Optical monomer, holographic recording medium, method of manufacture and related devices

Abstract

The application discloses an optical monomer, a holographic recording medium, a preparation method and related devices, wherein a chemical structure general formula of the optical monomer is shown as G1-G4, the optical monomer has high refractive index and low viscosity, the preparation method is simple, further, the application introduces the optical monomer with the above structure into a photopolymer type holographic recording medium, thereby obtaining a holographic recording medium with high sensitivity and high diffraction efficiency, and the application also provides a preparation method of the holographic recording medium, a volume holographic grating containing the holographic recording medium, a holographic optical element and an optical device.

Description

Technical Field

[0001] This application relates to the field of holographic materials technology, and in particular to an optical monomer, a holographic recording medium, a preparation method, and related apparatus. Background Technology

[0002] Photopolymers used to fabricate holographic recording media typically include components such as photosensitive dyes, initiators, chain transfer agents, writing monomers, film-forming resins, and plasticizers. Photopolymers utilize light to polymerize the writing monomers, which then combine with the film-forming resin to form a refractive index-modulated phase-type holographic grating, thus achieving holographic recording. Specifically, when the writing monomers located in the coherent bright region are consumed and their concentration decreases, unreacted writing monomers located in the coherent dark region rapidly migrate to the coherent bright region, squeezing the film-forming resin from the bright region into the dark region. Ultimately, this results in the refractive index of the coherent bright region approaching that of the writing monomers, and the refractive index of the coherent dark region approaching that of the film-forming resin, thereby forming a refractive index-modulated phase-type volume holographic grating.

[0003] Therefore, improving the performance of photopolymers generally requires the base resin to have a lower refractive index and the writing monomer to have a higher refractive index to increase the refractive index difference between the two. However, high-refractive-index monomers in related technologies usually have a high degree of molecular conjugation and often contain large π-conjugated systems such as fused rings, causing these monomers to be mostly solids or highly viscous liquids at room temperature. During holographic exposure, the high viscosity significantly hinders the diffusion and migration of monomer molecules, thereby reducing the refractive index difference between the writing monomer and the film-forming resin, leading to a decline in material performance. Summary of the Invention

[0004] This application aims to provide an optical monomer, a holographic recording medium, a preparation method, and related apparatus. The optical monomer has both high refractive index and low viscosity to improve the problem that the diffusion and migration of the writing monomer in the photopolymer holographic recording medium is hindered, resulting in a small difference in refractive index between the writing monomer and the film-forming resin, and thus a decrease in material performance.

[0005] In a first aspect, this application provides an optical unit, the general structural formula of which is shown in any of the following: , , , , where R1 represents methyl or hydrogen.

[0006] As can be seen from the above technical solutions, the optical monomer provided in the first aspect of this application has a diselenyl ether structure. Selenium atoms possess high atomic polarizability and molar refractivity, and the selenium groups (such as –Se–) have low steric hindrance, resulting in a more compact molecular chain and more polarization units per unit volume, significantly improving the monomer's refractive index. Simultaneously, the introduction of aromatic rings into the molecular structure reduces the free volume of the system molecules, further enhancing the monomer's refractive index. Specifically, the optical monomer has a refractive index greater than 1.6 and less than 1.75, effectively matching common photosensitive resin systems, reducing light scattering loss during holographic recording, and improving diffraction efficiency. Furthermore, the higher refractive index helps enhance the material's optical anisotropy, optimizing the resolution and storage capacity of the hologram. Further, compared to the highly conjugated structure of fused rings, the optical monomer provided in this application has a lower degree of conjugation, resulting in lower viscosity (viscosity <100 cP). Therefore, it is easier to diffuse and migrate during holographic exposure, ensuring a stable refractive index difference between the optical monomer (i.e., the recording monomer) and the film-forming resin.

[0007] Secondly, this application provides a method for preparing the aforementioned optical monomer, comprising the following steps: Under an inert environment, selenium powder, compound M1, catalyst and alkaline reagent are dissolved in a first solvent and reacted to obtain compound P1, wherein the compound M1 is selected from at least one of 4-iodophenol, 2-iodophenol, 4-iodobenzyl alcohol or 2-iodobenzyl alcohol; The compound P1 and the acid-binding agent are dissolved in an organic solvent, and compound M2 is added to react and obtain the optical monomer, wherein the compound M2 is acryloyl chloride or methacryloyl chloride, and the organic solvent includes a first solvent.

[0008] As can be seen from the above technical solutions, the method for preparing optical monomers provided in the second aspect of this application uses a cheap and stable selenium source to efficiently construct the main structural unit of diaryl diselenide through a coupling reaction, and further constructs the coupling sites of optical monomers through an acylation reaction. This preparation method not only has readily available raw materials and mild reaction conditions, but also has a high yield of the target monomer, making it easy to scale up production.

[0009] Thirdly, this application provides a photopolymer-type holographic recording medium, the raw material of which comprises the following components a) Component h); Component a) A compound having multiple isocyanate reactive functional groups; Component b) Polyisocyanate group compounds; Component c) The aforementioned optical monomers; Component d) Polymerizable monomers; Component e) Photosensitive initiation system; Component f) Chain transfer agent; Component g) Optional second catalyst; Component h) Optional additives.

[0010] As can be seen from the above technical solution, this application provides a photopolymer-type holographic recording medium containing the aforementioned optical monomer. By introducing an optical monomer with a diaryl diselenyl ether structure into the photopolymer-type holographic recording medium, which has low conjugation and high refractive index, the refractive index difference between the optical monomer (i.e., the recording monomer) and the film-forming resin can be significantly improved, thereby obtaining a photopolymer-type holographic recording medium with excellent properties such as high sensitivity and high diffraction efficiency. Specifically, the diffraction efficiency of the photopolymer-type holographic recording medium is greater than 95%, the sensitivity is greater than 100 cm / mJ, and the exposure dose is less than 20 mJ / cm. 2 The shrinkage rate is less than 0.3%.

[0011] Fourthly, this application provides a method for preparing the aforementioned photopolymer-type holographic recording medium, comprising: Weigh the compound having multiple isocyanate reactive functional groups, the polyisocyanate group compound, the optical monomer, the polymerizable monomer, the photoinitiator system, the chain transfer agent, the second catalyst, and the additive into a container, and stir until dissolved to form a mixed solution; The mixture solution is filtered using a filter membrane to obtain a first solution; The first solution is coated onto a substrate and dried to obtain the photopolymer holographic recording medium.

[0012] As can be seen from the above technical solutions, the preparation method of the photopolymer-based holographic recording medium provided in this application is simple to operate and low in cost. It can ensure the uniform dispersion of each component, improve the light transmittance and refractive index modulation of the holographic recording medium, thereby enhancing the resolution and diffraction efficiency of the hologram. In addition, the filtration step can effectively remove impurities, reduce light scattering, and improve the storage stability and imaging quality of the holographic medium.

[0013] Fifthly, this application provides a volume holographic recording grating, which is fabricated from the aforementioned photopolymer-type holographic recording medium by holographic exposure.

[0014] In a sixth aspect, this application provides a holographic optical element, which includes the aforementioned volume holographic recording grating.

[0015] In a seventh aspect, this application provides an optical device including the aforementioned holographic optical element.

[0016] As can be seen from the above technical solutions, this application also provides a related device made using the aforementioned photopolymer holographic recording medium, based on the fact that the photopolymer holographic recording medium has a sensitivity greater than 100 cm / mJ and an exposure dose less than 20 mJ / cm. 2 It also has excellent properties such as a recording grating diffraction efficiency greater than 95%.

[0017] Furthermore, based on a sensitivity greater than 100 cm / mJ, only extremely low exposure energy is required to form a stable grating, which can shorten exposure time, reduce laser power demand, increase recording speed, and reduce energy consumption efficiency, making it suitable for dynamic recording and low-power devices. With a shrinkage rate of less than 0.3%, accurate grating period precision can be ensured, avoiding optical distortion and reducing image quality. With an exposure energy below 20 mJ / cm... 2 This demonstrates that only a small amount of light energy is needed to complete the curing and photopolymerization of the photopolymer holographic recording medium, thus avoiding overheating and deformation of the material caused by high-energy exposure. Based on a diffraction efficiency greater than 95%, it indicates that almost all incident light energy is diffracted to the target direction by the grating, thereby reducing light energy loss and resulting in a clearer image. Therefore, target devices (such as volume holographic recording gratings, optical elements, and optical devices) fabricated using photopolymer holographic recording media possess optical properties such as high recording speed and clear imaging. Attached Figure Description

[0018] Figure 1 This application illustrates the photopolymer-type holographic recording medium 5 in Embodiment 5. Exposure characteristic curves of photopolymer holographic recording media 5-4; Figure 2 The exposure characteristic curves of ordinary photopolymer holographic recording media in Comparative Examples 1 to 4 of this application are shown. Detailed Implementation

[0019] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0020] It should be understood that, when used in this specification and the appended claims, the terms "comprising" and "including" indicate the presence of the described features, integrals, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, integrals, steps, operations, elements, components and / or collections thereof.

[0021] It should also be understood that the terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the scope of the application. As used in this specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms unless the context clearly indicates otherwise.

