CN115433313B - Holographic photopolymer material, holographic volume grating device and preparation method thereof - Google Patents
Holographic photopolymer material, holographic volume grating device and preparation method thereof Download PDFInfo
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- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 claims description 8
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 8
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
Abstract
The invention relates to a mixed reality grating waveguide lens material. In particular to a holographic photopolymer material, a holographic volume grating device and a preparation method thereof. The holographic photopolymer material comprises liquid crystal, a photoinitiator, a co-initiator, a first monomer, a second monomer, a third monomer and a solvent in percentage by mass; the first monomer is selected from one or more of isobornyl methacrylate, 2-phenoxyethyl methacrylate and benzyl methacrylate; the second monomer is selected from one or more of ethylene glycol dimethacrylate, 4 (ethoxy) bisphenol A dimethacrylate and 1, 3-butanediol dimethacrylate; the third monomer is trimethylolpropane triacrylate. The technical problem of low grating diffraction efficiency of the holographic body grating device is solved.
Description
Technical Field
The invention relates to the technical field of mixed reality grating waveguide lens materials, in particular to a holographic photopolymer material, a holographic volume grating device and a preparation method thereof.
Background
Mixed Reality, english name Mixed Reality, abbreviated MR. The mixed reality technology introduces virtual scene information in a display environment, and an interactive feedback information loop is built between the real time, the virtual world and a user, so that the sense of reality of user experience is enhanced, and the mixed reality technology has the characteristics of reality, real-time interactivity, conception and the like.
MR is a rapidly developing field, widely applied to industries such as industry, education and training, entertainment, property, medical treatment and the like, and fully applied to a plurality of links such as marketing, operation, materials, service and the like. Mixed reality covers the scope of computer Augmented Reality (AR) technology, and technologies in which Artificial Intelligence (AI) and Quantum Computing (QC) are considered to be significantly improved in productivity and performance in three great future, and MR technology will be applied in various industries with iterative development of human technologies, particularly high development of 5G networks and communication technologies.
Among the optical imaging elements, the optical waveguide technology is a comparatively distinctive optical component that meets the requirements of AR glasses, and is considered as an essential option for consumer-grade AR glasses due to its thinness and high transmission characteristics of external light. The basis of the waveguide structure is a light, thin and transparent glass substrate, and the high refractive index glass substrate is adopted, so that the optical waveguide can be generally divided into a geometric optical waveguide (Geometric Waveguide) and a diffraction optical waveguide (Difractive Waveguide) according to the coupling structure of light entering and exiting the waveguide. Geometric optical waveguides are so-called array optical waveguides, which realize image output and frame enlargement by stacking array mirrors, representing that optical companies are Lumus in israel, and mass-produced eyeglass products have not yet appeared on the market. The diffraction optical waveguide mainly comprises a surface relief grating waveguide (Surface Relief Grating) manufactured by utilizing a photoetching technology and a holographic body grating waveguide (Volumetric Holographic Grating) manufactured based on a holographic interference technology, wherein Hololens2 and Magic lens One belong to the former, the holographic body grating waveguide uses a holographic body grating element to replace the relief grating, and the Akonia company purchased by apple company adopts the holographic body grating, and Digilens is also dedicated to the direction. This technique is also under development, with better color performance, but the current limit on FOV is also greater.
The requirements of the mixed reality glasses waveguide lens on diffraction efficiency are relatively high, and particularly the holographic waveguide lens is high. However, the grating diffraction efficiency of the holographic volume grating device prepared by the existing holographic photopolymer material is not high, so that the holographic photopolymer material with high diffraction efficiency is needed to be used for preparing the mixed reality spectacle waveguide lens. In addition, the holographic photopolymer material in the prior art is required to be post-cured after being processed into a holographic volume grating device, and the preparation method is complex, low in production efficiency and high in production cost.
Disclosure of Invention
Based on the above, the invention provides a holographic photopolymer material, which solves the technical problem of low grating diffraction efficiency of a holographic body grating device.
The holographic photopolymer material comprises the following components in percentage by mass:
the first monomer is selected from one or more of isobornyl methacrylate, 2-phenoxyethyl methacrylate and benzyl methacrylate;
the second monomer is selected from one or more of ethylene glycol dimethacrylate, 4 (ethoxy) bisphenol A dimethacrylate and 1, 3-butanediol dimethacrylate;
the third monomer is trimethylolpropane triacrylate.
