WO2018066941A1 - Structure de cristal photonique colorimétrique et capteur à cristal photonique colorimétrique l'utilisant - Google Patents

Structure de cristal photonique colorimétrique et capteur à cristal photonique colorimétrique l'utilisant Download PDF

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WO2018066941A1
WO2018066941A1 PCT/KR2017/011005 KR2017011005W WO2018066941A1 WO 2018066941 A1 WO2018066941 A1 WO 2018066941A1 KR 2017011005 W KR2017011005 W KR 2017011005W WO 2018066941 A1 WO2018066941 A1 WO 2018066941A1
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refractive index
photonic crystal
formula
crystal structure
index layer
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PCT/KR2017/011005
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English (en)
Korean (ko)
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정서현
박종목
공호열
정유진
이세영
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한국화학연구원
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Priority claimed from KR1020160129149A external-priority patent/KR101803550B1/ko
Priority claimed from KR1020160129148A external-priority patent/KR101803549B1/ko
Application filed by 한국화학연구원 filed Critical 한국화학연구원
Publication of WO2018066941A1 publication Critical patent/WO2018066941A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
    • G02B5/0825—Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only
    • G02B5/0841—Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only comprising organic materials, e.g. polymers
    • 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
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • 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
    • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
    • G02B1/005—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials made of photonic crystals or photonic band gap materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/122—Basic optical elements, e.g. light-guiding paths
    • G02B6/1225—Basic optical elements, e.g. light-guiding paths comprising photonic band-gap structures or photonic lattices

Definitions

  • the present invention relates to a color conversion photonic crystal structure sensitive to changes in humidity, and a color conversion photonic crystal sensor using the same.
  • the present invention relates to a method for producing a color conversion photonic crystal structure capable of converting a color represented by adjusting a reflection wavelength.
  • a photonic crystal is a structure in which dielectric materials having different refractive indices are arranged periodically, and overlapping interference occurs between light scattered at each regular lattice point, so that light is not transmitted through a specific wavelength range.
  • a material that reflects light that is, forms an optical band gap.
  • photonic crystals use photons instead of electrons as a means of information processing, and thus, the speed of information processing is excellent and is emerging as a key material for improving the efficiency of the information industry.
  • the photonic crystal can be implemented as a one-dimensional structure in which photons move in the principal axis direction, a two-dimensional structure in which the photons move along a plane, or a three-dimensional structure in which the photons move freely in all directions throughout the material. It is easy to control the optical characteristics and can be applied to various fields.
  • photonic crystals may be applied to optical devices such as photonic crystal fibers, light emitting devices, photovoltaic devices, photonic crystal sensors, semiconductor lasers, and the like.
  • the Bragg stack is a photonic crystal having a one-dimensional structure, and can be easily manufactured by only stacking two layers having different refractive indices, and controlling the optical properties by controlling the refractive index and thickness of the two layers is easy. There is this. Due to these features, the Bragg stack is widely used for applications as photonic crystal sensors that detect electrical, chemical, and thermal stimuli as well as energy devices such as solar cells. Accordingly, studies have been made on various materials and structures for easily manufacturing a photonic crystal sensor excellent in sensitivity and reproducibility.
  • the present inventors have made intensive efforts to use a copolymer including a repeating unit including quaternary ammonium ions in one repeated layer of the Bragg stack as described below.
  • the present invention has been completed by confirming that a color conversion photonic crystal structure sensitive to change and a photonic crystal sensor exhibiting excellent sensitivity can be easily manufactured.
  • the present invention is to provide a color conversion photonic crystal structure sensitive to changes in humidity.
  • the present invention is to provide a color conversion photonic crystal sensor comprising the photonic crystal structure.
  • the present invention is to provide a method of manufacturing a color conversion photonic crystal structure that can display a desired color by adjusting the reflection wavelength.
  • the present invention is to provide a color conversion photonic crystal structure prepared according to the above production method.
  • the present invention is a first refractive index layer comprising a first polymer exhibiting a first refractive index, alternately stacked; And a second refractive index layer comprising a second polymer exhibiting a second refractive index,
  • the first refractive index and the second refractive index are different.
  • One of the first polymer and the second polymer provides a color converting photonic crystal structure, which is a copolymer represented by Formula 1 below:
  • R 1 and R 2 are, each independently, hydrogen or C1-3 alkyl
  • - X 1 to X 5 are, each independently, N + RX - or CR ', provided at least one of X 1 to X 5 is N + RX
  • R and R ' are each independently hydrogen, C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, C 7-20 alkylaryl or C 7-20 arylalkyl, X ⁇ is 1 Is an anionic
  • L 1 is O or NH
  • Y 1 is benzoylphenyl
  • Y 1 is unsubstituted or substituted with 1 to 4 substituents each independently selected from the group consisting of hydroxy, halogen, nitro, C 1-5 alkyl and C 1-5 alkoxy,
  • n1 and m1 are each independently an integer of 1 or more
  • n1 + m1 is 100-1,000.
  • the first refractive index layer comprises a first polymer exhibiting a first refractive index
  • the second refractive index layer comprises a second polymer exhibiting a second refractive index different from the first refractive index
  • One of the first polymer and the second polymer is a copolymer represented by the following formula (3),
  • R 5 and R 6 are each independently hydrogen or C 1-3 alkyl
  • X 11 to X 15 are each independently N or CR ′′, at least one of X 11 to X 15 is N,
  • R ′′ is hydrogen, C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, C 7-20 alkylaryl or C 7-20 arylalkyl,
  • L 3 is O or NH
  • Y 3 is benzoylphenyl
  • Y 3 is unsubstituted or substituted with 1 to 4 substituents each independently selected from the group consisting of hydroxy, halogen, nitro, C 1-5 alkyl and C 1-5 alkoxy,
  • n3 and m3 are each independently an integer of 1 or more
  • n3 + m3 is 100 to 1,000
  • R is hydrogen, C1-20 alkyl, C3-20 cycloalkyl, C6-20 aryl, C7-20 alkylaryl or C7-20 arylalkyl,
  • X is a leaving group
  • the present invention also provides a color conversion photonic crystal sensor comprising the photonic crystal structure.
  • the color conversion photonic crystal structure of the present invention is a high refractive index using a copolymer comprising a repeating unit derived from an acrylate or acrylamide monomer having a repeating unit containing a quaternary ammonium cation and a photoactive functional group. Including the layer, the color may be converted to be visually judged according to the change in humidity, and there is a characteristic that the photonic crystal sensor may be manufactured using the same.
  • a color conversion having a reflection wavelength to be implemented by adjusting the quaternization reaction conditions of nitrogen atoms present in the repeating unit of the copolymer included in one repeated layer There is a feature that a photonic crystal structure can be produced.
