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WO2019039821A1 - Structure cristalline photonique et capteur colorimétrique la comprenant - Google Patents

Structure cristalline photonique et capteur colorimétrique la comprenant Download PDF

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Publication number
WO2019039821A1
WO2019039821A1 PCT/KR2018/009561 KR2018009561W WO2019039821A1 WO 2019039821 A1 WO2019039821 A1 WO 2019039821A1 KR 2018009561 W KR2018009561 W KR 2018009561W WO 2019039821 A1 WO2019039821 A1 WO 2019039821A1
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Prior art keywords
refractive index
formula
copolymer
independently
repeating unit
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Korean (ko)
Inventor
정서현
박종목
공호열
이세영
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Korea Research Institute of Chemical Technology KRICT
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Korea Research Institute of Chemical Technology KRICT
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Priority claimed from KR1020170105488A external-priority patent/KR101996478B1/ko
Priority claimed from KR1020170105487A external-priority patent/KR102045994B1/ko
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Publication of WO2019039821A1 publication Critical patent/WO2019039821A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • 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
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • 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
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/29—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using visual detection
    • 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
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • 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
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/81—Indicating humidity

Definitions

  • the present invention relates to a color conversion photonic crystal structure and a color conversion sensor including the same.
  • a photonic crystal is a structure in which dielectric materials having different refractive indexes are periodically arranged, and superimposed interference occurs between light beams scattered at respective regular lattice points, so that light is not transmitted in a specific wavelength region band, , That is, a material that forms a photonic band gap.
  • photonic crystals are becoming a key material for improving the efficiency of information industry by using photons instead of electrons as a means of information processing.
  • the photonic crystal can be realized as a one-dimensional structure in which the photon moves in the direction of the main axis, a two-dimensional structure moving along the plane, or a three-dimensional structure freely moving in all directions through the entire material, It is easy to control the optical characteristics and is applicable to various fields.
  • photonic crystals can be applied to optical elements such as photonic crystal fibers, light emitting devices, photovoltaic devices, photonic crystal sensors, and semiconductor lasers.
  • the Bragg stack is a photonic crystal having a one-dimensional structure, which can be easily manufactured by only laminating two layers having different refractive indices, and has advantages of easy control of optical characteristics by controlling refractive index and thickness of the two layers . Due to this feature, the Bragg stack is widely used in photonic crystal sensors for sensing not only energy devices such as solar cells but also electrical, chemical and thermal stimuli. Accordingly, various materials and structures for easily manufacturing a photonic crystal sensor having excellent sensitivity and reproducibility have been studied.
  • the present invention provides a photonic crystal structure and a color conversion sensor including the same, more specifically, to provide a color conversion humidity sensor in which color is converted by a change in humidity and a sensor for inorganic acid conversion in which color is converted by contact with inorganic acid The purpose.
  • a liquid crystal display comprising: a first refractive index layer alternately stacked, the first refractive index layer comprising a first polymer exhibiting a first refractive index; And a second refractive index layer including a second polymer exhibiting a second refractive index,
  • first refractive index and the second refractive index are different from each other
  • R 1 and R 2 are each independently hydrogen or C 1-3 alkyl
  • R 3 is represented by the following formula (2) or (3)
  • L < 1 > is O or NH
  • Y < 1 > is benzoylphenyl
  • benzoylphenyl is unsubstituted or substituted with one to four substituents each independently selected from the group consisting of hydroxy, halogen, nitro, C 1-5 alkyl and C 1-5 alkoxy,
  • n 1 and m 1 each independently represents an integer of 1 or more
  • n 1 + m 1 is 100 to 2,000.
  • Y 2 is H, C 1-10 alkyl, C 1-10 aminoalkyl or ego,
  • k is an integer of 1 to 5.
  • X 1 to X 5 are each independently, N, N + RX-a, - or CR ', provided at least one of X 1 to X 5 is N or 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, and X - is monovalent Anion).
  • copolymer comprising the repeating unit represented by Formula 1 is a copolymer comprising a repeating unit represented by one formula selected from the following Formulas 1-1 to 1-3:
  • X 6 to X 10 are each independently, N, N + RX - or CR 'provided that, X 6 to X 10, at least one is N,
  • X 11 to X 15 are each independently N + RX - or CR ', at least one of X 11 to X 15 is N + RX -
  • R 1 , R 2 , R, R ', X - , L 1 , L 2 , Y 1 , Y 2 , n 1 and m 1 are as described above.
  • copolymer comprising the repeating unit represented by Formula 1 is a copolymer comprising repeating units represented by the following Formulas 1-4 or 1-5:
  • X 1 is N or N + R X - and X 2 to X 5 are each independently CR ';
  • X 2 is N or N + RX - , and X 1 , X 3 to X 5 are each independently CR '; or
  • X 3 is N or N + R X - , X 1 , X 2 , X 4 and X 5 are each independently CR '
  • R is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n- pentyl, isopentyl, neopentyl, tert- ,
  • X - is F -, Cl -, Br - , I -, ClO 4 -, SCN -, NO 3 -, or CH 3 CO 2 -, and, R 'is hydrogen, methyl, ethyl, or phenyl, the photonic crystal structure .
  • the other of the first polymer and the second polymer is a copolymer comprising a repeating unit represented by the following formula 4 or 5:
  • R 4 to R 7 are each independently hydrogen or C 1-3 alkyl
  • a 1 and A 2 are each independently a C 6-20 aromatic ring or C 2-20 hetero aromatic ring,
  • R 11 to R 13 are, each independently, hydroxy, cyano, nitro, amino, halogen, SO 3 H, SO 3 ( C 1- 5 alkyl), C 1-10 alkyl or C 1-10 alkoxy,
  • a1 to a3 are each independently an integer of 0 to 5
  • L 3 and L 4 are each independently O or NH
  • Y 3 and Y 4 are each independently benzoylphenyl
  • Y 3 and Y 4 are unsubstituted or substituted with one to four substituents each independently selected from the group consisting of hydroxy, halogen, nitro, C 1-5 alkyl and C 1-5 alkoxy,
  • n 2 and m 2 are each independently an integer of 1 or more
  • n 2 + m 2 is from 100 to 2,000
  • n 3 and m 3 are each independently an integer of 1 or more
  • n 3 + m 3 is 100 to 2,000).
  • R 4 to R 7 are each independently hydrogen or methyl
  • a 1 and A 2 are each independently a benzene ring or a naphthalene ring
  • R 11 to R 13 are each independently hydrogen, methyl, ethyl, Propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl
  • a1 to a3 are each independently 0, 1 or 2.
