CN112936849A - Preparation method and application of crystalline dynamic pattern based on photocuring molding - Google Patents
Preparation method and application of crystalline dynamic pattern based on photocuring molding Download PDFInfo
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- CN112936849A CN112936849A CN202110137459.6A CN202110137459A CN112936849A CN 112936849 A CN112936849 A CN 112936849A CN 202110137459 A CN202110137459 A CN 202110137459A CN 112936849 A CN112936849 A CN 112936849A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/386—Data acquisition or data processing for additive manufacturing
- B29C64/393—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y50/00—Data acquisition or data processing for additive manufacturing
- B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
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Abstract
The invention discloses a preparation method of a crystalline dynamic pattern based on photocuring molding, which comprises the following steps: heating the photosensitive resin to a temperature higher than the melting temperature, and injecting the heated photosensitive resin into a reaction tank to form a photosensitive resin precursor solution; irradiating the liquid photosensitive resin precursor liquid by digital light to initiate a cross-linking polymerization chemical reaction, and regulating and controlling the regional illumination time difference by a preset model to obtain a photocured material; placing the photo-cured material in a low-temperature environment with the crystallization temperature lower than that of the material, and naturally cooling the material to generate a crystalline dynamic pattern; the photosensitive resin precursor solution comprises a crystalline monofunctional monomer, a photoinitiator, and a photocuring polyfunctional monomer or oligomer. The invention also discloses application of the crystalline dynamic pattern obtained by the preparation method as readable information with timeliness. The crystalline pattern preparation method provided by the invention can be used in the fields of rapid two-dimensional image forming, information encryption, anti-counterfeiting and the like.
Description
Technical Field
The invention relates to the field of polymer processing and manufacturing, in particular to a preparation method and application of a crystalline dynamic pattern based on photocuring molding.
Background
The light curing forming technology is a forming technology using digital light as a processing means, and is mainly realized by combining a preset pattern in a computer, generating the pattern through continuous movement of a point light source or direct projection of surface projection, and carrying out light curing reaction in a pattern area to form. Due to the high degree of designability of the patterns, this approach has been widely used for industrial design, patterned modeling and direct fabrication of some products. The digital forming technology has the most outstanding advantage that complex patterns can be built quickly and highly self-defined.
Among the various stereolithography methods, digital surface projection is an efficient patterning means, which uses a higher resolution digital light processor to compile the projected pattern, thereby achieving regional exposure time differentiation. By utilizing the difference of the light curing time, researchers can realize the regulation and control of the properties of various materials and apply the regulation and control to different scenes. On the other hand, crystalline polymers macroscopically exhibit a decrease in material transparency due to the presence of crystalline and amorphous regions in the system, and transparency declines with increasing crystallinity. The crystalline material can release heat in the cooling process, and has application prospect in the field of phase change energy storage materials. For example, chinese patent publication No. CN108883573A discloses a patterning method and a patterning apparatus. Chinese patent publication No. CN107664919A, for example, discloses a method for preparing a patterned cured product and a patterned cured product obtained using the method.
The existing photocuring pattern regulation and control method has the following limitations:
(1) the physical mask is combined with a light source to irradiate to generate an area pattern, so that the physical mask is high in manufacturing cost and easy to generate a light path diffusion phenomenon.
(2) Dynamic patterns cannot be generated, namely, the contrast difference is completely determined by the illumination time, and the contrast difference cannot be changed in one-step molding.
(3) Patterning methods based on infrared detection are limited to the photothermal effect, i.e. the temperature difference due to the difference in the heat absorption capacity of the zones during continuous heating. There is no technical means for spontaneously generating infrared images in the market.
Disclosure of Invention
The invention aims to provide a crystallinity patterning method based on photocuring molding, which can adopt a digital photocuring means to controllably adjust the crystallization behavior of a material in a region so as to obtain a crystallinity pattern with transparency difference.
A preparation method of a crystalline dynamic pattern based on photocuring molding, comprising the following steps:
(1) heating the photosensitive resin to a temperature higher than the melting temperature, and injecting the heated photosensitive resin into a reaction tank to form a photosensitive resin precursor solution;
(2) irradiating the liquid photosensitive resin precursor liquid by digital light to initiate a cross-linking polymerization chemical reaction, and regulating and controlling the regional illumination time difference by a preset model to obtain a photocured material;
(3) placing the photo-cured material in a low-temperature environment with the crystallization temperature lower than that of the material, and naturally cooling the material to generate a crystalline dynamic pattern;
the photosensitive resin precursor solution comprises a crystalline monofunctional monomer, a photoinitiator and a photocuring polyfunctional monomer or oligomer, wherein the crystalline monofunctional monomer is a monofunctional (meth) acrylate, (meth) acrylamide or aromatic liquid crystal (meth) acrylate monomer with the crystallization temperature of 20 ℃ or above.
