WO2015102090A1 - Substrat composite, capteur optique, capteur à résonance localisée de plasmon de surface, leur utilisation, procédé de détection, filtre perméable sélectif vis-à-vis de l'humidité et capteur muni de celui-ci - Google Patents

Substrat composite, capteur optique, capteur à résonance localisée de plasmon de surface, leur utilisation, procédé de détection, filtre perméable sélectif vis-à-vis de l'humidité et capteur muni de celui-ci Download PDF

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WO2015102090A1
WO2015102090A1 PCT/JP2014/084485 JP2014084485W WO2015102090A1 WO 2015102090 A1 WO2015102090 A1 WO 2015102090A1 JP 2014084485 W JP2014084485 W JP 2014084485W WO 2015102090 A1 WO2015102090 A1 WO 2015102090A1
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layer
moisture
composite substrate
metal fine
fine particles
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PCT/JP2014/084485
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English (en)
Japanese (ja)
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松村　康史
靖 榎本
龍三 新田
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新日鉄住金化学株式会社
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Publication of WO2015102090A1 publication Critical patent/WO2015102090A1/fr

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    • 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
    • G01N21/55—Specular reflectivity
    • G01N21/552—Attenuated total reflection
    • G01N21/553—Attenuated total reflection and using surface plasmons
    • G01N21/554—Attenuated total reflection and using surface plasmons detecting the surface plasmon resonance of nanostructured metals, e.g. localised surface plasmon resonance
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (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
    • 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
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/105—Metal
    • 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
    • B32B2551/00—Optical elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • the present invention relates to, for example, a composite substrate using localized surface plasmon resonance, an optical sensor, a localized surface plasmon resonance sensor, a method for using the same, a detection method, a moisture selective permeability filter, and a sensor including the same About.
  • Nanometer-sized fine particles have a high geometric surface area and, in addition to the quantum size effect, exhibit optical property changes, melting points, high catalytic properties, high magnetic properties, and the like. From these facts, nanometer-sized microparticles are expected to have new functions that could not be obtained with bulk materials, such as improved chemical and physical conversion characteristics such as catalytic reaction and luminescence characteristics, electronic materials, catalytic materials, It is a very important material in various fields such as phosphor materials, luminescent materials, and pharmaceuticals. In particular, in the case of metal fine particles having a size of several nm to 100 nm, a phenomenon called localized surface plasmon resonance (LSPR) in which electrons in the fine particles interact with light of a specific wavelength to resonate. Have.
  • LSPR localized surface plasmon resonance
  • Non-Patent Documents 1, 2, 3, and 4 As a prior art focused on the detection of LSPR, it has been proposed to detect scattered light of LSPR by a single metal nanoparticle using a microscope with respect to metal nanoparticles two-dimensionally immobilized on a substrate.
  • Non-Patent Documents 1, 2, 3, and 4 Further, the present inventors have a three-dimensional network structure in which the matrix has a solid skeleton portion and voids formed by the solid skeleton portion, and the metal fine particles are three-dimensionally dispersed in the matrix.
  • Patent Document 1 has proposed a sensor using a metal fine particle dispersed composite.
  • Patent Document 2 an inorganic particle composite comprising a mixture of a metal that can be plastically deformed and inorganic particles that are not plastically deformed under the condition that the metal is plastically deformed is disclosed, although detailed investigation has not been made and the effect is unknown. The possibility of having light absorption due to resonance has been suggested (Patent Document 2).
  • sensor materials metal fine particle dispersion composite and inorganic particle composite
  • An optical system such as a light source and a photodetector and the sensor materials are exposed by a medium such as vapor, gas, or liquid. Therefore, there is a concern that these deteriorate over time or are contaminated and the sensing function is lowered. Therefore, further improvement in the sensing function and durability of sensors using these materials is desired.
  • the present invention provides a composite substrate that can be suitably used for sensor materials excellent in sensing function and durability, and a sensor using the composite substrate.
  • the present inventors have obtained the above problem by laminating a porous light reflecting member on a metal fine particle dispersed composite layer in which metal fine particles are dispersed in a matrix having voids.
  • the present invention has been completed.
  • the composite substrate of the present invention is A metal fine particle dispersed composite layer; A porous light reflecting member laminated on the metal fine particle dispersed composite layer; With The metal fine particle-dispersed composite layer comprises a solid skeleton part and a matrix having voids formed by the solid skeleton part, and metal fine particles fixed to the solid skeleton part, It is what has.
  • the solid skeleton part may contain a metal oxide or a metal hydroxide to form a three-dimensional network structure.
  • the solid skeleton may contain alumina, aluminum oxyhydroxide, or alumina hydrate.
  • the metal fine particles may have a portion exposed in the voids of the matrix, and may exist in a three-dimensionally dispersed state in the matrix.
  • the metal fine particles have an average particle diameter in the range of 1 nm to 100 nm, and the proportion of the metal fine particles in the particle diameter in the range of 1 nm to 100 nm is 50% or more. Also good.
  • the light reflectance of the light reflecting member at 590 nm may be 10% or more in the atmosphere.
  • a value obtained by dividing the porosity (%) of the porous body constituting the light reflecting member by the film thickness ( ⁇ m) may be 0.025 (% / ⁇ m) or more.
  • the light reflecting member may have an antifouling layer that transmits moisture and does not transmit oil or hydrocarbons.
  • the metal fine particles may be Au or Ag metal fine particles.
  • a transparent substrate may be further laminated on the metal fine particle dispersed composite layer.
  • the metal fine particles may cause localized surface plasmon resonance by interaction with light having a wavelength of 380 nm or more.
  • the optical sensor of the present invention includes the composite substrate.
  • the localized surface plasmon resonance sensor of the present invention is The composite substrate; A light source that emits light toward the composite substrate; A light receiving unit for receiving scattered light of localized surface plasmon resonance by metal fine particles in the composite substrate or reflected light from the light reflecting member; A spectroscopic device that measures the spectrum of the scattered light or the reflected light or a photodetector that measures the light intensity is provided.
  • the localized surface plasmon resonance sensor of the present invention may further include means for condensing the scattered light or the reflected light.
  • the localized surface plasmon resonance sensor of the present invention may further include a means for collecting the irradiation light.
  • the localized surface plasmon resonance sensor of the present invention may make the irradiation light from the light source incident obliquely with respect to the stacking direction of the composite substrate.
  • the light irradiation and the spectrum measurement may be performed via the transparent substrate.
  • the method of using the localized surface plasmon resonance sensor of the present invention is to use the metal fine particle dispersed composite layer in the localized surface plasmon resonance sensor by exposing it to the atmosphere or gas.
  • the method for using the localized surface plasmon resonance sensor of the present invention may be one in which the metal fine particle dispersed composite layer in the localized surface plasmon resonance sensor is exposed to a liquid.
  • the method for detecting an inorganic substance or an organic substance of the present invention uses the localized surface plasmon resonance sensor to detect the change in the spectrum, the change in the spectrum intensity, or the change in the light intensity due to the localized surface plasmon resonance. Originally, inorganic substances or organic substances are detected.
  • the method for producing a composite substrate of the present invention includes the following steps Ia to Id; Ia) preparing a raw slurry for forming the solid skeleton, Ib) a step of preparing a coating solution by mixing the raw material slurry and a metal compound that is a raw material of the metal fine particles, Ic) applying the coating solution on the transparent substrate and drying to form a coating film; Id) heat-treating the coating film to form the metal fine particle dispersed composite layer on the light reflecting member; It has.
  • the moisture selective permeability filter of the present invention includes a porous body having a large number of pores, and a moisture selective permeability layer that blocks the pores of the porous body.
  • the moisture selective permeability layer may contain one or more moisture permeable materials selected from resins and fluorine compounds.
  • the resin may be one or more selected from the group consisting of polystyrene, polyvinyl alcohol, polyvinyl butyral resin, PMMA, and polyvinyl acetate.
  • the moisture selective permeability layer may be formed of the moisture permeable material coated on the surface of the porous body.
  • the moisture selective permeability layer may be formed of the moisture permeable material impregnated in the porous body.
  • the moisture selective permeable layer includes a portion in which the moisture permeable material is coated on a surface of the porous body, and the moisture permeable material is impregnated in the porous body. May be included.
  • the moisture permeable material has a water vapor permeability of 1.0 g / m 2 ⁇ when measured under the conditions of 25 ° C. and 90% RH in the state of a film having a thickness of 25 ⁇ m. It may be 24h or longer.
  • the method for producing a moisture selective permeability filter of the present invention is a production of a moisture selective permeability filter comprising a porous body having a large number of pores and a moisture selective permeability layer that closes the pores of the porous body.
  • moisture-content selective permeability filter of this invention apply
  • the sensor of the present invention includes any one of the moisture selective permeability filters described above.
  • the sensor of the present invention is selected from the group consisting of a localized surface plasmon resonance sensor, a humidity sensor, a dew condensation sensor, a biosensor, a chemical sensor, a refractive index sensor, a QCM (quartz crystal microbalance), and a gas sensor. May be.
  • a porous light reflecting member is laminated on a metal fine particle dispersed composite layer in which metal fine particles are dispersed in a matrix having voids.
  • this is a sensing target. It also serves as an inlet for a medium such as a vapor, gas, or liquid.
  • a partition such as a transparent substrate is provided between the metal fine particle-dispersed composite layer and the optical system in the composite substrate, so that the optical system depends on the medium.
  • the light reflecting member also serves as a filter, contamination of the composite substrate itself with organic substances such as oil can be suppressed.
  • optical sensors such as localized surface plasmon resonance sensors, humidity sensors, condensation sensors, biosensors, chemical sensors, taste sensors, odor sensors, alcohol sensors, and refractive index sensors. It becomes possible to make it.
  • sensors such as QCM (quartz crystal microbalance), gas sensors, measurement devices, inspection kits for visually judging discoloration of composite substrates, metal catalysts using a matrix as a carrier, gas purification It can be applied to filters, water purification filters such as water.
  • the moisture selective permeability filter of the present invention uses a porous body as a base material, and has a moisture selective permeability layer that transmits moisture and does not transmit oil, hydrocarbons, etc.
  • the film is made thin. That is, in the moisture selective permeability filter of the present invention, the porous body gives the moisture selective permeability filter the necessary strength as a self-supporting membrane, and the moisture selective permeability layer blocks oil and the like while reducing the overall thickness as much as possible. The function is secured.
  • the moisture selective permeable filter of the present invention includes, for example, a localized surface plasmon resonance sensor, a humidity sensor, a dew condensation sensor, a biosensor, a chemical sensor, a refractive index sensor, a QCM (quartz crystal microbalance), and a gas sensor.
  • a localized surface plasmon resonance sensor for example, a humidity sensor, a dew condensation sensor, a biosensor, a chemical sensor, a refractive index sensor, a QCM (quartz crystal microbalance), and a gas sensor.
  • a localized surface plasmon resonance sensor for example, a humidity sensor, a dew condensation sensor, a biosensor, a chemical sensor, a refractive index sensor, a QCM (quartz crystal microbalance), and a gas sensor.
  • a protective film for maintaining sensing performance and enhancing durability.
  • FIG. 1A is a diagram illustrating a schematic configuration of a composite substrate 100 according to an embodiment of the present invention.
  • the composite substrate 100 includes a metal fine particle dispersed composite layer (hereinafter also referred to as “nanocomposite layer”) 10 and a porous light reflecting member 20 laminated on the nanocomposite layer 10.
  • nanocomposite layer a metal fine particle dispersed composite layer
  • porous light reflecting member 20 laminated on the nanocomposite layer 10.
  • the configuration and the manufacturing method will be described in the order of the nanocomposite layer 10 and the light reflecting member 20.
  • the nanocomposite layer 10 is not limited as long as it has a solid skeleton part, a matrix having voids formed by the solid skeleton part, and metal fine particles fixed to the solid skeleton part.
  • a preferred form of the nanocomposite layer 10 is composed of a metal fine particle-dispersed composite that causes localized surface plasmon resonance.
  • the sharper the absorption spectrum the higher the sensitivity of detection possible.
  • the size of the metal fine particles is controlled within a predetermined range; 2) The shape of the metal fine particles is uniform, 3) The metal fine particles are separated from each other in a state of maintaining a certain particle interval from the adjacent metal fine particles, 4) The volume filling ratio of the metal fine particles to the metal fine particle dispersed composite is controlled within a certain range. 5) The metal fine particles are present from the surface layer portion of the matrix and are distributed evenly while maintaining a predetermined inter-particle distance in the thickness direction. It is preferable that the metal fine particle dispersed composite has structural characteristics such as
  • the metal fine particle dispersed composite in order to apply the metal fine particle dispersed composite to a sensor application that senses the wavelength change of the localized surface plasmon resonance caused by the change of the external environment of the metal fine particle, In addition to the characteristics, 6)
  • the metal fine particles are exposed to the external environment, It is preferable to have structural characteristics such as
  • FIG. 2 schematically shows the structure of the matrix 1 in the nanocomposite layer 10.
  • FIG. 3 schematically shows a dispersion state of the metal fine particles 3 in a cross section in the thickness direction of the nanocomposite layer 10
  • FIG. 4 shows a cross section in a plane direction parallel to a plane orthogonal to the thickness direction of the nanocomposite layer 10.
  • 5 schematically shows a dispersion state of the metal fine particles 3, and FIG. 5 is an enlarged view illustrating the metal fine particles 3.
  • the larger metal particles 3 of the particle diameter D L of the adjacent metal fine particles 3 has a particle size of the fine metal particles 3 smaller represents a D S, simply when not distinguished from each other This is expressed as particle diameter D.
  • the nanocomposite layer 10 includes a matrix 1 having a solid skeleton 1a and voids 1b formed by the solid skeleton 1a, and metal fine particles 3 fixed to the solid skeleton 1a of the matrix 1.
  • the nanocomposite layer 10 preferably has at least one of the following structures a to c.
  • the solid skeleton 1a contains a metal hydroxide such as a metal oxide or a metal oxyhydroxide, and forms a three-dimensional network structure; b) The average particle size of the metal fine particles 3 is in the range of 1 nm to 100 nm, and the proportion of the metal fine particles having the particle size D in the range of 1 nm to 100 nm is 50% or more; c) The metal fine particle 3 has a portion exposed in the void 1 b of the matrix 1 and exists in a three-dimensionally dispersed state in the matrix 1.
  • a metal hydroxide such as a metal oxide or a metal oxyhydroxide
  • the matrix 1 has a solid skeleton 1a and voids 1b formed by the solid skeleton 1a.
  • the solid skeleton 1a may be, for example, an organic material such as a resin, vegetable fiber, or animal fiber, or an inorganic material such as ceramics, glass, or metal.
  • the material is not limited, but has heat resistance and chemical stability. From the viewpoint, it is preferable that a metal oxide or a metal hydroxide is contained and a three-dimensional network structure is formed as shown in a) above.
