A low-viscosity, high-refractive-index acrylate monomer, preparation and application thereof

Abstract

The present invention discloses a low-viscosity, high-refractive-index acrylic ester monomer, and its preparation and application. The general structural formula of the acrylic ester monomer is as follows, wherein R1, R2, and R3 each independently represent any one of an alkyl group with carbon atoms of C1 to C20, an alkylthio group with carbon atoms of C1 to C20, and an alkoxy group with carbon atoms of C1 to C20; R4 represents a methyl group or hydrogen; n represents an integer of 0 to 20, and m represents an integer of 1 to 20. The acrylic ester monomer has a high refractive index, a low viscosity, and a high solubility in a film-forming resin. When used in the preparation of a photopolymer holographic recording medium, a holographic recording medium with high sensitivity, high diffraction efficiency, high refractive index modulation, and low haze can be obtained, wherein the diffraction efficiency is greater than 90%, and the sensitivity is greater than 0.01 cm 2 / mJ, exposure is less than 20mJ / cm 2 , the haze is less than 3%, therefore, the prepared holographic recording medium is expected to be widely used in the fields of high-density optical storage and holographic optical elements.

Description

Technical Field

[0001] The present invention relates to the technical field of optical functional materials, and more specifically to a low-viscosity, high-refractive-index acrylic ester monomer, its preparation and application. Background Art

[0002] Holographic technology is a technology that can record all information such as the amplitude and phase of light waves. It has unique advantages in high-density data storage, holographic optical elements (HOEs), holographic anti-counterfeiting, holographic sensing, holographic lithography and other fields. Holographic data storage technology (HDS) has the advantages of low energy consumption, large capacity, fast access speed and long service life, and can achieve high-density and fast storage of information. As a diffractive optical element (DOE), HOEs have the characteristics of compact structure and light weight. They can replace traditional optical elements and have great application potential in head-mounted displays (HMDs). The holographic optical properties of the recording medium determine the quality of HOEs. Silver halide emulsion, dichromated gelatin, photodegradable polymer materials, photothermal conductive plastic materials, photorefractive materials, photopolymer materials, photoisomerized materials and metasurface materials are several typical holographic recording media. Among them, photopolymer materials are considered to be the preferred objects of future holographic recording medium materials due to their high photosensitivity, high resolution, simple preparation, low cost and no need for chemical / thermal post-treatment.

[0003] Photopolymer materials usually contain film-forming resins, writing monomers and photosensitive initiator systems, and their refractive index modulation is mainly determined by the difference in refractive index between the film-forming resin and the writing monomer. At present, the mainstream technical solution is to increase the refractive index modulation of the material by reducing the refractive index of the film-forming resin and increasing the refractive index of the writing monomer. In practical applications, high-refractive-index monomers often contain substituents such as aromatic rings and halogens with high molar refractive index and low molar volume, which is very different from the structure of low-refractive-index film-forming resins, which will seriously affect the solubility of the monomer in the film-forming resin. The introduction of alkyl chains can increase the solubility of the monomer in the film-forming resin, reduce the viscosity of the monomer, and effectively promote the diffusion and reaction of the monomer; however, the presence of alkyl chains will cause the refractive index of the writing monomer to decrease, so it is necessary to balance the relationship between the solubility and refractive index of the monomer when developing the writing monomer. Researchers are currently paying more attention to how to obtain high-refractive-index monomers, and have not paid too much attention to the problem of solubility. For example, Bayer has published a series of high refractive index monomers - trifunctional aromatic urethane acrylate (WO2008 / 125199), difunctional (meth) acrylate (WO2012 / 020061), aromatic diol ether (WO2015 / 161969), etc., one of which or a combination is used as a recording monomer, combined with a polyisocyanate-polyol matrix and a photoinitiator, to obtain high diffraction efficiency and high refractive index modulation in a photopolymer medium. Similarly, Marvin et al. (ACS Applied Materials Interfaces, 2018, Issue 10, Pages 1217-1224) synthesized a high refractive index (n = 1.6) monomer BPTPA, which has a high solubility in film-forming resins, but the monomer viscosity is high, which is not conducive to the diffusion and migration of the monomer during holographic recording. CN112759698B has developed a photopolymer composition, in which the writing monomer used includes an acrylate monomer with a refractive index of more than 1.55. In practical applications, the viscosity, refractive index and solubility of the monomer in the film-forming resin are important indicators that need to be paid attention to for high-performance photopolymers. The lower the viscosity of the monomer, the easier it is to diffuse and migrate during the holographic recording process, which is conducive to the rapid construction of the grating; the higher the refractive index of the monomer, the greater the difference between the refractive index of the polymer after polymerization and the refractive index of the film-forming resin, and the higher the diffraction efficiency of the grating; the better the solubility of the monomer in the film-forming resin, the more it can be added to the photopolymer, and the monomer is not easy to precipitate during storage, which is conducive to reducing the haze of the sample. Therefore, in order to broaden the application scope of acrylate monomers, it is very necessary to develop an acrylate monomer with a high refractive index, low viscosity and high solubility in the film-forming resin for the preparation of a photopolymer-type holographic recording material with isocyanate-alcohol as the film-forming resin and excellent properties such as high refractive index and angle selectivity. Summary of the invention

[0004] Based on the above problems, the first object of the present invention is to provide a low-viscosity, high-refractive-index acrylic ester monomer. The acrylic ester monomer has a high refractive index, a low viscosity and a high solubility in a film-forming resin, a refractive index of more than 1.6, and a viscosity of less than 9 mm. 2 / s, the addition of this monomer can significantly reduce the haze of the sample, and it can be stably dissolved in isocyanate-alcohol film-forming resin for more than one year.

[0005] The second object of the present invention is to provide a method for preparing the acrylic ester monomer mentioned above.

[0006] The third object of the present invention is to provide a method for preparing the acrylic ester monomer mentioned above.

[0007] The fourth object of the present invention is to provide a photopolymer holographic recording medium comprising the above-mentioned acrylic ester monomer. The holographic recording medium uses isocyanate-alcohol as a base resin and is combined with the acrylic ester monomer prepared by the present invention to exhibit high diffraction efficiency (>90%), high sensitivity (>0.01cm 2 / mJ) and low haze (<3%).