In one embodiment, the holographic photopolymer material has a viscosity between 15cP and 100cP at 25 ℃.
In one embodiment, the liquid crystal is selected from one or more of BL087, MLC6882, TL213 and P0616A.
In one embodiment, the photoinitiator is selected from one of rhodamine B, rose bengal, irgacure784 (diphenyl titanocene fluoride), and pyrrole methylene 597.
In one embodiment, the co-initiator is selected from N-phenylglycine or benzoyl peroxide.
In one embodiment, the solvent is selected from one or more of N-vinyl pyrrolidone, chloroform, tetrahydrofuran, and toluene.
In one embodiment, the method comprises the following steps of:
the first monomer is a mixture of isobornyl methacrylate and benzyl methacrylate;
the second monomer is a mixture of 4 (ethoxy) bisphenol A dimethacrylate and 1, 3-butanediol dimethacrylate.
In one embodiment, the method comprises the following steps of:
the first monomer is a mixture of benzoyl peroxide and 2-phenoxyethyl methacrylate;
the second monomer is ethylene glycol dimethacrylate.
The invention also provides a preparation method of the holographic body grating device, post-curing is not needed, the preparation method is simple, the production efficiency is high, and the production cost is low.
The preparation method of the holographic volume grating device comprises the following steps:
the holographic photopolymer material is poured into a liquid crystal box, placed in a dark room in a static state, and then subjected to interference exposure under the interference light field of a double-beam light source.
In one embodiment, the thickness of the liquid crystal cell is 5 μm to 10 μm.
In one embodiment, the resting time in the darkroom is 10min-30min.
In one embodiment, the included angle of the dual beam light source is 35 ° -60 °.
In one embodiment, the interference exposure time is 1min-5min, and the irradiation power is 5+ -1 mW/cm 2 。
The invention also provides a holographic body grating device prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
according to the holographic photopolymerizing material, acrylic monomers with different functionalities are added, the viscosities of the first monomer, the second monomer and the third monomer are different, the system viscosity of the material is very suitable for exposure processing through proportion adjustment, the movement of the monomers is convenient in the processing process, the double bond structure on each monomer molecule can be very convenient to participate in the reaction, so that the conversion rate of the double bonds is improved, the refractive index of the material is increased due to the improvement of the conversion rate of the double bonds, the refractive index modulation degree of a grating is improved, and the diffraction efficiency is improved, namely, the three monomers are added simultaneously, the conversion efficiency of the double bonds can be improved through the effective space movement of the monomers in the curing process, and only a small amount of solvent is needed to be added for dilution, so that the holographic body grating device prepared from the holographic photopolymerizing material has higher grating diffraction efficiency. In addition, when the formula is adopted to prepare the holographic grating device, the direction and the speed of the movement of the material are matched with the reaction speed of the raw materials, the double bond conversion rate is high, the post-curing is not needed, namely, the holographic grating with diffraction performance can be formed without the post-curing process after the exposure is finished, the processing time is shortened, and the processing efficiency is improved.
Drawings
Fig. 1 is a diffraction efficiency distribution diagram of the hologram body grating devices prepared in each of examples and comparative examples.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
A holographic photopolymer material comprising in mass percent:
the first monomer is selected from one or more of isobornyl methacrylate, 2-phenoxyethyl methacrylate and benzyl methacrylate;
the second monomer is selected from one or more of ethylene glycol dimethacrylate, 4 (ethoxy) bisphenol A dimethacrylate and 1, 3-butanediol dimethacrylate;
the third monomer is trimethylolpropane triacrylate.
According to the holographic photopolymerizing material, the acrylic monomers with different functionalities are added, the viscosities of the first monomer, the second monomer and the third monomer are different, the system viscosity of the material is very suitable for exposure processing through proportion adjustment, the movement of the monomers is convenient in the processing process, the double bond structure on each monomer molecule can be very convenient to participate in the reaction, so that the conversion rate of the double bonds is improved, the refractive index of the material is increased due to the improvement of the conversion rate of the double bonds, the refractive index modulation degree of a grating is improved, and the diffraction efficiency is improved, namely, the three monomers are added simultaneously, the conversion efficiency of the double bonds can be improved through the effective space movement of the monomers in the curing process, and only a small amount of solvent is needed to be added for dilution, so that the holographic body grating device prepared from the holographic photopolymerizing material has higher grating diffraction efficiency. In addition, when the formula is adopted to prepare the holographic grating device, the direction and the speed of the movement of the material are matched with the reaction speed of the raw materials, the double bond conversion rate is high, the post-curing is not needed, namely, the holographic grating with diffraction performance can be formed without the post-curing process after the exposure is finished, the processing time is shortened, and the processing efficiency is improved.