  • metal oxides silicon oxide (silica), aluminum oxide (alumina), titanium oxide (titania), vanadium oxide, tantalum oxide, iron oxide, magnesium oxide, zirconium oxide, and their hydration You can raise things. Further, an inorganic oxide containing a plurality of types of metal elements may be used. Among these, silica, alumina, titania and their hydrates are preferable, and alumina hydrate is more preferable.
  • These metal oxides can be produced by a known method such as a flame hydrolysis method in the gas phase of a metal chloride such as aluminum chloride, insoluble in water, and resistant to organic solvents, acid and alkali.
  • metal oxides are characterized by having high dispersibility in an aqueous solution, a slurry of metal oxide powder can be easily prepared.
  • the metal hydroxide include aluminum hydroxide, titanium hydroxide, a mixture of aluminum hydroxide and aluminum chloride, and aluminum oxyhydroxide, preferably aluminum oxyhydroxide. .
  • Various materials such as boehmite (including pseudoboehmite), gibbsite, diaspore, alumina, etc. are known as alumina, aluminum oxyhydroxide or alumina hydrate. Boehmite is most preferred.
  • boehmite means fine particles with high crystallinity of aluminum oxyhydroxide (AlOOH) or alumina hydrate (Al 2 O 3 .H 2 O), and pseudo boehmite is It means fine particles of low boehmite crystallinity, and all are described as boehmite in a broad sense without distinction.
  • This boehmite powder can be produced by a known method such as an aluminum salt neutralization method or an aluminum alkoxide hydrolysis method, is insoluble in water, and has organic solvent resistance, acid resistance and alkali resistance. It can be advantageously used as a component constituting one solid skeleton 1a. Moreover, since boehmite powder has the characteristic of having high dispersibility in an acidic aqueous solution, a slurry of boehmite powder can be easily prepared.
  • the porosity of the nanocomposite layer 10 is preferably in the range of 15 to 95%.
  • the porosity of the nanocomposite layer 10 is the apparent density (bulk density) calculated from the area, thickness and weight of the nanocomposite layer 10, the material forming the solid skeleton 1 a of the matrix 1, and the intrinsic properties of the metal fine particles 3.
  • the density (true density) that does not include voids calculated from the density and the composition ratio, it can be calculated according to the formula (A) described later.
  • the porosity is less than 15%, the openness to the external environment is lowered, and the utilization efficiency of the metal fine particles 3 may be lowered. Further, when the nanocomposite layer 10 is manufactured, for example, in the case of impregnating a preformed matrix 1 with a solution containing metal ions as a raw material of the metal fine particles 3, it becomes difficult to impregnate the entire matrix 1; It is difficult to obtain a uniform dispersion state. On the other hand, when the porosity exceeds 95%, the abundance ratio of the solid skeleton 1a and the metal fine particles 3 decreases, so that the mechanical strength decreases or the action of the metal fine particles 3 (for example, localized surface plasmon resonance effect). ) May decrease.
  • the volume ratio of the metal fine particles 3 to the voids 1b in the nanocomposite layer 10 is the same as that described above, from the viewpoint of efficiently using the high specific surface area and high activity of the metal fine particles 3, Preferably it is in the range of 0.08 to 50% with respect to the total capacity.
  • the thickness T of the matrix 1 (that is, the thickness of the nanocomposite 10) T varies depending on the particle diameter D of the metal fine particles 3, but in applications using localized surface plasmon resonance, for example, within the range of 20 nm to 20 ⁇ m. It is preferable to set the thickness within the range of 30 nm to 10 ⁇ m.
  • the nanocomposite layer 10 When the nanocomposite layer 10 is applied to an application using localized surface plasmon resonance, it is possible to use either localized surface plasmon resonance of a light reflection system or a light transmission system.
  • the matrix 1 When utilizing localized surface plasmon resonance of the transmission system, the matrix 1 preferably has light transmittance in order to generate localized surface plasmon resonance of the metal fine particles 3, for example, 250 nm or more, particularly 380 nm or more. It is preferable that the material transmits light having a wavelength of.
  • the solid skeleton 1a preferably contains alumina, aluminum oxyhydroxide, or alumina hydrate that easily forms a three-dimensional network structure.
  • alumina aluminum oxide
  • titanium oxide vanadium oxide
  • tantalum oxide titanium oxide
  • iron oxide magnesium oxide
  • zirconium oxide titanium oxide
  • tungsten oxide and other inorganic oxides containing multiple types of metal elements. These may be used alone or in combination.
  • the type of metal fine particles 3 and the dispersion method thereof are not particularly limited, and known types of particles and dispersion methods can be applied.
  • the metal fine particles 3 are formed by sputtering, vacuum deposition, application of a gold fine particle dispersion, impregnation or spray, or metal ions serving as precursors thereof. What is obtained by heat reduction is preferable.
  • the metal fine particles 3 are more preferably obtained by heating and reducing metal ions as precursors.
  • metal fine particles 3 for example, gold (Au), silver (Ag), copper (Cu), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), tin ( Metal species such as Sn), rhodium (Rh), and iridium (Ir) can be used. Further, alloys of these metal species (for example, platinum-cobalt alloy) can also be used. Among these, those that can be suitably used as metal species exhibiting localized surface plasmon resonance are gold (Au), silver (Ag), copper (Cu), palladium (Pd), platinum (Pt), tin ( Sn), rhodium (Rh), iridium (Ir).
  • Gold (Au), silver (Ag), and copper (Cu) are preferably mentioned as the metal species that cause localized surface plasmon resonance by interacting with light having a wavelength in the visible region at 380 nm or more, more preferably gold ( Au) and silver (Ag), and particularly gold (Au) is most desirable because it is hard to be oxidized and has good storage stability.
  • the shape of the metal fine particles 3 may be various shapes such as a sphere, a long sphere, a cube, a truncated tetrahedron, a digonal pyramid, a regular octahedron, a regular icosahedron, and a regular icosahedron.
  • a spherical shape with a sharp absorption spectrum due to resonance is most preferable.
  • the shape of the metal fine particles 3 can be confirmed by observing with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the average particle diameter of the metal microparticle 3 be an area average diameter when 100 arbitrary metal microparticles 3 are measured.
  • the spherical metal fine particles 3 are spheres and metal fine particles close to a sphere, and the ratio of the average major axis to the average minor axis is close to 1 or 1 (preferably 0.8 or more). Furthermore, the relationship between the major axis and the minor axis in each metal fine particle 3 is preferably in the range of major axis ⁇ minor axis ⁇ 1.35, more preferably in the range of major axis ⁇ minor axis ⁇ 1.25.
  • the metal fine particle 3 is not a sphere (for example, a regular octahedron)
  • the length of the metal fine particle 3 having the maximum edge length is defined as the major axis of the metal fine particle 3, and the length of the edge length is minimized.
  • the short diameter of the fine particles 3 the long diameter is further regarded as the particle diameter D of the metal fine particles 3.
  • the average particle diameter of the metal fine particles 3 is not particularly limited, but the average particle diameter is in the range of 1 nm to 200 nm and the ratio of the metal fine particles having the particle diameter in the range of 1 nm to 200 nm is 50% or more. Is preferred. In particular, when applied to applications using localized surface plasmon resonance, as shown in b) above, the average particle diameter of the metal fine particles 3 is in the range of 1 nm to 100 nm, and the particle diameter D is The ratio of the metal fine particles 3 within the range of 1 nm to 100 nm is preferably 50% or more.
  • the average particle diameter of the metal fine particles 3 is in the range of 3 nm to 100 nm, and the ratio of the metal fine particles 3 having the particle diameter D in the range of 1 nm to 100 nm is 50% or more.
  • the average particle diameter means an average value (median diameter) of the diameters of the metal fine particles 3.
  • the average particle diameter is set to 100 nm or less.
  • the nanocomposite layer 10 in which the maximum particle size of the metal fine particles 3 is about 50 to 75 nm or less has a relatively small particle size distribution, so that the absorption spectrum by localized surface plasmon resonance is sharp. It is easy to be done. Therefore, the nanocomposite layer 10 in which the maximum particle size of the metal fine particles 3 is about 50 to 75 nm or less is not particularly limited, and is a preferred embodiment.
  • the absorption spectrum by the localized surface plasmon resonance becomes a sharp peak by reducing the particle size distribution of the metal fine particles 3. Therefore, in this case as well, it is preferable to control the particle size distribution of the metal fine particles 3 to be small, but the particle size distribution of the metal fine particles 3 is not particularly limited.
  • the metal fine particles 3 are dispersed at a distance L between particles having a particle diameter D or larger, for example, by using the metal fine particles 3 as magnetic metal fine particles, it can be used as a magnetic material having excellent characteristics.
  • the particle diameter D when the metal fine particles 3 are not spherical is preferably 30 nm or less, more preferably 20 nm or less, and still more preferably 10 nm or less.
  • the shape of each metal fine particle 3 present in the matrix 1 is preferably 80% or more, more preferably 90% of the whole, compared to the shape of the metal fine particles 3 with others. The substantially same shape is good as described above, and a relatively substantially the same shape is particularly preferable.
  • metal fine particles 3 having a particle diameter D of less than 1 nm may also be present, and such a nanocomposite layer 10 is not particularly problematic because it hardly affects the localized surface plasmon resonance.
  • the metal fine particles 3 having a particle diameter D of less than 1 nm are preferably 10 parts by weight or less when the metal fine particles 3 are gold fine particles with respect to 100 parts by weight of the total amount of the metal fine particles 3 in the nanocomposite layer 10, for example. Is preferably 1 part by weight or less.
  • the metal fine particles 3 having a particle diameter D of less than 1 nm can be detected by, for example, an XPS (X-ray photoelectron spectroscopy) analyzer or an EDX (energy dispersive X-ray) analyzer.
  • XPS X-ray photoelectron spectroscopy
  • EDX energy dispersive X-ray
  • the average particle diameter of the metal fine particles 3 is preferably 1 nm or more, more preferably 3 nm or more, more preferably 10 nm or more and 100 nm or less. More preferably, the thickness is 20 nm to 100 nm. When the average particle diameter of the metal fine particles 3 is less than 1 nm, the intensity of the absorption spectrum due to localized surface plasmon resonance tends to be small.
  • the metal fine particles 3 preferably further interact with light and cause localized surface plasmon resonance.
  • the wavelength range in which localized surface plasmon resonance occurs varies depending on the particle diameter D, particle shape, metal type, interparticle distance L, refractive index of the matrix 1, etc. of the metal microparticles 3, but is locally determined by light having a wavelength of 380 nm or more, for example.
  • surface plasmon resonance is induced.
  • the presence state of the metal fine particles 3 is not limited, but preferably, in the matrix 1, the metal fine particles 3 are particles in the adjacent metal fine particles 3 without contacting each other. It exists at intervals equal to or larger than the larger particle diameter. That is, the spacing between adjacent metal fine particles 3 (inter-particle distance) L is larger metal particles 3 having a particle diameter D L or more in the adjacent metal fine particles 3, i.e., an L ⁇ D L. 5, the inter-particle distance L of the metal fine particles 3 is equal to or greater than the particle diameter D L of the metal fine particles 3 of larger. Therefore, the localized surface plasmon resonance characteristic of the metal fine particles 3 can be efficiently expressed.
  • the nanocomposite layer 10 used in the present embodiment it is preferable to thermally reduce metal ions that are precursors of the metal fine particles 3.
  • the thermal diffusion of the deposited metal fine particles 3 is facilitated, and the dispersed metal fine particles 3 are dispersed inside the matrix 1 at an interparticle distance L equal to or larger than the larger particle diameter DL of the adjacent metal fine particles 3.
  • the inter-particle distance L is smaller than the larger particle diameter D L , interference occurs between the particles during localized surface plasmon resonance, for example, two adjacent particles appear as one large particle.
  • localized surface plasmon resonance occurs in cooperation with, and a sharp absorption spectrum cannot be obtained.
  • the upper limit of the interparticle distance L is preferably controlled by the lower limit value of the volume fraction of the metal fine particles 3.
  • the metal fine particles 3 are preferably three-dimensionally dispersed inside the matrix 1. That is, when a cross section in the thickness direction of the matrix 1 having a three-dimensional network structure in the nanocomposite layer 10 and a cross section in a direction orthogonal to the thickness direction (cross section parallel to the surface of the matrix 1) are observed, FIGS. As shown in Fig. 5, a large number of metal fine particles 3 are scattered in the vertical direction and the horizontal direction with an inter-particle distance L equal to or larger than the particle diameter DL.
  • the metal fine particles 3 are single particles interspersed with an inter-particle distance L equal to or larger than the particle diameter DL.
  • the “single particle” means that each metal fine particle 3 in the matrix 1 exists independently, and does not include an aggregate of a plurality of particles (aggregated particles). That is, the single particle does not include aggregated particles in which a plurality of metal fine particles are aggregated by intermolecular force.
  • aggregated particles clearly confirm that a plurality of individual metal fine particles gather together to form one aggregate when observed with a transmission electron microscope (TEM), for example. Say things.
  • the metal fine particles 3 in the nanocomposite layer 10 are also understood as metal fine particles in which metal atoms generated by heat reduction are formed by aggregation due to its chemical structure. However, since it is considered that such metal fine particles are formed by metal bonds of metal atoms, it is distinguished from aggregated particles in which a plurality of particles are aggregated. For example, when observed with a transmission electron microscope (TEM), It is confirmed as one independent metal fine particle 3.
  • TEM transmission electron microscope
  • the absorption spectrum by the localized surface plasmon resonance becomes sharp and stable, and high detection accuracy is obtained.
  • the absorption spectrum due to localized surface plasmon resonance becomes broad or unstable, and when used in a device such as a sensor, high detection accuracy is obtained. It becomes difficult to obtain.
  • the aggregated particles or the particles dispersed at the inter-particle distance L equal to or smaller than the particle diameter D L exceeds 10%, the control of the particle diameter D becomes extremely difficult.
  • the volume fraction of the metal fine particles 3 in the matrix 1 is preferably 0.05 to 30% with respect to the nanocomposite layer 10.
  • the “volume fraction” is a value indicating the total volume of the metal fine particles 3 per unit volume of the nanocomposite layer 10 (including the void 1b) as a percentage. If the volume fraction of the metal fine particles 3 is less than 0.05%, the intensity of the absorption spectrum due to localized surface plasmon resonance is considerably reduced, and even if the thickness of the nanocomposite layer 10 is increased, the effect can be obtained. Hateful.
  • the metal fine particles 3 are provided with a portion exposed in the void 1b of the matrix 1, and are three-dimensionally in the matrix 1.
  • the metal fine particles 3 are efficiently arranged three-dimensionally with a high specific surface area, the utilization efficiency of the metal fine particles 3 can be increased.
  • the metal fine particles 3 can fully utilize the characteristic that the wavelength of resonance changes according to the change in the dielectric constant (refractive index) of the peripheral medium of the metal fine particles 3.
