WO2024107034A1 - Composition polymère photoréactive, support d'enregistrement optique la comprenant et procédé de fabrication d'une structure tridimensionnelle l'utilisant - Google Patents

Composition polymère photoréactive, support d'enregistrement optique la comprenant et procédé de fabrication d'une structure tridimensionnelle l'utilisant Download PDF

Info

Publication number
WO2024107034A1
WO2024107034A1 PCT/KR2023/018708 KR2023018708W WO2024107034A1 WO 2024107034 A1 WO2024107034 A1 WO 2024107034A1 KR 2023018708 W KR2023018708 W KR 2023018708W WO 2024107034 A1 WO2024107034 A1 WO 2024107034A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
polymer composition
block
photoreactive
polymer
Prior art date
Application number
PCT/KR2023/018708
Other languages
English (en)
Korean (ko)
Inventor
이승우
방준하
김광진
홍승재
임용준
백동재
Original Assignee
고려대학교 산학협력단
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020230158278A external-priority patent/KR102719988B1/ko
Application filed by 고려대학교 산학협력단 filed Critical 고려대학교 산학협력단
Publication of WO2024107034A1 publication Critical patent/WO2024107034A1/fr

Links

Images

Classifications

    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/09—Beam shaping, e.g. changing the cross-sectional area, not otherwise provided for
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/04—Processes or apparatus for producing holograms

