Solid optical material, method for producing the same, and use thereof

Abstract

The application discloses a kind of solid optical material and its preparation method, application, the solid optical material includes following raw materials: schiff base, polymer monomer and curing agent, wherein, the weight ratio of the schiff base and the polymer monomer satisfies:1:100000~1:1000;The structure of the schiff base is as follows:In the formula, R is selected from one of hydrogen, methyl, ethyl, propyl or butyl.According to the solid optical material of the application, the schiff base with photochromic performance is dispersed in the colorless transparent organic glass curing product, the light transmittance of the obtained solid optical material is high, the image is clear and stable after photochromic, and the image can be stored for a long time.

Description

Technical Field

[0001] This invention relates to the field of optical materials, and in particular to a solid optical material, its preparation method, and its applications. Background Technology

[0002] In related technologies, image display is mostly still at the two-dimensional level, including commercial display technologies and information storage technologies such as QR codes and barcodes. Based on human familiarity and perception of the three-dimensional spatial environment, there is an urgent need to develop three-dimensional display and storage technologies, especially in fields such as military, industry, aerospace, medicine, and new media.

[0003] In existing technologies, stimulus-responsive elements can achieve image display and information conversion based on their unique responses to light, heat, force, etc. Stimulus-responsive elements can be certain compounds with specific structures, such as diarylethylene, spiropyran, Schiff bases, and other photochromic materials. However, these materials, in solid, powder, or solution states, have short-lived color changes, which are detrimental to image observation and information storage. Summary of the Invention

[0004] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, one object of the present invention is to provide a solid optical material that provides a writable and erasable three-dimensional imaging material with a long image storage time.

[0005] Another objective of this invention is to provide a method for preparing solid optical materials.

[0006] Another object of the present invention is to propose an application of a solid optical material.

[0007] According to a first aspect of the present invention, a solid optical material comprises the following raw materials: a Schiff base, a polymer monomer, and a curing agent, wherein the weight ratio of the Schiff base to the polymer monomer satisfies 1:100000 to 1:1000; the structure of the Schiff base is shown below: In the formula, R is selected from hydrogen, methyl, ethyl, propyl or butyl.

[0008] According to a specific embodiment of the present invention, a solid-state optical material is obtained by dispersing a Schiff base with photochromic properties in a colorless and transparent cured organic glass substrate. The resulting solid-state optical material exhibits high light transmittance, clear and stable images after photochromic changes, and the images can be preserved for a relatively long time. Thus, the solid-state optical material provided by the present invention can undergo reversible photochromic changes under specific light source stimulation, thereby enabling the display of erasable patterns. Furthermore, the solid-state optical material of the present invention exhibits fast photochromic response, sensitive color change, and good fatigue resistance. Therefore, it has significant potential and practical application value. For example, it can be applied to various industries such as optical components, new displays, information storage, and construction.

[0009] According to some embodiments of the present invention, the polymer monomer includes at least one of epoxy resin and methyl methacrylate.

[0010] According to some embodiments of the present invention, when the polymer monomer is an epoxy resin, the curing agent includes at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; and / or when the polymer monomer is methyl methacrylate, the curing agent includes at least one of azobisisobutyronitrile, azobisisoheptanenitrile, and benzoyl peroxide.

[0011] According to some embodiments of the present invention, the weight ratio of the epoxy resin to the curing agent is 2.5 to 3.5:1; and / or the weight ratio of the methyl methacrylate to the curing agent is 100:1 to 10.

[0012] According to an embodiment of the second aspect of the present invention, the present invention provides a method for preparing a solid optical material according to an embodiment of the first aspect of the present invention, comprising the following steps: mixing a Schiff base in the specified material ratio with the curing agent and the polymer monomer, and curing to obtain a colorless and transparent solid optical material.

[0013] According to some embodiments of the present invention, the method includes the following steps: Step 1, dispersing the Schiff base in the specified material ratio into the polymer monomer, adding a curing agent; prepolymerizing, repolymerizing, and curing; wherein the prepolymerization temperature is 60℃~100℃; the repolymerization temperature is 30℃~50℃; and the curing temperature is 80℃~120℃; Step 2, cutting, grinding, and splicing the cured material from Step 1 to obtain a colorless and transparent solid optical material.

