Full-color photopolymer film as well as preparation method and application thereof

Abstract

The invention relates to the technical field of full-color photopolymers, and particularly discloses a full-color photopolymer film as well as a preparation method and application thereof. The invention provides a full-color photopolymer film. The full-color photopolymer film is specifically prepared from 40 to 50 parts of a writing monomer, 0.8 to 1.2 parts of a photosensitizer, 4 to 7.2 parts of a photoinitiator, 14 to 16 parts of polycaprolactone glycol, 21 to 25 parts of aliphatic polyether isocyanate, 4 to 6 parts of a cross-linking agent, 0.3 to 0.6 part of a defoaming agent, 0.8 to 1.2 parts of an antioxidant inhibitor, 0.8 to 1.2 parts of a catalyst and 5 to 8 parts of a solvent, the photosensitizer is formed by mixing 2, 5-bis ((2, 3, 6, 7-tetrahydro-1H, 5H-pyrido [3, 2, 1-ij] quinoline-9-yl) methylene) cyclopentyl-1-ketone and methylene blue, and the photosensitizer is formed by mixing 2, 5-bis ((2, 3, 6, 7-tetrahydro-1H, 5H-pyrido [3, 2, 1-ij] quinoline-9-yl) methylene By utilizing the technical scheme of the invention, 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] The present application relates to the technical field of full-color photopolymers, and in particular to a full-color photopolymer film and a preparation method and application thereof. Background Art

[0002] At present, holographic storage has a huge advantage in storage capacity. Due to its advantages such as high data transmission rate and short random storage time, it has attracted widespread attention from scientific researchers and is expected to play a huge role in the future field of digital data storage. The storage of information requires holographic storage materials with the ability to record holographic information, with the help of which the amplitude and phase information of the target object can be recorded and reproduced. There are many materials used in holographic storage, such as silver halide emulsion, dichromated gelatin, photochromic materials, photothermal plastics, liquid crystals, and photopolymer materials. Compared with conventional materials, photopolymers are a new type of holographic material. They have the advantages of simple preparation process, low price, no need for wet chemical treatment, and high diffraction efficiency. They have become the key research object in the field of holographic storage materials.

[0003] Prior art has focused on the research of water-soluble photopolymer materials that are sensitive to single wavelength red, green, and blue. Water-soluble photosensitive materials that are sensitive to single wavelengths are not only unable to fully and accurately reproduce all color information of holographic images when used for holographic recording, but are also relatively sensitive to humidity in the air, easily causing image fading and 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 that are sensitive to multiple wavelengths. Summary of the invention

[0004] In order to solve the above technical problems, the present application provides a full-color photopolymer film and a preparation method and application thereof.

[0005] The present application provides a full-color photopolymer film, specifically comprising the following components in parts by weight: 40-50 parts of a writing monomer, 0.8-1.2 parts of a photosensitizer, 4-7.2 parts of a photoinitiator, 14-16 parts of polycaprolactone diol with Mn=530-10000, 21-25 parts of an aliphatic polyether isocyanate, 4-6 parts of a cross-linking agent, 0.3-0.6 parts of a defoaming agent, 0.8-1.2 parts of an antioxidant inhibitor, 0.8-1.2 parts of a catalyst, and 5-8 parts of a solvent; The photosensitizer is composed of a mixture 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 a weight ratio of 1.0-1.2:1; The photoinitiator is selected from one or more of triethanolamine, N-phenylglycine, diethanolamine, o-chlorohexaarylbiimidazole, 1-methyl-5-mercapto-1H-tetrazole, and triarylsulfonium salts; The weight ratio of the photosensitizer to the photoinitiator is 1:5-6.

[0006] By using the above technical solution of the present application, a photosensitizer is formed by mixing 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-sensitive photosensitizer, and integrating them into the same system so that it is sensitive to red, green and blue wavelengths, which 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.

[0007] Preferably, the writing monomer is composed of a mixture of N-vinyl carbazole, 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.

[0008] 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.

[0009] Through experimental analysis, it can be known that the present application uses the above-mentioned weight ratio 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 to form a photosensitizer, which can further improve the performance of the full-color photopolymer film.

[0010] Preferably, the photoinitiator is composed of a mixture of o-chlorohexaarylbisimidazole and 1-methyl-5-mercapto-1H-tetrazole in a weight ratio of 0.5-1.5:0.5-1.5.