Optionally, the holographic photopolymer material has a viscosity between 15cP and 100cP at 25 ℃. The viscosity is controlled within the range, so that the direction and the speed of the movement of the material are more favorably matched with the reaction speed of the raw material, and the double bond conversion rate is improved.
It is understood that the liquid crystal is nematic liquid crystal, optionally selected from one or more of BL087, MLC6882, TL213 and P0616A.
Optionally, the photoinitiator is selected from one of rhodamine B, rose bengal, irgacure784 (diphenyl titanocene fluoride) and pyrrole methylene 597.
Wherein, rhodamine B has the molecular formula: c (C) 28 H 31 ClN 2 O 3 Rose Bengal is also known as rhodamine and has the formula: c (C) 20 H 2 Cl 4 I 4 Na 2 O 5 。
Alternatively, the co-initiator is selected from N-phenylglycine or benzoyl peroxide.
Optionally, the solvent is selected from one or more of N-vinyl pyrrolidone, chloroform, tetrahydrofuran and toluene.
In a preferred embodiment thereof, the holographic photopolymer material comprises in mass percent:
the first monomer is a mixture of isobornyl methacrylate and benzyl methacrylate;
the second monomer is a mixture of 4 (ethoxy) bisphenol A dimethacrylate and 1, 3-butanediol dimethacrylate.
In a preferred embodiment thereof, the holographic photopolymer material comprises in mass percent:
the first monomer is a mixture of benzoyl peroxide and 2-phenoxyethyl methacrylate;
the second monomer is ethylene glycol dimethacrylate.
It will be appreciated that the holographic photopolymer material can be obtained by uniformly mixing the above-described raw materials. Methods of homogenizing the materials include, but are not limited to, ultrasonic dispersion of the materials described above.
The preparation method of the holographic grating device does not need post-curing, and has the advantages of simplicity, high production efficiency and low production cost.
The preparation method of the holographic volume grating device comprises the following steps:
the holographic photopolymer material is poured into a liquid crystal box, placed in a dark room in a static state, and then subjected to interference exposure under the interference light field of a double-beam light source.
Alternatively, the thickness of the liquid crystal cell is 5 μm to 10 μm.
Alternatively, the time of resting in the darkroom is 10min-30min.
Optionally, the included angle of the dual-beam light source is 35 ° -60 °.
Optionally, the interference exposure time is 1min-5min, and the irradiation power is 5+ -1 mW/cm 2 。
A holographic body grating device prepared by the preparation method.
The following examples and comparative examples are further described, and the raw materials used in the following examples are commercially available unless otherwise specified, and the equipment used in the examples are commercially available unless otherwise specified. The following examples and comparative examples use the starting materials or suppliers thereof:
BL087, MLC6882, TL213 from Merck, and P0616A from Slichem.
4 (ethoxy) bisphenol A dimethacrylate was purchased from Tianjin Jiuzu New Material Co., ltd;
pyrrole methylene 597 was purchased from guangdong Weng Jiang chemical company, inc.
Example 1
The embodiment provides a holographic photopolymer material and a preparation method thereof, a holographic volume grating device and a preparation method thereof, and the preparation method comprises the following steps:
step 1), weighing the following raw materials in percentage by mass:
rose bengal 0.1%, N-phenylglycine 1%, isobornyl methacrylate 10%,4 (ethoxy) bisphenol A dimethacrylate 40%, trimethylolpropane triacrylate 5%, N-vinylpyrrolidone 5%, MLC 6882.9%.
Step 2) preparation of holographic photopolymer Material
The raw materials are uniformly mixed in ultrasonic dispersion equipment to obtain the holographic photopolymer material, and the viscosity of the holographic photopolymer material at 25 ℃ is measured according to GB/T22235-2008 DIN53229 determination of liquid viscosity. The results show that the viscosity of the holographic photopolymer material of example 1 is 86cP.