[0014] According to some embodiments of the present invention, the following steps are included: (1) uniformly mixing the polymer monomer and the curing agent; (2) dispersing the Schiff base in an organic solvent and then pouring it into the mixture obtained in step (1), stirring evenly to obtain a slurry; (3) curing the slurry at 25℃~100℃, cooling and demolding to obtain a solid optical material.

[0015] According to an embodiment of a third aspect of the present invention, the present invention provides an application of a solid optical material according to an embodiment of a first aspect of the present invention or a solid optical material prepared by a preparation method according to an embodiment of a second aspect of the present invention in erasable three-dimensional imaging.

[0016] According to some embodiments of the present invention, the method includes the following steps: irradiating the colorless and transparent solid optical material with ultraviolet light, causing the irradiated portion of the solid optical material to change from colorless to orange-yellow, thereby realizing three-dimensional display of the image; irradiating at least a portion of the orange-yellow solid optical material with visible light of 410nm to 650nm, causing the irradiated portion to return to colorless and transparent, thereby erasing the image.

[0017] According to some embodiments of the present invention, the following steps are included: 1. Using the colorless and transparent solid optical material as a display screen, using ultraviolet light as a writing light source, and using a scanning galvanometer to control the movement path of the writing light source, a target pattern is written on the display screen; 2. Using visible light of 410nm to 650nm as an erasure light source, and using a scanning galvanometer to control the movement path of the erasure light source, the pattern is erased.

[0018] According to some embodiments of the present invention, the method further includes the following steps: Third, ultraviolet light is used again as the writing light source, and the moving path of the writing light source is controlled by a scanning galvanometer, so that the target pattern can be written again, thereby realizing the repeated erasing and writing of three-dimensional images on solid optical materials.

[0019] According to some embodiments of the present invention, the erasing light source is incident from a direction perpendicular to the writing light source.

[0020] According to some embodiments of the present invention, at room temperature and natural light intensity of 300 Lux to 500 Lux, the image is saved for no less than 5 minutes.

[0021] According to some embodiments of the present invention, the power of the ultraviolet light source is W1, wherein W1 satisfies: 100mW≤W1≤500mW; and / or the power of the visible light source is W2, wherein W2 satisfies: 10mW≤W2≤100mW.

[0022] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0023] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0024] Figure 1 A flowchart of a method for preparing a solid optical material according to an embodiment of the present invention;

[0025] Figure 2 Absorption spectra and physical images of the solid optical material before and after photoinduction according to Embodiment 1 of the present invention;

[0026] Figure 3 Absorption spectra and physical images of the solid optical material before and after photoinduction according to Embodiment 2 of the present invention;

[0027] Figure 4 Absorption spectra and physical images of the solid optical material before and after photoinduction according to Embodiment 3 of the present invention;

[0028] Figure 5 : A schematic diagram of the erasable three-dimensional imaging process of solid optical material 1 according to Embodiment 1 of the present invention;

[0029] Figure 6 : A schematic diagram of the erasable three-dimensional imaging process of solid optical material 3 according to Embodiment 3 of the present invention;

[0030] Figure 7 : Absorption spectra and physical images of the solid optical material 4 before and after photo-induced emission according to Comparative Example 1 of the present invention;

[0031] Figure 8 The absorption spectra and physical images of the Schiff base solution before and after photoinduction according to Comparative Example 2 of the present invention are shown. Detailed Implementation

[0032] The embodiments of the present invention are described in detail below. The embodiments described with reference to the accompanying drawings are exemplary. The embodiments of the present invention are described in detail below.