[0011] Preferably, the photoinitiator is composed of a mixture of o-chlorohexaarylbisimidazole and 1-methyl-5-mercapto-1H-tetrazole in a weight ratio of 0.5-1:1-1.5.

[0012] Through experimental analysis, it can be known that the present application uses the above-mentioned weight ratio of o-chlorohexaarylbiimidazole and 1-methyl-5-mercapto-1H-tetrazole mixed to form a photoinitiator, which can further improve the performance of the full-color photopolymer film.

[0013] Preferably, the weight ratio of the polycaprolactone diol with Mn=530-10000 to AH2600 aliphatic isocyanate is 1.8-2.2:2.8-3.2.

[0014] Preferably, the cross-linking agent is 1-vinyl-2-pyrrolidone; the defoaming agent is BYK028; and the antioxidant inhibitor is 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester.

[0015] Preferably, the catalyst is selected from one or more of dibutyltin dilaurate and dimethyltin dineodecanoate; the solvent is selected from one or more of N-methylpyrrolidone, N,N-dimethylformamide, dichloromethane, chloroform and toluene.

[0016] In the second aspect, the present application provides a method for preparing the above-mentioned full-color photopolymer film, which specifically includes the following steps: conducting a light-proof experiment in a dark room, first adding the solvent into a flask, and then adding the polycaprolactone diol with Mn=530-10000, the photosensitizer, the photoinitiator, the cross-linker, the defoaming agent, the writing monomer, and the antioxidant inhibitor, heating the temperature to 80-90°C, stirring overnight, adding the aliphatic isocyanate and stirring for 20-40 minutes, then dripping the catalyst, stirring for 100-150 seconds, and then scraping and degassing in vacuum to obtain the film.

[0017] In a third aspect, the present application provides the use of the full-color photopolymer film in preparing optical elements or images or for image display or projection.

[0018] In summary, the technical solution of this application has the following effects: The technical solution of the present application utilizes photosensitizers with different photosensitizer ranges, and the photosensitizer is composed of a mixture of a blue-green photosensitizer 2,5-bis((2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinoline-9-yl)methylene)cyclopentan-1-one and a methylene blue red-sensitive photosensitizer, which are integrated into the same system to make it sensitive to red, green and blue wavelengths, so as to improve storage density and solve the problem of holographic image reproduction. The prepared full-color photopolymer film has high photosensitivity, dynamic storage range and high diffraction efficiency.

[0019] The technical solution of the present application uses polycaprolactone diol and aliphatic polyether isocyanate as raw materials, adopts non-water-soluble polyurethane as a matrix, and acrylate as a photosensitive monomer. Unlike previous reports that use an aqueous solution of polyvinyl alcohol as a matrix for the photosensitive monomer, it solves the problems of image disappearance in the air and difficulty in preservation; at the same time, it increases its refractive index modulation degree Δn and improves the diffraction efficiency. DETAILED DESCRIPTION

[0020] The present application is further described in detail below in conjunction with examples, comparative examples and performance testing experiments. These examples should not be construed as limiting the scope of protection claimed in the present application. Example

[0021] Examples 1-7 Examples 1-7 each provide a full-color photopolymer film.

[0022] The difference between the full-color photopolymer films in the above embodiments is that the amounts of the raw material components are different, as shown in Table 1.

[0023] The specific steps of the method for preparing the full-color photopolymer film in the above embodiment are as follows: According to the dosage of each raw material shown in Table 1, a light-proof experiment was carried out in a dark room. First, the solvent N-methylpyrrolidone was added to the flask, and then Mn=530-10000 polycaprolactone diol (from Sigma-Aldrich), photosensitizer (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 (from Bidex Pharmaceuticals) in a weight ratio of 1.1:1 and methylene blue), photoinitiator (composed of o- Chlorohexaarylbiimidazole, 1-methyl-5-mercapto-1H-tetrazole), crosslinker 1-vinyl-2-pyrrolidone, defoamer BYK028 and writing monomer (composed of N-vinylcarbazole, ethoxylated bisphenol fluorene diacrylate, bisphenol A-dimethacrylate, o-phenylphenylethoxy acrylate in a weight ratio of 2:7:15:18), antioxidant inhibitor 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, the temperature is heated to 85°C, stirred overnight, aliphatic isocyanate (AH2600, from AEKYUNG CHEMICAL CO., LTD) is added and stirred for 30 minutes, then catalyst dibutyltin dilaurate is dropped, stirred for 100-150 seconds, and then it is scraped on the TAC film. After vacuum defoaming for 1 hour, a full-color photopolymer film with a thickness of 5 microns is obtained.

