sensor

Abstract

To provide a sensor that excels in resistance to humidity effects, is capable of measuring highly hydrophilic gases such as ethanol and aldehyde without significantly attenuating electric signals even under a relatively high humidity condition, and which has a sensitive film whose coating throughput is high.SOLUTION: Provided is a sensor having a sensitive film, wherein the sensitive film has an absorption peak in a 1600-1800 cm-1 region and in a 1350-1450 cm-1 region in an infrared total reflection absorption measurement, and the peak strength ratio (A / B) of an absorption peak maximum (A) in the 1600-1800 cm-1 region to an absorption peak maximum (B) in the 1350-1450 cm-1 region is 0.1 to 4.0.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a sensor. [Background technology]

[0002] Sensors generally have a detection element (receptor) that enables highly sensitive and selective detection of target analytes. A wide variety of materials are used as receptors, including self-assembled monolayers, monolayers, DNA / RNA, proteins, antigens / antibodies, and polymers. With the recent development of AI and IoT, new applications are expected in the field of olfactory / gas sensors. In recent years, the waste of fruit and vegetables due to over-ripening during food transportation has been recognized as a major global problem. As fruit and vegetables ripen, they emit unique gases such as ethylene, ethanol, and acetaldehyde. When using sensors to manage food quality, it is particularly important to track the ethanol and aldehydes that result from anaerobic respiration of food.

[0003] Patent document 1 describes a sensor in which a porous or granular material is coated on a sensor body of a type that detects physical parameters, and the sensor detects analyte molecules based on a change in the physical parameter caused by the analyte molecules being adsorbed by the porous or granular material.

[0004] Patent Document 2 describes a nanomechanical sensor that uses a receptor material made of a low moisture-absorbing material to prevent the receptor layer from being adversely affected by water. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2016 / 121155 [Patent Document 2] International Publication No. 2018 / 221283 Summary of the Invention [Problem to be solved by the invention]

[0006] The technology described in Patent Document 1 achieves high sensitivity, selectivity, and stability, but the electrical signal is significantly attenuated except in a dry atmosphere, greatly limiting the environments in which it can be used as an olfactory sensor.

[0007] The technology described in Patent Document 2 can reduce the effect of water contained in the sample on the sensor output, expanding the range of use of the sensor. However, the low solubility of the receptor material tends to reduce throughput when applying ink.

[0008] The present invention has been made in consideration of the problems associated with the above-mentioned conventional technology, and its purpose is to provide a sensor having a sensitive film that has excellent resistance to humidity influences, is capable of measuring highly hydrophilic gases such as ethanol and aldehydes without significant attenuation of the electrical signal even under conditions of relatively high humidity, and has a high coating throughput. [Means for solving the problem]

[0009] In order to solve the above problems, the inventors of the present invention have conducted extensive research and experiments, and as a result have unexpectedly found that the above problems can be solved, thereby completing the present invention.

[0010] That is, the present invention includes the following aspects. [1] A sensor having a sensitive membrane, The sensitive film has a wavelength of 1600 to 1800 cm in infrared total reflection absorption measurement. -1 and 1350-1450 cm -1 has an absorption peak in the region 1350~1450cm -1 The absorption peak maximum (B) in the region of 1600 to 1800 cm -1 The peak intensity ratio (A / B) of the absorption peak maximum (A) in the region is 0.1 to 4.0. sensor. [2] 1350~1450cm -1 The absorption peak in the region includes an absorption peak derived from an interatomic bond between a silicon atom and an aromatic carbon atom. [1] The sensor described in [1]. [3] 1600~1800cm -1 The absorption peak in the region includes an absorption peak due to a carbonyl group. The sensor according to [1] or [2]. [4] 1600~1800cm -1 The absorption peak in the region of includes the absorption peak of a carbonyl group forming an amide bond. The sensor according to any one of [1] to [3]. [5] The sensitive film has the formula RSiO 3 / 2 (wherein R represents an organic functional group), The sensor according to any one of [1] to [4]. [6] The organic functional group contains at least one amide bond. [5] The sensor described in [5]. [7] The organic functional group contains at least one type of aromatic ring. The sensor according to [5] or [6]. [8] It is a surface stress sensor. The sensor according to any one of [1] to [7]. [Effects of the Invention]

[0011] According to the present invention, a sensor can be provided which has a sensitive film that has excellent resistance to humidity influences, can measure highly hydrophilic gases such as ethanol and aldehydes without significant attenuation of the electrical signal even under relatively high humidity conditions, and has a high application throughput (hereinafter simply referred to as throughput). [Brief explanation of the drawings]

[0012] [Figure 1] 1 shows examples of optical microscope photographs of chips coated with the sensitive films of Example 1 and Comparative Example 3. [Figure 2] 1 shows the results of microscopic ATR spectra of Example 1 and Comparative Example 1. [Figure 3] 1 shows the response to ethanol at humidity levels of 0% and 50% in Example 1. [Figure 4] 1 shows the responsiveness to ethanol at humidity levels of 0% and 50% in Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0013] The following describes in detail an embodiment of the present invention (hereinafter referred to as "the present embodiment"); however, the present invention is not limited to this embodiment, and various modifications are possible without departing from the spirit of the present invention.

[0014] 1. Sensor The sensor of this embodiment is a sensor having a sensitive film, and the sensitive film has a wavelength of 1600 to 1800 cm in infrared total reflection absorption measurement. -1 and 1350-1450 cm -1 It has an absorption peak in the region of 1350 to 1450 cm -1 The absorption peak maximum (B) in the region of 1600 to 1800 cm -1 The sensor has a peak intensity ratio (A / B) of the maximum absorption peak (A) in this region of 0.1 to 4.0.

[0015] The sensor of the present embodiment includes, but is not limited to, a sensor body that detects physical parameters, such as, but not limited to, surface stress, stress, force, surface tension, pressure, mass, elasticity, Young's modulus, Poisson's ratio, resonant frequency, frequency, volume, thickness, viscosity, density, magnetic force, magnetic quantity, magnetic field, magnetic flux, magnetic flux density, electrical resistance, electrical quantity, permittivity, power, electric field, charge, current, voltage, electric potential, mobility, electrostatic energy, capacitance, inductance, reactance, susceptance, admittance, impedance, conductance, plasmon, refractive index, luminous intensity, temperature, and various other physical parameters.

[0016] The sensor of this embodiment is not particularly limited, but may be, for example, a sensor in which a sensitive film (sometimes referred to as a "receptor layer" in this technical field) is provided directly on the sensor body. That is, the sensor of this embodiment can be configured to detect, by the sensor body, a change in a physical parameter caused by the sensitive film adsorbing sample molecules. As described above, the sensor body that can be used in this embodiment is not particularly limited, as long as it detects a change caused in the sensitive film disposed on its surface by the adsorption of a substance to be detected.

[0017] Furthermore, the sensor of this embodiment can be used as a surface stress sensor (MSS). The surface stress sensor is preferably a four-point fixed piezoelectric element type surface stress sensor. In this case, the surface stress sensor can be fabricated by coating at least a part of the surface of the sensor body made of a piezoelectric element with a sensitive film. When the coated sensitive film adsorbs the detection target substance, the stress change induced in the sensitive film is detected and the body outputs a signal.