[0033] The following is for reference. Figures 2-4 A solid-state optical material according to an embodiment of the present invention is described, comprising the following raw materials: a Schiff base, a polymer monomer, and a curing agent. Here, the Schiff base is a photochromic material capable of undergoing a color-changing reaction upon light stimulation. The polymer monomer is induced to undergo a polymerization reaction by the curing agent, thereby curing to obtain a cured plexiglass. The cured plexiglass is suitable as a carrier for optical imaging or a storage device for optical imaging. The solid-state optical material of the invention is formed by dispersing the Schiff base in the cured plexiglass.

[0034] The weight ratio of Schiff base to polymer monomer satisfies 1:100000 to 1:1000. With this setting, the content of Schiff base in solid optical materials is appropriate, so that solid optical materials can not only form clear images, but also have high light transmittance and good imaging effect.

[0035] The structure of Schiff bases is shown below:

[0036] In the formula, R is selected from hydrogen, methyl, ethyl, propyl, or butyl. With this configuration, the trifluoromethyl group at the ortho position of the hydroxyl group is an electron-withdrawing group, which facilitates charge transfer. Therefore, the Schiff base color-changing phenomenon of the present invention is more pronounced, and the color-changing image can be stored for a longer time. Specifically, the photochromic effect of the Schiff base molecule requires two necessary conditions: (1) after photoexcitation, the enol structure undergoes an excited-state intramolecular proton transfer (ESIPT) to become a cis-ketone structure; (2) under continuous photoexcitation, the benzene surrounding the CN bond of salicylaldehyde twists, the cis-ketone isomerizes to obtain a trans-ketone structure, and the Schiff base molecule produces a color change. The Schiff base of the present invention has a trifluoromethyl group with strong electron-withdrawing ability at the 3 position of salicylaldehyde, which can promote the ESIPT process, thus making it easier to exhibit photochromic properties. Furthermore, since the cis-ketone molecule is metastable and has a very short lifetime at room temperature, it will quickly return to the ground state before isomerizing to a trans-ketone, making it difficult to observe photochromic changes. The solid-state optical material provided by this invention disperses Schiff bases within a polymer, allowing the Schiff base molecules to exist within the rigid structure of the polymer. This creates a suitable photochromic environment for these state-switchable molecules, extending the lifetime of metastable cis-ketone molecules. Therefore, the probability of observing a significant photochromic phenomenon is greater. Furthermore, under visible light in the 410nm–650nm range, more molecules undergo isomerization to form trans-ketones, and the photochromic phenomenon disappears.

[0037] According to a specific embodiment of the present invention, a solid-state optical material is obtained by dispersing a Schiff base with photochromic properties in a colorless and transparent cured organic glass substrate. The resulting solid-state optical material exhibits high light transmittance, clear and stable images after photochromic changes, and can retain images for a relatively long period. Thus, the solid-state optical material provided by the present invention can undergo reversible photochromic changes under specific light source stimulation, presenting erasable and rewritable images. Furthermore, it exhibits fast photochromic response, high sensitivity, and good fatigue resistance. Therefore, it has significant potential and practical application value. For example, it can be applied in various industries such as optical components, new displays, information storage, and construction.

[0038] According to some embodiments of the present invention, the polymer monomer includes at least one of epoxy resin and methyl methacrylate. This configuration allows for the wide availability of polymer monomers, facilitates curing and molding, provides a suitable environment for the photochromic nature of the Schiff base of the present invention, and results in a solid optical material with high transparency. Specifically, when the polymer monomer is methyl methacrylate, the transparency and color-changing effect of the solid optical material are better; when the polymer monomer is epoxy resin, the fabrication method of the solid optical material is simpler.

[0039] According to some embodiments of the present invention, when the polymer monomer is epoxy resin, the curing agent includes at least one selected from ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine. With this configuration, the curing agent can effectively promote the curing and polymerization of the epoxy resin, forming the solid optical material of the present invention.

[0040] According to some embodiments of the present invention, when the polymer monomer is methyl methacrylate, the curing agent includes at least one selected from azobisisobutyronitrile, azobisisoheptanenitrile, and benzoyl peroxide. With this configuration, the curing agent can effectively promote the curing and polymerization of methyl methacrylate, forming the solid optical material of the present invention.