[0024] Table 1 Amount of each raw material component in Examples 1-7 Embodiment 8-11 Examples 8-11 each provide a full-color photopolymer film.

[0025] The difference between the full-color photopolymer film in the above embodiment and that in embodiment 1 is that the types of acrylate writing monomers are different, as shown below.

[0026] In Example 8, the writing monomer is composed of a mixture of ethoxylated bisphenol fluorene diacrylate, bisphenol A-dimethacrylate, and o-phenylphenethoxy acrylate in a weight ratio of 7:15:18.

[0027] In Example 9, the writing monomer is composed of a mixture of N-vinyl carbazole, ethoxylated bisphenol fluorene diacrylate, bisphenol A-dimethacrylate, and o-phenylphenethoxy acrylate in a weight ratio of 3:4:5:24.

[0028] In Example 10: the writing monomer is composed of a mixture of N-vinyl carbazole, ethoxylated bisphenol fluorene diacrylate, bisphenol A-dimethacrylate, and o-phenylphenethoxy acrylate in a weight ratio of 1.5:10:20:15.

[0029] In Example 11: the writing monomer is composed of a mixture of N-vinyl carbazole, ethoxylated bisphenol fluorene diacrylate, bisphenol A-dimethacrylate, and o-phenylphenethoxy acrylate in a weight ratio of 2.5:5:10:22.

[0030] The other process parameters in the above embodiment are the same as those in embodiment 1.

[0031] Examples 12-14 Examples 12-14 each provide a full-color photopolymer film.

[0032] The difference between the full-color photopolymer film in the above embodiment and that in embodiment 1 is that the types of photosensitizers are different, as shown below.

[0033] In Example 12: 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.

[0034] In Example 13: 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 1:1.

[0035] In Example 14: 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 1.2:1.

[0036] The other process parameters in the above embodiment are the same as those in embodiment 1.

[0037] Examples 15-18 Examples 15-18 each provide a full-color photopolymer film.

[0038] The difference between the full-color photopolymer film in the above embodiment and that in embodiment 1 is that the types of photosensitizers are different, as shown below.

[0039] In Example 15: the photoinitiator is composed of a mixture of triethanolamine and 1-methyl-5-mercapto-1H-tetrazole in a weight ratio of 0.7:1.5.

[0040] In Example 16: the photoinitiator is composed of a mixture of o-chlorohexaarylbiimidazole and N-phenylglycine in a weight ratio of 0.7:1.5.

[0041] In Example 17: the photoinitiator is composed of a mixture of o-chlorohexaarylbiimidazole and 1-methyl-5-mercapto-1H-tetrazole in a weight ratio of 1.5:0.7.

[0042] In Example 18: the photoinitiator is composed of a mixture of o-chlorohexaarylbiimidazole and 1-methyl-5-mercapto-1H-tetrazole in a weight ratio of 0.5:1.5.

[0043] The other process parameters in the above embodiment are the same as those in embodiment 1.

[0044] Comparative Example Comparative Examples 1-3 Comparative Examples 1-3 each provide a full-color photopolymer film.

[0045] The difference between the full-color photopolymer film in the comparative example and Example 1 is that the amounts of the raw material components are different, as shown in Table 2.

[0046] Table 2 The amount of each raw material component in Comparative Examples 1-3 The process parameters in the above comparative example are the same as those in Example 1.

[0047] Comparative Examples 4-5 Comparative Examples 4-5 respectively provide a full-color photopolymer film.

[0048] The differences between the full-color photopolymer film in the comparative example and Example 1 are specifically as follows.

[0049] In Comparative Example 4: 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 alkaline green 4 red light photosensitizer in a weight ratio of 1.1:1.

[0050] In Comparative Example 5: 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 red light photosensitizer in a weight ratio of 1:1.1.

[0051] Performance testing (1) Diffraction efficiency: During exposure, red light 633nm, green light 532nm, and blue light 460nm are used as detection light to measure the diffraction efficiency.

[0052] (2) Refractive index modulation degree Δn: The refractive index modulation degree of the material is determined by measuring the diffraction efficiency using the Kogelnik coupled wave theory; the refractive index modulation degree of blue light Δn (λ=460nm); the refractive index modulation degree of green light Δn (λ=532nm); the refractive index modulation degree of red light Δn (=633nm).

