RU2325680C2 - Photopolymer recording media for three-dimensional optical memory for very-large-scale information capacity - Google Patents

Abstract

FIELD: physics.

SUBSTANCE: invention pertains to organic light sensitive recording media and can be used for making archival three-dimensional holographic optical memory with large scale information capacity. The photopolymer recording medium is described. It consists of solid triplexed polymer films or glass plates and light-sensitive layer between them, including unsaturated compounds, which are capable of ion-radical photopolymerisation; a system providing for photoactivation through radiation in the 400-600nm range and consisting of photochromic compounds and co-initiator. The light sensitive layer contains photochromic compounds with a long mean life of the photo-induced state or thermal irreversible photochromic bonds, and not necessarily, polymer binder, plasticizer and non-polymerisation organic liquid with a large refractive index. There is also proposed usage of such a recording medium in devices for three-dimensional holographic memory of large scale capacity.

EFFECT: design of three dimensional holographic optical memory of large scale information capacity and simplification of the optical device for recoding holograms.

9 cl, 12 tbl, 57 ex, 1 dwg

Description

FIELD OF TECHNOLOGY

The present invention relates to the field of organic photosensitive recording media and can be used to create archival three-dimensional holographic optical memory with ultra-high information capacity, which is currently very relevant, especially in connection with the development of modern high-capacity databases for telecommunication communication systems and space technology. The possibility of creating such an optical memory is based on recording so-called deep holograms, in particular, in a thick photopolymerizing recording medium, due to photo-induced changes in the refractive index resulting from changes in the density of matter. Holograms are created by irradiating the photosensitive layer of the recording medium with suitable laser radiation. The degree of polymerization of the layer depends on the density of the intensity of the activating radiation in the recording medium. The resulting image, which is a set of lines of varying intensity, is recorded as a change in polymer density. The resulting polymer having a refractive index different from the refractive index of the original monomer will be characterized by a refractive index depending on the intensity of the activating radiation in different parts of the photosensitive layer. These differences during the restoration of the phase of the light wave form a reconstructed image. Registration of deep holograms is achieved as a result of photobleaching of the photosensitive component of the medium during the registration of the hologram and, therefore, the penetration of laser radiation deep into the recording medium. The recording of deep holograms in a thick layer leads to a high angular selectivity for recording holograms and image restoration and, as a result, its extra-large information capacity.

BACKGROUND

Known photopolymerizable media, consisting of monomer-oligomeric compositions and photoinitiating systems, which used photobleaching dyes and co-initiators (Carretero L., Blaya S., Mallavia R., et al. // Appl. Opt., 1998, V.37, P.4496).

The disadvantage of such media is that to obtain phase holograms in them, additional post-exposure light and heat treatments are required, which complicates their use in archive optical memory devices.

Closest to the claimed photopolymerizable recording media are media containing photochromic spiropyrans, which are intended for use in stereophotolithography devices for producing three-dimensional polymer objects (US patent No. 5230986, IPC G03A 007/028). They contain olefin-unsaturated compounds polymerized by free radicals generated by a photoinitiating system consisting of an electron-donating co-initiator and a photochromic compound from the class of iodine-containing indoline benzospiopyranes of the following type:

The colored merocyanine form of these compounds is a sensitizer of radical generation. It can be obtained in two ways. One of them is the irradiation of a photopolymerizable medium with UV light absorbed by the initial spiran form. Photopolymerization is carried out by visible radiation absorbed by the merocyanine form of the photochromic compound. A second method for preparing the merocyanine form is to heat a photopolymerizable medium, resulting in a colored photo-induced form of spiropyran. Thermally obtained merocyanine form, absorbing visible radiation, also provides photogeneration of free radicals, leading to the radical polymerization of olefinic unsaturated monomers. Such photopolymerizable recording media spontaneously desensitize after turning off UV illumination or cooling the layer.

