Composition for sensitive film, sensitive film, odor detection element, and odor sensor

Abstract

To provide a composition for a sensitive film that enables acquisition of a sensitive film capable of detecting a wide variety of odor components.SOLUTION: The present invention relates to a composition for a sensitive film that is usable for a sensitive film of an odor detection element, the composition comprising a cyclic olefin resin (A), the cyclic olefin resin (A) comprising a structural unit represented by formula (1) and a structural unit represented by formula (2). (In the formula, R11 represents a group containing a hydroxyl group, and R21 represents any one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and a group in which one or more hydrogen atoms of an alkyl group having 1 to 10 carbon atoms are substituted with fluorine atoms).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a composition for a sensitive film, a sensitive film, an odor detecting element, and an odor sensor. [Background technology]

[0002] The odor detection element includes a sensitive film for adsorbing odorous substances. As a technology relating to the sensitive film of an odor detection element, for example, the technology described in Patent Document 1 can be mentioned.

[0003] Patent document 1 describes a gas detection device consisting of a sensitive film and a transducer, characterized in that the organic polymer film used as the sensitive film is primarily composed of a copolymer made of two or more different monomers. Patent Document 1 describes that a sensitive membrane with high sensitivity and fast response speed is provided for a gas detection device that detects gas by utilizing the phenomenon of gas molecule adsorption onto the sensitive membrane. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-013055 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a composition for a sensitive film that can obtain a sensitive film capable of detecting a wide variety of odor components. [Means for solving the problem]

[0006] According to the present invention, there are provided a composition for a sensitive film, a sensitive film, an odor detecting element, and an odor sensor, as shown below.

[0007] [1] A composition for a sensitive film that can be used for a sensitive film of an odor detection element, Contains a cyclic olefin resin (A), The cyclic olefin resin (A) comprises a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2): [ka] (In the formula (1), R 11 indicates a group containing a hydroxy group) [ka] (In the formula (2), R 21 represents any one selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and groups in which one or more hydrogen atoms of an alkyl group having 1 to 10 carbon atoms have been substituted with a fluorine atom) [2] The composition for sensitive films according to [1], wherein the content of the structural unit represented by the formula (1) in the cyclic olefin resin (A) is 10 mol % or more and 90 mol % or less, when the total of all structural units in the cyclic olefin resin (A) is 100 mol %. [3] The composition for sensitive films according to [1] or [2], wherein the content of the structural unit represented by the formula (2) in the cyclic olefin resin (A) is 10 mol % or more and 90 mol % or less, when the total of all structural units in the cyclic olefin resin (A) is 100 mol %. [4] The composition for sensitive film according to any one of [1] to [3] above, wherein the structural unit represented by formula (1) above includes a structural unit represented by the following formula (1-a): [ka] [5] In the formula (2), R 21 is any one selected from the group consisting of a butyl group and a group in which all of the hydrogen atoms of the butyl group have been substituted with fluorine atoms. [6] The composition for sensitive films according to any one of [1] to [5], wherein the content of the cyclic olefin resin (A) in the composition for sensitive films is 50% by mass or more when the total amount of non-volatile components in the composition for sensitive films is 100% by mass. [7] The composition for sensitive film according to any one of [1] to [6] above, wherein the cyclic olefin resin (A) has a weight average molecular weight (Mw) of 5,000 or more and 1,000,000 or less. [8] The composition for a sensitive film according to any one of [1] to [7] above, wherein the composition for a sensitive film has a 5% mass loss temperature of 280° C. or higher. [9] A sensitive film of an odor detection element, comprising the composition for a sensitive film according to any one of [1] to [8] above.

[10] The sensitive film according to [9] above, having a thickness of 10 nm or more and 1000 nm or less.

[11] An odor detection element comprising the sensitive film according to [9] or

[10] above.

[12] Equipped with two or more odor detection elements, The odor detection element includes a first odor detection element and a second odor detection element, the second odor detection element is capable of detecting a different type of gas from that detected by the first odor detection element; An odor sensor, wherein at least one selected from the group consisting of the first odor detection element and the second odor detection element is the odor detection element described in

[11] above. [Effects of the Invention]

[0008] According to the present invention, a composition for a sensitive film can be provided that can obtain a sensitive film that can detect a wide variety of odor components. [Brief explanation of the drawings]

[0009] [Figure 1]1 is a cross-sectional view schematically showing an example of the structure of an odor detection element of the present embodiment. [Figure 2] FIG. 2 is a diagram for explaining a gas detection test method in an example. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the drawings are simplified and do not correspond to actual dimensional proportions. Numerical ranges "A to B" represent A or more and B or less unless otherwise specified.