Step 3) preparing a holographic volume grating device
Filling the holographic photopolymer material into a liquid crystal box, and controlling the thickness of the liquid crystal box to be 10 mu m; placing the poured liquid crystal box in a darkroom for 30min, and then placing the liquid crystal box in an interference light field of a double-beam light source with an included angle of 60 ℃ for interference exposure for 5min, wherein the irradiation power is 5mW/cm 2 Obtaining the holographic body grating device.
Step 4) diffraction efficiency test
And testing the diffraction efficiency of the holographic body grating device by using a grating diffraction efficiency tester.
The diffraction efficiency profile of the holographic grating device prepared in example 1 is shown in fig. 1, in which the abscissa represents the angle of the grating, and the diffraction efficiency values measured at different angles are different, and the highest point, i.e., the maximum value, generally represents the diffraction efficiency of the grating. As can be seen from fig. 1, the diffraction efficiency of the holographic volume grating device prepared in example 1 was 62%.
Example 2
The embodiment provides a holographic photopolymer material and a preparation method thereof, a holographic volume grating device and a preparation method thereof, and the preparation method comprises the following steps:
step 1), weighing the following raw materials in percentage by mass:
irgacure 784.5%, benzoyl peroxide 1.5%, 2-phenoxyethyl methacrylate 26%, ethylene glycol dimethacrylate 26%, trimethylolpropane triacrylate 6%, N-vinylpyrrolidone 7.5%, chloroform 2.5%, BL 087%.
Step 2) preparation of holographic photopolymer Material
The above raw materials were uniformly mixed in an ultrasonic dispersion apparatus to obtain a holographic photopolymer material, the viscosity of which was measured at 25℃and the test method was the same as in example 1.
The results show that the viscosity of the holographic photopolymer material of example 2 is 29cP.
Step 3) preparing a holographic volume grating device
Filling the holographic photopolymer material into a liquid crystal box, and controlling the thickness of the liquid crystal box to be 10 mu m; placing the poured liquid crystal box in a darkroom for 30min, and then placing the liquid crystal box in an interference light field of a double-beam light source with an included angle of 60 ℃ for interference exposure for 5min, wherein the irradiation power is 5mW/cm 2 Obtaining the holographic body grating device.
Step 4) diffraction efficiency test
The diffraction efficiency of the above-mentioned holographic volume grating device was tested in the same manner as in example 1.
As shown in fig. 1, the diffraction efficiency profile of the holographic volume grating device prepared in example 2 shows that the diffraction efficiency of the holographic volume grating device prepared in example 2 is 66% from fig. 1.
Example 3
The embodiment provides a holographic photopolymer material and a preparation method thereof, a holographic volume grating device and a preparation method thereof, and the preparation method comprises the following steps:
step 1), weighing the following raw materials in percentage by mass:
rhodamine B1.0%, benzoyl peroxide 2.5%, 2-phenoxyethyl methacrylate 40%,1, 3-butanediol dimethacrylate 10%, trimethylolpropane triacrylate 5%, N-vinylpyrrolidone 6%, TL 213.5%.
Step 2) preparation of holographic photopolymer Material
The above raw materials were uniformly mixed in an ultrasonic dispersion apparatus to obtain a holographic photopolymer material, the viscosity of which was measured at 25℃and the test method was the same as in example 1.
The results show that the viscosity of the holographic photopolymer material of example 3 is 37cP.
Step 3) preparing a holographic volume grating device
Filling the holographic photopolymer material into a liquid crystal box, and controlling the thickness of the liquid crystal box to be 10 mu m; placing the poured liquid crystal box in a darkroom for 30min, and then placing the liquid crystal box in an interference light field of a double-beam light source with an included angle of 60 ℃ for interference exposure for 5min, wherein the irradiation power is 5mW/cm 2 Obtaining the holographic body grating device.
Step 4) diffraction efficiency test
The diffraction efficiency of the above-mentioned holographic volume grating device was tested in the same manner as in example 1.
The diffraction efficiency profile of the holographic volume grating device prepared in example 3 is shown in fig. 1, and as can be seen from fig. 1, the diffraction efficiency of the holographic volume grating device prepared in example 3 is 58%.