[0008] A fifth object of the present invention is to provide a holographic optical element comprising the photopolymer holographic recording medium as described above.

[0009] A sixth object of the present invention is to provide a photopolymer holographic storage optical disc comprising the photopolymer holographic recording medium as described above.

[0010] In order to achieve the above first object, the present invention adopts the following technical scheme:

[0011] The present invention discloses an acrylic acid ester monomer, and the general structural formula of the acrylic acid ester monomer is as follows:

[0012]

[0013] Wherein, R1, R2, and R3 each independently represent any one of an alkyl group having carbon atoms of C1 to C20, an alkylthio group having carbon atoms of C1 to C20, and an alkoxy group having carbon atoms of C1 to C20;

[0014] R4 represents methyl or hydrogen;

[0015] n represents an integer of 0-20, and m represents an integer of 1-20.

[0016] Furthermore, the general structural formula of the acrylic acid ester monomer is as follows:

[0017]

[0018] Furthermore, R1, R2, and R3 each independently represent any one of an alkyl group having carbon atoms of C1 to C4, an alkylthio group having carbon atoms of C1 to C4, and an alkoxy group having carbon atoms of C1 to C4;

[0019] R4 represents methyl or hydrogen;

[0020] n represents an integer of 1-10, and m represents an integer of 1-5.

[0021] In order to achieve the above second purpose, the present invention adopts the following technical solutions:

[0022] The present invention discloses a method for preparing the acrylic ester monomer as described above, comprising the following steps:

[0023] S1. Dissolve compound P1 in anhydrous tetrahydrofuran under ice bath, slowly add sodium hydride (dispersed in liquid paraffin), stir and react at room temperature for 0.5-3h, slowly add compound P2 dropwise, wherein the molar ratio of compound P1, sodium hydride and compound P2 is 1:1-2:1-2, stir and react for 5-40min, then add dilute hydrochloric acid dropwise to quench the reaction, extract the reaction solution with dichloromethane, dry the organic phase over anhydrous sodium sulfate, remove excess solvent by rotary evaporation, and separate by column chromatography to obtain compound P3;

[0024]

[0025] S2. Add a solution containing acryloyl chloride or methacryloyl chloride dropwise to a solution containing compound P3 and triethylamine under an ice bath, wherein the molar ratio of compound P3, triethylamine, acryloyl chloride or methacryloyl chloride is 1:1-5:1-2. The reaction is carried out for 0.5-1h. After the reaction is completed, dilute hydrochloric acid is added dropwise, and the mixture is washed with NaCl solution, NaHCO3 solution and water in sequence. The organic phase is dried over anhydrous sodium sulfate, the solvent is removed by rotary evaporation, and the mixture is separated by column chromatography to obtain the obtained product.

[0026]

[0027] In step S1 of the preparation method, sodium hydride is first used to capture the hydrogen on the thiol group of compound P1, which is beneficial for the subsequent reaction between compound P1 and compound P2.

[0028] In order to achieve the third object, the present invention adopts the following technical solutions:

[0029] The present invention discloses another method for preparing the acrylic ester monomer as described above, comprising the following steps:

[0030] S1, dissolving compound P1, compound P2 and NaOH in a mixed solution of ethanol and water, wherein the molar ratio of compound P1, compound P2 and NaOH is 1:1-4:1-4, heating to 50-120°C for reaction for 1-12h, extracting with dichloromethane after the reaction, drying the organic phase over anhydrous sodium sulfate, removing excess solvent by rotary evaporation, and separating by column chromatography to obtain P3;

[0031]

[0032] S2. Add a solution containing acryloyl chloride or methacryloyl chloride dropwise to a solution containing compound P3 and triethylamine under an ice bath, wherein the molar ratio of compound P3, triethylamine, acryloyl chloride or methacryloyl chloride is 1:1-5:1-2. The reaction is carried out for 0.5-1h. After the reaction is completed, dilute hydrochloric acid is added dropwise, and the mixture is washed with NaCl solution, NaHCO3 solution and water in sequence. The organic phase is dried over anhydrous sodium sulfate, the solvent is removed by rotary evaporation, and the mixture is separated by column chromatography to obtain the obtained product.

[0033]

[0034] In order to achieve the fourth objective, the present invention adopts the following technical solutions:

[0035] The present invention discloses a photopolymer holographic recording medium. The raw materials of the photopolymer holographic recording medium include the above-mentioned acrylic ester monomers.

[0036] Furthermore, when preparing the photopolymer holographic recording medium, the raw materials include the following components a) to h);

[0037] Component a) a compound having multiple isocyanate-reactive functional groups;

[0038] Component b) a polyisocyanate compound;

[0039] Component c) acrylic acid ester monomer disclosed in the present invention;

[0040] Component d) other polymerizable monomers;

[0041] Component e) a photoinitiator;

[0042] Component f) chain transfer agent;

[0043] Component g) catalyst;

[0044] Component h) additives;

[0045] Wherein, based on the total weight of the photopolymer holographic recording medium, the content of the acrylic ester monomer is 0.1 to 45 wt %.

[0046] It should be noted that two important components in the photopolymer holographic recording medium are a low-refractive-index film-forming resin and a high-refractive-index writing monomer. Component a) and component b) can form a film-forming resin, while component c) and component d) are equivalent to writing monomers.

[0047] Furthermore, the mass ratio of the component a), component b), component c), component d), component e), component f), component g) and component h) is 20-70:0.1-50:0.1-45:0.1-60:0.1-4:0.1-3:0.1-3:0.1-7.

[0048] Furthermore, the photopolymer holographic recording medium may also selectively add a component i) a photosensitizer; preferably, the mass ratio of the component i) to the component e) is 0.001-1:0.1-4.