  • the structural characteristics of such a nanocomposite layer 10 are that the nanocomposite layer 10 uses a localized surface plasmon resonance, a dew condensation sensor, a humidity sensor, a dew condensation sensor, a biosensor, a chemical sensor, a gas sensor, a refractive index sensor, It is optimally applied to taste sensors, odor sensors, alcohol sensors, etc.
  • the nanocomposite layer 10 is formed by, for example, observing the cross section of the matrix 1 with a transmission electron microscope or the like. 3 may appear to overlap each other.
  • the metal fine particles 3 are in a state where a certain distance or more is maintained, and are dispersed as completely independent single particles. Further, since the metal fine particles 3 are physically or chemically fixed by the three-dimensional network-like solid skeleton 1a, the metal fine particles 3 can be prevented from agglomerating and dropping with time, and thus can be stored for a long time. Even when the nanocomposite layer 10 is used repeatedly, aggregation and dropping of the metal fine particles 3 are suppressed.
  • the nanocomposite layer 10 having the above-described configuration has a form in which the metal fine particles 3 are dispersed in a three-dimensional and non-uniform manner in a state where the inter-particle distance L is more than a certain level in the matrix 1 having a three-dimensional network structure.
  • most of the surface of the metal fine particle 3 is exposed in the void 1b communicating with the external space in the matrix 1, so that the dielectric constant (refractive index) of the peripheral medium of the metal fine particle 3 included in the metal fine particle 3 is changed. It is possible to sufficiently develop the characteristic that the wavelength of resonance changes according to the above.
  • the nanocomposite layer 10 is suitable for use in a condensation sensor, a humidity sensor, a condensation sensor, a biosensor, a chemical sensor, a gas sensor, a refractive index sensor, a taste sensor, an odor sensor, an alcohol sensor, and the like, and has a simple configuration. Makes it possible to detect with high accuracy.
  • the light reflecting member 20 is a porous body, and preferably has a wavelength that causes localized surface plasmon resonance (for example, in the range of 300 nm to 900 nm when the metal fine particles 3 are made of gold or silver, palladium, In the case of platinum, it is formed of a material having a property of reflecting light (within a range of 250 nm to 900 nm). Examples of such materials include organic substrates such as polyester, PTFE, vegetable fibers, and animal fibers, and inorganic substrates such as glass, alumina, and metals, and porous materials.
  • porous forms include non-woven fabrics, woven fabrics, meshes, membrane filters, sintered particles, foamed sheets, non-porous substrates, drilling, punching, plasma and other physical etching, chemical etching, etc. What was formed is mentioned. More preferred are filter paper, non-woven fabric made of polyester, glass fiber filter paper, PTFE membrane filter, and porous alumina membrane filter.
  • FIG. 1A a laminated body in which the nanocomposite layer 10 and the light reflecting member 20 are stacked in close contact with each other is illustrated.
  • the nanocomposite layer 10 and the light reflecting member 20 are not necessarily provided in close contact with each other.
  • the light reflecting member 20 may be provided at an arbitrary distance from the nanocomposite layer 10.
  • the light reflecting member 20 is preferably used as a light reflecting member of a light reflecting sensor. Therefore, the light reflection member 20 should just be a thing which can reflect the light of a specific wavelength according to the kind of light source or a sensor.
  • the light reflecting member 20 has a localized surface plasmon resonance wavelength (for example, 300 to 900 nm when the metal fine particles 3 are made of gold or silver). In the case of being composed of palladium and platinum, those reflecting within 250 nm to 900 nm can be used.
  • the light reflectance within the above wavelength range is preferably 10% or more in the atmosphere, more preferably 30% or more, and even more preferably 50% or more.
  • the composite substrate 100 can be preferably used as a light reflecting member in a localized surface plasmon resonance sensor.
  • the light reflectance of the light reflecting member 20 is less than 10%, when used as a light reflecting member in a localized surface plasmon resonance sensor, the light does not reach the light receiving part sufficiently, and the sensitivity as the sensor is lowered. There is a tendency.
  • the wavelength is not limited to 590 nm, as long as the reflectance falls within the above range according to the wavelength used.
  • the composite substrate 100 is used for a light reflecting sensor other than the localized surface plasmon resonance sensor, the light reflecting member 20 has a reflectance comparable to the above reflectance according to the wavelength to be used. I just need it.
  • the light reflecting member 20 plays a role of an inlet for a medium such as vapor, gas, liquid or the like to be sensed in addition to the role as a light reflecting member. From this point of view, it is preferable that the porous body constituting the light reflecting member 20 has a porosity that allows the medium to be efficiently transmitted according to the film thickness. Further, the light reflecting member 20 plays a role of a filter and also has an action of suppressing contamination of the nanocomposite layer 10 by the medium. From such a viewpoint, it is preferable that impurities in the medium can be removed.
  • the film thickness of the light reflecting member 20 (same as the thickness T1 of the porous body in FIG. 1A) is, for example, preferably 1000 ⁇ m or less, and more preferably in the range of 10 to 1000 ⁇ m.
  • the porosity of the light reflecting member 20 may be relatively small.
  • the film thickness T1 of the porous body is relatively large, the porosity needs to be relatively large. Therefore, the value of the ratio of the porosity (%) of the porous body to the film thickness T1 ( ⁇ m) of the porous body as the light reflecting member 20, that is, the porosity (%) of the porous body is set to the thickness T1 (
  • the value divided by ⁇ m) is preferably 0.025 (% / ⁇ m) or more, for example, and more preferably in the range of 0.05 to 2.00 (% / ⁇ m).
  • the preferable average pore diameter of the light reflecting member 20 is in the range of 1 nm to 1 ⁇ m.
  • the average pore diameter is less than 1 nm, the introduction speed of the medium into the nanocomposite layer 10 decreases, and the sensitivity and response speed of the medium sensing tend to decrease.
  • the average pore diameter exceeds 1 ⁇ m, the removal efficiency of impurities in the medium tends to decrease.
  • the average pore diameter can be measured by a mercury intrusion method.
  • the light reflecting member 20 may include an antifouling layer for preventing contaminants from entering the nanocomposite layer 10 through the porous pores.
  • an antifouling layer for preventing contaminants from entering the nanocomposite layer 10 through the porous pores.
  • contaminants such as oil and hydrocarbons in the atmosphere are adsorbed on the nanocomposite layer 10, for example, the sensing sensitivity is lowered and the reproducibility of sensing is lowered. Therefore, the reproducibility of sensing by the composite substrate 100 can be maintained by providing the light reflecting member 20 with a moisture permeable antifouling layer that can block oil and hydrocarbons while allowing moisture to permeate.
  • the antifouling layer may be formed, for example, by coating the light reflecting member 20 with a moisture permeable material constituting the antifouling layer, or may be formed by impregnation, or a combination of both.
  • FIG. 1B, FIG. 1C, and FIG. 1D are drawings for explaining a schematic configuration of a composite substrate 100 according to another embodiment of the present invention in which a light-reflecting member 20 is provided with an antifouling layer.
  • FIG. 1B is a diagram illustrating a schematic configuration of the composite substrate 100 including the light reflecting member 20 having the antifouling layer 30 by coating.
  • the antifouling layer 30 is coated on the surface of the light reflecting member 20 (the side opposite to the side laminated on the nanocomposite layer 10).
  • the total thickness of the light reflecting member 20 is the sum of the thickness T1 of the porous body and the thickness T2 of the antifouling layer 30.
  • the fine antifouling layer 30 does not expose the pores of the porous light reflecting member 20 to the outside, and is sealed, so that only moisture can pass through the antifouling layer 30 and the nanocomposite layer 10 is contaminated. Is prevented.
  • the antifouling layer 30 by coating may be a laminate of antifouling layers made of a plurality of different materials.
  • FIG. 1C is a diagram illustrating a schematic configuration of the composite substrate 100 including the light reflecting member 20 having the antifouling layer 30 by impregnation.
  • the antifouling layer 30 is formed as an impregnation layer so as to enter from the surface of the light reflecting member 20 (the side opposite to the side laminated on the nanocomposite layer 10) to the inside with a thickness T2. .
  • the entire thickness of the light reflecting member 20 remains the same as the thickness T1 of the porous body.
  • the pores in the antifouling layer 30 are sealed with the antifouling material buried therein, and therefore, other than moisture cannot pass through the antifouling layer 30, and contamination of the nanocomposite layer 10 is prevented.
  • FIG. 1D is a diagram illustrating a schematic configuration of the composite substrate 100 including the light reflecting member 20 having the antifouling layer 30 by coating and impregnation.
  • the antifouling layer 30 is formed on the surface of the light reflecting member 20 (on the side opposite to the side laminated with the nanocomposite layer 10), and enters the coating layer 30A and the inside from the surface.
  • the impregnated layer 30B formed as described above.
  • the thickness T2 of the antifouling layer 30 is the sum of the thickness T3 of the coating layer 30A and the thickness T4 of the impregnation layer 30B.
  • the total thickness of the light reflecting member 20 is the sum of the thickness T1 of the porous body and the thickness T3 of the coating layer 30A.
  • the pores in the antifouling layer 30 are sealed with the antifouling material buried therein, and therefore, other than moisture cannot pass through the antifouling layer 30, and contamination of the nanocomposite layer 10 is prevented.
  • the material constituting the antifouling layer 30 can be used without particular limitation as long as it is a material that transmits moisture and does not transmit oil, hydrocarbons, or the like (hereinafter sometimes referred to as “moisture permeable material”).
  • the moisture-permeable material has a water vapor permeability of 1.0 g / m 2 ⁇ 24 h or more when measured under the conditions of 25 ° C. and 90% RH in a film having a thickness of 25 ⁇ m, for example. Can be selected as one criterion.
  • the moisture permeable material that can be used for the antifouling layer 30 for example, a material such as a resin or a fluorine compound can be used. These can be used in combination of two or more.
  • a resin known synthetic resins and natural resins are used. Among these resins, polystyrene, polyethylene, and the like, because they can achieve both moisture permeation performance (that is, performance that allows water to permeate quickly) and moisture selective permeation performance (that is, performance that blocks oil, hydrocarbons, etc.).
  • Polypropylene, polyvinyl alcohol, acrylic resins (acrylic acid ester, methacrylic acid ester, etc.), vinyl resins such as polyvinyl acetate, polyimide resins such as polyimide and silicone polyimide, and polyester resins such as PET and PEN are preferable. More preferably, polystyrene, polyethylene, polypropylene, PET, polyvinyl alcohol, polyvinyl butyral resin, PMMA, polyvinyl acetate, polyimide, silicone polyimide, or the like can be used. These resins can be used in combination of two or more.
  • the resin is polystyrene, polyvinyl alcohol, polyvinyl butyral resin, PMMA, or polyvinyl acetate, and it is most preferable to use polystyrene.
  • the weight average molecular weight in the case of using a resin as the moisture permeable material may be selected in an appropriate range according to the material.
  • a resin for example, when polystyrene is used as the resin, it is preferably in the range of 30,000 to 500,000 in order to reliably block oil and hydrocarbons while allowing the permeation of moisture.
  • moisture permeable materials that can be used as the antifouling layer 30 include, for example, polystyrene (average molecular weight 380,000, manufactured by Toyo Styrene Co., Ltd.), heat resistant polystyrene (average molecular weight 220,000, manufactured by Toyo Styrene Co., Ltd.), polyvinyl alcohol 500 (Manufactured by Kanto Chemical Co., Inc.), polyvinyl butyral resin (ESREC BM-1, manufactured by Sekisui Chemical Co., Ltd.), PMMA (average molecular weight Mw 120,000, manufactured by Sigma Aldrich), polyvinyl acetate (average molecular weight Mw 50,000, manufactured by Alfa Aesar), Commercial products such as fluorine-based coating agents (FS1010TH-0.5, manufactured by Fluoro Technology) can be mentioned. These can be used in combination of two or more.
  • fluorine-based coating agents FS1010TH-0.5, manufactured by Fluoro Technology
  • moisture permeable materials other than the above include polyamic acid resins and epoxy resins. These may be commercially available or prepared by polymerization.
  • the thickness T2 of the antifouling layer 30 can be selected in an appropriate range according to its material and use in order to reliably block oil and hydrocarbons while allowing the permeation of moisture.
  • the thickness T2 is preferably in the range of 0.1 to 5 ⁇ m, More preferably within the range of ⁇ 3 ⁇ m.
  • the thickness T2 is preferably in the range of 5 to 80 ⁇ m because the embodiment illustrated in FIG. 1C is employed.
  • the thickness T2 is the sum of the thickness T3 and the thickness T4. It becomes.
  • the thickness T3 is preferably in the range of 0.1 to 5 ⁇ m, more preferably in the range of 0.1 to 3 ⁇ m
  • the thickness T4 is preferably in the range of 5 to 80 ⁇ m, and more preferably in the range of 5 to 30 ⁇ m. .
  • the light reflecting member 20 can be manufactured by applying a coating liquid containing a moisture permeable material to a porous body and drying it to form the antifouling layer 30 having a coating layer and / or an impregnation layer.
  • the method for applying the moisture permeable material on the porous body is not particularly limited, and for example, the moisture permeable material can be applied by a coater such as a comma, a die, a knife, or a lip.
  • the coating solution may contain, for example, water, an acidic aqueous solution, an alkaline aqueous solution, an organic solvent, an organic acid, an organic amine, an ionic liquid, or the like depending on the material of the moisture permeable material.
  • the coating liquid containing the moisture permeable material is applied to the porous body as described above and dried, followed by heat treatment. It is preferable to do. Although the reason is not certain, it is estimated that the antifouling layer 30 becomes denser by the heat treatment. As a result, it is considered that the selectivity of not allowing moisture other than water to pass through is maintained while maintaining moisture permeability.
  • the heating temperature is preferably higher than the softening temperature of the moisture permeable material and lower than the decomposition temperature.
  • the heat treatment time is appropriately determined depending on the material and structure of the porous body of the light reflecting member 20 and the moisture permeable material, but the moisture permeable material softens and flows, resulting in a denser structure. It is desirable that the time is sufficient.
  • the heating temperature is preferably 110 ° C. to 150 ° C.
  • the heat treatment time is preferably 10 minutes to 120 minutes.
  • FIG. 1E is a diagram illustrating a schematic configuration example of the composite substrate 100 including the transparent substrate 40.
  • the transparent substrate 40 is preferably laminated on the surface of the nanocomposite layer 10 opposite to the surface on which the light reflecting member 20 is laminated (see FIG. 7).
  • the transparent substrate 40 can be applied to the composite substrate 100 of any embodiment shown in FIGS. 1A to 1D.
  • the material of the transparent substrate 40 is not limited, but for example, when applied to an application using localized surface plasmon resonance, the wavelength (for example, the metal fine particle 3 is used to generate localized surface plasmon resonance).
  • It can be formed of a material having a property of transmitting light in the range of 300 to 900 nm when composed of gold or silver, and within the range of 250 to 900 nm when composed of palladium or platinum.