The disadvantage of such photopolymerizable recording media is that their use necessitates the use of an additional source of light or thermal energy in the process of recording holograms by visible laser radiation, which complicates the design of the device that provides volumetric images. Another disadvantage is that constant UV illumination or heating of the medium maintains a constant concentration of the merocyanine form and, thus, prevents the penetration of light into the depth of the recording medium. This excludes the possibility of recording deep holograms and, therefore, reduces the angular sensitivity of the medium and its information capacity. In addition, heating of the recording medium leads to an increase in thermal distortions of the interference pattern and, therefore, reduces the resolution. In addition, such media are liquid, which necessitates the use of long-term post-exposure light processing of the photosensitive layer after the registration of holograms. This leads to an unreasonable increase in energy costs and the formation time of optical memory in such environments.

The mentioned drawbacks are due to the fact that photochromic compounds with insufficient life time of the photoinduced form were used as photosensitizers in photopolymerizing recording media. In addition, in the composition of such a medium there is no polymer binder or components that promote photopolymerization of the medium in the process of recording holograms.

SUMMARY OF THE INVENTION

The aim of this invention is to increase the angular sensitivity of the photopolymerizable recording medium to hologram recording and image recovery by recording deep holograms in thick photosensitive layers, which ensures the creation of a three-dimensional holographic optical memory of ultrahigh information capacity, as well as the simplification of the optical hologram recording device.

This goal is achieved by the fact that these photopolymerizable recording medium (photopolymerizable composition) contain:

- as photosensitizers:

- either photochromic compounds with a long lifetime of the photoinduced form, in particular:

- benzthiazoline spiropyrans (I):

Table I Spectral-kinetic characteristics of photochromic transformations of used benzthiazoline spiropyrans (BTSP) in photopolymerizable compositions Compound R Spectral characteristics of the photoinduced form, λ _max , nm The reaction rate constant of thermal bleaching of the photo-induced form, k × 10 ³ , s ^-1 BTSP 1 C ₁₆ H ₃₃ 580 2.9 BTSP 2 C ₆ H ₅ 610 6.1 BTSP 3 β-naphthol 605 9.0 BTSP 4 C ₃ H ₇ 572 5.2

- derivatives of phenoxynaphthacinquinone (II):

Table II The structure and spectral properties of photochromic derivatives of phenoxynaphthacinquinones (FNH) in photopolymerizable compositions Compound Structure Spectral characteristics of the photoinduced form, λ _max , nm The reaction rate constant of thermal bleaching of the photo-induced form, k × 10 ⁸ , s ^-1 FNH 1

453
480 1,0 FNH 2

447
478 1,1

- either thermally irreversible photochromic compounds, in particular:

- digitariethenes (III)

Table III The structure and spectral properties of photochromic digetariethenes (DHE) in photopolymerizable compositions Compound Structure Spectral characteristics of the photoinduced form, λ _max , nm DHE 1

510 DHE 2

520 DHE 4

420
560
600

- fulgimides (IV):

Table IV The structure and spectral properties of photochromic fulgimides (FGM) in the photopolymerizable composition Compound Structure Spectral characteristics of the photoinduced form, λ _max , nm FGM 1

520

- as a polymerization (s) compound (s):

- α, ω-bis (methacryloyloxy-ethyleneoxycarbonyloxy) ethyleneoxyethylene (OKM-2);

- trimethylolpropane triacrylate (TATMP);

- bisphenol-A-bis (glycidyl methacrylate) (bisGMA);

- N-vinylpyrrolidone (VP);

- glycerol trimethacrylate (TMG);

- as a polymer binder:

a polymer compound, in particular:

- polymethylmethacrylate (PMMA);

- polystyrene (PS);

- as co-initiators, i.e. radical-forming compounds, in particular:

- dimethylethanolamine (DMEA);

- triethanolamine (TEA);

2,2-dimethoxy-2-phenylacetophenone dimethylbenzylketal (DMBC) (Irgacure 651);

- as a non-polymerizable organic liquid with a high refractive index, in particular:

- bromobenzene (BB, n = 1,588);

- chlorobenzene (CB, n = 1.522);

- as a plasticizer, in particular:

- dibutyl phthalate (DBP), in the following ratio of components (in wt.%):

- photochromic compound (s) 0.04-5.0 - co-initiator (s) 1,5-7,24 polymerization compound (s) 3.0-98.26 - polymer binder 0-95.46 - plasticizer 0-5.0 - high refractive index liquid 0-3.0.