  • copolymer comprising the repeating unit represented by Formula 4 is a copolymer including a repeating unit represented by the following Formula 4-1:
  • n 2 and m 2 of the definition is as defined above.
  • copolymer comprising the repeating unit represented by Formula 5 is a copolymer comprising a repeating unit represented by the following Formula 5-1 or 5-2:
  • n 3 and m 3 are as defined above.
  • the photonic crystal structure further comprising a copolymer having a repeating unit represented by the following Chemical Formulas 1-6, wherein the refractive index layer comprising a copolymer comprising the repeating unit represented by Chemical Formula (1-3)
  • X 16 to X 20 are each independently N or CR ', at least one of X 16 to X 20 is N,
  • R 1 , R 2 , R ', L 1 , Y 1 , n 1 and m 1 are as described above.
  • the molar ratio of the copolymer comprising the repeating unit represented by Formula 1-3 to the copolymer including the repeating unit represented by Formula 1-6 is 90:10 to 10:90.
  • the photonic crystal structure is swollen by an external stimulus to shift a reflected wavelength to cause color conversion.
  • the total number of layers of the first refractive index layer and the second refractive index layer is 3 to 30 layers, respectively.
  • the first refractive index layer is a high refractive index layer having a thickness of 50 to 160 nm and the second refractive index layer is a low refractive index layer having a thickness of 25 to 150 nm.
  • a sensor comprising a photonic crystal structure of the top 1.
  • copolymer comprising the repeating unit represented by the formula (1) is a copolymer comprising a repeating unit represented by the following formula (1-1) or (1-2):
  • X 6 to X 10 are each independently, N, N + RX - or CR 'provided that, X 6 to X 10, at least one is N,
  • R 1 , R 2 , R, R ', X - , L 1 , L 2 , Y 1 , Y 2 , n 1 and m 1 are as described above.
  • the photonic crystal structure is swollen by contact with inorganic acid to shift the reflection wavelength.
  • the inorganic acid is HF, HCl, HBr or HI.
  • copolymer comprising the repeating unit represented by Formula 1 is a copolymer comprising a repeating unit represented by Formula 1-3:
  • X 11 to X 15 are each independently N + RX - or CR ', at least one of X 11 to X 15 is N + RX -
  • R 1 , R 2 , R, R ', X - , L 1 , L 2 , Y 1 , Y 2 , n 1 and m 1 are as described above.
  • the photonic crystal structure is swollen with a change in humidity to shift the reflection wavelength.
  • the color can be changed so that it can be visually judged according to a change in humidity, and a photonic crystal color conversion humidity sensor can be manufactured using the same,
  • the color can be changed so as to be visually judged according to the type of inorganic acid, and it is possible to manufacture a photonic crystal color conversion inorganic acid detection sensor by using the color.
  • FIG. 1 schematically shows a structure of a photonic crystal structure according to an embodiment of the present invention.
  • FIG. 2 is a graph showing changes in thickness and refractive index of the low refractive index layer prepared in Example 1 according to the type of inorganic acid to be reacted.
  • Example 3 shows a color conversion photograph and a reflected wavelength change according to the type of inorganic acid reacted in the color conversion inorganic acid detection sensor prepared in Example 2-1.
  • Example 4 shows the color conversion photograph and the reflected wavelength change according to the type of inorganic acid reacted in the color conversion inorganic acid detection sensor prepared in Example 2-2.
  • FIG. 5 shows color conversion photographs and reflected wavelength changes according to kinds of inorganic acids to be reacted in the color conversion inorganic acid detection sensor prepared in Example 2-3.
  • Fig. 6 shows a color conversion photograph and a reflected wavelength change according to the type of inorganic acid reacted in the color conversion inorganic acid detection sensor prepared in Example 3-1.
  • Example 7 shows a color conversion photograph and a reflected wavelength change according to the type of inorganic acid to be reacted in the color conversion inorganic acid detection sensor prepared in Example 3-2.
  • Example 8 is a color conversion photograph and a reflected wavelength change according to the type of inorganic acid reacted in the color conversion inorganic acid detection sensor prepared in Example 3-3.
  • Example 9 is a color conversion photograph of the color conversion inorganic acid detection sensor prepared in Example 4 according to the kind and concentration of the reacted inorganic acid.
  • FIG. 10 shows the results of Ellipsometer / Surface profiler according to quadrification of the low refractive index layer according to an embodiment of the present invention.
  • FIG. 11 is a graph showing the results of an Ellipsometer / Surface profiler according to quadrification of a low refractive index layer according to an embodiment of the present invention, wherein (a) shows the low refractive index layer before the quaternization reaction of chloropropane, (b) (C) is a low refractive index layer before the quaternization reaction of bromopropane, (d) is a low refractive index layer after quaternization reaction of bromopropane, (e) is a low refractive index layer before quaternization reaction of iodopropane, (G) is a low refractive index layer before the quaternization reaction of benzylchloride, and (h) is a low refractive index layer after quaternization reaction of benzylchloride.
  • FIG. 12 shows color conversion according to the counter ion change of the quaternization reaction R group or ammonium ion of the photonic crystal structure according to an embodiment of the present invention.
  • FIG. 13 illustrates reflected wavelength conversion according to changes in counter ions of ammonium ions in a photonic crystal structure according to an embodiment of the present invention.
  • 16 is a diagram illustrating reflection wavelength conversion according to humidity change of a photonic crystal structure according to an embodiment of the present invention.
  • FIG 17 illustrates color conversion according to the quadrature reaction time of the photonic crystal structure according to an embodiment of the present invention.
  • FIG. 18 shows reflected wavelength conversion according to the quadrification reaction time of the photonic crystal structure according to an embodiment of the present invention.
  • the term 'photonic crystal' used in the present invention refers to a structure in which dielectric materials having different refractive indexes are periodically arranged, superimposed interference occurs between light scattered at each regular grid point, Means a material that selectively reflects light without transmitting light, that is, forms a light band gap.
  • a photonic crystal is a material having a high speed of information processing using a photon in place of an electron as a means of information processing. It is a one-dimensional structure in which a photon moves in the direction of a main axis, a two-dimensional structure moving along a plane, Dimensional structure that can move freely to the three-dimensional structure.
  • the present invention can be applied to optical elements such as photonic crystal fibers, light emitting devices, photovoltaic devices, color conversion films, and semiconductor lasers by controlling optical characteristics by controlling the photonic bandgap of photonic crystals.
  • the term 'photonic crystal structure' used in the present invention is a Bragg stack having a one-dimensional photonic crystal structure produced by alternately stacking materials having different refractive indexes.