  • examples of such materials include inorganic transparent substrates such as glass and quartz, transparent conductive films such as indium tin oxide (ITO) and zinc oxide, or polyimide resin, PET resin, acrylic resin, MS resin, MBS resin, Examples thereof include transparent synthetic resins such as ABS resin, polycarbonate resin, silicone resin, siloxane resin, and epoxy resin.
  • the thickness of the transparent substrate 40 is not particularly limited, but can be set in the range of 1 ⁇ m to 10 mm, for example.
  • the transparent substrate 40 is not necessarily provided in close contact with the nanocomposite layer 10, and the transparent substrate 40 may be provided at an arbitrary distance from the nanocomposite layer 10.
  • the transparent substrate 40 is disposed as a partition between the nanocomposite layer 10 and the optical system in the composite substrate 100 so that the optical system is not exposed by the medium.
  • the device can be designed easily. This effect makes it possible to improve the sensing function and durability of optical sensors such as localized surface plasmon resonance sensors, humidity sensors, condensation sensors, biosensors, chemical sensors, and refractive index sensors.
  • optical sensor Next, the optical sensor of the present invention will be described in detail.
  • the optical sensor of the present invention includes the composite substrate 100 of the present invention.
  • a porous light reflecting member 20 is laminated on a metal fine particle dispersed composite layer (nanocomposite layer) 10 in which metal fine particles 3 are dispersed in a matrix 1 having voids 1b.
  • a metal fine particle dispersed composite layer (nanocomposite layer) 10 in which metal fine particles 3 are dispersed in a matrix 1 having voids 1b.
  • it also serves as an inlet for a medium such as vapor, gas, or liquid to be sensed. For this reason, variations in the structural design of the optical sensor are increased, which is effective in reducing the size and weight of the optical sensor.
  • a partition such as a transparent substrate is provided between the nanocomposite layer 10 and the optical system in the composite substrate 100 so that the optical system is not exposed by the medium.
  • the device can be designed easily.
  • the light reflecting member 20 also serves as a filter, contamination of the composite substrate 100 itself by the medium can be suppressed. With the above effects, it is possible to improve the sensing function and durability of optical sensors such as a localized surface plasmon resonance sensor, a humidity sensor, a dew condensation sensor, a biosensor, a chemical sensor, and a refractive index sensor.
  • LSPR sensor localized surface plasmon resonance sensor
  • FIG. 6 shows a configuration example of the LSPR sensor.
  • the LSPR sensor 200 includes a composite substrate 100, a light source 101, a spectroscope 102, a light projecting / receiving unit 103, and a lens 104 as a condensing unit.
  • the light source 101 emits light having a wavelength that can generate LSPR.
  • the spectroscope 102 detects the spectrum of the scattered light received by the light projecting / receiving unit 103.
  • the light projecting / receiving unit 103 is constituted by a coaxial Y-type optical fiber capable of projecting and receiving light, for example.
  • the lens 104 is an optical lens that collects the irradiation light 110 from the light projecting / receiving unit 103 and the scattered light 120 generated in the nanocomposite layer 10 of the composite substrate 100.
  • the light projecting / light receiving unit 103 and the lens 104 emit light from an oblique direction with respect to the stacking direction of the composite substrate 100 (direction perpendicular to the surface of the light reflecting member 20 and the surface of the nanocomposite layer 10). It is arranged to irradiate.
  • the “oblique direction” refers to a direction inclined at least 1 degree with respect to the stacking direction of the composite substrate 100.
  • the oblique direction is more preferably 5 degrees or more, and further preferably 10 degrees or more.
  • the angle of light incident on the composite substrate 100 can be adjusted using light reflecting means such as a mirror.
  • the nanocomposite layer 10 is disposed so as to face the lens 104 and the light projecting / receiving unit 103.
  • the irradiation light 110 condensed through the lens 104 enters the nanocomposite layer 10, passes through the nanocomposite layer 10, and enters the light reflecting member 20.
  • a part of the scattered light 120 generated by LSPR in the nanocomposite layer 10 is collected by the lens 104 and received by the light projecting / receiving unit 103.
  • the transparent substrate isolates the lens 104 and the light projecting / receiving unit 103 from the subject.
  • the transparent substrate is provided to prevent the lens 104 and the light projecting / receiving unit 103 from being exposed to the sample.
  • the scattered light 120 by LSPR from the nanocomposite layer 10 and the light reflecting member 20 can be efficiently collected, and the sensing function and durability can be improved.
  • FIG. 7 shows another configuration example of the LSPR sensor.
  • the LSPR sensor 1000 includes a nanocomposite layer 1001, a light reflecting member 1002 laminated on one side of the nanocomposite layer 1001, and a transparent glass substrate laminated on the nanocomposite layer 1001 on the opposite side of the light reflecting member 1002. 1003, and a composite substrate 1004. Further, the LSPR sensor 1000 is a light source 1005 that can irradiate a light beam by changing an angle with respect to the stacking direction of the composite substrate 1004, and a light that detects reflected light of the light beam emitted from the light source 1005 toward the composite substrate 1004. And a detector 1006. The light source 1005 emits light toward the transparent glass substrate 1003.
  • the LSPR sensor 1000 is configured such that a gas or liquid serving as an analyte flows along the surface of the light reflecting member 1002 (the surface opposite to the surface laminated with the nanocomposite layer 1001).
  • the inorganic substance or the organic substance in the specimen passes through the pores of the light reflecting member 1002 and reaches the nanocomposite layer 1001.
  • the sensing sensitivity is lowered, and sensing responsiveness and reproducibility are lowered.
  • the light reflecting member 1002 by applying the light reflecting member 20 having the antifouling layer 30 capable of blocking oil, hydrocarbons and the like while allowing moisture to pass therethrough, Contamination of the composite layer 1001 can be prevented, and responsiveness and sensing reproducibility in the LSPR sensor 1000 can be maintained.
  • 1B to 1D can be disposed as the light reflecting member 1002 so that the antifouling layer 30 is exposed to the outside.
  • the light reflecting member 20 having a predetermined light reflectance according to the wavelength to be used as described above.
  • the plasmon resonance generating part in the composite substrate 100 can be manufactured as follows, for example. First, the manufacturing method of the nanocomposite layer 10 that is the most important in the plasmon resonance generating portion will be described in detail.
  • the solid skeleton 1a a material containing alumina, aluminum oxyhydroxide or alumina hydrate is used, and as the metal fine particles 3, the precursor metal ions are heated and reduced. The thing using what is obtained by is demonstrated.
  • the method for producing the nanocomposite layer 10 can be broadly divided into a method (I) in which the metal fine particles 3 are dispersed in the process of forming the matrix 1 and a method (II) in which the metal fine particles 3 are dispersed in the previously formed matrix 1. is there. From the viewpoint of reducing the number of manufacturing steps of the nanocomposite layer 10 and maintaining high dispersibility, the method (I) is preferable.
  • the method (I) includes the following steps Ia) to Id).
  • the method (II) includes the following steps IIa) to IId).
  • IIa) a step of preparing a slurry containing alumina, aluminum oxyhydroxide or alumina hydrate for forming the solid skeleton 1a;
  • IIb) A matrix having a solid skeleton portion 1a having a three-dimensional network structure and voids 1b formed by the solid skeleton portion 1a by applying the slurry onto a substrate, drying, and then heat-treating the slurry.
  • Forming 1, IIc) A solution containing metal ions as a raw material of the metal fine particles 3 is added to the matrix 1 so that the metal element is in the range of 0.5 to 480 parts by weight with respect to 100 parts by weight of the solid content of the slurry.
  • a step of impregnating, and IId) a step of depositing a particulate metal that becomes the metal fine particles 3 by reducing the metal ions by heat treatment after the step IIc.
  • boehmite powder or alumina powder containing aluminum oxyhydroxide (or alumina hydrate) can be suitably used.
  • Boehmite (trade name), Disperal HP15 (trade name) manufactured by CONDEA, VERSAL (TM) ALUMINA (trade name) manufactured by Union Showa Co., Ltd., Cerasur (trade name) manufactured by Kawai Lime Industry Co., Ltd., CAM9010 (trade name) manufactured by Kogyo Co., Ltd., Alumina Sol 520 (trade name) manufactured by Nissan Chemical Co., Ltd., Alumina Sol-10A (trade name) manufactured by Kawaken Fine Chemical Co., Ltd., SECO-045U manufactured by Seiko International Co., Ltd.
  • the boehmite powder used in one embodiment of the present invention is, for example, in the range of 10 nm to 2 ⁇ m in average particle diameter having particle shapes such as cubic, needle-like, rhomboid plate and intermediate shapes thereof, and wrinkled sheets.
  • the solid skeleton 1a can be formed by bonding the end faces or surfaces of these fine particles, and the solid skeleton 1a can form a three-dimensional network structure.
  • the average particle size of the boehmite powder here is a value calculated by a laser diffraction method.
  • the slurry containing boehmite powder is prepared by mixing boehmite powder and a polar solvent such as water or alcohol and then adjusting the mixed solution to be acidic.
  • a metal compound as a raw material for the metal fine particles 3 is added to this slurry and mixed uniformly to prepare a coating solution.
  • the slurry is prepared by dispersing boehmite powder in a solvent such as water or a polar organic solvent.
  • the boehmite powder to be used is preferably in the range of 5 to 40 parts by weight with respect to 100 parts by weight of the solvent. It is preferable to prepare it in the range of 10 to 25 parts by weight.
  • Solvents used are, for example, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, ethylene glycol, ethoxyethanol, ⁇ -butrolactone, glycerin, N, N-dimethyl.
  • Examples include formamide, N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone, and the like. Two or more of these solvents can be used in combination.
  • the mixed solution is desirably subjected to a dispersion treatment in order to improve the dispersibility of the boehmite powder.
  • the dispersion treatment can be performed by, for example, a method of stirring at room temperature for 5 minutes or more, a method using ultrasonic waves, or the like.
  • a known dispersant may be added.
  • Specific examples include polyvinyl alcohol, alkyl acetalized polyvinyl alcohol, and silane coupling agents.
  • DISPERBYK-102, DISPERBYK-180, DISPERBYK-2015 (trade name) manufactured by Big Chemie Japan Co., Ltd., and the like can be used.
  • PH Adjust the pH of the mixture to 5 or less as necessary so that the boehmite powder can be uniformly dispersed.
  • the pH adjuster for example, formic acid, acetic acid, glycolic acid, oxalic acid, propionic acid, malonic acid, succinic acid, adipic acid, maleic acid, malic acid, tartaric acid, citric acid, benzoic acid, phthalic acid, Add organic acids such as isophthalic acid, terephthalic acid, glutaric acid, gluconic acid, lactic acid, aspartic acid, glutamic acid, pimelic acid, suberic acid, inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, and salts thereof as appropriate. Good. In addition, you may use a pH adjuster individually or in mixture of multiple. By adding the pH adjuster, the particle size distribution of the boehmite powder may change as compared with the case where the pH adjuster is not added, but there is no particular
  • a metal compound as a raw material for the metal fine particles 3 is further added to the slurry prepared as described above to obtain a coating solution.
  • the amount of the metal compound to be added is in the range of 0.5 to 480 parts by weight as a metal element with respect to 100 parts by weight of the solid content of the slurry.
  • the viscosity of the coating solution may increase. In this case, it is desirable to adjust the viscosity to an optimum by appropriately adding the above solvent.
  • the metal compound contained in the coating solution prepared by the method (I) or the metal compound contained in the solution containing the metal ion prepared by the method (II) can be used without particular limitation.
  • a salt of the metal, an organic carbonyl complex, or the like can be used as the metal compound.
  • the metal salt include hydrochloride, sulfate, acetate, oxalate, and citrate.
  • organic carbonyl compound capable of forming an organic carbonyl complex with the above metal species examples include ⁇ -diketones such as acetylacetone, benzoylacetone and dibenzoylmethane, and ⁇ -ketocarboxylic acid esters such as ethyl acetoacetate. it can.
  • the metal compound include H [AuCl 4 ], Na [AuCl 4 ], AuI, AuCl, AuCl 3 , AuBr 3 , NH 4 [AuCl 4 ] ⁇ n 2 H 2 O, Ag (CH 3 COO), AgCl , AgClO 4 , Ag 2 CO 3 , AgI, Ag 2 SO 4 , AgNO 3 , Ni (CH 3 COO) 2 , Cu (CH 3 COO) 2 , CuCl 2 , CuSO 4 , CuBr 2 , Cu (NH 4 ) 2 Cl 4 , CuI, Cu (NO 3 ) 2 , Cu (CH 3 COCH 2 COCH 3 ) 2 , CoCl 2 , CoCO 3 , CoSO 4 , Co (NO 3 ) 2 , NiSO 4 , NiCO 3 , NiCl 2 , NiBr 2 , Ni (NO 3 ) 2 , NiC 2 O 4 , Ni (H 2 PO 2 ) 2 ,
  • a binder component can be blended as necessary for the purpose of improving the strength, transparency, glossiness, and the like of the matrix 1.
  • Suitable binder components that can be used in combination with aluminum oxyhydroxide include, for example, polyvinyl alcohol or modified products thereof, cellulose derivatives such as gum arabic, carboxymethylcellulose, hydroxyethylcellulose, SBR latex, NBR latex, and functional group modification.
  • Polymer latex vinyl copolymer latex such as ethylene vinyl acetate copolymer, water-soluble cellulose, polyvinylpyrrolidone, gelatin or modified product thereof, starch or modified product thereof, casein or modified product thereof, maleic anhydride or copolymer thereof
  • Polymer acrylate copolymer, polyacrylic acid and its copolymer, polyamic acid (polyimide precursor), tetraethoxysilane, 3-aminopropyltriethoxysilane, 3- Minopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1 , 3-dimethylbutylidene) propylamine, silane compounds such as N-phenyl-3-aminopropyltrime
  • the titanium compound can be mentioned. These are particularly excellent in dispersibility of aluminum oxyhydroxide and can be suitably used.
  • the silane compound, aluminum compound, and titanium compound also have an effect of improving the strength of the solid skeleton portion of the formed matrix.
  • These binder components can be used alone or in combination. These binder components can be appropriately blended regardless of the presence or absence of a metal compound, and the blending amount is preferably in the range of 3 to 100 parts by weight with respect to 100 parts by weight of the solid content of the slurry. Preferably it is in the range of 4 to 20 parts by weight.
  • the above-mentioned slurry and coating liquid may include a thickener, a lubricant, a fluidity modifier, a surfactant, an antifoaming agent, a water-resistant agent, a release agent, and a fluorescent whitening agent as necessary. It is also possible to add an ultraviolet absorber, an antioxidant and the like within a range not impairing the effects of the present invention.
  • the method for applying a coating solution containing a metal compound or a slurry not containing a metal compound is not particularly limited.
  • a lip coater, knife coater, comma coater, blade coater, air knife coater, roll coater, curtain coater It can be applied by a bar coater, gravure coater, die coater, spin coater, spray or the like.
  • the base material used for coating when the nanocomposite layer 10 is peeled off from the base material and used for a sensor or the like, or when the base material is attached to the nanocomposite layer 10, localized surface plasmon resonance of a light reflection system is performed. When using, there is no restriction in particular.