In the invention, the photosensitive resin precursor liquid contains active functional groups, and can initiate polymerization reaction by a photoinitiator under the irradiation of light; the polymerization temperature is maintained above the melting point of the precursor solution. Preferably, the gel rate of the precursor solution must be sufficiently fast to ensure the accuracy of the patterning.
The polymer with the crystalline pattern is prepared by adopting a special crystalline monomer as a precursor liquid main body through a photocuring technology, and the crystallization behavior area of the material is adjustable. By regulating and controlling the difference of the regional crystallization behaviors, the crystallization kinetics of the material is further controlled, so that a high-definition steady-state crystalline pattern or a transient crystalline pattern with timeliness can be obtained. In addition, by utilizing the crystallization heat release effect of the material, in the cooling process, high-definition thermal images can be formed due to the sequence of the region crystallization, and then the cooling thermal images can be hidden, so that the special advantage of transient infrared encryption is achieved.
The resin comprises, by mass, 60-95% of monofunctional monomer, 5-30% of polyfunctional crosslinking agent and 0.1-5% of photoinitiator.
Preferably, the photosensitive resin precursor solution comprises 75-95% of a crystalline photocurable monomer, 5-20% of a multifunctional monomer or oligomer, and 0.1-5% of a photoinitiator in terms of mass fraction.
The crystalline monofunctional monomer is selected from hexadecyl (meth) acrylate and an alkyl isomeric compound thereof, octadecyl (meth) acrylate and an alkyl isomeric compound thereof, eicosyl (meth) acrylate and an alkyl isomeric compound thereof, docosyl (meth) acrylate and an alkyl isomeric compound thereof, and ditetradecyl (meth) acrylate and an alkyl isomeric compound thereof, dodecyl (methyl) acrylamide and alkyl isomeric compound thereof, tetradecyl (methyl) acrylamide and alkyl isomeric compound thereof, hexadecyl (methyl) acrylamide and alkyl isomeric compound thereof, octadecyl (methyl) acrylamide and alkyl isomeric compound thereof, 4- (6-acryloyloxyhexyloxy) -4 '-cyanobiphenyl or 4- (6-acryloyloxyoctyloxy) -4' -cyanobiphenyl, or a combination of at least two of the above.
The photoinitiator is selected from one or a combination of at least two of benzoin and derivatives, benzil, alkyl benzophenones, acyl ortho-oxide, benzophenone or thioxanthone.
Preferably, the photoinitiator is selected from one or a combination of at least two of benzoin, benzoin dimethyl ether, diphenylethanone, dimethoxyphenylacetophenone, hydroxyalkyl phenone, aroyl phosphorus oxide, benzophenone, 2, 4-dihydroxy benzophenone or thiopropoxy thioxanthone.
The crosslinking agent is a polyfunctional (meth) acrylate or (meth) acrylamide monomer, including polyfunctional (meth) acrylate or (meth) acrylamide monomers having a crystallization temperature of 20 ℃ or higher.
The multifunctional monomer or oligomer is selected from one or a combination of at least two of aliphatic multifunctional (meth) acrylate, aliphatic multifunctional (meth) acrylate oligomer with the molecular weight range of 100-500000Da, aromatic multifunctional (meth) acrylate and aromatic multifunctional (meth) acrylate oligomer with the molecular weight range of 100-500000 Da.
The multifunctional monomer is selected from one or more of ethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, pentanediol diacrylate, hexanediol diacrylate, heptanediol diacrylate, octanediol diacrylate, nonanediol diacrylate, decanediol diacrylate, trimethylolpropane triacrylate, four-arm polyethylene glycol acrylate with a molecular weight of 1000-50000Da, diethylene glycol diacrylate phthalate, diethylene glycol diacrylate isophthalate, diethylene glycol diacrylate terephthalate or polyethylene glycol diacrylate with a molecular weight of 1000-50000 Da.
In the step (2), the wavelength of the light source used for the digital light irradiation is in the range of 200nm-800 nm.