[0022] It should also be further understood that the term “and / or” as used in this application specification and the appended claims means any combination of one or more of the associated listed items and all possible combinations, and includes such combinations.

[0023] The following detailed description of some embodiments of this application is provided in conjunction with the accompanying drawings. Unless otherwise specified, the following embodiments and features can be combined with each other.

[0024] It should be noted that the terms "photopolymer holographic recording medium" and "holographic recording medium" are equivalent in this application, "volume holographic grating" is equivalent to "phase-type volume holographic grating", "holographic grating" and "recording grating", and "substrate resin" is equivalent to "film-forming resin".

[0025] It should be understood that photopolymer-based holographic recording media materials used for holographic recording achieve holographic recording by using light to polymerize writing monomers, which then form a refractive index-modulated phase-type holographic grating with the film-forming resin. Specifically, when the writing monomers in the coherent bright region are consumed and their concentration decreases, the unreacted writing monomers in the coherent dark region rapidly migrate to the coherent bright region, squeezing the film-forming resin in the bright region into the coherent dark region. Ultimately, the refractive index of the coherent bright region approaches the refractive index of the writing monomers, and the refractive index of the coherent dark region approaches the refractive index of the film-forming resin, thus forming a refractive index-modulated phase-type volume holographic grating.

[0026] It should be noted that photopolymer-based holographic recording media with superior performance typically require the film-forming resin to have a lower refractive index and the writing monomer to have a higher refractive index in order to increase the difference in refractive index between the two.

[0027] However, in existing technologies, high-refractive-index monomers typically have a high degree of conjugation. Large π-conjugated systems (such as fused ring structures) result in monomer molecules with rigid, large planar structures and high viscosity. At room temperature, they are usually solids or highly viscous liquids, making them prone to local aggregation and unable to diffuse and migrate. This leads to a small difference in refractive index between the writing monomer and the film-forming resin, resulting in decreased material performance. Consequently, the grating's ability to control incident light is reduced, light energy loss is excessive, and optical devices suffer from low diffraction efficiency and unclear imaging, failing to meet the growing user demands.

[0028] Based on this, this application provides an optical monomer as a component of a writing monomer, the general chemical formula of which is shown in any of the following: , , or , where R1 represents methyl or hydrogen.

[0029] In this embodiment, the optical monomer has a diselenyl ether structure. It should be noted that selenium atoms possess high atomic polarizability and molar refractive index, and selenium groups (such as –Se–) have low steric hindrance, resulting in more compact molecular chain packing and more polarization units per unit volume. Therefore, it can significantly improve the monomer's refractive index. Simultaneously, the introduction of aromatic rings into the molecular structure reduces the free volume of the system molecules, further enhancing the monomer's refractive index. Specifically, the optical monomer has a refractive index greater than 1.6 and less than 1.75, effectively matching common photosensitive resin systems, reducing light scattering loss during holographic recording, and improving diffraction efficiency. Furthermore, the higher refractive index helps enhance the material's optical anisotropy, optimizing the resolution and storage capacity of the hologram. Further, compared to the highly conjugated structure of fused rings, the optical monomer provided in this application has a lower degree of conjugation, resulting in lower viscosity (viscosity <100 cP). Therefore, it is easy to diffuse and migrate during holographic exposure, ensuring a stable refractive index difference between the optical monomer (i.e., the recording monomer) and the film-forming resin.

[0030] For example, an optical monomer can be a compound having the following chemical structural formula: , , or It should be noted that the above optical components are merely illustrative examples, and the optical components provided in this application are not limited to these.

[0031] Furthermore, this application also provides a method for preparing the above-mentioned optical monomer, comprising the following steps S1 and S2: Step S1: Under an inert environment, selenium powder, compound M1, a first catalyst, and an alkaline reagent are dissolved in a first solvent to react and obtain compound P1, wherein compound M1 is selected from at least one of 4-iodophenol, 2-iodophenol, 4-iodobenzyl alcohol, or 2-iodobenzyl alcohol.

[0032] It should be understood that selenium powder is a conventionally available commercial chemical raw material, and its main component is elemental selenium. In other words, step S1 is essentially a coupling reaction between elemental selenium and compound M1 under the action of a catalyst and a basic reagent. It should also be understood that an inert environment, such as an inert gas atmosphere, helps maintain the stability of the reaction system, thereby preventing the destruction of sensitive reaction substrates or intermediates. For example, if step S1 is carried out in an inert gas atmosphere, elemental selenium (selenium powder) can be protected from oxidation, thereby improving the yield of the target monomer. Inert gases include, but are not limited to, nitrogen and argon. It should also be understood that those skilled in the art can provide inert protection for the reaction according to actual needs, and this application does not limit this.

[0033] Therefore, the compound P1 obtained by step S1 reaction includes at least compounds having the following chemical structural formulas: , , or .

[0034] In some embodiments, the molar ratio of selenium powder to compound M1 is (2-2.3):1, which allows compound M1 to be almost completely consumed in the reaction system of step S1, effectively increasing the yield of compound P1. Typically, but not limitingly, the molar ratio of selenium powder to compound M1 can be, for example, 2:1, 2.1:1, 2.2:1, or 2.3:1, etc.

[0035] Furthermore, in some examples, the reaction effect was better when the selenium powder, compound M1, catalyst and alkaline reagent were refluxed at 60~100℃ for 10 h~20 h in step S1.

[0036] For example, under nitrogen protection, 2 equivalents of selenium powder, 1 equivalent of compound M1, 0.5 equivalents of nano-copper oxide particles, and 1 equivalent of potassium hydroxide were dissolved in anhydrous dimethyl sulfoxide. The reaction system was refluxed at 60–100 °C for approximately 10–20 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and deionized water was added to the reaction mixture. The mixture was extracted three times with ethyl acetate. After washing with brine and drying with anhydrous sodium sulfate, excess solvent was removed by rotary evaporation. The mixture was then purified by column chromatography to obtain compound P1.

[0037] It is understandable that, during the stirring process at room temperature, 2 equivalents of selenium powder and 1 equivalent of compound M1 can be dissolved in anhydrous dimethyl sulfoxide first, and then 0.5 equivalents of nano copper oxide particles can be added. Subsequently, the reaction system is purged with nitrogen for protection and 1 equivalent of potassium hydroxide is added under heating conditions of 60~100℃. After the addition is complete, the reaction system is refluxed at 60~100℃ for about 10~20 hours.

[0038] That is, the order in which selenium powder, compound M1, the first catalyst and the alkaline reagent are added in step S1 is not limited in this application.

[0039] In addition, the alkaline reagent can not only activate elemental selenium and promote its dissolution in the reaction system to participate in the coupling reaction, but also neutralize the byproducts generated in the reaction. The alkaline reagent includes, but is not limited to, at least one of potassium hydroxide, potassium carbonate, sodium carbonate, and cesium carbonate. In some embodiments, when the molar ratio of compound M1 to the alkaline reagent is 1:(1–1.5), the acid byproduct generated in the reaction can be completely neutralized, and compound M1 can be activated, resulting in a better reaction effect. Typically, but not limitingly, the molar ratio of compound M1 to the alkaline reagent can be, for example, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, or 1:1.5, etc.

[0040] The first solvent includes at least dimethyl sulfoxide and N,N-dimethylformamide. The first catalyst includes, but is not limited to, at least one of nano-copper oxide and cuprous iodide. Preferably, the first catalyst is nano-copper oxide, which has a large specific surface area, many surface active sites, high catalytic activity, and can be repeatedly recycled. In some embodiments, the molar ratio of compound M1 to the first catalyst is 1:(0.1 to 0.5), which can increase the reaction rate, accelerate the reaction process, and ensure that the reaction proceeds efficiently without causing other side reactions due to the presence of excess first catalyst. Typically, but not limitingly, the molar ratio of compound M1 to the first catalyst may be, for example, 1:0.1, 1:0.2, 1:0.3, 1:0.4, or 1:0.5.

[0041] Step S2: Dissolve compound P1 and an acid-binding agent in an organic solvent, and add compound M2 to react and obtain an optical monomer. Compound M2 is acryloyl chloride or methacryloyl chloride.

[0042] The organic solvent includes a first solvent, specifically including but not limited to one or more of methanol, ethanol, petroleum ether, dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, acetonitrile, benzene, toluene, N,N-dimethylformamide, dimethyl sulfoxide, dimethoxyethane, and 1,4-dioxane. It should be noted that the above solvents are merely illustrative, and the solvents that can be used in this application are not limited to these.

[0043] It is understood that in step S2, compound P1 is activated by the acid-binding agent to generate a more reactive alkoxy group, thereby enhancing nucleophilicity and further promoting the substitution reaction between compound P1 and compound M2, thus yielding the optical monomer. In some specific examples, the reaction is usually carried out at 0°C (i.e., in an ice bath), and compound M2 is added dropwise to the mixed solution of compound P1 and the acid-binding agent at 0°C to avoid local overheating or excessive concentration that could trigger side reactions. A reaction time of 0.5 h to 3 h typically yields better reaction results.