[0049] Further, different wide-band responses can be achieved by regulating the type of photosensitizer. When a photoinitiator with an adapted wavelength is selected in the raw material of the photopolymer holographic recording medium of the present invention, the photosensitizer may not be added. The photosensitizer is a dye with a high electron transfer efficiency under light, including but not limited to cyanine dyes, fluorescein dyes, coumarin ketone dyes, nitrogen-containing aromatic heterocyclic compounds, aromatic amine compounds, benzylcycloalkane ketone compounds or any mixture of these compounds in any proportion. Exemplarily, the photosensitizer includes one or more of new methylene blue, thionine, basic yellow, chlorinated pinacol, rhodamine 6G, gallocyanine, ethyl violet, Victoria blue R, lapis lazuli blue, methylene blue, Astrazon Orange G, Darrow red, pyrrole red Y, basic red 29, quinaldine red, crystal violet, ethyl violet, brilliant green, pyri11lium I, azure A, crystal violet white nitrile, malachite green white nitrile, etc.

[0050] Furthermore, the additives include one or more of a defoamer, a leveling agent, a plasticizer and a dewatering agent.

[0051] Furthermore, when the additive includes a defoaming agent, the content of the defoaming agent is not more than 3 wt % based on the total mass of the photopolymer type holographic recording medium.

[0052] Furthermore, when the additive includes a leveling agent, the content of the leveling agent is no more than 3 wt % based on the total mass of the photopolymer type holographic recording medium.

[0053] Furthermore, when the additive includes a plasticizer, the content of the plasticizer is not more than 3 wt % based on the total mass of the photopolymer type holographic recording medium.

[0054] Furthermore, when the additive includes a dehydrating agent, the content of the dehydrating agent is not more than 3 wt % based on the total mass of the photopolymer type holographic recording medium.

[0055] Furthermore, the defoamer is a silicone defoamer, such as BYK-011, BYK-012, BYK-014, BYK-023, BYK-051N, BYK-085, BYK-1610, BYK-1707, BYK-1740, BYK-1760 produced by BYK, DC65, AFE-7820 produced by Dow Corning, or a mixture of these defoamers in any proportion.

[0056] Furthermore, the leveling agent is an organosilicon surface additive, such as BYK-302, BYK-306, BYK-307, BYK-327, BYK-329, BYK-333, BYK-356, BYK-358, BYK-378, BYK-3455, BYK-3566 produced by BYK, or a mixture of these surface additives in any proportion.

[0057] Furthermore, the plasticizer is toluene, xylene, dimethylformamide, dimethylacetamide, glycerol, phthalate or a mixture of these compounds in any proportion.

[0058] Furthermore, the dehydrating agent includes but is not limited to p-toluenesulfonyl isocyanate, triethyl orthoformate, CUWR-WB20 dehydrating agent of Guangzhou Yourun Synthetic Materials Co., Ltd., ALT-201 dehydrating agent of Anxiang Elite Chemical Co., Ltd., PCCI dehydrating agent of Shanghai Ruhr Chemical Trading Co., Ltd., etc.

[0059] Furthermore, in the compound having multiple isocyanate-reactive functional groups, the isocyanate-reactive functional group is a hydroxyl group; selected from compounds with a low refractive index and two or more hydroxyl functional groups; preferably selected from: tetraethylene glycol, trimethylolethane, glycerol, triethanolamine, polyester polyols with a molecular weight of 200 to 2000, polycarbonate polyols, and polyether polyols.

[0060] Furthermore, the polyisocyanate compound is selected from compounds with low refractive index and two or more isocyanate groups; preferably hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, (2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-triyl)tris(hexamethylene)isocyanate, butane-1,4-diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.

[0061] Furthermore, the other polymerizable monomers are selected from at least one of alkenyl naphthalene compounds, alkenyl anthracene compounds, alkenyl benzene compounds, acrylic compounds, acrylate compounds, methacrylate compounds, N-vinyl pyrrole, N-vinyl carbazole, N-vinylimidazole, N-vinyl indole, N-vinyl pyrrolidone, and trans-N-3-ynyl butenyl carbazole.

[0062] Illustratively, the alkenylbenzene compound can be selected from styrene, 2-chlorostyrene, 2-bromostyrene, 3-chlorostyrene, 3-bromostyrene, 4-chlorostyrene, 4-bromostyrene, p-(chloromethyl)styrene, p-(bromomethyl)styrene, and the like.

[0063] Illustratively, the acrylic compound may be acrylic acid and its derivatives.

[0064] Exemplarily, the acrylate compound can be selected from pentabromophenyl acrylate, pentachlorophenyl acrylate, phenoxyethyl acrylate, pentabromobenzyl acrylate, 2-naphthyl acrylate, 1,4-di(2-thionaphthyl)2-butyl acrylate, phenoxyethoxyethyl acrylate, bisphenol A diacrylate, tetrabromobisphenol A diacrylate, 2-phenoxyethyl acrylate, benzyl acrylate, p-chlorophenyl acrylate, 2,4,6-trichlorophenyl acrylate, p-bromophenyl acrylate, 2,4,6-tribromophenyl acrylate, propane-2,2-diylbis[(2,6-dibromo-4,1-phenylene)oxy(2-{[3,3,3-tri(4-chlorophenyl)propionyl]oxy}propane-3,1-diyl)oxyethane-2,1-diyl]diacrylate, and the like.

[0065] Exemplarily, the methacrylate compound can be selected from 2-phenoxyethyl methacrylate, benzyl methacrylate, p-bromophenyl methacrylate, p-chlorophenyl methacrylate, 2,4,6-trichlorophenyl methacrylate, pentabromophenyl methacrylate, pentachlorophenyl methacrylate, phenoxyethyl methacrylate, phenoxyethoxyethyl methacrylate, 1,4-di(2-thionaphthyl) 2-butyl methacrylate, pentabromobenzyl methacrylate, 2-naphthyl methacrylate, bisphenol A dimethacrylate, tetrabromobisphenol A dimethacrylate, and the like.

[0066] For example, the alkenyl anthracene compound may be selected from 2-vinyl anthracene, 9-vinyl anthracene, and the like.

[0067] For example, the alkenyl naphthalene compound may be selected from 1-vinyl naphthalene, 2-vinyl naphthalene and the like.