Definitions

  • the present invention relates to a photoreactive polymer composition, an optical recording medium containing the same, and a method of manufacturing a three-dimensional structure using the same.
  • a hologram recording medium records information by changing the refractive index within the recording medium through an exposure process, and reproduces the information by reading the change in the refractive index within the recorded recording medium.
  • the optical interference pattern can be easily stored as a hologram by photopolymerization of low-molecular monomers, so optical lenses, mirrors, deflection mirrors, filters, diffusion screens, diffraction members, light guides, and waveguides , holographic optical elements that function as projection screens and/or masks, media and light diffusion plates in optical memory systems, optical wavelength splitters, and reflective and transmissive color filters can be used in various fields.
  • a photoreactive polymer composition for hologram production includes a polymer binder (matrix), a monomer, and a photoinitiator, and laser interference light is irradiated to a photosensitive film prepared from this composition to induce local photopolymerization of the monomer.
  • the refractive index increases in areas where there is a relatively large amount of monomer, and the refractive index becomes relatively low in areas where there is a relatively large amount of polymer binder, resulting in refractive index modulation.
  • This refractive index modulation creates a diffraction grating.
  • U.S. Patent 4,942,102 July 17, 1990 discloses acrylic and/or vinyl type monomers, polymer binders (polyvinyl acetate, polyvinyl acetal, polyvinyl formal ( A photoreactive polymer composition using polyvinyl formal or polyvinyl butyral), a plasticizer, and a photoinitiation system is disclosed, and US Patent 4,959,284 (September 25, 1990) discloses a photoreactive polymer composition using cyclo as a monomer component.
  • a photoreactive polymer composition using diethylamino) phenyl] Methylene ⁇ ) (DEAW) is disclosed.
  • One technical problem to be solved by the present invention is to provide a photoreactive polymer composition that can be used in the production of a three-dimensional structure and an optical recording medium containing the same.
  • Another technical problem to be solved by the present invention is to provide a photoreactive polymer composition that can be used to produce holograms and an optical recording medium containing the same.
  • Another technical problem to be solved by the present invention is to provide a photoreactive polymer composition with high light sensitivity and an optical recording medium containing the same.
  • Another technical problem to be solved by the present invention is to provide a photoreactive polymer composition with an improved monomer diffusion rate and an optical recording medium containing the same.
  • Another technical problem to be solved by the present invention is to provide a photoreactive polymer composition with improved recording speed and an optical recording medium containing the same.
  • Another technical problem to be solved by the present invention is to provide a photoreactive polymer composition with improved recording efficiency and an optical recording medium containing the same.
  • the present invention provides a photoreactive polymer composition.
  • the photoreactive polymer composition includes a polymer matrix, a monomer, and a photoinitiator, wherein the polymer matrix is a copolymer of a first block forming the main chain and a second block forming a side branch. ) may include.
  • the first polymer included in the first block includes a polymer with a degree of polymerization (DP) of less than 300, and the second polymer included in the second block has a lower DP than the first polymer. May contain polymers.
  • DP degree of polymerization
  • the photoreactive polymer composition may include one that reacts with light with a wavelength of 300 nm to 800 nm.
  • the first block may include poly-norbornene
  • the second block may include poly(methyl methacrylate).
  • the polymer matrix includes a copolymer represented by ⁇ Formula 1> below, wherein the first block includes a compound represented by A in ⁇ Formula 1> and the second block has ⁇ Formula 1> It may include the compound represented by B in 1>.
  • the first block may include Poly(2-(2-bromoisobutyryloxy)ethyl methacrylate), and the second block may include Poly(methyl methacrylate).
  • the polymer matrix includes a copolymer represented by ⁇ Formula 2> below, wherein the first block includes a compound represented by A in ⁇ Formula 2> and the second block has ⁇ Formula 2> 2> may include a compound represented by B.
  • the monomer is capable of radical polymerization and may have a refractive index of 1.4 to 1.6.
  • the photoinitiator may include a dye, a photoinitiator, or a combination thereof that absorbs light and generates radicals.
  • the photoreactive polymer composition includes a radical photoinitiator, a monomer capable of radical polymerization, and a copolymer of a norbornene-based first block and an acrylate-based second block. It may include a polymer matrix containing.
  • the polymer matrix includes a copolymer represented by ⁇ Formula 1> below, wherein the first block includes a compound represented by A in ⁇ Formula 1> and the second block has ⁇ Formula 1> It may include the compound represented by B in 1>.
  • the photoreactive polymer composition includes a radical photoinitiator, a monomer capable of radical polymerization, an acrylate-based first block with a relatively large molecular weight, and an acrylate with a relatively small molecular weight. It may include a copolymer of an (acrylate)-based second block.
  • the polymer matrix includes a copolymer represented by ⁇ Formula 2> below, wherein the first block includes a compound represented by A in ⁇ Formula 2> and the second block is ⁇ It may include a compound represented by B in Formula 2>.
  • the present invention provides an optical recording medium.
  • the optical recording medium includes a polymer matrix, a monomer, and a photoinitiator, wherein the polymer matrix is a copolymer of a first block forming a main chain and a second block forming side branches. It may include a photo-reactive composition containing a.
  • the present invention provides a method for manufacturing a three-dimensional structure.