[0041] According to some embodiments of the present invention, the weight ratio of epoxy resin to curing agent satisfies 2.5 to 3.5:1. This setting ensures an appropriate amount of curing agent is added, which is beneficial for the curing agent to fully induce the polymerization of polymer monomers to obtain a uniform polymer. It also effectively avoids the influence of the curing agent on the Schiff base, facilitating the curing of the polymer monomers to obtain the colorless and transparent solid optical material of the present invention.

[0042] According to some embodiments of the present invention, the weight ratio of methyl methacrylate to curing agent satisfies 100:1 to 10. This setting ensures an appropriate amount of curing agent is added, which is beneficial for the curing agent to fully induce the polymerization of the polymer monomers to obtain a uniform polymer. It also effectively avoids the influence of the curing agent on the Schiff base, facilitating the curing of the polymer monomers to obtain the colorless and transparent solid optical material of the present invention.

[0043] According to an embodiment of a second aspect of the present invention, the present invention provides a method for preparing a solid optical material according to an embodiment of a first aspect of the present invention. The method includes the following steps: mixing a Schiff base in the above-mentioned material ratio with a curing agent and a polymer monomer, and curing the mixture to obtain a colorless and transparent solid optical material.

[0044] According to a specific embodiment of the present invention, a method for preparing solid optical materials involves mixing and reacting a Schiff base with a curing agent and a polymer monomer, followed by heating and curing to obtain a colorless and transparent solid optical material. The preparation method is simple, suitable for mass production, and the obtained solid optical material has high application value.

[0045] According to some embodiments of the present invention, the method includes the following steps: Step 1, dispersing Schiff base in a certain material ratio into polymer monomers, adding a curing agent; prepolymerizing, repolymerizing, and curing; wherein the prepolymerization temperature is 60℃~100℃; the repolymerization temperature is 30℃~50℃; and the curing temperature is 80℃~120℃; Step 2, cutting, grinding, and splicing the cured material in Step 1 to obtain a colorless and transparent solid optical material.

[0046] According to a specific embodiment of the present invention, a method for preparing solid-state optical materials involves dispersing Schiff bases into the polymer-formed solid during the polymerization process of polymer monomers, ensuring uniform dispersion of the Schiff bases within the solid-state optical material. Furthermore, curing promotes the shaping of the solid-state optical material, and post-processing such as cutting and polishing produces a solid-state optical material with a regular morphology, facilitating its application.

[0047] Optionally, the present invention can divide the curing process into two stages: primary curing and secondary curing. The primary curing temperature is lower and the time is longer, forming a uniform and stable state through slow curing. The secondary curing temperature is higher and the time is shorter, which strengthens the primary curing. This is more conducive to forming a uniform solid optical material with excellent optical properties.

[0048] According to some embodiments of the present invention, in combination Figure 1 The process includes the following steps: (1) mixing the polymer monomer and the curing agent evenly; (2) dispersing the Schiff base in an organic solvent and then pouring it into the mixture obtained in step (1), stirring evenly to obtain a slurry; (3) curing the slurry at 25℃~100℃, cooling and demolding to obtain a solid optical material.

[0049] According to a specific embodiment of the present invention, the preparation method of solid optical materials involves dispersing the Schiff base in an organic solvent, which facilitates its uniform dispersion in the mixture of polymer monomer and curing agent. The solid optical material is then obtained through curing, cooling, and demolding. This method involves fewer steps and is simpler to prepare. Furthermore, vacuum degassing can be performed before curing the slurry to prevent the formation of air bubbles during the curing process, which could affect imaging performance.

[0050] According to some embodiments of the present invention, the organic solvent is at least one selected from dichloromethane, dichloroethane, ethyl acetate, toluene, and N,N-dimethylformamide.

[0051] According to some embodiments of the present invention, the molar concentration of Schiff base molecules in organic solvents is 1 mol / L to 5 mol / L.

[0052] According to an embodiment of the third aspect of the present invention, the present invention provides an application of a solid optical material according to an embodiment of the first aspect of the present invention or a solid optical material prepared by the preparation method according to the second aspect of the present invention in erasable three-dimensional imaging.

