JP6352517B1 - Composition for temperature sensor - Google Patents

Abstract

Disclosed is a composition comprising a π-conjugated polymer compound and a fluorine-substituted conjugated low-molecular compound capable of increasing the resistance change with temperature as a temperature sensor. A temperature sensor composition comprising the following (a) and (b): (A) A π-conjugated polymer compound having a HOMO level of 4.8 eV or more and less than 5.5 eV (b) a fluorine-substituted conjugated low-molecular compound that further satisfies any of the following requirements: B, N, Has one of the atoms of S in the skeleton. Has a fullerene skeleton.

Description

  The present invention relates to a composition comprising a π-conjugated polymer compound and a fluorine-substituted conjugated low-molecular compound used in a temperature sensor that detects a temperature change by a change in resistance value with temperature.

  Conventionally, as a temperature sensor, a thermistor using a sintered body of an inorganic oxide has been widely put into practical use. The thermistor is suitable for temperature measurement at one point, but it is necessary to arrange a plurality of devices in order to measure a planar temperature distribution. As a temperature sensor for detecting a planar temperature distribution, a temperature sensor using polypyrrole, polyaniline, poly (3,4-ethylenedioxythiophene) (PEDOT) doped with an acid is disclosed (Patent Document 1, non-patent document 1). Patent Document 1) shows that the resistance value changes with temperature. In addition, a temperature sensor array in which a doped polyaniline is used as a temperature sensing element to detect a temperature distribution on a curved surface and is disposed on a flexible substrate is disclosed (Patent Document 2).

Japanese Unexamined Patent Publication No. 03-211702 WO2012 / 001465

Synthetic Metals vol.159 (2009) p.1174.

  However, the temperature-sensitive sensor using a polymer semiconductor such as polypyrrole or PEDOT doped with an acid does not sufficiently change the resistance value depending on the temperature.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition comprising a π-conjugated polymer compound and a fluorine-substituted conjugated low-molecular compound capable of increasing the change in resistance value due to temperature as a temperature sensor. And

  The composition for a temperature sensor according to one embodiment of the present invention includes a π-conjugated polymer compound having a specific HOMO (maximum occupied orbital) level and a specific fluorine-substituted conjugated low-molecular compound.

That is, the composition of this invention is a composition for temperature sensors containing the following (a) and (b).
(A) a π-conjugated polymer compound having a HOMO level of 4.8 eV or more and less than 5.5 eV (b) a fluorine-substituted conjugated low-molecular compound that further satisfies any of the following requirements: B, N, It has any atom of S. It has a fullerene skeleton.

  ADVANTAGE OF THE INVENTION According to this invention, the composition for temperature sensors which can be formed on a flexible substrate with a printing method, and has a big resistance value change by temperature can be provided.

Graph showing time dependency of temperature and resistance value using temperature sensor device A Graph showing temperature and resistance value repetition characteristics using temperature sensor device A Graph showing temperature and resistance change using temperature sensor device A in the range of -5 ° C to 105 ° C Graph showing temperature dependence of temperature and resistance change using temperature sensor device H

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be.

[Composition]
First, the composition of the present invention will be described. The composition of this invention will not be specifically limited if it is a composition containing the following (a) and (b).
(A) a π-conjugated polymer compound having a HOMO level of 4.8 eV or more and less than 5.5 eV (b) a fluorine-substituted conjugated low-molecular compound that further satisfies any of the following requirements: B, N, In the present invention, the high molecular compound means a compound having a main chain in the molecule bonded by a covalent bond and having a weight average molecular weight of about 10,000 or more. . In the present invention, the low molecular weight compound means a compound other than the above high molecular compound, and typically means a compound having a molecular weight of 5000 or less. The π-conjugated polymer compound contained in the composition of the present invention preferably has at least one aromatic ring as a repeating unit. An aromatic ring is a ring structure showing aromaticity, and is a structure in which the number of electrons contained in the π-electron system on the ring is 4n + 2 (n = 0, 1, 2, 3, ...) . In the present invention, “having a ring as a repeating unit” means having a group obtained by removing a plurality (typically two) of hydrogen from a cyclic compound as a repeating unit. Examples of aromatic rings include hydrocarbon aromatic rings such as benzene rings and heteroaromatic rings such as thiophene rings. When the π-conjugated polymer compound has an aromatic ring as a repeating unit, π-conjugation easily spreads between adjacent aromatic rings and carrier conductivity is improved.