[0044] Among them, acid-binding agents include, but are not limited to, triethylamine, pyridine, N,N Diisopropylethylamine, 4 One or more of dimethylaminopyridine, tetrabutylammonium bromide, potassium carbonate, ammonium carbonate, and sodium carbonate.

[0045] It should be further understood that, because compound M2 (i.e., acryloyl chloride or methacryloyl chloride) is a highly reactive acylating agent, it is prone to side reactions, leading to a reduction in the amount actually participating in the target reaction. Therefore, it is usually necessary to use an excess to compensate for the consumption by side reactions and ensure that sufficient acryloyl chloride reacts with the substrate. In addition, since the acid-binding agent needs to provide basic conditions to promote the deprotonation of compound P1 and neutralize the hydrochloric acid generated in the reaction to prevent the decomposition of the substrate or product, the acid-binding agent is also usually used in excess. Specifically, in some examples, the molar ratio of compound P1, acid-binding agent, and compound M2 is 1:(2-8):(3-6).

[0046] Typical, but not limiting, molar ratios of compound P1, acid-binding agent, and compound M2 can be, for example, 1:2:3, 1:2:3, 1:2:4, 1:2:5, 1:2:6, 1:3:3, 1:3:3, 1:4:5, 1:4:4, 1:7:3, 1:8:3, or 1:8:6.

[0047] In some specific examples, the reaction is more effective when the reaction solvent in step S2 is any one of dichloromethane, trichloromethane, and ethyl acetate.

[0048] For example, 1 equivalent of compound P1 and 2-8 equivalents of triethylamine were dissolved in dichloromethane under ice bath conditions. After stirring for 10 min, 2-6 equivalents of acryloyl chloride or methacryloyl chloride were added dropwise to the mixed solution of compound P1 and triethylamine at 0 °C. After the reaction was complete, dilute hydrochloric acid was added dropwise to remove excess acryloyl chloride or methacryloyl chloride. The mixture was then washed successively with saturated NaCl solution, saturated NaHCO3 solution, and deionized water. The organic phase was dried over anhydrous sodium sulfate, and excess solvent was removed by rotary evaporation. The target optical monomer was then obtained by column chromatography.

[0049] In this embodiment, selenium powder is a commercial chemical raw material that is inexpensive and readily available. The synthetic strategy of using selenium powder to construct diaryl diselenide not only has the advantages of low cost, mild preparation conditions, environmental friendliness, and high yield of target monomer, but also facilitates large-scale production.

[0050] This application also provides a photopolymer holographic recording medium, including a writing monomer, which includes an optical monomer and a polymerizable monomer.

[0051] It should be understood that the refractive index of the optical element is positively correlated with the refractive index of the writing element; that is, when the refractive index of the optical element is high, the refractive index of the resulting writing element is also high.

[0052] Furthermore, in some embodiments, the raw material of the photopolymer-type holographic recording medium includes the following component a) Component h): Component a) A compound having multiple isocyanate reactive functional groups. Component b) Polyisocyanate group compounds, Component c) at least one of the aforementioned optical monomers G1-G4, Component d) Polymerizable monomers, Component e) Photosensitive initiation system, Component f) Chain transfer agent, Component g) Optional second catalyst, Component h) Optional additives, Among them, compounds with multiple isocyanate reactive functional groups and polyisocyanate group compounds form film-forming resins.

[0053] In this embodiment, an optical monomer with a high refractive index is used as a component of the writing monomer, thereby allowing the writing monomer and the film-forming resin to have a greater refractive index difference, thus forming a photopolymer-type holographic recording material with excellent properties such as high sensitivity and high diffraction efficiency. Specifically, in some examples, the photopolymer-type holographic recording medium has a sensitivity greater than 100 cm / mJ, a recording grating diffraction efficiency greater than 95%, a shrinkage rate less than 0.3%, and an exposure dose less than 20 mJ / cm. 2 .

[0054] More specifically, in some examples, the composition and content of photopolymer-type holographic recording media are as follows: Component a) 10 wt% to 50 wt% of compounds having multiple isocyanate reactive functional groups. Component b) Polyisocyanate group compound 10 wt%~50 wt%. Component c) Optical monomers 1 wt%~30 wt%. Component d) Polymerizable monomers 10 wt%~40 wt%. Component e) Photoinitiator system 0.1 wt%~3 wt%. Component f) Chain transfer agent 0.1 wt%~3 wt%. Component g) Second catalyst 0.1 wt%~5 wt%, Component h) Additives 0.1 wt%~10 wt%.

[0055] Specifically, the content of component a) can be, for example, 10 wt%, 20 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, and 50 wt%, etc.; the content of component b) can be, for example, 10 wt%, 20 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, and 50 wt%, etc.; the content of component c) can be, for example, 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, and 30 wt%, etc.; the content of component d) can be, for example, 10 wt%, 20 wt%, 30 wt%, 35 wt%, and 40 wt%, etc.; the content of component e) can be, for example, 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, and 3 wt%, etc.; and the content of component f) can be, for example, 0.1 wt%, 0.5 wt%, 1 ... The content of component g) can be, for example, 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, and 5 wt%, and the content of component h) can be, for example, 0.1 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, and 10 wt%, etc.

[0056] More specifically, in some optional examples, the photopolymer-type holographic recording medium containing optical monomers comprises the following components in the following amounts: component a) 10 wt% of a compound having multiple isocyanate reactive functional groups, component b) 30 wt% of a polyisocyanate-based compound, component c) 30 wt% of an optical monomer, component d) 20 wt% of a polymerizable monomer, component e) 1 wt% of a photoinitiator system, component f) 1 wt% of a chain transfer agent, component g) 1 wt% of a second catalyst, and component h) 7 wt% of an additive.

[0057] In some optional examples, the photopolymer-type holographic recording medium containing optical monomers comprises the following components in the following amounts: component a) 25 wt% of a compound having multiple isocyanate reactive functional groups, component b) 32 wt% of a polyisocyanate-based compound, component c) 3 wt% of an optical monomer, component d) 24 wt% of a polymerizable monomer, component e) 3 wt% of a photoinitiator system, component f) 3 wt% of a chain transfer agent, component g) 3 wt% of a second catalyst, and component h) 7 wt% of an additive.

[0058] In some optional examples, the photopolymer-type holographic recording medium containing optical monomers comprises the following components in the following amounts: component a) 49.5 wt% of a compound having multiple isocyanate reactive functional groups, component b) 15 wt% of a polyisocyanate-based compound, component c) 2 wt% of an optical monomer, component d) 23 wt% of a polymerizable monomer, component e) 1 wt% of a photoinitiator system, component f) 1 wt% of a chain transfer agent, component g) 2 wt% of a second catalyst, and component h) 6.5 wt% of an additive.

[0059] In some optional examples, the photopolymer-type holographic recording medium containing optical monomers comprises the following components in the following amounts: component a) 24 wt% of a compound having multiple isocyanate reactive functional groups, component b) 15 wt% of a polyisocyanate-based compound, component c) 1 wt% of an optical monomer, component d) 40 wt% of a polymerizable monomer, component e) 3 wt% of a photoinitiator system, component f) 3 wt% of a chain transfer agent, component g) 5 wt% of a second catalyst, and component h) 9 wt% of an additive.

[0060] In some optional examples, the photopolymer-type holographic recording medium containing optical monomers comprises the following components in the following amounts: component a) 10 wt% of a compound having multiple isocyanate reactive functional groups, component b) 50 wt% of a polyisocyanate-based compound, component c) 20 wt% of an optical monomer, component d) 10 wt% of a polymerizable monomer, component e) 2.9 wt% of a photoinitiator system, component f) 0.1 wt% of a chain transfer agent, component g) 2 wt% of a secondary catalyst, and component h) 5 wt% of an additive.

[0061] In some optional examples, the photopolymer-type holographic recording medium containing optical monomers comprises the following components in the following amounts: component a) 33 wt% of a compound having multiple isocyanate reactive functional groups, component b) 21.9 wt% of a polyisocyanate-based compound, component c) 20 wt% of an optical monomer, component d) 11 wt% of a polymerizable monomer, component e) 2 wt% of a photoinitiator system, component f) 2.5 wt% of a chain transfer agent, component g) 0.1 wt% of a secondary catalyst, and component h) 9.5 wt% of an additive.

[0062] In some optional examples, the photopolymer-type holographic recording medium containing optical monomers comprises the following components in the following amounts: component a) 25 wt% of a compound having multiple isocyanate reactive functional groups, component b) 30 wt% of a polyisocyanate-based compound, component c) 10 wt% of an optical monomer, component d) 25 wt% of a polymerizable monomer, component e) 0.2 wt% of a photoinitiator system, component f) 0.8 wt% of a chain transfer agent, component g) 3 wt% of a secondary catalyst, and component h) 6 wt% of an additive.

[0063] In some optional examples, the photopolymer-type holographic recording medium containing optical monomers comprises the following components in the following amounts: component a) 35 wt% of a compound having multiple isocyanate reactive functional groups, component b) 15 wt% of a polyisocyanate-based compound, component c) 21 wt% of an optical monomer, component d) 28.6 wt% of a polymerizable monomer, component e) 0.1 wt% of a photoinitiator system, component f) 0.1 wt% of a chain transfer agent, component g) 0.1 wt% of a secondary catalyst, and component h) 0.1 wt% of an additive.