[0018] Furthermore, a different type of sensor body may be used, but is not particularly limited to, for example, a QCM (quartz crystal microbalance) device. A QCM device is a mass sensor that measures minute changes in mass by utilizing the property that when a substance is adsorbed onto the electrode surface of a quartz crystal oscillator to which an AC electric field is applied, the resonant frequency decreases depending on the mass, viscoelasticity, etc. of the adsorbate, and is capable of in-situ measurement. When the sensor body of this embodiment is applied as a QCM device, for example, by forming the sensitive film of this embodiment on the surface of the electrode, the sensor body detects the mass change that occurs when the sensitive film adsorbs the substance to be detected, and outputs a signal.

[0019] Furthermore, various conductive materials can be used as the electrodes of the QCM, and when the sensitive film of this embodiment is made conductive, the sensitive film can also be used as the electrodes of the QCM.

[0020] In this embodiment, the term "adsorption" refers to a phenomenon in which the concentration of another substance that acts as an adsorbate at the interface of any object increases compared to the surrounding area of ​​the interface, and includes not only physical adsorption but also chemical adsorption due to chemical bonding or biochemical action.

[0021] 1.1.Sensitive membrane The sensitive film in this embodiment has a wavelength of 1600 to 1800 cm in infrared total reflection absorption measurement. -1 and 1350-1450 cm -1 It has an absorption peak in the region of 1350 to 1450 cm -1 The absorption peak maximum (B) in the region of 1600 to 1800 cm -1 The peak intensity ratio (A / B) of the maximum absorption peak (A) in this region is 0.1 to 4.0.

[0022] When the peak intensity ratio (A / B) is in the range of 0.1 to 4.0, the sensor having the sensitive film has excellent resistance to humidity influence and excellent throughput.

[0023] In calculating the above absorption peaks and peak intensity ratios (A / B), the baseline where no peaks existed was set to an absorbance of 0 for baseline correction. A peak was defined as one whose maximum absorbance value was 0.02 or greater.

[0024] Here, the above 1350~1450cm -1 The absorption peak maximum (B) in the region of 1600 to 1800 cm -1 The peak intensity ratio (A / B) of the absorption peak maximum (A) in this region is not particularly limited, but can be adjusted, for example, by changing the amount of carbonyl groups introduced into the organic functional groups.

[0025] Also, the above 1350~1450cm -1 It is preferable that the absorption peak in the region includes an absorption peak derived from an interatomic bond between a silicon atom and an aromatic carbon atom, which tends to result in excellent resistance to humidity effects.

[0026] Here, the above 1350~1450cm -1 The absorption peak in this region is not particularly limited, but for example, when the sensitive film has an organic functional group derived from a silane coupling agent, it can be adjusted by changing the type of organic functional group.

[0027] Also, 1600~1800cm -1 The absorption peak in this region preferably includes an absorption peak derived from a carbonyl group, and more preferably includes an absorption peak derived from a carbonyl group that forms an amide bond. This tends to improve throughput.

[0028] Here, the above 1600 to 1800 cm -1 The absorption peak in this region is not particularly limited, but for example, when the sensitive film has an organic functional group derived from a silane coupling agent, it can be adjusted by changing the type of organic functional group.

[0029] 1.1.1. Organic-inorganic hybrids The sensitive film in this embodiment is made of RSiO 2 from the viewpoint of having high sensitivity, excellent resistance to humidity influence, and not significantly attenuating the sensitivity and electrical signal even in a relatively high humidity environment. 3 / 2 It is preferable that the compound contains a structure represented by the formula: where R represents an organic functional group. 3 / 2 Hereinafter, a molecular chain containing a structure represented by the formula (I) is also referred to as an organic-inorganic hybrid.

[0030] RSiO 3 / 2 There is no particular limitation on the method for introducing the structure represented by the formula (1), but an example thereof is to include a silane coupling agent in the monomer unit constituting the sensitive film.

[0031] The sensitive film in this embodiment may have a uniform thickness distribution of the organic-inorganic hybrid, or may have a coffee-ring shape in which the thickness is thicker at the edges. In the case of a coffee-ring shape, the thickness of the thinnest part of the sensitive film in the center and the thickest part of the edge are typically preferably 10 nm to 50 μm. From the viewpoint of shortening the drying time during production and increasing productivity, the thickness is preferably 10 nm to 30 μm, and from the viewpoint of increasing sensitivity, it is more preferably 10 nm to 20 μm. Furthermore, the maximum thickness of the sensitive film in this embodiment is preferably 30 μm or less.

[0032] In order to use the surface stress sensor (MSS) coated with the sensitive film of this embodiment as an olfactory sensor, it is preferable that the organic functional groups and gas molecules interact with each other in the gas phase and diffuse into the sensitive film, generating stress, thereby detecting the gas.

[0033] In this embodiment, the organic-inorganic hybrid preferably has an organic group having a carbonyl group (for example, a carboxyl group, an ester group, a urethane group, a urea group, an amide group, etc.). Among these, an organic group having an amide group is preferred. Examples of the organic group having an amide group include -NH-CO-R 1Examples of organic groups include those represented by R 1 The alkyl group may be a linear or branched hydrocarbon group (e.g., a linear or branched C alkyl group such as a 3-chloropropyl group or an octyl group) which may have a substituent such as a halogen atom. 1-8 alkyl group), an alicyclic hydrocarbon group (e.g., a C alkyl group such as a cyclohexyl group) which may have a substituent such as a halogen atom, 5-6 a monovalent alicyclic hydrocarbon group (e.g., a C cycloalkyl group such as a cyclohexyl group) which may have a substituent such as a halogen atom; 5-6 cycloalkyl groups), and aromatic hydrocarbon groups which may have a substituent such as a halogen atom (for example, a phenyl group, a pentafluorophenyl group, etc.).

[0034] In this embodiment, the organic-inorganic hybrid preferably contains an organic functional group containing one or more aromatic rings. When the organic functional group contains an aromatic ring, humidity resistance tends to be further improved. The aromatic ring can be appropriately selected based on the intended use of the sensor and is not particularly limited. Examples of the aromatic ring include aromatic hydrocarbon groups such as phenyl, naphthyl, p-tolyl, and biphenyl; substituted aromatic hydrocarbon groups such as 4-chlorophenyl, 4-methoxyphenyl, 4-aminophenyl, and pentafluorophenyl; heterocyclic hydrocarbon groups such as 3-furyl, 3-thienyl, 2-pyridyl, 3-pyridyl, and 4-pyridyl; and metallocenes such as ferrocenyl. The organic functional group used in this embodiment can be appropriately selected and may contain one or more of the above-mentioned aromatic rings.

[0035] In the organic-inorganic hybrid, a spacer structure such as an alkanediyl group (having 1 to 18 carbon atoms), an ether group, a carbonyl group, a carboxyl group, an amide group, a urethane bond, a urea bond, an imide group, or an imine group may be sandwiched between the carbonyl group and the silicon atom, or between the aromatic ring and the silicon atom. Hereinafter, a structure having a spacer between the aromatic ring and the silicon atom will also be referred to as having a "structure not directly bonded to an aromatic ring." From the viewpoint of responsiveness and sensitivity, it is preferable that such a spacer not be sandwiched between the aromatic ring and the silicon atom, and that the aromatic carbon atom be directly bonded to the silicon atom in the organic-inorganic hybrid (hereinafter, also referred to as having a "structure directly bonded to an aromatic ring").