[0053] According to specific embodiments of the present invention, the photochromic properties of the solid-state optical material of the present invention enable its application in the field of erasable 3D imaging. This provides more raw materials for research on erasable 3D imaging. Furthermore, the raw materials for the solid-state optical material of the present invention are inexpensive and readily available, and the preparation process is simple. The imaging process using the solid-state optical material of the present invention is also simple. For example, the movement path of the light source within the solid-state optical material can be controlled using devices such as scanning galvanometers, enabling the presentation of erasable patterns. This allows the solid-state optical material of the present invention to be applied in various fields such as optical components, novel displays, information storage, and architecture.

[0054] According to some embodiments of the present invention, the method includes the following steps: irradiating a colorless and transparent solid optical material with ultraviolet light, causing the irradiated portion of the solid optical material to change from colorless to orange-yellow, thereby achieving three-dimensional image display. With this configuration, the Schiff base of the ultraviolet-irradiated portion of the solid optical material changes from an enol structure to a cis-ketone structure, and from colorless to orange-yellow, thus enabling the writing of a three-dimensional image into the colorless and transparent solid optical material of the present invention.

[0055] At least a portion of the orange-yellow solid optical material is irradiated with visible light in the 410nm-650nm range. The irradiated portion regains its colorless and transparent state, thus erasing the image. With this configuration, when irradiated with visible light in the 410nm-650nm range, the Schiff base in the irradiated area changes from a cis-ketone structure to an enol structure, restoring the orange-yellow solid optical material to its colorless and transparent state. Furthermore, the path of the irradiation can be controlled as needed to erase the orange-yellow portion or all of the solid optical material, thereby achieving image erasure or trimming. Preferably, irradiation with visible light in the 450nm-550nm range results in a faster erasure speed.

[0056] According to a specific embodiment of the present invention, a three-dimensional image is written into a solid optical material by ultraviolet light irradiation, and the image is erased by visible light irradiation in the range of 410 nm to 650 nm. Thus, the writing and erasure of a three-dimensional image are achieved in a solid optical material formed from Schiff bases and polymer monomers, facilitating observation and application.

[0057] According to some embodiments of the present invention, the following steps are included: 1. Using a colorless and transparent solid optical material as the display screen, using ultraviolet light as the writing light source, and using a scanning galvanometer to control the movement path of the writing light source, a target pattern is written on the display screen; 2. Using visible light of 410nm to 650nm as the erasure light source, and using a scanning galvanometer to control the movement path of the erasure light source, the pattern is erased.

[0058] According to a specific embodiment of the present invention, by controlling the movement paths of the writing light source and the erasing light source through a scanning galvanometer, precise imaging can be achieved in solid optical materials with high image clarity.

[0059] According to some embodiments of the present invention, the method further includes the following steps: Third, ultraviolet light is used again as the writing light source, and the moving path of the writing light source is controlled by a scanning galvanometer, so that the target pattern can be written again, thereby realizing the repeated erasing and writing of three-dimensional images on solid optical materials.

[0060] According to specific embodiments of the present invention, imaging and erasure can be repeated in solid optical materials. This results in high availability.

[0061] According to some embodiments of the present invention, the erasing light source is incident from a direction perpendicular to the writing light source. This arrangement allows for faster image erasure while facilitating image trimming.

[0062] According to some embodiments of the present invention, at room temperature and natural light intensity of 300 to 500 Lux, the image storage time is no less than 5 minutes. This setting allows the image to remain stable for a longer period, facilitating observation and storage. In a dark environment, the image storage time will be even longer.

[0063] According to some embodiments of the present invention, the power of the ultraviolet light source is W1, wherein W1 satisfies: 100mW ≤ W1 ≤ 500mW. The power of the visible light source is W2, wherein W2 satisfies: 10mW ≤ W2 ≤ 100mW. This provides sufficient energy for imaging the solid-state optical material of the present invention.

[0064] According to some optional embodiments of the present invention, the wavelength of the ultraviolet light is λ1, wherein λ1 satisfies: 365nm≤λ1≤395nm.