[0064] In this embodiment, by rationally controlling the composition ratio of the photopolymer holographic recording medium, the various components can work together fully, and the holographic performance of the final photopolymer holographic recording medium will not deteriorate due to an excess or deficiency of a certain component. This ensures that the final photopolymer holographic recording medium has better overall holographic performance, thereby achieving high resolution, high diffraction efficiency and long-term stability.

[0065] In some embodiments, the optical monomer accounts for 0.1 wt% to 30 wt% of the total photopolymer holographic recording medium.

[0066] Typically, but not limitingly, the content of optical monomers in the entire photopolymer holographic recording medium can be 0.1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, or any range of two values.

[0067] In this embodiment, the content of optical monomers ranges from 0.1 to 30 wt% to ensure that sufficient active monomers are provided to participate in photopolymerization so that the resulting writing monomers have a sufficient concentration to achieve the concentration difference between the bright and dark areas after the reaction under light.

[0068] In some embodiments, the isocyanate reactive functional group is a hydroxyl group. Compounds having multiple isocyanate reactive functional groups include compounds with a refractive index ranging from 1.50 to 1.55 and having two or more hydroxyl functional groups.

[0069] For example, compounds having multiple isocyanate reactive functional groups include compounds with a refractive index of 1.50, 1.51, 1.52, 1.53, 1.54, 1.55 or any value between any two of these values, and compounds having two or more hydroxyl functional groups.

[0070] Optionally, the polyisocyanate-based compound includes compounds with a refractive index ranging from 1.50 to 1.55 and having two or more isocyanate groups.

[0071] For example, polyisocyanate compounds include compounds with a refractive index of 1.50, 1.51, 1.52, 1.53, 1.54, 1.55 or any value between any two of these values, and which have two or more isocyanate groups.

[0072] In this embodiment, a compound with multiple isocyanate reactive functional groups and a refractive index between 1.50 and 1.55 and having two or more hydroxyl functional groups forms a low-refractive-index film-forming resin with a polyisocyanate compound having a refractive index between 1.50 and 1.55 and having two or more isocyanate groups. The low-refractive-index film-forming resin and the high-refractive-index writing monomer (i.e., including the aforementioned optical monomer) form a significant refractive index difference (Δn≥0.1), which can enhance the diffraction efficiency of the holographic grating and avoid the increase in background noise caused by the high refractive index of the substrate itself.

[0073] In some embodiments, the isocyanate reactive functional group is a hydroxyl group, and the molar ratio of hydroxyl group to isocyanate functional group is 1:1. That is, in the film-forming resin that forms a photopolymer type holographic recording medium, the molar ratio of hydroxyl group in the compound having multiple isocyanate reactive functional groups to isocyanate functional group in the polyisocyanate group compound is 1:1.

[0074] Furthermore, in some examples, compounds having multiple isocyanate reactive functional groups may be, for example, 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, neopentanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1 4-Cyclohexanediol, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, 1,2,4-butanetriol, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tripentaerythritol, bis(trimethylolpropane), polyethylene glycol with a molecular weight of 200–2000, polypropylene glycol with a molecular weight of 200–2000, polytetramethylene ether glycol with a molecular weight of 200–2000, polytetrahydrofuran with a molecular weight of 200–2000, 1,4-butenylene glycol, 1,4-butynediol, 1,2-decanediol, 1,2-dodecadiol, 2-methyl-1,3-propanediol, 1,7-heptanediol, 1,9-nonanediol, 2,2-diethyl-1, 3-Propanediol, 1,4-Dimethylolcyclohexane, 1,2,3-Hexanetriol, 1,2,4-Hepanetriol, 1,3,5-Pentanetriol, Poly(oxypropylene)triol, Poly(ε-caprolactone)diol, Poly(ε-caprolactone)triol, Poly(propylene carbonate)diol, Poly(butadiene)diol, Hydrogenated poly(butadiene)diol, Poly(ethylene adipate)diol, Poly(butylene adipate)diol, Poly(1,4-butanediol adipate)diol, Poly(glycerol sebacate)diol, Trimethylolpropane ethoxylate (TMP-EO), Trimethylolpropane propoxylate, Pentaerythritol ethoxylate, Glyceryl ethoxylate, Glyceryl propoxylate, Ethylene Diaminetetra(propoxylated), diethylenetriaminepenta(propoxylated), partially hydrolyzed polyvinyl alcohol, poly(1,2-butanediol), poly(1,3-propanediol), poly(1,4-butanediol), poly(1,6-hexanediol), poly(neopentyl glycol), poly(3-methyl-1,5-pentanediol), poly(1,4-cyclohexanediol), tris(2-hydroxyethyl)isocyanurate, N,N,N',N'-tetra(2-hydroxypropyl)ethylenediamine, 2,2,3-trimethyl-1,3-pentanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-pentanediol, 1,3-butanediol, or 2-methyl-2,4-pentanediol, but not limited thereto.

[0075] For example, trimethylolpropane ethoxylates are typically trifunctional polyether polyols obtained by reacting trimethylolpropane (TMP) with ethylene oxide (EO). Trimethylolpropane ethoxylates with different EO addition numbers have different molecular weights, viscosities, etc. For instance, TMP... 3EO (also known as polyether TMP) 3) A trimethylolpropane ethoxylate with a total EO addition number of 3, obtained by the addition of trimethylolpropane to 3 mol of ethylene oxide (EO), containing 3 free terminal hydroxyl groups and a molecular weight of 266. Polyisocyanate compounds include, but are not limited to, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, (2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-triyl)tri(hexamethylene)isocyanate, butane-1,4-diisocyanate, isophorone diisocyanate, or dicyclohexylmethane diisocyanate, etc.

[0076] In some examples, the polymerizable monomer is selected from at least one of alkenylnaphthalene compounds, alkenylanthracene compounds, alkenylbenzene compounds, acrylic compounds, methacrylic acid compounds, acrylate compounds, methacrylate compounds, N-vinylpyrrole, N-vinylcarbazole, N-vinylimidazol, N-vinylindole, N-vinylpyrrolidone, or trans-N-3-yntynebutenylcarbazole.

[0077] Among them, alkenylbenzene compounds include, but are not limited to, styrene, 2-chlorostyrene, 2-bromostyrene, 3-chlorostyrene, 3-bromostyrene, 4-chlorostyrene, 4-bromostyrene, p-(chloromethyl)styrene, or p-(bromomethyl)styrene.

[0078] For example, methacrylic acid compounds can be methacrylic acid and its derivatives. For instance, methacrylate compounds 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-bis(2-thionaphthyl)2-butyl methacrylate, pentabromobenzyl methacrylate, 2-naphthyl methacrylate, bisphenol A dimethacrylate, or tetrabromobisphenol A dimethacrylate, etc.

[0079] In specific examples, acrylate compounds include, but are not limited to, 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, or propane-2,2-diylbis[(2,6-dibromo-4,1-phenylene)oxy(2-{[3,3,3-tris(4-chlorophenyl)propionyl]oxy}propane-3,1-diyl)oxyethane-2,1-diyl]diacrylate, etc.

[0080] In specific examples, vinylanthracene compounds may be selected from 2-vinylanthracene, 9-vinylanthracene, etc.

[0081] In specific examples, vinylnaphthalene compounds can be selected from 1-vinylnaphthalene, 2-vinylnaphthalene, etc.

[0082] In some implementations, the photoinitiation system is composed of a photosensitizer and a photoinitiator, which work synergistically to construct a broadband visible light initiation system. The photosensitizer selectively absorbs laser energy at specific wavelengths (e.g., 532 nm or 633 nm) and activates the photoinitiator through an energy transfer mechanism, thereby significantly expanding the system's photosensitive wavelength range. Therefore, different broadband responses can be achieved by controlling the type of photosensitizer. Under irradiation with light within a specific wavelength range, the photosensitizer in the photoinitiation system is activated accordingly, absorbs light energy, and transfers the light energy to the photoinitiator. This allows the photoinitiator to be activated under light radiation of more frequencies. The activated photoinitiator efficiently generates active free radicals, rapidly initiating monomer polymerization reactions, thus enabling the construction of a holographic grating structure. This improves the photosensitivity of the photopolymer-based holographic recording medium and enhances compatibility with lasers of different wavelengths, providing a more flexible light source selection scheme for holographic storage.

[0083] It is understandable that when a photoinitiator with a suitable wavelength is selected in the raw materials of a photopolymer holographic recording medium, a photosensitizer may not be added. For example, when the photoinitiator is diacetic titanium (Irgacure 784), a photosensitizer may not be added. This highly reactive orange solid photoinitiator can initiate the polymerization reaction of unsaturated resins under visible or ultraviolet light.

