Blue-sensitive photopolymer film as well as preparation method and application thereof

Abstract

The invention relates to the technical field of blue-sensitive photopolymer photosensitive materials, in particular to a blue-sensitive photopolymer film and a preparation method and application thereof. The blue-sensitive photopolymer film is prepared from the following raw materials in parts by mass: 40 to 45 parts of write-in monomer, 20 to 25 parts of polyester polyol, 14 to 16 parts of aliphatic isocyanate, 1 to 2 parts of blue light photosensitizer, 2 to 4 parts of photoinitiator, 5 to 10 parts of cross-linking agent, 5 to 10 parts of antioxidant inhibitor, 0.4 to 0.6 part of catalyst, 0.5 to 0.6 part of defoaming agent and 5 to 9 parts of solvent. The blue-sensitive photopolymer film disclosed by the invention has the characteristics of good moisture-proof effect, long storage time, relatively high diffraction efficiency, relatively high refractive index modulation degree, high sensitivity, low exposure energy and the like, and is an ideal holographic recording material.

Description

Technical Field

[0001] The present application relates to the technical field of blue-sensitive photopolymer photosensitive materials, and in particular to a blue-sensitive photopolymer film and a preparation method and application thereof. Background Art

[0002] In the field of AR optical waveguides, there are two types of holographic gratings: surface relief gratings and volume holographic gratings. The market for volume holographic gratings discloses a photopolymer formulation comprising a chemically cross-linked matrix polymer, a writing monomer, and a photoinitiator system, which can be used to produce holographic media and thereby produce bright and easily visible holograms with high refractive index contrast and low thickness.

[0003] Photopolymer is a new type of holographic material. Compared with conventional silver salt materials, dichromated gelatin, etc., it has the advantages of good optical properties, high cost performance, and support for large-scale production. At present, researchers have conducted more research on red and green sensitive photopolymers, and there are fewer reports on blue sensitive photopolymers. The reported blue sensitive photopolymers are almost all water-soluble blue sensitive photopolymers, with polyvinyl alcohol as the substrate and acrylamide as the writing monomer. This system has a low refractive index modulation degree, low diffraction efficiency, easy to deliquesce, and difficult to preserve. Common water-soluble photopolymer systems have relatively high requirements for the environment, especially the preservation performance of holograms will be affected by environmental conditions such as ambient temperature, humidity and light. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present application provides a blue-sensitive photopolymer film and a preparation method and application thereof. The blue-sensitive photopolymer of the present application is an oily (water-insoluble) blue-sensitive photopolymer system, with polyurethane (formed by the reaction of polyester polyol and aliphatic isocyanate) as a substrate and a composite acrylate monomer as a writing monomer. The blue-sensitive photopolymer film prepared has the characteristics of good moisture-proof effect, long storage time, high diffraction efficiency, high refractive index modulation, high sensitivity and low exposure energy. The oily blue-sensitive photopolymer film prepared by the present application is used to shoot a reflective hologram, which is reproduced under white light to obtain a clear image and has good preservation performance, and is an ideal holographic recording material.

[0005] In a first aspect, the present application provides a blue-sensitive photopolymer film, which adopts the following technical solution: A blue-sensitive photopolymer film comprises the following raw materials, measured by weight: 40-45 parts of a writing monomer, 20-25 parts of a polyester polyol, 14-16 parts of an aliphatic isocyanate, 1-2 parts of a blue light photosensitizer, 2-4 parts of a photoinitiator, 5-10 parts of a cross-linking agent, 5-10 parts of an antioxidant inhibitor, 0.4-0.6 parts of a catalyst, 0.5-0.6 parts of a defoaming agent, and 5-9 parts of a solvent.

