Full-color photopolymer film, preparation method and application thereof

Abstract

The application relates to the technical field of full-color photopolymer, and specifically discloses a full-color photopolymer film, a preparation method and application thereof. The full-color photopolymer film provided by the application specifically comprises 40-50 parts of writing monomers, 0.8-1.2 parts of photosensitizers, 4-7.2 parts of photoinitiators, 14-16 parts of polycaprolactone glycol, 21-25 parts of aliphatic polyether isocyanate, 4-6 parts of crosslinking agents, 0.3-0.6 parts of defoaming agents, 0.8-1.2 parts of anti-oxidation inhibitors, 0.8-1.2 parts of catalysts and 5-8 parts of solvents; the photosensitizer is composed of 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)cyclopentan-1-one and methylene blue. By using the technical scheme, the full-color photopolymer with high red, blue and green light diffraction efficiency and high refractive index modulation degree can be obtained.

Description

Technical Field

[0001] This application relates to the technical field of full-color photopolymers, specifically to a full-color photopolymer thin film, its preparation method, and its application. Background Technology

[0002] Currently, holographic storage holds a significant advantage in terms of storage capacity. Its high data transmission rate and short random access time have attracted widespread attention from researchers, and it is expected to play a crucial role in the future of digital data storage. Information storage requires holographic storage materials capable of recording holographic information, which record and reproduce the amplitude and phase information of the target object. Many materials are used in holographic storage, such as silver halide emulsions, dichromate gelatin, photochromic materials, photothermal conductive plastics, liquid crystals, and photopolymer materials. Photopolymers, compared to conventional materials, are a novel type of holographic material. Their simple preparation process, low cost, lack of wet chemical treatment, and high diffraction efficiency have made them a key research focus in the field of holographic storage materials.

[0003] Existing technologies have extensively studied water-soluble photopolymer materials sensitive to single wavelengths of red, green, and blue. However, water-soluble photosensitive materials sensitive to single wavelengths cannot accurately reproduce all the color information of a holographic image when used for holographic recording. They are also sensitive to humidity in the air, which can easily cause image loss and make them difficult to preserve. In order to achieve greater storage density and accurate reproduction of holographic images, it is of great significance to study non-water-soluble photopolymers sensitive to multiple wavelengths. Summary of the Invention

[0004] To address the aforementioned technical problems, this application provides a full-color photopolymer thin film, its preparation method, and its application.

[0005] This application provides a full-color photopolymer film, specifically comprising the following components in parts by weight: 40-50 parts of writing monomer, 0.8-1.2 parts of photosensitizer, 4-7.2 parts of photoinitiator, 14-16 parts of polycaprolactone diol with Mn=530-10000, 21-25 parts of aliphatic polyether isocyanate, 4-6 parts of crosslinking agent, 0.3-0.6 parts of defoamer, 0.8-1.2 parts of antioxidant inhibitor, 0.8-1.2 parts of catalyst, and 5-8 parts of solvent;

[0006] The photosensitizer is composed of a mixture of 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)cyclopentan-1-one and methylene blue in a weight ratio of 1.0-1.2:1.

[0007] The photoinitiator is selected from one or more of triethanolamine, N-phenylglycine, diethanolamine, o-chlorohexaaryldiimidazole, 1-methyl-5-mercapto-1H-tetrazole, and triarylthionium salt;

[0008] The weight ratio of the photosensitizer to the photoinitiator is 1:5-6.

[0009] Using the above-mentioned technical solution of this application, a photosensitizer is composed of a blue-green photosensitizer 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)cyclopentan-1-one and a methylene blue-red photosensitizer, which are fused into the same system to make it photosensitive to red, green and blue wavelengths. This is used to improve storage density and solve the problem of holographic image reproduction. The prepared holographic color-sensitive photopolymer has high photosensitivity, dynamic storage range and high diffraction efficiency.

[0010] Preferably, the writing monomer is composed of N-ethylenecarbazole, ethoxylated bisphenol fluorene diacrylate, bisphenol A-dimethacrylate, and o-phenylphenoxyacrylate in a weight ratio of 1.5-2.5:5-10:10-20:15-22.

[0011] Preferably, the photosensitizer is composed of a mixture of 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)cyclopentan-1-one and methylene blue in a weight ratio of 1.05-1.15:1.

[0012] Experimental analysis shows that the photosensitizer composed of 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinoline-9-yl)methylene)cyclopentan-1-one and methylene blue in the above weight ratio can further improve the performance of the full-color photopolymer film.

[0013] Preferably, the photoinitiator is composed of o-chlorohexaaryldiimidazole and 1-methyl-5-mercapto-1H-tetrazole in a weight ratio of 0.5-1.5:0.5-1.5.