  • the photonic crystal structure is formed by a periodic difference in the refractive index of the laminated structure Refers to a structure in which light of a specific wavelength range can be reflected and the reflection wavelength is shifted by an external stimulus to change the reflection color. Specifically, partial reflection of light occurs at the boundary of each layer of the structure, and many of these reflected waves interfere structurally and light of a specific wavelength having high intensity can be reflected.
  • the shift of the reflected 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.
  • the optical characteristics of the photonic crystal structure can be controlled by controlling the refractive index and the thickness, and can be produced in the form of a coating film coated on a separate substrate or substrate, or in the form of a free standing film.
  • the present invention provides a photonic crystal structure in which color is converted by an external stimulus.
  • the external stimulus for converting the color of the photonic crystal structure may be, for example, inorganic acid or humidity.
  • the color conversion photonic crystal structure of the present invention comprises: a first refractive index layer which is alternately stacked and includes a first polymer exhibiting a first refractive index; And a second refractive index layer including a second polymer exhibiting a second refractive index, wherein the first refractive index and the second refractive index are different from each other.
  • 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 low refractive index layer has the low refractive index layer
  • the polymer included in the low refractive index layer having a relatively low refractive index among the two types of layers included in the photonic crystal structure according to the present invention is a polymer having a repeating unit represented by the following formula (1) as one of the first polymer and the second polymer: Is a copolymer comprising:
  • R 1 and R 2 are each independently hydrogen or C 1-3 alkyl
  • R 3 is represented by the following formula (2) or (3)
  • L < 1 > is O or NH
  • Y < 1 > is benzoylphenyl
  • benzoylphenyl is unsubstituted or substituted with one to four substituents each independently selected from the group consisting of hydroxy, halogen, nitro, C 1-5 alkyl and C 1-5 alkoxy,
  • n 1 and m 1 each independently represents an integer of 1 or more
  • n 1 + m 1 is 100 to 2,000.
  • Y 2 is H, C 1-10 alkyl, C 1-10 aminoalkyl or ego,
  • k is an integer of 1 to 5.
  • X 1 to X 5 are each independently, N, N + RX-a, - or CR ', provided at least one of X 1 to X 5 is N or 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, and X - is monovalent Anion.
  • the copolymer containing the repeating unit represented by the formula ( 1 ) may further contain a repeating unit derived from an acrylate or acrylamide monomer having a photoactive functional group (Y 1 ) It is possible to make the photopolymerization.
  • the copolymer containing the repeating unit represented by the above formula ( 1 ) is a copolymer obtained by randomly copolymerizing an acrylate or an acrylamide monomer having a styrene-based monomer and a photoactive functional group (Y 1 ) And may be a random copolymer in which repeating units are randomly arranged with respect to each other.
  • the copolymer containing the repeating unit represented by the formula (1) may be a block copolymer in which a block of repeating units between the square brackets of the formula (1) is linked by a covalent bond.
  • it may be an alternating copolymer in which the repeating units between the square brackets of Formula 1 are arranged to be crossed, or a graft copolymer in which any one repeating unit is bonded in the form of a branch.
  • the shape is not limited.
  • the copolymer containing the repeating unit represented by the formula (1) according to the present invention may exhibit a refractive index of 1.5 to 1.7, for example.
  • a photonic crystal structure that reflects light of a desired wavelength can be realized by a refractive index difference with a polymer used in a high refractive index layer described later.
  • R 1 and R 2 each independently may be hydrogen or methyl.
  • R 1 and R 2 may be hydrogen.
  • X 1 is N or N + RX - , and X 2 to X 5 are each independently CR ';
  • X 2 is N or N + RX - , and X 1 , X 3 to X 5 are each independently CR '; or
  • X- 3 is N or N + RX - is and, 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 selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n- pentyl, isopentyl, neopentyl, Or phenylethyl, and R 'may be hydrogen, methyl, ethyl, or phenyl.
  • X - is a mono-valent anion, for example, X - is F - , Cl - , Br - , I - , ClO 4 - , SCN - , NO 3 - , or CH 3 CO 2 - can be.
  • halogen anions such as F - , Cl - , Br - , or I - are preferred from the standpoint of ease of quaternization reaction described below.
  • Y 1 may be unsubstituted or benzoylphenyl substituted with C 1-3 alkyl.
  • Y < 1 > is benzoylphenyl, it may be advantageous in terms of ease of photocuring.
  • n 1 represents the total number of repeating units containing a repeating unit derived from a fluoroalkyl acrylamide-based monomer or quaternary ammonium ion in the copolymer
  • m 1 represents a photoactive functional group in the copolymer Y & lt ; 1 > ) of the repeating unit derived from an acrylate or an acrylamide-based monomer.
  • the copolymer having the repeating unit represented by Formula 1 may have a molar ratio of n 1 : m 1 of 100: 1 to 100: 50, and a number average molecular weight of 10,000 to 200,000 g / mol.
  • the copolymer having the repeating unit represented by Formula 1 may have a molar ratio of n 1 : m 1 of 100: 1 to 100: 40, specifically 100: 5 to 100: 35.
  • the copolymer comprising repeating units represented by the above formula (1) has a number average molecular weight of 10,000 to 300,000 g / mol, specifically 30,000 to 180,000 g / mol, more specifically 50,000 to 80,000 g / mol Lt; / RTI > Within the above range, it is possible to produce a copolymer having a low refractive index and easy photocuring.
  • the copolymer comprising the repeating unit represented by the formula (1) may be one of the copolymers comprising the repeating units represented by the following formulas (1-1) to (1-3):
  • X 6 to X 10 are each independently, N, N + RX - or CR 'provided that, X 6 to X 10, at least one is N,
  • X 11 to X 15 are each independently N + RX - or CR ', at least one of X 11 to X 15 is N + RX -
  • R 1 , R 2 , R, R ', L 1 , L 2 , Y 1 , Y 2 , n 1 and m 1 are as described above.
  • a copolymer containing a repeating unit represented by the general formula (1-1) or (1-2) By including a copolymer containing a repeating unit represented by the general formula (1-1) or (1-2), it has a low refractive index and is excellent in chemical properties such as thermal stability, chemical resistance, oxidation stability, and transparency.
  • the hydrophilicity may be increased to better respond to external stimuli such as moisture.
  • the repeating unit containing the quaternary ammonium ion has counter ions (X < - >) ion-bonded to the quaternary ammonium cations, and the photonic crystals It is possible to manufacture a structure.