  • the base material is preferably light-transmitting, for example, a glass substrate, made of a transparent synthetic resin A substrate or the like can be used.
  • the transparent synthetic resin include polyimide resin, PET resin, acrylic resin, MS resin, MBS resin, ABS resin, polycarbonate resin, silicone resin, siloxane resin, and epoxy resin.
  • the nanocomposite 10 is peeled from the base material and used for a sensor or the like, for example, there is no particular limitation, but organic materials such as the above-mentioned transparent synthetic resin, polyester, PTFE, vegetable fiber, animal fiber, etc. Examples include inorganic substrates such as material substrates, glass, alumina, and metals.
  • a light reflecting member that is a sintered body of particles, a foam sheet, or a non-porous substrate formed with through holes by drilling, punching, plasma or other physical etching, chemical etching, or the like may be used.
  • the drying method is not particularly limited, and for example, the drying may be performed under a temperature condition in the range of 60 to 150 ° C. and taking a time in the range of 1 to 60 minutes.
  • the matrix 1 is formed by heat-treating the coating film at 150 ° C. or higher, more preferably 170 ° C. or higher.
  • the heat treatment temperature is lower than 150 ° C., the formation of the three-dimensional network structure of the matrix 1 may not occur sufficiently.
  • the upper limit of the heat treatment temperature is preferably within a range that does not affect the control of the particle diameter and interparticle distance of the metal fine particles 3 due to decomposition and melting of the metal fine particles 3, and can be set to 600 ° C. or less, for example.
  • the reduction of the metal ions and the dispersion of the precipitated fine metal particles 3 are preferably performed by a heat treatment in the range of 150 to 600 ° C., more preferably in the range of 170 to 550 ° C., and further preferably 200 to 400 ° C. be able to.
  • the heat treatment temperature is less than 150 ° C.
  • the metal ions are not sufficiently reduced, and it may be difficult to make the average particle diameter of the metal fine particles 3 equal to or more than the above-mentioned lower limit (1 nm).
  • the heat treatment temperature is less than 150 ° C., the thermal diffusion in the matrix 1 of the metal fine particles 3 precipitated by the reduction may not occur sufficiently.
  • the formation of the matrix 1 and the formation and dispersion of the metal fine particles 3 by reduction of metal ions can be simultaneously performed in one heating step.
  • the solution containing metal ions is impregnated therein and further heated to form and disperse the metal fine particles 3 by reduction of the metal ions.
  • the metal ion-containing solution used in the above method (II) preferably contains a metal ion in the range of 1 to 20% by weight as a metal element.
  • the metal element can be within the range of 0.5 to 480 parts by weight with respect to 100 parts by weight of the solid content of the slurry.
  • the impregnation method in the above method (II) is not particularly limited as long as it is a method in which a solution containing metal ions can contact at least the surface of the formed matrix 1, and a known method can be used.
  • a known method can be used.
  • an immersion method, a spray method, a brush coating method, a printing method, or the like can be used.
  • the impregnation temperature may be 0 to 100 ° C., preferably 20 to 40 ° C.
  • the particle diameter D and the interparticle distance L of the metal fine particles 3 can be controlled by the heating temperature and heating time in the reduction step, the content of metal ions contained in the matrix 1, and the like.
  • the present inventors have found that when the heating temperature and heating time in heat reduction are constant and the absolute amount of metal ions contained in the matrix 1 is different, the particle diameter D of the deposited metal fine particles 3 is different. Was getting. Also, when performing heating reduction without control of the heating temperature and the heating time was also obtained knowledge that it may be smaller than the larger particle diameter D L of the metal fine particles 3 adjacent inter-particle distance L .
  • the heat treatment in the reduction process can be performed in a plurality of steps.
  • the interparticle distance control process of holding until the distance L becomes a predetermined range can be performed.
  • the particle diameter D and the interparticle distance L can be controlled more precisely by adjusting the first and second heating temperatures and the heating time.
  • the reason why heat reduction is adopted as the reduction method is that the particle diameter D and the interparticle distance L can be controlled relatively easily by controlling the reduction treatment conditions (particularly the heating temperature and the heating time), and from the lab scale to the production scale.
  • the heat reduction can be performed, for example, in an inert gas atmosphere such as Ar or N 2 , in a vacuum of 1 to 5 KPa, or in the air, and gas phase reduction using a reducing gas such as hydrogen can also be used. Is possible.
  • metal ions present in the matrix 1 can be reduced, and individual metal fine particles 3 can be deposited in an independent state by thermal diffusion.
  • the metal fine particles 3 thus formed have a substantially uniform shape while maintaining a certain inter-particle distance L, and the metal fine particles 3 are three-dimensionally dispersed in the matrix 1 without unevenness.
  • the shape and particle diameter D of the metal fine particles 3 are homogenized, and the nanocomposite 10 is obtained in which the metal fine particles 3 are uniformly deposited and dispersed in the matrix 1 at a substantially uniform interparticle distance L. be able to.
  • the particle diameter D of the metal fine particles 3 and the matrix 1 The distribution state of the metal fine particles 3 can also be controlled.
  • the particle diameter D of the metal fine particles 3 can be suppressed to a smaller level and even more uniform, and even if the amount of metal ions in the coating film is increased. , The formation of aggregated particles can be prevented. This is because polyvinyl alcohol having a large number of —OH groups becomes an electron donor during the heat reduction of metal ions and functions as a reducing agent to promote reduction of metal ions, so that there is no polyvinyl alcohol present. It is considered that more metal nuclei are formed and each grows independently to form the metal fine particles 3.
  • the metal fine particles 3 formed at the time of heat reduction of the metal ions are not enlarged, and the metal fine particles 3 dispersion can proceed. Therefore, by adding polyvinyl alcohol as a reducing agent, the absorption spectrum and the scattered light spectrum by LSPR of the nanocomposite 10 become sharp, and high-precision detection is possible when used for various sensing devices. In order to exhibit such a function, it is considered that the polyvinyl alcohol is preferably present in the state of being close to the metal fine particles 3 to be generated.
  • polyvinyl alcohol and metal ions are preferably in a sufficiently mixed state, and polyvinyl alcohol is added to the coating solution containing the metal compound of method (I) and the solution containing the metal ion of method (II). It is advantageous to keep it in a mixed state.
  • the polyvinyl alcohol gasifies and disappears by heating at a temperature equal to or higher than the thermal decomposition temperature of the polyvinyl alcohol, but the polyvinyl alcohol is added to the coating solution containing the metal compound or the solution containing the metal ion.
  • the mixture is sufficiently mixed, a large number of voids which are traces of polyvinyl alcohol are formed in the vicinity of the metal fine particles 3.
  • the polyvinyl alcohol does not have a function as a binder that reinforces the solid skeleton 1a of the matrix 1.
  • Polyvinyl alcohol may be added before the heat treatment in steps Id and IId.
  • polyvinyl alcohol may be added before the heat reduction treatment in step IId.
  • Alcohol can be added in the step of impregnating the solution containing metal ions in step IIc. Since polyvinyl alcohol is a water-soluble polymer, it can be easily mixed in the slurry or coating solution by dissolving it in water, for example. In addition, after adding polyvinyl alcohol, it is preferable to stir the said slurry and coating liquid uniformly.
  • the degree of polymerization of polyvinyl alcohol used as the reducing agent is preferably in the range of 10 to 5000, for example, and more preferably in the range of 50 to 3000.
  • the molecular weight of polyvinyl alcohol is, for example, preferably in the range of 440 to 220,000, and more preferably in the range of 2200 to 132000.
  • polyvinyl alcohol may evaporate earlier than when it acts as a reducing agent during nanocomposite production by heating.
  • the saponification degree of polyvinyl alcohol is preferably higher because the —OH group produced by saponification acts on the reduction of metal ions, for example, preferably 30% or more, and more preferably 50% or more.
  • the amount of polyvinyl alcohol used to function as a reducing agent for metal ions is generally set according to the amount of metal compound. Can be determined. For example, three electrons are required to reduce Au ions of chloroauric acid tetrahydrate, and as described above, polyvinyl alcohol can supply two electrons per —OH group. For each gold acid tetrahydrate, 3/2 polyvinyl alcohol —OH groups are required. From this, the usage-amount (calculated weight ratio) of polyvinyl alcohol with respect to a metal compound can be calculated
  • the amount of addition in the case of functioning polyvinyl alcohol as a reducing agent depends on the saponification degree of polyvinyl alcohol. For example, if the saponification degree of polyvinyl alcohol is 88%, 1 part by weight of the metal compound The content is preferably in the range of 0.1 to 50 parts by weight, and more preferably in the range of 0.15 to 20 parts by weight.
  • the manufacturing method of the nanocomposite of the present embodiment can include an optional step other than the above.
  • the nanocomposite 10 may include a step of heat treating the nanocomposite 10 at a temperature equal to or higher than the thermal decomposition start temperature of polyvinyl alcohol.
  • an organic substance derived from polyvinyl alcohol remaining in the nanocomposite 10 hereinafter also referred to as “polyvinyl alcohol-derived component” can be thermally decomposed and gasified to be removed. .
  • the nanocomposite 10 When the nanocomposite 10 is applied to a sensor application using LSPR, it is preferable to remove the polyvinyl alcohol-derived component remaining in the nanocomposite 10 because it causes a decrease in detection sensitivity. Since the thermal decomposition starting temperature of the polyvinyl alcohol-derived component is about 200 ° C., in this step, the nanocomposite 10 can be decomposed almost completely at 200 ° C. or higher, preferably 300 ° C. or higher, more preferably polyvinyl alcohol-derived component. Heat to a temperature of 450 ° C or higher.
  • the heat treatment is preferably performed in a temperature range in which the solid skeleton portion 1a and the metal fine particles 3 constituting the nanocomposite 10 are not affected by decomposition or melting, and the upper limit of the heat treatment temperature can be set to 600 ° C. or less, for example.
  • the organic substance derived from polyvinyl alcohol includes, for example, polyvinyl alcohol that has not been consumed as a reducing agent.
  • polyvinyl alcohol is oxidized during heat treatment (for example, the alcohol part becomes a ketone). This refers to a modified or decomposed product of polyvinyl alcohol having a changed structure.
  • the heat treatment can be performed simultaneously with the heat treatment in step Id and step IId. That is, by performing the heat treatment in one step simultaneously with the heat treatment, the metal ions of the metal compound are reduced by heating to precipitate the particulate metal that becomes the metal fine particles 3, and the polyvinyl alcohol-derived component is pyrolyzed and gasified. To remove.
  • the lower limit of the temperature of the heat treatment here is preferably 200 ° C. or higher, more preferably 300 ° C. or higher, and the upper limit of the temperature of the heat treatment is preferably 600 ° C. or lower, more preferably 550 ° C. or lower. .
  • the nanocomposite layer 10 can be manufactured as described above. In addition, also when using solid skeleton parts other than boehmite as the matrix 1, it can manufacture according to the said manufacturing method.
  • the composite substrate 100 in the LSPR sensor 200 can be manufactured by, for example, the following two methods.
  • the first method is a method of using the light reflecting member 20 (which may include a protective layer) instead of the base material used in the process of producing the nanocomposite layer 10.
  • the light reflecting member 20 which may include a protective layer
  • a laminate in which the light reflecting member 20 and the protective layer (if necessary) are laminated in this order is prepared.
  • the matrix 1 having the solid skeleton 1a and the voids 1b is formed by applying a slurry for forming a metal layer, impregnating a solution containing metal ions after forming the solid skeleton 1a, and then heat-treating each. And precipitation of the metal fine particles 3 can be performed.
  • the composite substrate 100 can be manufactured in parallel with the manufacture of the nanocomposite layer 10.
  • the nanocomposite layer 10 and the light reflecting member 20 are separately manufactured, and then the nanocomposite layer 10 is disposed on the surface of the light reflecting member 20. And fixing.
  • the nanocomposite layer 10 and the light reflecting member 20 may have any means (for example, adhesion with an adhesive, for example, at the periphery of the nanocomposite layer 10 so as not to affect the occurrence of localized surface plasmon resonance). It can be fixed by bonding with a press).
  • the present inventors have formed a moisture permeation layer that combines a water-permeable material with a porous body having a large number of pores to block the pores of the porous body. It has been found that the above problems can be solved by doing so.
  • the moisture selective permeable filter 300 includes a porous body 310 having a large number of pores (not shown) and a moisture selective permeable layer 320 that closes the pores of the porous body 310.
  • the porous body 310 is a sheet-like member having a large number of pores.
  • the material constituting the porous body 310 include organic materials such as polyester, PTFE (polytetrafluoroethylene), plant fibers, and animal fibers, inorganic materials such as glass, alumina, and metals, and porous materials. What is the quality.
  • porous forms here include non-woven fabrics, woven fabrics, meshes, membrane filters, sintered particles, foam sheets, and non-porous substrates with drilling, punching, plasma and other physical or chemical etching. What was formed is mentioned.
  • the porous body 310 include filter paper, polyester nonwoven fabric, glass fiber filter paper, PTFE membrane filter, porous alumina membrane filter, and the like.
  • the strength required to establish the moisture selective permeable filter 300 as a self-supporting membrane is given, and the reactivity with a sensing medium such as vapor, gas, or liquid is low, and the pore diameter or porosity is low. It is most preferable to use a porous alumina membrane filter because it is easy to control.
  • the porous body 310 may be any material that can reflect light of a specific wavelength according to the type of light source or sensor.
  • the porous body 310 has a localized surface plasmon resonance wavelength (for example, 300 when metal fine particles are formed of gold or silver). Those reflecting within a range of ⁇ 900 nm can be used.
  • the light reflectance at a wavelength of 590 nm is preferably 10% or more in the atmosphere, more preferably 30% or more, and further preferably 50% or more.
  • the moisture selective transmission filter 300 can be preferably used as a light reflecting member in the localized surface plasmon resonance sensor.
  • the light reflectance of the porous body 310 is less than 10%, when used as a light reflecting member in a localized surface plasmon resonance sensor, the light does not reach the light receiving part sufficiently, and the sensitivity as the sensor is lowered. There is a tendency.
  • the wavelength is not limited to 590 nm, as long as the reflectance falls within the above range according to the wavelength used.
  • the moisture selective transmission filter 300 is used for a light reflection sensor other than the localized surface plasmon resonance sensor, the porous body 310 has a reflectance comparable to the above reflectance according to the wavelength to be used. What is necessary is just to have.
  • the porous body 310 can serve as an inlet for a medium such as vapor, gas, or liquid to be sensed. From this point of view, it is preferable that the porous body 310 has a porosity that allows the medium to efficiently pass through according to the film thickness. In addition, the porous body 310 plays a role of a filter and has an action of suppressing contamination of the sensor itself by the medium. From such a viewpoint, it is preferable that impurities in the medium can be removed.
  • the film thickness T11 of the porous body 310 is, for example, preferably 1000 ⁇ m or less, and more preferably in the range of 10 to 1000 ⁇ m.