[0036] Furthermore, from the viewpoint of humidity resistance, the organic-inorganic hybrid of this embodiment preferably comprises a copolymer structure of a monomer unit having a directly bonded aromatic ring structure and a monomer unit having a non-directly bonded aromatic ring structure and a carbonyl group. Furthermore, from the viewpoint of achieving both humidity resistance and selectivity to various gas molecules, the organic-inorganic hybrid of this embodiment preferably comprises a copolymer structure of a monomer unit having a directly bonded aromatic ring structure and a monomer unit having an aromatic ring structure and a carbonyl group. Furthermore, from the viewpoint of responsiveness to highly polar gases and odor molecules, the organic functional group of this embodiment preferably comprises a functional group containing one or more atoms selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, halogen atoms such as fluorine, chlorine, bromine, and iodine atoms, boron atoms, and phosphorus atoms. Among these, from the viewpoint of stability, the organic functional group preferably comprises a functional group containing one or more atoms selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, and fluorine atoms.

[0037] Specific examples of the organic functional group other than those described above in this embodiment include, but are not limited to, linear or branched hydrocarbon groups which may have a substituent such as a halogen atom (for example, linear or branched C groups such as a 3-chloropropyl group or an octyl group). 1-8 alkyl group), an alicyclic hydrocarbon group (e.g., a C alkyl group such as a cyclohexyl group) which may have a substituent such as a halogen atom, 5-6cycloalkyl group), organic groups having an unsaturated bond (for example, vinyl group, allyl group, (meth)acrylic group, (meth)acryloyloxy alkyl group (for example, (meth)acryloyloxy C such as (meth)acryloyloxypropyl group) 1-3 alkyl group), organic groups having an oxygen atom (for example, an epoxy group, a glycidyloxy alkyl group (for example, a glycidyloxy C group such as a 3-glycidyloxypropyl group), 1-3 alkyl group), (epoxycycloalkyl) alkyl group (e.g., 2-(3,4-epoxycyclohexyl) ethyl group, etc.), hydroxy group, alkyl ether group), organic group having a sulfur atom (e.g., mercapto group, mercapto alkyl group (e.g., mercapto C such as mercaptopropyl group, etc.) 1-3 alkyl group), sulfide group), organic group having a nitrogen atom (for example, amino group (for example, primary amino group, secondary amino group, tertiary amino group), amino alkyl group (for example, amino C such as aminopropyl group) 1-3 Examples of suitable organic functional groups include alkyl groups, (aminoalkylamino)alkyl groups (e.g., 3-(2-aminoethylamino)propyl groups), imidazolyl groups, imidazolylalkyl groups (e.g., 3-(2-imidazolin-1-yl)propyl groups), alkylaminoalkyl groups (e.g., 3-(dimethylamino)propyl groups), oxime groups, imide groups, imine groups, nitrile groups, halogen groups, and organic groups having a phosphorus atom (e.g., phosphonic groups, phosphate groups). Among these, an amide group is preferred from the viewpoint of excellent throughput. From the viewpoint of availability, the organic functional group is preferably one or more selected from the group consisting of optionally substituted linear or branched hydrocarbon groups, optionally substituted alicyclic hydrocarbon groups, optionally substituted aromatic hydrocarbon groups, vinyl groups, allyl groups, (meth)acryloyloxyalkyl groups, glycidyloxyalkyl groups, (epoxycycloalkyl)alkyl groups, mercaptoalkyl groups, aminoalkyl groups, (aminoalkylamino)alkyl groups, imidazolylalkyl groups, alkylaminoalkyl groups, and hydroxy groups. These functional groups can be appropriately selected and used, and one type can be used alone, or two or more types can be used in combination.

[0038] Among them, the organic functional group is preferably an organic functional group derived from a silane coupling agent.The silane coupling agent is not particularly limited, but examples thereof include hydrolyzable metal oxides such as alkoxysilane, acetoxysilane, or chlorosilane.Among these, the hydrolyzable metal oxide is preferably alkoxysilane in view of ease of handling and versatility of functional group, and more preferably trifunctional alkoxysilane in view of reactivity.

[0039] Trifunctional alkoxysilanes may be copolymerized with mono-, di-, or tetrafunctional alkoxysilanes, etc., but copolymerization with tetrafunctional alkoxysilanes is preferred from the viewpoint of increasing the Young's modulus of the organic-inorganic hybrid and improving its sensitivity.

[0040] The trifunctional alkoxysilane is not particularly limited, but for example, a silane coupling agent having a methoxy group, an ethoxy group, or an isopropoxy group in the alkoxy group can be used.

[0041] The aromatic silane coupling agent is not particularly limited, and examples thereof include phenyltrialkoxysilane, nitrobenzeneamidotrialkoxysilane, benzyltrialkoxysilane, 4-chlorophenyltrialkoxysilane, phenylaminopropyltrialkoxysilane, 4-aminophenyltrialkoxysilane, naphthyltrialkoxysilane, 4-methoxytrialkoxysilane, pentafluorophenyltrialkoxysilane, ferrocenyltrialkoxysilane, biphenyltrialkoxysilane, 3-furyltrialkoxysilane, 3-thienyltrialkoxysilane, 2-pyridyltrialkoxysilane, 3-pyridyltrialkoxysilane, and 4-pyridyltrialkoxysilane, but are not limited thereto.

[0042] The non-aromatic silane coupling agent is not particularly limited, but examples thereof include 3-(2-aminoethylamino)propyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, vinyltrialkoxysilane, cyclohexyltrialkoxysilane, 3-glycidyloxypropyltrialkoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrialkoxysilane, 3-(dimethylamino)propyltrialkoxysilane, 3-(2-imidazolin-1-yl)propyltrialkoxysilane, 3-aminopropyltrialkoxysilane, 3-(methacryloyloxy)propyltrialkoxysilane, 3-(acryloyloxy)propyltrialkoxysilane, allyltrialkoxysilane, methyltrialkoxysilane, and ethyltrialkoxysilane. Examples of suitable alkoxysilanes include, but are not limited to, alkoxysilane, propyltrialkoxysilane, butylalkoxysilane, hexyltrialkoxysilane, octyltrialkoxysilane, decyltrialkoxysilane, dodecyltrialkoxysilane, octadecyltrialkoxysilane, 3-ureidopropyltrialkoxysilane, cyclohexylaminopropyltrialkoxysilane, hexafluorophenyltrialkoxysilane, 3-chloropropyltrialkoxysilane, 3-bromopropyltrialkoxysilane, 3-piperazinopropyltrialkoxysilane, 3-morpholinopropyltrialkoxysilane, 3-allylaminopropyltrialkoxysilane, norbornyltrialkoxysilane, and piperidinopropyltrialkoxysilane.

[0043] When two or more types of silane coupling agents are copolymerized, the molar ratio of aromatic silane coupling agent to non-aromatic silane coupling agent is preferably 1:10 to 1:5, more preferably 1:5 to 1:1 from the viewpoint of heat resistance, and more preferably 1:1 to 10:1 from the viewpoint of suppressing a decrease in signal intensity under humid conditions.

[0044] The organic functional groups in the sensor of this embodiment can be identified by subjecting the sensitive film on the sensor body to surface elemental analysis such as scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDX), X-ray photoelectron spectroscopy (XPS), or infrared attenuated total reflection spectroscopy (ATR).