  • the method of manufacturing the three-dimensional structure includes a polymer matrix, a monomer, and a photoinitiator, wherein the polymer matrix is a copolymer of a first block forming the main chain and a second block forming a side branch.
  • Preparing an optical recording medium in which a photoreactive composition containing a (copolymer) is prepared on a substrate making light modulated by a light modulation element to have a three-dimensional pattern structure incident on the photoreactive polymer composition of the optical recording medium. It may include a step of reacting light having the three-dimensional pattern structure with the photo-reactive polymer composition, and recording a three-dimensional pattern structure on the photo-reactive polymer composition.
  • the photoreactive polymer composition according to an embodiment of the present invention includes a polymer matrix, a monomer, and a photoinitiator, wherein the polymer matrix is a copolymer of a first block forming the main chain and a second block forming side branches. ) may include. Accordingly, photosensitivity can be improved and the diffusion rate of monomer can be improved, which can improve recording speed and recording efficiency.
  • FIG. 1 is a diagram for explaining the process of manufacturing a polymer matrix of a photoreactive polymer composition according to a first embodiment of the present invention.
  • Figure 2 is a diagram for explaining the process of activating the photoinitiator of the photoreactive polymer composition according to the first embodiment of the present invention.
  • Figure 3 is a diagram for explaining the polymer matrix manufacturing process of the photoreactive polymer composition according to the second embodiment of the present invention.
  • Figures 4 and 5 are schematic diagrams of a three-dimensional structure manufacturing apparatus using a photoreactive polymer composition according to an embodiment of the present invention.
  • FIG. 6 is a diagram illustrating an example of a metasurface mask that can be used as a light modulation device.
  • Figure 7 is a diagram showing an example of a pattern formed when light is irradiated to a photoreactive polymer composition.
  • Figures 8 and 9 are diagrams to explain the difference between an area irradiated with light and an area not irradiated with light in a photoreactive polymer composition.
  • Figure 10 is a diagram to explain the physical property gradient within the pattern formed as light is irradiated to the photoreactive polymer composition.
  • Figure 11 is a diagram for explaining the products produced in steps S13 and S14 during the manufacturing process of the polymer matrix according to Experimental Example 1 of the present invention.
  • Figures 12 and 13 are graphs showing the results of experiments to confirm the products produced in steps S13 and S14 during the manufacturing process of the polymer matrix according to Experimental Example 1 of the present invention.
  • Figure 14 is a diagram showing the results of an experiment to confirm the product produced in step S21 during the manufacturing process of the polymer matrix according to Experimental Example 2 of the present invention.
  • Figures 15 and 16 are diagrams showing the results of an experiment to confirm the product produced in step S22 during the manufacturing process of the polymer matrix according to Experimental Example 2 of the present invention.
  • Figure 17 is a photograph taken of the optical recording medium according to Comparative Example 1-1 of the present invention.
  • Figure 18 is a diagram for explaining the results of measuring the thickness and diffraction efficiency of an optical recording medium according to Comparative Example 1-1 of the present invention.
  • Figure 19 is a photograph taken of the optical recording medium according to Experimental Example 1-1 of the present invention.
  • Figure 20 is a diagram for explaining the results of measuring the thickness and diffraction efficiency of an optical recording medium according to Experimental Example 1-1 of the present invention.
  • Figure 21 is a photograph taken of the optical recording medium according to Comparative Example 1-2 of the present invention.
  • Figure 22 is a diagram for explaining the results of measuring the thickness and diffraction efficiency of an optical recording medium according to Comparative Example 1-2 of the present invention.
  • Figure 23 is a photograph taken of the optical recording medium according to Experimental Example 1-2 of the present invention.
  • Figure 24 is a diagram for explaining the results of measuring the thickness and diffraction efficiency of an optical recording medium according to Experimental Example 1-2 of the present invention.
  • first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are merely used to distinguish one component from another. Accordingly, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiment. Additionally, in this specification, 'and/or' is used to mean including at least one of the components listed before and after.
  • connection is used to include both indirectly connecting a plurality of components and directly connecting them.
  • Figure 1 is a diagram for explaining the process of manufacturing a polymer matrix of a photoreactive polymer composition according to a first embodiment of the present invention
  • Figure 2 is a diagram showing the process of activating a photoinitiator of a photoreactive polymer composition according to a first embodiment of the present invention. This is a drawing to explain the process.
  • the photoreactive polymer composition according to the first embodiment of the present invention may include a polymer matrix, a monomer, a photoinitiator, and a solvent.
  • the polymer matrix may be included in an amount of 20 wt%
  • the monomer may be included in an amount of 16 wt% to 18 wt%
  • the photoinitiator may be included in an amount of 2 wt% or more and 4 wt% or less
  • the solvent may be included in an amount of 60 wt%, but is not limited to the above-described composition.
  • the polymer matrix may include a copolymer of a first block forming the main chain and a second block forming a side branch.
  • the first block may include a first polymer with a relatively high molecular weight. More specifically, the first polymer may include a polymer with a degree of polymerization (DP) of less than 300.
  • the first polymer may include poly-norbornene (PNB).