[0011] The main components of odors are broadly classified into nine components. If a sensitive membrane can detect a wide variety of odor components out of these nine, it is thought that an odor sensor that can be applied to a wider range of odors can be provided.

[0012] The present invention provides a composition for a sensitive film that can obtain a sensitive film capable of detecting a wide variety of odor components.

[0013] [Sensor-sensitive film composition] The composition for a sensitive film of this embodiment is a composition for a sensitive film that can be used in a sensitive film of an odor detection element, and contains a cyclic olefin resin (A), and the cyclic olefin resin (A) contains a structural unit represented by formula (1) and a structural unit represented by formula (2).

[0014] Furthermore, the sensitive film may adsorb moisture, gas components, etc. in the atmosphere, which may cause the detection sensitivity to decrease from the initial value. One method for preventing this decrease in detection sensitivity is to remove the components adsorbed on the sensitive film by heating. In this method for removing the components adsorbed on the sensitive film by heating, depending on the type of adsorbed component, it is necessary to heat the sensitive film at a high temperature. Therefore, there is a demand for improved heat resistance of the sensitive film.

[0015] From the viewpoint of further improving the heat resistance of the composition for sensitive films of this embodiment, the 5% mass loss temperature of the composition for sensitive films is preferably 280°C or higher, more preferably 290°C or higher, even more preferably 300°C or higher, more preferably 310°C or higher, even more preferably 320°C or higher, and even more preferably 330°C or higher, and the upper limit is not particularly limited, but may be, for example, 400°C or lower, 390°C or lower, or 370°C or lower. Here, the 5% mass loss temperature of the composition for a sensitive film means a value calculated by TG-DTA measurement. More specifically, the 5% mass loss temperature of the composition for a sensitive film means the temperature at which the mass decreases by 5% based on the mass at the start of thermogravimetry. Here, the conditions for thermogravimetry are: measurement atmosphere: air, temperature range: 40°C or higher, and heating rate: 5°C / min (temperature range of 40°C to 120°C), 10°C / min (temperature range of 120°C or higher).

[0016] The shape of the composition for sensitive film of this embodiment is not particularly limited, and examples thereof include membrane, varnish, sheet, and film.

[0017] Each of the components of the sensitive film composition of this embodiment will be specifically described below.

[0018] <Cyclic olefin resin (A)> The composition for sensitive film of this embodiment contains a cyclic olefin resin (A), and the cyclic olefin resin (A) contains a structural unit represented by formula (1) and a structural unit represented by formula (2).

[0019] The cyclic olefin resin (A) contains a structural unit represented by formula (1).

[0020] [ka]

[0021] In formula (1), R 11 represents a group containing a hydroxy group. The group containing a hydroxy group preferably contains a fluorine atom. The group containing a hydroxy group may have, for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 5 carbon atoms.

[0022] Here, the group containing a hydroxy group is a concept that also includes the hydroxy group itself.

[0023] The structural unit represented by formula (1) preferably includes a structural unit represented by formula (1-a).

[0024] [ka]

[0025] The content of the structural unit represented by formula (1) in the cyclic olefin resin (A) is preferably 10 mol % or more and 90 mol % or less, more preferably 15 mol % or more and 85 mol % or less, and even more preferably 20 mol % or more and 80 mol % or less, when the total of all structural units in the cyclic olefin resin (A) is 100 mol %.

[0026] The cyclic olefin resin (A) contains a structural unit represented by formula (2).

[0027] [ka]

[0028] In formula (2), R 21 represents any one selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and groups in which one or more hydrogen atoms of an alkyl group having 1 to 10 carbon atoms have been substituted with a fluorine atom.

[0029] In formula (2), R 21 In the formula, the alkyl group having 1 to 10 carbon atoms preferably has 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 3 to 5 carbon atoms.