The invention also provides application of the crystalline dynamic pattern obtained by the preparation method as readable information with timeliness.
The readable information with timeliness comprises timeliness information obtained by transparency change and application of timeliness infrared encryption information.
The readable information with timeliness is a two-dimensional code.
In the invention, the polymer material of the crystalline dynamic pattern is prepared by digital photocuring, and the used light source comprises a digital point light source, a digital surface light source, a physical mask auxiliary light forming method and the like, and the digital surface light source is taken as an example for demonstration.
The preparation method provided by the invention is to obtain a polymer material with a dynamic crystallization pattern by a digital projection technology. The key steps of the method are that a digital area light source is used for carrying out area selective exposure, the crystalline photosensitive resin precursor liquid in a molten state is solidified into a film, and the film is naturally cooled to generate dynamic crystallization behavior.
The transparent reaction tank in the step (1) is made of glass or materials which do not swell in the hot precursor liquid. The thickness of the reaction tank can be adjusted between 1 μm and 1 cm.
In the step (2), the wavelength of the light source used for the digital light irradiation is in the range of 200nm-800 nm. Further, the digital light source in step (2) is a commercial DLP projector, and the wavelength band emitted by the DLP projector light source is 400-700 nm. DLP projectors may also use light sources in the ultraviolet band of less than 400nm to replace the light sources in DLP projectors. The preset model can complete slicing operation in a computer, edit exposure information of each layer, and then import the exposure information into a DLP projector to realize illumination polymerization, and the regional exposure difference is the overlapping effect of multiple layers of exposure information. The illumination time is determined according to the model structure and can be adjusted between 1 and 500 s. In addition, the regional regulation and control of illumination can also be realized by utilizing a gray level image method, namely each layer of slice exposure pattern can contain different light intensity, namely a gray level pattern, and the regional exposure difference is realized by utilizing the difference of the light intensity. The intensity of the grey scale exposure may be continuously adjustable between 1% maximum intensity and 100% maximum intensity.
In step (3), the low-temperature environment temperature is lower than the crystallization temperature of the material. The low-temperature environment temperature can be adjusted between minus 80 ℃ and 25 ℃.
The invention also provides application of the crystalline dynamic pattern obtained by the preparation method as readable information with timeliness.
The readable information with timeliness includes timeliness information obtained by transparency change and application of timeliness infrared encryption information (infrared visualized dynamic pattern).
The readable information with timeliness is a two-dimensional code.
Preferably, the dynamic infrared visualization pattern is a region crystalline material realized by DLP photocuring, and the crystalline material can be applied to the field of infrared encryption.
Particularly, the invention realizes the reversal of transparency difference by reasonably controlling the crystallization behaviors of different areas, so that the method can be used for preparing the crystallization information with timeliness, such as two-dimensional codes with timeliness. In addition, due to the heat release effect in the crystallization process, the infrared thermal image information with timeliness can be obtained due to the regional heat release difference in the cooling process, and the method has important significance for an encryption system in a special environment.
The invention provides a method for initiating the polymerization reaction of crystalline monomers by utilizing photocuring polymerization reaction, and a polymer with a crystalline pattern is obtained by determining the crystallization behavior of a material due to the exposure time of digital light, and the dynamic pattern is generated in the natural cooling process. In addition, due to crystallization heat release difference, the material can spontaneously generate high-definition infrared images in the natural cooling process, and the material has the special advantage of infrared readability.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with a complex template method, a physical mask method and the like, the DLP photopolymerization method used in the invention is simple and convenient to operate, can realize dynamic pattern conversion without doping specific fluorescent dye, and has good universality.
(2) Compared with other photoetching methods and spraying technologies, the method provides a simpler and more convenient implementation means.
Drawings
FIG. 1 is a schematic diagram of a digital projection apparatus and device according to the present invention;
FIG. 2 is a schematic view of a photo-polymerization condition of a photosensitive resin precursor solution provided by the present invention;
FIG. 3 is a graph of the crystalline dynamic pattern change, including two different patterns, prepared in example 1;
FIG. 4 is a display of the dynamic time-sensitive two-dimensional code in application example 1;
fig. 5 is a display of the application example 1 as infrared encryption information.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the invention as claimed is not limited to the scope of the examples.