  • the second block may include a second polymer with a relatively low molecular weight. More specifically, the second polymer may include a polymer with a lower DP than the first polymer.
  • the second polymer may include poly(methyl methacrylate) (PMMA).
  • the first block forming the main chain and the second block forming the side branches can form a copolymer.
  • Various polymers may be used as the first polymer and the second polymer. That is, the types of polymers that can be used as the first polymer of the first block and the second polymer of the second block are not limited.
  • a problem may occur in which the polymer film is not properly formed.
  • a polymer having a higher DP than the first polymer is used as the second polymer, a problem in which the polymer matrix becomes entangled may occur.
  • the polymer matrix may include a graft copolymer of PNB and PMMA (PNB-g-PMMA),
  • the polymer matrix can be expressed as ⁇ Formula 1> below.
  • the first block may be defined as a block containing the compound represented by A in ⁇ Formula 1>
  • the second block may be defined as a block containing the compound represented by B in ⁇ Formula 2>.
  • the polymer matrix as shown in Figure 1, is a compound represented by ⁇ Formula 3> and a compound represented by ⁇ Formula 4> with tetraethylammonium (TEA) and toluene.
  • TEA tetraethylammonium
  • first intermediate represented by ⁇ Formula 5> (S11)
  • second intermediate represented by ⁇ Formula 7> (S12)
  • the second intermediate is methyl methacrylate (Methyl methacrylate) , MMA), Copper(I) bromide, Cubr, N,N,N',N'',N''-Pentamethyldiethylenetriamine (PMDETA), and anisole to form ⁇ Formula 8>.
  • the ⁇ Formula 3> to ⁇ Formula 8> are as follows.
  • a copolymer of a first block forming the main chain and a second block forming a side branch e.g., PNB-g-PMMA
  • a linear polymer e.g.
  • the monomer diffusion rate of the photoreactive polymer composition can be improved compared to the case where Linear PMMA
  • recording speed and recording efficiency using the photoreactive polymer composition can be significantly improved.
  • the monomer is a material capable of radical polymerization.
  • the refractive index is relatively high in areas where a relatively large amount of polymer formed by the monomer exists, and the area where the polymer matrix is present in a relatively large amount.
  • the refractive index is relatively low, resulting in refractive index modulation, and a diffraction grating can be created by this refractive index modulation.
  • the monomer may have a refractive index of 1.4 to 1.6.
  • the monomer has a refractive index other than the above-mentioned refractive index, when recording a structure for hologram purposes, diffraction of the recorded medium may not occur properly, which may cause a problem in which the function as a hologram is lost.
  • the monomer may include either acrylate or acrylamide.
  • benzyl methacrylate (BZMA) represented by ⁇ Formula 9> may be used as the monomer.
  • the monomer is a (meth)acrylate-based ⁇ , ⁇ -unsaturated carboxylic acid derivative, specifically (meth)acrylate, (meth)acrylamide, and (meth)acrylonitrile.
  • it may include (meth)acrylic acid, or a compound containing a vinyl group or a thiol group, but is not limited thereto.
  • the photoinitiator is a compound that is activated by light and can initiate the polymerization of a compound containing a photoreactive functional group such as the monomer.
  • the photoinitiator may include a dye, a photoinitiator, or a combination thereof that absorbs light and generates radicals.
  • the photoinitiator may include a radical photopolymerization initiator.
  • the photoinitiator may include a photocationic polymerization initiator or a photoanionic polymerization initiator.
  • irgacure represented by ⁇ Formula 10> below may be used as the photoinitiator, and in this case, an activation reaction by light may occur as shown in FIG. 2.
  • methylorange, methylenblue, etc. may be used as the photoinitiator, but are not limited thereto.
  • the solvent is used to disperse the above-mentioned components (polymer matrix, monomer, and photoinitiator), and according to one embodiment, solvents such as ketones, alcohols, acetates, and ethers may be used.
  • the solvent may be ketones such as methyl ethyl canone, methyl isobutyl ketone, acetylacetone, or isobutyl ketone, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, or t-butanol.
  • Alcohols such as ethyl acetate, i-propyl acetate, acetates such as polyethylene glycol monomethyl ether acetate, ethers such as tetrahydrofuran or propylene glycol monomethyl ether, or mixtures of two or more thereof can be used. there is.
  • Figure 3 is a diagram for explaining the polymer matrix manufacturing process of the photoreactive polymer composition according to the second embodiment of the present invention.
  • the photoreactive polymer composition according to the second embodiment of the present invention may include a polymer matrix, a monomer, a photoinitiator, and a solvent.
  • the polymer matrix may be included in an amount of 19 wt%
  • the monomer may be included in an amount of 19 wt%
  • the photoinitiator may be included in an amount of 2 wt%.
  • the solvent may be included in an amount of 60 wt%, but is not limited to the above-described composition.
  • the polymer matrix may include a copolymer of a first block forming the main chain and a second block forming a side branch.
  • the first block may include a first polymer with a relatively high molecular weight.
  • the first polymer may include poly(2-(2-bromoisobutyryloxy)ethyl methacrylate) (PBiBEM).
  • the second block may include a second polymer with a relatively low molecular weight.
  • the second polymer may include poly(methyl methacrylate) (PMMA).
  • PBiBEM has been exemplarily described as the first polymer
  • PMMA has been exemplarily described as the second polymer
  • the first block forming the main chain and the second block forming the side branches can form a copolymer.
  • Various polymers may be used as the first polymer and the second polymer. That is, the types of polymers that can be used as the first polymer of the first block and the second polymer of the second block are not limited.
  • the polymer matrix may include a graft copolymer of PBiBEM and PMMA (PBiBEM-g-PMMA),
  • PBiBEM-g-PMMA graft copolymer of PBiBEM and PMMA
  • the polymer matrix can be expressed as ⁇ Formula 2> below.
  • the first block may be defined as a block containing the compound represented by A in ⁇ Formula 2>