The novelty of the claimed photopolymerizable recording media consists in the use of photosensitizers that provide registration of holograms with laser radiation of the visible spectral range, photochromic compounds with a long life time of the photoinduced colored form or thermally irreversible photochromic compounds with a certain ratio of components, namely: photochromic compounds, co-initiator polymers as well as optionally a polymeric binder, plastic Ator and nepolimerizatsionnosposobnoy liquid with a high refractive index. Unlike the prototype mentioned above, the use of such photosensitizers eliminates the need for continuous use of a UV radiation source or heating device in addition to a laser that emits in the visible range. In this case, it is sufficient to irradiate the photopolymerizing recording medium with short-term incoherent UV radiation before recording holograms. The desensitization of the medium after the registration of holograms is carried out by short-term exposure to incoherent visible radiation absorbed by the photo-induced form of the photochromic compound. As a result, the cost of the recording device is reduced and the resolution of the recording medium is increased. Another distinguishing feature is the possibility of photo-curing the photosensitive layer to the required value during the photoinduced production of the sensitizer by introducing, as a co-initiator, into the recording medium of the photo-initiator, providing photopolymerization of the polymerization compound (s) under the influence of UV radiation, in particular 2-dimethoxy -2-phenylacetophenone dimethylbenzyl ketal (Irgacure 651).

The study and analysis of the well-known scientific, technical and patent literature showed that the complete set of features characterizing these technical solutions was not previously known, i.e. The claimed solutions meet the criterion of "novelty."

The invention is explained further using examples and with reference to the drawing, which shows the angular dependence of the magnitude of the diffraction efficiency (DE) of the diffraction gratings at an emission intensity of an argon laser of 5.5 mW / cm ² .

DETAILED DESCRIPTION OF THE EMBODIMENTS OF THE INVENTION

Example 1

A sample of the photopolymerizable recording medium was prepared as follows: 1) a solution of the solid photochromic compound ФНХ 1 in N-vinylpyrrolidone (VP) was separately prepared; 2) a mixture of polymerization-capable compounds (OKM-2 and TATMT), as well as a DMEA co-initiator was added to the resulting solution; 3) the resulting solution was thoroughly mixed; 4) the mixed solution was evacuated for 20 minutes to remove air bubbles from the solution; 5) the evacuated solution was applied to a dacron film with a dividing pad of a given thickness and was coated with a second dacron film on top. The result was triplex material.

The mass content of the components of the recording medium is presented in the attached table 1 (sample 1).

To evaluate the photoinduced change in the refractive index of the photopolymerizing layer, which determines the possibility of recording phase holograms, an IRF-22 refractometer (Russia) was used. A few drops of the test sample were applied to the surface of the measuring prism of the refractometer with a glass rod and the head of the device was carefully closed. The refractive index of the initial solution was measured. Then, the photosensitive layer located between the prisms was irradiated with UV light from a DRSh-250 lamp through a UFS-6 light filter emitting radiation with λ = 366 nm for 1 min in order to convert the photochromic compound from the original colorless to photoinduced colored form. The refractive index of the layer was measured a second time. After that, the colored solution was irradiated with visible light with λ> 400 nm from the illuminator OI-18 for 5 min. The refractive index was then measured a third time. The efficiency of photopolymerization of a layer under the influence of visible radiation was evaluated by the difference in refractive indices after irradiation of the layer with UV light and visible radiation (Δn = n ^type -n ^UV ).

For this sample, the magnitude of the photoinduced change in the refractive index was Δn = 0.0020 (table 1, sample 1), which proves the possibility of recording phase holograms on this sample of a photopolymerizable recording medium.

Example 2

By the method specified in example 1, a sample was prepared with the same composition, with the exception of the co-initiator and the mass content of the components (table 1, sample 2).

The measurement results of the photoinduced change in the refractive index, measured by the method described in example 1, are also presented in table 1 (sample 1), the data of which indicate the possibility of recording phase holograms on the prepared sample.

Example 3

By the method described in example 1, a sample was prepared with the same composition in which bromobenzene (BB) was used instead of N-vinylpyrrolidone (VP). The composition and mass content of the components are presented in table 1 (sample 3).

The measurement results of the photoinduced change in the refractive index, measured by the method described in example 1, are also presented in table 1 (sample 3), the data of which indicate the possibility of recording phase holograms on the prepared sample.