  • FIG. 1 schematically illustrates a structure of a color conversion photonic crystal structure according to an embodiment.
  • FIG. 2A shows the reflection wavelength and the color conversion photograph of the photonic crystal structures prepared in Examples 1-1 to 1-9.
  • 2B shows a specular reflection diagram of the photonic crystal structures prepared in Examples 1-1 to 1-9.
  • 3A shows reflection wavelengths and color conversion photographs of the photonic crystal structures prepared in Examples 2-1 to 2-9.
  • 3B shows the specular reflectance of the photonic crystal structures prepared in Examples 2-1 to 2-9.
  • 4A shows the reflection wavelengths and color conversion photographs of the photonic crystal structures prepared in Examples 3-1, 3-2, 4-1, 4-2, 5-1, and 5-2.
  • 4B shows the specular reflectance of the photonic crystal structures prepared in Examples 3-1, 4-1, and 5-1.
  • 4C shows the specular reflectance of the photonic crystal structure prepared in Examples 3-2, 4-2, and 5-2.
  • FIG. 5A shows the reflection wavelength and the color conversion photograph of the photonic crystal structures prepared in Examples 6-1 and 6-2.
  • 5B shows the specular reflectance of the photonic crystal structures prepared in Examples 6-1 and 6-2.
  • FIG. 6A illustrates a reflection wavelength and a color conversion photograph of the photonic crystal structure prepared in Example 7 according to humidity change.
  • FIG. 6A illustrates a reflection wavelength and a color conversion photograph of the photonic crystal structure prepared in Example 7 according to humidity change.
  • FIG. 6B shows a specular reflection diagram of the photonic crystal structure prepared in Example 7 according to humidity change.
  • FIG. 7A illustrates a reflection wavelength and a color conversion photograph of the photonic crystal structure manufactured in Example 8 according to humidity change.
  • FIG. 7A illustrates a reflection wavelength and a color conversion photograph of the photonic crystal structure manufactured in Example 8 according to humidity change.
  • FIG. 7B shows a specular reflection diagram of the photonic crystal structure prepared in Example 8 according to humidity change.
  • 8A shows the reflection wavelength measurement results of the photonic crystal structures prepared in Examples 9-1 to 9-5.
  • the term 'color conversion photonic crystal structure' used in the present invention is a Bragg stack having a one-dimensional photonic crystal structure manufactured by repeatedly stacking materials having different refractive indices, and having a specific wavelength due to a periodic difference in refractive index of the stacked structures.
  • the light may reflect light in an area, and the reflected wavelength refers to a structure shifted by an external stimulus to convert a reflected color.
  • partial reflection of light occurs at the boundary of each layer of the structure, and many of these reflected waves can structurally interfere to reflect light of a specific wavelength having high intensity.
  • the shift of the reflection wavelength due to the external stimulus occurs as the wavelength of the scattered light changes as the lattice structure of the material forming the layer is changed by the external stimulus.
  • Such a color conversion photonic crystal structure may be manufactured in the form of a coating film coated on a separate substrate or a substrate, or in the form of a free standing film, and includes an optical device such as a photonic crystal fiber, a light emitting device, a photovoltaic device, a photonic crystal sensor, a semiconductor laser, and the like. It can be applied to.
  • the color conversion photonic crystal structure may be used in biosensors such as optical sensors, glucose sensors, protein sensors, DNA sensors, disease diagnosis sensors, portable diagnostic sensors, and the like, such as environmental elements for chemical and species detection. The application is not limited.
  • the color conversion photonic crystal structure of the present invention the first refractive index layer comprising a first polymer exhibiting a first refractive index, alternately stacked; And a second refractive index layer comprising a second polymer exhibiting a second refractive index, wherein the first refractive index and the second refractive index are different.
  • the first refractive index layer may be a high refractive index layer
  • the second refractive index layer may be a low refractive index layer
  • the first refractive index layer may be a low refractive index layer
  • the second refractive index layer may be a high refractive index layer
  • the term 'high refractive index layer' used in the present invention means a layer having a relatively high refractive index among two kinds of layers included in the photonic crystal structure.
  • the polymer included in the high refractive index layer is a copolymer represented by the following formula (1):
  • R 1 and R 2 are each independently hydrogen or C 1-3 alkyl
  • - X 1 to X 5 are, each independently, N + RX - or CR ', provided at least one of X 1 to X 5 is N + RX
  • R and R ' are each independently hydrogen, C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, C 7-20 alkylaryl or C 7-20 arylalkyl, X ⁇ is 1 Is an anionic
  • L 1 is O or NH
  • Y 1 is benzoylphenyl
  • Y 1 is unsubstituted or substituted with 1 to 4 substituents each independently selected from the group consisting of hydroxy, halogen, nitro, C 1-5 alkyl and C 1-5 alkoxy,
  • n1 and m1 are each independently an integer of 1 or more
  • n1 + m1 is 100-1,000.
  • the copolymer represented by Chemical Formula 1 includes a repeating unit containing quaternary ammonium ions
  • the polymer has a higher refractive index and hydrophilicity than the polymer containing no quaternary ammonium ions, thereby better responding to external stimuli such as moisture. can do.
  • the repeating unit including the quaternary ammonium ion has a counter ion (X ⁇ ) which is ion-bonded with the quaternary ammonium cation, and thus the refractive index of the high refractive index layer is changed according to the type of the counter ion. It is possible to produce a photonic crystal structure exhibiting color.
  • the refractive index may vary according to the number of quaternary ammonium ions and the type of the relative ions in the copolymer, a color conversion photonic crystal structure having a desired reflection wavelength may be implemented by adjusting the refractive index.
  • the copolymer represented by Chemical Formula 1 further includes repeating units derived from an acrylate or acrylamide-based monomer having a photoactive functional group (Y 1 ), so that photocuring itself is performed without a separate photoinitiator or crosslinker. It may be possible.
  • the copolymer represented by Chemical Formula 1 is a random copolymer of styrene monomer and an acrylate or acrylamide monomer having a photoactive functional group (Y 1 ), and the repeating units between the square brackets of Chemical Formula 1 are random from each other. It may be a random copolymer arranged so as to.
  • the copolymer represented by Formula 1 may be a block copolymer in which blocks of repeating units between square brackets of Formula 1 are connected by covalent bonds. Also, alternatively, it may be an alternating copolymer in which the repeating units between the brackets of Formula 1 are arranged alternately, or may be a graft copolymer in which any one of the repeating units is combined in a branched form. The form is not limited.
  • the copolymer represented by Formula 1 may exhibit a refractive index of 1.5 to 1.7.
  • a photonic crystal structure reflecting light of a desired wavelength may be implemented by a difference in refractive index with the polymer represented by Chemical Formula 1.