  • the second block may be defined as a block containing the compound represented by B in ⁇ Formula 2>.
  • the polymer matrix includes a compound represented by ⁇ Formula 11> and a compound represented by ⁇ Formula 12> with tetraethylammonium (TEA) and dichloromethane.
  • TEA tetraethylammonium
  • S21 of mixing with (dichloromethane, DCM) at 0°C to form an inimer (Inimer 1) represented by ⁇ Formula 13>, the compound represented by ⁇ Formula 14> as the inimer (Inimer 1), no.
  • a copolymer of a first block forming the main chain and a second block forming a side branch e.g., PBiBEM-g-PMMA
  • a linear polymer e.g.
  • the monomer diffusion rate of the photoreactive polymer composition can be improved compared to the case where Linear PMMA
  • recording speed and recording efficiency using the photoreactive polymer composition can be significantly improved.
  • the monomer is a material capable of radical polymerization.
  • the refractive index is relatively high in areas where a relatively large amount of polymer formed by the monomer exists, and the area where the polymer matrix is present in a relatively large amount.
  • the refractive index is relatively low, resulting in refractive index modulation, and a diffraction grating can be created by this refractive index modulation.
  • the monomer may include either acrylate or acrylamide.
  • benzyl methacrylate (BZMA) represented by ⁇ Formula 9> may be used as the monomer.
  • the monomer is a (meth)acrylate-based ⁇ , ⁇ -unsaturated carboxylic acid derivative, specifically (meth)acrylate, (meth)acrylamide, and (meth)acrylonitrile.
  • it may include (meth)acrylic acid, or a compound containing a vinyl group or thiol group, but is not limited thereto.
  • the photoinitiator is a compound that is activated by light and can initiate the polymerization of a compound containing a photoreactive functional group such as the monomer.
  • the photoinitiator may include a radical photopolymerization initiator.
  • the photoinitiator may include a photocationic polymerization initiator or a photoanionic polymerization initiator.
  • irgacure represented by ⁇ Formula 10> below may be used as the photoinitiator, and in this case, an activation reaction by light may occur as shown in FIG. 2.
  • methylorange, methylenblue, etc. may be used as the photoinitiator, but are not limited thereto.
  • the solvent is used to disperse the above-mentioned components (polymer matrix, monomer, and photoinitiator), and according to one embodiment, solvents such as ketones, alcohols, acetates, and ethers may be used.
  • the solvent may be ketones such as methyl ethyl canone, methyl isobutyl ketone, acetylacetone, or isobutyl ketone, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, or t-butanol.
  • Alcohols such as ethyl acetate, i-propyl acetate, acetates such as polyethylene glycol monomethyl ether acetate, ethers such as tetrahydrofuran or propylene glycol monomethyl ether, or mixtures of two or more thereof can be used. there is.
  • the photoreactive polymer composition according to the above-described first embodiment and the photoreactive polymer composition according to the second embodiment can be used as a medium for optical recording.
  • an optical recording medium may be prepared by coating the photoreactive polymer composition according to the above embodiments on a substrate.
  • Figures 4 and 5 are schematic diagrams of a three-dimensional structure manufacturing apparatus using a photoreactive polymer composition according to an embodiment of the present invention
  • Figure 6 is a diagram showing an example of a metasurface mask that can be used as a light modulation element.
  • FIG. 7 is a diagram showing an example of a pattern formed as light is irradiated to a photoreactive polymer composition
  • FIGS. 8 and 9 illustrate the difference between an area irradiated with light and an area not irradiated to the photoreactive polymer composition.
  • Figure 10 is a diagram for explaining the physical property gradient within the pattern formed as light is irradiated to the photoreactive polymer composition.
  • the three-dimensional structure manufacturing apparatus includes a light source (1), a first lens (2), a second lens (3), an optical modulation element (4), and an optical recording medium (5). It can be included.
  • the light source 1 is for generating light, and according to one embodiment, it can generate laser light, which is a coherent single light.
  • the first lens 2 and the second lens 3 may be disposed in a direction in which the light L 1 generated from the light source 1 is irradiated.
  • the first lens 2 and the second lens 3 may transmit light L 1 generated from the light source 1 .
  • the light L 1 generated from the light source 1 may transmit the first lens 2 and then the second lens 3 .
  • the first lens 2 and the second lens 3 are beam expanders and can expand the size of the light L 1 generated from the light source 1.
  • the first lens 2 and the second lens 3 may be omitted. However, if the first lens 2 and the second lens 3 are omitted, it may become difficult to manufacture a large area of the finally created three-dimensional structure.
  • the first lens 2 and the second lens 3 are arranged in the direction in which the light L 1 generated from the light source 1 is irradiated, so that the light L 1 generated from the light source 1 is irradiated. ) By increasing the size, large-area manufacturing of the final three-dimensional structure can be made more easily.
  • Light L 1 transmitted through the first lens 2 and the second lens 3 may be provided to the light modulation element 4 .
  • the light L 1 provided to the light modulation device 4 may transmit the light modulation device 4
  • the transmitted light L 2 may be light modulated by the light modulation device 4 .
  • the light modulation device 4 polarizes and/or diffracts the light (L 1 ) to form a spatial change in intensity, and includes a photo mask, a phase modulation mask, a meta-surface mask, Diffraction grating, etc. may be used, but are not limited thereto.
  • the light modulation device 4 generates diffracted lights of different orders (for example, 0th order, +1st order, -1st order, etc.) with respect to the incident light (L 1 ).
  • light L 2 having a three-dimensional pattern structure (for example, a structure in which spatial changes in intensity are arranged three-dimensionally) can be generated through interference of the generated diffracted lights. That is, the light L 1 may be modulated into light L 2 having a three-dimensional pattern structure by passing through the light modulation element 4 .