Example 4
The embodiment provides a holographic photopolymer material and a preparation method thereof, a holographic volume grating device and a preparation method thereof, and the preparation method comprises the following steps:
step 1), weighing the following raw materials in percentage by mass:
pyrrole methylene 597.5%, benzoyl peroxide 5%, isobornyl methacrylate 19%, benzyl methacrylate 7%,4 (ethoxy) bisphenol A dimethacrylate 22%, trimethylolpropane triacrylate 6%, N-vinyl pyrrolidone 4.5%, toluene 1.5%, BL 087.5%.
Step 2) preparation of holographic photopolymer Material
The above raw materials were uniformly mixed in an ultrasonic dispersion apparatus to obtain a holographic photopolymer material, the viscosity of which was measured at 25℃and the test method was the same as in example 1.
The results show that the viscosity of the holographic photopolymer material of example 4 is 74cP.
Step 3) preparing a holographic volume grating device
Filling the holographic photopolymer material into a liquid crystal box, and controlling the thickness of the liquid crystal box to be 10 mu m; placing the poured liquid crystal box in a darkroom for 30min, and then placing the liquid crystal box in an interference light field of a double-beam light source with an included angle of 60 ℃ for interference exposure for 5min, wherein the irradiation power is 5mW/cm 2 Obtaining the holographic body grating device.
Step 4) diffraction efficiency test
The diffraction efficiency of the above-mentioned holographic volume grating device was tested in the same manner as in example 1.
As shown in fig. 1, the diffraction efficiency profile of the holographic volume grating device prepared in example 4 shows that the diffraction efficiency of the holographic volume grating device prepared in example 4 is 61% from fig. 1.
Example 5
The embodiment provides a holographic photopolymer material and a preparation method thereof, a holographic volume grating device and a preparation method thereof, and the preparation method comprises the following steps:
step 1), weighing the following raw materials in percentage by mass:
1% of rose bengal, 1% of N-phenylglycine, 16% of isobornyl methacrylate, 3% of benzyl methacrylate, 21% of 4 (ethoxy) bisphenol A dimethacrylate, 3% of 1, 3-butanediol dimethacrylate, 10% of trimethylolpropane triacrylate, 4% of tetrahydrofuran, 1% of chloroform and 40% of P0616A.
Step 2) preparation of holographic photopolymer Material
The above raw materials were uniformly mixed in an ultrasonic dispersion apparatus to obtain a holographic photopolymer material, the viscosity of which was measured at 25℃and the test method was the same as in example 1.
The results show that the viscosity of the holographic photopolymer material of example 4 is 71cP.
Step 3) preparing a holographic volume grating device
Filling the holographic photopolymer material into a liquid crystal box, and controlling the thickness of the liquid crystal box to be 10 mu m; placing the poured liquid crystal box in a darkroom for 30min, then placing in an interference light field of a double-beam light source with an included angle of 60 deg., performing interference exposure for 5min, and irradiatingThe power of the light is 5mW/cm 2 Obtaining the holographic body grating device.
Step 4) diffraction efficiency test
The diffraction efficiency of the above-mentioned holographic volume grating device was tested in the same manner as in example 1.
As shown in fig. 1, the diffraction efficiency profile of the holographic volume grating device prepared in example 5 shows that the diffraction efficiency of the holographic volume grating device prepared in example 5 is 74% from fig. 1.
Comparative example 1
The comparative example provides a holographic photopolymer material and a preparation method thereof, a holographic volume grating device and a preparation method thereof, and the steps are as follows:
step 1), weighing the following raw materials in percentage by mass:
1% of rose bengal, 5% of N-phenylglycine, 32% of dipentaerythritol hydroxy pentaacrylate, 20% of trimethylolpropane triacrylate, BL087, 37% of N-vinylpyrrolidone.
Step 2) preparation of holographic photopolymer Material
The above raw materials were uniformly mixed in an ultrasonic dispersion apparatus to obtain a holographic photopolymer material, the viscosity of which was measured at 25℃and the test method was the same as in example 1.
The results show that the viscosity of the holographic photopolymer material of comparative example 1 is 141cP.
Step 3) preparing a holographic volume grating device
Filling the holographic photopolymer material into a liquid crystal box, and controlling the thickness of the liquid crystal box to be 10 mu m; placing the poured liquid crystal box in a darkroom for 30min, and then placing the liquid crystal box in an interference light field of a double-beam light source with an included angle of 60 ℃ for interference exposure for 5min, wherein the irradiation power is 5mW/cm 2 Obtaining the holographic body grating device.