[0030] In formula (2), R 21 In the formula, the group in which one or more hydrogen atoms of an alkyl group having 1 to 10 carbon atoms have been substituted with a fluorine atom preferably has 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 3 to 5 carbon atoms. In formula (2), R 21 In the formula, the group in which one or more hydrogen atoms of an alkyl group having 1 to 10 carbon atoms are substituted with fluorine atoms is preferably a group in which all hydrogen atoms of an alkyl group having 1 to 10 carbon atoms are substituted with fluorine atoms, more preferably a group in which all hydrogen atoms of an alkyl group having 2 to 6 carbon atoms are substituted with fluorine atoms, and even more preferably a group in which all hydrogen atoms of an alkyl group having 3 to 5 carbon atoms are substituted with fluorine atoms.

[0031] In formula (2), R 21 is preferably any one selected from the group consisting of a butyl group and a group in which one or more hydrogen atoms of a butyl group have been substituted with fluorine atoms, and more preferably any one selected from the group consisting of a butyl group and a group in which all of the hydrogen atoms of a butyl group have been substituted with fluorine atoms.

[0032] The content of the structural unit represented by formula (2) in the cyclic olefin resin (A) is preferably 10 mol % or more and 90 mol % or less, more preferably 15 mol % or more and 85 mol % or less, and even more preferably 20 mol % or more and 80 mol % or less, when the total of all structural units in the cyclic olefin resin (A) is 100 mol %.

[0033] The weight average molecular weight (Mw) of the cyclic olefin resin (A) is preferably 5,000 or more and 1,000,000 or less, more preferably 10,000 or more and 750,000 or less, even more preferably 30,000 or more and 600,000 or less, and still more preferably 50,000 or more and 500,000 or less. The weight average molecular weight (Mw) of the cyclic olefin resin can be determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0034] From the viewpoint of further improving the heat resistance of the composition for sensitive films, the 5% mass loss temperature of the cyclic olefin resin (A) is preferably 280°C or higher, more preferably 290°C or higher, even more preferably 300°C or higher, more preferably 310°C or higher, even more preferably 320°C or higher, and even more preferably 330°C or higher.The upper limit is not particularly limited, but may be, for example, 400°C or lower, 390°C or lower, or 370°C or lower. Here, the 5% mass loss temperature of the cyclic olefin resin means a value measured by a value calculated by TG-DTA measurement. More specifically, the 5% mass loss temperature of the cyclic olefin resin means a temperature at which the mass decreases by 5% based on the mass at the start of thermogravimetry. Here, the conditions for thermogravimetry are: measurement atmosphere: air, temperature range: 40°C or higher, and heating rate: 5°C / min (temperature range of 40°C to 120°C), 10°C / min (temperature range of 120°C or higher).

[0035] The content of cyclic olefin resin (A) in the composition for sensitive films of this embodiment is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 97% by mass or more, and is, for example, 100% by mass or less, when the total non-volatile components in the composition for sensitive films is 100% by mass.

[0036] The content of cyclic olefin resin (A) in the composition for sensitive films of this embodiment is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 97% by mass or more, and is, for example, 100% by mass or less, when the total of all components in the composition for sensitive films is 100% by mass.

[0037] The cyclic olefin resin (A) can be produced, for example, by a known method, more specifically, by polymerizing monomers capable of forming each structural unit by any method. Examples of monomers capable of forming the structural unit represented by formula (1) include 3-(bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)propan-2-ol. Examples of monomers capable of forming the structural unit represented by formula (2) include 5-butylbicyclo[2.2.1]hept-2-ene and 5-nonafluorobutyl-2-norbornene.

[0038] The cyclic olefin resin (A) may be a single cyclic olefin resin, or may contain two or more cyclic olefin resins.

[0039] <Other ingredients> The composition for sensitive film of the present embodiment may contain other components in addition to the cyclic olefin resin (A) as appropriate. Examples of other components include organic solvents, antioxidants, surfactants, leveling agents, storage stabilizers, etc. The content of other components is an appropriate amount.

[0040] The composition for sensitive film of this embodiment can be obtained, for example, by mixing the components.

[0041] [Sensitive membrane] The sensitive film of this embodiment is a sensitive film of an odor detection element, and contains the sensitive film composition of this embodiment.

[0042] The thickness of the sensitive film of this embodiment is preferably 10 nm or more and 1000 nm or less, more preferably 100 nm or more and 800 nm or less, and even more preferably 300 nm or more and 500 nm or less.