  • R 1 and R 2 may be each independently hydrogen or methyl.
  • R 1 and R 2 can be hydrogen.
  • X 1 is N + RX ⁇
  • X 2 to X 5 are each independently CR ′;
  • X 2 is N + RX ⁇ , and X 1 , X 3 to X 5 are each independently CR ′; or
  • X 3 is N + RX ⁇
  • X 1 , X 2 , X 4 and X 5 are each independently CR ′.
  • R is C 1-10 alkyl, C 6-10 aryl, or C 7-10 arylalkyl, and R ′ may be hydrogen or C 1-10 alkyl.
  • R is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, phenyl, benzyl, Or phenylethyl and R 'may be hydrogen, methyl, ethyl, or phenyl.
  • X - is, for the anion of a monovalent (mono-valent), for example, X - is F -, Cl -, Br - , I -, ClO 4 -, SCN-, NO 3 -, or CH 3 CO 2 - it can be.
  • a halogen anion such as F ⁇ , Cl ⁇ , Br ⁇ , or I ⁇ is preferable in view of the ease of quaternization reaction described later.
  • Y 1 may be benzoylphenyl unsubstituted or substituted with C 1-3 alkyl.
  • Y 1 is benzoylphenyl, it may be advantageous in view of ease of photocuring.
  • n1 means the total number of repeating units including quaternary ammonium ions in the copolymer
  • m1 is a repeat derived from an acrylate or acrylamide monomer having a photoactive functional group in the copolymer Means the total number of units.
  • the copolymer represented by Formula 1 may have a molar ratio of n1: m1 of 100: 1 to 100: 20, for example, 100: 1 to 100: 10, and for example, 100: 5 to 100: 10. have.
  • the copolymer represented by Chemical Formula 1 may have a number average molecular weight (Mn) of 10,000 to 300,000 g / mol, for example, 30,000 to 180,000 g / mol. In the above range, it is possible to produce a copolymer having a refractive index in the above-described range and easy photocuring.
  • the copolymer represented by Chemical Formula 1 may be one of the copolymers represented by the following Chemical Formulas 1-1 to 1-3:
  • the high refractive index layer may further include a copolymer represented by the following formula (3):
  • R 5 and R 6 are each independently hydrogen or C 1-3 alkyl
  • X 11 to X 15 are each independently N or CR ′′, at least one of X 11 to X 15 is N,
  • R ′′ is hydrogen, C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, C 7-20 alkylaryl or C 7-20 arylalkyl,
  • L 3 is O or NH
  • Y 3 is benzoylphenyl
  • Y 3 is unsubstituted or substituted with 1 to 4 substituents each independently selected from the group consisting of hydroxy, halogen, nitro, C 1-5 alkyl and C 1-5 alkoxy,
  • n3 and m3 are each independently an integer of 1 or more
  • n3 + m3 is 100-1,000.
  • the high refractive index layer further comprises a copolymer represented by Chemical Formula 3 in the copolymer represented by Chemical Formula 1, metal ions and complexes may be better formed.
  • the molar ratio of the copolymer represented by Chemical Formula 1 and the copolymer represented by Chemical Formula 3 in the high refractive index layer may be 100: 0 to 1:99.
  • the high refractive index layer includes the copolymer represented by the formula (1) and the copolymer represented by the formula (3) simultaneously, the copolymer represented by the formula (1) and the formula (3) in the high refractive index layer
  • the molar ratio of copolymer represented may be 90:10 to 10:90.
  • the copolymer represented by Chemical Formula 3 further includes repeating units derived from an acrylate or acrylamide-based monomer having a photoactive functional group (Y 3 ), so that photocuring by itself is performed without a separate photoinitiator or crosslinker. It may be possible.
  • the copolymer represented by Chemical Formula 3 is randomly copolymerized with styrene-based monomers and an acrylate or acrylamide-based monomer having a photoactive functional group (Y 3 ). It may be a random copolymer arranged so as to.
  • the copolymer represented by Formula 3 may be a block copolymer in which blocks of repeating units between the brackets of Formula 3 are connected by covalent bonds.
  • it may be an alternating copolymer in which the repeating units between the brackets of Formula 3 are arranged alternately, or may be a graft copolymer in which any one of the repeating units is combined in a branched form, but the arrangement of the repeating units The form is not limited.
  • the copolymer represented by Formula 3 may exhibit a refractive index of 1.5 to 1.7.
  • the refractive index of the copolymer represented by Formula 3 and the copolymer represented by Formula 1 may be different.
  • the copolymer represented by the formula (2) is present without reacting with the compound represented by the formula (4) in the quaternization reaction (Quarternization) of the method for producing a photonic crystal structure described later. That is, the copolymer represented by Formula 1 is prepared by the reaction of the copolymer represented by Formula 3 with the compound represented by Formula 4.
  • R is hydrogen, C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, C 7-20 alkylaryl or C 7-20 arylalkyl,
  • X is a leaving group
  • the copolymer represented by Formula 1 is produced by quaternization reaction of the structure represented by the compound represented by Formula 4 by laminating a structure having a high refractive index layer containing the copolymer represented by Formula 3, the quaternization reaction
  • the copolymer represented by Chemical Formula 3, which does not participate in, may remain in the finally prepared photonic crystal structure. Therefore, the molar ratio of the copolymer represented by Chemical Formula 1 and the copolymer represented by Chemical Formula 3 in the high refractive index layer may be adjusted according to the quaternization reaction conditions.
  • R 5 and R 6 may be each independently hydrogen or methyl.
  • R 5 and R 6 can be hydrogen.
  • X 11 is N and X 12 to X 15 are each independently CR ′′;
  • X 12 is N and X 11 , X 13 to X 15 are each independently CR ′′; or
  • X 13 is N and X 11 , X 12 , X 14 and X 15 may each independently be CR ′′.
  • R ′′ may be hydrogen or C 1-10 alkyl.
  • R ′′ may be hydrogen, methyl, ethyl, or phenyl.
  • X 1 is N + RBr ⁇
  • X 11 is N
  • X 2 to X 5 and X 12 to X 15 are CH;
  • a 2 X N + RBr - a, and X 12 is N, X 1, X 3 to X 5, X 11 and X 13 to X 15 is CH; or
  • R is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, phenyl, benzyl, or phenyl May be ethyl.
  • This is due to the copolymer represented by the formula (1) derived from the copolymer represented by the formula (3) as described above.
  • Y 3 may be unsubstituted or benzoylphenyl substituted with C 1-3 alkyl.
  • Y 3 is benzoylphenyl, it may be advantageous in view of the ease of photocuring.
  • n3 means the total number of repeating units including N-membered 6-membered heterocyclic group in the copolymer
  • m3 is from an acrylate or acrylamide monomer having a photoactive functional group in the copolymer The total number of derived repeating units.