Example 4

By the method described in example 1, a sample was prepared with the same composition in which chlorobenzene (CB) was used instead of N-vinylpyrrolidone (VP). The composition and mass content of the components are presented in table 1 (sample 4).

The measurement results of the photo-induced change in the refractive index, measured by the method described in example 1, are also presented in table 1 (sample 4), the data of which indicate the possibility of recording phase holograms on the prepared sample.

Examples 5-7

By the method specified in example 1, photopolymerizable layers with the same photochromic compound were prepared, the composition of which was introduced as an additional co-initiator by the UV photoinitiator DMBK, which provides photo-curing of the layer under the action of incoherent UV radiation used to obtain the photoinduced form of the photochromic compound. Since DMBK is a solid, it was introduced into the VP solution at the first stage of sample preparation. The specific composition and mass content of the components in the samples are presented in table 2 (samples 5-7).

The measurement results of the photo-induced change in the refractive index, measured by the method described in example 1, are also presented in table 2, the data of which indicate the possibility of photo-curing of the layer under the influence of UV radiation, used for photo-induced photosensitizer sensitive to visible radiation, as well as recording phase holograms in prepared samples under the action of laser radiation of the visible range. The degree of photocuring was estimated by the difference in the refractive indices of the layer after UV irradiation and the initial sample (Δn = n ^UV- n ^ref ).

Examples 8-21

By the method described in example 1, photopolymerizable layers with a photochromic compound ФНХ 2 were prepared, which included one of the co-initiators was a DMBK UV photoinitiator, which provides photo-curing of the layer under the influence of incoherent UV radiation used to obtain the photoinduced form of the photochromic compound. Since DMBK is a solid, it was introduced into the VP at the first stage of sample preparation. The specific composition and mass content of the components in the samples are presented in table 3 (samples 8-21).

The measurement results of the photo-induced change in the refractive index, measured by the method described in example 6, are also presented in table 3, the data of which indicate the possibility of photo-curing of the layer under the influence of UV radiation, used for photo-induced photosensitizer sensitive to visible radiation, as well as recording phase holograms in prepared samples.

Examples 22-24

By the method described in example 1, photopolymerizable layers with a photochromic compound ФНХ 2 were prepared, which included one of the co-initiators was a DMBK UV photoinitiator, which provides photo-curing of the layer under the influence of incoherent UV radiation used to obtain the photoinduced form of the photochromic compound. Since DMBK is a solid, it was introduced into the VP at the first stage of sample preparation. In addition, the composition of photopolymerizable media included a polymer binder, which was used PMMA. For this, an additional stage of sample preparation was introduced, namely, the dissolution of PMMA in chloroform. This solution was added to a solution of the photochromic compound and DMBA in VP. Chloroform was removed from the photosensitive composition during evacuation of samples. The specific composition and mass content of the components in the samples are presented in table 4 (samples 22-24).

The measurement results of the photo-induced change in the refractive index, measured by the method described in example 1, are also presented in table 4, the data of which indicate the possibility of photo-curing of the layer under the influence of UV radiation, used for photo-induced photosensitizer sensitive to visible radiation, as well as recording phase holograms in prepared samples.

Examples 25 and 26

By the method specified in example 1, samples of photopolymerizable media were prepared on the basis of the photochromic compound BTSP 1, to which either N-vinylpyrrolidone (VP) or bromobenzene (BB) was introduced. The composition and mass content of the components are presented in table 5 (samples 25 and 26).

The measurement results of the photoinduced change in the refractive index, measured by the method described in example 1, are also presented in the same table, the data of which indicate the possibility of recording phase holograms in the prepared samples.

Examples 27-45

By the method described in Example 1, photopolymerizable layers with BTSC photochromic compounds were prepared, into which DM UVB photoinitiator was introduced as one of the co-initiators, providing photo-curing of the layer under the action of incoherent UV radiation used to obtain the photoinduced form of the photochromic compound. Since DMBK is a solid, it was introduced into the VP at the first stage of sample preparation. The specific composition and mass content of the components in the samples are presented in table 6 (samples 27-45).