[0014] Preferably, the photoinitiator is composed of a mixture of o-chlorohexaaryldiimidazole and 1-methyl-5-mercapto-1H-tetrazole in a weight ratio of 0.5-1:1-1.5.

[0015] Experimental analysis shows that the photoinitiator composed of o-chlorohexaarylbisimidazole and 1-methyl-5-mercapto-1H-tetrazole in the above weight ratio can further improve the performance of full-color photopolymer films.

[0016] Preferably, the weight ratio of Mn=530-10000 polycaprolactone diol to AH2600 aliphatic isocyanate is 1.8-2.2:2.8-3.2.

[0017] Preferably, the crosslinking agent is 1-vinyl-2-pyrrolidone; the defoaming agent is BYK028; and the antioxidant inhibitor is diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.

[0018] Preferably, the catalyst is selected from one or more of dibutyltin dilaurate and dimethyltin dinedecanoate; the solvent is selected from one or more of N-methylpyrrolidone, N,N-dimethylformamide, dichloromethane, chloroform, and toluene.

[0019] Secondly, this application provides a method for preparing the above-mentioned full-color photopolymer film, which specifically includes the following steps: conducting a light-shielding experiment in a dark room, first adding the solvent to a flask, then adding the Mn=530-10000 polycaprolactone diol, the photosensitizer, the photoinitiator, the crosslinking agent, the defoamer, the writing monomer, and the antioxidant inhibitor, heating the temperature to 80-90℃, stirring overnight, adding the aliphatic isocyanate and stirring for 20-40 minutes, then adding the catalyst dropwise, stirring for 100-150 seconds, then coating by scraping, and obtaining the film after vacuum defoaming.

[0020] Thirdly, this application provides the use of the above-mentioned full-color photopolymer film in the preparation of optical elements or images or for image display or projection.

[0021] In summary, the technical solution of this application has the following effects:

[0022] The technical solution of this application utilizes photosensitizers with different photosensitive ranges. The photosensitizer is composed of a blue-green photosensitizer 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)cyclopentan-1-one and a methylene blue-red photosensitizer. These photosensitizers are fused into the same system to make the system photosensitive to red, green and blue wavelengths. This is used to improve storage density and solve the problem of holographic image reproduction. The resulting full-color photopolymer film has high photosensitivity, dynamic storage range and high diffraction efficiency.

[0023] The technical solution of this application uses polycaprolactone diol and aliphatic polyether isocyanate as raw materials, and adopts non-water-soluble polyurethane as matrix and acrylate as photosensitive monomer. Unlike the previously reported use of polyvinyl alcohol aqueous solution as matrix for photosensitive monomer, it solves the problems of image de-image in air and difficulty in preservation. At the same time, it improves its refractive index modulation Δn and enhances diffraction efficiency. Detailed Implementation

[0024] The present application will be further described in detail below with reference to embodiments, comparative examples and performance test results. These embodiments should not be construed as limiting the scope of protection claimed in this application.

[0025] Example

[0026] Examples 1-7

[0027] Examples 1-7 each provide a full-color photopolymer film.

[0028] The difference between the full-color photopolymer films in the above embodiments is that the amount of each raw material component is different, as shown in Table 1.

[0029] The specific steps of the preparation method of the full-color photopolymer film in the above embodiments are as follows:

[0030] Following the amounts of each raw material shown in Table 1, a light-protected experiment was conducted in a dark room. First, the solvent N-methylpyrrolidone was added to the flask. Then, polycaprolactone diol (Mn = 530-10000, sourced from Sigma-Aldrich), photosensitizer (composed of 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)cyclopentan-1-one (sourced from Bid Pharmaceuticals) and methylene blue in a weight ratio of 1.1:1), and photoinitiator (composed of o-...) in a weight ratio of 0.7:1.5... The mixture consists of a mixture of chlorohexaaryldiimidazole and 1-methyl-5-mercapto-1H-tetrazole, a crosslinking agent of 1-vinyl-2-pyrrolidone, a defoamer of BYK028, and a writing monomer (composed of N-ethylenecarbazole, ethoxylated bisphenol fluorene diacrylate, bisphenol A-dimethacrylate, and o-phenylphenoxy ethoxyacrylate in a weight ratio of 2:7:15:18), and an antioxidant inhibitor of diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate. The mixture is heated to 85°C and stirred overnight. An aliphatic isocyanate (AH2600, from AEKYUNG CHEMICAL CO.,LTD) is added and stirred for 30 min. Then, the catalyst dibutyltin dilaurate is added dropwise and stirred for 100-150 s. The mixture is then coated onto a TAC film. After vacuum defoaming for 1 h, a 5-micron thick full-color photopolymer film is obtained.

[0031] Table 1. Dosage of each raw material component in Examples 1-7

[0032]

[0033]

[0034] Examples 8-11

[0035] Examples 8-11 each provide a full-color photopolymer film.