[0045] In this embodiment, from the viewpoint of sensitivity and stability in a humid environment, the porosity as a volume fraction of the sensitive film is 10% or less. From the viewpoint of further improving sensitivity, it is more preferably 5% or more, and from the viewpoint of suppressing a decrease in sensitivity in a humid environment, it is even more preferably 3% or less. The porosity is determined, for example, by the ratio of the filler and RSiO 3 / 2 The porosity can be adjusted to fall within the above range by, for example, adjusting the ratio of the structure represented by the formula:

[0043] In addition, the porosity is not particularly limited, but is, for example, a value measured by the following method or a method that will be understood by those skilled in the art to be equivalent thereto.

[0046] After dicing to form a cross section, the sensitive film is fixed to the processing stage and processed using FIB milling, followed by cross-sectional SEM observation. The microstructured layer is then cut from the image obtained through cross-sectional SEM observation, and the voids present in the organic-inorganic hybrid are extracted. For extraction, the image can be binarized using image analysis software, taking advantage of the bright contrast around the voids due to the edge effect and the dark contrast of the voids themselves. Alternatively, binarization can be performed by coloring the microstructured layer white and the voids, substrate, and background black. Additionally, areas that cannot be fully captured by binarization can be manually identified and supplemented. The ratio of the area of ​​the voids in the extracted void image to the area of ​​the microstructured layer and the voids can be calculated as the void fraction in the microstructured layer. This procedure can be performed on several fields of view, and the average value obtained can be used to determine the void fraction.

[0047] The porosity of the sensitive film as a volume fraction is preferably 10% or less, which allows highly hydrophilic gases such as ethanol and aldehyde to be measured with high sensitivity without significant attenuation of the electric signal even under relatively high humidity conditions, and furthermore tends to allow continuous measurement without deterioration of the sensitive film even after reflow treatment or long-term use.

[0048] 1.1.2. Method for producing organic-inorganic hybrids The method for producing an organic-inorganic hybrid is not particularly limited, but it is mainly produced by the sol-gel method. Specifically, a hydrolyzable silane compound (including a silane coupling agent) is hydrolyzed and condensed under acidic or basic conditions in the presence of water to produce a condensate of the silane coupling agent, i.e., RSiO 3 / 2 An organic-inorganic hybrid containing a structure represented by the following formula can be obtained.

[0049] Among these, it is more preferable to carry out hydrolysis, condensation and surface modification of the silane coupling agent in the presence of a catalyst, from the viewpoint of being able to adjust the reaction rates of hydrolysis and condensation.

[0050] Examples of catalysts include acid catalysts and base catalysts. Acid catalysts are not particularly limited, but include inorganic acids and organic acids. Inorganic acids include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid, etc. Organic acids include, but are not limited to, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, citraconic acid, malic acid, glutaric acid, etc. Base catalysts include, for example, inorganic bases and organic bases. Examples of inorganic bases include, but are not limited to, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkali or alkaline earth metal carbonates such as lithium carbonate, potassium carbonate, and sodium carbonate; and metal bicarbonates such as potassium bicarbonate and sodium bicarbonate. Examples of organic bases include, but are not limited to, trialkylamines such as triethylamine and ethyldiisopropylamine; N,N-dialkylaniline derivatives having 1 to 4 carbon atoms such as N,N-dimethylaniline and N,N-diethylaniline; and pyridine derivatives that may have an alkyl substituent having 1 to 4 carbon atoms, such as pyridine and 2,6-lutidine. These catalysts can be used alone or in combination.

[0051] Furthermore, it is preferable to add a catalyst in an amount that brings the pH of the hydrolysis and condensation reaction system to a range of 0.01 to 6.0 or a range of 8 to 14 in terms of reaction efficiency, and it is more preferable to carry out the sol-gel reaction under basic conditions of pH 8 to 14 in order to further increase the efficiency.

[0052] The hydrolysis and condensation for producing an organic-inorganic hybrid can also be carried out in an organic solvent. Examples of organic solvents that can be used in the condensation reaction include alcohols, esters, ketones, ethers, aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, and amide compounds.

[0053] Examples of the alcohol include, but are not limited to, monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol; and monoethers of polyhydric alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether.

[0054] Examples of the esters include, but are not limited to, methyl acetate, ethyl acetate, butyl acetate, γ-butyrolactone, etc. Examples of the ketones include, but are not limited to, acetone, methyl ethyl ketone, methyl isoamyl ketone, etc.

[0055] In addition to the above-mentioned polyhydric alcohol monoethers, the ethers include, but are not limited to, polyhydric alcohol ethers in which all of the hydroxyl groups of polyhydric alcohols have been alkyl-etherified, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; tetrahydrofuran; 1,4-dioxane; and anisole.

[0056] Examples of the aliphatic hydrocarbon compound include, but are not limited to, hexane, heptane, octane, nonane, and decane.

[0057] Examples of the aromatic hydrocarbon compound include, but are not limited to, benzene, toluene, and xylene.

[0058] Examples of the amide compound include, but are not limited to, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0059] Among the above solvents, alcohols such as methanol, ethanol, isopropanol, and butanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; and amide compounds such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferred because they are easily miscible with water. These solvents may be used alone or in combination.

[0060] When a filler is blended into an organic-inorganic hybrid, the organic-inorganic hybrid may be produced in the presence of the filler, or the filler may be blended into the organic-inorganic hybrid. A condensate of a silane coupling agent may be dissolved in a commercially available dispersion filler, or the filler and silane coupling agent may be dispersed using a ball mill, jet mill, or the like, or an alkoxysilane and filler may be simultaneously condensed to produce a hybrid. However, a production method in which an alkoxysilane and a filler are simultaneously condensed is more preferred in terms of improving the solvent dispersibility of the filler and improving inkjet coating properties. When a colloidal filler is treated by a sol-gel method in the presence of a silane coupling agent, the condensate of the silane coupling agent is arranged so that it fills the gaps while modifying the surface of the filler, and the pore volume can be adjusted by adjusting the amount of alkoxysilane as desired. If hydroxyl groups are present on the filler surface, the surface hydroxyl groups and the hydroxyl groups generated by hydrolysis of the alkoxysilane interact and form ether bonds through a condensation reaction, thereby increasing the compatibility between the filler and the condensate and resulting in a more stable sensitive film.

[0061] The filler can also be surface-modified using an organic functional group, and the modification can be carried out by surface-modifying the filler in a state where it is dispersed in a dispersion medium. Specifically, for example, an organic-inorganic hybrid is produced by adding the above-mentioned silane coupling agent to a uniform dispersion of a metal oxide containing alcohol and water in the presence of a catalyst.

[0062] The organic-inorganic hybrid may be recovered by separating the precipitate or gel by centrifugation or filtration, or may be isolated by removing the volatile solvent using an evaporator or the like.

[0063] The introduction of organic functional groups into the organic-inorganic hybrid can be confirmed by ATR. Wavenumber: 1600-1800 cm -1The carbonyl group (C=O bond) can be identified based on the absorption peak in the region of

[0043] . The substituent having a C=O bond is not particularly limited, but examples thereof include a carbonyl group, an amide group, a urea group, a urethane group, an ester group, a carboxylic acid group, and an acid anhydride group.

[0064] Among these, amide groups, urea groups, and ester groups are preferred from the viewpoint of organic-inorganic hybrid synthesis, and amide groups are more preferred from the viewpoint of solubility in organic solvents and throughput. The reasons for this are thought to be, but are not limited to, as follows: The nitrogen-hydrogen atom bond (NH bond) of the amide group forms a hydrogen bond with molecules in the solvent that becomes the ink, thereby improving solubility.