[0006] By adopting the above technical scheme, the writing monomer: as the main reaction monomer, participates in the photopolymerization reaction to form a polymer network structure. It determines the diffraction efficiency, exposure sensitivity and optical quality of the material. Polyester polyol: reacts with aliphatic isocyanate to form polyurethane, which serves as the base of the polymer system and provides good film-forming properties and mechanical properties. Aliphatic isocyanate: reacts with polyester polyol to form polyurethane, which serves as the base of the polymer system and provides good film-forming properties and mechanical properties. Blue light photosensitizer: absorbs blue light energy, initiates photopolymerization reaction, and improves the exposure sensitivity of the material. Photoinitiator: promotes the progress of photopolymerization reaction, improves the exposure sensitivity and diffraction efficiency of the material. Cross-linking agent: participates in the photopolymerization reaction, increases the cross-linking density of the polymer network, and improves the refractive index modulation degree and storage time of the material. Antioxidant inhibitor: inhibits the oxidative degradation of the material during the preparation and storage process, and prolongs the storage time of the material. Catalyst: accelerates the formation reaction of polyurethane, improves the preparation efficiency and performance of the material. Defoamer: eliminates bubbles generated during the preparation process and improves the optical quality of the film surface. Solvent: adjusts the viscosity of the system to facilitate coating and film formation. Through the synergistic effect of the above components, the blue-sensitive photopolymer film of the present invention has the characteristics of good moisture-proof effect, long storage time, high diffraction efficiency, high refractive index modulation, high sensitivity and low exposure energy, and is an ideal holographic recording material.

[0007] Preferably, the writing monomer is any two or more of N-vinyl carbazole, ethoxylated bisphenol fluorene diacrylate, bisphenol A-dimethacrylate, pentaerythritol tetraacrylate, and ethoxylated trimethylolpropane triacrylate.

[0008] Preferably, the writing monomer includes at least N-vinyl carbazole and bisphenol A-dimethacrylate, and the mass ratio of the N-vinyl carbazole to the bisphenol A-dimethacrylate is 0.08-0.22:1.

[0009] By adopting the above technical scheme, firstly, N-vinyl carbazole is a compound with high refractive index and good optical properties. It can improve the diffraction efficiency and exposure sensitivity of the film, so that the holographic image is clearer and brighter. In addition, N-vinyl carbazole also has the characteristics of good moisture-proof effect and long storage time, which helps to improve the preservation performance of the material. Secondly, bisphenol A-dimethacrylate is a commonly used crosslinking agent, which can react with polyester polyol and aliphatic isocyanate to form a polyurethane network structure. This structure can enhance the mechanical strength and stability of the film, while improving its moisture-proof effect and storage time. In addition, bisphenol A-dimethacrylate can also increase the refractive index modulation of the film, thereby improving the contrast and clarity of the holographic image. Finally, the synergistic effect between N-vinyl carbazole and bisphenol A-dimethacrylate is manifested in that they jointly improve the diffraction efficiency and exposure sensitivity of the film. The high refractive index and good optical properties of N-vinyl carbazole combined with the crosslinking effect of bisphenol A-dimethacrylate enable the film to form a holographic image faster when exposed and have a higher diffraction efficiency. In addition, since both N-vinyl carbazole and bisphenol A-dimethacrylate have the characteristics of moisture-proof effect and long storage time, they jointly improve the storage performance of the film. In summary, by adding writing monomers N-vinyl carbazole and bisphenol A-dimethacrylate and controlling their mass fraction ratio to 0.08-0.22:1, the performance indicators of the blue-sensitive photopolymer film, such as diffraction efficiency, exposure sensitivity, optical quality, moisture-proof effect and storage time, can be greatly optimized.

[0010] Preferably, the writing monomer is composed of N-vinyl carbazole, ethoxylated bisphenol fluorene diacrylate and bisphenol A-dimethacrylate in a mass ratio of 0.1:1:1.