  • the refractive index can be changed according to the number of the quaternary ammonium ions in the copolymer and the type of counter ions, and the color conversion photonic crystal structure having a desired reflection wavelength can be realized by controlling the refractive index.
  • the copolymer containing the repeating unit represented by the above-mentioned formula (1) may be one of the copolymers comprising the repeating unit represented by the following formula (1-4) or (1-5)
  • the low refractive index layer comprising a copolymer including the repeating unit represented by Formula 1-3 may further include a copolymer including a repeating unit represented by the following Formula 1-6:
  • X 16 to X 20 are each independently N or CR ', at least one of X 16 to X 20 is N,
  • R 1 , R 2 , R ', L 1 , Y 1 , n 1 and m 1 are as described above.
  • the copolymer containing the repeating unit represented by the above Chemical Formula 1-3 further contains a copolymer containing the repeating unit represented by the above Chemical Formula 1-6, complex formation with metal ions may be better.
  • the molar ratio of the copolymer including the repeating unit represented by Formula 1-3 to the copolymer including the repeating unit represented by Formula 1-6 in the low refractive index layer may be 100: 0 to 1: 99 have.
  • the low refractive index layer simultaneously contains a copolymer including the repeating unit represented by the above Chemical Formula (1-3) and a copolymer including the repeating unit represented by the above Chemical Formula (1-6), the low refractive index layer
  • the molar ratio of the copolymer including the repeating unit represented by Formula 1-3 to the copolymer including the repeating unit represented by Formula 1-6 may be 90:10 to 10:90.
  • the copolymer containing the repeating unit represented by the general formula (1-6) can be prepared by reacting the RX compound (wherein R is as defined in the above formula (1)) in the quarternization reaction of the process for producing a photonic crystal structure , And X is a leaving group capable of forming a monovalent anion by a nucleophilic substitution reaction with a copolymer containing a repeating unit represented by the formula (1-6). That is, the copolymer containing the repeating unit represented by the formula 1-3 is prepared by the reaction of the copolymer containing the repeating unit represented by the above formula 1-6 with the R-X compound.
  • the copolymer comprising the repeating unit represented by Formula 1-3 is obtained by reacting a photocrystalline structure in which a low refractive index layer containing a copolymer containing the repeating unit represented by Formula 1-6 is laminated, And the copolymer containing the repeating unit represented by the above formula (1-6) not participating in the quaternization reaction may remain in the finally prepared photonic crystal structure. Therefore, the molar ratio of the copolymer containing the repeating unit represented by the above formula (1-3) and the copolymer containing the repeating unit represented by the above formula (1-6) in the low refractive index layer can be controlled according to the quaternization reaction conditions .
  • the polymer contained in the high refractive index layer which is a layer having a relatively high refractive index, of the two types of layers included in the photonic crystal structure according to the present invention is not a copolymer represented by the formula (1) (Meth) acrylate-based compounds, (meth) acrylamide-based compounds, vinyl groups (meth) acrylate-based compounds, and the like can be given. Containing aromatic compounds, dicarboxylic acids, xylylene, alkylene oxides, arylene oxides, and derivatives thereof. These may be used alone or in combination of two or more.
  • the polymer contained in the high refractive index layer may contain one or more repeating units derived from the following monomers: methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (Meth) acrylate, 1-phenylethyl (meth) acrylate, 2-phenylethyl (meth) acrylate, (Meth) acrylate monomers such as m-nitrobenzyl (meth) acrylate,?
  • -Naphthyl (meth) acrylate and benzoylphenyl (meth) acrylate (Meth) acrylamides such as methyl (meth) acrylamide, ethyl (meth) acrylamide, isobutyl (meth) acrylamide, (Meth) acrylamide monomers such as (meth) acrylamide and benzoylphenyl (meth) acrylamide; Styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, o-methoxystyrene and 4-methoxy-2-methylstyrene; aromatic monomers such as p-divinylbenzene, 2-vinylnaphthalene, vinylcarbazole and vinylfluorene; Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxy
  • a repeating unit derived from a styrene-based monomer and a repeating unit derived from one of (meth) acrylate and (meth) acrylamide in view of favorable difference in refractive index difference and ease of photocuring.
  • the other of the first polymer and the second polymer which is not the copolymer represented by the formula (1) used in the high refractive index layer, may be a copolymer containing a repeating unit represented by the following formula (4) or have:
  • R 4 to R 7 are each independently hydrogen or C 1-3 alkyl
  • a 1 and A 2 are each independently a C 6-20 aromatic ring or C 2-20 hetero aromatic ring,
  • R 11 to R 13 are, each independently, hydroxy, cyano, nitro, amino, halogen, SO 3 H, SO 3 ( C 1- 5 alkyl), C 1-10 alkyl or C 1-10 alkoxy,
  • a1 to a3 are each independently an integer of 0 to 5
  • L 3 and L 4 are each independently O or NH
  • Y 3 and Y 4 are each independently benzoylphenyl
  • Y 3 and Y 4 are unsubstituted or substituted with one to four substituents each independently selected from the group consisting of hydroxy, halogen, nitro, C 1-5 alkyl and C 1-5 alkoxy,
  • n 2 and m 2 are each independently an integer of 1 or more
  • n 2 + m 2 is from 100 to 2,000
  • n 3 and m 3 are each independently an integer of 1 or more
  • n 3 + m 3 is 100 to 2,000).
  • the copolymer containing the repeating unit represented by the general formula (4) or (5) contains a repeating unit derived from a styrene-based monomer and a repeating unit derived from a carbazole-based monomer, a high refractive index layer can be realized because the refractive index is high.
  • the copolymer containing the repeating unit represented by the above formula (4) or (5) may further include a repeating unit derived from an acrylate or acrylamide monomer having photoactive functional groups (Y 3 and Y 4 ) Or photo-curing may be possible without a cross-linking agent.
  • the copolymer containing the repeating unit represented by the above formula (4) or (5) is a copolymer obtained by randomly copolymerizing an acrylate or acrylamide monomer having a styrene-based monomer and a photoactive functional group (Y 3 and Y 4 ) 4 or 5 may be random copolymers in which the repeating units between the square brackets are randomly arranged with respect to each other.
  • the copolymer including the repeating unit represented by the formula (4) may be a block copolymer in which the block of repeating units between the square brackets of the formula (4) is linked by a covalent bond.
  • it may be an alternating copolymer in which repeating units between the square brackets of Formula 4 are crossed, or a graft copolymer in which any one repeating unit is bonded in a branched form.
  • the shape is not limited.
  • the copolymer containing the repeating unit represented by the formula (5) may be a block copolymer in which the block of repeating units between the square brackets in the formula (5) is connected by a covalent bond.