[0068] Furthermore, the photoinitiator is an initiator that can be activated by actinic radiation and initiates polymerization of the corresponding polymerizable groups, including but not limited to aromatic ketone compounds, benzoin and its derivatives, benzil ketal, acylphosphine oxide, aryl ammonium borate, chromium salt, aryl diazonium salt, onium salt, organometallic compound or any mixture of these compounds. For example, it includes one or more of benzophenone, alkylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, anthrone and halogenated benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacylphosphine oxide, phenyl dihydroxyacetate, camphorquinone, α-aminoalkylphenone, α,α-dialkoxyacetophenone, α-hydroxyalkylphenone, triphenylhexyl borate tetrabutylammonium, tri-(3-fluorophenyl)hexylborate tetrabutylammonium, tri-(3-chloro-4-methylphenyl)hexylborate tetrabutylammonium, ferrocenyl compounds, iodonium salts, sulfonium salts, hexaarylbiimidazoles, etc.

[0069] Furthermore, the chain transfer agent is a thiol compound, including but not limited to one or more of dodecyl mercaptan, mercaptoethanol, hexanethiol, phenylethyl mercaptan, 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, etc.

[0070] Furthermore, the catalyst is a tertiary amine catalyst and an organic metal catalyst, including but not limited to triethylenediamine, bis(dimethylaminoethyl) ether, dimethylethanolamine, 2-(2-dimethylamino-ethoxy)ethanol, trimethylhydroxyethylpropylenediamine, N,N-bis(dimethylaminopropyl)isopropanolamine, dibutyltin dilaurate, stannous octoate, potassium carboxylate catalysts and bismuth carboxylate catalysts.

[0071] In order to achieve the fifth object, the present invention adopts the following technical solutions:

[0072] The present invention discloses a holographic optical element, the raw material of which includes the photopolymer holographic recording medium as described above.

[0073] In order to achieve the sixth object, the present invention adopts the following technical solutions:

[0074] The invention discloses a photopolymer holographic storage optical disc, the raw material of which includes the photopolymer holographic recording medium as described above.

[0075] Exemplarily, the preparation of the photopolymer holographic storage optical disc refers to patent CN200910237040.7.

[0076] The beneficial effects of the present invention are as follows:

[0077] The present invention discloses a class of acrylic ester monomers with high refractive index, low viscosity and high solubility in film-forming resin, wherein the refractive index is above 1.6 and the viscosity is below 9 mm 2 / s, and can be stably dissolved in isocyanate-alcohol film-forming resin for more than one year. The acrylic ester monomer is used in the preparation of photopolymer holographic recording media, giving the holographic recording media a variety of excellent properties such as high sensitivity, high diffraction efficiency, high refractive index modulation and low haze. Its diffraction efficiency is greater than 90%, and its sensitivity is greater than 0.01cm 2 / mJ, exposure is less than 20mJ / cm 2 , the haze is less than 3%, and the photopolymer holographic recording medium provided by the present invention has stable performance, can be stored for a long time under light-proof conditions, and can achieve high-quality storage and reproduction of information after exposure. It has broad application prospects in the fields of high-density optical storage and holographic optical elements. BRIEF DESCRIPTION OF THE DRAWINGS

[0078] The specific implementation modes of the present invention are further described in detail below in conjunction with the accompanying drawings.

[0079] Figure 1 A comparison chart of 532 nm laser exposure characteristic curves of 0.005 mm thick photopolymer holographic recording media of Example 4 of the present invention and Comparative Example 1 is shown.

[0080] Figure 2 A comparison of 405 nm laser exposure characteristic curves of 0.5 mm thick photopolymer holographic recording media of Example 5 of the present invention and Comparative Example 2 is shown.

[0081] Figure 3 A comparison chart of 633 nm laser exposure characteristic curves of 0.05 mm thick photopolymer holographic recording media of Example 6 of the present invention and Comparative Example 3 is shown.

[0082] Figure 4 The following is a comparison chart of the exposure characteristic curves of the 0.05 mm thick photopolymer holographic recording medium of Example 4 of the present invention at different spatial frequencies.

[0083] Figure 5 A comparison of 532 nm laser exposure characteristic curves of the photopolymer holographic recording media of Examples 7 to 10 of the present invention is shown.

[0084] Figure 6 The Bragg selection angle curve of the holographic grating of the 0.005 mm photopolymer holographic recording medium of Example 5 of the present invention is shown under exposure at a spatial frequency of 2650 lines / mm.

[0085] Figure 7The Bragg selection angle curve of the holographic grating of the 0.5 mm thick photopolymer holographic recording medium of Example 6 of the present invention is shown under exposure at a spatial frequency of 2650 lines / mm.

[0086] Figure 8 A comparison of the UV-visible transmittance curves of the sample prepared in Example 4 before exposure, without recording grating photobleaching, and with recording grating photobleaching is shown. DETAILED DESCRIPTION

[0087] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0088] Example 1

[0089] Synthesis of compound G1-1

[0090] (1) Compound 1 (40 mmol), compound 2 (100 mmol) and NaOH (150 mmol) were dissolved in a mixed solution of ethanol and water, heated to 90°C for reaction for 6 h, and extracted with dichloromethane after the reaction was completed. The organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. A colorless oily liquid was obtained by column chromatography, which was compound 3 with a yield of about 90%.

[0091]

[0092] (2) Compound 3 (20 mmol) and triethylamine (40 mmol) were dissolved in 50 mL of dichloromethane under ice bath, stirred for 10 min, acryloyl chloride (30 mmol) was dissolved in 30 mL of dichloromethane, and then added dropwise to the mixed solution of compound 3 and triethylamine at 0°C, and reacted for 1 hour. After the reaction was complete, dilute hydrochloric acid was added dropwise to remove excess acryloyl chloride, and the mixture was washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. The colorless oily liquid was separated by column chromatography to obtain compound G1-1 with a yield of about 95%.