  • the porosity of the porous body 310 may be relatively small.
  • the film thickness T11 is relatively large, the porosity needs to be relatively large. Therefore, the value of the ratio of the porosity (%) of the porous body 310 to the film thickness T11 ( ⁇ m) of the porous body 310, that is, the porosity (%) of the porous body 310 is the thickness T11 ( ⁇ m).
  • the divided value is preferably 0.025 (% / ⁇ m) or more, and more preferably in the range of 0.05 to 2.00 (% / ⁇ m).
  • the preferable average pore size of the porous body 310 is, for example, in the range of 1 nm to 1 ⁇ m.
  • the average pore diameter is less than 1 nm, the introduction speed of the medium decreases, and the sensitivity and response speed of the medium sensing tend to decrease.
  • the average pore diameter exceeds 1 ⁇ m, the removal efficiency of impurities in the medium tends to decrease.
  • the average pore diameter can be measured, for example, by a mercury intrusion method.
  • the moisture selective permeation layer 320 may be formed by coating the porous body 310 with a material that transmits moisture and does not transmit oil, hydrocarbons, or the like (hereinafter sometimes referred to as “moisture permeable material”). It may be formed by impregnation, or a combination of both. 8, 9, and 10 show different modes of the moisture selective permeable layer 320 in the moisture selective permeable filter 300. 8 to 10, the moisture selective transmission layer 320 is provided on one side of the sheet-like porous body 310, but the moisture selective transmission layer 320 may be provided on both sides of the porous body 310.
  • FIG. 8 is a diagram illustrating a schematic configuration of a moisture selective permeable filter 300 having a moisture selective permeable layer 320 by coating.
  • the moisture selective permeable layer 320 is coated on the surface of the porous body 310.
  • the total thickness of the moisture selective permeable filter 300 is the sum of the thickness T11 of the porous body 310 and the thickness T12 of the moisture selective permeable layer 320. Since the fine pores of the porous body 310 are sealed without being exposed to the outside by the dense moisture selective permeation layer 320, moisture permeation is allowed, but oil other than moisture permeates through the moisture permeation selective layer 320. Can not. Accordingly, the moisture selective permeability filter 300 of FIG. 8 exhibits moisture permeability selectively in the thickness direction.
  • the moisture selective transmission layer 320 by coating may be formed by laminating a plurality of layers of different materials.
  • FIG. 9 is a diagram illustrating a schematic configuration of a moisture selective permeable filter 300 having a moisture selective permeable layer 320 by impregnation.
  • the moisture selective permeation layer 320 is formed as an impregnation layer having a thickness T ⁇ b> 12 so as to enter the inside from the surface of the porous body 310.
  • the entire thickness of the moisture selective permeability filter 300 is equal to the thickness T11 of the porous body 310.
  • the pores in the moisture selective permeable layer 320 are sealed by being filled with a moisture permeable material. 320 cannot be transmitted. Accordingly, the moisture selective permeability filter 300 of FIG. 9 exhibits moisture permeability selectively in the thickness direction.
  • the moisture selective permeation layer 320 by impregnation may be a combination of impregnation layers made of a plurality of different materials.
  • FIG. 10 is a diagram illustrating a schematic configuration of a moisture selective permeable filter 300 having a moisture selective permeable layer 320 by coating and impregnation.
  • the moisture selective permeation layer 320 has a coating layer 320A formed on the surface of the porous body 310 and an impregnation layer 320B formed so as to enter the inside from the surface.
  • the thickness T12 of the moisture selective transmission layer 320 is the sum of the thickness T13 of the coating layer 320A and the thickness T14 of the impregnation layer 320B.
  • the total thickness of the moisture selective permeability filter 300 is the sum of the thickness T11 of the porous body 310 and the thickness T13 of the coating layer 320A.
  • the fine pores on the surface of the porous body 310 are sealed without being exposed to the outside by the dense coating layer 320 ⁇ / b> A, and the pores in the impregnation layer 320 ⁇ / b> B inside the porous body 310 are Since the moisture permeable material is buried and sealed, only moisture can penetrate the moisture selective transmission layer 320. Accordingly, the moisture selective permeability filter 300 of FIG. 10 exhibits moisture permeability selectively in the thickness direction.
  • the coating layer 320A may be formed by stacking a plurality of layers of different materials.
  • the impregnation layer 320B may be a combination of impregnation layers made of a plurality of different materials. Furthermore, the material of the coating layer 320A and the impregnation layer 320B may be different.
  • the material constituting the moisture selective transmission layer 320 can be used without particular limitation as long as it is a material that transmits moisture and does not transmit oil, hydrocarbons, and the like.
  • the moisture permeable material has a water vapor permeability of 1.0 g / m 2 ⁇ 24 h or more when measured under conditions of 25 ° C. and 90% RH in a state of a film having a thickness of 25 ⁇ m, for example. Can be selected as one criterion.
  • the moisture permeable material that can be used for the moisture selective permeable layer 320 for example, a material such as a resin or a fluorine compound can be used. These can be used in combination of two or more.
  • a resin for example, polystyrene, polyethylene, polypropylene, PET, polyvinyl alcohol, polyvinyl butyral resin, PMMA, polyvinyl acetate, polyimide, silicone polyimide, and the like can be used. These resins can be used in combination of two or more.
  • polystyrene should be used because it can achieve both moisture permeation performance (that is, the ability to permeate water quickly) and moisture selective permeation performance (that is, the ability to block oil, hydrocarbons, etc.). Is most preferred.
  • the weight average molecular weight in the case of using a resin as the moisture permeable material may be selected in an appropriate range according to the material.
  • a resin for example, when polystyrene is used as the resin, it is preferably in the range of 30,000 to 500,000 in order to reliably block oil and hydrocarbons while allowing the permeation of moisture.
  • moisture permeable materials that can be used as the moisture selective permeable layer 320 include, for example, polystyrene (average molecular weight 380,000, manufactured by Toyo Styrene Co., Ltd.), heat resistant polystyrene (average molecular weight 220,000, manufactured by Toyo Styrene Co., Ltd.), polyvinyl alcohol 500 (manufactured by Kanto Chemical Co., Inc.), polyvinyl butyral resin (ESREC BM-1, manufactured by Sekisui Chemical Co., Ltd.), PMMA (average molecular weight 120,000, manufactured by Sigma Aldrich), polyvinyl acetate (average molecular weight 50,000, manufactured by Alfa Aesar) And commercial products such as fluorine-based coating agents (FS1010TH-0.5, manufactured by Fluoro Technology). These can be used in combination of two or more.
  • polystyrene average molecular weight 380,000, manufactured by Toyo Styrene Co., Ltd.
  • moisture permeable materials other than the above include polyimide resins, silicone polyimide resins, polyamic acid resins, epoxy resins, acrylic resins, and the like. These may be commercially available or prepared by polymerization.
  • the thickness T12 of the moisture selective permeation layer 320 can be selected in an appropriate range according to the material and application in order to reliably block oil and hydrocarbons while allowing moisture permeation.
  • the thickness T12 is preferably in the range of 0.1 to 5 ⁇ m, More preferably within the range of ⁇ 3 ⁇ m.
  • the moisture permeable material is a material impregnated in the porous body 310 (for example, polystyrene)
  • the embodiment illustrated in FIG. 9 is used, and therefore the thickness T12 is preferably in the range of 5 to 80 ⁇ m.
  • the thickness T12 is the sum of the thickness T13 and the thickness T14. It becomes.
  • the thickness T13 is preferably in the range of 0.1 to 5 ⁇ m, more preferably in the range of 0.1 to 3 ⁇ m
  • the thickness T14 is preferably in the range of 5 to 80 ⁇ m, and more preferably in the range of 5 to 30 ⁇ m. .
  • the moisture selective permeable filter 300 may have an arbitrary layer in addition to the porous body 310 and the moisture selective permeable layer 320 as long as the effects of the invention are not impaired.
  • the entire thickness of the moisture selective permeability filter 300 can be selected in an appropriate range according to the material and application.
  • the water vapor permeability of the entire moisture selective permeability filter 300 can be selected within an appropriate range depending on the material and application.
  • the moisture selective permeability filter 300 configured as described above has a high water vapor transmission rate by providing the porous body 310 with a moisture selective permeability layer 320 that transmits moisture and does not transmit oil, hydrocarbons, and the like.
  • the film is made thin. That is, in the moisture selective permeability filter 300, the porous body 310 provides the moisture selective permeability filter 300 with a necessary strength as a self-supporting film, and the moisture selective permeability layer 320 reduces oil content and the like while reducing the overall thickness as much as possible. The shut-off function is secured.
  • the moisture selective permeable filter 300 is preferably applied to sensors and measurement devices such as localized surface plasmon resonance sensors, humidity sensors, dew condensation sensors, biosensors, chemical sensors, refractive index sensors, gas sensors, and QCMs. it can.
  • the moisture selective permeability filter 300 can be used as a protective film that is thin and has sufficient strength and an excellent blocking function against oil while maintaining a high water vapor permeability in sensors equipped with the filter. Therefore, by applying the moisture selective permeability filter 300, in the above-mentioned sensors, the simple function prevents the device from being enlarged, prevents the sensing function from being lowered, and improves the durability and the reliability of the sensor. Can be made.
  • the moisture selective permeability filter 300 can be applied to various inspection kits, metal catalysts using a matrix as a carrier, gas purification filters, liquid purification filters such as water, and the like. is there.
  • the moisture selective permeable filter 300 is manufactured by applying a coating liquid containing a moisture permeable material to the porous body 310 and drying it to form the moisture selective permeable layer 320 having a coating layer and / or an impregnated layer. Can do.
  • the method for applying the moisture permeable material onto the porous body 310 is not particularly limited, and for example, it can be applied with a coater such as a comma, a die, a knife, or a lip.
  • the coating solution may contain, for example, water, an acidic aqueous solution, an alkaline aqueous solution, an organic solvent, an organic acid, an organic amine, an ionic liquid, or the like depending on the material of the moisture permeable material. Further, when the moisture selective transmission layer 320 is formed in multiple layers or formed of a plurality of types of materials, it is preferable to repeat application of a coating solution containing a moisture permeable material and drying.
  • ⁇ Heat treatment> When the moisture selective permeable filter 300 is applied to an optical sensor, it is preferable to heat-treat after forming the moisture selective permeable layer 320 as described above in order to further improve reproducibility. The reason is not clear, but it is presumed that the moisture selective transmission layer 320 becomes denser by the heat treatment. As a result, it is considered that the selectivity of not allowing moisture other than water to pass through is maintained while maintaining moisture permeability.
  • the heating temperature is preferably higher than the softening temperature of the moisture permeable material and lower than the decomposition temperature.
  • the heat treatment time is appropriately determined depending on the material and structure of the porous body 310 and the moisture permeable material, but is sufficient for the moisture permeable material to soften and flow to form a denser structure. It is desirable that For example, when the porous body 310 is porous alumina and the moisture permeable material is polystyrene, the heating temperature is preferably 110 ° C. to 150 ° C., and the heat treatment time is preferably 10 minutes to 120 minutes.
  • LSPR sensor localized surface plasmon resonance
  • the LSPR sensor 1000 includes a nanocomposite layer 1001, a light reflecting member 1002 laminated on one side of the nanocomposite layer 1001, and a transparent glass substrate laminated on the nanocomposite layer 1001 on the opposite side of the light reflecting member 1002. 1003, and a composite substrate 1004. Further, the LSPR sensor 1000 is a light source 1005 that can irradiate a light beam by changing an angle with respect to the stacking direction of the composite substrate 1004, and a light that detects reflected light of the light beam emitted from the light source 1005 toward the composite substrate 1004. And a detector 1006. The light source 1005 emits light toward the transparent glass substrate 1003.
  • the LSPR sensor 1000 is configured such that a gas or liquid serving as an analyte flows along the surface of the light reflecting member 1002 (the surface opposite to the surface on which the nanocomposite layer 1001 is laminated).
  • the inorganic substance or organic substance in the specimen passes through the pores of the porous light reflecting member 1002 and reaches the nanocomposite layer 1001.
  • the nanocomposite layer 1001 is composed of a metal fine particle-dispersed composite that generates localized surface plasmon resonance.
  • Metal fine particles having a particle size of several nanometers to 100 nm generate localized surface plasmon resonance in which electrons in the fine particles interact with light of a specific wavelength to resonate.
  • the resonance wavelength changes according to the change in the dielectric constant (refractive index) of the peripheral medium of the fine particles.
  • a metal fine particle-dispersed composite a publicly known one can be used. For example, as shown in Examples below, a matrix having a solid skeleton formed of boehmite and the like and voids formed by the solid skeleton, And metal fine particles fixed to the solid skeleton.
  • the LSPR sensor 1000 having the above configuration can detect an inorganic substance or an organic substance present in a gas or a liquid based on a change in scattering spectrum, a change in scattering spectrum intensity, or a change in scattered light intensity due to LSPR. .
  • the moisture selective permeable filter 300 of the present invention that can block oil and hydrocarbons while allowing moisture to pass through as the light reflecting member 1002, contamination of the nanocomposite layer 1001 can be prevented, and the LSPR sensor 1000 can be prevented. Can maintain responsiveness and reproducibility of sensing.
  • the moisture selective permeable filter 300 illustrated in FIGS. 8 to 10 can be used as the light reflecting member 1002.
  • the moisture selective permeability shown in FIGS. 8 to 10 is such that the porous body 310 faces the nanocomposite layer 1001 and the moisture selective permeation layer 320 is exposed to the outside (incoming / exiting side of the specimen).
  • the filter 300 By disposing the filter 300, the light reflecting member 1002 can be used.
  • the moisture selective permeable filter 300 plays a role of an inlet for a medium such as a vapor, gas, or liquid, which is a sensing target, in addition to the role of the light reflecting member 1002. Therefore, the use of the moisture selective permeability filter 300 increases variations in the structural design of the optical sensor, and is effective in reducing the size and weight of the optical sensor. Furthermore, by using the moisture selective permeability filter 300, it is possible to easily design an apparatus in which the optical system is not exposed by the medium. Further, contamination of the nanocomposite layer 1001 itself with a medium can be suppressed.
  • a medium such as a vapor, gas, or liquid
  • the LSPR sensor 1000 detects moisture such as a humidity sensor and a dew condensation sensor, for example. It can be preferably used for a sensor.
  • the average particle diameter of the metal fine particles was measured by crushing the sample and dispersing it in ethanol, and then dropping the obtained dispersion onto a metallic mesh with a carbon support film to prepare a transmission electron microscope (TEM; JEM-2000EX manufactured by JEOL Ltd. was used for observation.
  • the average particle diameter of the metal fine particles was the area average diameter.
  • the porosity of the metal fine particle dispersed composite layer includes the apparent density (bulk density) calculated from the area, thickness and weight of the metal fine particle dispersed composite layer, the material forming the solid skeleton part of the matrix, and the inherent density of the metal fine particles. Using the density without voids (true density) calculated from the composition ratio, the porosity was calculated according to the following formula (A).