  • it may be an alternating copolymer in which the repeating units between the square brackets in the formula (5) are arranged to be crossed, or a graft copolymer in which any one repeating unit is bonded in a branched form.
  • the shape is not limited.
  • the copolymer containing the repeating unit represented by the above formula (4) or (5) may exhibit a refractive index of 1.51 to 1.8. In the above-mentioned range, a photonic crystal structure reflecting light of a desired wavelength can be realized due to the difference in refractive index between the polymer and the polymer containing the repeating unit represented by the formula (1).
  • R 4 to R 7 each independently may be hydrogen or methyl.
  • R 4 to R 7 may be hydrogen.
  • a 1 and A 2 each independently may be a benzene ring or a naphthalene ring.
  • a 1 and A 2 can each independently be a benzene ring.
  • R 11 to R 13 each independently may be hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.
  • a1 means the number of R 11 , which may be 0, 1 or 2, and when a 1 is 2 or more, R 11 of 2 or more may be the same or different from each other.
  • a2 and a3 may also be understood with reference to a1 and the structures of formulas (4) and (5), and may be 0, 1, or 2.
  • Y 3 and Y 4 each independently may be unsubstituted or benzoylphenyl substituted with C 1-3 alkyl.
  • Y 3 and Y 4 are benzoylphenyl, they are advantageous from the standpoint of ease of photocuring.
  • N 2 represents the total number of repeating units derived from the styrene-based monomer in the copolymer
  • m 2 represents the number of repeating units derived from an acrylate or acrylamide monomer having a photoactive functional group in the copolymer It means the total number.
  • the copolymer comprising the repeating unit represented by Formula 4 according to the present invention may have a molar ratio of n 2 : m 2 of 100: 1 to 100: 50, for example, 100: 30 to 100: 50.
  • the copolymer containing the repeating unit represented by the formula (4) may have a number average molecular weight (Mn) of 10,000 to 100,000 g / mol, for example, 10,000 to 50,000 g / mol.
  • Mn number average molecular weight
  • the copolymer comprising the repeating unit represented by the formula (4) according to the present invention may be a copolymer comprising repeating units represented by the following formula (4-1)
  • n 2 and m 2 of the definition is as defined above.
  • n 3 represents the total number of repeating units derived from the carbazole-based monomer in the copolymer
  • m 3 represents a repeating unit derived from an acrylate or acrylamide monomer having a photoactive functional group in the copolymer .
  • the copolymer comprising the repeating unit represented by Chemical Formula 5 according to the present invention may have a molar ratio of n 3 : m 3 of 100: 1 to 100: 50, for example, 100: 1 to 100: 40.
  • the copolymer containing the repeating unit represented by Formula 3 may have a number average molecular weight (Mn) of 10,000 to 500,000 g / mol, for example, 10,000 to 350,000 g / mol.
  • Mn number average molecular weight
  • the copolymer containing the repeating unit represented by the formula (5) may be a copolymer comprising the repeating unit represented by the following formula (5-1) or (5-2):
  • n 3 and the definition of m 3 are as defined above).
  • a color conversion photonic crystal structure includes a first refractive index layer disposed on the 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 And alternately repeatedly stacked.
  • the color conversion photonic crystal structure may further include a substrate on the other surface on which the second refractive index layer of the first refractive index layer disposed at the lowermost portion is not disposed, depending on the application. Therefore, in this case, the substrate may be positioned at the lowermost part of the color conversion photonic crystal structure.
  • a color conversion photonic crystal structure 10 includes a substrate 11 and a first refractive index layer 13 and a second refractive index layer 15 alternately stacked on the substrate 11 ).
  • the first refractive index layer 13 may be located at the top of the color conversion photonic crystal structure. Therefore, the first refractive index layer 13 is further laminated on the laminated body in which the first refractive index layer 13 and the second refractive index layer 15 are alternately laminated, and the photonic crystal structure has the refractive index layer of the odd number of layers Lt; / RTI > In this case, as will be described later, the constructive interference between the lights reflected at the interface of each layer increases, so that the intensity of the reflected wavelength of the photonic crystal structure can be increased.
  • the substrate 11 may be formed of a carbon-based material having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling and waterproofing, metal foil, thin glass, silicon (Si), plastic, polyethylene (PE) Paper, skin, clothing, or wearable material such as, but not limited to, polyethylene terephthalate (PET), polypropylene (PP), and the like, and may be made of various materials that are flexible or non- Can be used.
  • a carbon-based material having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling and waterproofing, metal foil, thin glass, silicon (Si), plastic, polyethylene (PE) Paper, skin, clothing, or wearable material such as, but not limited to, polyethylene terephthalate (PET), polypropylene (PP), and the like, and may be made of various materials that are flexible or non- Can be used.
  • the first refractive index layer 13 alternately stacked on the substrate 11 comprises a first polymer having a first refractive index n1 and the second refractive index layer 15 has a second refractive index n2, ≪ / RTI >
  • the 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.
  • it is possible to control the reflection of light of a desired wavelength by controlling the difference between the refractive indexes within the above-mentioned 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 is a low refractive index layer.
  • the photonic crystal structure 10 has a high refractive index layer / A low refractive index layer / a high refractive index layer / a low refractive index layer / a high refractive index layer may be sequentially stacked.
  • 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 is a high refractive index layer.
  • the photonic crystal structure 10 is formed on the substrate 11 with a low refractive index layer / And a structure in which a high refractive index layer / a low refractive index layer / a high refractive index layer / a low refractive index layer are sequentially laminated.
  • the ratio of the thickness of the low refractive index layer to the thickness of the high refractive index layer may be from 1: 4 to 1: 0.5.
  • the thickness of the low refractive index layer may be 25 to 150 nm
  • the thickness of the high refractive index layer may be 50 to 160 nm.
  • the structure is a high refractive index layer in which the first refractive index layer is formed to a thickness of 50 to 160 nm in terms of ease of color conversion, the second refractive index layer is a low refractive index layer formed in a thickness of 25 to 150 nm, A structure in which the refractive index layer is located at the top is preferable.
  • FIG. 1 shows only the photonic crystal structure 10 having a total of five layers, but the total number of the photonic crystal structure layers is not limited thereto. Specifically, the total number of layers of the first refractive index layer and the second refractive index layer may be 3 to 30 layers. In the case of the structure laminated in the above-mentioned range, interference of the light reflected from each layer boundary surface is sufficiently generated, and the reflection intensity can be such that a change in color due to an external stimulus is detected.