The π-conjugated polymer compound contained in the composition of the present invention preferably has at least one condensed ring as a repeating unit. By having a condensed ring as a repeating unit, the planarity of the main chain skeleton of the π-conjugated polymer compound is improved, and carrier conductivity is improved by facilitating π-π stacking between main chains. In addition, the condensed ring increases the molecular structure, suppresses molecular vibration due to thermal motion, and reduces carrier scattering.
The condensed ring contained in the repeating unit includes thienothiophene, dithienothiophene, benzothiophene, dibenzothiophene, benzodithiophene, fluorene, cyclopentadithiophene, indacenodithiophene, dithienoindacenodithiophene, naphthodicyclopenta Examples include dithiophene, benzothienodicyclopentadithiophene, thienopyrrole dione, dithienopyran, dithienosilol, benzothiadiazole, benzobisthiadiazole, pyridalthiadiazole (thiadiazolopyridine), dihydropyrrolopyrrole, isoindigo and the like, fluorene, cyclo Pentadithiophene, dithienopyran, benzothiadiazole, pyridalthiadiazole, dihydropyrrolopyrrole, dihydropyrrolopyrrole, etc. are preferred, Black pentadienyl thiophene, Jichienopiran, benzothiadiazole, pyridinium Daruchi thiadiazole, more preferably from the plane of the main chain skeleton of the dihydro pyrrolo pyrrole π-conjugated polymer compound is further improved.

  These ring structures contained in the repeating unit may have a substituent for improving the solubility in an organic solvent and improving the planarity of the main chain skeleton. Examples of the substituent include an alkyl group having 4 to 24 carbon atoms, an alkoxy group having 4 to 24 carbon atoms, an oxo group, a halogen atom (chlorine, fluorine, bromine, iodine, etc., preferably fluorine), and the like. Are preferably an alkyl group, an oxo group, or a halogen atom (chlorine, fluorine, bromine, iodine, etc., preferably fluorine). As the alkyl group having 4 to 24 carbon atoms, an alkyl group having a branch having 8 or more carbon atoms is more preferable because solubility in an organic solvent becomes higher. The number of substituents per ring structure is not particularly limited, and examples thereof include 1 to 5, 1 to 3, 1 to 2, and the like. Here, in the case of a condensed ring, one ring structure counts the entire condensed ring as one.

  Further, as the repeating unit of the π-conjugated polymer compound, a donor-acceptor type π-conjugated polymer compound having a donor repeating unit and an acceptor repeating unit is more preferable. By adopting the donor-acceptor type, the interaction between molecules is promoted, the planarity of the main chain skeleton of the π-conjugated polymer compound is improved, and the π-π stacking between the main chains is facilitated. The conductivity is improved.

  Examples of the repeating unit having a donor ring include thiophene, thienothiophene, dithienothiophene, benzothiophene, dibenzothiophene, benzodithiophene, fluorene, cyclopentadithiophene, indacenodithiophene, dithienoindacenodithiophene, Naphthodicyclopentadithiophene, benzothienodicyclopentadithiophene, thienopyrroledione, dithienopyran, dithienosilole are exemplified, fluorene, cyclopentadithiophene, dithienopyran are preferred, and cyclopentadithiophene, dithienopyran have donor properties of repeating units It is more preferable because it is more enhanced. These repeating units may further have a substituent.