[0084] In some examples, the mass ratio of photosensitizer to photoinitiator is (0.001~1):(0.1~3). Typical, but not limiting, the mass ratio of photosensitizer to photoinitiator can be 0.001:0.1, 0.005:0.2, 0.01:0.3, 0.02:0.5, 0.05:1.0, 0.1:0.5, 0.2:1.0, 0.3:1.2, 0.5:1.5, 1:0.1, 0.6:2.0, 0.8:2.0, 0.9:2.5, 1.0:2.0, 0.01:0.5, 0.1:1.0, 0.3:1.5, 0.5:2.0, or 1.0:3.0, etc. By adjusting the ratio of photosensitizer and photoinitiator within the above range, the energy transfer efficiency of the photosensitizer and the free radical yield of the photoinitiator can be balanced, avoiding energy waste caused by excessive photosensitizer or side reactions caused by excessive initiator. This allows for efficient initiation of the polymerization reaction while controlling the reaction rate within a reasonable range, thus controlling the grating formation speed within a certain range and ensuring the light transmittance of the photopolymer holographic recording medium, thereby achieving excellent diffraction efficiency.

[0085] Among them, photosensitizers are dyes that have high electron transfer efficiency under light irradiation, including but not limited to cyanine dyes, fluorescein dyes, coumarin ketone dyes, nitrogen-containing aromatic heterocyclic compounds, aromatic amine compounds, and benzylidene cycloalkanes ketone compounds.

[0086] For example, the photosensitizer may be one or more of the following: neomethylene blue, thionine, basic yellow, pinacyanin chloride, rhodamine 6G, gallium cyanide, ethyl violet, Victoria blue R, azurite blue, methylene blue, basic orange 21, darone red, pyrrole red Y, basic red 29, quinaldinium red, crystal violet, brilliant green, pyrylium I, azurite A, crystal violet cyanocyanate, malachite green cyanocyanate, etc.

[0087] Photoinitiators are initiators that can be activated by photochemical radiation and initiate polymerization reactions of corresponding polymerizable groups. They include, but are not limited to, aromatic ketones, benzoin and its derivatives, benzoyl ketals, acylphosphine oxides, ammonium arylboronate, chromium salts, aryl diazonium salts, onium salts, or organometallic compounds.

[0088] Specifically, the photoinitiator can be one or more of the following: benzophenone, alkylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, anthrone and halogenated benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, diacylphosphine oxide, phenyl dihydroxyacetate, camphorquinone, α-aminoalkylphenyl ketone, α,α-dialkoxyacetophenone, α-hydroxyalkylphenyl ketone, tetrabutylammonium triphenylhexylborate, tetrabutylammonium tri-(3-fluorophenyl)hexylborate, tetrabutylammonium tri-(3-chloro-4-methylphenyl)hexylborate, ferrocene compounds, iodonium salts, thiodonium salts, or hexaaryldiimidazole.

[0089] As a chain transfer agent, the chain transfer agent can control the polymer chain length within a certain reasonable range and effectively prevent excessive polymerization, ensuring that the final holographic recording medium has the required optical properties and diffraction efficiency.

[0090] In some embodiments, the chain transfer agent may be, for example, a thiol compound. Exemplary examples include one or more of dodecyl mercaptoethanol, mercaptoethanol, hexamethylene mercaptoethanol, phenylethyl mercaptoethanol, 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, but not limited thereto.

[0091] It is understandable that the molecular weight of the polymerized optical monomers and polymerizable monomers can be controlled by the photoinitiator system, the amount of chain transfer agent used, and the reaction conditions, and the amount used can be appropriately adjusted according to their types.

[0092] As a second catalyst, the second catalyst can effectively increase the reaction rate of related components and increase the consumption rate of related components after exposure, thereby quickly forming a concentration difference of monomers in the bright and dark areas and realizing a phase-type volume holographic grating with refractive index modulation.

[0093] In some embodiments, the second catalyst is selected from at least one of tertiary amine catalysts and organometallic catalysts, such as triethylenediamine, bis(dimethylaminoethyl) ether, dimethylethanolamine, 2-(2-dimethylaminoethoxy)ethanol, trimethylhydroxyethylpropanediamine, N,N-bis(dimethylaminopropyl)isopropanolamine, dibutyltin dilaurate, stannous octoate, potassium carboxylate catalysts, and bismuth carboxylate catalysts, but is not limited thereto.

[0094] For example, additives can be selected from at least one of defoamers, leveling agents, plasticizers, and dehydrating agents. For instance, as defoamers, defoamers include silicone defoamers and silicone-free polymeric defoamers. Defoamers are mainly used to eliminate or suppress bubbles generated during material preparation and photocuring to ensure high resolution, high diffraction efficiency, and structural uniformity of the hologram.

[0095] Specifically, the defoamer can be selected from BYK-011, BYK-012, BYK-014, BYK-023, BYK-051N, BYK-085, BYK-1610, BYK-1707, BYK-1740, and BYK-1760 manufactured by BYK Corporation, DC65 and AFE-7820 manufactured by Dow Corning, or any mixture of these defoamers in any proportion, but is not limited thereto. Among them, the BYK series defoamers have excellent defoaming performance, good compatibility with other components, and good dispersibility. BYK-011, BYK-012, BYK-014, and BYK-051N are silicone-free polymeric defoamers. DC65 is a water-based ink that dries quickly, provides good printing results, and is not easily peeled off. AFE-7820 has highly efficient defoaming performance. The defoamer content in the photopolymer holographic recording medium is less than or equal to 3 wt%. Typically, but not limitingly, the defoamer content in the photopolymer holographic recording medium can be 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, etc.

[0096] In a specific example, the leveling agent is an organosilicon surface additive, and the leveling agent accounts for less than or equal to 3 wt% of the photopolymer holographic recording medium. Typically, but not limitingly, the leveling agent content in the photopolymer holographic recording medium can be 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, etc.

[0097] The leveling agent may be selected from BYK series leveling agents with excellent leveling properties manufactured by BYK Corporation, such as BYK-302, BYK-306, BYK-307, BYK-327, BYK-329, BYK-333, BYK-356, BYK-358, BYK-378, BYK-3455, BYK-3566, or any proportion of these surface additives, but is not limited thereto.

[0098] As a plasticizer, the plasticizer increases the plasticity of the polymer by intercalating between polymer molecular chains, weakening intermolecular stress, increasing molecular chain mobility, and reducing crystallinity. In specific examples, the plasticizer may be selected from one or more of toluene, xylene, dimethylformamide, dimethylacetamide, glycerol, and phthalates, but is not limited to these. The plasticizer content in the photopolymer holographic recording medium is less than or equal to 3 wt%. Typically, but not limitingly, the plasticizer content in the photopolymer holographic recording medium may be 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, etc.

[0099] It is understandable that residual moisture in photopolymer-based holographic recording media may cause hydrolysis and failure of the photoinitiator system (such as the photoinitiator), reducing photosensitivity. Simultaneously, moisture can react with isocyanate groups (-NCO) involved in film-forming resin, generating urea bonds and releasing CO2, leading to bubbles or microstructural defects. Therefore, adding a dehydrating agent to maintain system dryness ensures the efficiency of the photopolymerization reaction, thereby improving the uniformity of the holographic grating and the storage life of the medium.

[0100] As dehydrating agents, dehydrating agents include, but are not limited to, p-toluenesulfonyl isocyanate, triethyl orthoformate, CUWR-WB20 dehydrating agent from Guangzhou Yourun Synthetic Materials Co., Ltd., ALT-201 dehydrating agent from Anxiang Elite Chemical Co., Ltd., and PCCI dehydrating agent from Shanghai Luer Chemical Trading Co., Ltd.

[0101] In some embodiments, the content of the dehydrating agent in the photopolymer holographic recording medium is less than or equal to 3 wt%. Typically, but not limitingly, the content of the dehydrating agent in the photopolymer holographic recording medium can be 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, etc.

[0102] This application also provides a method for preparing a photopolymer-based holographic recording medium, the method comprising the following steps S301 and S302: Step S301: Weigh components a), b), c), d), e), f), g), and h) into a container and stir until dissolved to form a mixture solution.

[0103] Step S302: Filter the mixture solution using a filter membrane to obtain a first solution, coat the first solution onto a substrate, and dry it to obtain the photopolymer holographic recording medium.

[0104] For example, drying is carried out in a dark room with a humidity of 10% to 85% and a temperature of 20°C to 50°C.

[0105] Furthermore, this application provides a volume holographic recording grating, which is fabricated from the aforementioned photopolymer-type holographic recording medium through holographic exposure.

[0106] It is understandable that volume holographic recording gratings are fabricated by exposing photopolymer holographic recording media using the principle of light interference. Therefore, the holographic optical properties of the photopolymer holographic recording media determine the quality of the volume holographic recording grating.

[0107] Specifically, in some examples, the photopolymer holographic recording medium proposed in this application has a sensitivity greater than 100 cm / mJ, a recording grating diffraction efficiency greater than 95%, a shrinkage rate less than 0.3%, and an exposure amount less than 20 mJ / cm. 2 It has excellent properties.

[0108] It is understood that the volume holographic recording grating made from this photopolymer holographic recording medium also possesses the advantages of the aforementioned photopolymer holographic recording medium. In other words, the volume holographic recording grating proposed in this application has high sensitivity, greater than 100 cm / mJ, and a recording grating diffraction efficiency greater than 95%, a shrinkage rate less than 0.3%, and an exposure amount less than 20 mJ / cm. 2 Advantages.