As shown in fig. 1, the present invention employs a digital projection apparatus for preparing a dynamic crystalline pattern, comprising: the system comprises a computer 1, a DLP projector 2, a glass sheet 3 and a silicone rubber sheet 4; the resin tank composed of the glass sheet and the gasket is filled with a melted photosensitive resin precursor solution 5. The method of the present invention is not limited to the use of glass sheets with spacers as shown in FIG. 1, but may also be used with an integrated heatable transparent resin bath (ensuring no swelling by the molten precursor).
The DLP projector 2 is connected with the computer 1 through a G code, and projected patterns are transmitted to the DLP projector 2 after being sliced by a three-dimensional model which is designed by the computer 1; exposure patterns generated by the DLP projector 2 are projected to the surface of the melted photosensitive resin precursor liquid 5, and then different patterns are continuously exposed to be superposed to form regional exposure time differences. After the solidification is finished, the solid polymer film material obtained by solidification is placed in a low-temperature environment, and the preparation of the crystallization pattern can be realized.
Example 1 crystalline dynamic Pattern preparation based on octadecyl acrylate
Raw materials:
a) octadecyl acrylate (SA): j & K company;
b) hexanediol diacrylate (HDDA): Sigma-Aldrich;
c) phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide (Irgacure 819): Sigma-Aldrich;
the monomer and other substances are uniformly mixed according to a certain proportion (mass fraction SA: HDDA: Irgacure 819: 100:10:1), and the digital projection equipment and the device diagram which are illustrated in the figure 1 are adopted to carry out cyclic projection, exposure and curing: the wave band emitted by the DLP projector light source is 400-700 nm. The exposure pattern is shown in fig. 2, the first projection time is 8s, and the projection pattern is a rectangular spot. And then, projecting the cup and face model, wherein the cup area is illuminated, the face area is not illuminated, and the illumination time is 8 s. The difference in crystallinity and transmittance is achieved by generating the difference in area exposure (face area 8s, cup area 16s) by superposition.
Fig. 2 shows the dynamic crystallization behavior inside the polymer film due to regional high molecular structure differences at the completion of photocuring (temperature above crystallization temperature). Due to the difference in exposure time, the crosslink density of the polymer network is differentiated, and in the high crosslink density region (cup region), the crystalline side chains tend to be closely arranged due to the formation of the polymer network, so that the crystallization phenomenon occurs first. In contrast, in the low cross-linking density region (facial region), there are many free crystalline monomers, and the monomers are not easy to arrange rapidly to form crystals, so the crystals are slow, but because there is no limitation of high cross-linking network, the monomers can move freely, the degree of crystallization is greater in the equilibrium state of the crystals, and lower light transmittance is embodied.
Fig. 3 shows the dynamic pattern transitions achieved based on the described principle, including the molten state, crystalline state 1, crystalline state 2. Including a cup and face pattern, a black and white grid pattern. In the model of the black-and-white grid, the illumination time of the four corners and the central square is 16s, and the illumination time of the rest squares is 8 s.
Application example 1
Fig. 4 and 5 show the application of the dynamic time-sensitive two-dimensional code and dynamic infrared information encryption prepared according to example 1.
In fig. 4, a dynamic time-sensitive two-dimensional code is shown, and a two-dimensional code pattern can be scanned and read in a specific time period. Specifically, in the two-dimensional code in the upper row of fig. 4, the illumination time of the two-dimensional code region is 8s, the background illumination time is 24s, and the cured polymer film can be read after being cooled to 140s at 20 ℃. By adjusting different illumination time combinations as shown in the lower row of fig. 4, the illumination time of the two-dimensional code area is 8s, the background illumination time is 12s, and the polymer film can be read only when the temperature is reduced by 70-100s at 20 ℃.
Fig. 5 illustrates a dynamic infrared information encryption system. The crystalline pattern that has solidified into a film is placed on a complex background and the crystalline information can be hidden. By heating and melting, and then cooling, information written in the polymer film is displayed in the infrared image due to the difference of crystallization heat release time, and the information cannot be distinguished by naked eyes.
Claims (10)
1. A preparation method of a crystalline dynamic pattern based on photocuring molding is characterized by comprising the following steps:
(1) heating the photosensitive resin to a temperature higher than the melting temperature, and injecting the heated photosensitive resin into a reaction tank to form a photosensitive resin precursor solution;
(2) irradiating the liquid photosensitive resin precursor liquid by digital light to initiate a cross-linking polymerization chemical reaction, and regulating and controlling the regional illumination time difference by a preset model to obtain a photocured material;
(3) placing the photo-cured material in a low-temperature environment with the crystallization temperature lower than that of the material, and naturally cooling the material to generate a crystalline dynamic pattern;
the photosensitive resin precursor solution comprises a crystalline monofunctional monomer, a photoinitiator and a photocuring polyfunctional monomer or oligomer, wherein the crystalline monofunctional monomer is a monofunctional (meth) acrylate, (meth) acrylamide or aromatic liquid crystal (meth) acrylate monomer with the crystallization temperature of 20 ℃ or above.