  • the meta-surface mask includes a base substrate and a pattern structure disposed on the base substrate to be spaced apart from each other, and the light (L 1 ) transmitted through the meta-surface mask forms a three-dimensional pattern. It can be modulated into light (L 2 ) having a structure.
  • the spacing d between the patterns P of the pattern structure and the wavelength ⁇ of the light L 1 irradiated to the light modulation device 4 may satisfy ⁇ Equation 1> below. .
  • phase and diffraction can be controlled independently depending on the location by arranging structures (metatoms) of different shapes spatially, and the degree of freedom in spatial arrangement of each metaatom is high, so the ⁇ Equation 2> A more complex 3D interference pattern can be created.
  • the pattern structure of the meta-surface mask may be formed of at least one of silicon, silica (SiO 2 ), TiO 2 , quartz, Ge, GaAs, or Au, and the base substrate may be made of glass, It may be formed of at least one of SiO 2 , TiO 2 , quartz, or a transparent polymer.
  • the optical recording medium 5 may include a substrate (S) and a photoreactive polymer composition (LPM) provided on the substrate (S).
  • S substrate
  • LPM photoreactive polymer composition
  • the modulated light (L 2 ) is irradiated to the photo-reactive polymer composition (LPM)
  • the monomer in the photo-reactive polymer composition (LPM) is irradiated to the area (P 1 ) to which the modulated light (L 2 ) is irradiated.
  • photoreactive monomers may diffuse and form a polymer using the monomers. Accordingly, the content of the polymer increases relatively in the area (P 1 ) to which the modulated light (L 2 ) is irradiated within the photoreactive polymer composition (LPM), while the modulated light (L 2 ) is irradiated to the area (P 1 ).
  • the content of the polymer matrix may be relatively high in the unused area (P 2 ).
  • a gradient of physical properties may be formed within the area P 1 to which the modulated light L 2 is irradiated. More specifically, as shown in FIG. 10, the gradient of physical properties in the direction from the first side wall (SW 1 ) to the second side wall (SW 2 ) of the area (P 1 ) to which the modulated light (L 2 ) is irradiated
  • a profile having a profile can be formed.
  • the gradient of physical properties may be formed in the form of a sine wave.
  • the gradient of physical properties may be formed in a gradually decreasing or gradually increasing form.
  • the gradient of physical properties may be formed in a form that increases and then decreases, or decreases and then increases.
  • the three-dimensional pattern structure of the modulated light (L 2 ) may be reflected in the photoreactive polymer composition (LPM).
  • LPM photoreactive polymer composition
  • the light L 1 generated from the light source L has a three-dimensional pattern structure (for example, a structure in which spatial changes in intensity are arranged three-dimensionally) by the light modulation element 4. It is modulated with light (L 2 ), and as the modulated light (L 2 ) is incorporated into the photo-reactive polymer composition (LPM), a three-dimensional pattern structure may be recorded on the photo-responsive polymer composition (LPM). Because of this, a three-dimensional structure with a three-dimensional pattern structure recorded on the photoreactive polymer composition (LPM) can be manufactured.
  • a three-dimensional pattern structure for example, a structure in which spatial changes in intensity are arranged three-dimensionally
  • Figure 11 is a diagram for explaining the products produced in steps S13 and S14 during the manufacturing process of the polymer matrix according to Experimental Example 1 of the present invention
  • Figures 12 and 13 are diagrams of the polymer matrix according to Experimental Example 1 of the present invention. This is a graph showing the results of experiments to confirm the products produced in steps S13 and S14 during the manufacturing process.
  • step S13 third intermediate
  • step S14 photoreactive polymer composition during the manufacturing process of the polymer matrix according to Experimental Example 1
  • the product produced in step S13 is defined as NB-PMMA
  • the product produced in step S14 is defined as PNB-g-PMMA.
  • the intensity (Intensity, a.u.) according to time (Time, min) was measured for each of NB-PMMA, the product produced in step S13, and PNB-g-PMMA, the product produced in step S14.
  • the results are shown, and referring to Figure 13, the NMR analysis results are shown for each of NB-PMMA, the product produced in step S13, and PNB-g-PMMA, the product produced in step S14.
  • FIGS. 12 and 13 it can be confirmed that NB-PMMA and PNB-g-PMMA were produced in steps S13 and S14, respectively.
  • Figure 14 is a diagram showing the results of an experiment to confirm the product produced in step S21 during the manufacturing process of the polymer matrix according to Experimental Example 2 of the present invention
  • Figures 15 and 16 are the polymer matrix according to Experimental Example 2 of the present invention
  • This is a diagram showing the results of an experiment to confirm the product produced in step S22 during the manufacturing process.
  • the structural formula and NMR analysis results of the product produced in step S21 during the manufacturing process of the polymer matrix according to Experimental Example 2 are shown
  • Figure 15 shows the S22 during the manufacturing process of the polymer matrix according to Experimental Example 2.
  • the structural formula of the product generated in the step and the results of measuring the intensity (A.U.) according to time (Time, min) are shown.
  • FIG. 16 it is generated in step S22 during the manufacturing process of the polymer matrix according to Experimental Example 2.
  • the results of NMR analysis of the product are shown. As can be seen in Figures 14 to 16, it can be confirmed that the reactions in steps S21 and S22 were easily performed.
  • the optical recording medium according to Experimental Example 1-1 was manufactured by coating the photoreactive polymer composition according to Experimental Example 1 on a substrate to a thickness of 200 ⁇ m.
  • the photoreactive polymer composition according to Experimental Example 1 was used, but PNB with a molecular weight of 270k was used.