  • the reflection wavelength (?) Of the color converting photonic crystal structure can be determined by the following equation (1):
  • N1 and n2 denote the refractive indexes of the first refractive index layer and the second refractive index layer, respectively, and d1 and d2 denote the thicknesses of the first refractive index layer and the second refractive index layer, respectively. Therefore, it is possible to realize a desired reflection wavelength (?) By adjusting the kinds of the first and second polymers described below, the thicknesses of the first and second refractive index layers, and the total number of the first and second refractive index layers have.
  • the reflection wavelength of the photonic crystal structure is shifted by the swelling of the first polymer and / or the second polymer contained in the photonic crystal structure due to the external stimulus.
  • the first polymer and / or the second polymer is swollen, the crystal lattice structure of each refractive index layer is changed, and the shape of light scattered at each layer interface is changed. That is, the photonic crystal structure exhibits the converted color due to the shifted reflection wavelength? ', And the existence of the external stimulus can be confirmed by the color conversion of the photonic crystal structure.
  • the reflection wavelength (?) And the shifted reflection wavelength (? ') Of the photonic crystal structure are within the visible light range of 380 nm to 760 nm, the color conversion of the photonic crystal structure can be easily confirmed visually.
  • the intensity of the external stimulus is high, the degree of change of the crystal lattice structure of the first polymer and the second polymer is increased and the reflected wavelength is further shifted, so that the intensity of the external stimulus can be detected according to the implemented color.
  • the color conversion of the photonic crystal structure appears due to a change in humidity or a contact of an inorganic acid with a reflection wavelength shifted. That is, the shift of the reflection wavelength of the photonic crystal structure is caused by a change in refractive index and an increase in thickness of the copolymer represented by the formula (1) upon moisture absorption or contact with inorganic acid.
  • the photonic crystal structure when the photonic crystal structure is in contact with water or inorganic acid, for example, when the photonic crystal structure is exposed to air containing moisture or inorganic acid or impregnated with water or inorganic acid as liquid,
  • the copolymer absorbs water or inorganic acid and swells, thereby changing its thickness.
  • the copolymer represented by the above formula (1) reacts with quaternary ammonium cations and counter anions thereof because of its excellent reactivity with water having a high polarity. Accordingly, the reflection wavelength of the photonic crystal structure according to Formula 1 can be shifted.
  • the shifted reflection wavelength (? ') Is in the range of 380 nm to 760 nm, so that the color change can be visually observed.
  • the photonic crystal structure can shift the reflection wavelength to a longer wavelength depending on the humidity, the higher the moisture content, or the type and concentration of the inorganic acid. Therefore, the shifted reflection wavelength? 'Of the photonic crystal structure may have a larger value than the reflection wavelength? Without the external stimulus.
  • the photonic crystal structure according to the present invention as described above can be produced by a manufacturing method including, for example, the following steps:
  • the description of the first refractive index, the first polymer, the second refractive index, the second polymer, the first refractive index layer and the second refractive index layer is as described above.
  • a first dispersion composition and a second dispersion composition are prepared.
  • Each dispersion composition can be prepared by dispersing the polymer in a solvent, wherein the dispersion composition is used as a term to indicate various states such as solution phase, slurry phase or paste phase.
  • the solvent may be any solvent capable of dissolving the first and second polymers, and the first and second polymers may each be contained in an amount of 0.5 to 20% by weight based on the total weight of the dispersion composition. In the above-mentioned range, it is possible to prepare a dispersion composition having a viscosity suitable for being applied on a substrate.
  • the first dispersion composition may comprise a solvent and a first polymer
  • the second dispersion composition may comprise a solvent and a second polymer.
  • it may not contain a separate photoinitiator and crosslinking agent for photo-curing, or inorganic particles. Therefore, the photonic crystal structure can be manufactured more easily and economically, and deviations in optical characteristics according to the position of the photonic crystal structure manufactured can be reduced without adding any additive.
  • the prepared first dispersion composition is coated on a substrate or a substrate, and then light irradiation is performed to produce a first refractive index layer, and thereafter, the second dispersion composition prepared on the first refractive index layer is applied
  • the second refractive index layer can be manufactured by performing light irradiation.
  • the dispersion composition may be applied to a substrate or a refractive index layer by spin coating, dip coating, roll coating, screen coating, spray coating, But are not limited to, spin casting, flow coating, screen printing, ink jet, or drop casting.
  • the light irradiation step may be performed by irradiating a 365 nm wavelength under a nitrogen condition.
  • the benzophenone moiety contained in the polymer acts as a photoinitiator, and a photocured refractive index layer can be produced.
  • the first refractive index layer and the second refractive index layer can be alternately laminated, and a photonic crystal structure having, for example, 3 to 30 laminated layers can be manufactured.
  • a quaternization reaction can be performed by contacting the compound with a compound represented by RX have.
  • the quaternization reaction is a nucleophilic substitution reaction of RX with the nitrogen atom of the copolymer containing the repeating unit represented by the above formula (1-6) in the low refractive index layer, and the R group is bonded to the nitrogen atom having the non- ammonium cation and X- - anions is produced.
  • the copolymer containing the repeating unit represented by the above formula (1-6) is converted into a copolymer containing the repeating unit represented by the above formula (1), more specifically, the repeating unit represented by the above formula (1-3) Is less than 100%, not only a copolymer including the repeating unit represented by the above formula (1-3) but also a copolymer including the repeating unit represented by the above formula (1-6) is present in the low refractive index layer. Therefore, it is possible to manufacture a photonic crystal structure having a composition of a desired low refractive index layer by controlling quaternization reaction conditions.
  • the color conversion sensor according to the present invention may include one or more of the photonic crystal structures described above.
  • the color conversion humidity sensor may include 2 or more, or 2 to 100, photonic crystal structures, but the number is not limited.
  • Each of the plurality of photonic crystal structures may independently have the same kind of the first and second polymers, the thicknesses of the first and second refractive index layers and / or the total number of the first and second refractive index layers stacked Or may be different.
  • the color conversion photocrystalline sensor converts color upon contact with an external stimulus, the type and amount of the external stimulus can be confirmed by observing the converted color. In addition, when the contact with the external stimulus is interrupted, it can be quickly restored to its original state, and it can be reused repeatedly.
  • the color conversion inorganic acid detection sensor according to the present invention may more specifically include one or a plurality of photonic crystal structures including a copolymer including a repeating unit represented by the above-mentioned formula (1-1) or (1-2).
  • the color conversion photocrystalline sensor is different in color depending on the kind thereof, for example, HF, HCl, HBr or HI upon contact with the inorganic acid, so that the type of inorganic acid can be confirmed by observing the converted color.