[0093] 1 H NMR (400MHz, CDCl3) δ7.26(s,4H),6.41(d,1H),6.12(dd,1H),5.83(d,1H),4.13(t,2H),3.38(t,2H),2.38(s,3H). 13C NMR (101MHz, CDCl3) δ166.5,135.8,132.8,131.3,128.2,128.1,63.7,39.1,14.8.

[0094]

[0095] Synthesis of compound G1-2

[0096] (1) Compound 4 (40 mmol), compound 5 (100 mmol) and NaOH (150 mmol) were dissolved in a mixed solution of ethanol and water, heated to 90°C for reaction for 6 h, and extracted with dichloromethane after the reaction was completed. The organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. Compound 6 was separated by column chromatography to obtain a colorless oily liquid with a yield of about 90%.

[0097]

[0098] (2) Compound 6 (20 mmol) and triethylamine (40 mmol) were dissolved in 50 mL of dichloromethane under ice bath, stirred for 10 min, acryloyl chloride (30 mmol) was dissolved in 30 mL of dichloromethane, and then added dropwise to the mixed solution of compound 6 and triethylamine at 0°C, and reacted for 1 hour. After the reaction was complete, dilute hydrochloric acid was added dropwise to remove excess acryloyl chloride, and the mixture was washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. Compound G1-2 was obtained as a colorless oily liquid by column chromatography, with a yield of about 95%.

[0099] 1 H NMR(400MHz, CDCl3)δ7.18-7.10(m,4H),6.48(d,1H),6.40(d,1H),3.97(t,2H) ,3.62(t,2H),2.89-2.84(m,4H),2.07(s,3H),2.01(s,3H),1.60-1.61(m,4H). 13 C NMR (101MHz, CDCl3) δ167.2,136.6,136.0,135.4,125.7,125.2,122.2,64.9,36.9,36.4,36.2,27.9,26.4,17.9,14.7.

[0100]

[0101] Synthesis of Compound G1-3

[0102] (1) Compound 7 (40 mmol), compound 8 (100 mmol) and NaOH (150 mmol) were dissolved in a mixed solution of ethanol and water, heated to 90°C for reaction for 6 h, and extracted with dichloromethane after the reaction was completed. The organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. Compound 9 was separated by column chromatography to obtain a colorless oily liquid with a yield of about 90%.

[0103]

[0104] (2) Compound 9 (20 mmol) and triethylamine (40 mmol) were dissolved in 50 mL of dichloromethane under ice bath, stirred for 10 min, acryloyl chloride (30 mmol) was dissolved in 30 mL of dichloromethane, and then added dropwise to the mixed solution of compound 9 and triethylamine at 0°C, and reacted for 1 hour. After the reaction was complete, dilute hydrochloric acid was added dropwise to remove excess acryloyl chloride, and the mixture was washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. Compound G1-3 was obtained by column chromatography separation as a colorless oily liquid with a yield of about 95%.

[0105] 1 H NMR(400MHz, CDCl3)δ7.26(d,2H),7.09(d,2H),6.41(d,1H),6.12(dd,1H),5.83(d,1H),4 .27(t,2H),3.77(m,4H),3.63-3.52(m,6H),3.40(s,3H),3.27(t,4H),1.60-1.61(m,4H). 13 C NMR (101MHz, CDCl3) δ166.5,142.1,135.3,131.3,128.2,125.3,72.5,72.2,71.6,69.4,68.7,64.8,59.3,39.7.

[0106]

[0107] Example 2

[0108] Synthesis of compound G2-1

[0109] (1) Compound 10 (20 mmol) was dissolved in anhydrous tetrahydrofuran under ice bath conditions, sodium hydride (25 mmol, dispersed in liquid paraffin) was slowly added, and the mixture was stirred at room temperature for 1 h. Compound 11 was slowly added dropwise, and after stirring for 10 min, dilute hydrochloric acid was slowly added dropwise to quench the reaction. The reaction solution was extracted with dichloromethane, and the organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. Compound 12 was separated by column chromatography;

[0110]

[0111] (2) Compound 12 (20 mmol) and triethylamine (40 mmol) were dissolved in 50 mL of dichloromethane under ice bath and stirred for 10 min. Methacryloyl chloride (30 mmol) was dissolved in 30 mL of dichloromethane and then added dropwise to the mixed solution of compound 12 and triethylamine at 0°C and reacted for 1 hour. After the reaction was complete, dilute hydrochloric acid was added dropwise to remove excess methacryloyl chloride. The mixture was washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase was dried over anhydrous sodium sulfate and the excess solvent was removed by rotary evaporation. Compound G2-1 was obtained by column chromatography as a colorless oily liquid with a yield of about 95%.

[0112] 1 H NMR(400MHz, CDCl3)δ6.86(s,3H),6.48(d,1H),6.40(d,1H),3.97(t,2H),3.62 (t,4H),2.84(t,4H),2.07(s,6H),2.01(s,3H),1.64-1.60(m,4H),1.29(m,2H). 13 C NMR (101MHz, CDCl3) δ167.2,136.8,136.0,125.2,118.6,65.6,36.9,36.7,36.2,29.9,28.3,24.7,17.9,14.7.

[0113]

[0114] Synthesis of compound G2-2

[0115] (1) Compound 13 (20 mmol) was dissolved in anhydrous tetrahydrofuran under ice bath conditions, sodium hydride (25 mmol, dispersed in liquid paraffin) was slowly added, and the reaction was stirred at room temperature for 1 h. Compound 14 was slowly added dropwise. After stirring for 10 min, dilute hydrochloric acid was slowly added dropwise to quench the reaction. The reaction solution was extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. Compound 15 was separated by column chromatography;

[0116]

[0117] (2) Compound 15 (20 mmol) and triethylamine (40 mmol) were dissolved in 50 mL of dichloromethane under ice bath and stirred for 10 min. Methacryloyl chloride (30 mmol) was dissolved in 30 mL of dichloromethane and then added dropwise to the mixed solution of compound 15 and triethylamine at 0°C and reacted for 1 hour. After the reaction was complete, dilute hydrochloric acid was added dropwise to remove excess methacryloyl chloride. The mixture was washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase was dried over anhydrous sodium sulfate and the excess solvent was removed by rotary evaporation. Compound G2-2 was obtained by column chromatography to obtain a colorless oily liquid with a yield of about 95%.