[0053] Test results: as shown in Table 3.

[0054] Table 3 Performance test results of full-color photopolymer films in Examples 1-18 and Comparative Examples 1-5 Combined with 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 the present 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, and can obtain a red light diffraction efficiency>33%, a green light diffraction efficiency>40%, a blue light diffraction efficiency>30%; and a full-color photopolymer with a refractive index modulation degree ≥0.032.

[0055] By comparing the performance test results of the full-color photopolymer film in Examples 1, 8-11, it can be seen that the present application uses a mixture of N-vinyl carbazole, 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 to form a writing monomer, which can further improve the performance of the full-color photopolymer film.

[0056] By comparing the performance test results of the full-color photopolymer films in Examples 1 and 12-14, it can be seen that the present application uses a photosensitizer composed of a mixture 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 a weight ratio of 1.05-1.15:1 to further improve the performance of the full-color photopolymer film.

[0057] By comparing the performance test results of the full-color photopolymer films in Examples 1 and 15-18, it can be seen that the present application uses a mixed photoinitiator of o-chlorohexaarylbisimidazole and 1-methyl-5-mercapto-1H-tetrazole in a weight ratio of 0.5-1.5:0.5-1.5 to further improve the performance of the full-color photopolymer film.

[0058] Although the present invention has been described in detail above with general descriptions and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements may be made thereto based on the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. A full-color photopolymer film, characterized in that: Specifically, it includes 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 Mn=530-10000 polycaprolactone diol, 21-25 parts of aliphatic polyether isocyanate, 4-6 parts of cross-linking agent, 0.3-0.6 parts of defoaming agent, 0.8-1.2 parts of antioxidant inhibitor, 0.8-1.2 parts of catalyst, and 5-8 parts of solvent; The photosensitizer is composed of a mixture 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 a weight ratio of 1.0-1.2:1; The photoinitiator is selected from one or more of triethanolamine, N-phenylglycine, diethanolamine, o-chlorohexaarylbiimidazole, 1-methyl-5-mercapto-1H-tetrazole, and triarylsulfonium salts; The weight ratio of the photosensitizer to the photoinitiator is 1:5-6.

2. The full-color photopolymer film according to claim 1, characterized in that: The writing monomer is composed of a mixture of N-vinyl carbazole, 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.

3. The full-color photopolymer film according to claim 1, characterized in that: The photosensitizer is composed of a mixture 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 a weight ratio of 1.05-1.15:

1.

4. The full-color photopolymer film according to claim 1, characterized in that: The photoinitiator is composed of a mixture of o-chlorohexaarylbisimidazole and 1-methyl-5-mercapto-1H-tetrazolyl in a weight ratio of 0.5-1.5:0.5-1.

5.

5. The full-color photopolymer film according to claim 5, characterized in that: The photoinitiator is composed of a mixture of o-chlorohexaarylbisimidazole and 1-methyl-5-mercapto-1H-tetrazolyl in a weight ratio of 0.5-1:1-1.

5.

6. The full-color photopolymer film according to claim 1, characterized in that: The weight ratio of the polycaprolactone diol with Mn=530-10000 and the AH2600 aliphatic isocyanate is 1.8-2.2:2.8-3.

2.

7. The full-color photopolymer film according to claim 1, characterized in that: The cross-linking agent is 1-vinyl-2-pyrrolidone; the defoaming agent is BYK028; and the antioxidant inhibitor is 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester.

8. The full-color photopolymer film according to claim 1, characterized in that: The catalyst is selected from one or more of dibutyltin dilaurate and dimethyltin dineodecanoate; the solvent is selected from one or more of N-methylpyrrolidone, N,N-dimethylformamide, dichloromethane, chloroform and toluene.

9. The method for preparing a full-color photopolymer film according to any one of claims 1 to 8, characterized in that: The specific steps include: A light-proof experiment is carried out in a dark room. First, the solvent is added into a flask, and then the polycaprolactone diol with Mn=530-10000, the photosensitizer, the photoinitiator, the cross-linking agent, the defoaming agent, the writing monomer, and the antioxidant inhibitor are added. The temperature is heated to 80-90° C. and stirred overnight. The aliphatic isocyanate is added and stirred for 20-40 minutes. Then, the catalyst is dropped into the flask and stirred for 100-150 seconds. Then, the flask is applied by scraping and the product is obtained after vacuum defoaming.

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

Images