[0043] [Odor detection element] The odor detection element of this embodiment includes the sensitive film of this embodiment. FIG. 1 is a cross-sectional view showing a schematic example of the structure of the odor detection element of this embodiment. In FIG. 1, the odor detection element 100 includes a sensitive film 10 on a piezoelectric vibrator 50 , and the piezoelectric vibrator 50 includes a piezoelectric layer 20 and an electrode 30 .

[0044] The piezoelectric vibrator 50 is, for example, any one selected from the group consisting of a QCM (Quartz Crystal Microbalance) element, an FBAR (Film Bulk Acoustic Resonator) element, and a SAW (Surface Acoustic Wave) element.

[0045] When the piezoelectric vibrator 50 is a QCM element, the piezoelectric layer 20 is made of quartz crystal.

[0046] When the piezoelectric vibrator 50 is an FBAR element, the piezoelectric vibrator 50 is bonded to a substrate (not shown) made of Si or the like, and the piezoelectric layer 20 is a thin film made of aluminum nitride (AlN), zinc oxide (ZnO) or the like.

[0047] When the piezoelectric vibrator 50 is a SAW element, the electrode 30 is an IDT (Inter-Digital Transducer: comb-shaped electrode), and the piezoelectric layer 20 is made of LiTaO3, LiNbO3, or the like.

[0048] The method for manufacturing the odor detection element 100 is not particularly limited, but an example is a method in which a solution containing the sensitive film composition of this embodiment is applied to one surface of the piezoelectric vibrator 50 and dried to form the sensitive film 10. The application method is not particularly limited, and examples include application using a spray device, application using a roll coater, application using a bar coater, spin coating, letterpress printing, intaglio printing, etc., and among these, application using a spray device is preferred from the viewpoint of preventing application to areas other than the intended location and damage to the piezoelectric vibrator 50.

[0049] [Odor sensor] The odor sensor of this embodiment includes two or more odor detection elements, at least one of which is the odor detection element of this embodiment.

[0050] The odor sensor of this embodiment preferably comprises two or more odor detection elements, the odor detection elements comprising a first odor detection element and a second odor detection element, the second odor detection element being capable of detecting a different type of gas than the first odor detection element, and at least one selected from the group consisting of the first odor detection element and the second odor detection element being the odor detection element of this embodiment. That is, the odor sensor of this embodiment preferably includes a plurality of odor detection elements with different gas selectivities. In the odor sensor of this embodiment, more preferably, both the first odor detection element and the second odor detection element are the odor detection elements of this embodiment.

[0051] The odor sensor of this embodiment may have two or more odor detection elements whose sensitive membranes are made of the same type of material, or may have two or more odor detection elements whose sensitive membranes are made of different types of material; however, from the perspective of detecting a larger number of odors, it preferably has two or more odor detection elements whose sensitive membranes are made of different types of material.

[0052] The odor sensor of this embodiment may include, for example, a sensor substrate, a semiconductor integrated circuit, a temperature and humidity sensor, and the like, as appropriate.

[0053] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted. Furthermore, the present invention is not limited to the above-described embodiment, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention. [Example]

[0054] The present embodiment will be described in detail below based on examples and comparative examples, but the present embodiment is not limited to the descriptions of these examples.

[0055] [Example 1] A monomer solution containing 5-butylbicyclo[2.2.1]hept-2-ene (BuNB, 16.9 g, 112.5 mmol), 3-(bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)propan-2-ol (HFANB, 10.3 g, 37.5 mmol), and 40.2 g of butyl acetate was weighed into a suitable reaction vessel, stirred, dissolved, and then dissolved in nitrogen by bubbling. The internal temperature was then raised to and maintained at 90°C. In a separate vessel, a catalyst solution was prepared by weighing [Pd(OAc)(MeCN)(P(i-Pr)3)2]FABA (Pd-1206, 0.0052 g, 0.004 mmol), N-dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA, 0.0086 g, 0.011 mmol), and 3.3 g of butyl acetate. After stirring and dissolving, the dissolved oxygen was removed by nitrogen bubbling. The catalyst solution was added to the monomer solution and reacted at 90 °C for 2 hours. The reaction mixture was then quenched by adding triethylsilane (0.1358 g). The mixture was cooled to room temperature and diluted with 300 g of toluene. The diluted solution was poured into a large amount of methanol to precipitate the polymer. The polymer was then filtered, washed with methanol, and vacuum-dried at 100 °C for 16 hours. The polymer yield was 17.7 g, a 65% yield. The polymer had a weight average molecular weight Mw of 430,000 and a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 13.6. The resulting polymer was designated as the cyclic olefin resin of Example 1.