The measurement results of the photo-induced change in the refractive index, measured by the method described in example 6, are also presented in table 6, the data of which indicate the possibility of photo-curing of the layer under the influence of UV radiation, used for photo-induced photosensitizer sensitive to visible radiation, as well as recording phase holograms in prepared samples.

Examples 46-48

By the method specified in example 1, photopolymerizable layers with a BSPP 3 photochromic compound were prepared, which included one of the co-initiators as a DMBK UV photoinitiator, which provides photo-curing of the layer under the influence of incoherent UV radiation used to obtain the photoinduced form of the photochromic compound. Since DMBK is a solid, it was introduced into the VP at the first stage of sample preparation. In addition, a polymer binder, namely PMMA, was used in the composition of photopolymerizable media. For this, an additional stage of sample preparation was introduced, namely, the dissolution of PMMA in chloroform. This solution was added to a solution of the photochromic compound BTSP 3 and the DMBC co-initiator in VP. Chloroform was removed from the photosensitive composition during the evacuation of samples. Along with PMMA, a DBP plasticizer was used, introduced into the same solvent. The specific composition and mass content of the components in the samples are presented in table 7 (samples 46-48).

The measurement results of the photo-induced change in the refractive index, measured by the method described in example 1, are also presented in table 7, the data of which indicate the possibility of photo-curing of the layer under the influence of UV radiation, used for photo-induced photosensitizer sensitive to visible radiation, as well as recording phase holograms in prepared samples.

Examples 49 and 50

By the method described in example 1, photopolymerizable layers with a BSPP 1 photochromic compound were prepared, which included one of the co-initiators was a DMBK UV photoinitiator, which provides photo-curing of the layer under the influence of incoherent UV radiation used to obtain the photoinduced form of the photochromic compound. Since DMBK is a solid, it was introduced into the VP at the first stage of sample preparation. In addition, a polymer binder, namely PS, was used in the composition of photopolymerizable media. For this, an additional stage of sample preparation was introduced, namely, the dissolution of PS in chloroform. This solution was added to a solution of the photochromic compound BTSP 1 and the DMBK co-initiator in VP. Chloroform was removed from the photosensitive composition during the evacuation of samples. Along with PS, we used a DBP plasticizer introduced into the same solvent. The specific composition and mass content of the components in the samples are presented in table 7 (samples 49 and 50).

The measurement results of the photo-induced change in the refractive index, measured by the method described in example 1, are also presented in table 7, the data of which indicate the possibility of photo-curing of the layer under the influence of UV radiation, used for photo-induced photosensitizer sensitive to visible radiation, as well as recording phase holograms in prepared samples.

Examples 51-57

By the method described in Example 1, photopolymerizable layers with photochromic compounds of DHE and FGM were prepared, the compositions of which contained and did not contain UV photoinitiator DMBK, which provides photo-curing of the layer under the action of incoherent UV radiation used to obtain the photoinduced form of the photochromic compound. Since DMBK is a solid, it was introduced into the VP solution at the first stage of sample preparation. The specific composition and mass content of the components in the samples are presented in table 8 (samples 51-57).

The measurement results of the photo-induced change in the refractive index, measured by the method described in example 6, are also presented in table 8, the data of which indicate the possibility of photo-curing of the layer in the presence of DMBK under the influence of UV radiation, used for photo-induced photosensitizer sensitive to visible radiation, as well as registration of phase holograms in prepared samples.

Example 58

A sample of a photopolymerizable recording medium prepared by the method described in Example 23 was used to register holograms in order to measure the angular sensitivity of a holographic recording medium, which determines its information capacity. For this, a photopolymerizable layer was placed between two Dacron films separated by a 0.5 mm thick polymer spacer, the central part of which was cut out and filled with a photopolymerizable composition.