[0065] Whether the carbonyl group is derived from a carbonyl group that forms an amide bond can be determined by the 3000-3400 cm -1 This can be determined by observing the stretching vibration of the N-H bond in the region of . Alternatively, it can be confirmed by using X-ray photoelectron spectroscopy such as XPS.

[0066] Wave number 1350~1450cm -1 Based on the absorption peak in the region, the bond between a silicon atom and a carbon atom (Si-C bond) can be identified.

[0067] This can also be confirmed by measuring thermal weight loss. In order to eliminate the influence of adsorbed water, the thermal weight loss rate of the organic component (the inorganic filler (i) and the organic functional group (ii) combined) from 150°C to 1000°C is preferably 3% to 75% from the viewpoint of sensitivity, more preferably 5% to 65% from the viewpoint of humidity resistance, and even more preferably 5% to 60% from the viewpoint of thermal stability. That is, the amount of organic functional groups in the organic-inorganic hybrid in this embodiment is not particularly limited, but is preferably 75% by weight or less, more preferably 65% ​​by weight or less, from the viewpoint of a balance between responsiveness to analytes and stability of the sensitive membrane.

[0068] Filler The sensitive film in this embodiment preferably further contains a filler. The use of a filler can improve the Young's modulus of the organic-inorganic hybrid and enhance sensitivity. The filler in this embodiment is not particularly limited and can be selected from various known fillers. Specific examples include, but are not limited to, one or more selected from the group consisting of polymer beads such as polystyrene, polymethyl methacrylate, and polyphenylene oxide, spherical particles such as acrylic latex, metal nitrides such as silicon nitride, metal oxides such as silica, zirconia, titania, zinc oxide, aluminum oxide, and tin oxide, composite metal compounds such as barium titanate, strontium titanate, and ITO, and inorganic metal fillers such as gold, silver, copper, palladium, platinum, iron, and aluminum.

[0069] In this embodiment, the filler is preferably an inorganic filler from the viewpoints of dispersibility and coatability. From the same viewpoints, in this embodiment, metal compounds such as silica, zirconia, titania, and alumina, and inorganic metal fillers such as gold, silver, copper, palladium, platinum, iron, and aluminum are preferred. Metal oxides such as silica and zirconia are more preferred because they are less affected by moisture in humid conditions, and silica is even more preferred from the viewpoint of economy. The inventors have found that, particularly when silica is used, the attenuation of response to common hydrophilic gases such as ethanol and acetaldehyde is significantly improved even in humid conditions. The reasons for this are thought to be as follows, but are not limited to the following. Specifically, the hydroxyl groups present in the silica skeleton and bonded to silicon atoms are relatively hydrophobic compared to the titania skeleton or hydroxyl groups bonded to titanium atoms in Patent Document 1, and therefore, hydrophobic interactions are thought to suppress adsorption inhibition due to moisture.

[0070] The shape of the filler is not particularly limited, but is preferably spherical, rod-like, plate-like, fibrous, or a combination of two or more of these, and more preferably spherical or chain-like. Note that the term "spherical" as used herein means a nearly spherical shape, including not only a perfect sphere but also a spheroid, an oval, etc.

[0071] The size of the spherical filler is not particularly limited, but from the viewpoint of maintaining the dispersibility of the ink, i.e., improving the coatability in inkjet printing, the average primary particle diameter is preferably 100 μm or less, from the viewpoint of improving sensitivity, more preferably 500 nm or less, and from the viewpoint of further reducing voids, even more preferably 200 nm or less. Here, the average primary particle diameter refers to the number average value. The average primary particle diameter is the number average value of 50 particles measured by the method using a scanning electron microscope described in the Examples section of this specification, or by a method that is understood by those skilled in the art to be equivalent thereto.

[0072] The chain-like filler preferably has a continuous chain-like structure, and preferred examples thereof include a structure in which spherical particles are continuously connected in a straight line, a structure in which they are connected in a branched manner, a structure in which they are connected in a bent manner, or a structure in which they are connected in a ring (also referred to as a "pearl necklace" structure), or a structure in which many thread-like structures are entangled and not observed as individual continuous spheres (also referred to as a "network" structure).

[0073] Fillers that form a continuous chain structure cannot be easily defined by the primary particle diameter assuming a spherical shape, but the chain width can be observed by observation with a transmission or scanning electron microscope. The chain width is 1 nm to 200 nm, preferably 1 nm to 100 nm from the viewpoint of increasing the surface area, and more preferably 1 nm to 85 nm from the viewpoint of gas responsiveness. The average primary particle diameter is the number average value of 50 particles measured by the method using a scanning electron microscope described in the Examples section of this specification, or a method that is understood by those skilled in the art to be equivalent thereto, and is defined as the chain width.

[0074] Such metal oxides as fillers can be produced by the sol-gel method using a metal oxide precursor having tetrafunctional hydrolyzable groups such as alkoxy and chloro, or commercially available products can also be used. Examples of metal oxide precursors having tetrafunctional hydrolyzable groups include tetraalkoxysilane, tetrachlorosilane, tetraalkoxytitanium, and tetraacetoxyzirconium. These tetrafunctional hydrolyzable metal inorganic oxides may be copolymerized with trifunctional hydrolyzable metal oxides, and the shape can be controlled by adjusting the concentration, temperature, pH, water content, etc. of the reaction system. For example, when a filler is produced by emulsion polymerization, RSiO may be present on the filler side. 3 / 2 It is conceivable that a structure represented by the following formula can be obtained, but a filler having such a structure in the sensitive film is treated as an organic-inorganic hybrid in this embodiment.

[0075] Commercially available fillers that can be used include the LEVASIL series (manufactured by H.C. Starck Co., Ltd.), the Quatron PL series (manufactured by Fuso Chemical Co., Ltd.), and the OSCAL series (manufactured by Catalysts and Chemicals Industries Co., Ltd.); powdery silica particles include, for example, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, and Aerosil OX50 (manufactured by Nippon Aerosil Co., Ltd.), Sildex H31, Sildex H32, Sildex H51, Sildex H52, Sildex H121, and Sildex H122 (manufactured by Asahi Glass Co., Ltd.), E220A and E220 (manufactured by Nippon Silica Industry Co., Ltd.), SYLYSIA 470 (manufactured by Fuji Silysia Chemical Industries Ltd.), SG Flake (manufactured by Nippon Sheet Glass Co., Ltd.), IPA-ST, IPA-ST-L, IPA-ST-ZL, ST-XS, ST-S, ST-30, ST-50T, ST-30L,ST-YL, ST-ZL,MP-1040, MP-2040,MP-4540M,ST-OXS, ST-OS, ST-O, ST-O-40, ST-OL, ST-OYL, ST-NXS, ST-NS, ST-N, ST-N-40,ST-CXS,ST-C, ST-CM, ST-AK, ST-AK-L, ST-AK-YL, OZ-S30K, SZ-S30K-AC, OZ-S30M, Cernax CX-S505M, IPA-ST-UP, MEK-ST-UP, ST-UP, ST-PS-S, ST-PS-M, ST-OUP, ST-PS-SO, ST-PS-MO, ST-AK-PS-S, etc. (manufactured by Nissan Chemical Co., Ltd.), SRD-K, SRD-M, SXR-CM, SZR-K, Examples of powder fillers include Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, and Aerosil OX50 (all manufactured by Nippon Aerosil Co., Ltd.), Sildex H31, Sildex H32, Sildex H51, Sildex H52, Sildex H121, and Sildex H122 (all manufactured by Asahi Glass Co., Ltd.), Sildex E220A and Sildex E220 (all manufactured by Nippon Silica Industry Co., Ltd.), SYLYSIA 470 (manufactured by Fuji Silysia Chemical Co., Ltd.), and SG Flake (manufactured by Nippon Sheet Glass Co., Ltd.).