[0011] By adopting the above technical scheme, N-vinyl carbazole is a compound containing a nitrogen heterocycle and has good photosensitivity. In the blue-sensitive photopolymer film, N-vinyl carbazole, as a part of the writing monomer, can improve the photosensitivity of the film, making it easier to undergo polymerization reaction under blue light irradiation. At the same time, N-vinyl carbazole can also increase the refractive index modulation of the film, thereby improving the diffraction efficiency. Ethoxylated bisphenol fluorene diacrylate is a compound containing two acrylate groups and has high reactivity. In the blue-sensitive photopolymer film, ethoxylated bisphenol fluorene diacrylate, as a part of the writing monomer, can copolymerize with N-vinyl carbazole and bisphenol A-dimethacrylate to form a cross-linked network structure. This structure helps to improve the optical quality of the film and the storage time of the material. Bisphenol A-dimethacrylate is a compound containing two acrylate groups and has high reactivity. In the blue-sensitive photopolymer film, bisphenol A-dimethacrylate, as a part of the writing monomer, can copolymerize with N-vinyl carbazole and ethoxylated bisphenol fluorene diacrylate to form a cross-linked network structure. This structure helps to improve the optical quality of the film and the material storage time. In summary, the synergistic effect between N-vinyl carbazole, ethoxylated bisphenol fluorene diacrylate and bisphenol A-dimethacrylate is mainly reflected in their joint participation in the polymerization reaction of the blue-sensitive photopolymer film to form a cross-linked network structure, thereby improving the optical quality of the film, the material storage time and the diffraction efficiency. At the same time, the characteristics of these three compounds also make the blue-sensitive photopolymer film have good moisture-proof effect, high sensitivity and low exposure rate.

[0012] Preferably, the writing monomer is composed of N-vinyl carbazole, ethoxylated trimethylolpropane triacrylate, and bisphenol A-dimethacrylate in a mass ratio of 0.2:0.5:1.

[0013] By adopting the above technical solution, N-vinyl carbazole is used as a photosensitive monomer. It has a high absorption capacity for blue light and can react quickly under light to form free radicals to start the polymerization reaction. Its presence can increase the efficiency of the photoinitiator and improve the photopolymerization rate, thereby improving the sensitivity and exposure efficiency of the material. Ethoxylated trimethylolpropane triacrylate (EO-TMPTA): EO-TMPTA is a multifunctional acrylate that can provide multiple reaction sites and promote the increase of crosslinking density. During the photopolymerization process, it can crosslink with N-vinyl carbazole and other monomers to form a three-dimensional network structure, which helps to improve the hardness, wear resistance and chemical resistance of the polymer film. At the same time, due to its multifunctional characteristics, EO-TMPTA can also improve the diffraction efficiency and refractive index modulation. Bisphenol A-dimethacrylate (Bis-A EME): Bisphenol A-dimethacrylate is a bifunctional monomer that acts as a diluent and crosslinker in the system. It can adjust the viscosity of the system, making the coating process easier, and participate in the crosslinking reaction during the curing process to enhance the stability of the polymer network. In addition, Bis-A EME can also improve the optical properties of the polymer, such as transparency and refractive index. In summary, the synergistic effects between N-vinyl carbazole, ethoxylated trimethylolpropane triacrylate and bisphenol A-dimethacrylate are mainly reflected in the following aspects: N-vinyl carbazole provides high photosensitivity and fast polymerization initiation. EO-TMPTA improves the density and mechanical properties of the polymer network through multi-functional cross-linking. Bis-A EME acts as a diluent and cross-linking agent, adjusts the viscosity of the system and participates in the cross-linking reaction, while improving the optical properties. This combination not only improves the diffraction efficiency and exposure sensitivity of the blue-sensitive photopolymer film, but also improves the optical quality of the film surface, the material storage time and the moisture-proof effect, making it an ideal holographic recording material.

[0014] Preferably, the photoinitiator is one or more of triethanolamine, N-phenyldiethanolamine and diethanolamine, preferably triethanolamine.

[0015] Preferably, the solvent is one or more of N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), dichloromethane, chloroform and toluene; preferably N,N-dimethylformamide (DMF).

[0016] Preferably, the antioxidant inhibitor is 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester; the cross-linking agent is N-vinyl pyrrolidone (NVP); the blue light photosensitizer is acridine orange; the molecular weight of the polyester polyol is 400-3000; the aliphatic isocyanate is aliphatic isocyanate Wanhua HT-100; the catalyst is organic bismuth catalyst DY-20; and the defoaming agent is BYK-058.