Before recording the hologram, a sample of the recording medium was irradiated with incoherent UV light from a DRSh-250 lamp through a UFS-6 light filter, which transmits radiation with λ = 366 nm for 1 min. In this case, the sample acquired color. Holographic gratings were recorded in a scheme with symmetrical beams extracted from an argon (Ar) laser beam emitting at a wavelength of λ = 488 nm with an intensity of 5.5 mW / cm ² . After recording the hologram, the sample was illuminated with the visible light of the OI-18 illuminator until the sample was completely bleached. To restore, we used the radiation of a helium-neon (He-Ne) laser emitting coherent light with a wavelength of λ = 633 nm. Radiation diffraction was recorded in real time using a photodetector located at a Brewster angle. The angular dependence was determined by changing the angle of inclination of the recording and regenerating laser beams and with successive preliminary irradiation of the sample with UV and visible light for each registered hologram. The obtained dependence is presented in the drawing, which indicates a high angular sensitivity of the prepared sample, ensuring the use of this recording medium to create a three-dimensional optical memory with high information capacity.

Example 59

A sample of a photopolymerizable recording medium made by the method described in Example 58 was characterized in that glass plates were used instead of dacron films for the manufacture of triplex material.

The registration of holograms with a positive result was carried out by the method described in example 58.

Table 1 Sample No. Photochromic compound (wt.%) Co-initiator (wt.%) Polymerization compounds (wt.%) Non-polymerization-capable liquid (wt.%) Photoinduced change in refractive index, Δn = n ^type -n ^UV DMEA Tea OKM-2 TATMT VP BB HB one FNH 1 (0.25) 2,33 - 89.10 4.90 3.42 - - 0.0020 2 FNH 1 (0.25) - 2,37 89.10 4.95 3.33 - - 0.0045 3 FNH 1 (0.25) 2.28 - 89.77 4.99 - 2.71 - 0.0060 four FNH 1 (0.25) 2.25 - 89.69 - - - 2.86 0.0051

table 2 Sample No. Photochromic compound (wt.%) Co-initiator (wt.%) Polymerization compounds (wt.%) Photoinduced Change in Refractive Index, An DMEA DMBK OKM-2 TATMT BisGMA TGM VP Δn = n ^UV -n ^ref Δn = n ^view -n ^UV 5 FNH 1 (0.24) 2.18 0.41 88.90 4.94 - - 3.33 0.0107 0.0094 6 FNH 1 (0.41) 2.25 0.52 69.82 23.28 - - 3.72 0.0125 0.0025 7 FNH 1 (0.29) 2,35 0.40 - - 46.59 46.60 3.77 0.0148 0.0070

Table 3 Sample No. Photochromic compound (wt.%) Co-initiator (wt.%) Polymerization compounds (wt.%) Photoinduced change in refractive index, Δn DMEA Tea DMBK OKM-2 TATMT Bis GMA VP Δn = n ^UV -n ^ref Δn = n ^view -n ^UV 8 FNH 2 (0.24) 2.26 - 0.43 88.43 4.91 - 3.73 0.0015 0.0040 9 FNH 2 (0.23) 2.21 - 0.44 46.67 46.67 - 3.78 0.0015 0.0045 10 FNH 2 (0.22) 2.26 - 0.44 93.35 - - 3.73 0.0027 0.0060 eleven FNH 2 (0.25) 2.16 - 0.52 - 93.24 - 3.83 0.0143 0.0012 12 FNH 2 (0.25) 2.22 - 0.46 86.76 4.82 - 5.49 0.0063 0.0072 13 FNH 2 (0.21) 2.14 - 0.39 82.94 4.47 - 10.85 0.0055 0.0095 fourteen FNH 2 (0.22) 1.19 - 0.49 89.36 4.96 - 3.78 0.0120 0.0060 fifteen FNH 2 (0.22) 5.24 - 0.38 85.69 4.76 - 3.71 0.0033 0.0070 16 FNH 2 (0.23) 2,33 - 1.27 87.56 4.86 - 3.75 0.0149 0.0030 17 FNH 2 (0.22) 2.15 - 5.09 84.30 4.68 - 3.56 0.0190 0.0030 eighteen FNH 2 (0.05) 2,35 - 0.63 88.33 4.91 - 3.73 0.0160 0.0010 19 FNH 2 (4.80) 2.16 - 0.35 84.36 4.67 - 3.66 0.0015 0.0025 twenty FNH 2 (0.21) - 5.76 0.66 85.05 4.73 - 3,59 0.0130 0.0065 21 FNH 2 (0.29) 2.26 - 0.48 - - 93.24 3.73 0.0055 0.0105