  Examples of the repeating unit having an acceptor ring include benzothiadiazole, benzobisthiadiazole, pyridalthiadiazole (thiadiazolopyridine), diketopyrrolopyrrole, and isoindigo, and benzothiadiazole, benzothiadiazole, pyridalthiadiazole, Diketopyrrolopyrrole is preferable, and benzothiadiazole, pyridalthiadiazole, and diketopyrrolopyrrole are more preferable because the acceptor property of the repeating unit can be further enhanced. These repeating units may further have a substituent.

  As a combination of a repeating unit having a donor ring and a repeating unit having an acceptor ring, a combination of dithienopyran and benzothiadiazole, dithienopyran and pyridalthiadiazole, fluorene and triphenylamine, diketopyrrolopyrrole and quarterthiophene is preferable. The combination of dithienopyran and benzothiadiazole or dithienopyran and pyridalthiadiazole is particularly preferable because the difference in donor property and acceptor property is increased and the interaction between molecules is enhanced.

  The π-conjugated polymer compound contained in the composition of the present invention may have a repeating unit having a π-conjugated molecule in addition to the condensed ring as a repeating unit. For example, thiophene, bithiophene, terthiophene, quarterthiophene, and triphenylamine are exemplified, and quarterthiophene is more preferable because the thiophene rings easily π-π stack with each other.

  In the present invention, the lower limit of the HOMO level of the π-conjugated polymer compound is 4.8 eV, but the HOMO level is preferably 5.0 eV or more. In the present invention, the upper limit of the HOMO level of the π-conjugated polymer compound is 5.5 eV, but the HOMO level is preferably 5.4 eV or less. In a preferred embodiment of the present invention, the π-conjugated polymer compound preferably has a HOMO level in the range of 5.0 eV to less than 5.5 eV, and in the range of 5.0 eV to 5.4 eV. Those are more preferred. When the HOMO level is less than 4.8 eV, the π-conjugated polymer compound is easily oxidized and becomes unstable. In addition, when the HOMO level is 5.5 eV or more, when mixed with a fluorine-substituted conjugated low molecular compound, electrons are difficult to move from the π-conjugated high molecular compound to the fluorine-substituted conjugated low molecular compound, resulting in poor carrier generation efficiency. . In the present invention, the HOMO level of the π-conjugated polymer compound can be measured by photoelectron spectroscopy.

  The fluorine-substituted conjugated low molecular compound is added to adjust the resistance value of the π-conjugated polymer compound. Electrons move from the HOMO level of the π-conjugated polymer compound to the LUMO level (lowest orbital) of the fluorine-substituted conjugated low molecule, whereby hole carriers are generated in the π-conjugated polymer compound, and the generated carrier The conductivity (resistance value) can be adjusted by the number. In order for the electron transfer to the LUMO level of the fluorine-substituted conjugated low molecule to occur efficiently, the LUMO level of the fluorine-substituted conjugated low molecule has a small difference from the HOMO level of the π-conjugated polymer compound, or the π-conjugated polymer It should be lower than the HOMO level of the compound. As the fluorine-substituted conjugated low-molecular compound, a conjugated low-molecular compound substituted with as many fluorine atoms as possible is more preferable because the LUMO level can be lowered. Further, a fluorine-substituted conjugated low molecular compound having any one of B, N, and S atoms, or a fluorine-substituted conjugated low molecular compound having a fullerene skeleton is particularly preferable.