[0056] [Example 2] A polymer was synthesized in the same manner as in Example 1, except that the monomer solution consisted of BuNB (22.5 g, 150 mmol), HFANB (41.1 g, 150 mmol), and 80.2 g of butyl acetate, the catalyst solution consisted of Pd-1206 (0.0362 g, 0.030 mmol), DANFABA (0.0600 g, 0.075 mmol), and 7.6 g of butyl acetate, and 0.318 g of triethylsilane was added at the end of the reaction. The polymer yield was 31.0 g, a 49% yield. The polymer had a weight-average molecular weight (Mw) of 350,000 and a polydispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of 3.02. The resulting polymer was designated the cyclic olefin resin of Example 2.

[0057] [Example 3] A polymer was synthesized in the same manner as in Example 1, except that the monomer solution consisted of BuNB (5.6 g, 37.5 mmol), HFANB (30.8 g, 112.5 mmol), and 40.2 g of butyl acetate, the catalyst solution consisted of Pd-1206 (0.0241 g, 0.020 mmol), DANFABA (0.0401 g, 0.050 mmol), and 4.4 g of butyl acetate, and 0.1823 g of triethylsilane was added at the end of the reaction. The polymer yield was 5.6 g, a 15% yield. The polymer had a weight-average molecular weight (Mw) of 190,000 and a polydispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of 3.00. The resulting polymer was designated the cyclic olefin resin of Example 3.

[0058] [Example 4] A polymer was synthesized in the same manner as in Example 1, except that the monomer solution consisted of 5-nonafluorobutyl-2-norbornene (CFNB, 25.5 g, 75 mmol), HFANB (20.6 g, 150 mmol), and 25.1 g of butyl acetate, and the catalyst solution consisted of Pd-1206 (0.0362 g, 0.030 mmol), DANFABA (0.0601 g, 0.075 mmol), and 5.5 g of butyl acetate. The reaction temperature was 100 °C, and the reaction time was 22 hours. At the end of the reaction, 0.2303 g of triethylsilane was added to quench the reaction, and heptane was used instead of methanol for polymer reprecipitation. The polymer yield was 15.2 g, a 33% yield. The polymer had a weight-average molecular weight (Mw) of 79,700 and a polydispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of 3.36. The resulting polymer was designated as the cyclic olefin resin of Example 4.

[0059] [Comparative Example 1] A polymer was synthesized in the same manner as in Example 1, except that the monomer solution consisted of BuNB (86.5 g, 576 mmol), 19.2 g of 1-octene, and 722.2 g of toluene, and the catalyst solution consisted of Pd-1206 (0.0139 g, 0.0115 mmol), DANFABA (0.0369 g, 0.0461 mmol), and 6.0 g of toluene. The reaction temperature was 55°C and the reaction time was 2 hours. At the end of the reaction, 0.480 g of triethylsilane was added to quench the reaction, and acetone was used instead of methanol for reprecipitation of the polymer. The polymer yield was 58.0 g, a 67% yield. The polymer had a weight-average molecular weight (Mw) of 430,000 and a polydispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of 5.06. The resulting polymer was designated the cyclic olefin resin of Comparative Example 1.

[0060] Comparative Example 2 A polymer was synthesized in the same manner as in Example 1, except that the monomer solution consisted of 5-nonafluorobutyl-2-norbornene (CFNB, 18.7 g, 60 mmol) and 3.6 g of 1,3-bis(trifluoromethyl)benzene, and the catalyst solution consisted of Pd-1206 (0.0181 g, 0.015 mmol), DANFABA (0.0300 g, 0.0375 mmol), and 2.6 g of 1,3-bis(trifluoromethyl)benzene. The reaction temperature was 100 °C and the reaction time was 28 hours. At the end of the reaction, the reaction was quenched by adding 0.0937 g of triethylsilane, and toluene was used instead of methanol for polymer reprecipitation. The polymer yield was 7.1 g, a 38% yield. Because this polymer was insoluble in THF, the GPC eluent, the weight-average molecular weight (Mw) and dispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) were unknown. The obtained polymer was designated as the cyclic olefin resin of Comparative Example 2.