[0017] In a second aspect, the present application provides a method for preparing a blue-sensitive photopolymer film, using the following technical solution: As a general technical concept, the present application also provides a method for preparing the above-mentioned blue-sensitive photopolymer film, comprising the following steps: The light-proof experiment was carried out in a dark room. The solvent was first added into the flask according to the mass fractions, and then the polyester polyol, blue light photosensitizer, photoinitiator, cross-linker, writing monomer, antioxidant inhibitor and defoamer were added. The temperature was heated to 80-90°C and stirred for 24 hours. Then, aliphatic isocyanate was added and stirred for 30 minutes. Then, the catalyst was dropped and stirred for 1 minute to obtain a colloidal solution. The colloidal solution was then scraped onto a glass substrate or a PET film. After gelation, the blue-sensitive photopolymer film was obtained after vacuum degassing.

[0018] In a third aspect, the present application provides an application of a blue-sensitive photopolymer film, using the following technical solution: As a general technical concept, the present application also provides the application of the above-mentioned blue-sensitive photopolymer film in AR-HUD, optical holographic storage, high-end anti-counterfeiting, AR-near-eye display and holographic sensing.

[0019] In summary, the present application includes at least one of the following beneficial technical effects: 1. Good moisture-proof effect: Polyurethane is used as the substrate, which has good moisture-proof properties, so that the prepared blue-sensitive photopolymer film can still maintain good optical properties in a humid environment.

[0020] 2. Long shelf life: By adding antioxidant inhibitors and cross-linking agents, the antioxidant properties and stability of the material are improved, thereby extending the shelf life of the material.

[0021] 3. High diffraction efficiency: By adding writing monomers, the diffraction efficiency of the blue-sensitive photopolymer film is optimized, making the holographic image clearer.

[0022] 4. Higher refractive index modulation: The polyurethane substrate is generated by reacting polyester polyols with specific molecular weight and aliphatic isocyanate, which increases the refractive index modulation and is beneficial to improving the quality of holographic images.

[0023] 5. High sensitivity and low exposure energy: The use of blue light photosensitizers and photoinitiators improves the sensitivity of the material and reduces the exposure rate, making the light intensity required for shooting holographic images lower, which is beneficial to protect the sample from light damage.

[0024] 6. High optical quality of the film surface: By adding defoaming agent, bubbles and defects on the material surface are reduced, and the optical quality of the film surface is improved.

[0025] 7. Ideal holographic recording material: The oily blue-sensitive photopolymer film prepared in this application is used to shoot a reflective hologram, which is reproduced under white light to obtain a clear image with good preservation performance. It is an ideal holographic recording material. DETAILED DESCRIPTION

[0026] The embodiments of the present application will be described in detail below in conjunction with the examples, but it will be appreciated by those skilled in the art that the following examples are only used to illustrate the present application and should not be considered as limiting the scope of the present application. In the examples, if specific conditions are not specified, they are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0027] In the following examples, 1 portion means 10 g.

[0028] Example 1 A blue-sensitive photopolymer film comprises the following raw materials by weight: 40 parts of a writing monomer, 20 parts of a polyester polyol (molecular weight of 400), 14 parts of aliphatic isocyanate Wanhua HT-100, 1 part of acridine orange, 2 parts of diethanolamine, 5 parts of N-vinyl pyrrolidone (NVP), 5 parts of diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 0.4 parts of an organic bismuth catalyst DY-20, 0.5 parts of a defoaming agent BYK-058, and 5 parts of N-methylpyrrolidone (NMP), wherein the writing monomer consists of 20 parts of N-vinyl carbazole and 20 parts of pentaerythritol tetraacrylate; The above-mentioned method for preparing a blue-sensitive photopolymer film comprises the following steps: A light-proof experiment was carried out in a dark room. N-methylpyrrolidone (NMP) was first added to a flask according to the mass fractions, and then polyester polyol, acridine orange, diethanolamine, N-vinylpyrrolidone (NVP), writing monomer, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester and defoamer BYK-058 were added. The temperature was heated to 80°C and stirred for 24 hours. Then, aliphatic isocyanate Wanhua HT-100 was added and stirred for 30 minutes. Then, organic bismuth catalyst DY-20 was dropped and stirred for 1 minute to obtain a colloidal solution. The colloidal solution was then scraped onto a glass substrate. After gelation, the blue-sensitive photopolymer film was obtained after vacuum degassing.