Table 4 Sample No. Photochromic compound (wt.%) Co-initiator (wt.%) Polymerization auxiliary compound (s) (wt.%) Binder (wt.%) Plasticizer (wt.%) Photoinduced change in refractive index, Δn DMEA DMBK OKM-2 VP PMMA DBF Δn = n ^UV -n ^ref Δn = n ^view -n ^UV 22 FNH 2 (0.22) 2.25 0.55 46.61 3.74 46.63 - 0.0045 0.0093 23 FNH 2 (0.23) 2.16 0.51 - 3.83 93.27 - 0.0025 0.0050 24 FNH 2 (0.25) 2.20 0.50 - 3.73 88.32 5,0 0.0020 0.0045

Table 5 Sample No. Photochromic compound (wt.%) Co-initiator (wt.%) Polymerization compounds (wt.%) Non-polymerization liquid (wt.%) Photoinduced change in refractive index, Δn = n ^type -n ^UV DMEA OKM-2 TATMT VP BB 25 BTSP 1 (0.27) 2,33 89.58 4.97 2.99 - 0.0020 26 BTSP 1 (0.26) 2.19 89.59 4.98 - 2.98 0,0005

Table 6 Sample No. Photochromic compound (wt.%) Co-initiator (wt.%) Polymerization compounds (wt.%) Photoinduced change in refractive index, Δn DMEA Tea DMBK OKM-2 TATMT BisGMA TGM VP Δn = n ^UV -n ^ref Δn = n ^view -n ^UV 27 BTSP 1 (0.28) 2.18 - 0.54 89.10 4.95 - - 2.94 0.0042 0.0177 28 BTSP 1 (0.25) 2,31 - 0.49 - 23.98 69.85 - 3.82 0.0010 0.0160 29th BTSP 1 (0.28) 2,34 - 0.84 - - 46.39 46.39 3.76 0.0040 0.0145 thirty BTSP 2 (0.44) 2.15 - 0.65 88.05 4.89 - - 3.82 0.0025 0.0060 31 BTSP 3 (0.25) 2.25 - 0.59 46.59 46.59 - - 3.73 0.0028 0.0048 32 BTSP 3 (0.24) 2.16 - 0.53 - 93.25 - - 3.82 0,0005 0,0005 33 BTSP 3 (0.27) 2,36 - 0.58 93.16 - - - 3.73 0.0020 0.0065 34 BTSP 3 (0.22) 2.13 - 0.68 82,20 4.84 - - 5.03 0.0015 0.0045 35 BTSP 3 (0.24) 1.99 - 0.56 81.56 4,53 - - 11.12 0.0030 0.0075 36 BTSP 3 (0.23) 1.09 - 0.47 89.46 4.97 - - 3.78 0,0005 0.0070 37 BTSP 3 (0.24) 4.76 - 0.57 85.75 4.76 - - 3.53 0.0010 0.0030 38 BTSP 3 (0.25) 2.17 - 0.13 88.77 4.93 - - 3.75 0,0003 0.0040 39 BTSP 3 (0.26) 2.17 - 4.85 84.55 4.69 - - 3.48 0.0078 0,0100 40 BTSP 3 (0.04) 2,36 - 0.46 88.40 4.91 - - 3.83 0.0025 0.0020 41 BTSP 3 (2.51) 2.21 - 0.58 86.76 4.79 - - 3,55 0.0015 0.0025 42 BTSP 3 (0.22) - 5.71 0.53 85.29 4.74 - - 3,51 0.0080 0.0010 43 BTSP 3 (0.24) 2,35 - 0.51 - - 93.17 - 3.73 0.0225 0.0080 44 BTSP 3 (0.28) 2.21 - 0.77 88.08 4.89 - - 3.77 0,0005 0.0055 45 BTSP 4 (0.28) 2.25 - 0.53 88.30 4.91 - - 3.73 0,0005 0.0170