[0076] 1.3.Other Ingredients The sensitive film in this embodiment may contain, in addition to the organic-inorganic hybrid, components such as, but not limited to, any particles, ionic compounds, resins, low-molecular-weight compounds, etc. The components are not particularly limited, but for example, they may be blended into a coating liquid and applied to the surface of the sensor body, thereby obtaining a sensor having a sensitive film containing the additives.

[0077] 2. Sensor manufacturing method The sensor of this embodiment can be manufactured by any method, including, but not limited to, various methods for forming a sensitive film on the sensor body. The sensitive film of this embodiment can be manufactured by, for example, dispersing an organic-inorganic hybrid in an organic solvent to prepare a coating liquid and then coating the sensor body with the coating liquid. An inkjet device can be suitably used to apply the coating liquid to the sensor chip. The inkjet device ejects droplets of the coating liquid (hereinafter also referred to as ink), which are applied to the sensor to form the sensitive film. An example of a sensitive film formed on a chip is shown in FIG. 1. The sensor 1 is configured to have a chip 3 corresponding to the sensor body and a sensitive film 2 formed on its surface. In the example shown in FIG. 1, such a configuration is provided in four locations.

[0078] The method for coating the organic-inorganic hybrid on the surface of the sensor body (e.g., the MSS sensor body) is not particularly limited, but examples thereof include coating methods using dip coating, spray coating, spin coating, inkjet spotting, casting, doctor blade, etc.

[0079] For coating on a 300 μmφ MSS membrane, the inkjet or microjet method is preferred, and from the viewpoint of productivity, the microjet method is more preferred.

[0080] The sensitive membrane can be produced, for example, by dispersing the organic-inorganic hybrid in an organic solvent and applying the resulting dispersion onto the MSS chip. The organic-inorganic hybrid is dispersed in the organic solvent at a concentration of 0.1 g / L to 50 g / L to form a coating solution. From the viewpoint of productivity, the concentration is preferably 0.5 to 50 g / L, and from the viewpoint of preventing nozzle clogging, a concentration of 0.5 to 15 g / L is more preferable.

[0081] The organic solvent for dispersing the organic-inorganic hybrid may be any solvent in which the organic-inorganic hybrid can be dispersed, and the boiling point is preferably 80°C to 250°C, more preferably 100°C to 250°C to prevent a decrease in productivity due to nozzle clogging, and more preferably 100°C to 200°C to shorten the drying time and increase productivity.

[0082] Examples of the organic solvent include, but are not limited to, alcohol solvents, ester solvents, ketone solvents, ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and amide solvents.

[0083] Examples of alcohol solvents include, but are not limited to, monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol; and monoethers of polyhydric alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether.

[0084] Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, and γ-butyrolactone.

[0085] Examples of the ketone solvent include, but are not limited to, acetone, methyl ethyl ketone, and methyl isoamyl ketone.

[0086] Examples of the ether solvent include, but are not limited to, polyhydric alcohol ethers in which all of the hydroxyl groups of polyhydric alcohols have been alkyl-etherified, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; tetrahydrofuran; 1,4-dioxane; anisole; and the like.

[0087] Examples of the aliphatic hydrocarbon solvent include, but are not limited to, hexane, heptane, octane, nonane, and decane.

[0088] Examples of aromatic hydrocarbon solvents include, but are not limited to, benzene, toluene, and xylene.

[0089] Examples of the amide solvent include, but are not limited to, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0090] These organic solvents may be used alone or in combination of two or more.

[0091] Among these organic solvents, N,N-dimethylformamide and propylene glycol monomethyl ether are preferred because of their excellent safety and solubility. In particular, when the organic-inorganic hybrid of this embodiment has an amide group in the organic functional group, it is preferable to use N,N-dimethylformamide as the organic solvent from the viewpoint of improving throughput. The reason for this is thought to be as follows, but is not limited to: It is thought that the nitrogen-hydrogen bond (NH bond) of the amide group of the organic-inorganic hybrid forms a hydrogen bond with molecules in the solvent that will become the ink, thereby improving solubility. [Example]

[0092] Hereinafter, the present embodiment will be specifically described with reference to examples and comparative examples, but the present embodiment is not limited to these.

[0093] The surface of the sensor body made of a piezoelectric element was coated with the sensitive film prepared in each example of this embodiment to prepare the above-mentioned surface stress type sensor, and various physical properties of the sensors of each example and comparative example were evaluated according to the following (1) to (3).

[0094] (1) Identification of organic functional groups in organic-inorganic hybrids and calculation of peak intensity ratios The organic functional groups in the organic-inorganic hybrid were identified by measuring the sensitive film on the sensor body using the ATR method under the following conditions. -1 Absorbance of the maximum absorption peak in the region of 1350-1450cm -1 The peak intensity ratio was calculated from the absorbance at the maximum of the absorption peak in the region (A / B).

[0095] (Measurement conditions) Equipment used: IRAffinity-1 (Shimadzu) Measurement method: ATR method (prism: ZnSe) Detector; DLATGS Aperture size: auto IR incident angle to ATR crystal: 30° Resolution; 4cm -1 Number of scans: 32

[0096] (2) Humidity resistance At 25°C, 250 ppm ethanol was used for 60 minutes, followed by a 60-minute nitrogen purge, which was repeated three times. The signal from the third measurement was used. The attenuation rate (%) was calculated as 100 x ("the intensity of the third signal measured under dry conditions" - "the intensity of the third signal measured under 50% RH") / ("the intensity of the third signal measured under dry conditions"). The attenuation rate was used to evaluate humidity resistance according to the following criteria. [Evaluation criteria] S: The attenuation rate is 20% or less. A: The attenuation rate is more than 20% and less than 40%. B: The attenuation rate is more than 40% and less than 60%. C: The attenuation rate is over 60%.

[0097] (3) Throughput The organic-inorganic hybrid was dispersed in an organic solvent and applied at an ink concentration of 15 mg / mL. The throughput was evaluated according to the following evaluation criteria. [Evaluation criteria] A: The coating was successful. B: The nozzle was clogged midway, causing splits and other issues. C: Precipitation of the sample occurred.

[0098] Example 1 A 2000 mL separable flask was charged with 288 g of water, 32 g of 28% aqueous ammonia, and 188 g of 2-propanol. A solution of 43.4 g of phenyltrimethoxysilane and 46.6 g of 4-(trimethoxysilyl)benzeneamine in 340 g of 2-propanol was added and reacted at 80 °C for 3 hours. After cooling, the reaction mixture was filtered and isolated. After thoroughly washing the sample with ethanol and drying under vacuum at 80 °C, 5 g of the precipitate was dissolved in 500 mL of N,N-dimethylacetamide in a 2000 mL separable flask, and 1.5 g of triethylamine was added. Then, 4.1 g of o-toluoyl chloride was added at 0 °C and reacted at room temperature for 30 minutes. After cooling to 0 °C, the reaction mixture was quenched by adding saturated aqueous sodium bicarbonate. The mixture was extracted three times with ethyl acetate, washed with saturated brine, dehydrated over anhydrous magnesium sulfate, and concentrated under reduced pressure using an evaporator. 10 mL of ethyl acetate was added to the solution, and the resulting solution was dropped into a stirring hexane / ethyl acetate (10:1) solution. The precipitated solid was isolated by filtration. The sample was thoroughly washed and dried under vacuum at 80 °C, then dissolved in DMF to a concentration of 15 g / mL. A 2-propanol dispersion of silica microparticles (IPA-ST-ZL, a Nissan Chemical product) was adjusted to 15 mg / mL in DMF, and the above solution was mixed in a 6:4 ratio to obtain a coating solution. Thirteen drops of the coating solution (300 pL per drop) were applied to the surface of an MSS placed on a hot plate at 40 °C using an inkjet device, yielding a surface stress sensor with a sensitive film. The sensor's appearance is shown in Figure 1.

