeyer flask. Make it acidic with hydrochloric acid, filter the crude product of the precipitate, dissolve it in methylene chloride and transfer it to the separatory funnel again. Wash it several times with water and transfer 10 to the Erlenmeyer flask. The mixture was dried over anhydrous magnesium sulfate, and the solvent was evaporated, and the residue was recrystallized from trimethylbenzene/hexane to give the desired product. The yield was 1.92 g (yield 60%). (Synthesis Stage 3: Olefin Polystyrene (pst) polymer - synthesis) a poly(p-chloromercaptostyrene) (Mn = 2. 6xl04, Mw / Mn &gt; 1.40) (3·07 g, 2〇_1) TMPNC (5 49 g, & leg 〇 1) was dissolved in dimethyl hydrazine (DMSO; 40 ml), and kg-diazabicyclo-[5,4,0]-7-undecene was added thereto. (DBU; 3·2 g, 22 Curry 1), heated at 70 ° C for 6 hours at 312XP / invention manual (supplement) / 96 · 〇 8 / 96 η 4965 46 200804968. After the reaction, add a large amount of methanol to kill again 'The solid to be filtered was further precipitated twice with tetrahydrofuran/nonanol and then the solvent was completely removed by a vacuum dryer to obtain the desired product. The yield was 5.4 g (yield 70%). It is NBD-PS. [Example 1] &lt;Sample Preparation&gt; 5, 10, 15, 20-tetrakis[3,5-bis(trifluoromethyl)phenyl]-21H, 23H-purple platinum (作为) As a sensitizer (A), a sample (n) was synthesized using nbd-PS synthesized in Example 1 above as a polymer (β), and a sample was prepared as an optical recording medium in the following manner. NBD-1^(1〇幻与5,1〇,15,2〇一:二_吱喘溶液,洗鎿The film was dried on a glass substrate to form a film having a thickness of 200 //m as a sample. The specific method of casting was as follows. _ Leave on a glass slide substrate and leave it in the dark for 12 hours for drying. After that, the 敎 之 供 烽 烽 设置 设置 设置 设置 设置 设置 设置 严 严 严 严 严 π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π Cover and fix the holder with a clip in 8 (rc oven) [Scheme 2] Transmitting a 50-inch smooth recording medium (sample <sample preparation> using 2, 2,: 5 - ~ / light pure pharmacy) Μ — ^ 2'2': 5, 2 &quot; ~TerthiQPhene) (manufactured by Zhishen Co., Ltd.) as a sensitizer (1), in addition, 312 purchase specification _6-_611 Na 200804968 using the NBD-PS synthesized in the above Synthesis Example 1. As the polymer (B), a sample was produced as an optical recording medium in the following manner. That is, NBD-PS (1.0 g) synthesized in Synthesis Example 1 and 2,2':5,2&quot;-trithiophene (2) Mg) is dissolved in a mixed solvent of mercaptoethyl ketone/nonylbenzene = 1.8/1.2 (ml), cast on a glass substrate and dried to form a film having a thickness of 50 /zm as a sample. The method was carried out in the same manner as in Example 1. [Example 3] • 2, 2': 5, 2"-trithiophene (manufactured by Wako Pure Chemical Industries Co., Ltd.) was used as an increase. The sensation (A), in addition, poly(vinyl cinnamate) (manufactured by Aldrich, average Mw = 200000 (GPC measurement)) as the polymer (B), A sample was prepared as an optical recording medium in the following manner. That is, poly(vinylcinnamate) (1·〇g) and 2,2′:5,2n-trithiophene (2 mg) were dissolved in mercaptoethyl group. In a mixed solvent of ketone/nonylbenzene = 1.8/1·2 (ml), it was cast on a glass substrate and dried to form a film having a thickness of 50 //m as a sample. Further, the casting method was the same as in Example 1. [Example 4] - Use 2,2:5,2''-tripty-three-septe-5-tetyl acid (2,2':5,2"-Terthiophene-5-carboxaldehyde) (Tokyo Chemical Industry Co., Ltd.) As a sensitizer (A), a poly(vinyl cinnamic acid vinegar) (manufactured by Aldrich Co., Ltd., average Mw = 200000 (GPC measurement)) was used as the polymer (b), and a sample was produced in the following manner. 312XP / invention manual (supplement) / 96-08/96114965 48 200804968 and as an optical recording medium. That is, will be poly (Ethyl cinnamic acid vinegar) (10 g) Thiophene (2 mg) was dissolved in methyl ethyl ketone / ,, ·, 2 m _ dithiane vehicle, the frit on a glass substrate subjected to dry mixing of the film as a sample. The thickness was 5". The casting method was carried out in the same manner as in Example 1. [Example 5] ==1,4-bis[2-(5-phenyl)] stupid (1,4_b) pJ^rrlyl)]benzene) (Tokyo Chemical Industry Co., Ltd.) was used as a sensitizer (A), and a sample medium was prepared in the following manner by using the compound PS of the above Synthesis Example i as the polymer (8). Feng Youzhen, the NBD_ps (i 〇 and H bis[2-(5-phenylcarbazolyl))benzene (2 mg) synthesized in the synthesis example i was dissolved in methyl ethyl ketone / toluene = K8 In a mixed solvent of /1.2 (ml), the film was cast on a glass substrate and dried to form a film having a thickness of 50. The casting method was carried out in the same manner as in Example 1. [Example 6] Using 4, 4 '-bis(diethylamino)benzophenone (manufactured by Hodogaya Chemical Co., Ltd.) as a sensitizer (A), and -NBD-PS synthesized in the above Synthesis Example 1 was used as the polymer (B) A sample was prepared as an optical recording medium in the following manner: ° That is, 'NBD-PS (1.0 g) synthesized in