Examples of the fluorine-substituted conjugated low molecular compound having any atom of B, N, and S include 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, 2,2 ′. (Perfluoronaphthalene-2,6-diylidene) dimalononitrile, tris (pentafluorophenyl) borane, 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, 4-isopropyl-4′-methyldiphenyliodoniumtetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triphenylmethylium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, molybdenum tris (1,2-bis (Trifluoromethyl) eta 1,2-dithiolene), molybdenum tris- (1- (methoxycarbonyl) -2- (trifluoromethyl) ethane-1,2-dithiolene), molybdenum tris- (1-trifluoroacetyl) -2- ( Trifluoromethyl) ethane-1,2-dithiolene) and the like. In the present invention, a fluorine-substituted conjugated low molecular compound having a boron atom is preferred among fluorine-substituted conjugated low molecular compounds having any one of B, N, and S atoms. 3 or 4 phenyl groups substituted with fluorine or a perfluoroalkyl group (for example, a perfluoroalkyl group having 1 to 3 carbon atoms, preferably perfluoromethyl) among fluorine-substituted conjugated low molecular compounds having a boron atom A compound bonded to boron or a salt thereof is preferable, and a compound or salt thereof wherein four phenyl groups substituted with fluorine or a perfluoroalkyl group are bonded to boron is more preferable, and four phenyl groups substituted with fluorine are replaced with boron. More preferred are bound compounds or salts thereof. Examples of the phenyl group substituted with fluorine include a phenyl group substituted with 1 to 5 (preferably 3 to 5, more preferably 5) fluorine. Examples of the phenyl group substituted with a perfluoroalkyl group include a phenyl group substituted with 1 to 5 (preferably 2 to 4, more preferably 3) perfluoroalkyl groups. A compound that forms a salt with a compound in which 3 or 4 phenyl groups substituted with fluorine or a perfluoroalkyl group are bonded to boron is not particularly limited. For example, 4-isopropyl-4′-methyldiphenyliodonium, tetrabutyl Ammonium, N, N, -dimethylanilinium, tetraphenylphosphonium, tri-tert-butylphosphonium, and triphenylmethylinium. As the fluorinated fullerene, those in which 2 to 80% of the number of hydrogen atoms of the unsubstituted fullerene are substituted with fluorine are preferred, and those in which 60 to 80% are substituted with fluorine are preferred. Examples of the fluorinated fullerene include C ₆₀ F ₃₆ , C ₆₀ F ₄₈ , and C ₇₀ F ₅₄ . Among these fluorine-substituted conjugated low-molecular compounds, tris (pentafluorophenyl) borane, 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, N, N, -dimethylanilinium tetrakis (pentafluorophenyl) ) Borate, triphenylmethylinium tetrakis (pentafluorophenyl) borate, molybdenum tris (1,2-bis (trifluoromethyl) ethane-1,2-dithiolene), molybdenum tris- (1- (methoxycarbonyl) -2 -(Trifluoromethyl) ethane-1,2-dithiolene), molybdenum tris- (1-trifluoroacetyl) -2- (trifluoromethyl) ethane-1,2-dithiolene), and fluorinated fullerene C ₆₀ F ₃₆ 4-iso Propyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, N, N, -dimethylanilinium tetrakis (pentafluorophenyl) borate, and fluorinated fullerene C ₆₀ F ₃₆ have high doping efficiency and temperature sensor characteristics. From the viewpoint that stability can be increased, 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate and N, N, -dimethylanilinium tetrakis (pentafluorophenyl) borate are particularly preferable.

  The addition amount of the fluorine-substituted conjugated low-molecular compound may be appropriately selected depending on the characteristics required for the temperature sensor to be used. When the total mass of the π-conjugated polymer compound and the fluorine-substituted conjugated low-molecular compound is 100% by mass For example, the range of 0.1% by mass to 30% by mass is preferable, and the range of 1% by mass to 20% by mass is more preferable. Setting the addition amount of the fluorine-substituted conjugated low-molecular compound to the π-conjugated polymer compound within the above range is preferable because the resistance value can be appropriately lowered and the change in resistance value with respect to temperature can be increased.

[Temperature sensor device]
A temperature sensor device can be obtained by depositing the composition for a temperature sensor of the present invention between a pair of electrodes.