[0109] It should also be understood that a sensitivity greater than 100 cm / mJ indicates that only extremely low exposure energy is required to form a stable grating, which can shorten exposure time, reduce laser power requirements, increase recording speed, and reduce energy consumption efficiency, making it suitable for dynamic recording and low-power devices. A diffraction efficiency greater than 95% means that almost all incident light energy is diffracted to the target direction by the grating, thereby reducing light energy loss and resulting in a clearer image. Exposure energy is required to be below 20 mJ / cm. 2 This demonstrates that only a small amount of light energy is needed to complete the curing and photopolymerization process of the photopolymer holographic recording medium, avoiding overheating and deformation caused by high-energy exposure. A shrinkage rate of less than 0.3% ensures accurate grating period precision, preventing optical distortion and reducing image quality. Furthermore, the photopolymer holographic recording medium provided in this application significantly increases the refractive index difference between the writing monomer and the film-forming resin by using a high-refractive-index optical monomer as a component of the writing monomer and matching it with a low-refractive-index film-forming resin. This further enhances the refractive index modulation of the photopolymer holographic recording medium, thereby strengthening the diffraction capability of the grating and contributing to a wider field of view.

[0110] Furthermore, this application also provides a holographic optical element, which includes the aforementioned volume holographic recording grating. This holographic optical element includes, but is not limited to, an optical waveguide.

[0111] It is understood that the holographic optical element proposed in this application, since the volume holographic recording grating contains the aforementioned photopolymer holographic recording medium, also has the advantages of the photopolymer holographic recording medium of this application, and thus has optical performance such as fast recording speed and clear imaging.

[0112] Furthermore, this application also provides an optical device, including the holographic optical element as described above. This optical device includes, but is not limited to, head-up displays (HUDs), augmented reality (AR) devices, virtual reality (VR) devices, and photopolymer-type holographic storage optical discs, wherein the photopolymer-type holographic storage optical disc can be erasable and rewritable and records in real time, making it suitable for storing large amounts of data and providing very fast data transfer speeds. Therefore, the optical device exhibits excellent optical performance, provides a clear image, and can store large amounts of data.

[0113] For example, AR devices include, but are not limited to, AR glasses.

[0114] The optical monomer, the preparation method of the optical monomer, and the photopolymer holographic recording medium containing the optical monomer are described below with reference to specific embodiments.

[0115] Example 1 Synthesis of optical monomer G1-1

[0116] Selenium powder (20 mmol) and compound M1-1 (10 mmol) were dissolved in anhydrous dimethyl sulfoxide (30 mL) at room temperature. Nano-sized copper oxide particles (5 mmol) were added, and the mixture was purged under nitrogen protection. Potassium hydroxide (10 mmol) was added to the reaction system at 60–100 °C. After the addition was complete, the mixture was heated and stirred at 60–100 °C for approximately 10–20 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, and deionized water was added. The mixture was extracted three times with ethyl acetate. After washing with brine and drying with anhydrous sodium sulfate, excess solvent was removed by rotary evaporation. The mixture was then purified by column chromatography to obtain compound P1-1.

[0117]

[0118] Under ice bath conditions, compound P1-1 (5 mmol) and triethylamine (10 mmol) were dissolved in dichloromethane (20 mL). After stirring for 10 min, acryloyl chloride (30 mmol) was added dropwise to the mixed solution of compound P1-1 and triethylamine at 0 °C. After the reaction was complete, dilute hydrochloric acid was added to remove excess acryloyl chloride. The mixture was washed successively with saturated NaCl solution, saturated NaHCO3 solution, and deionized water. The organic phase was dried over anhydrous sodium sulfate, and excess solvent was removed by rotary evaporation. The optical monomer G1-1 of this application was obtained by column chromatography with a yield of 94.6%.

[0119] The characterization data are as follows: 1 H NMR (600 MHz, CDCl3) δ 7.40 (d, 4H), 7.27 (d, 4H), 6.09 (dd, 2H), 5.93 – 5.80 (m, 4H), 5.12 (s, 4H). 13 C NMR (151 MHz, CDCl3) δ 166.57, 136.44, 132.43, 131.43, 128.93,128.27, 128.17, 66.70. Example 2 Synthesis of optical monomer G2-1

[0120] Under nitrogen protection, selenium powder (22 mmol), compound M1-2 (10 mmol), nano-copper oxide particles (3 mmol), and potassium carbonate (15 mmol) were dissolved in anhydrous dimethyl sulfoxide. The reaction system was heated and stirred at 60–100 °C for approximately 10–20 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and deionized water was added. The mixture was extracted three times with ethyl acetate. After washing with brine and drying with anhydrous sodium sulfate, excess solvent was removed by rotary evaporation. The mixture was then purified by column chromatography to obtain compound P1-2.

[0121]

[0122] Compound P1-2 (10 mmol) and... N,N Diisopropylethylamine (35 mmol) was dissolved in dichloromethane (20 mL), stirred for 10 min, and then methacryloyl chloride (50 mmol) was added dropwise to compound P1-2 at 0 °C. N,N The reaction was carried out in a mixed solution of diisopropylethylamine. After the reaction was completed, dilute hydrochloric acid was added dropwise to remove excess methacryloyl chloride. The mixture was then washed successively with saturated NaCl solution, saturated NaHCO3 solution, and deionized water. The organic phase was dried over anhydrous sodium sulfate, and excess solvent was removed by rotary evaporation. The optical monomer G2-1 of this application was obtained by column chromatography with a yield of 97.3%.

[0123] The characterization data are as follows: 1 H NMR (600 MHz, CDCl3) δ 7.39 (d, 4H), 7.08 (d, 4H), 6.43 (d, 2H), 6.18 (d, 2H), 2.00 (s, 6H). 13 C NMR (151 MHz, CDCl3) δ 166.32, 151.97, 135.76, 133.70, 127.38,125.59, 122.10, 18.27. Example 3 Synthesis of optical monomer G3-1

[0124] Under nitrogen protection, selenium powder (21 mmol), compound M1-3 (10 mmol), nano-copper oxide particles (4 mmol), and potassium hydroxide (12 mmol) were dissolved in anhydrous N,N-dimethylformamide. The reaction system was heated and stirred at 60–100 °C for approximately 10–20 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and deionized water was added. The mixture was extracted three times with ethyl acetate. After washing with brine and drying with anhydrous sodium sulfate, excess solvent was removed by rotary evaporation. The mixture was then purified by column chromatography to obtain compound P1-3.

[0125]

[0126] Under ice bath conditions, compound P1-3 (10 mmol) and pyridine (50 mmol) were dissolved in dichloromethane (30 mL). After stirring for 10 min, acryloyl chloride (60 mmol) was added dropwise to the mixed solution of compound P1-3 and pyridine at 0 °C. After the reaction was complete, dilute hydrochloric acid was added to remove excess acryloyl chloride. The mixture was washed successively with saturated NaCl solution, saturated NaHCO3 solution, and deionized water. The organic phase was dried over anhydrous sodium sulfate, and excess solvent was removed by rotary evaporation. The optical monomer G3-1 of this application was obtained by column chromatography with a yield of 95.7%.

[0127] The characterization data are as follows: 1 H NMR (600 MHz, CDCl3) δ 7.78 (d, 2H), 7.39 (d, 2H), 7.31 – 7.23 (m,4H), 6.10 (dd, 2H), 5.91 – 5.84 (m, 4H), 5.23 (s, 4H). 13 C NMR (151 MHz, CDCl3) δ 166.56, 137.19, 131.73, 131.43, 130.89,129.23, 128.25, 127.92, 127.51, 66.56. Example 4 Synthesis of optical monomer G4-1

[0128] Selenium powder (23 mmol) and compound M1-4 (10 mmol) were dissolved in anhydrous dimethyl sulfoxide (30 mL) at room temperature. Nano-sized copper oxide particles (2 mmol) were added, and the mixture was purged under nitrogen protection. Cesium carbonate (12 mmol) was added to the reaction system at 60–100 °C. After the addition was complete, the mixture was heated and stirred at 60–100 °C for approximately 10–20 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, and deionized water was added. The mixture was extracted three times with ethyl acetate. After washing with brine and drying with anhydrous sodium sulfate, excess solvent was removed by rotary evaporation. The mixture was then purified by column chromatography to obtain compound P1-4.

[0129]

[0130] Under ice bath conditions, compound P1-4 (10 mmol) and triethylamine (40 mmol) were dissolved in dichloromethane (20 mL). After stirring for 10 min, methacryloyl chloride (30 mmol) was added dropwise to the mixed solution of compound P1-4 and triethylamine at 0 °C. After the reaction was complete, dilute hydrochloric acid was added to remove excess methacryloyl chloride. The mixture was washed successively with saturated NaCl solution, saturated NaHCO3 solution, and deionized water. The organic phase was dried over anhydrous sodium sulfate, and excess solvent was removed by rotary evaporation. The optical monomer G4-1 of this application was obtained by column chromatography with a yield of 98%.