the above Synthesis Example 1 and 4,4,~bis(diethylamino)benzophenone (2) Mg) Solution to methyl ethyl ketone / methyl 312XP / invention manual (supplement) / 96.96114965 49 200804968 dry and shaped: in a mixed solvent 'casting on a glass substrate for dry extraction and degree 50 # m film as a sample. ― Furthermore, the casting method is carried out in the same manner as in the examples. [Example 7], H2, 2',: 5, 2&quot;-three (four) (Wako Pure Chemicals Co., Ltd. made 1 is a sensitizer (1) In addition, 'Polymer (trade name: manufactured by Osaka Gas Co., Ltd.) was used as the polymer (β), and a sample was prepared as an optical recording medium in the following manner. · 〇g) and 2, 2' :5, 2,·-trisole (2 mg) dissolved: xanthene ethyl ketone / toluene = 1 / 8 / 1 · 2 (ιη1) mixed solvent, cast in The ruthenium substrate was dried to form a film having a thickness of 5 Å. The film of the melon was used as a sample. The casting method was the same as that of Example 1. <Measurement> Fig. 10 is a schematic view showing the outline of the measurement system used in the present example. Figure 312XP / Invention Manual (supplement) /96-08/96114965 50 200804968, the light emitted from the laser 1 is indicated by a dotted line At this time, 'the bisector of the angle formed by the two beams is perpendicular to the recording surface, and 'the vibration plane of the electric field vector of the two beams obtained by the splitting is parallel to the plane containing the two beams intersecting. ^ While irradiating the recording surface with light [L1] from the wavelength of 533 nm of the laser 1, the light of the wavelength 405 nm [L2] is irradiated from the laser 2, and is reflected by the mirror [M3], and irradiated to the sample. [Samp 1 e] on the recording surface. At this time, light (L2) having a wavelength of 405 nm is irradiated to the intersection of the light at 532 nm on the recording surface [L1] so as to be perpendicular to the recording surface. Furthermore, in Fig. 1A, the light emitted from the laser 2 is indicated by a little lock line. In addition, the light [L2] transmitted through the sample [Sample] is irradiated to the beam stopper [BS, Beam stopper] °; by the interference from the laser light [Li, L2] of the laser 1 and the laser 2, the sample is sampled. A full image is recorded on the recording layer of [Sample]. After the hologram is recorded, the light of 405 nm is blocked [L2], and one of the two beams of 532 nm [L1] obtained by the splitting brake is blocked to be irradiated to the same angle as that at the time of recording. Recording surface. The diffracted light is recorded using a power meter (not shown) and a detector (manufactured by NEWp® RT Co., Ltd. 2930-C, 918-SL) [PD1, PD2]. The holographic diffraction efficiency is provided by the ratio of the intensity of the diffracted light to the intensity of the incident light. &gt;&lt;Results> The results of measurement of the sample prepared by the above preparation method using the above measurement method are shown in the following table. Furthermore, in the above embodiments, the beam intensity at the time of recording is set to 1 Wcm-2 for the laser beam intensity 312XP/invention specification (supplement)/96·_6ιι 4965 51 200804968, respectively. The irradiation time for recording β = shot 1 and laser 2 set to 80 mWcnf2 is 3 sec seconds in the embodiment i, 5 sec in the second embodiment, and in the examples 3 to 7. 2 leap seconds. [Table 1] [Table 1: Measurement results of winding rate] ----—Example 4 Bu·〇15 I 0.00Q2j^~7r

According to the above results, the recording material can be obtained for holographic recording. In addition, it can be seen that in any of the above embodiments, even if the recorded sample is exposed to light of 532 nm [L1], the recording state does not change, and in the absence of the gate light [L2] of 405 nm, Causes holographic recording, not sensitized by continuous light. Thereby, it is confirmed that non-destructive reading can be performed. [Example 8] _ (Measurement of excitation energy of sensitizer (A) 2, 2: 5, 2Π-trisole and polymer (b)) Document IE (J. Chem. Soc., Faraday Trans.) 1,73 (1 977) 1319), the sensitization of 2,2:2,2"-trithiophene as a sensitizer (A) was measured. The third harmonic of the Q-switch YAG laser was used. The wave or the fourth chopping wave is used as the laser light source. In addition, the light filling from T1 to S0 is measured. The result of the measurement can be judged that the absorption end of the absorption of τι-τη is 600 nm, and the energy of T1 - S0 is 720 nm. The results show that the SO-Τη energy is 330 nm. 312XP/Invention Manual (Supplement)/96-08/96114965 52 200804968 Secondly, the T1 from the NBD-PS as the polymer (B) is measured to the SQ in the same way. The result is that the τ 1 - S 0 energy is 400 nm. According to the results, the sensitizer (Α) 2, 2, : 5, 2Π-three sighs The order does not have the sufficient energy to chemically change the polymer NBD-PS reactive group, and the energy for starting the reaction is supplied to the reactive group from the Τη