[0118] 1 H NMR(400MHz, CDCl3)δ7.02(d,2H),6.91(m,1H),6.41(d,1H),6.12(dd,1H),5 .83(d,1H),4.20(t,2H),2.94(m,6H),1.97(m,2H),1.41(m,4H),0.99(t,6H). 13 C NMR (101MHz, CDCl3) δ166.5,142.3,131.8,131.3,128.2,118.7,64.2,33.3,32.1,26.4,21.6,13.0.

[0119]

[0120] Synthesis of compound G2-3

[0121] (1) Compound 16 (20 mmol) was dissolved in anhydrous tetrahydrofuran under ice bath conditions, sodium hydride (25 mmol, dispersed in liquid paraffin) was slowly added, and the mixture was stirred at room temperature for 1 h. Compound 17 was slowly added dropwise, and after stirring for 10 min, dilute hydrochloric acid was slowly added dropwise to quench the reaction. The reaction solution was extracted with dichloromethane, and the organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. Compound 18 was separated by column chromatography;

[0122]

[0123] (2) Compound 18 (20 mmol) and triethylamine (40 mmol) were dissolved in 50 mL of dichloromethane under ice bath and stirred for 10 min. Methacryloyl chloride (30 mmol) was dissolved in 30 mL of dichloromethane and then added dropwise to the mixed solution of compound 18 and triethylamine at 0°C and reacted for 1 hour. After the reaction was complete, dilute hydrochloric acid was added dropwise to remove excess methacryloyl chloride. The mixture was washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase was dried over anhydrous sodium sulfate and the excess solvent was removed by rotary evaporation. Compound G2-3 was obtained by column chromatography to obtain a colorless oily liquid with a yield of about 95%.

[0124] 1 H NMR(400MHz, CDCl3)δ7.16(d,1H),7.02(d,1H),7.00(s,1H),6.41(d,1H),6.12(dd,1H),5.83 (d,1H),4.27(t,2H),3.77(m,6H),3.63(t,2H),3.55-3.52(m,12H),3.40(s,6H),3.27(t,6H). 13 C NMR (101MHz, CDCl3) δ166.5,142.3,138.5,133.0,131.3,128.2,127.2,124.5,122.4,72.5,71.6,70.1,69.7,69.4,64.8,59.3,40.1,39.7.

[0125]

[0126] Example 3

[0127] Synthesis of compound G3-1

[0128] (1) Compound 19 (40 mmol), compound 20 (100 mmol) and NaOH (150 mmol) were dissolved in a mixed solution of ethanol and water, heated to 90°C for reaction for 6 h, and extracted with dichloromethane after the reaction was completed. The organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. Compound 21 was obtained as a colorless oily liquid by column chromatography with a yield of about 90%.

[0129]

[0130] (2) Compound 21 (20 mmol) and triethylamine (40 mmol) were dissolved in 50 mL of dichloromethane under ice bath and stirred for 10 min. Acryloyl chloride (30 mmol) was dissolved in 30 mL of dichloromethane and then added dropwise to the mixed solution of compound 21 and triethylamine at 0°C and reacted for 1 hour. After the reaction was complete, dilute hydrochloric acid was added dropwise to remove excess acryloyl chloride. The mixture was washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase was dried over anhydrous sodium sulfate and the excess solvent was removed by rotary evaporation. Compound G3-1 was obtained by column chromatography as a colorless oily liquid with a yield of about 95%.

[0131] 1 H NMR (400MHz, CDCl3) δ6.76(s,2H),6.41(d,1H),6.12(dd,1H),5.83(d,1H),4.27(t,2H),3.77(t,8H),3.63(t,2H),3.27-3.23(m,17H). 13 C NMR (101MHz, CDCl3) δ166.5,142.5,133.2,131.3,128.2,118.8,74.7,72.2,68.7,64.8,58.6,40.1,39.4,39.0.

[0132]

[0133] Synthesis of compound G3-2

[0134] (1) Compound 22 (40 mmol), compound 23 (100 mmol) and NaOH (150 mmol) were dissolved in a mixed solution of ethanol and water, heated to 90°C for reaction for 6 h, and extracted with dichloromethane after the reaction was completed. The organic phase was dried over anhydrous sodium sulfate, and the excess solvent was removed by rotary evaporation. Compound 24 was obtained as a colorless oily liquid by column chromatography with a yield of about 90%.

[0135]

[0136] (2) Compound 24 (20 mmol) and triethylamine (40 mmol) were dissolved in 50 mL of dichloromethane under ice bath and stirred for 10 min. Acryloyl chloride (30 mmol) was dissolved in 30 mL of dichloromethane and then added dropwise to the mixed solution of compound 24 and triethylamine at 0°C and reacted for 1 hour. After the reaction was complete, dilute hydrochloric acid was added dropwise to remove excess acryloyl chloride. The mixture was washed with saturated NaCl solution, saturated NaHCO3 solution and deionized water in sequence. The organic phase was dried over anhydrous sodium sulfate and the excess solvent was removed by rotary evaporation. Compound G3-2 was obtained by column chromatography as a colorless oily liquid with a yield of about 95%.

[0137] 1 H NMR(400MHz, CDCl3)δ6.76(s,2H),6.48(d,1H),6.40(d,1H),4.13(t,2H),3.38 (t,2H),2.94-2.89(m,6H),2.01(s,3H),1.60(m,6H),1.44(m,6H),0.92(t,9H). 13 C NMR (101MHz, CDCl3) δ167.2,142.5,136.0,133.2,125.2,118.8,64.0,58.3,36.4,36.0,32.4,21.6,17.9,13.4.

[0138]

[0139] Example 4

[0140] This embodiment provides a photopolymer holographic recording medium, and its raw material components are shown in Table 1; wherein G1-1 is the sample obtained in Example 1.