  • the copolymer represented by Formula 3 may have a molar ratio of n3: m3 of 100: 1 to 100: 20, for example, 100: 1 to 100: 10, and for example, 100: 5 to 100: 10. have.
  • the copolymer represented by Chemical Formula 3 may have a number average molecular weight (Mn) of 10,000 to 300,000 g / mol, for example, 30,000 to 180,000 g / mol. In the above range, it is possible to produce a copolymer having a refractive index in the above-described range and easy photocuring.
  • the copolymer represented by Chemical Formula 3 may be one of the copolymers represented by the following Chemical Formulas 3-1 to 3-3:
  • n3 and m3 are as defined above.
  • the term 'low refractive index layer' used in the present invention means a layer having a relatively low refractive index among two kinds of layers included in the photonic crystal structure.
  • the polymer included in the low refractive index layer is not the copolymer represented by Chemical Formula 1, but is another of the first polymer and the second polymer, and includes a structural unit derived from the following monomer, It may exhibit low refractive index relative to the copolymers represented: fluoroalkyl acrylamides, fluoroalkyl acrylates and derivatives thereof. These can be applied individually or in mixture of 2 or more types.
  • copolymers by copolymerization of the fluoroalkyl acrylamide, fluoroalkyl acrylate and derivatives thereof with other monomers can also be used.
  • the other of the first polymer and the second polymer may be a copolymer represented by the following formula (2):
  • R 3 and R 4 are each independently hydrogen or C 1-3 alkyl
  • A is C 1-10 fluoroalkyl
  • L 2 is O or NH
  • Y 2 is benzoylphenyl
  • Y 2 is unsubstituted or substituted with 1 to 4 substituents each independently selected from the group consisting of hydroxy, halogen, nitro, C 1-5 alkyl and C 1-5 alkoxy,
  • n2 and m2 are each independently an integer of 1 or more,
  • n2 + m2 is 100-1,000.
  • the copolymer represented by the formula (2) includes a repeating unit derived from a fluoroalkyl (A) acrylate monomer
  • the refractive index is lower than that of the polymer not containing the repeating unit, and the thermal stability, chemical resistance, and oxidation Excellent chemical properties such as stability and excellent transparency.
  • 'fluoroalkyl' refers to a functional group in which one or more fluorine atoms are substituted for the hydrogen atom of alkyl, wherein one or more fluorine atoms may be substituted for the hydrogen atom of the side chain as well as the terminal of C 1-10 alkyl, , Two or more fluorine atoms may be all bonded to one carbon atom, or each may be bonded to two or more carbon atoms.
  • the refractive index becomes lower and the hydrophobicity may increase, thereby controlling the difference in refractive index between the high refractive index layer and the low refractive index layer according to the number of fluorine atoms.
  • Color conversion photonic crystal structure having a reflection wavelength can be implemented.
  • the copolymer represented by Chemical Formula 2 may further include a repeating unit derived from an acrylate or acrylamide monomer having a photoactive functional group (Y 2 ), and may be photocurable by itself without a separate photoinitiator or crosslinking agent. .
  • the copolymer represented by Formula 2 is a square bracket of Formula 2 prepared by random copolymerization of a fluoroalkyl (A) acrylate monomer and an acrylate or acrylamide monomer having a photoactive functional group (Y 2 ). It may be a random copolymer in which repeating units in between are randomly arranged with each other.
  • the copolymer represented by Formula 2 may be a block copolymer in which blocks of repeating units between the brackets of Formula 2 are connected by covalent bonds.
  • it may be an alternating copolymer in which the repeating units between the brackets of Formula 2 are arranged alternately, or may be a graft copolymer in which any one of the repeating units is combined in a branched form, but the arrangement of the repeating units The form is not limited.
  • the copolymer represented by Formula 2 may exhibit a refractive index of 1.3 to 1.5.
  • a photonic crystal structure reflecting light of a desired wavelength may be implemented by a difference in refractive index with the copolymer represented by Chemical Formula 1 used in the above-described high refractive index layer.
  • R 3 and R 4 may be each independently hydrogen or methyl.
  • R 3 and R 4 can be hydrogen.
  • A may be C1-5 fluoroalkyl.
  • A is fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 1,2-difluoroethyl, 2,2-difluoroethyl, 1,1,2-trifluoroethyl, 1,2,2-trifluoroethyl, 2,2,2-trifluoroethyl, 1-fluoropropyl, 2- Fluoropropyl, 1,1-difluoropropyl, 1,2-difluoropropyl, 2,2-difluoropropyl, 1,1,2-trifluoropropyl, 1,2,2-trifluoro Ropropyl, 2,2,2-trifluoropropyl, 1-fluorobutyl, 2-fluorobutyl, 1,1-difluorobutyl, 1,2-difluorobutyl, 2,2-difluoro Robutyl, 1,1,2-trifluoromethyl,
  • Y 2 may be unsubstituted or benzoylphenyl substituted with C 1-3 alkyl.
  • Y 2 is benzoylphenyl, it is advantageous in view of the ease of photocuring.
  • n2 means the total number of repeating units derived from the fluoroalkyl acrylate-based monomer in the copolymer
  • m2 is an acrylate or acryl having a photoactive functional group (Y 2 ) in the copolymer
  • Y 2 photoactive functional group
  • the copolymer represented by Formula 2 may have a molar ratio of n 2: m 2 of 100: 1 to 100: 10 and a number average molecular weight of 10,000 to 100,000 g / mol.
  • the copolymer represented by Formula 2 may have a molar ratio of n 2: m 2 of 100: 1 to 100: 5, specifically 100: 1 to 100: 2.
  • the copolymer represented by Chemical Formula 2 may have a number average molecular weight of 20,000 to 80,000 g / mol, specifically 20,000 to 60,000 g / mol. In the above range, it is possible to produce a copolymer having a refractive index in the above-described range and easy photocuring.
  • the copolymer represented by Chemical Formula 2 may be one of the copolymers represented by the following Chemical Formulas 2-1 to 2-3:
  • n2 and m2 are as defined above.
  • the color conversion photonic crystal structure according to the present invention includes a first refractive index layer disposed on a lowermost portion, a second refractive index layer disposed on the first refractive index layer, and a first refractive index layer and a second refractive index layer on the second refractive index layer. It is alternately repeated to have a stacked structure.
  • the color conversion photonic crystal structure may further include a substrate on the other surface of the first refractive index layer of the first refractive index layer disposed on the lowermost part according to the use. Therefore, in this case, the substrate may be positioned at the bottom of the color conversion photonic crystal structure.