level. (Industrial availability) The present invention is expressly applicable to any field in the industry, and is particularly suitable for use in an optical recording medium such as a holographic recording medium. The present invention will be described in detail with reference to the specific embodiments. In addition, this application is based on the patent application filed on April 28, 2006 (Japanese Patent Application No. 2006-126394), and all the basins are referred to by reference. Eight [Simplified Drawing] Figure 1 FIG. 2 is a schematic diagram showing the state of electron transfer accompanying photon absorption. FIG. 2 is a schematic diagram showing the state of electron transfer accompanying photon absorption. FIG. 3 is a schematic diagram showing the electron transfer accompanying photon absorption: The sensitizer is relative to the reverse image. The sensation and the change of the reaction base - the third example] 2ΧΡ/invention specification (supplement)/96,/96114965 200804968 Fig. 5(a) to Fig. 5(c) In the case where the sensitizer has an oxidized electron arrangement with respect to the reaction group, an example of the electron arrangement of the sensitizer and the reaction group at the time of reading is shown. Fig. 6 is a view showing the photoreactive composition of the present invention. ,read A diagram showing an example of changes in the sensitizer (A) and the reactive group (C). Fig. 7 (a) to Fig. 7 (c) show the increase in readout in the photoreactive composition of the present invention, respectively. A diagram showing an example of the electronic arrangement of the sensory substance (A) and the reaction group (c). Fig. 8(a) to Fig. 8(c) are respectively shown in the photoreactive composition of the present invention, and the reactive group (C) is In the case of reduction and activation, an example of an electronic arrangement of the sensitizer (A) and the reaction group (C) at the time of writing is shown. 9(a) to 9(c) show the sensitizer (A) at the time of writing, when the reaction group (C) is activated by energy transfer in the photoreactive composition of the present invention, respectively. An example of an electronic arrangement of the reactive group (C). Fig. 10 is a view schematically showing the outline of a measurement system used in the embodiment of the present invention. [Main component symbol description] BS L Bu L2 M M2, M3 PBS PD1, PD2 Beam damper Light Mirror Polarizing beam splitter Detector 312ΧΡ/Invention manual (supplement)/96-08/96114965 54

Claims (1)

200804968 X. Patent Application Range: 1 · A photoreactive composition comprising: a sensitizer (A) excited by absorption of photons; and a reactive group (C) capable of chemical conversion The polymer (B); , the sensitizer (A) has a reduced electron configuration with respect to the reactive group (C). 2. The photoreactive composition according to claim 1, wherein the sensitizer (A) is excited by absorbing two or more photons. 3. The photoreactive composition of claim 2, wherein the Lu sensitizer (A) is excited by absorbing photons of two or more different wavelengths. 4. The photoreactive composition of claim 3, wherein the sensitizer (A) is a multi-stage excited sensitizer which is excited by a photon of the first excitation light to be single-excited State, thereafter, is transferred to the lowest triplet excited state by inter-system conversion, and then excited to be higher than the lowest triplet excited state by absorbing photons of the second excitation light of different wavelengths from the first excitation light Excited state. 5. A photoreactive composition as claimed in claim 1 wherein, in the case where the sensitizer (A) is excited, the reactive group is acted upon by the excited sensitizer (A) The chemical conversion is carried out, and the optical characteristics of the photoreactive composition are changed. 6. The photoreactive composition of claim 1, wherein the chemical conversion is an isomerization reaction. An optical material comprising the photoreactive composition of claim 1 of the patent application. 8. An optical recording material characterized by comprising an optical material of the patent application No. 312XP / invention specification (supplement) / 96-08/96114965 55 200804968. A volume hologram recording material characterized by the optical recording material of the eighth aspect. Patent - From 10 optical recording media, characterized in that it has a layer containing an optical recording material of the eighth item of the patent _ scope. A method of optical recording of an optical recording medium, characterized in that said excitation light is applied to said layer of an optical recording medium of claim 10 of the patent. 12. The optical recording method of an optical recording medium according to the ninth aspect of the invention, wherein the reference light is irradiated while the excitation light is irradiated, and the hologram is recorded on the layer by interference of the excitation light and the reference light. . 312χρ/Invention Manual (supplement)/96-08/96114965 56