[0036] The difference between the above embodiments and the full-color photopolymer film in Embodiment 1 is that the types of monomers written with acrylate are different, as detailed below.

[0037] In Example 8: the written monomer is composed of a mixture of bisphenol fluorene diacrylate, bisphenol A-dimethacrylate and o-phenylphenoxyacrylate in a weight ratio of 7:15:18.

[0038] In Example 9: the written monomer is composed of N-ethylene carbazole, ethoxylated bisphenol fluorene diacrylate, bisphenol A-dimethacrylate and o-phenylphenoxy acrylate in a weight ratio of 3:4:5:24.

[0039] In Example 10: the written monomer was composed of N-ethylenecarbazole, ethoxylated bisphenol fluorene diacrylate, bisphenol A-dimethacrylate and o-phenylphenoxy acrylate in a weight ratio of 1.5:10:20:15.

[0040] In Example 11: the written monomer was composed of N-ethylene carbazole, ethoxylated bisphenol fluorene diacrylate, bisphenol A-dimethacrylate and o-phenylphenoxy acrylate in a weight ratio of 2.5:5:10:22.

[0041] All other process parameters in the above embodiments are the same as those in Embodiment 1.

[0042] Examples 12-14

[0043] Examples 12-14 each provide a full-color photopolymer film.

[0044] The difference between the above embodiments and the full-color photopolymer film in Embodiment 1 is that the types of photosensitizers are different, as detailed below.

[0045] In Example 12: The photosensitizer was composed of a mixture of 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)cyclopentan-1-one and methylene blue in a weight ratio of 1.05:1.

[0046] In Example 13: The photosensitizer was composed of a mixture of 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)cyclopentan-1-one and methylene blue in a weight ratio of 1:1.

[0047] In Example 14: The photosensitizer was composed of a mixture of 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)cyclopentan-1-one and methylene blue in a weight ratio of 1.2:1.

[0048] All other process parameters in the above embodiments are the same as those in Embodiment 1.

[0049] Examples 15-18

[0050] Examples 15-18 each provide a full-color photopolymer film.

[0051] The difference between the above embodiments and the full-color photopolymer film in Embodiment 1 is that the types of photosensitizers are different, as detailed below.

[0052] In Example 15: the photoinitiator was composed of a mixture of triethanolamine and 1-methyl-5-mercapto-1H-tetrazole in a weight ratio of 0.7:1.5.

[0053] In Example 16: the photoinitiator was composed of o-chlorohexaaryldiimidazole and N-phenylglycine in a weight ratio of 0.7:1.5.

[0054] In Example 17: the photoinitiator was composed of o-chlorohexaaryldiimidazole and 1-methyl-5-mercapto-1H-tetrazole in a weight ratio of 1.5:0.7.

[0055] In Example 18: the photoinitiator was composed of o-chlorohexaaryldiimidazole and 1-methyl-5-mercapto-1H-tetrazole in a weight ratio of 0.5:1.5.

[0056] All other process parameters in the above embodiments are the same as those in Embodiment 1.

[0057] Comparative Example

[0058] Comparative Examples 1-3

[0059] Comparative Examples 1-3 each provide a full-color photopolymer film.

[0060] The difference between the above comparative example and the full-color photopolymer film in Example 1 is that the amount of each raw material component is different, as shown in Table 2.

[0061] Table 2 shows the dosage of each raw material component in Comparative Examples 1-3.

[0062]

[0063]

[0064] In the above comparative examples, the process parameters are the same as those in Example 1.

[0065] Comparative Example 4-5

[0066] Comparative Examples 4 and 5 each provide a full-color photopolymer film.

[0067] The differences between the above comparative examples and the full-color photopolymer film in Example 1 are as follows.

[0068] In Comparative Example 4, the photosensitizer was composed of a mixture of 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)cyclopentan-1-one and basic green 4 red photosensitizer in a weight ratio of 1.1:1.

[0069] In Comparative Example 5, the photosensitizer was composed of a mixture of 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)cyclopentan-1-one and methylene blue-red photosensitizer in a weight ratio of 1:1.1.

[0070] Performance testing

[0071] (1) Diffraction efficiency: During exposure, red light 633nm, green light 532nm, and blue light 460nm are used as probe light to measure its diffraction efficiency.

[0072] (2) Refractive index modulation Δn: The refractive index modulation of the material is determined by measuring the diffraction efficiency using Kogelnik coupled-wave theory; blue light refractive index modulation Δn (λ = 460 nm); green light refractive index modulation Δn (λ = 532 nm); red light refractive index modulation Δn (λ = 633 nm).

[0073] Test results are shown in Table 3.