[0065] Specific exemplary embodiments

[0066] Example 1

[0067] A solid optical material comprises the following raw materials: Schiff base, polymer monomer and curing agent, wherein the weight ratio of Schiff base to polymer monomer satisfies: 1:10000;

[0068] The structure of a Schiff base is shown below: In the general molecular formula, when R is a hydrogen atom, the structural formula of Schiff base 1 is as follows:

[0069]

[0070] During the photochromic reaction of Schiff bases, the structure undergoes the following changes:

[0071] In the reaction formula, UV refers to the conditions of ultraviolet light irradiation, and Vis refers to visible light within the wavelength range defined by this invention.

[0072] Its preparation method includes the following steps:

[0073] Step 1: Mix 0.01g Schiff base powder with 100g methyl methacrylate, add 0.2g benzoyl peroxide curing agent, and perform prepolymerization at 80℃, low-temperature polymerization at 40℃, and high-temperature curing at 100℃ to obtain a crude product of solid optical material.

[0074] Step 2: Cut, grind, and polish the obtained crude product to obtain the colorless and transparent solid optical material 1 of this invention.

[0075] The absorption spectra and physical images of the aforementioned solid optical material 1 before and after photochromism are shown below. Figure 2 As shown. The photochromic process includes the following steps:

[0076] 1. After irradiating the above solid optical material with 365nm ultraviolet light for 1 second, it is colored (the irradiated part turns orange-yellow). At this time, the absorption wavelength of the solid optical material is red-shifted.

[0077] 2. When the discolored part of the solid optical material is irradiated with 450nm visible light for 2s, the discolored part fades and becomes colorless and transparent. At this time, the absorption wavelength returns to the initial state.

[0078] Example 2

[0079] A solid optical material comprises the following raw materials: Schiff base, polymer monomer and curing agent, wherein the weight ratio of Schiff base to polymer monomer satisfies: 1:10000;

[0080] The structure of a Schiff base is shown below: In the general molecular formula, when R is butyl, the Schiff base structure is as follows:

[0081]

[0082] During the photochromic reaction of Schiff bases, the structure undergoes the following changes:

[0083] In the reaction formula, UV refers to the conditions of ultraviolet light irradiation, and Vis refers to visible light within the wavelength range defined by this invention.

[0084] Its preparation method includes the following steps:

[0085] Step 1: Mix 0.01g Schiff base powder with 100g methyl methacrylate, add 0.2g benzoyl peroxide curing agent, and perform prepolymerization at 80℃, low-temperature polymerization at 40℃, and high-temperature curing at 100℃ to obtain a crude product of solid optical material.

[0086] Step 2: Cut, grind, and polish the obtained crude product to obtain the colorless and transparent solid optical material 2 of this invention.

[0087] The absorption spectra and physical images of the aforementioned solid optical material 2 before and after photochromism are shown below. Figure 3 As shown. The photochromic process includes the following steps:

[0088] 1. After irradiating the above solid optical material with 365nm ultraviolet light for 1 second, it is colored (the irradiated part turns orange-yellow). At this time, the absorption wavelength of the solid optical material is red-shifted.

[0089] 2. When the discolored part of the solid optical material is irradiated with 450nm visible light for 2s, the discolored part fades and becomes colorless and transparent. At this time, the absorption wavelength returns to the initial state.

[0090] Example 3

[0091] A solid optical material comprises the following raw materials: Schiff base, polymer monomer and curing agent, wherein the weight ratio of Schiff base to polymer monomer satisfies: 1:7500;

[0092] The molecular structure of Schiff bases is the same as that in Example 1.

[0093] Its preparation method includes the following steps:

[0094] (1) 75g of epoxy resin and 25g of triethylenetetramine are mixed evenly.

[0095] (2) Dissolve 0.01g Schiff base powder in 0.1mL dichloromethane and pour it into the mixture obtained in step (1), and stir evenly to obtain a slurry;

[0096] (3) The slurry from step (2) was degassed under vacuum for 5 minutes and cured at 30°C for 24 hours to obtain a polymer. The polymer was demolded to obtain the colorless and transparent solid optical material 3 of the present invention.