  • HF HF
  • HCl HCl
  • HBr HBr
  • HI HI
  • the color conversion humidity sensor according to the present invention may include one or a plurality of photonic crystal structures including a copolymer including a repeating unit represented by the above-mentioned Formula 1-3.
  • the color conversion photonic crystal sensor Since the color conversion photonic crystal sensor is different in color depending on the kind of the copolymer in the photonic crystal structure upon contact with moisture, the humidity can be confirmed by observing the converted color. In addition, the color conversion photonic crystal sensor can quickly recover to its original state when contact with an external stimulus is interrupted, and can be reused repeatedly.
  • Mn number average molecular weight
  • PDI molecular weight distribution
  • Tg glass transition temperature: Measured using differential scanning calorimeter (DSC).
  • the poly (4VP-BPAA) prepared in Preparation Example 1 was dissolved to 2 wt% to prepare a low refractive index dispersion composition.
  • the low refractive index dispersion composition was coated on a glass substrate at 4,000 rpm using a spin coater and cured at a wavelength of 254 nm for 3 minutes to form a low refractive index layer.
  • the low refractive index dispersion composition was prepared by dissolving Poly (4VP-BPAA) prepared in Preparation Example 1 to 2 wt%, and the poly (VK-BPA) prepared in Preparation Example 3 was dissolved to 2 wt% A dispersion composition was prepared.
  • the above high refractive index dispersion composition was coated on a glass substrate using a spin coater at 3,000 rpm for 50 seconds and then cured at 254 nm for 3 minutes to prepare a high refractive index layer.
  • the low refractive index dispersion composition was coated on the high refractive index layer using a spin coater at 3,000 rpm for 50 seconds and then cured at 254 nm for 3 minutes to prepare a low refractive index layer.
  • the high refractive index layer and the low refractive index layer were repeatedly laminated on the low refractive index layer to manufacture a photonic crystal structure in which a total of seven refractive index layers were laminated.
  • a high refractive index dispersion composition was applied at 4,500 rpm, and 11 layers of refractive index layers were laminated, and the same procedure as in Example 2-1 was used.
  • the low refractive index dispersion composition was prepared by dissolving the poly (DMAEMA-BPAA) prepared in Preparation Example 2 to 2 wt%, and the poly (VK-BPA) prepared in Preparation Example 3 was dissolved to 2 wt% A dispersion composition was prepared.
  • the high refractive index dispersion composition was coated on a PET substrate using a spin coater at 3,000 rpm for 50 seconds and then cured at 254 nm for 3 minutes to prepare a high refractive index layer.
  • the low refractive index dispersion composition was coated on the high refractive index layer using a spin coater at 3,000 rpm for 50 seconds and then cured at 254 nm for 2 minutes to prepare a low refractive index layer.
  • the high refractive index layer and the low refractive index layer were repeatedly laminated on the low refractive index layer to manufacture a photonic crystal structure in which 11 refractive index layers were stacked.
  • the low refractive index dispersion composition was prepared by dissolving Poly (DMAEMA-BPAA) to 3 wt%, and the high refractive index dispersion composition was prepared by dissolving poly (VK-BPA) to 1.5 wt% , And a total of nine refractive index layers were laminated on one another.
  • a refractive index dispersion composition was prepared by dissolving poly (VK-BPA) in an amount of 1.5 wt%, applying a high refractive index dispersion composition at 4,000 rpm, and curing for 2 minutes to laminate a total of five refractive index layers.
  • VK-BPA dissolving poly
  • the low refractive index dispersion composition was prepared by dissolving the poly (4VP-BPAA) prepared in Preparation Example 1 to 2 wt%, and the poly (VK-BPA) prepared in Preparation Example 3 was dissolved to 2 wt% A dispersion composition was prepared.
  • the above high refractive index dispersion composition was coated on a PVC film using a spin coater at 3,500 rpm for 50 seconds and then cured at 254 nm for 3 minutes to prepare a high refractive index layer.
  • the low refractive index dispersion composition was coated on the high refractive index layer using a spin coater at 3,500 rpm for 50 seconds and then cured at 254 nm for 3 minutes to prepare a low refractive index layer.
  • the high refractive index layer and the low refractive index layer were repeatedly laminated on the low refractive index layer to manufacture a photonic crystal structure in which a total of seven refractive index layers were laminated.
  • Poly (4VP-BPAA) prepared in Preparation Example 1 was dissolved in ethanol to prepare a low refractive index dispersion composition.
  • the low refractive index dispersion composition was coated on a glass substrate at 4,000 rpm 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 low refractive index layer was formed was placed in an ethanol solution to remove unhardened portions.
  • the glass substrate on which the low refractive index layer was formed was placed in a 100 ml vial containing 10 ml of DMF and 226 ⁇ l of chloropropane, quaternarized at 70 ° C for 72 minutes, washed with ethanol and then dried.
  • the low refractive index dispersion composition was prepared by dissolving Poly (4VP-BPAA) prepared in Preparation Example 1 in ethanol, and the poly (VK-BPA) prepared in Preparation Example 3 was dissolved in tetrahydrofuran to prepare a high refractive index dispersion composition Respectively.
  • the high refractive index dispersion composition was coated on a glass substrate using a spin coater at 6,000 rpm for 50 seconds and then cured at 254 nm for 3 minutes to form a high refractive index layer.
  • the glass substrate on which the high refractive index layer was formed was placed in a tetrahydrofuran solution to remove uncured portions.
  • the low refractive index dispersion composition was coated on the high refractive index layer using a spin coater at 4,000 rpm for 50 seconds 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 a methanol solution to remove unhardened portions.
  • a high refractive index layer and a low refractive index layer were repeatedly laminated on the low refractive index layer to produce a structure in which a total of seven refractive index layers were stacked.
  • the structure was placed in a 100 ml vial containing 10 ml of DMF and 226 ⁇ l of chloropropane, quaternarized at 70 ° C. for 48 minutes, washed with ethanol and dried to obtain a photonic crystal structure Respectively.
  • a photonic crystal structure was prepared in the same manner as in Example 6-1 except that the poly (VK-BPA) was changed to 2 wt%.
  • the low refractive index layer prepared in Example 1 was treated with 30% HF, HCl and HBr solutions at a concentration of 100 ppm, and the thickness of the low refractive index layer The refractive index was measured, and the results are shown in Fig. In this case, 'Initial' means a thin film before reaction with an inorganic acid.
  • the low refractive index layer prepared in the above example exhibits different refractive indexes and thicknesses depending on the type of inorganic acid. More specifically, it can be seen that the refractive index increases with HF, HCl, and HBr.