  • Example 1-1 An LSPR sensor having the same configuration as that shown in FIG. 7 was prepared except that a metal gold fine particle dispersion layer (hereinafter sometimes referred to as “metal gold fine particle dispersion layer 1001”) was formed as the nanocomposite layer 1001. That is, the LSPR sensor 1000 includes a metal gold fine particle dispersion layer 1001, a light reflecting member 1002 laminated on one side of the metal gold fine particle dispersion layer 1001, and a metal gold fine particle dispersion layer on the opposite side of the light reflecting member 1002. A composite substrate 1004 having a transparent glass substrate 1003 laminated on 1001 is provided.
  • the LSPR sensor 1000 is a light source 1005 that can irradiate a light beam by changing an angle with respect to the stacking direction of the composite substrate 1004, and a light that detects reflected light of the light beam emitted from the light source 1005 toward the composite substrate 1004. And a detector 1006.
  • the gold complex-containing slurry was applied to a transparent glass substrate 1003 (thickness 0.7 mm) using a spin coater (trade name: SPINCOATER 1H-DX2 manufactured by Mikasa Co., Ltd.), and then at 70 ° C. for 3 minutes.
  • the metal gold fine particle dispersion layer 1001 (thickness 1.52 ⁇ m) colored red was formed by drying at 130 ° C. for 10 minutes and further heat treatment at 280 ° C., 10 minutes and 500 ° C. for 1 hour.
  • the metal gold fine particles formed in the metal gold fine particle dispersion layer 1001 are completely independent from each other in the region from the surface layer portion of the metal gold fine particle dispersion layer 1001 to the thickness direction.
  • the characteristics of the metal gold fine particle dispersion layer 1001 were as follows. 1) Porosity of metal gold fine particle dispersion layer 1001; 60.1% 2) Shape of metal gold fine particles: almost spherical, average particle size: 24.9 nm, minimum particle size: 12.5 nm, maximum particle size: 40.3 nm, ratio of particles in the range of 1 nm to 100 nm; 100 % 3) Volume fraction of metal gold fine particles with respect to metal gold fine particle dispersed layer 1001; 1.8%, same weight fraction; 22.6 wt%
  • an absorption peak with a peak top of 521 nm and an absorbance of 0.224 at a wavelength of 590 nm is observed, and the absorption spectrum in water is a peak.
  • An absorption peak with a top at 536 nm and an absorbance at a wavelength of 590 nm of 0.587 was observed.
  • the peak wavelength variation with respect to the unit refractive index variation of the observed absorption peak and the absorbance variation at the wavelength of 590 nm were 46.5 nm and 1.15, respectively.
  • a light reflecting member 1002 (polyester nonwoven fabric, porosity 82%, thickness 110 ⁇ m, reflectance 68% at a wavelength of 590 nm) was laminated on the metal gold fine particle dispersion layer 1001 to form a composite substrate 1004.
  • a visible light source of a halogen lamp is used as the light source 1005, an instantaneous multi-photometry system (manufactured by Otsuka Electronics Co., Ltd., MCPD-3700), and a light projecting / receiving coaxial Y-type optical fiber.
  • the reflectance was measured by using the composite substrate 1004 to make light incident in the vertical direction from the surface of the transparent glass substrate 1003 and detecting the reflected light.
  • the reflectance was measured by using a laminate of only the transparent glass substrate 1003 and the light reflecting member 1002 without the metal gold fine particle dispersion layer 1001 as a reference, and measuring the relative reflectance.
  • air with a relative humidity of 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90% at a temperature of 30 ° C. is used.
  • the relative humidity around 1004 was varied.
  • the measured values of the reflectance of the composite substrate 1004 at a wavelength of 590 nm are 60.4% at a temperature of 30 ° C. and a relative humidity of 10%, and 52.2% at a temperature of 30 ° C. and a relative humidity of 90%. 2%.
  • FIG. 11 shows the change over time in the reflectance at a wavelength of 590 nm of the composite substrate 1004 with respect to the stepwise change in relative humidity, measured in Example 1-1.
  • Example 1-2 In the configuration of the LSPR sensor 1000 of FIG. 7, light is incident from an angle of 45 degrees with respect to the stacking direction of the composite substrate 1004 from the transparent glass substrate 1003 side of the composite substrate 1004, and reflected by detecting reflected light.
  • the humidity response was evaluated in the same manner as in Example 1-1 except that the rate was measured.
  • the measured value of the reflectance of the composite substrate 1004 at a wavelength of 590 nm is 50.3% at a temperature of 30 ° C. and a relative humidity of 10%, and 39.7% at a temperature of 30 ° C. and a relative humidity of 90%.
  • the amount of change was 10.6%.
  • Example 1-3 In the configuration of the LSPR sensor 1000 in FIG. 7, a transparent glass substrate of a composite substrate 1004 using an LED having a central wavelength of 590 nm with a condensing lens as the light source 1005 and a photodiode with a condensing lens as the photodetector 1006.
  • the output voltage from the photodiode was measured as the intensity of the reflected light by entering light in the vertical direction from the surface 1003 and detecting the reflected light at an angle of 30 degrees with respect to the stacking direction of the composite substrate 1004. Except for this, the humidity response evaluation was performed in the same manner as in Example 1-1.
  • the output voltage from the photodiode measured as the intensity of the reflected light from the composite substrate 1004 is 2.55 V at a temperature of 30 ° C. and a relative humidity of 10%, and 2.08 V at a temperature of 30 ° C. and a relative humidity of 90%.
  • the voltage change amount was 0.47V.
  • FIG. 12 shows the change with time of the output voltage from the photodiode with respect to the step change in the relative humidity, measured in Example 1-3.
  • Example 1-4 A composite substrate 1004 was prepared in the same manner as in Example 1-1 except that glass fiber filter paper (porosity 80%, thickness about 0.7 mm, reflectance 79% at a wavelength of 590 nm) was used as the light reflecting member 1002. Fabricated and evaluated for humidity responsiveness. As a result of the evaluation, the measured value of the reflectance of the composite substrate 1004 at a wavelength of 590 nm is 62.6% at a temperature of 30 ° C. and a relative humidity of 10%, and 50.4% at a temperature of 30 ° C. and a relative humidity of 90%. The amount of change was 12.2%.
  • Example 1-5 The composite was made in the same manner as in Example 1-1 except that a PTFE membrane filter (pore diameter 0.2 ⁇ m, porosity 85%, thickness 68 ⁇ m, reflectance 62% at a wavelength of 590 nm) was used as the light reflecting member 1002.
  • a substrate 1004 was fabricated and humidity response evaluation was performed. As a result of the evaluation, the measured value of the reflectance of the composite substrate 1004 at a wavelength of 590 nm is 59.8% at a temperature of 30 ° C. and a relative humidity of 10%, and 51.9% at a temperature of 30 ° C. and a relative humidity of 90%. The amount of change was 7.9%.
  • Example 1-6 The composite was made in the same manner as in Example 1-1 except that a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at a wavelength of 590 nm) was used as the light reflecting member 1002.
  • a substrate 1004 was fabricated and humidity response evaluation was performed. As a result of the evaluation, the measured value of the reflectance of the composite substrate 1004 at a wavelength of 590 nm is 76.2% at a temperature of 30 ° C. and a relative humidity of 10%, and 60.2% at a temperature of 30 ° C. and a relative humidity of 90%. The amount of change was 16.0%.
  • Example 1-1 Except that a non-porous aluminum-deposited glass substrate (aluminum deposition thickness of 200 nm, glass substrate thickness of 0.7 mm, reflectance of 95% at a wavelength of 590 nm) was used as the light reflecting member 1002, the same as in Example 1-1. Thus, a composite substrate was produced and the humidity response was evaluated. As a result of the evaluation, the measured value of the reflectance of the composite substrate at a wavelength of 590 nm was 65.0% at a temperature of 30 ° C. and a relative humidity of 10%, and 64.7% at a temperature of 30 ° C. and a relative humidity of 90%. The amount was 0.3%.
  • Example 1-2 A composite substrate was produced in the same manner as in Example 1-1, except that a non-porous white alumina substrate (alumina substrate thickness 1.0 mm, reflectance 92% at a wavelength of 590 nm) was used as the light reflecting member 1002. The humidity response was evaluated. As a result of the evaluation, the measured value of the reflectance of the composite substrate at a wavelength of 590 nm was 62.1% at a temperature of 30 ° C. and a relative humidity of 10%, and 61.7% at a temperature of 30 ° C. and a relative humidity of 90%. The amount was 0.4%.
  • ⁇ Preparation of light reflecting member with antifouling layer> On the surface of a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman), 5 wt. Of polystyrene (average molecular weight 380,000, manufactured by Toyo Styrene Co., Ltd.) After applying 30 ⁇ l of a toluene solution dissolved at a concentration of%, the light reflecting member E1 with an antifouling layer (moisture selective transmission filter E1) was prepared by drying.
  • a light reflecting member E1 with an antifouling layer was laminated on the metal gold fine particle dispersion layer 1001 produced in Example 1-1 to form a laminated composite substrate E1.
  • the reflectance was measured by entering light in the vertical direction from the surface side and detecting the reflected light.
  • the reflectance was measured by using a laminate of only the transparent glass substrate 1003 and the light reflecting member 1002 without the metal gold fine particle dispersion layer 1001 as a reference, and measuring the relative reflectance at a wavelength of 580 nm.
  • FIG. 13 is a diagram for explaining a response speed evaluation method, and shows a model of temporal change in reflectance and relative humidity.
  • the response speed to humidity change is based on the time (change time: 2 minutes) until the change from 10% RH to 20% RH as a result of measurement with a commercially available humidity sensor (HP23, manufactured by Rotronic). (See FIG. 13).
  • a change time of 4 minutes or less was judged as acceptable ( ⁇ ), preferably within 3 minutes ( ⁇ ), more preferably within 2 minutes ((). Those with a change time exceeding 4 minutes were determined to be impossible (x).
  • FIG. 14 is a diagram for explaining a method for evaluating reproducibility, and shows a variation model when the reflectance measurement is repeated a plurality of times.
  • the variation rate was calculated from the baseline change amount A of the reflectance at a wavelength of 590 nm in the first and third measurements and the peak height B in the third measurement according to the following equation. .
  • Fluctuation rate (%) (A / B) ⁇ 100
  • the reproducibility was evaluated as acceptable ( ⁇ ) when the fluctuation rate was within ⁇ 5%, preferably within ⁇ 2% ( ⁇ ), and more preferably within ⁇ 1% ( ⁇ ). Those with a fluctuation rate exceeding ⁇ 5% were judged as impossible ( ⁇ ).
  • the reproducibility evaluation result of ⁇ and ⁇ is “OK”, and the reproducibility evaluation result is ⁇ and X, “impossible”. evaluated.
  • the response time with respect to humidity change was 2 minutes, and the response was determined to be ⁇ .
  • the reproducibility evaluation result was a variation rate of 1.0%, and the reproducibility was judged as ⁇ .
  • the overall evaluation was “OK”.
  • Example 2-2 1 wt. Of polystyrene (average molecular weight 380,000, manufactured by Toyo Styrene Co., Ltd.) on the surface of a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at wavelength 590 nm, 13 mm ⁇ , manufactured by Whatman) After applying 20 ⁇ l of a toluene solution dissolved at a concentration of%, it was dried to prepare a light reflecting member E2 with an antifouling layer (moisture selective transmission filter E2).
  • a porous alumina membrane filter pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at wavelength 590 nm, 13 mm ⁇ , manufactured by Whatman
  • the light reflecting member E2 with antifouling layer was laminated on the metal gold fine particle dispersion layer 1001 produced in Example 1-1 to form a laminated composite substrate E2. And according to the humidity responsiveness evaluation method, the multilayer composite substrate E2 was evaluated.
  • Example 2-3 1 wt. Of polystyrene (average molecular weight 380,000, manufactured by Toyo Styrene Co., Ltd.) on the surface of a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at wavelength 590 nm, 13 mm ⁇ , manufactured by Whatman) After applying 30 ⁇ l of a toluene solution dissolved at a concentration of%, the light-reflecting member E3 (moisture selective transmission filter E3) with an antifouling layer was prepared by drying.
  • polystyrene average molecular weight 380,000, manufactured by Toyo Styrene Co., Ltd.
  • a porous alumina membrane filter pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at wavelength 590 nm, 13 mm ⁇ , manufactured by Whatman
  • the light reflecting member E3 with antifouling layer was laminated on the metal gold fine particle dispersed layer 1001 produced in Example 1-1 to form a laminated composite substrate E3. And according to the humidity responsiveness evaluation method, the multilayer composite substrate E3 was evaluated.
  • Example 2-4 1 wt. Of polystyrene (average molecular weight 380,000, manufactured by Toyo Styrene Co., Ltd.) on the surface of a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at wavelength 590 nm, 13 mm ⁇ , manufactured by Whatman) After applying 50 ⁇ l of a toluene solution dissolved at a concentration of%, the light-reflecting member E4 with an antifouling layer (moisture selective transmission filter E4) was prepared by drying.
  • polystyrene average molecular weight 380,000, manufactured by Toyo Styrene Co., Ltd.
  • a porous alumina membrane filter pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at wavelength 590 nm, 13 mm ⁇ , manufactured by Whatman
  • a light reflecting member E4 with antifouling layer (moisture selective transmission filter E4) was laminated on the metal gold fine particle dispersed layer 1001 produced in Example 1-1 to form a laminated composite substrate E4. And according to the humidity-responsiveness evaluation method, the multilayer composite substrate E4 was evaluated.
  • Example 2-5 Two light reflecting members with antifouling layer E3 (moisture selective transmission filter E3) were stacked on the metal gold fine particle dispersion layer 1001 produced in Example 1-1 to form a laminated composite substrate E5. And according to the humidity-responsiveness evaluation method, the multilayer composite substrate E5 was evaluated.
  • Example 2-6 The light reflecting member E1 with antifouling layer and the light reflecting member E3 with antifouling layer (moisture selective transmission filter E1 and moisture selective transmission filter E3) are stacked on the metal gold fine particle dispersion layer 1001 prepared in Example 1-1. Lamination was performed to form a laminated composite substrate E6. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate E6 was evaluated.
  • Example 2-7 Two light reflecting members E1 (moisture selective transmission filter E1) with an antifouling layer were stacked on the metal gold fine particle dispersion layer 1001 prepared in Example 1-1 to form a laminated composite substrate E7. And according to the humidity responsiveness evaluation method, the multilayer composite substrate E7 was evaluated.
  • a light reflecting member C1 with antifouling layer (moisture selective transmission filter C1) was laminated on the metal gold fine particle dispersion layer 1001 produced in Example 1-1 to form a laminated composite substrate C1. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate C1 was evaluated.
  • the light reflecting member C2 with antifouling layer was laminated on the metal gold fine particle dispersed layer 1001 produced in Example 1-1 to form a laminated composite substrate C2. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate C2 was evaluated.