[0029] Example 2 A blue-sensitive photopolymer film, comprising the following raw materials by weight: 45 parts of a writing monomer, 25 parts of a polyester polyol (molecular weight of 3000), 16 parts of aliphatic isocyanate Wanhua HT-100, 2 parts of acridine orange, 4 parts of N-phenyldiethanolamine, 10 parts of N-vinylpyrrolidone (NVP), 10 parts of diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 0.6 parts of an organic bismuth catalyst DY-20, 0.6 parts of a defoaming agent BYK-058, and 9 parts of toluene, wherein the writing monomer consists of 20 parts of bisphenol A-dimethacrylate and 25 parts of ethoxylated trimethylolpropane triacrylate; The above-mentioned method for preparing a blue-sensitive photopolymer film comprises the following steps: A light-proof experiment was carried out in a dark room. Toluene was first added to the flask according to the mass fractions, and then polyester polyol, acridine orange, N-phenyldiethanolamine, N-vinyl pyrrolidone (NVP), writing monomer, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester and defoamer BYK-058 were added. The temperature was heated to 90°C and stirred for 24 hours. Then, aliphatic isocyanate Wanhua HT-100 was added and stirred for 30 minutes. Then, organic bismuth catalyst DY-20 was dropped and stirred for 1 minute to obtain a colloidal solution. The colloidal solution was then scraped onto the PET film. After gelation, the blue-sensitive photopolymer film was obtained after vacuum degassing.

[0030] Example 3 A blue-sensitive photopolymer film comprises the following raw materials by weight: 43 parts of a writing monomer, 22 parts of a polyester polyol (molecular weight of 1000), 15 parts of aliphatic isocyanate Wanhua HT-100, 1.5 parts of acridine orange, 3 parts of triethanolamine, 7 parts of N-vinyl pyrrolidone (NVP), 7 parts of diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 0.5 parts of an organic bismuth catalyst DY-20, 0.55 parts of a defoaming agent BYK-058, and 7 parts of N,N-dimethylformamide (DMF), wherein the writing monomer is composed of N-vinyl carbazole and bisphenol A-dimethacrylate in a weight ratio of 0.08:1; The above-mentioned method for preparing a blue-sensitive photopolymer film comprises the following steps: A light-proof experiment was carried out in a dark room. According to the mass fractions, N,N-dimethylformamide (DMF) was first added to the flask, and then polyester polyol, acridine orange, triethanolamine, N-vinyl pyrrolidone (NVP), writing monomer, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester and defoamer BYK-058 were added. The temperature was heated to 85°C and stirred for 24 hours. Then, aliphatic isocyanate Wanhua HT-100 was added and stirred for 30 minutes. Then, organic bismuth catalyst DY-20 was dropped and stirred for 1 minute to obtain a colloidal solution. The colloidal solution was then scraped onto the PET film. After gelation, the blue-sensitive photopolymer film was obtained after vacuum degassing.

[0031] Example 4 The same as the embodiment 3, except that: the writing monomer is composed of N-vinyl carbazole and bisphenol A-dimethacrylate in a mass ratio of 0.22:1.

[0032] Example 5 The same as the embodiment 3, except that: the writing monomer is composed of N-vinyl carbazole and bisphenol A-dimethacrylate in a mass ratio of 0.12:1.

[0033] Example 6 The same as the embodiment 3, except that: the writing monomer is composed of N-vinyl carbazole, ethoxylated bisphenol fluorene diacrylate, and bisphenol A-dimethacrylate in a mass ratio of 0.1:1:1.

[0034] Example 7 The same as the embodiment 3, except that: the writing monomer is composed of N-vinyl carbazole, ethoxylated trimethylolpropane triacrylate, and bisphenol A-dimethacrylate in a mass ratio of 0.2:0.5:1.