Table 7 Sample No. Photochromic compound (wt.%) Co-initiators (wt.%) Polymerization (s) compound (s) (wt.%) Plasticizer (wt.%) Binder (wt.%) Photoinduced change in refractive index, Δn DMEA DMBK OKM-2 VP DBF PMMA PS Δn = n ^UV -n ^ref Δn = n ^view -n ^UV 46 BTSP 3 (0.23) 2.25 0.66 46.57 3.72 - 46.57 - 0.0010 0.0105 47 BTSP 3 (0.29) 2.10 0.42 - 3.84 - 93.39 - 0.0060 0.0160 48 BTSP 3 (0.25) 2.25 0.59 - 3.73 4.12 89.27 - 0.0030 0.0135 49 BTSP 1 (0.26) 2.15 0.71 51,2 3.71 - - 41.97 0.0015 0.0125 fifty BTSP 1 (0.25) 2.10 0.51 - 3.89 4.26 - 89.08 0.0035 0.0141

Table 8 Sample No. Photochromic compound (wt.%) Co-initiator (wt.%) Polymerization compounds (wt.%) Photoinduced change in refractive index, Δn DMEA Tea DMBK OKM-2 TATMT Bis GMA TGM VP Δn = n ^UV -n ^ref Δn = n ^view -n ^UV 51 DHE 1 (0.22) - 2.18 - 88.66 4.98 - - 2.96 0.0000 0,0100 52 DHE 1 (0.26) 2,33 - 0.70 89.02 4.98 - - 2.93 0.0075 0.0160 53 DHE 1 (0.48) 2.25 - 0.52 69.70 23,23 - - 3.82 0.0138 0.0035 54 DHE 1 (0.42) 2,31 - 0.50 - - 46.5 46.5 3.73 0,0005 0.0115 55 DHE 2 (0.24) 2.25 - 0.44 88.33 4.91 - - 3.83 0.0160 0.0045 56 DHE 3 (0.39) 2.16 - 0.49 88.26 4.91 - - 3.79 0.0019 0.0040 57 FGM 1 (0.26) 2.06 - 0.69 88.22 4.91 - - 3.79 0,0200 0.0020

Claims (9)

1. A photopolymerizable recording medium consisting of solid triplexed polymer films or glass plates and a photosensitive layer located between them, including at least one unsaturated compound capable of ion-radical photopolymerization, a system that provides photoactivation by radiation in the spectral region 400-600 nm and consisting of at least one photochromic compound and at least one co-initiator, characterized in that the photosensitive layer contains photochr mnoe compound with a long lifetime photoinduced shape or a thermally irreversible photochromic compound and, optionally, polymeric binder, plasticizer and nepolimerizatsionnosposobnuyu organic liquid with a large refractive index at the following component ratio, wt.%: photochromic compound (s) 0.04-5.0 co-initiator (s) 1,5-7,24 polymerization compound (s) 3.0-98.26 polymer binder 0-95.46 plasticizer 0-5.0 high refractive index liquid 0-3.0 2. The photopolymerizable medium according to claim 1, characterized in that the photochromic compound with a long photoinduced form, which is a sensitizer, is selected from the group of benzthiazoline spiopyranes and phenoxy derivatives of quinones. 3. The photopolymerizable medium according to claim 1, characterized in that the thermally irreversible photochromic compound, which is a sensitizer, is selected from the group of classes of digitariethenes and fulgimides. 4. The photopolymerizable medium according to claim 1, characterized in that one of the co-initiators is a UV photoinitiator, for example 2,2-dimethoxy-2-phenylacetophenone dimethylbenzylketal (DMBC) (Irgacure 651). 5. Photopolymerizable medium according to claim 1, characterized in that the unsaturated polymerization compound is an unsaturated acrylic oligomer selected from the group consisting of α, ω-bis (methacroxyloxy-ethyleneoxycarbonyloxy) ethyleneoxyethylene (OKM-2); trimethylolpropane triacrylate (TATMP); bisphenol-A-bis (glycidyl methacrylate) (bisGMA); N-vinylpyrrolidone (VP); glycerol trimethacrylate (TMG). 6. Photopolymerizable medium according to claim 1, characterized in that the polymer binder is a polymethyl methacrylate. 7. The photopolymerizable medium according to claim 1, characterized in that the non-polymerizable organic liquid with a high refractive index is bromobenzene (BB). 8. The photopolymerizable medium according to claim 1, characterized in that the plasticizer is dibutyl phthalate (DBP). 9. The use of photopolymerizable recording medium according to claim 1 in devices of three-dimensional holographic memory of extra-large capacity.

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