  • a color conversion photonic crystal structure 10 may include a substrate 11 and a first refractive index layer 13 and a second refractive index layer 15 alternately stacked on the substrate 11. It is composed of
  • the first refractive index layer 13 may be positioned on the top of the color conversion photonic crystal structure. Accordingly, the first refractive index layer 13 is further laminated on the laminate in which the first refractive index layer 13 and the second refractive index layer 15 are alternately stacked, so that the photonic crystal structure includes an odd refractive index layer. Can have In this case, constructive interference between the lights reflected at the interface of each layer is increased, as described later, so that the intensity of the reflection wavelength of the photonic crystal structure can be increased.
  • the substrate 11 is a carbon-based material, metal foil, thin glass, silicon (Si), plastic, polyethylene (PE), polyethylene having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling and waterproofing It may be a polymer film such as terephthalate (PET), polypropylene (PP), paper, skin, clothing, or a wearable material, but is not limited thereto, and various materials that are flexible or not flexible depending on the intended application. Can be used.
  • a difference between the first refractive index n1 and the second refractive index n2 may be 0.01 to 0.5.
  • the difference between the first refractive index n1 and the second refractive index n2 may be 0.05 to 0.3, specifically 0.1 to 0.2.
  • the difference between the refractive indices increases, the optical band gap of the photonic crystal structure increases, so that the light having a desired wavelength may be reflected by adjusting the difference between the refractive indices within the above-described range.
  • the first refractive index n1 may be 1.5 to 1.7
  • the second refractive index n2 may be 1.3 to 1.5
  • the first refractive index layer 13 is a high refractive index layer
  • the second refractive index layer 15 corresponds to a low refractive index layer, so that the photonic crystal structure 10 is disposed on the substrate 11.
  • the low refractive index layer / high refractive index layer / low refractive index layer / high refractive index layer may have a structure stacked sequentially.
  • the first refractive index n1 may be 1.3 to 1.5
  • the second refractive index n2 may be 1.5 to 1.7
  • the first refractive index layer 13 is a low refractive index layer
  • the second refractive index layer 15 corresponds to a high refractive index layer, so that the photonic crystal structure 10 is formed on the substrate 11.
  • the high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer may have a structure that is sequentially stacked.
  • the ratio of the thickness of the low refractive index layer to the thickness of the high refractive index layer may be 1: 4 to 1: 0.5.
  • the thickness of the low refractive index layer is 25 to 70 nm
  • the thickness of the high refractive index layer may be 50 to 160 nm.
  • the photonic crystal structure is a high refractive index layer formed with a thickness of 50 to 160 nm
  • the second refractive index layer is a low refractive index layer formed with a thickness of 25 to 70 nm in terms of easy color conversion
  • the high refractive index layer is located at the top.
  • the total number of stacked layers of the photonic crystal structure is not limited thereto. Specifically, the total number of stacked layers of the first refractive index layer and the second refractive index layer may be 5 to 30 layers.
  • the interference of the reflected light at each layer boundary surface is sufficiently generated to have a reflection intensity such that a change in color due to an external stimulus is detected.
  • the reflection wavelength ⁇ of the color conversion photonic crystal structure 10 may be determined by Equation 1 below:
  • n1 and n2 are the refractive indices of the first and second refractive index layers 13 and 15, respectively, and d1 and d2 are the refractive indices of the first and second refractive index layers 13 and 15, respectively.
  • the color conversion photonic crystal structure 10 When there is no external stimulus, the color conversion photonic crystal structure 10 exhibits a reflection wavelength ⁇ corresponding to a visible light region of 380 to 760 nm according to Equation 1 to confirm the reflection color by the photonic crystal structure. Can be.
  • the color conversion photonic crystal structure 10 When the color conversion photonic crystal structure 10 is positioned in an environment subject to external stimulation, the crystal lattice of the first polymer and the second polymer constituting the first refractive index layer 13 and the second refractive index layer 15, respectively As the structure is changed, the photonic crystal structure 10 reflects the shifted wavelength [lambda] 'as the shape scattered at each layer boundary is changed. Therefore, the color implemented by the photonic crystal structure can be converted as compared with the case where there is no external stimulus. If the intensity of the external stimulus is high, since the degree of change of the crystal lattice structure of the first polymer and the second polymer is increased and the reflection wavelength is further shifted, the intensity of the external stimulus can be detected according to the color to be implemented.
  • the reflection wavelength is shifted as the humidity changes. That is, the shift in the reflection wavelength of the photonic crystal structure 10 is due to the change in the refractive index of the copolymer represented by Formula 1 included in the high refractive index layer and the increase in the thickness of the high refractive index layer when absorbing moisture.
  • the high refractive index layer of the photonic crystal structure in which moisture is absorbed may have a thickness of 1 to 3 times that of the high refractive index layer of the photonic crystal structure 10.
  • the copolymer represented by Chemical Formula 1 absorbs moisture. And swelling, thereby changing the thickness of the high refractive index layer.
  • the copolymer represented by Chemical Formula 1 is excellent in reactivity with water having high polarity, including quaternary ammonium cation and its counter anion. Therefore, the reflected wavelength of the photonic crystal structure 10 according to Equation 1 may be shifted.
  • the shifted reflection wavelength ⁇ ′ is within a range of 380 nm to 760 nm, so that color change can be observed with the naked eye.
  • the reflection wavelength [lambda] and the shifted reflection wavelength [lambda] ' can be measured by a device such as a reflectometer.
  • the reflection wavelength may be shifted to a longer wavelength. Therefore, the shifted reflection wavelength ⁇ ′ of the photonic crystal structure may have a larger value than the reflection wavelength ⁇ in the absence of an external magnetic pole.
  • the color conversion photonic crystal structure is manufactured by alternately stacking different refractive index layers, and in order to change the color represented by the photonic crystal structure, a new photonic crystal structure may be newly changed by changing a material included in each layer or varying the thickness of each layer. Shall be prepared.
  • the prepared photonic crystal structure is contacted with the quaternization reaction material, but to prepare a photonic crystal structure showing the color to be implemented by adjusting the type and the reaction conditions of the quaternization reaction material. Therefore, when using the manufacturing method according to the present invention, it is possible to easily adjust the reflection wavelength of the photonic crystal structure by using the already prepared photonic crystal structure without producing a new photonic crystal structure.
  • Step 1 Step of manufacturing the bulb structure (step 1)
  • the step 1 is a Bragg stack having a structure in which the first refractive index layer and the second refractive index layer are laminated alternately, the first refractive index layer comprises a first polymer exhibiting a first refractive index, the second refractive index layer is A step of manufacturing a light bulb structure comprising a second polymer exhibiting a second refractive index different from the first refractive index.