2. The method for preparing a crystalline dynamic pattern based on photocuring molding according to claim 1, wherein the photosensitive resin precursor solution comprises 75-95% of a crystalline photocuring monomer, 5-20% of a multifunctional monomer or oligomer, and 0.1-5% of a photoinitiator in terms of mass fraction.
3. The method for preparing a crystalline dynamic pattern based on photocuring molding according to claim 1 or 2, characterized in that the crystalline monofunctional monomer is selected from the group consisting of hexadecyl (meth) acrylate and its alkyl isomeric compound, octadecyl (meth) acrylate and its alkyl isomeric compound, eicosyl (meth) acrylate and its alkyl isomeric compound, docosyl (meth) acrylate and its alkyl isomeric compound, ditetradecyl (meth) acrylate and its alkyl isomeric compound, dodecyl (meth) acrylamide and its alkyl isomeric compound, tetradecyl (meth) acrylamide and its alkyl isomeric compound, hexadecyl (meth) acrylamide and its alkyl isomeric compound, octadecyl (meth) acrylamide and its alkyl isomeric compound, 4- (6-acryloyloxyhexyloxy) -4' -cyanobiphenyl or 4- One or a combination of at least two of (6-acryloyloxyoctyloxy) -4' -cyanobiphenyl.
4. The method for preparing a crystalline dynamic pattern based on photocuring molding according to claim 1 or 2, characterized in that the photoinitiator is selected from one or a combination of at least two of benzoin and derivatives, benzil, alkyl benzophenones, acyl ortho-oxides, benzophenones or thioxanthones.
5. The method for preparing a crystalline dynamic pattern based on photocuring molding as claimed in claim 2, wherein the multifunctional monomer or oligomer is selected from one or a combination of at least two of aliphatic multifunctional (meth) acrylate, aliphatic multifunctional (meth) acrylate oligomer with molecular weight range of 100-500000Da, aromatic multifunctional (meth) acrylate, and aromatic multifunctional (meth) acrylate oligomer with molecular weight range of 100-500000 Da.
6. The method for preparing a crystalline dynamic pattern based on photocuring molding according to claim 2, wherein the multifunctional monomer is selected from one or more of ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol diacrylate, pentanediol diacrylate, hexanediol diacrylate, heptanediol diacrylate, octanediol diacrylate, nonanediol diacrylate, decanediol diacrylate, trimethylolpropane triacrylate, four-arm polyethylene glycol acrylate with molecular weight of 1000-50000Da, diethylene glycol diacrylate phthalate, diethylene glycol diacrylate isophthalate, diethylene glycol diacrylate terephthalate or polyethylene glycol diacrylate with molecular weight of 1000-50000 Da.
7. The method for preparing a crystalline dynamic pattern based on photocuring molding according to claim 1, wherein in the step (2), the wavelength of the light source used for the digital light irradiation is in the range of 200nm to 800 nm.
8. Use of the crystalline dynamic pattern obtained by the production method according to any one of claims 1 to 7 as readable information having time-sensitivity.
9. The method for preparing a crystalline dynamic pattern based on photocuring molding and the application thereof as claimed in claim 8, wherein the readable information with timeliness comprises timeliness information obtained by transparency change and application of timeliness infrared encryption information.
10. The application of claim 8 or 9, wherein the readable information with timeliness is a two-dimensional code.
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| CN105904726A (en) * | 2016-04-15 | 2016-08-31 | 浙江大学 | A method of constructing a polymer three-dimensional structure based on a digitlization projection technique |
| CN110202784A (en) * | 2019-06-13 | 2019-09-06 | 中国科学院兰州化学物理研究所 | A kind of gray scale DLP Method of printing |
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| CN105904726A (en) * | 2016-04-15 | 2016-08-31 | 浙江大学 | A method of constructing a polymer three-dimensional structure based on a digitlization projection technique |
| CN110202784A (en) * | 2019-06-13 | 2019-09-06 | 中国科学院兰州化学物理研究所 | A kind of gray scale DLP Method of printing |
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