Step 4) diffraction efficiency test
The diffraction efficiency of the above-mentioned holographic volume grating device was tested in the same manner as in example 1.
As shown in fig. 1, the diffraction efficiency profile of the holographic volume grating device prepared in comparative example 1 shows that the diffraction efficiency of the holographic volume grating device prepared in comparative example 1 is 48%.
Comparative example 2
The present comparative example provides a holographic photopolymer material and a method of making the same, a holographic volume grating device and a method of making the same, substantially as in example 5, with the main difference that no third monomer is added, the steps being as follows:
step 1), weighing the following raw materials in percentage by mass:
1% of rose bengal, 1% of N-phenylglycine, 16% of isobornyl methacrylate, 3% of benzyl methacrylate, 26% of 4 (ethoxy) bisphenol A dimethacrylate, 8% of 1, 3-butanediol dimethacrylate, 4% of tetrahydrofuran, 1% of chloroform and 40% of P0616A.
Step 2) preparation of holographic photopolymer Material
The above raw materials were uniformly mixed in an ultrasonic dispersion apparatus to obtain a holographic photopolymer material, the viscosity of which was measured at 25℃and the test method was the same as in example 1.
The results show that the viscosity of the holographic photopolymer material of comparative example 2 is 116cP.
Step 3) preparing a holographic volume grating device
Filling the holographic photopolymer material into a liquid crystal box, and controlling the thickness of the liquid crystal box to be 10 mu m; placing the poured liquid crystal box in a darkroom for 30min, and then placing the liquid crystal box in an interference light field of a double-beam light source with an included angle of 60 ℃ for interference exposure for 5min, wherein the irradiation power is 5mW/cm 2 Obtaining the holographic body grating device.
Step 4) diffraction efficiency test
The diffraction efficiency of the above-mentioned holographic volume grating device was tested in the same manner as in example 1.
As shown in fig. 1, the diffraction efficiency profile of the holographic volume grating device prepared in comparative example 2 shows that the diffraction efficiency of the holographic volume grating device prepared in comparative example 2 is 24% from fig. 1.
Comparative example 3
This comparative example provides a holographic photopolymer material and a method of making the same, a holographic volume grating device and a method of making the same, substantially as in example 5, with the main difference being that the first monomer is replaced with ethoxyphenol acrylate and the second monomer is replaced with 1, 6-hexanediol diacrylate, as follows:
step 1), weighing the following raw materials in percentage by mass:
1% of rose bengal, 1% of N-phenylglycine, 19% of ethoxyphenol acrylate, 24% of 1, 6-hexanediol diacrylate, 10% of trimethylolpropane triacrylate, 4% of tetrahydrofuran, 1% of chloroform and 40% of P0616A.
Step 2) preparation of holographic photopolymer Material
The above raw materials were uniformly mixed in an ultrasonic dispersion apparatus to obtain a holographic photopolymer material, the viscosity of which was measured at 25℃and the test method was the same as in example 1.
The results show that the viscosity of the holographic photopolymer material of comparative example 3 is 54cP.
Step 3) preparing a holographic volume grating device
Filling the holographic photopolymer material into a liquid crystal box, and controlling the thickness of the liquid crystal box to be 10 mu m; placing the poured liquid crystal box in a darkroom for 30min, and then placing the liquid crystal box in an interference light field of a double-beam light source with an included angle of 60 ℃ for interference exposure for 5min, wherein the irradiation power is 5mW/cm 2 Obtaining the holographic body grating device.
Step 4) diffraction efficiency test
The diffraction efficiency of the above-mentioned holographic volume grating device was tested in the same manner as in example 1.
As can be seen from fig. 1, the diffraction efficiency profile of the holographic volume grating device prepared in comparative example 3 is 19%.