[0074] Table 3 Performance test results of full-color photopolymer films in Examples 1-18 and Comparative Examples 1-5

[0075]

[0076]

[0077] Referring to Table 3, by comparing the performance test results of the full-color photopolymer films in Examples 1-18 and Comparative Examples 1-5, it can be seen that the technical solution of this application uses polyurethane as the base material, acrylate as the monomer, and reasonably controls the amount of each raw material component to prepare a holographic photopolymer, which can obtain a full-color photopolymer with red light diffraction efficiency >33%, green light diffraction efficiency >40%, blue light diffraction efficiency >30%, and refractive index modulation ≥0.032.

[0078] By comparing the performance test results of the full-color photopolymer films in Examples 1 and 8-11, it can be seen that the writing monomers composed of N-ethylenecarbazole, ethoxylated bisphenol fluorene diacrylate, bisphenol A-dimethacrylate, and o-phenylphenoxyacrylate in a weight ratio of 1.5-2.5:5-10:10-20:15-22 can further improve the performance of the full-color photopolymer films.

[0079] By comparing the performance test results of the full-color photopolymer films in Examples 1 and 12-14, it can be seen that the photosensitizer composed of 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)cyclopentan-1-one and methylene blue in a weight ratio of 1.05-1.15:1 can further improve the performance of the full-color photopolymer film.

[0080] By comparing the performance test results of the full-color photopolymer films in Examples 1 and 15-18, it can be seen that the photoinitiator composed of o-chlorohexaaryldiimidazole and 1-methyl-5-mercapto-1H-tetrazole in a weight ratio of 0.5-1.5:0.5-1.5 can further improve the performance of the full-color photopolymer film.

[0081] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A full-color photopolymer film, characterized by, Specifically comprising the following components by weight: 40-50 parts of writing monomer, 0.8-1.2 parts of photosensitizer, 4-7.2 parts of photoinitiator, 14-16 parts of Mn=530-10000 polycaprolactone diol, 21-25 parts of aliphatic isocyanate AH2600, 4-6 parts of crosslinking agent, 0.3-0.6 parts of defoaming agent, 0.8-1.2 parts of antioxidant inhibitor, 0.8-1.2 parts of catalyst, 5-8 parts of solvent; The writing monomer is composed of N-vinylcarbazole, ethoxylated bisphenol fluorene diacrylate, bisphenol A dimethacrylate, and o-phenylphenethoxy acrylate in a weight ratio of 1.5-2.5:5-10:10-20:15-22; The photosensitizer is composed of 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)cyclopentan-1-one and methylene blue in a weight ratio of 1.0-1.2:1; The photoinitiator is composed of o-chlorinated hexaaryl bisimidazole and 1-methyl-5-mercapto-1H-tetrazole in a weight ratio of 0.5-1.5:0.5-1.5; The weight ratio of the photosensitizer to the photoinitiator is 1:5-6.

2. The full-color photopolymer film according to claim 1, wherein The photosensitizer is composed of 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)cyclopentan-1-one and methylene blue in a weight ratio of 1.05-1.15:

1.

3. The full-color photopolymer film according to claim 1, wherein The photoinitiator is composed of o-chlorinated hexaaryl bisimidazole and 1-methyl-5-mercapto-1H-tetrazole in a weight ratio of 0.5-1:1-1.

5.

4. The full-color photopolymer film according to claim 1, wherein The weight ratio of the Mn=530-10000 polycaprolactone diol to the aliphatic isocyanate AH2600 is 1.8-2.2:2.8-3.

2.

5. The full-color photopolymer film according to claim 1, wherein The crosslinking agent is 1-vinyl-2-pyrrolidone; the defoaming agent is BYK028; and the antioxidant inhibitor is 3,5-di-tert-butyl-4-hydroxybenzyl phosphonic acid diethyl ester.

6. The full-color photopolymer film according to claim 1, wherein The catalyst is selected from one or more of dibutyltin dilaurate and dimethyltin di-neodecanoate; and the solvent is selected from one or more of N-methylpyrrolidone, N,N-dimethylformamide, dichloromethane, chloroform, and toluene.

7. The method of claim 1-6, wherein the method further comprises the step of: Specifically comprising the following steps: The experiment is carried out in a dark room. First, the solvent is added to a flask, then the Mn=530-10000 polycaprolactone diol, the photosensitizer, the photoinitiator, the crosslinking agent, the defoaming agent, and the writing monomer, the antioxidant inhibitor are added, the temperature is heated to 80-90℃, and stirring is performed overnight. Then, the aliphatic isocyanate AH2600 is added and stirred for 20-40 min, the catalyst is added dropwise, stirring is performed for 100-150 s, then scraping is performed, and vacuum defoaming is performed to obtain the product.

8. Use of the full-color photopolymer film according to any one of claims 1-6 for the preparation of optical elements or images or for image display or projection.

Images