[0061] Comparative Example 3 A polymer was synthesized in the same manner as in Example 1, except that the monomer solution consisted of HFANB (61.7 g, 225 mmol) and 64.8 g of butyl acetate, and the catalyst solution consisted of Pd-1206 (0.0302 g, 0.025 mmol), DANFABA (0.0600 g, 0.075 mmol), and 3.1 g of butyl acetate. The reaction temperature was 95°C and the reaction time was 7 hours. At the end of the reaction, 0.617 g of triethylsilane was added to quench the reaction, and heptane was used instead of methanol for polymer reprecipitation. The polymer yield was 18.9 g, a 31% yield. The polymer had a weight-average molecular weight (Mw) of 180,000 and a polydispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of 2.67. The resulting polymer was designated the cyclic olefin resin of Comparative Example 3.

[0062] [Evaluation and Measurement] <Weight average molecular weight (Mw) of cyclic olefin resin> The weight average molecular weight (Mw) of the cyclic olefin resin is determined from a calibration curve of standard polystyrene (PS) obtained by GPC measurement, and a polystyrene-equivalent value is used. The measurement conditions are as follows. Measurement equipment: Tosoh gel permeation chromatography equipment HLC-8320GPC Column: Tosoh TSK-GEL Supermultipore HZ-M Detector: RI detector for liquid chromatography Measurement temperature: 40℃ Solvent: THF Sample concentration: 2.0 mg / ml

[0063] <5% mass loss temperature of cyclic olefin resin> The 5% mass loss temperature of the cyclic olefin resin was calculated by TG-DTA measurement. Specifically, the temperature at which the mass of the cyclic olefin resin decreased by 5% based on the mass at the start of thermogravimetry was defined as the 5% mass loss temperature of the cyclic olefin resin. The measurement conditions are as follows. Measurement equipment: NETZSCH STA 2500 Regulus high-sensitivity differential differential thermobalance Measurement atmosphere: Atmospheric Temperature range: 40℃~400℃ Heating rate: 5°C / min (40°C to 120°C temperature range), 10°C / min (120°C to 400°C temperature range)

[0064] <Odor detection evaluation> (Production of odor detection element) The cyclic olefin resin was dissolved in a solvent (acetone, tetrahydrofuran, and Novec 7100 manufactured by 3M Co.) to prepare a resin solution, the resin concentration in the resin solution being 0.5 to 1% by mass. A resin solution was applied to the gold electrode surface of a QCM (Quartz Crystal Microbalance) type odor detector by spray coating, and the solvent was removed by heating to obtain an odor detection element equipped with a resin film made of a cyclic olefin resin. At this time, the resin film was formed to a thickness of 500 to 1000 nm.

[0065] (Production of an odor detection device) An odor detection device was fabricated that included an odor detection element with a resin film, an oscillation circuit, and a detector. The odor detection element is electrically connected to the oscillation circuit. An oscillator circuit oscillates at an oscillation frequency related to the resonant frequency of the oscillator. The resonant frequency of an oscillator can be defined as either the resonant frequency (fr) at the oscillator's resonance point or the anti-resonant frequency (fa) at the anti-resonant point, or any frequency in between. It is thought that an oscillator circuit oscillates at a frequency near the resonant frequency. When a specific substance adheres to the sensitive film (resin film), the mass of the oscillator increases, causing the resonant frequency to decrease, and therefore the oscillation frequency to decrease. The detector detects the oscillation frequency as a detection value related to the resonant frequency of the vibrator.

[0066] (Gas detection test) Figure 2 is a diagram for explaining the gas detection test method in the examples. In Figure 2, "MFC" stands for "Mass Flow Controller." First, dry air was flowed into the odor detector from the gas generator at a constant flow rate for 30 seconds to stabilize the sensor operation, and then gas was flowed into the odor detector at the same flow rate as the dry air flow rate for 210 seconds. The change in frequency when the gas flow reached equilibrium or after a certain time had passed was taken as the gas sensitivity. The gas detection test was also conducted at room temperature (25°C).