[0131] The characterization data are as follows: 1 H NMR (600 MHz, CDCl3) δ 7.74 (d, 2H), 7.38 – 7.26 (m, 4H), 7.12 (d,2H), 6.19 (d, 2H), 5.62 (d, 2H), 2.00 (s, 6H). 13 C NMR (151 MHz, CDCl3) δ 166.18, 149.90, 135.42, 131.55, 129.20,126.70, 124.60, 123.85, 120.45, 18.32. Example 5 Photopolymer-type holographic recording media 5-1 to 5-4 were prepared using the optical monomers described in Examples 1-4. The preparation method involved mixing all components thoroughly, filtering the mixture using a filter membrane, coating the resulting filtrate onto a substrate, and drying it in a darkroom at a humidity of 10%–85% and a temperature of 20°C–50°C to obtain the photopolymer-type holographic recording media (hereinafter referred to as holographic recording media). The specific components and contents of photopolymer-type holographic recording media 5-1 to 5-4 are shown in Tables 1 to 4.

[0132] Table 1

[0133] Table 2

[0134] Table 3

[0135] Table 4

[0136] Comparative Example 1 Compared with the photopolymer-type holographic recording medium 5 in Example 5 The components of 1 are roughly the same, except that the optical monomer G1-1 is not added in the comparative example, but 27.7 wt% of p-(chloromethyl)styrene is added to obtain a common photopolymer type holographic recording medium 1.

[0137] Comparative Example 2 Compared with the photopolymer-type holographic recording medium 5 in Example 5 The components of 2 are roughly the same, except that the optical monomer G2-1 is not added in the comparative example, but 47 wt% of 2-phenoxyethyl methacrylate is added to obtain a common photopolymer type holographic recording medium 2.

[0138] Comparative Example 3 Compared with the photopolymer-type holographic recording medium 5 in Example 5 The components of 3 are roughly the same, except that the optical monomer G3-1 is not added in the comparative example, but 40 wt% of 3-bromostyrene is added to obtain a common photopolymer holographic recording medium 3.

[0139] Comparative Example 4 Compared with the photopolymer-type holographic recording medium 5 in Example 5 The components of 4 are roughly the same, except that the optical monomer G4-1 is not added in the comparative example, but 47 wt% of 2-naphthalene acrylate is added, thus obtaining a common photopolymer type holographic recording medium 4.

[0140] Test case (1) Test the refractive index and viscosity of the optical monomers synthesized in Examples 1 to 4.

[0141] The refractive index of the optical components in Examples 1-4 was tested using an Abbe refractometer at a temperature of 20°C. The test method was in accordance with the national standard GB / T 6488-2022. The test results are shown in Table 5 below.

[0142] The viscosity of the optical monomers in Examples 1-4 was tested using a viscometer at a temperature of 25°C. The test method was carried out according to the rotation method in GB / T 10247 2008. The test results are shown in Table 5 below.

[0143] (2) The performance of the photopolymer holographic recording media 5-1 to 5-4 containing optical monomers in Example 5 and the ordinary photopolymer holographic recording media prepared in the comparative example were tested, and the results are shown in Table 6.

[0144] (a) During testing, the various holographic recording media in Example 5 can be exposed to lasers of different wavelengths depending on the photosensitive system, with an exposure intensity of 3 mW / cm². 2 .

[0145] The detection light source uses a 785nm wavelength solid-state 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 a photodetector. The single grating diffraction efficiency (η) of the photopolymer holographic recording medium is calculated by formula (1), and the photosensitivity (S) of the photopolymer holographic recording medium is calculated by formula (2).

[0146]

[0147] In the formula, η is the diffraction efficiency, and I d For diffracted light, I t denoted as transmitted light, S as photosensitivity, E as exposure energy, and ΔE as the exposure energy required to achieve maximum diffraction efficiency.

[0148] (b) The shrinkage rate of the photopolymer holographic recording medium containing optical monomers in Example 5 and the ordinary photopolymer holographic recording medium of the comparative example were tested at 25°C using a step tester. The test method was carried out in accordance with ASTM D2732 standard, and the shrinkage rate β of the photopolymer holographic recording medium was calculated by formula (3).

[0149]

[0150] In the formula, d0 is the initial thickness of the sample before exposure, and dp is the polymerized thickness of the sample after exposure.

[0151] Table 5. Refractive index and viscosity of the optical monomers prepared in Examples 1-4

[0152] Table 6. Holographic performance parameters of the holographic recording media of Example 5 and the comparative example.

[0153] Please refer to Tables 5 and 6. Table 5 shows the refractive index and viscosity data of the optical monomers prepared in Examples 1-4 of this application, and Table 6 shows the holographic performance parameters of the photopolymer holographic recording medium measured when optical monomers 1 to 4 are applied to the photopolymer holographic recording medium.

[0154] As shown in Table 5, the refractive indices of optical monomers G1-1, G2-1, G3-1, and G4-1 provided in the embodiments of this application are between 1.65 and 1.67. The high refractive indices of these optical monomers, when applied to photopolymer holographic recording media, can further enhance the refractive index difference between the writing monomer and the film-forming resin, thereby improving the refractive index modulation of the holographic recording medium to generate a stronger grating structure and increase the grating storage density. Simultaneously, the low viscosity of optical monomers G1-1, G2-1, G3-1, and G4-1 facilitates their migration and diffusion during holographic exposure, resulting in a holographic recording medium with uniform texture and excellent performance.

[0155] Please see Figure 1 , Figure 2 According to Table 6, the photopolymer holographic recording media 5-1 to 5-4 provided in this application contain the aforementioned optical monomers G1-1, G2-1, G3-1, and G4-1, respectively. Therefore, the exposure amount of the resulting photopolymer holographic recording media is 4.77 mJ / cm². 2 ~ 7.19 mJ / cm 2 The diffraction efficiency was 97.04% ~ 98.65%, the sensitivity was 137.01 cm / mJ ~ 208.19 cm / mJ, and the shrinkage rate was 0.15% ~ 0.29%, while the exposure of the ordinary photopolymer holographic recording media 1 to 4 prepared in Comparative Examples 1 to 4 was 23.09 mJ / cm. 2 ~ 78.12 mJ / cm 2The diffraction efficiency is 19.83% to 51.97%, and the sensitivity is 5.70 cm / mJ to 31.22 cm / mJ. That is, the exposure of the photopolymer holographic recording medium provided in this application is much less than that of the ordinary holographic recording medium prepared in the comparative example. Moreover, the diffraction efficiency and sensitivity of the photopolymer holographic recording medium provided in this application are much higher than those of the ordinary holographic recording medium prepared in the comparative example. This means that the holographic recording medium provided in this application has high light energy utilization, significantly improved brightness and clarity of holographic display, faster data transmission speed, and the material is not prone to overheating and deformation due to high-energy exposure. At the same time, the grating period accuracy is accurate, and the risk of optical distortion is reduced.

[0156] Specifically, such as Figure 1 and Figure 2 As shown, comparing the photopolymer holographic recording medium 5-1 containing the optical monomer G1-1 of this application with the ordinary photopolymer holographic recording medium 1 of Comparative Example 1, comparing the photopolymer holographic recording medium 5-2 containing the optical monomer G2-1 of this application with the ordinary photopolymer holographic recording medium 2 of Comparative Example 2, comparing the photopolymer holographic recording medium 5-3 containing the optical monomer G3-1 of this application with the ordinary photopolymer holographic recording medium 3 of Comparative Example 3, and comparing the photopolymer holographic recording medium 5-4 containing the optical monomer G4-1 of this application with the ordinary photopolymer holographic recording medium 4 of Comparative Example 4, it can be seen that the photopolymer holographic recording medium containing the optical monomer of this application has a higher diffraction efficiency and requires a lower exposure.

[0157] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in this application, and these modifications or substitutions should all be covered within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. An optical unit, characterized in that, Its general chemical structural formula is shown in any of the following: , , , , where R1 represents methyl or hydrogen.

2. The optical unit according to claim 1, characterized in that, The optical monomer comprises at least the following compounds with the following chemical structural formulas: 、 、 、 。 3. A method for preparing an optical monomer as described in claim 1, characterized in that, Includes the following steps: In an inert environment, selenium powder, compound M1, a first catalyst, and an alkaline reagent are dissolved in a first solvent to react and obtain compound P1, wherein the compound M1 is selected from at least one of 4-iodophenol, 2-iodophenol, 4-iodobenzyl alcohol, or 2-iodobenzyl alcohol. The compound P1 and the acid-binding agent are dissolved in an organic solvent, and compound M2 is added to react and obtain the optical monomer, wherein the compound M2 is acryloyl chloride or methacryloyl chloride, and the organic solvent includes a first solvent.

4. The preparation method according to claim 3, characterized in that, The first solvent is selected from at least one of dimethyl sulfoxide or N,N-dimethylformamide; And / or, the first catalyst is selected from one or more of nano-copper oxide or cuprous iodide; And / or, the alkaline reagent is selected from one or more of potassium hydroxide, potassium carbonate, or cesium carbonate; And / or, the organic solvent is selected from one or more of methanol, ethanol, petroleum ether, dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, acetonitrile, benzene, toluene, N,N-dimethylformamide, dimethyl sulfoxide, dimethoxyethane, or 1,4-dioxane; And / or, the acid-binding agent is selected from triethylamine, pyridine, N,N Diisopropylethylamine, 4 One or more of dimethylaminopyridine, tetrabutylammonium bromide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium acetate, sodium hydroxide, potassium hydroxide, calcium oxide, and potassium tert-butoxide.