  • 'reflection wavelength shift' means a value obtained by shifting the reflection wavelength of the photonic crystal structure after the reaction with respect to the reflection wavelength of the photonic crystal structure before reaction with the inorganic acid.
  • the inorganic acid detection sensor prepared in Examples 2-1 to 3-3 significantly shifts the reflection wavelength due to the reaction with the inorganic acid, thereby exhibiting clear color conversion.
  • the shifted reflection wavelength corresponds to the visible light region, and the color conversion according to the inorganic acid detection can be visually observed.
  • the reflection wavelength was changed differently depending on the type of inorganic acid, the type and concentration of the copolymer contained in each refractive index layer, and the total lamination of the refractive index layers.
  • the inorganic acid detection sensor prepared in Example 4 varied in color depending on the type and concentration of inorganic acid, and it could be observed with naked eyes.
  • the inorganic acid detection sensor according to the present invention shows a clear color conversion by reaction with inorganic acid, and it can be seen that various inorganic acids generated in various industrial fields and households can be easily detected.
  • FIGS. 10 and 11 In order to confirm whether the physical properties of the photonic crystal structure were changed according to the R group change and the counter ion change of the ammonium ion in the RX compound for quadrification, the thickness and the refractive index of the low refractive index layer prepared in Examples 5-1 to 5-4 And the results are shown in FIGS. 10 and 11.
  • 'Before' means a low refractive index layer before the quaternization reaction.
  • the low refractive index layer prepared in the above example exhibits different refractive indexes and thicknesses depending on changes in the counter ion of the ammonium ion and the R group as the substituent of the ammonium ion.
  • the color of the photonic crystal structure prepared in Examples 6-1 to 6-4 was observed in order to confirm the R conversion and the color change according to the counter ion change of the ammonium ion in the RX compound for quaternization, USB 4000, Ocean Optics), and the results are shown in Figs. 12 to 14.
  • the 'reflected wavelength shift' refers to a value obtained by shifting the reflection wavelength of the photonic crystal structure after quadrification to the reflection wavelength of the photonic crystal structure before quadrification.
  • Example 7 In order to confirm the degree of color conversion according to the change of humidity, the photonic crystal structure manufactured in Example 7 was measured at relative humidity of 11%, 23%, 33%, 43%, 52%, 68%, 75%, 85% %, The changed color was observed. The result was shown in FIG. 15. The specular reflectance was measured using a reflectometer (USB 4000, Ocean Optics). The results are shown in FIG.
  • the photonic crystal structure manufactured in Example 7 has a clearly shifted reflection wavelength according to the change of the relative humidity, and is excellent in sensitivity to changes in moisture. Also, it can be seen that the reflected wavelength of the photonic crystal structure shifts in a direction in which the wavelength becomes longer as the relative humidity increases. At this time, the shifted reflection wavelength corresponds to the visible light region, and the change of the reflection wavelength of the photonic crystal structure can be visually observed, and it can be confirmed that the photonic crystal structure according to the embodiment can be used for the relative humidity verification.
  • the color of the photonic crystal structure prepared in Example 8 was observed by observing the color of the photonic crystal structure using a reflectometer (USB 4000, Ocean Optics) The results are shown in Fig.
  • the photonic crystal structure manufactured in the above embodiment changes the reflection wavelength according to the quadrature reaction time. Specifically, it can be seen that as the quaternization reaction time increases, the reflection wavelength becomes longer and shifts to a longer wavelength.
  • the composition of the copolymer contained in the low refractive index layer is changed by changing the compounds for the quaternization and the quadrature reaction time, and as the refractive index of the low refractive index layer is changed, It is possible to confirm the change of humidity by indicating the reflected wavelength.
  • first refractive index layer 15 second refractive index layer

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Abstract

La présente invention utilise une structure de cristal photonique qui change de couleur lorsqu'un stimulus externe est appliqué à celle-ci, de telle sorte qu'il est possible de changer de couleur en fonction d'acides inorganiques correspondant à des stimuli externes de façon à déterminer visuellement le type d'acide inorganique, et ainsi il est possible de fabriquer un capteur colorimétrique à cristal photonique pour la détection d'acides inorganiques à l'aide de la structure de cristal photonique ; et elle utilise une structure de cristal photonique qui change de couleur en fonction des changements d'humidité, de sorte qu'il est possible de changer de couleur en fonction des changements d'humidité de façon à déterminer visuellement l'humidité, et ainsi il est possible de fabriquer un capteur d'humidité colorimétrique à cristaux photoniques à l'aide de la structure de cristal photonique.
PCT/KR2018/009561 2017-08-21 2018-08-21 Structure cristalline photonique et capteur colorimétrique la comprenant Ceased WO2019039821A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR1020170105488A KR101996478B1 (ko) 2017-08-21 2017-08-21 광결정 구조체 및 색변환 습도 센서
KR1020170105487A KR102045994B1 (ko) 2017-08-21 2017-08-21 광결정 구조체 및 무기산 검지 센서
KR10-2017-0105488 2017-08-21
KR10-2017-0105487 2017-08-21

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WO2019039821A1 true WO2019039821A1 (fr) 2019-02-28

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Citations (3)

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US20150122017A1 (en) * 2012-05-11 2015-05-07 Postech Academy-Industry Foundation Chromogenic humidity sensor
US20160252625A1 (en) * 2014-10-29 2016-09-01 The University Of Massachusetts Photonic polymer multilayers for colorimetric radiation sensing
KR101769093B1 (ko) * 2016-03-25 2017-08-17 한국화학연구원 색변환 광결정 구조체 및 이를 이용한 색변환 광결정 센서

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150122017A1 (en) * 2012-05-11 2015-05-07 Postech Academy-Industry Foundation Chromogenic humidity sensor
US20160252625A1 (en) * 2014-10-29 2016-09-01 The University Of Massachusetts Photonic polymer multilayers for colorimetric radiation sensing
KR101769093B1 (ko) * 2016-03-25 2017-08-17 한국화학연구원 색변환 광결정 구조체 및 이를 이용한 색변환 광결정 센서

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AULASEVICH, A .: "Optical waveguide spectroscopy for the investigation of protein-functionalized hydrogel films", MACROMOLECULAR RAPID COMMUNICATIONS, 2009, XP055577312 *
SHARMA, N.: "Molecularly imprinted polymer waveguides for direct optical detection of low-molecular-weight analytes", MACROMOLECULAR CHEMISTRY AND PHYSICS, 2014, XP055577311 *

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