[0067] Gas detection tests were conducted using the following nine gases, adjusting the gas concentrations. Gas types: ammonia, hydrogen sulfide, acetic acid, ethanol, toluene, acetone, 2,3-dimethylpentane (2,3-dmp), ethyl acetate, acetaldehyde

[0068] In the gas detection test, if a signal of 15 Hz or more was shown as a frequency change even when the gas concentration was 10 ppm or less, the gas was evaluated as having good detection sensitivity. Table 1 shows the number of gases out of nine that had good detection sensitivity.

[0069] The evaluation results of the detection sensitivity for each gas species are shown in Table 2. The evaluation criteria are as follows: AA: Even when the gas concentration was 5 ppm or less, a signal of 15 Hz or more was observed as a frequency shift. A: When the gas concentration was 5 ppm or less, no signal of 15 Hz or more was observed as a frequency change, and when the gas concentration was between 5 ppm and 10 ppm, a signal of 15 Hz or more was observed as a frequency change. B: When the gas concentration is 10 ppm or less, no signal of 15 Hz or more is shown as a frequency change.

[0070] The results of measurement and evaluation for each example and each comparative example are shown in Table 1 and Table 2. In Table 1, the abbreviations for the raw material monomers are as follows. BuNB: 5-butylbicyclo[2.2.1]hept-2-ene HFANB: 3-(bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)propan-2-ol C4F9NB: 5-nonafluorobutyl-2-norbornene

[0071] [Table 1]

[0072] [Table 2]

[0073] The number of gas species for which the cyclic olefin resins of the Examples had good detection sensitivity was greater than that of the cyclic olefin resins of the Comparative Examples. That is, it can be understood that the composition for a sensitive film of this embodiment makes it possible to obtain a sensitive film that can detect a wide variety of odor components. [Explanation of symbols]

[0074] 10 Sensitive membrane 20 Piezoelectric layer 30 electrodes 50 Piezoelectric vibrator 100 Odor detection element

Claims

1. A composition for a sensitive film that can be used for a sensitive film of an odor detection element, Contains a cyclic olefin resin (A), The cyclic olefin resin (A) contains a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). 【Chemical 1】 (In the formula (1), R １１ indicates a group containing a hydroxy group) 【Chemistry 2】 (In the formula (2), R ２１ represents any one selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and groups in which one or more hydrogen atoms of an alkyl group having 1 to 10 carbon atoms have been substituted with a fluorine atom)

2. 2. The composition for sensitive films according to claim 1, wherein the content of the structural unit represented by formula (1) in the cyclic olefin resin (A) is 10 mol % or more and 90 mol % or less, when the total of all structural units in the cyclic olefin resin (A) is 100 mol %.

3. 3. The composition for sensitive films according to claim 1, wherein the content of the structural unit represented by formula (2) in the cyclic olefin resin (A) is 10 mol % or more and 90 mol % or less, when the total of all structural units in the cyclic olefin resin (A) is 100 mol %.

4. 3. The composition for sensitive film according to claim 1, wherein the structural unit represented by formula (1) includes a structural unit represented by the following formula (1-a): 【Chemistry 3】

5. In the formula (2), R ２１ 3. The composition for a sensitive film according to claim 1, wherein is any one selected from the group consisting of a butyl group and a group in which all of the hydrogen atoms of the butyl group have been substituted with fluorine atoms.

6. A composition for a sensitive film as described in claim 1 or 2, wherein the content of the cyclic olefin resin (A) in the composition for a sensitive film is 50 mass% or more when the total non-volatile components in the composition for a sensitive film is 100 mass%.

7. 3. The composition for a sensitive film according to claim 1, wherein the cyclic olefin resin (A) has a weight average molecular weight (Mw) of 5,000 or more and 1,000,000 or less.

8. The composition for a sensitive film according to claim 1 or 2, wherein the composition for a sensitive film has a 5% mass loss temperature of 280°C or higher.

9. A sensitive film of an odor detecting element, comprising the composition for a sensitive film according to claim 1 or 2.

10. The sensitive film according to claim 9, having a thickness of 10 nm or more and 1000 nm or less.

11. An odor detection element comprising the sensitive film according to claim 9.

12. Two or more odor detection elements are provided, The odor detection element includes a first odor detection element and a second odor detection element, the second odor detection element is capable of detecting a different type of gas from that detected by the first odor detection element; An odor sensor, wherein at least one selected from the group consisting of the first odor detection element and the second odor detection element is the odor detection element according to claim 11.

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