5. The preparation method according to claim 3 or 4, characterized in that, The molar ratio of the selenium powder to the compound M1 is (2.1–2.3):1; And / or, the molar ratio of compound M1 to the first catalyst is 1:(0.1 to 0.5); And / or, the molar ratio of the compound M1 to the base reagent is 1:(1 to 1.5).

6. The preparation method according to claim 3 or 4, characterized in that, The reaction of dissolving selenium powder, compound M1, catalyst and alkaline reagent in a first solvent includes heating and stirring at 60~100℃ for 10 h~20 h. And / or, the step of dissolving the compound P1 and the acid-binding agent in an organic solvent and adding compound M2 to react includes adding compound M2 at 0°C and reacting for 0.5 h to 3 h.

7. A photopolymer-based holographic recording medium, characterized in that, Its raw materials include the following components a) Component h); Component a) A compound having multiple isocyanate reactive functional groups; Component b) Polyisocyanate group compounds; Component c) The optical monomer as described in claim 1; Component d) Polymerizable monomers; Component e) Photosensitive initiation system; Component f) Chain transfer agent; Component g) Optional second catalyst; Component h) Optional additives.

8. The photopolymer-type holographic recording medium according to claim 7, characterized in that, The composition and content of the photopolymer-type holographic recording medium are as follows: Component a) 10 wt% to 50 wt% of compounds having multiple isocyanate reactive functional groups; Component b) Polyisocyanate group compounds 10 wt%~50 wt%; Component c) Optical monomers 1 wt%~30 wt%; Component d) Polymerizable monomers 10 wt%~40 wt%; Component e) Photoinitiator system 0.1 wt%~3 wt%; Component f) Chain transfer agent 0.1 wt%~3 wt%; Component g) Second catalyst 0.1 wt%~5 wt%; Component h) Additives 0.1 wt%~10 wt%.

9. The photopolymer-type holographic recording medium according to claim 7, characterized in that, The optical monomer accounts for 0.1 wt% to 30 wt% of the total content of the photopolymer holographic recording medium. And / or, the isocyanate reactive functional group is a hydroxyl group, and the molar ratio of the hydroxyl group in component a) the compound having a plurality of isocyanate reactive functional groups to the isocyanate functional group in component b) the polyisocyanate group compound is 1:

1.

10. The photopolymer-type holographic recording medium according to claim 7, characterized in that, The isocyanate reactive functional group is hydroxyl; and the compound having multiple isocyanate reactive functional groups includes compounds with a refractive index ranging from 1.50 to 1.55 and having two or more hydroxyl functional groups. And / or, the polyisocyanate-based compound includes compounds with a refractive index ranging from 1.50 to 1.55 and having two or more isocyanate groups; And / or, the polymerizable monomer is selected from at least one of alkenylnaphthalene compounds, alkenylanthracene compounds, alkenylbenzene compounds, acrylic compounds, methacrylic acid compounds, acrylate compounds, methacrylate compounds, N-vinylpyrrole, N-vinylcarbazole, N-vinylimidazol, N-vinylindole, N-vinylpyrrolidone, and trans-N-3-yntynebutenylcarbazole; And / or, the photoinitiating system includes a photosensitizer and a photoinitiator; And / or, the chain transfer agent is a thiol compound; And / or, the second catalyst is selected from at least one of tertiary amine catalysts and organometallic catalysts; And / or, the additives include at least one of defoamers, leveling agents, plasticizers, and dehydrating agents.

11. The photopolymer-type holographic recording medium according to claim 10, characterized in that, The compounds having multiple isocyanate reactive functional groups include 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, neopentanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, and 1,4-cyclohexanediol. Alcohols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, 1,2,4-butanetriol, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tripentaerythritol, bis(trimethylolpropane), polyethylene glycol with a molecular weight of 200–2000, polypropylene glycol with a molecular weight of 200–2000, polytetramethylene ether glycol with a molecular weight of 200–2000, polytetrahydrofuran with a molecular weight of 200–2000, 1,4-butenylene glycol, 1,4-butynediol, 1,2-decanediol, 1,2-dodecadiol, 2-methyl-1,3-propanediol, 1,7-heptanediol, 1,9-nonanediol, 2,2-diethyl- 1,3-Propane glycol, 1,4-Dimethylolcyclohexane, 1,2,3-Hexanetriol, 1,2,4-Hepanetriol, 1,3,5-Pentanetriol, Poly(oxypropylene)triol, Poly(ε-caprolactone)diol, Poly(ε-caprolactone)triol, Poly(propylene carbonate)diol, Poly(butadiene)diol, Hydrogenated poly(butadiene)diol, Poly(ethylene adipate)diol, Poly(butylene adipate)diol, Poly(1,4-butanediol adipate)diol, Poly(glycerol sebate)diol, Trimethylolpropane ethoxylate, Trimethylolpropane propoxylate, Pentaerythritol ethoxylate, Glyceryl ethoxylate, Glyceryl propoxylate, Ethylene glycol At least one of the following: amine tetra(propoxylate), diethylenetriaminepenta(propoxylate), partially hydrolyzed polyvinyl alcohol, poly(1,2-butanediol), poly(1,3-propanediol), poly(1,4-butanediol), poly(1,6-hexanediol), poly(neopentyl glycol), poly(3-methyl-1,5-pentanediol), poly(1,4-cyclohexanediol), tris(2-hydroxyethyl)isocyanurate, N,N,N',N'-tetra(2-hydroxypropyl)ethylenediamine, 2,2,3-trimethyl-1,3-pentanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-pentanediol, 1,3-butanediol, or 2-methyl-2,4-pentanediol; And / or, the polyisocyanate group compound includes at least one of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, (2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-triyl)tri(hexamethylene)isocyanate, butane-1,4-diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate; And / or, the chain transfer agent comprises at least one of dodecyl mercaptan, mercaptoethanol, hexamethylene mercaptan, phenylethyl mercaptan, 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol, and 4-methyl-4H-1,2,4-triazole-3-thiol; And / or, the second catalyst comprises at least one of the following: triethylenediamine, bis(dimethylaminoethyl) ether, dimethylethanolamine, 2-(2-dimethylaminoethoxy)ethanol, trimethylhydroxyethylpropanediamine, N,N-bis(dimethylaminopropyl)isopropanolamine, dibutyltin dilaurate, stannous octoate, potassium carboxylate catalysts, and bismuth carboxylate catalysts.

12. The photopolymer-type holographic recording medium according to claim 10, characterized in that, The photosensitizer includes at least one of cyanine dyes, fluorescein dyes, coumarin ketone dyes, nitrogen-containing aromatic heterocyclic compounds, aromatic amine compounds, and benzylidene cycloalkane ketone compounds; And / or, the photoinitiator is selected from at least one of aromatic ketones, benzoin and its derivatives, benzoyl ketal, acylphosphine oxide, ammonium arylboronate, chromium salts, aryl diazonium salts, onium salts and organometallic compounds; And / or, the mass ratio of the photosensitizer to the photoinitiator is (0.001~1): (0.1~3).

13. The photopolymer-type holographic recording medium according to claim 10, characterized in that, The defoamer is a silicone defoamer and / or a silicone-free polymeric defoamer, and the content of the defoamer in the photopolymeric holographic recording medium is less than or equal to 3 wt%. And / or, the leveling agent is an organosilicon surface additive, and the leveling agent accounts for less than or equal to 3 wt% of the photopolymer-type holographic recording medium; And / or, the plasticizer is selected from at least one of toluene, xylene, dimethylformamide, dimethylacetamide, glycerol, and phthalates, and the plasticizer accounts for less than or equal to 3 wt% of the photopolymer holographic recording medium; And / or, the dehydrating agent includes at least one of p-toluenesulfonyl isocyanate, triethyl orthoformate, CUWR-WB20 dehydrating agent, ALT-201 dehydrating agent, or PCCI dehydrating agent, wherein the dehydrating agent accounts for less than or equal to 3 wt% of the photopolymer holographic recording medium.

14. A method for preparing a photopolymer-type holographic recording medium as described in any one of claims 7-13, characterized in that, Weigh the compound having multiple isocyanate reactive functional groups, the polyisocyanate group compound, the optical monomer, the polymerizable monomer, the photoinitiator system, the chain transfer agent, the second catalyst, and the additive into a container, and stir until dissolved to form a mixed solution; The mixture solution is filtered using a filter membrane to obtain a first solution; The first solution is coated onto a substrate and dried to obtain the photopolymer holographic recording medium.

15. The preparation method according to claim 14, characterized in that, The drying process is carried out in a dark room with a humidity of 10% to 85% and a temperature of 20°C to 50°C.

16. A volume holographic recording grating, characterized in that, The volumetric holographic recording grating is prepared by holographic exposure of the photopolymer holographic recording medium as described in any one of claims 7-13.

17. A holographic optical element, characterized in that, Includes the volume holographic recording grating as described in claim 16.

18. An optical device, characterized in that, Includes the holographic optical element as described in claim 17.

Images