  Specifically, a pair of electrode patterns is formed on an insulating substrate using an oxide such as ITO, a metal such as gold, silver, copper, chromium, nickel, or aluminum. A temperature sensor device can be formed by forming a temperature sensor composition layer by a coating method using a solution of the temperature sensor composition thereon. Further, a pair of electrode patterns may be formed on the temperature sensor composition layer, or a temperature sensor composition layer may be formed between the pair of electrode patterns.

  As the insulating substrate, a ceramic substrate, a glass substrate, and a film such as PET, PEN, or polyimide can be used. A film such as PET, PEN, or polyimide is preferable because it can be a flexible temperature sensor device.

  The pair of electrode patterns can be formed by sputtering, vapor deposition, or printing. Since the manufacturing cost can be reduced, it is preferable to form by a printing method using Ag paste, Cu paste or the like.

  As an electrode pattern, an electrode interval (channel length) and an electrode width (channel width) may be appropriately selected depending on characteristics required for the temperature sensor to be used. The channel length is in the range of 5 μm to 200 μm, Is in the range of 10 μm to 5000 μm.

  The temperature sensor composition solution can be obtained by dissolving a π-conjugated polymer compound and a fluorine-substituted conjugated low-molecular compound in an organic solvent. The solution may be obtained by mixing a π-conjugated polymer compound and a fluorine-substituted conjugated low-molecular compound in a solid and then dissolving it in an organic solvent. Alternatively, each of the π-conjugated polymer compound and the fluorine-substituted conjugated low-molecular compound is organic. You may mix, after melt | dissolving in a solvent.

  The organic solvent used in the temperature sensor composition solution is not particularly limited as long as the π-conjugated polymer compound and the fluorine-substituted conjugated low-molecular compound are dissolved, but halogen solvents such as dichlorobenzene, tetrahydrofuran, anisole, and the like. Hydrocarbon solvents such as ether solvents, toluene, xylene, mesitylene, tetralin, cyclohexylbenzene, and mixed solvents thereof can be used, but toluene, xylene, mesitylene, tetralin, cyclohexyl are available because of their low environmental impact. Hydrocarbon solvents such as benzene and mixed solvents thereof are preferred.

  The solid content concentration of the temperature sensor composition solution may be appropriately selected according to the method of forming the temperature sensor composition layer, and examples thereof include a range of 0.1% by mass to 20% by mass.

  Examples of the method for forming the temperature sensor composition layer include a printing method using a solution of the temperature sensor composition, for example, an inkjet method, a dispenser method, a reverse printing method, a doctor blade method, a gravure printing method, and a screen printing method. Illustrated.

  The thickness of the temperature sensor composition layer is not particularly limited and may be appropriately selected depending on the characteristics required for the temperature sensor to be used. For example, a range of 10 nm to 5 μm is exemplified, and a range of 30 nm to 5 μm is preferable. A range of 50 nm to 300 nm is more preferable for a flexible temperature sensor device.

  A protective layer may be provided on the temperature sensor composition layer. The material for the protective layer is not particularly limited as long as the characteristics of the temperature sensor are not hindered, but it is preferably formed by a coating method using a solvent that does not dissolve the temperature sensor composition. Teflon, polystyrene, polymethacrylic acid Examples include methyl resin.

The resistance value of the composition layer used in the temperature sensor device can be adjusted by the electrode shape of the temperature sensor device and the film thickness of the composition layer for the temperature sensor, but the resistance value at 25 ° C. (R25) It is preferably 1 × 10 ³ Ω or more and 1 × 10 ⁸ Ω or less, and being adjusted to 1 × 10 ⁴ Ω or more and 1 × 10 ⁷ Ω or less is suitable as a temperature sensor for detecting temperature. Is particularly preferable.

  A ratio (R25 / R60) of the resistance value (R25) at 25 ° C. and the resistance value (R60) at 60 ° C. can be used as a guide for the resistance value change due to the temperature of the temperature sensor device. R25 / R60 is preferably 1.8 or more, and more preferably 2.0 or more. When R25 / R60 is less than 1.8, the resistance value change due to temperature is small, and sufficient performance as a temperature sensor device cannot be obtained.