[0097] The absorption spectra and physical images of the aforementioned colorless and transparent solid optical material 3 before and after photoinduction are shown below. Figure 4 As shown.

[0098] The photochromic process includes the following steps:

[0099] 1. After irradiating the above solid optical material with 365nm ultraviolet light for 1 second, it is colored (the irradiated part turns orange-yellow). At this time, the absorption wavelength of the solid optical material is red-shifted.

[0100] 2. When the discolored part of the solid optical material is irradiated with 450nm visible light for 2s, the discolored part fades and becomes colorless and transparent. At this time, the absorption wavelength returns to the initial state.

[0101] Example 4

[0102] The application of solid optical material 1 in erasable 3D imaging according to Example 1 includes the following steps:

[0103] 1. Using the rectangular solid optical material 1 of Example 1 as the display screen, 365nm ultraviolet light is used as the writing light source, and the scanning galvanometer 1 controls the movement path of the writing light source to write an "arrow" pattern on the display screen. The image is then observed after the light source is turned off.

[0104] 2. Using 450nm blue light as the erasure light source, the scanning galvanometer 2 controls the movement path of the erasure light source, which enters from the vertical direction of the writing light source to erase the pattern.

[0105] Third, turn on the 365nm ultraviolet light again and use scanning galvanometer 1 to switch the movement path of the writing light source. The "pentagram" pattern can then be written again, achieving erasable 3D imaging. The specific process can be combined with... Figure 5 understand.

[0106] Example 5:

[0107] The application of solid optical material 3 in erasable 3D imaging in Example 3 is as follows:

[0108] 1. Using the cubic solid optical material 3 of Example 3 as the display screen, 365nm ultraviolet light is used as the writing light source. The scanning galvanometer 1 controls the movement path of the writing light source and writes an "arrow" pattern on the display screen. The light source is then turned off to observe the image.

[0109] 2. Using 450nm blue light as the erasure light source, the scanning galvanometer 2 controls the movement path of the erasure light source, which enters from the vertical direction of the writing light source to erase the pattern.

[0110] Third, turn on the 365nm ultraviolet light again and use scanning galvanometer 1 to switch the movement path of the writing light source. The "pentagram" pattern can then be written again, achieving erasable 3D imaging. The specific process can be combined with... Figure 6 understand.

[0111] Comparative Example 1:

[0112] Comparison 1 is basically the same as Example 1, except that the salicylaldehyde in the Schiff base does not have a trifluoromethyl group at the 3-position, and the structure is shown below:

[0113]

[0114] Its preparation method includes the following steps:

[0115] Step 1: Mix 0.01g Schiff base salicylaldehyde aniline with 100g methyl methacrylate, add 0.2g curing agent benzoyl peroxide, and perform prepolymerization at 80℃, low-temperature polymerization at 40℃, and high-temperature curing at 100℃ to obtain the crude product of solid optical material.

[0116] Step 2: The obtained rough product is cut, ground, and polished to obtain the colorless and transparent solid optical material 4 of this invention. The absorption spectra and photographs of the above-mentioned colorless and transparent solid optical material 4 before and after photoinduction are shown below. Figure 7 As shown. The photochromic process includes the following steps:

[0117] When the above-mentioned colorless and transparent solid optical material is irradiated with 365nm ultraviolet light for 1 second, the coloring is not obvious and the absorption wavelength has almost no red shift.

[0118] This indicates that the trifluoromethyl group in the Schiff base structure promotes photochromism.

[0119] Comparative Example 2:

[0120] Observe the photochromic changes of Schiff bases in solution:

[0121] The Schiff base 1 from Example 1 was dispersed in an organic solvent, and the specific method is as follows:

[0122] 0.01 g of Schiff base 1 powder was mixed thoroughly with 100 g of dichloromethane solution. 2 mL of this mixture was then used to test the absorption spectra before and after photoinduction and photographed. The results are as follows: Figure 8 As shown, after 1 second of irradiation with 365nm ultraviolet light, the solution did not change color significantly, and the absorption wavelength did not change significantly, indicating that it is difficult to observe photochromism in Schiff bases in solution.