As can be seen from comparison of the examples and the comparative examples, the diffraction efficiency of the holographic body grating device manufactured in the examples 1-5 is significantly higher than that of the comparative examples 1-3, the viscosities of the first monomer, the second monomer and the third monomer are different due to the addition of acrylic monomers with different functionalities, the system viscosities of the materials are very suitable for exposure processing through proportion adjustment, the movement of the monomers is convenient in the processing process, the double bond structure on each monomer molecule can participate in the reaction very conveniently, the conversion rate of double bonds is improved, the refractive index of the materials is increased, the refractive index modulation degree of gratings is improved, and the diffraction efficiency is improved, that is, the three monomers in the examples 1-5 are simultaneously added, the conversion efficiency of double bonds can be improved through the effective space movement of the monomers in the curing process, and the holographic body grating device manufactured by the obtained holographic photopolymerized material has higher diffraction efficiency.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A holographic photopolymer material, comprising in mass percent:
30% -40% of liquid crystal;
0.1 to 1.5 percent of photoinitiator;
1% -5% of a co-initiator;
10% -40% of a first monomer;
10% -40% of a second monomer;
5% -10% of a third monomer;
5% -10% of solvent;
the first monomer is selected from one or more of isobornyl methacrylate, 2-phenoxyethyl methacrylate and benzyl methacrylate;
the second monomer is selected from one or more of ethylene glycol dimethacrylate, 4 (ethoxy) bisphenol A dimethacrylate and 1, 3-butanediol dimethacrylate;
the third monomer is trimethylolpropane triacrylate;
the liquid crystal is nematic liquid crystal.
2. The holographic photopolymer material of claim 1, wherein the holographic photopolymer material has a viscosity between 15cP and 100cP at 25 ℃.
3. Holographic photopolymer material according to claim 2, wherein the liquid crystal is selected from one or several of BL087, MLC6882, TL213 and P0616A.
4. The holographic photopolymer material of claim 2, wherein the photoinitiator is selected from one of rhodamine B, rose bengal, irgacure784, and pyrrole methylene 597.
5. Holographic photopolymer material according to claim 2, wherein the co-initiator is selected from N-phenylglycine or benzoyl peroxide.
6. Holographic photopolymer material according to claim 2, wherein the solvent is selected from one or more of N-vinyl pyrrolidone, chloroform, tetrahydrofuran and toluene.
7. The preparation method of the holographic volume grating device is characterized by comprising the following steps of:
a holographic photopolymer material according to any one of claims 1 to 6 is poured into a liquid crystal cell, placed stationary in a dark room, and then subjected to interference exposure under the interference light field of a dual beam light source.
8. The method of manufacturing a holographic grating device of claim 7, wherein the interference exposure time is 1min-5min and the illumination power is 5 ± 1mW/cm 2 。
9. The method of manufacturing a holographic volume grating device of claim 7, in which the included angle between the two light beam sources is between 35 ° and 60 °.
10. A holographic volume grating device prepared by the method of any one of claims 7-9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5942157A (en) * | 1996-07-12 | 1999-08-24 | Science Applications International Corporation | Switchable volume hologram materials and devices |
| JP2008209932A (en) * | 2008-03-12 | 2008-09-11 | Sony Corp | Polarization selecting hologram optical device |
| CN101551542A (en) * | 2009-05-14 | 2009-10-07 | 复旦大学 | Electric control switch type holographic polymer dispersed liquid crystal diffractive beam splitter |
| WO2013013532A1 (en) * | 2011-07-26 | 2013-01-31 | 华中科技大学 | Method for preparing colorful three-dimensional hologram based on holographic polymer dispersed liquid crystal grating |
-
2021
- 2021-06-04 CN CN202110625837.5A patent/CN115433313B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5942157A (en) * | 1996-07-12 | 1999-08-24 | Science Applications International Corporation | Switchable volume hologram materials and devices |
| JP2008209932A (en) * | 2008-03-12 | 2008-09-11 | Sony Corp | Polarization selecting hologram optical device |
| CN101551542A (en) * | 2009-05-14 | 2009-10-07 | 复旦大学 | Electric control switch type holographic polymer dispersed liquid crystal diffractive beam splitter |
| WO2013013532A1 (en) * | 2011-07-26 | 2013-01-31 | 华中科技大学 | Method for preparing colorful three-dimensional hologram based on holographic polymer dispersed liquid crystal grating |
Non-Patent Citations (2)
| Title |
|---|
| Improvement of the Performance of Transmission Holographic Grating by Hydrolysis-induced Change of the Property of Polymer Matrix;Xin WANG et al;《Polymer Journal》;第40卷(第7期);第601-606页 * |
| 基于丙烯酸酯的全息聚合物分散液晶光栅的动力学理论研究;郑致刚 等;《物理学报》;第56卷(第1期);第15-24页 * |
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