  • the first refractive index layer may be a high refractive index layer
  • the second refractive index layer may be a low refractive index layer
  • the first refractive index layer may be a low refractive index layer
  • the second refractive index layer may be a high refractive index layer
  • composition / structure is as described above in the photonic crystal structure except that the precursor structure has a high refractive index layer of the following composition / specification.
  • the term 'high refractive index layer' used in the present invention means a layer having a relatively high refractive index among two kinds of layers included in the bulb structure.
  • the polymer included in the high refractive index layer is a copolymer represented by the following formula (3):
  • R 5 and R 6 are each independently hydrogen or C 1-3 alkyl
  • X 11 to X 15 are each independently N or CR ′′, at least one of X 11 to X 15 is N,
  • R ′′ is hydrogen, C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, C 7-20 alkylaryl or C 7-20 arylalkyl,
  • L 3 is O or NH
  • Y 3 is benzoylphenyl
  • Y 3 is unsubstituted or substituted with 1 to 4 substituents each independently selected from the group consisting of hydroxy, halogen, nitro, C 1-5 alkyl and C 1-5 alkoxy,
  • n3 and m3 are each independently an integer of 1 or more
  • n3 + m3 is 100-1,000.
  • the light bulb structure may be a high refractive index layer having a thickness of 50 to 120 nm, and a second refractive index layer having a thickness of 25 to 70 nm.
  • Such precursor structures can be manufactured by a manufacturing method comprising the following steps:
  • a first dispersion composition and a second dispersion composition are prepared.
  • Each dispersion composition can be prepared by dispersing a polymer in a solvent, where the dispersion composition is used as a term indicating various states such as solution phase, slurry phase or paste phase.
  • the solvent may be used as long as it can dissolve the first and second polymers, and the first and second polymers may be included in an amount of 0.5 to 5 wt% based on the total weight of the dispersion composition.
  • a dispersion composition having a viscosity suitable for being applied onto a substrate can be prepared.
  • the first dispersion composition may consist of a solvent and a first polymer
  • the second dispersion composition may consist of a solvent and a second polymer.
  • the photocuring agent may not include a separate photoinitiator and a crosslinking agent or inorganic particles. Therefore, the photonic crystal structure can be manufactured more easily and economically, and the dispersion of the optical properties according to the position of the prepared photonic crystal structure can be reduced by not including a separate additive.
  • spin coating dip coating, roll coating, screen coating, spray coating, or the like may be applied by applying the dispersion composition onto a substrate or a refractive index layer.
  • Spin casting, flow coating, screen printing, ink jet, drop casting, or the like may be used, but is not limited thereto.
  • the light irradiation step may be performed by a method of irradiating light of 190 ⁇ 380 nm wavelength.
  • the photocured refractive index layer may be prepared by acting as a photoinitiator of the benzophenone moiety contained in the polymer by the light irradiation.
  • steps a) and b) are repeated several times to produce a bulb structure having a total number of stacked layers of 5 to 30 layers.
  • the total number of stacked layers is odd, it means that the step a) of forming the first refractive index layer is repeated one more time than the step b).
  • Step 2 is a step of preparing a photonic crystal structure by contacting the precursor structure prepared in step 1 with a compound represented by the following formula (4) of the copolymer represented by the formula (3) contained in the high refractive index layer of the precursor structure
  • a compound represented by the following formula (4) of the copolymer represented by the formula (3) contained in the high refractive index layer of the precursor structure The quaternization reaction of the N nitrogen atom with the compound represented by Formula 4 converts the quaternary ammonium ion into quaternary ammonium cation:
  • the quaternization reaction is a nucleophilic substitution reaction between the nitrogen atom of the copolymer represented by Chemical Formula 3 and the compound represented by Chemical Formula 4 of the high refractive index layer. - the anion is produced. Accordingly, the copolymer represented by Chemical Formula 3 is converted into the copolymer represented by Chemical Formula 1 by reacting with the compound represented by Chemical Formula 4.
  • the composition and thickness of the high refractive index layer of the photonic crystal structure manufactured by the step 2 is different from that of the precursor structure.
  • the refractive index of the high refractive index layer of the photonic crystal structure is changed, and the reflection wavelength and the color of the photonic crystal structure are changed.
  • the photonic crystal structure prepared in step 2) may have a reflection wavelength in visible light of 380 to 760 nm, and thus display colors.
  • the reflection wavelength of the photonic crystal structure may be determined by Equation 1 described above.
  • the reflected wavelength of the photonic crystal structure is different from the reflected wavelength of the bulb structure due to the difference in the composition and thickness of the high refractive index layer.
  • the reflection wavelength of the photonic crystal structure may be longer than the reflection wavelength of the precursor structure. This is because the copolymer represented by Chemical Formula 3 is shifted to a longer wavelength as the contact time with the compound represented by Chemical Formula 4 increases.
  • the manufacturing method of the present invention by adjusting the type and reaction conditions of the compound represented by the formula (4) participating in the quaternization reaction, the implementation of the photonic crystal structure having the desired reflection wavelength without the need to prepare a new photonic crystal structure It is possible.
  • the method may further include performing a counterion exchange reaction of the photonic crystal structure.
  • the counterion exchange reaction means exchanging the X ⁇ anion of the copolymer represented by Chemical Formula 4 with another anion, and for this purpose, the photonic crystal structure may be contacted with an anion supply compound. Through this, it is possible to manufacture a new photonic crystal structure having a reflection wavelength different from the photonic crystal structure.
  • a color conversion photonic crystal sensor including the color conversion photonic crystal structure described above is provided.
  • the color conversion photonic crystal sensor may be used as a humidity sensor. Specifically, the color conversion photonic crystal sensor is different in color depending on its type when in contact with moisture, it is possible to confirm the humidity by observing the converted color. In addition, the color conversion photonic crystal sensor is not only the color conversion is clear according to the humidity, it can be quickly restored to the original state when contact with the external stimulus is interrupted, it is possible to reuse repeatedly.
  • Triethylamine A product of 99% purity TCI (Tokyo Chemical Industry) was used.
  • Tetrahydrofuran A Burdick & jackson product having a purity of 99.99% was used.
  • Azobisisobutyronitrile Purified by JUNSEI from 98% purity.
  • N- (2,2,2-trifluoroethyl) acrylate TCI (Tokyo Chemical Industry) company of purity 98% was used.
  • Mn number average molecular weight
  • Tg glass transition temperature
  • Refractive index It measured by ellipsometer.
  • the high refractive index dispersion composition was prepared by dissolving Poly (4VP-BPAA) prepared in Preparation Example 1 in propanol, and the low refractive index dispersion composition was prepared by dissolving Poly (FEA-BPAA) prepared in Preparation Example 2 in ethyl acetate. .
  • the high refractive index dispersion composition was applied on a glass substrate for 30 seconds using a spin coater and then cured at 365 nm for 5 minutes to form a high refractive index layer.