[0035] Comparative Example 1 The same as the embodiment 3, except that: the writing monomer is N-vinyl carbazole.

[0036] Comparative Example 2 The same as Example 3, except that: the writing monomer is ethoxylated bisphenol fluorene diacrylate.

[0037] Comparative Example 3 The same as embodiment 3, except that: the writing monomer is bisphenol A-dimethacrylate.

[0038] Comparative Example 4 The same as embodiment 3, except that: the writing monomer is ethoxylated trimethylolpropane triacrylate.

[0039] Performance testing The blue-sensitive photopolymer films prepared in each embodiment and each comparative example were tested for the following properties, and the specific results are shown in Table 1; Diffraction efficiency test: The prepared blue-sensitive photopolymer film is placed on the sample stage, and the laser (450nm) is used as the exposure light source and the laser (450nm) is used as the detection light source to measure the real-time diffraction efficiency curve. In the test, the light intensity of each blue light (450nm) is controlled at 20mW / cm 2 The exposure time is about 60s. At the same time, blue light (450nm) is used as the detection light source. The changes of the transmitted light intensity and the diffracted light intensity of the blue light with time are measured at the same time. Then the diffraction efficiency value is obtained by the following calculation formula of diffraction efficiency: Among them, I 1 is the diffracted light intensity, I 2 is the transmitted light intensity; The refractive index modulation Δn is calculated as: Where λ is the wavelength of the detection light source, i.e. 450nm, 2θ is the angle between the two green light beams, and η max is the maximum diffraction efficiency, d is the film thickness; Calculation method of photosensitivity S: where η max is the maximum value of the diffraction efficiency, E is the exposure when the diffraction efficiency reaches the maximum, and d is the film thickness.

[0040] Table 1 Performance test Analyzing the data in Table 1, we can see that: 1) The blue-sensitive photopolymer films prepared in Examples 1 to 7 have the characteristics of good moisture-proof effect, long storage time, high diffraction efficiency, high refractive index modulation, high sensitivity and low exposure energy. The oily blue-sensitive photopolymer film prepared in this application is used to shoot a reflection hologram, which is reproduced under white light to obtain a clear image and has good storage performance, and is an ideal holographic recording material.

[0041] 2) A comparative analysis of the performance of the blue-sensitive photopolymer films prepared in combination with Examples 3 to 5 and Comparative Examples 1 and 3 shows that the write monomer is composed of N-vinyl carbazole and bisphenol A-dimethacrylate in a mass ratio of 0.08-0.22:1. By utilizing the synergistic effect between N-vinyl carbazole and bisphenol A-dimethacrylate and controlling their mass ratio to 0.08-0.22:1, the performance indicators of the blue-sensitive photopolymer film, such as diffraction efficiency, exposure sensitivity, refractive index modulation, exposure energy and storage time, can be greatly optimized.

[0042] 3) The comparative analysis of the performance of the blue-sensitive photopolymer film obtained in combination with Example 6 and Comparative Examples 1 to 3 shows that the writing monomer is composed of N-vinyl carbazole, ethoxylated bisphenol fluorene diacrylate, and bisphenol A-dimethacrylate in a mass ratio of 0.1:1:1. By utilizing the synergistic effect between N-vinyl carbazole, ethoxylated bisphenol fluorene diacrylate and bisphenol A-dimethacrylate, they jointly participate in the polymerization reaction of the blue-sensitive photopolymer film to form a cross-linked network structure, thereby improving the optical quality of the film, the material storage time and the diffraction efficiency. The performance indicators of the blue-sensitive photopolymer film, such as diffraction efficiency, exposure sensitivity, refractive index modulation, exposure energy and storage time, are significantly optimized.

[0043] 4) A comparative analysis of the performance of the blue-sensitive photopolymer film prepared in combination with Example 7 and Comparative Examples 1, 3 and 4 shows that the write monomer is composed of N-vinyl carbazole, ethoxylated trimethylolpropane triacrylate and bisphenol A-dimethacrylate in a mass ratio of 0.2:0.5:1. The synergistic effect between N-vinyl carbazole, ethoxylated trimethylolpropane triacrylate and bisphenol A-dimethacrylate is utilized to significantly optimize the performance indicators of the blue-sensitive photopolymer film, such as diffraction efficiency, exposure sensitivity, refractive index modulation, exposure energy and storage time.