[0099] The organic functional group species were identified and the peak intensity ratio was calculated as described in (1) above. The results are shown in Figure 2 and Table 1. Figure 3 shows the results of examining the effect of humidity resistance based on the method described in (2) above. At 0% humidity (dry conditions), the maximum amplitude was 4.52 mV, and at 50% humidity, the maximum amplitude was 2.86 mV. The effect of humidity resistance calculated using the method described above was 37%. Furthermore, the throughput was evaluated using the method (3) above. Since the ink could be dissolved to a concentration of 15 mg / ml and could be applied, it was rated A. The following examples and comparative examples were also evaluated in the same manner as described above.

[0100] <Example 2> A 2000 mL separable flask was charged with 288 g of water, 32 g of 28% aqueous ammonia, and 340 g of 2-propanol. A solution of 71.5 g of phenyltrimethoxysilane and 21.6 g of 3-aminopropyltrimethoxysilane in 207 g of 2-propanol was added and reacted at 80 °C for 3 hours. After cooling, the precipitate was isolated by filtration. After thoroughly washing the sample with ethanol and drying under vacuum at 80 °C, 5 g of the precipitate was dissolved in 500 mL of N,N-dimethylacetamide in a 2000 mL separable flask, and 1.5 g of triethylamine was added. Then, 1.5 g of p-toluoyl chloride was added at 0 °C and reacted at room temperature for 30 minutes. After the reaction, the reaction mixture was cooled to 0 °C and saturated aqueous sodium bicarbonate was added to terminate the reaction. The mixture was extracted three times with ethyl acetate, washed with brine, dehydrated over anhydrous magnesium sulfate, and concentrated under reduced pressure using an evaporator. 10 mL of ethyl acetate was added thereto and the resulting solution was added dropwise to the stirred hexane solution, and the precipitated solid was isolated by filtration.

[0101] Example 3 The procedure of Example 2 was repeated except that 1.5 g of p-toluoyl chloride was changed to 2.4 g of 2,4,6-trichlorobenzoyl chloride.

[0102] Example 4 The procedure of Example 2 was repeated except that 1.5 g of p-toluoyl chloride was added dropwise to 0.8 g of acetyl chloride in a hexane / ethyl acetate=10 / 1 solution instead of in a hexane solution.

[0103] <Example 5> The procedure of Example 2 was repeated except that 1.5 g of p-toluoyl chloride was added dropwise to 1.1 g of methoxyacetyl chloride in a hexane / ethyl acetate=10 / 1 solution instead of in a hexane solution.

[0104] Example 6 The procedure of Example 2 was repeated except that 1.5 g of p-toluoyl chloride was added dropwise to 2.3 g of pentafluorobenzoyl chloride in a hexane solution, instead of a hexane / ethyl acetate=10 / 1 solution.

[0105] Example 7 The procedure of Example 2 was repeated except that 1.5 g of p-toluoyl chloride was changed to 2.1 g of 2,3,4,5-tetrafluorobenzoyl chloride.

[0106] Example 8 The procedure of Example 1 was repeated except that 4.1 g of o-toluoyl chloride was added dropwise to a hexane solution instead of a 10 / 1 hexane / ethyl acetate solution containing 3.1 g of 3,4-difluorobenzoyl chloride.

[0107] Example 9 The procedure of Example 1 was repeated except that 4.1 g of o-toluoyl chloride was changed to 4.1 g of pentafluorobenzoyl chloride.

[0108] Example 10 The procedure of Example 1 was repeated except that 4.1 g of o-toluoyl chloride was added dropwise to 3.9 g of 4-phenylbenzoyl chloride in a hexane / ethyl acetate=1 / 1 solution instead of a 10 / 1 solution of hexane / ethyl acetate.

[0109] Example 11 The procedure of Example 1 was repeated except that 4.1 g of o-toluoyl chloride was added dropwise to 2.6 g of 2-thenoyl chloride in a hexane / ethyl acetate=1 / 1 solution instead of a 10 / 1 solution of hexane / ethyl acetate.

[0110] Example 12 The procedure of Example 1 was repeated except that 4.1 g of o-toluoyl chloride was added dropwise to a hexane solution containing 1.3 g of heptafluorobutyryl chloride instead of a hexane / ethyl acetate=10 / 1 solution.

[0111] Example 13 The procedure of Example 1 was repeated except that 4.1 g of o-toluoyl chloride was changed to 3.7 g of 4-(trifluoromethyl)benzoyl chloride.

[0112] Example 14 The procedure of Example 1 was repeated except that 4.1 g of o-toluoyl chloride was changed to 1.9 g of methoxyacetyl chloride.

[0113] Example 15 The procedure of Example 1 was repeated except that 4.1 g of o-toluoyl chloride was added dropwise to 2.3 g of 2-furoyl chloride in a hexane / ethyl acetate=1 / 1 solution instead of a 10 / 1 solution of hexane / ethyl acetate.

[0114] Example 16 The procedure of Example 1 was repeated except that 4.1 g of o-toluoyl chloride was added dropwise to 2.5 g of benzoyl chloride in a hexane / ethanol=7 / 3 solution instead of a hexane / ethyl acetate=10 / 1 solution.

[0115] Example 17 The procedure of Example 1 was repeated except that 4.1 g of o-toluoyl chloride was added dropwise to 4.4 g of 2,4,6-trichlorobenzoyl chloride in a hexane / ethyl acetate=1 / 1 solution instead of a 10 / 1 solution of hexane / ethyl acetate.

[0116] Example 18 The procedure of Example 1 was repeated except that 4.1 g of o-toluoyl chloride was added dropwise to 3.6 g of acetyl chloride in a hexane / ethyl acetate=1 / 1 solution instead of a hexane / ethyl acetate=10 / 1 solution.

[0117] Example 19 The procedure of Example 1 was repeated except that 4.1 g of o-toluoyl chloride was replaced with 3.8 g of 2,3,4,5-tetrafluorobenzoyl chloride.

[0118] Example 20 The procedure of Example 2 was repeated except that 1.5 g of p-toluoyl chloride was added dropwise to 1.4 g of benzoyl chloride in a hexane / ethyl acetate=10 / 1 solution instead of in a hexane solution.

[0119] <Example 21> The procedure of Example 1 was repeated except that 4.1 g of o-toluoyl chloride was changed to 3.1 g of 3,4-difluorobenzoyl chloride.