  • the glass substrate on which the high refractive index layer was formed was placed in a propanol solution to remove uncured portions.
  • the low refractive index dispersion composition was applied on the high refractive index layer for 30 seconds using a spin coater, and then cured at 365 nm for 5 minutes to form a low refractive index layer.
  • the glass substrate on which the high refractive index layer and the low refractive index layer were formed was placed in an ethyl acetate solution to remove the uncured portion.
  • a high refractive index layer and a low refractive index layer was repeatedly stacked on the low refractive index layer, thereby preparing a light bulb structure in which a total of seven refractive index layers were laminated.
  • the precursor was placed in a 100 ml vial containing 10 ml of DMF and 226 ⁇ l of benzyl bromide (1.9 ⁇ 10 ⁇ 3 mol), quaternized at 50 ° C. for 20 minutes, washed with ethanol, and dried. To prepare a photonic crystal structure.
  • Example 1-1 except that the quaternization reaction time was changed to 40 minutes, 1 hour, 1 hour 20 minutes, 1 hour 40 minutes, 2 hours, 2 hours 20 minutes, 2 hours 40 minutes, and 3 hours, respectively. Using the same method as in the photonic crystal structure was prepared.
  • the high refractive index dispersion composition was applied for 30 seconds using a spin coater, and then cured for 5 minutes at 365 nm to form a high refractive index layer.
  • the low refractive index dispersion composition was applied for 30 seconds using a spin coater, followed by 5 at 365 nm. After curing for a minute to form a low refractive index layer, these were repeatedly laminated, and thus a photonic crystal structure was obtained in the same manner as in Example 1-1, except that a precursor structure in which a total of seven refractive index layers were laminated was manufactured. Was prepared.
  • Example 2-1 except that the quaternization reaction time was changed to 40 minutes, 1 hour, 1 hour 20 minutes, 1 hour 40 minutes, 2 hours, 2 hours 20 minutes, 2 hours 40 minutes, and 3 hours, respectively. Using the same method as in the photonic crystal structure was prepared.
  • the high refractive index dispersion composition was applied for 30 seconds using a spin coater, and then cured for 5 minutes at 365 nm to form a high refractive index layer.
  • the low refractive index dispersion composition was applied for 30 seconds using a spin coater, followed by 5 at 365 nm. After curing for a minute to form a low refractive index layer, they were repeatedly laminated to prepare a precursor structure in which a total of seven refractive index layers were laminated, and then the precursor structure was prepared by 10 ml of DMF and 142 ⁇ l bromoethane (1.9 ⁇ ).
  • a photonic crystal structure was prepared in the same manner as in Example 3-1, except that the quaternization reaction time was changed to 24 hours.
  • Example 3-1 The precursor prepared in Example 3-1 was placed in 100 ml vial containing 10 ml of DMF and 173 ⁇ l of bromopropane (1.9 ⁇ 10 ⁇ 3 mol), and quaternized at 50 ° C. for 5 hours, followed by ethanol. After washing with and dried to prepare a photonic crystal structure.
  • a photonic crystal structure was prepared in the same manner as in Example 4-1, except that the quaternization reaction time was changed to 24 hours.
  • Example 3-1 The precursor structure prepared in Example 3-1 was placed in 100 ml vial containing 10 ml of DMF and 226 ⁇ l of benzyl bromide (1.9 ⁇ 10 ⁇ 3 mol), and quaternized at 50 ° C. for 20 minutes. Washed with ethanol and dried to prepare a photonic crystal structure.
  • a photonic crystal structure was prepared in the same manner as in Example 5-1, except that the quaternization reaction time was changed to 24 hours.
  • the high refractive index dispersion composition was applied for 30 seconds using a spin coater, and then cured for 5 minutes at 365 nm to form a high refractive index layer.
  • the low refractive index dispersion composition was applied for 30 seconds using a spin coater, followed by 5 at 365 nm. After curing for a minute to form a low refractive index layer, they are repeatedly laminated to prepare a precursor structure in which a total of seven refractive index layers are laminated,
  • a photonic crystal structure was prepared in the same manner as in Example 6-1, except that the quaternization reaction time was changed to 24 hours.
  • the high refractive index dispersion composition was applied for 30 seconds using a spin coater, and then cured for 5 minutes at 365 nm to form a high refractive index layer.
  • the low refractive index dispersion composition was applied for 30 seconds using a spin coater, followed by 5 at 365 nm. After curing for a minute to form a low refractive index layer, they are repeatedly laminated to prepare a precursor structure in which a total of 13 refractive index layers are laminated,
  • the precursor structure was placed in 100 ml vial containing 10 ml of Hexane and 142 ⁇ l of bromoethane (1.9 ⁇ 10 -3 mol), and after quaternization at 50 ° C. for 48 hours, washed with ethanol and dried. , Except that a photonic crystal structure was produced, a photonic crystal structure was produced in the same manner as in Example 1-1.
  • the high refractive index dispersion composition was applied for 30 seconds using a spin coater, and then cured for 5 minutes at 365 nm to form a high refractive index layer.
  • the low refractive index dispersion composition was applied for 30 seconds using a spin coater, followed by 5 at 365 nm. After curing for a minute to form a low refractive index layer, they are repeatedly laminated to prepare a precursor structure in which a total of 13 refractive index layers are laminated,
  • the precursor was placed in a 100 ml vial containing 10 ml of DMF and 226 ⁇ l of benzyl bromide (1.9 ⁇ 10 ⁇ 3 mol), quaternized at 50 ° C. for 110 minutes, washed with ethanol, and dried.
  • a photonic crystal structure was produced in the same manner as in Example 1-1, except that the photonic crystal structure was prepared.
  • Example 5-1 The photonic crystal structure prepared in Example 5-1 was placed in 100 ml vial containing 1% of copper (2) perchlorate hexahydrate (Cu (ClO 4 ) 2 6H 2 O), and subjected to counter ion exchange reaction. Prepared.
  • a photonic crystal structure was prepared in the same manner as in Example 9-1, except that the counterion exchange reaction time was changed to 6 hours, 19 hours, 27 hours, and 44 hours, respectively.
  • the quaternized Poly ((4VP-BPAA) copolymer structure included in the high refractive index layer according to the type change of the RX compound prepared in Example is shown in Table 5.
  • the high refractive index layer is 4 If the conversion to the differential poly ((4VP-BPAA) copolymer is not 100%, the poly ((4VP-BPAA) copolymer and the quaternized Poly ((4VP-BPAA) copolymer are included at the same time.
  • the Poly (FEA-BPAA) copolymer included in the low refractive index layer the description was omitted because there is no change in the polymer before and after the quaternization.