[0141] The holographic recording medium is prepared using the raw materials recorded in Table 1, comprising the following steps: under red light conditions, into a 500 mL container with a stirring device, the components in Table 1 are added in sequence, and after the addition is completed, the components are fully stirred at room temperature for 15 minutes, and dust and other impurities are removed through a filter with a pore size of 0.45 microns, and then injected into a 80 mm×35 mm×0.5 mm / 0.05 mm / 0.005 mm glass container. After room temperature curing is completed, the holographic recording medium can be obtained.

[0142] Table 1

[0143]

[0144]

[0145] Example 5

[0146] The experimental process is the same as that of Example 4, the only difference being that the raw materials of the photopolymer holographic recording medium are shown in Table 2, wherein G2-1 is the sample obtained in Example 2.

[0147] Table 2

[0148]

[0149] Example 6

[0150] The experimental process is the same as that of Example 4, the only difference being that the raw materials of the photopolymer holographic recording medium are shown in Table 3, wherein G3-1 is the sample obtained in Example 3.

[0151] Table 3

[0152]

[0153] Embodiments 7 to 10

[0154] The experimental process is the same as that of Example 4, except that the raw materials of the photopolymer holographic recording medium are shown in Table 4, wherein G1-1 is the sample obtained in Example 1. The proportions of compound G1-1 in the photopolymer holographic recording medium in Examples 7 to 10 are 7.84 wt%, 15.68 wt%, 23.52 wt%, and 31.36 wt%, respectively.

[0155] Table 4

[0156]

[0157] Comparative Example 1

[0158] The experimental process is the same as that of Example 4, except that the raw materials of the photopolymer holographic recording medium are shown in Table 5.

[0159] Table 5

[0160]

[0161] Comparative Example 2

[0162] The experimental process is the same as that of Example 5, except that the raw materials of the photopolymer holographic recording medium are shown in Table 6.

[0163] Table 6

[0164]

[0165]

[0166] Comparative Example 3

[0167] The experimental process is the same as that of Example 6, except that the raw materials of the photopolymer holographic recording medium are shown in Table 7.

[0168] Table 7

[0169]

[0170] Test Example 1

[0171] (1) The refractive index and viscosity of the acrylic ester monomers of Examples 1-3 were tested. The results are shown in Table 8. The holographic properties of the photopolymer holographic recording media of Examples 4-6 and Comparative Examples 1-3 were evaluated and compared. The results are shown in Table 8. Figures 1 to 3 , as shown in Tables 9-10.

[0172] The evaluation method includes the following steps:

[0173] Solid-state lasers with wavelengths of 405nm, 532nm, and 633nm were used as light sources. After passing through a beam expander, beam splitter, and half-wave plate, two beams of 8mm diameter with the same light intensity were obtained. The two beams intersected in the prepared holographic recording medium for exposure. The normal of the recording medium bisected the two beams. The angle between the two beams was 58° to 90°, corresponding to a resolution of 1800 to 2600 lp / mm and a light intensity of 2.91 mW / cm 2 The detection light source is a 785nm wavelength solid laser that does not react with the recording medium. The detection light is incident on the exposure area from the Bragg angle. The transmitted light and diffracted light are monitored in real time by the photodetector. The single grating diffraction efficiency (η) of the 0.05mm thick photopolymer sample and the photosensitivity (S) of the recording medium are calculated by formulas (1) to (2). The incident angle of the detection light is changed by a rotating stage, and the diffracted light is read out near the Bragg angle to measure the Bragg selection angle of the holographic grating.

[0174]

[0175]

[0176] Where η is the diffraction efficiency, η max is the highest diffraction efficiency, I d is the diffracted light, I t is the transmitted light, S is the photosensitivity, and ΔE is the exposure energy when the highest diffraction efficiency is achieved.

[0177] (2) The photopolymer holographic recording performance and the haze of the samples of Examples 7 to 10 with different monomer addition amounts were evaluated according to the method of evaluation (1). The results are as follows: Figure 5 As shown in Table 9.

[0178] (3) The exposure rates of the photopolymer holographic recording medium of Example 4 at different spatial frequencies (respectively: 1800 lines / mm, 2650 lines / mm, 3600 lines / mm) were evaluated. The results are as follows: Figure 4 shown.

[0179] (4) The Bragg selection angle curve of the holographic grating of the photopolymer holographic recording medium of Examples 5 and 6 was evaluated under exposure at a spatial frequency of 2650 lines / mm. The results are as follows: Figure 6 , Figure 7 As shown. Figure 6 As shown, the selection angle of the 0.005 mm thick sample is as high as 8°, which can provide users with a large field of view and fully meet the application requirements of the fourth purpose of the present invention; Figure 7As shown, the selection angle of the 0.5 mm thick sample is only 0.2°, which can achieve multi-angle multiplexing when performing holographic optical storage, fully meeting the application requirements of the third purpose of the present invention.

[0180] (5) The photopolymer holographic recording medium of Example 4 is exposed to light to obtain a holographic grating, and then photobleached to obtain a transparent holographic grating.

[0181] Comparison of the photopolymer holographic recording medium before exposure, the sample without recording grating after photobleaching, and the sample with recording grating after photobleaching (100mW / cm 2 , 2h) of UV-visible light transmittance, the results are as follows Figure 8 shown.

[0182] Table 8 Refractive index and viscosity of the acrylic monomers synthesized in Examples 1-3

[0183] monomer G1-1 G1-2 G1-3 G2-1 G2-2 G2-3 G3-1 G3-2 Refractive Index 1.60 1.62 1.60 1.62 1.61 1.60 1.63 1.64 <![CDATA[Viscosity (mm 2 / s)]]> 6.48 5.35 6.92 8.56 7.17 9.48 8.97 8.34

[0184] Note: The kinematic viscosity of the monomer was measured using a glass capillary viscometer, and the refractive index of the monomer was tested using a WYA-3S digital Abbe refractometer from Shanghai Yidian Physical Optical Instrument Co., Ltd.