[0044] The above embodiments are only used to explain the technical solutions of the present application rather than to limit them. Although the above embodiments provide a specific description of the present application, relevant technical personnel should understand that the specific implementation methods of the present application can still be modified or replaced by equivalents, and any modifications and equivalent replacements that do not depart from the spirit and scope of the present application should be included in the protection scope of the present application.

Claims

1. A blue-sensitive photopolymer film, characterized in that: The preparation raw materials include the following in parts by mass: 40-45 parts of writing monomer, 20-25 parts of polyester polyol, 14-16 parts of aliphatic isocyanate, 1-2 parts of blue light photosensitizer, 2-4 parts of photoinitiator, 5-10 parts of cross-linking agent, 5-10 parts of antioxidant inhibitor, 0.4-0.6 parts of catalyst, 0.5-0.6 parts of defoaming agent and 5-9 parts of solvent.

2. A blue-sensitive photopolymer film according to claim 1, characterized in that: The writing monomer is any two or more of N-vinyl carbazole, ethoxylated bisphenol fluorene diacrylate, bisphenol A-dimethacrylate, pentaerythritol tetraacrylate, and ethoxylated trimethylolpropane triacrylate.

3. A blue-sensitive photopolymer film according to claim 2, characterized in that: The writing monomer includes at least N-vinyl carbazole and bisphenol A-dimethacrylate, and the mass ratio of the N-vinyl carbazole to the bisphenol A-dimethacrylate is 0.08-0.22:

1.

4. A blue-sensitive photopolymer film according to claim 3, characterized in that: The writing monomer is composed of N-vinyl carbazole, ethoxylated bisphenol fluorene diacrylate and bisphenol A-dimethacrylate in a mass ratio of 0.1:1:

1.

5. The blue-sensitive photopolymer film according to claim 3, characterized in that: The writing monomer is composed of N-vinyl carbazole, ethoxylated trimethylolpropane triacrylate and bisphenol A-dimethacrylate in a mass ratio of 0.2:0.5:

1.

6. The blue-sensitive photopolymer film according to claim 1, characterized in that: The photoinitiator is one or more of triethanolamine, N-phenyldiethanolamine and diethanolamine, preferably triethanolamine.

7. A blue-sensitive photopolymer film according to claim 1, characterized in that: The solvent is one or more of N-methylpyrrolidone, N,N-dimethylformamide, dichloromethane, chloroform and toluene, preferably N,N-dimethylformamide.

8. The blue-sensitive photopolymer film according to claim 1, characterized in that: The antioxidant inhibitor is 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester; the cross-linking agent is N-vinyl pyrrolidone; the blue light photosensitizer is acridine orange; the molecular weight of the polyester polyol is 400-3000; the aliphatic isocyanate is aliphatic isocyanate Wanhua HT-100; the catalyst is organic bismuth catalyst DY-20; and the defoaming agent is BYK-058.

9. A method for preparing a blue-sensitive photopolymer film according to any one of claims 1 to 8, characterized in that: The following steps are involved: The light-proof experiment was carried out in a dark room. The solvent was first added into the flask according to the mass fractions, and then the polyester polyol, blue light photosensitizer, photoinitiator, cross-linker, writing monomer, antioxidant inhibitor and defoamer were added. The temperature was heated to 80-90°C and stirred for 24 hours. Then, aliphatic isocyanate was added and stirred for 30 minutes. Then, the catalyst was dropped and stirred for 1 minute to obtain a colloidal solution. The colloidal solution was then scraped onto a glass substrate or a PET film. After gelation, the blue-sensitive photopolymer film was obtained after vacuum degassing.

10. An application of a blue-sensitive photopolymer film as claimed in any one of claims 1 to 8 in AR-HUD, optical holographic storage, high-end anti-counterfeiting, AR-near-eye display and holographic sensing.

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