  • Test Example 2 quaternization With change in reaction time Color conversion observe
  • the photonic crystal structure prepared in the above example changes the reflection wavelength according to the quaternization reaction time. Specifically, it can be seen that as the quaternization reaction time increases, the reflection wavelength becomes longer and shifts to longer wavelengths.
  • Test Example 3 According to the substituent change of ammonium ion Color conversion observe
  • Examples 3-1, 3-2, and 4-1 to confirm the color conversion according to the R group change and the quaternization reaction time thereof in the R-Br compound for quaternization represented by the formula (4) Colors of the photonic crystal structures prepared in, 4-2, 5-1, and 5-2 were observed, and specular reflectances of the photonic crystal structures were measured using a reflectometer (USB 4000, Ocean Optics), and the results are illustrated in FIGS. 4A and 4B.
  • FIGS. 4A and 4B USB 4000, Ocean Optics
  • the specular reflectance graphs of the photonic crystal structures prepared in 3-2, 4-2 and 5-2 are shown.
  • the 'reflection wavelength shift' means a value in which the reflection wavelength of the photonic crystal structure is shifted after the quaternization reaction with respect to the reflection wavelength of the photonic crystal structure before the quaternization reaction.
  • the photonic crystal structure prepared in the above example shows different reflection wavelengths according to the change of the R group, which is a substituent of ammonium ions, and as the reaction time increases, the reflection wavelength is longer as in the test example 2 above. It can be seen that it is shifted to a longer wavelength.
  • the quaternization reaction of poly (4VP-BPAA) was terminated before 5 hours because the reaction time was no longer changed when the reaction time was increased from 5 hours to 24 hours in the case of quaternization using benzyl bromide. It is understood.
  • Test Example 4 Counter ion change of ammonium ion Color conversion observe
  • the reflection wavelength is increased as the quaternization reaction time increases. It can be seen that it is longer and shifted to longer wavelengths.
  • the composition of the copolymer included in the high refractive index layer is changed by changing the compound for quaternization and controlling the quaternization reaction time, so that the refractive index of the high refractive index layer is changed, thereby causing photonic crystals. It can be seen that the structure exhibits the converted reflection wavelength.
  • Test Example 5 according to the humidity change Color conversion observe
  • the photonic crystal structure prepared in Example 7 was subjected to an environment of 11%, 23%, 33%, 43%, 52%, 68%, 75% and 85% relative humidity, respectively. After exposure to the changed color was observed and the results are shown in Figure 6a, the specular reflectance was measured using a reflectometer (USB 4000, Ocean Optics) and the results are shown in Figure 6b.
  • Example 8 the photonic crystal structure prepared in Example 8 was exposed to an environment of 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 87% relative humidity, respectively, and then changed color. Observed the result is shown in Figure 7a, the specular reflectance was measured using a reflectometer (USB 4000, Ocean Optics) and the result is shown in Figure 7b.
  • the photonic crystal structures prepared in Examples 7 and 8 have a clear shift in reflection wavelength according to changes in relative humidity, and thus have excellent sensitivity to changes in moisture.
  • the reflection wavelength of the photonic crystal structure is shifted in a direction in which the wavelength increases as the relative humidity increases.
  • the shifted reflection wavelength corresponds to the visible light region, so that the change in the reflection wavelength of the photonic crystal structure may be observed with the naked eye, and thus the photonic crystal structure according to the embodiment may be used to confirm the relative humidity.
  • Test Example 6 According to the change of counter ion of ammonium ion Color conversion observe
  • the specular reflectance of the photonic crystal structures prepared in Examples 9-1 to 9-5 by using a reflectometer USB 4000, Ocean Optics
  • the reflection wavelength and the reflection wavelength shift measurement results are shown in FIG. 6A
  • the specular reflection graph is shown in FIG. 6B.
  • the reflection wavelength of the photonic crystal structure can be changed not only through the quaternization reaction but also through the exchange reaction of the counter ion of the quaternized copolymer.
  • first refractive index layer 15 second refractive index layer

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Abstract

La présente invention concerne une structure de cristal photonique colorimétrique comprenant une couche à indice de réfraction élevé utilisant un copolymère comprenant simultanément une unité de répétition contenant un ion ammonium quaternaire et une unité de répétition dérivée d'un monomère à base d'acrylate ou d'acrylamide ayant un groupe fonctionnel photoactif. La structure de cristal photonique colorimétrique peut effectuer une conversion de couleur, qui est visuellement reconnaissable selon le changement d'humidité, et peut être utilisée pour fabriquer un capteur à cristal photonique. La présente invention concerne également un procédé de fabrication d'une structure de cristal photonique colorimétrique, le procédé comprenant une étape de quaternisation des atomes d'azote présents dans les unités de répétition du copolymère inclus dans une couche qui sont répétées, et une structure de cristal photonique colorimétrique ayant une longueur d'onde de réflexion à réaliser peut être fabriquée en contrôlant les conditions de réaction de quaternisation.
PCT/KR2017/011005 2016-10-06 2017-09-29 Structure de cristal photonique colorimétrique et capteur à cristal photonique colorimétrique l'utilisant WO2018066941A1 (fr)

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Citations (4)

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JP2004170447A (ja) * 2002-11-15 2004-06-17 Mitsubishi Gas Chem Co Inc スルフィド基を有する化合物を用いたフォトニック結晶
US20120293802A1 (en) * 2009-10-16 2012-11-22 Opalux Incorporated Photonic crystal combinatorial sensor
US20130015417A1 (en) * 2007-09-27 2013-01-17 Massachusetts Institute Of Technology Broad wavelength range chemically-tunable photonic materials
US20160252625A1 (en) * 2014-10-29 2016-09-01 The University Of Massachusetts Photonic polymer multilayers for colorimetric radiation sensing

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Publication number Priority date Publication date Assignee Title
JP2004170447A (ja) * 2002-11-15 2004-06-17 Mitsubishi Gas Chem Co Inc スルフィド基を有する化合物を用いたフォトニック結晶
US20130015417A1 (en) * 2007-09-27 2013-01-17 Massachusetts Institute Of Technology Broad wavelength range chemically-tunable photonic materials
US20120293802A1 (en) * 2009-10-16 2012-11-22 Opalux Incorporated Photonic crystal combinatorial sensor
US20160252625A1 (en) * 2014-10-29 2016-09-01 The University Of Massachusetts Photonic polymer multilayers for colorimetric radiation sensing

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Title
TIAN: "Colorful Humidity Sensitive Photonic Crystal Hydrogel", JOURNAL OF MATERIALS CHEMISTRY, vol. 18, no. 10, 25 January 2008 (2008-01-25), pages 1053 - 1160, XP055585230, DOI: doi:10.1039/b717368g *

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