  • the optical recording medium according to Experimental Example 1-2 was manufactured by coating the photoreactive polymer composition according to Experimental Example 1 on a substrate to a thickness of 50 ⁇ m.
  • the photoreactive polymer composition according to Experimental Example 1 was used, but PNB with a molecular weight of 270k was used.
  • An optical recording medium according to Comparative Example 1-1 was manufactured by coating a photoreactive polymer composition containing linear PMMA with a molecular weight of 350k on a substrate to a thickness of 200 ⁇ m.
  • An optical recording medium according to Comparative Example 1-2 was manufactured by coating a photoreactive polymer composition containing linear PMMA with a molecular weight of 350k on a substrate to a thickness of 25 ⁇ m.
  • FIG. 17 is a photograph taken of the optical recording medium according to Comparative Example 1-1 of the present invention
  • FIG. 18 is a view illustrating the results of measuring the thickness and diffraction efficiency of the optical recording medium according to Comparative Example 1-1 of the present invention.
  • FIG. 17 a photograph of the optical recording medium according to Comparative Example 1-1 is shown
  • FIG. 18 shows the results of measuring the thickness and diffraction efficiency of the optical recording medium according to Comparative Example 1-1.
  • Figure 18 (a) shows the thickness ( ⁇ m) measurement results according to the horizontal direction (mm)
  • Figure 18 (b) shows the diffraction efficiency (D.E. max: 1) measurement results according to time (s). indicates.
  • D.E. max shows the diffraction efficiency
  • the optical recording medium according to Comparative Example 1-1 was formed with an average thickness of 200 ⁇ m, and as can be seen in (b) of FIG. 18, the optical recording medium according to Comparative Example 1-1 It was confirmed that the recording medium had a diffraction efficiency of about 20%.
  • FIG. 19 is a photograph taken of the optical recording medium according to Experimental Example 1-1 of the present invention
  • FIG. 20 is a view illustrating the results of measuring the thickness and diffraction efficiency of the optical recording medium according to Experimental Example 1-1 of the present invention. am.
  • FIG. 19 a photograph of the optical recording medium according to Experimental Example 1-1 is shown, and FIG. 20 shows the results of measuring the thickness and diffraction efficiency of the optical recording medium according to Experimental Example 1-1.
  • Figure 20 (a) shows the thickness ( ⁇ m) measurement results along the horizontal direction (mm)
  • Figure 20 (b) shows the diffraction efficiency (D.E. max: 1) measurement results according to time (s). indicates.
  • the optical recording medium according to Experimental Example 1-1 was formed with an average thickness of 200 ⁇ m, and as can be seen in (b) of FIG. 20, the optical recording medium according to Experimental Example 1-1 was formed. It was confirmed that the recording medium had a diffraction efficiency of about 60%.
  • FIG. 21 is a photograph taken of the optical recording medium according to Comparative Example 1-2 of the present invention
  • FIG. 22 is a view illustrating the results of measuring the thickness and diffraction efficiency of the optical recording medium according to Comparative Example 1-2 of the present invention. am.
  • FIG. 21 shows a photograph taken of the optical recording medium according to Comparative Example 1-2
  • FIG. 22 shows the thickness and diffraction efficiency measurement results of the optical recording medium according to Comparative Example 1-2.
  • Figure 22 (a) shows the thickness ( ⁇ m) measurement results along the horizontal direction (mm)
  • Figure 22 (b) shows the diffraction efficiency (D.E. max: 1) measurement results according to time (s). indicates.
  • the optical recording medium according to Comparative Example 1-2 was formed with an average thickness of 25 ⁇ m, and as can be seen in (b) of FIG. 22, the optical recording medium according to Comparative Example 1-2 was formed. It was confirmed that the recording medium had a diffraction efficiency of about 0%.
  • FIG. 23 is a photograph taken of the optical recording medium according to Experimental Example 1-2 of the present invention
  • FIG. 24 is a view illustrating the results of measuring the thickness and diffraction efficiency of the optical recording medium according to Experimental Example 1-2 of the present invention. am.
  • FIG. 24 shows the results of measuring the thickness and diffraction efficiency of the optical recording medium according to Experimental Example 1-2.
  • Figure 24 (a) shows the thickness ( ⁇ m) measurement results along the horizontal direction (mm)
  • Figure 24 (b) shows the diffraction efficiency (D.E. max: 1) measurement results according to time (s). indicates.
  • the optical recording medium according to Experimental Example 1-2 was formed with an average thickness of 50 ⁇ m, and as can be seen in (b) of FIG. 24, the optical recording medium according to Experimental Example 1-2 was formed. It was confirmed that the recording medium had a diffraction efficiency of about 7%.
  • the photoreactive polymer composition according to an embodiment of the present application, an optical recording medium containing the same, and a method of manufacturing a three-dimensional structure using the same can be used in various industrial fields such as semiconductors, secondary batteries, displays, photocatalysts, hydrogen, and PUF.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une composition polymère photoréactive. La composition polymère photoréactive comprend une matrice polymère, un monomère et un photo-initiateur, la matrice polymère pouvant contenir un copolymère d'un premier bloc constituant une chaîne principale et d'un second bloc constituant une branche latérale.
PCT/KR2023/018708 2022-11-18 2023-11-20 Composition polymère photoréactive, support d'enregistrement optique la comprenant et procédé de fabrication d'une structure tridimensionnelle l'utilisant WO2024107034A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
KR10-2022-0155214 2022-11-18
KR10-2022-0155206 2022-11-18
KR20220155206 2022-11-18
KR20220155214 2022-11-18
KR10-2023-0009891 2023-01-26
KR20230009891 2023-01-26
KR10-2023-0158278 2023-11-15
KR1020230158278A KR102719988B1 (ko) 2022-11-18 2023-11-15 광반응성 고분자 조성물, 이를 포함하는 광 기록 매체, 이를 이용한 3차원 구조체의 제조 방법