[0123] In the description of this invention, "a plurality of" means two or more.

[0124] In the description of this specification, references to terms such as "one embodiment," "some embodiments," "illustrative embodiment," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example.

[0125] Although embodiments of the invention have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.

Claims

1. A solid optical material, characterized in that, The raw materials include: Schiff base, polymer monomer and curing agent, wherein the weight ratio of the Schiff base to the polymer monomer satisfies: 1:100000 to 1:1000; The structure of the Schiff base is shown below: In the formula, R is selected from methyl, ethyl, propyl or butyl; The polymer monomer includes at least one of epoxy resin and methyl methacrylate; When the polymer monomer is an epoxy resin, the curing agent includes at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; and / or When the polymer monomer is methyl methacrylate, the curing agent includes at least one of azobisisobutyronitrile, azobisisoheptanenitrile, and benzoyl peroxide; The weight ratio of the epoxy resin to the curing agent is 2.5 to 3.5:

1.

2. A method for preparing a solid optical material according to claim 1, characterized in that, Includes the following steps: The Schiff base in the specified material ratio is mixed with the curing agent and the polymer monomer, and then cured to obtain a colorless and transparent solid optical material.

3. The preparation method according to claim 2, characterized in that, Includes the following steps: Step 1: Disperse the Schiff base in the specified material ratio into the polymer monomer, add a curing agent; then prepolymerize, repolymerize, and cure. The prepolymerization temperature is 60℃~100℃; the repolymerization temperature is 30℃~50℃; and the curing temperature is 80℃~120℃. Step 2: Cut, grind, and splice the cured material from Step 1 to obtain a colorless and transparent solid optical material.

4. The preparation method according to claim 2, characterized in that, Includes the following steps: (1) The polymer monomer and the curing agent are mixed evenly; (2) After dispersing the Schiff base in an organic solvent, pour it into the mixture obtained in step (1) and stir until homogeneous to obtain a slurry; (3) The slurry is solidified at 25℃~100℃, cooled and demolded to obtain solid optical material.

5. The application of a solid optical material according to claim 1 or a solid optical material prepared by any one of claims 2-4 in erasable three-dimensional imaging.

6. The application according to claim 5, characterized in that, Includes the following steps: By irradiating a colorless and transparent solid optical material with ultraviolet light, the irradiated part of the solid optical material changes from colorless to orange-yellow, thereby realizing the three-dimensional display of the image; At least a portion of the orange-yellow solid optical material is irradiated with visible light in the range of 410nm to 650nm, and the irradiated portion returns to colorless and transparent, thus erasing the image.

7. The application according to claim 5, characterized in that, Includes the following steps:

1. Using a colorless and transparent solid optical material as the display screen, ultraviolet light as the writing light source, and a scanning galvanometer to control the movement path of the writing light source, a target pattern is written on the display screen.

2. Visible light in the range of 410nm to 650nm is used as the erasure light source, and the moving path of the erasure light source is controlled by a scanning galvanometer to erase the pattern.

8. The application according to claim 7, characterized in that, It also includes the following steps: Third, by using ultraviolet light as the writing light source again and using a scanning galvanometer to control the movement path of the writing light source, the target pattern can be written again, realizing the repeated erasing and writing of three-dimensional images on solid optical materials.

9. The application according to claim 7, characterized in that, The erasing light source enters from the direction perpendicular to the writing light source.

10. The application according to any one of claims 5-9, characterized in that, At room temperature and natural light intensity of 300 Lux to 500 Lux, the image should be saved for no less than 5 minutes.

11. The application according to any one of claims 6-9, characterized in that, The power of the ultraviolet light source is W1, wherein W1 satisfies: 100mW ≤ W1 ≤ 500mW; and / or The power of the visible light source is W2, wherein W2 satisfies: 10mW≤W2≤100mW.

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