[0185] Table 9 Holographic performance parameters of holographic recording media

[0186] Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 <![CDATA[Exposure dose (mJ / cm 2 )]]> 7.99 7.19 7.57 22.9 9.5 22.0 Diffraction efficiency (%) 94.84 94.68 96.49 24.3 10.6 42.3 <![CDATA[Sensitivity (10 -3 cm 2 / mJ)]]> 121.88 135.33 129.76 21.5 34.3 29.6

[0187] Table 10 Holographic performance parameters and stability of holographic recording media of Examples 7 to 10

[0188] Example 7 Example 8 Example 9 Example 10 Example 10 Example 10 Example 10 Storage time 5 days 5 days 5 days 5 days 3 months 6 months 1 year <![CDATA[Exposure dose (mJ / cm 2 )]]> 15.69 8.70 7.19 5.23 5.13 5.25 5.22 Diffraction efficiency (%) 94.63 93.26 92.51 95.11 94.21 94.56 95.62 <![CDATA[Sensitivity (10 -3 cm 2 / mJ)]]> 62.00 111.00 133.77 186.47 189.20 185.22 187.33 Haze(%) 2.98 2.15 1.53 0.87 0.87 0.87 0.87

[0189] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. An acrylic acid ester monomer, characterized in that: The general structural formula of the acrylic acid ester monomer is as follows: Wherein, R1, R2, and R3 each independently represent any one of an alkyl group having carbon atoms of C1 to C20, an alkylthio group having carbon atoms of C1 to C20, and an alkoxy group having carbon atoms of C1 to C20; R4 represents methyl or hydrogen; n represents an integer of 0-20, and m represents an integer of 1-20.

2. The acrylic acid ester monomer according to claim 1, characterized in that: The general structural formula of the acrylic acid ester monomer is as follows:

3. The acrylic acid ester monomer according to claim 1 or 2, characterized in that: R1, R2, and R3 each independently represent any one of an alkyl group having carbon atoms of C1 to C4, an alkylthio group having carbon atoms of C1 to C4, and an alkoxy group having carbon atoms of C1 to C4; R4 represents methyl or hydrogen; n represents an integer of 1-10, and m represents an integer of 1-5.

4. The method for preparing an acrylic acid ester monomer according to any one of claims 1 to 3, characterized in that: The steps include: S1. Dissolve compound P1 in anhydrous tetrahydrofuran under ice bath, add sodium hydride, stir and react at room temperature for 0.5-3h, add compound P2 dropwise, wherein the molar ratio of compound P1, sodium hydride and compound P2 is 1:1-2:1-2, stir and react for 5-40min, then add dilute hydrochloric acid dropwise to quench the reaction, extract the reaction solution with dichloromethane, dry the organic phase over anhydrous sodium sulfate, remove excess solvent by rotary evaporation, and separate by column chromatography to obtain compound P3; S2. Add a solution containing acryloyl chloride or methacryloyl chloride dropwise to a solution containing compound P3 and triethylamine under an ice bath, wherein the molar ratio of compound P3, triethylamine, acryloyl chloride or methacryloyl chloride is 1:1-5:1-2. The reaction is carried out for 0.5-1h. After the reaction is completed, dilute hydrochloric acid is added dropwise, and the mixture is washed with NaCl solution, NaHCO3 solution and water in sequence. The organic phase is dried over anhydrous sodium sulfate, the solvent is removed by rotary evaporation, and the mixture is separated by column chromatography to obtain the obtained product.

5. The method for preparing an acrylic acid ester monomer according to any one of claims 1 to 3, characterized in that: The steps include: S1, dissolving compound P1, compound P2 and NaOH in a mixed solution of ethanol and water, wherein the molar ratio of compound P1, compound P2 and NaOH is 1:1-4:1-4, heating to 50-120°C for reaction for 1-12h, extracting with dichloromethane after the reaction, drying the organic phase over anhydrous sodium sulfate, removing excess solvent by rotary evaporation, and separating by column chromatography to obtain P3; S2. Add a solution containing acryloyl chloride or methacryloyl chloride dropwise to a solution containing compound P3 and triethylamine under an ice bath, wherein the molar ratio of compound P3, triethylamine, acryloyl chloride or methacryloyl chloride is 1:1-5:1-2. The reaction is carried out for 0.5-1h. After the reaction is completed, dilute hydrochloric acid is added dropwise, and the mixture is washed with NaCl solution, NaHCO3 solution and water in sequence. The organic phase is dried over anhydrous sodium sulfate, the solvent is removed by rotary evaporation, and the mixture is separated by column chromatography to obtain the obtained product.

6. A photopolymer holographic recording medium, characterized in that: The raw materials of the photopolymer holographic recording medium include the acrylic ester monomer as claimed in any one of claims 1 to 3.

7. The photopolymer holographic recording medium according to claim 6, wherein: The raw materials of the photopolymer holographic recording medium include the following components a) to h); Component a) a compound having multiple isocyanate-reactive functional groups; Component b) a polyisocyanate compound; Component c) acrylic acid ester monomers; Component d) other polymerizable monomers; Component e) a photoinitiator; Component f) chain transfer agent; Component g) optionally a catalyst; Component h) optional additives; Wherein, component c) is an acrylic acid ester monomer as described in any one of claims 1 to 3; The content of the component c) is 0.1 to 45 wt % based on the total mass of the photopolymer holographic recording medium.

8. The photopolymer holographic recording medium according to claim 6, wherein: The mass ratio of the components a), b), c), d), e), f), g) and h) is 20-70: 0.1-50: 0.1-45: 0.1-60: 0.1-4: 0.1-3: 0.1-3: 0.1-7.

9. The photopolymer holographic recording medium according to claim 6, wherein: The raw materials of the photopolymer holographic recording medium further include: component i) a photosensitizer.

10. The photopolymer holographic recording medium according to claim 9, wherein: The mass ratio of the component i) to the component e) is 0.001-1:0.1-4.

11. A holographic optical element, characterized in that: The raw material thereof comprises the photopolymer holographic recording medium as claimed in any one of claims 6 to 10.

12. A photopolymer holographic storage optical disc, characterized in that: The raw material thereof comprises the photopolymer holographic recording medium as claimed in any one of claims 6 to 10.

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