  • silicon coating agent KR251, manufactured by Shin-Etsu Chemical Co., Ltd.
  • a porous alumina membrane filter pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman
  • Two light reflecting members C3 with antifouling layer were laminated on the metal gold fine particle dispersed layer 1001 produced in Example 1-1 to form a laminated composite substrate C3. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate C3 was evaluated.
  • Two light reflecting members with antifouling layer C4 (moisture selective transmission filter C4) were laminated on the metal gold fine particle dispersed layer 1001 produced in Example 1-1 to form a laminated composite substrate C4. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate C4 was evaluated.
  • Two light-reflective members with antifouling layer C5 (moisture selective transmission filter C5) were laminated on the metal gold fine particle dispersion layer 1001 produced in Example 1-1 to form a laminated composite substrate C5. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate C5 was evaluated.
  • a light reflecting member C6 with an antifouling layer was laminated on the metal gold fine particle dispersion layer 1001 produced in Example 1-1 to form a laminated composite substrate C6. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate C6 was evaluated.
  • the light reflecting member C7 with antifouling layer was laminated on the metal gold fine particle dispersion layer 1001 produced in Example 1-1 to form a laminated composite substrate C7. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate C7 was evaluated.
  • Example 2-8 On the surface of a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectivity 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman), polyvinyl alcohol 500 (manufactured by Whatman Chemical Co.) has a concentration of 5 wt%. After applying 60 ⁇ l of the aqueous solution dissolved in step 1, the light reflecting member E8 with antifouling layer (moisture selective transmission filter E8) was prepared by drying.
  • Two light reflecting members E8 with antifouling layer were laminated on the metal gold fine particle dispersed layer 1001 produced in Example 1-1 to form a laminated composite substrate E8. And according to the humidity responsiveness evaluation method, the multilayer composite substrate E8 was evaluated.
  • Example 2-9 On the surface of a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectivity 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman), polyvinyl alcohol 500 (manufactured by Whatman Chemical Co.) has a concentration of 5 wt%. After applying 30 ⁇ l of the aqueous solution dissolved in step 1, the light reflecting member E9 (moisture selective transmission filter E9) with an antifouling layer was prepared by drying.
  • Example 2-10 On the surface of a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectivity 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman), polyvinyl butyral resin (ESREC BM-1, manufactured by Sekisui Chemical Co., Ltd.) After applying 20 ⁇ l of a toluene solution in which 5) was dissolved at a concentration of 5 wt%, drying was performed to prepare a light-reflective member E10 (moisture selective transmission filter E10) with an antifouling layer.
  • a porous alumina membrane filter pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectivity 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman
  • polyvinyl butyral resin ESREC BM-1, manufactured by Sekisui Chemical Co., Ltd.
  • Two light reflecting members E10 with an antifouling layer (moisture selective transmission filter E10) were laminated on the metal gold fine particle dispersion layer 1001 produced in Example 1-1 to form a laminated composite substrate E10. And according to the humidity-responsiveness evaluation method, the multilayer composite substrate E10 was evaluated.
  • Example 2-11 On the surface of a porous alumina membrane filter (pore diameter 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectivity 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman), 5 wt% of PMMA (average molecular weight Mw 120,000, manufactured by Sigma-Aldrich) After applying 20 ⁇ l of a toluene solution dissolved at a concentration of%, the antireflective layer-attached light reflecting member E11 (moisture selective transmission filter E11) was prepared by drying.
  • PMMA average molecular weight Mw 120,000
  • Two light reflecting members E11 with antifouling layer (moisture selective transmission filter E11) were laminated on the metal gold fine particle dispersed layer 1001 produced in Example 1-1 to form a laminated composite substrate E11. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate E11 was evaluated.
  • Example 2-12 On the surface of a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman), polyvinyl acetate (average molecular weight Mw 50,000, manufactured by Alfa Aesar) After applying 20 ⁇ l of a toluene solution dissolved at a concentration of 5 wt%, the antireflective layer-attached light reflecting member E12 (moisture selective transmission filter E12) was prepared by drying.
  • a porous alumina membrane filter pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman
  • polyvinyl acetate average molecular weight Mw 50,000, manufactured by Alfa Aesar
  • Two light reflecting members E12 with antifouling layer were laminated on the metal gold fine particle dispersion layer 1001 produced in Example 1-1 to form a laminated composite substrate E12. And according to the humidity responsiveness evaluation method, the multilayer composite substrate E12 was evaluated.
  • Example 2-13 On the surface of a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman), polyvinyl acetate (average molecular weight Mw 50,000, manufactured by Alfa Aesar) After applying 30 ⁇ l of a toluene solution dissolved at a concentration of 1 wt%, a light reflecting member E13 with an antifouling layer (moisture selective transmission filter E13) was prepared by drying.
  • a porous alumina membrane filter pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman
  • polyvinyl acetate average molecular weight Mw 50,000, manufactured by Alfa Aesar
  • Two light reflecting members E13 with antifouling layer were laminated on the metal gold fine particle dispersed layer 1001 produced in Example 1-1 to form a laminated composite substrate E13. And according to the humidity responsiveness evaluation method, the multilayer composite substrate E13 was evaluated.
  • Example 2-14 On the surface of a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectivity 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman), polyvinyl butyral resin (ESREC BM-1, manufactured by Sekisui Chemical Co., Ltd.) After applying 30 ⁇ l of a toluene solution dissolved in a concentration of 0.2 wt%, a light reflecting member E14 with an antifouling layer (moisture selective transmission filter E14) was prepared by drying.
  • a porous alumina membrane filter pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectivity 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman
  • polyvinyl butyral resin ESREC BM-1, manufactured by Sekisui Chemical Co., Ltd.
  • Two light reflecting members E14 with an antifouling layer were laminated on the metal gold fine particle dispersed layer 1001 produced in Example 1-1 to form a laminated composite substrate E14. And according to the humidity responsiveness evaluation method, the multilayer composite substrate E14 was evaluated.
  • Example 2-15 On the surface of a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectivity 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman), polyvinyl butyral resin (ESREC BM-1, manufactured by Sekisui Chemical Co., Ltd.) After applying 30 ⁇ l of a toluene solution dissolved in a concentration of 1.0 wt%, a light reflecting member E15 with an antifouling layer (moisture selective transmission filter E15) was prepared by drying.
  • a porous alumina membrane filter pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectivity 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman
  • polyvinyl butyral resin ESREC BM-1, manufactured by Sekisui Chemical Co., Ltd.
  • Two light reflecting members E15 moisture selective transmission filter E15 with an antifouling layer were laminated on the metal gold fine particle dispersion layer 1001 produced in Example 1-1 to form a laminated composite substrate E15. And according to the humidity-responsiveness evaluation method, the multilayer composite substrate E15 was evaluated.
  • a silicon coating agent (KR251, manufactured by Shin-Etsu Chemical Co., Ltd.) is applied to the surface of a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman). After applying 30 ⁇ l of a toluene solution dissolved at a concentration of 0.0 wt%, drying was performed to prepare a light reflection member C8 with an antifouling layer (moisture selective transmission filter C8).
  • Two light reflecting members C8 with antifouling layer were laminated on the metal gold fine particle dispersion layer 1001 produced in Example 1-1 to form a laminated composite substrate C8. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate C8 was evaluated.
  • Two light reflecting members C9 with antifouling layer were laminated on the metal gold fine particle dispersion layer 1001 produced in Example 1-1 to form a laminated composite substrate C9. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate C9 was evaluated.
  • Example 2-16 On the surface of a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectivity 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman), heat-resistant polystyrene (average molecular weight 220,000, manufactured by Toyo Styrene Co., Ltd.) After applying 30 ⁇ l of a toluene solution dissolved in a concentration of 1.0 wt%, the light reflection member E16 with antifouling layer (moisture selective transmission filter E16) was prepared by drying.
  • a porous alumina membrane filter pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectivity 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman
  • heat-resistant polystyrene average molecular weight 220,000, manufactured by Toyo Styrene Co., Ltd.
  • Two light reflecting members E16 with antifouling layer were laminated on the metal gold fine particle dispersion layer 1001 produced in Example 1-1 to form a laminated composite substrate E16. And according to the humidity responsiveness evaluation method, the multilayer composite substrate E16 was evaluated.
  • Example 2-17 On the surface of a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman), PMMA (average molecular weight Mw 120,000, manufactured by Sigma-Aldrich) 1 After applying 30 ⁇ l of a toluene solution dissolved at a concentration of 0.0 wt%, drying was performed to prepare a light reflecting member E17 with an antifouling layer (moisture selective transmission filter E17).
  • a porous alumina membrane filter pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman
  • PMMA average molecular weight Mw 120,000, manufactured by Sigma-Aldrich
  • Two light reflecting members E17 with antifouling layer (moisture selective transmission filter E17) were laminated on the metal gold fine particle dispersion layer 1001 produced in Example 1-1 to form a laminated composite substrate E17. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate E17 was evaluated.
  • Example 2-18 On the surface of a porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectance 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman), polystyrene (average molecular weight 380,000, manufactured by Toyo Styrene) 1 After applying 30 ⁇ l of a toluene solution dissolved at a concentration of 0.0 wt%, and then drying, 40 ⁇ l of a fluorine-based coating agent (FS1010TH-0.5, manufactured by Fluorsurf) is applied and dried to provide a light reflecting member with an antifouling layer E18 (moisture selective permeation filter E18) was prepared.
  • a fluorine-based coating agent FS1010TH-0.5, manufactured by Fluorsurf
  • a light reflecting member E18 with antifouling layer was laminated on the metal gold fine particle dispersion layer 1001 produced in Example 1-1 to form a laminated composite substrate E18. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate E18 was evaluated.
  • a light reflecting member C10 with an antifouling layer (moisture selective transmission filter C10) and an untreated porous alumina membrane filter are laminated on the metal gold fine particle dispersed layer 1001 prepared in Example 1-1 to form a laminated composite substrate C10. did. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate C10 was evaluated.
  • Example 2-11 An untreated porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectivity 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman Co., Ltd.) produced in Example 1-1 is a metal gold fine particle dispersion layer 1001 A laminated composite substrate 1 for comparison was formed. Then, according to the humidity responsiveness evaluation method, the comparative laminated composite substrate 1 was evaluated.
  • Example 2-12 An untreated porous alumina membrane filter (pore size 0.02 ⁇ m, porosity 25%, thickness 67 ⁇ m, reflectivity 58% at a wavelength of 590 nm, 13 mm ⁇ , manufactured by Whatman Co., Ltd.) produced in Example 1-1 is a metal gold fine particle dispersion layer 1001 Two layers were stacked on top of each other to form a comparative laminated composite substrate 2. Then, according to the humidity response evaluation method, the comparative laminated composite substrate 2 was evaluated.
  • the gold complex-containing slurry was applied to a transparent glass substrate 1003 (thickness 0.7 mm) using a spin coater (trade name: SPINCOATER 1H-DX2 manufactured by Mikasa Co., Ltd.), and then at 70 ° C. for 3 minutes.
  • a metal gold fine particle dispersion layer 1001 (thickness 0.80 ⁇ m) colored red was formed.
  • the metal gold fine particles formed in the metal gold fine particle dispersion layer 1001 are completely independent from each other in the region from the surface layer portion of the metal gold fine particle dispersion layer 1001 to the thickness direction.
  • the characteristics of the metal gold fine particle dispersion layer 1001 were as follows. 1) Porosity of metallic gold fine particle dispersion layer 1001; 60%. 2) Shape of metal gold fine particles: almost spherical, average particle size: 22.0 nm, minimum particle size: 8.0 nm, maximum particle size: 45.8 nm, ratio of particles in the range of 1 to 100 nm; 100 %. 3) Volume fraction of metal gold fine particles with respect to metal gold fine particle dispersed layer 1001; 4.44%, same weight fraction; 43.15 wt%
  • the transmission absorption spectrum of LSPR in the air by the metal gold fine particles of the metal gold fine particle dispersion layer 1001 has an absorption peak with a peak top of 523 nm and an absorbance at a wavelength of 590 nm of 0.330, and the absorption spectrum in water is a peak.
  • An absorption peak with a top of 535 nm and an absorbance of 0.717 at a wavelength of 590 nm was observed.
  • the peak wavelength variation with respect to the unit refractive index variation of the observed absorption peak and the absorbance variation at the wavelength of 590 nm were 41.1 nm and 1.43, respectively.
  • the light reflecting member E19B (moisture selective transmission filter E19B) with antifouling layer was produced by further heating the light reflecting member E19A with antifouling layer (moisture selective transmission filter E19A) at 125 ° C. for 1 hour in the atmosphere.
  • a light reflecting member E19B with an antifouling layer was laminated on the metal gold fine particle dispersion layer 1001 to form a laminated composite substrate E19. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate E19 was evaluated.
  • the laminated composite substrate E19 had a variation rate close to 0 and extremely good reproducibility.
  • Example 2-20 Two light reflecting members E19B with an antifouling layer (moisture selective transmission filter E19B) were stacked on the metal gold fine particle dispersion layer 1001 to form a laminated composite substrate E20. And according to the humidity responsiveness evaluation method, the multilayer composite substrate E20 was evaluated. The multilayer composite substrate E20 had a variation rate close to 0 and extremely good reproducibility.
  • Example 2-21 One light reflecting member E19A with antifouling layer (moisture selective transmission filter E19A) was laminated on the metal gold fine particle dispersion layer 1001 to form a laminated composite substrate E21. And according to the humidity responsiveness evaluation method, the multilayer composite substrate E21 was evaluated.
  • Example 2-22 Two light reflecting members E19A with an antifouling layer (moisture selective transmission filter E19A) were laminated on the metal gold fine particle dispersion layer 1001 to form a laminated composite substrate E22. Then, according to the humidity responsiveness evaluation method, the multilayer composite substrate E22 was evaluated.

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Abstract

La présente invention concerne un substrat composite (100) muni d'une couche nanocomposite (10) et d'un élément poreux réfléchissant la lumière (20) stratifié sur la couche nanocomposite (10). La couche nanocomposite (10) comprend une matrice (1) ayant un squelette solide (1a) et des interstices (1b) formés par le squelette solide (1a) et comportant de fines particules métalliques (3) fixées au squelette solide (1a) de la matrice (1). Le squelette solide (1a) comprend un oxyde de métal ou un hydroxyde de métal tel qu'un oxyhydroxyde de métal et forme une structure de réseau tridimensionnelle. L'élément réfléchissant la lumière (20) est poreux et est de préférence constitué d'un matériau réfléchissant une lumière dont la longueur d'onde génère une résonance localisée de plasmon de surface.
PCT/JP2014/084485 2013-12-30 2014-12-26 Substrat composite, capteur optique, capteur à résonance localisée de plasmon de surface, leur utilisation, procédé de détection, filtre perméable sélectif vis-à-vis de l'humidité et capteur muni de celui-ci WO2015102090A1 (fr)

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