Publications (1)

Publication Number Publication Date
WO2024107034A1 true WO2024107034A1 (fr) 2024-05-23

Family

ID=91085154

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2023/018708 WO2024107034A1 (fr) 2022-11-18 2023-11-20 Composition polymère photoréactive, support d'enregistrement optique la comprenant et procédé de fabrication d'une structure tridimensionnelle l'utilisant

Country Status (1)

Country Link
WO (1) WO2024107034A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140100513A (ko) * 2011-11-14 2014-08-14 신닛테츠 수미킨 가가쿠 가부시키가이샤 감광성 재료, 홀로그래픽 기록 매체, 및 홀로그래픽 기록 방법
US20170227846A1 (en) * 2014-10-24 2017-08-10 Flexterra, Inc. Photopatternable Compositions and Methods of Fabricating Transistor Devices Using Same
CN107043445A (zh) * 2017-05-09 2017-08-15 长春理工大学 一种刚性刷状嵌段共聚物及合成方法
JP2019113573A (ja) * 2016-05-09 2019-07-11 コニカミノルタ株式会社 体積ホログラム記録層形成用組成物およびホログラフィック光学素子

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140100513A (ko) * 2011-11-14 2014-08-14 신닛테츠 수미킨 가가쿠 가부시키가이샤 감광성 재료, 홀로그래픽 기록 매체, 및 홀로그래픽 기록 방법
US20170227846A1 (en) * 2014-10-24 2017-08-10 Flexterra, Inc. Photopatternable Compositions and Methods of Fabricating Transistor Devices Using Same
JP2019113573A (ja) * 2016-05-09 2019-07-11 コニカミノルタ株式会社 体積ホログラム記録層形成用組成物およびホログラフィック光学素子
CN107043445A (zh) * 2017-05-09 2017-08-15 长春理工大学 一种刚性刷状嵌段共聚物及合成方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HE DI; ARISAKA YOSHINORI; MASUDA KENICHI; YAMAMOTO MITSUYA; TAKEDA NAOYA: "A photoresponsive soft interface reversibly controls wettability and cell adhesion by conformational changes in a spiropyran-conjugated amphiphilic block copolymer", ACTA BIOMATERIALIA, ELSEVIER, AMSTERDAM, NL, vol. 51, 18 January 2017 (2017-01-18), AMSTERDAM, NL, pages 101 - 111, XP029943185, ISSN: 1742-7061, DOI: 10.1016/j.actbio.2017.01.049 *

Similar Documents

Publication Publication Date Title
WO2020055096A1 (fr) Support d'hologramme
WO2019054756A1 (fr) Plaque de guidage de lumière de diffraction et procédé de fabrication de plaque de guidage de lumière de diffraction
WO2020067668A1 (fr) Support d'hologramme
WO2022169307A1 (fr) Composition photopolymère pour formation d'hologramme, support d'enregistrement d'hologramme et dispositif optique
WO2019083247A1 (fr) Plaque de guidage de lumière diffractée et procédé de fabrication d'une plaque de guidage de lumière diffractée
WO2017039209A1 (fr) Substrat de fenêtre de couverture et dispositif d'affichage d'image comprenant celui-ci
WO2019031786A1 (fr) Élément optique, élément de polarisation et dispositif d'affichage
WO2012067349A2 (fr) Composé polymère, et composition de film protecteur de réserve comprenant celui-ci pour un procédé d'exposition par immersion dans un liquide
WO2019132242A1 (fr) Plaque polarisante et dispositif d'affichage optique la comprenant
WO2012064074A1 (fr) Composition de résine photosensible, et film isolant diélectrique et dispositif électronique l'employant
WO2024107034A1 (fr) Composition polymère photoréactive, support d'enregistrement optique la comprenant et procédé de fabrication d'une structure tridimensionnelle l'utilisant
WO2018128336A1 (fr) Particule d'émulsion, émulsion en comprenant, procédé de fabrication d'une émulsion
WO2010090406A2 (fr) Composition de résine photosensible colorée, et filtre de couleur et afficheur à cristaux liquides la comprenant
WO2024107033A1 (fr) Appareil et procédé de fabrication de structure de motif à géométrie de motif tridimensionnelle en utilisant une composition de polymère photoréactif, et structure de motif ainsi fabriquée
WO2022182157A1 (fr) Composition de résine photosensible pour former des parois de séparation, structure de paroi de séparation fabriquée à l'aide de celle-ci, et dispositif d'affichage comprenant des parois de séparation
WO2021132865A1 (fr) Composé de résine polymère, son procédé de production, et composition de résine photosensible le comprenant
WO2024117657A1 (fr) Film photopolymère, composition pour former un film photopolymère, support d'enregistrement d'hologramme et dispositif optique
WO2024107032A1 (fr) Structure optique et son procédé de fabrication
EP3625596A1 (fr) Élément optique, élément de polarisation et dispositif d'affichage
WO2014104639A1 (fr) Film optique stratifié et plaque de polarisation l'intégrant
WO2020080785A1 (fr) Composé, composition de conversion de couleur et film de conversion de couleur le comprenant, unité de rétroéclairage le comprenant, dispositif d'affichage le comprenant, et procédé de fabrication de film de conversion de couleur
WO2024106773A1 (fr) Composition photopolymère, film photopolymère, support d'enregistrement d'hologramme, élément optique et procédé d'enregistrement holographique
WO2024085619A1 (fr) Support d'enregistrement d'hologramme, composition pour former une couche de photopolymère, et élément optique
WO2020130437A1 (fr) Composition de précurseur de polyimide, et procédé de production de polyimide et film de polyimide l'utilisant
KR102719988B1 (ko) 광반응성 고분자 조성물, 이를 포함하는 광 기록 매체, 이를 이용한 3차원 구조체의 제조 방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23892096

Country of ref document: EP

Kind code of ref document: A1