[0120] <Example 22> A 2000 mL separable flask was charged with 250 g of water, 17.2 g of 28% aqueous ammonia, and 110 g of 2-propanol, and a solution of 50 g of 4-(trimethoxysilyl)benzeneamine in 230 g of 2-propanol was reacted at 80 °C for 3 hours. After cooling, the precipitate was isolated by filtration. After thoroughly washing the sample with ethanol and drying under vacuum at 80 °C, 5 g of the precipitate was dissolved in 500 mL of N,N-dimethylacetamide in a 2000 mL separable flask, and 1.5 g of triethylamine was added. Then, 2.1 g of benzoyl chloride was added at 0 °C and the reaction was continued at room temperature for 30 minutes. After the reaction, the reaction mixture was cooled to 0 °C and saturated aqueous sodium bicarbonate was added to terminate the reaction. The mixture was extracted three times with ethyl acetate, washed with brine, dehydrated over anhydrous magnesium sulfate, and concentrated under reduced pressure using an evaporator. 10 mL of ethyl acetate was added thereto and the resulting solution was added dropwise to a stirred hexane / ethyl acetate=10 / 1 solution, and the precipitated solid was isolated by filtration.

[0121] Example 23 The procedure of Example 22 was repeated except that 2.6 g of o-toluoyl chloride was changed to 2.6 g of o-toluoyl chloride.

[0122] Example 24 The procedure of Example 2 was repeated except that 1.5 g of p-toluoyl chloride was added dropwise to 2.3 g of diphenylcarbamoyl chloride in a hexane solution, instead of in a hexane / ethyl acetate=10 / 1 solution.

[0123] Example 25 The procedure of Example 1 was repeated except that 4.1 g of o-toluoyl chloride was added dropwise to 4.1 g of diphenylcarbamoyl chloride in a hexane / ethyl acetate=1 / 1 solution instead of a hexane / ethyl acetate=10 / 1 solution.

[0124] Example 26 A solution of 4.8 g of ethyl 4-(triethoxysilyl)benzoate in 14.1 g of 2-propanol was added to 9.4 g of water, 1.0 g of 28% aqueous ammonia, and 14.9 g of 2-propanol in a 500 mL separable flask, and the mixture was allowed to react at 80°C for 3 hours. After air-cooling the reaction solution, the precipitate was isolated by filtration. The sample was thoroughly washed and dried under vacuum at 80°C, and then dissolved in DMF to a concentration of 15 g / mL. The subsequent procedures were carried out in accordance with Example 1.

[0125] <Comparative Example 1> Polystyrene (Aldrich, weight-average molecular weight 35,000) was dissolved in DMF to a concentration of 10 g / mL. A 2-propanol dispersion of IPA-ST-ZL (a Nissan Chemical product) was adjusted to 10 mg / mL in DMF, and the above solution was mixed in a 6:4 ratio to obtain a coating solution. Twenty drops of the coating solution, each 300 pL, were applied to the surface of an MSS placed on a hot plate at 40°C using an inkjet device, yielding a surface stress sensor with a sensitive film. As in Example 1, the response signal to 100 ppm of ethanol at 0% and 30% humidity was confirmed, and the results are shown in Figure 4. Throughput was evaluated. When the ink concentration was 15 mg / mL, sample precipitation occurred, so it was rated C.

[0126] <Comparative Example 2> Silica-titania particles (granular) were synthesized according to the method described in WO2016 / 121155. They were synthesized by co-hydrolysis and condensation polymerization of aminopropyltrimethoxysilane and titanium tetraisopropoxide (TTIP) in an aqueous solution of ammonia-based isopropanol (IPA) containing octadecylamine (ODA). The synthesis reaction was carried out using a Teflon microreactor with a Y-shaped microchannel. Four precursor solutions were prepared: Solution 1: aminopropyltrimethoxysilane / IPA, Solution 2: HO / IPA / ammonia, Solution 3: TTIP / IPA, and Solution 4: HO / IPA. Solutions 1 through 4 were prepared with the same volume. The precursor solutions were simultaneously delivered at a constant rate using a syringe pump. Solutions 1 and 2, and Solutions 3 and 4 were mixed in parallel microreactors, respectively, and the solutions discharged from both reactors were further mixed in another microreactor to form a single reaction solution. The reaction solution was poured into a separately prepared precursor solution 5: ODA / HO / IPA, and stirred at a constant speed until the end of the pouring. After that, it was left to stand at room temperature to obtain a nanoparticle (NH-STNP) dispersion. 3 / 2 The structure represented by the formula was confirmed, and this was treated as an organic-inorganic hybrid. After air-cooling the reaction solution, the precipitate was isolated by centrifuging at 6000 rpm for 10 minutes. The precipitate was then dissolved in DMAc and reacted with benzoyl chloride in the presence of triethylamine to modify the amino groups to amides. This was then dissolved in N,N-dimethylformamide to a concentration of 1 g / mL to obtain a coating solution. 300 droplets of the coating solution, each 300 pL, were applied to the surface of an MSS placed on a hot plate at 80 °C using a microjet to obtain a surface stress sensor with a sensitive film. Throughput was evaluated. At an ink concentration of 15 mg / mL, sample precipitation occurred, so the result was designated C.

[0127] <Comparative Example 3> A solution of 54.2 g of phenyltrimethoxysilane in 120 g of 2-propanol was added to 180 g of water, 20 g of 28% ammonia water, and 215 g of 2-propanol in a 2000 mL separable flask and reacted at 80 °C for 3 hours. After cooling the reaction mixture, the precipitate was isolated by filtration. The sample was thoroughly washed with ethanol, dried under vacuum at 80 °C, and then dissolved in DMF to a concentration of 10 g / mL. A 2-propanol dispersion of IPA-ST-ZL (a Nissan Chemical product) adjusted to 10 mg / mL in DMF was mixed with the above solution in a 6:4 ratio to obtain a coating solution. Twenty droplets of the coating solution, each 300 pL, were applied to the surface of an MSS placed on a hot plate at 40 °C using an inkjet device to obtain a surface stress sensor with a sensitive film. Throughput was evaluated. At an ink concentration of 15 mg / mL, nozzle clogging and splitting occurred, resulting in a grade of B. Its appearance is shown in Figure 1.

[0128] The results of the above measurements (1) to (3) performed on each of the above examples and comparative examples are shown in Table 1 below.

[0129] [Table 1] [Industrial Applicability]

[0130] The sensor of the present invention can be used as an olfactory sensor for breath testing and odor management in hotels, automobiles, factories, and the like.

Claims

1. A sensor having a sensitive membrane, The sensitive film has a wavelength of 1600 to 1800 cm in infrared total reflection absorption measurement. -1 and 1350-1450 cm -1 has an absorption peak in the region the absorption peak in the region of 1350 to 1450 cm −1 includes an absorption peak derived from an interatomic bond between a silicon atom and an aromatic carbon atom; the absorption peak in the region of 1600 to 1800 cm −1 includes an absorption peak derived from a carbonyl group; The above 1350 to 1450 cm -1 The absorption peak maximum (B) in the region of 1600 to 1800 cm -1 The peak intensity ratio (A / B) of the absorption peak maximum (A) in the region of sensor.

2. The above 1600 to 1800 cm -1 The absorption peak in the region of includes the absorption peak of a carbonyl group forming an amide bond. The sensor of claim 1 .

3. The sensitive film has the formula RSiO 3 / 2 (wherein R represents an organic functional group), The sensor according to claim 1 or 2.

4. the organic functional group contains at least one amide bond; The sensor of claim 3.

5. The organic functional group contains at least one type of aromatic ring.

5. The sensor according to claim 3 or 4.

6. It is a surface stress sensor. A sensor according to any one of claims 1 to 5.

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