  The temperature sensor device can be used as a single device, or a plurality of temperature sensor devices can be arranged and used as a temperature sensor array. By using a temperature sensor array, a planar temperature distribution can be measured. Furthermore, the temperature distribution of the curved surface can be measured by making the substrate flexible.

  The temperature sensor array can be used in a passive matrix system in which a temperature sensor composition layer is formed at the intersection of electrodes formed in a matrix, or for a switching transistor and a temperature sensor at the intersection of electrodes formed in a matrix. An active matrix method in which a composition layer is formed can also be used. In addition, a sensor array that can measure the distribution of multiple physical properties is formed by placing an active layer, such as a pressure-sensitive layer, that can measure other physical properties at the intersection of electrodes formed in a matrix. can do.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

  The HOMO level of the π-conjugated polymer compound was measured using an atmospheric photoelectron spectrometer (AC-2 manufactured by Riken Keiki Co., Ltd.).

  To measure the temperature sensor characteristics, change the temperature with a Peltier element hot plate (Umper UTD70U100F), measure the resistance value using a power source (Agilent B2912A), and measure the thermocouple voltage with a data logger (Hioki Electric ( The temperature was taken in and converted by Memory Hilogger LR8431).

Example 1
[Creation of composition]
Repeating unit A (5,5-di-3,7-dimethyloctyl-5H-Dithieno [3,2-b: 2 ′, 3′-d] having a condensed ring by the method described in Example 63 of WO2011 / 052709 pyran) and a repeating unit B (Pyridal [2,1,3] thiadiazole) were synthesized. The HOMO level of the π-conjugated polymer compound A was 5.0 eV. The π-conjugated polymer compound A was dissolved in tetralin to prepare a 2% by mass solution of tetralin. Separately, fluorinated fullerene C ₆₀ F ₃₆ (manufactured by Material Technology Research Ltd.) was dissolved in tetralin to prepare a 2 mass% tetralin solution. Subsequently, the prepared π-conjugated polymer compound A and a 2 mass% tetralin solution of C ₆₀ F ₃₆ were mixed at a mass ratio of 87.5: 12.5, and π-conjugated polymer compound A and C ₆₀ F ₃₆ were mixed. A 2% by mass tetralin solution of Composition A containing 12.5% by mass of C ₆₀ F ₃₆ with respect to a total amount of 100% by mass was prepared.

[Create temperature sensor device]
A pair of electrode patterns with a width of 100 μm and a channel length of 20 μm are formed on a glass substrate by reverse printing using nano silver ink (ULVAC T2-D12), fired at 180 ° C. for 1 hour, and a low-resistance Ag electrode did. A thin film of composition A was formed to a thickness of 100 nm by the dispenser method using the solution of composition A on this electrode, baked at 80 ° C. for 10 minutes, and dried. Further, a Teflon solution was formed on the Ag electrode by a dispenser method so as to cover the thin film of the composition A with a thickness of about 5 μm, baked at 80 ° C. for 1 hour, dried, and a temperature sensor device A was prepared.

[Measurement of temperature sensor characteristics]
On the hot plate of the Peltier element, a thermocouple was fixed on the glass substrate near the temperature sensor device A and the electrode. The hot plate was set to 25 ° C., and a resistance value of 6.8 × 10 ⁵ Ω at 25 ° C. and 10 V was obtained. Also, the resistance value and temperature change when applying a pulse voltage (pulse width 10 ms, pulse voltage 10 V, pulse period 500 ms) by repeatedly changing the temperature of the hot plate between 20 ° C. and 65 ° C. (4 ° C./min) Was measured. FIG. 1 shows a time change in temperature and resistance value, and FIG. 2 is a graph in which the temperature is plotted on the horizontal axis and the resistance value is plotted on the vertical axis. The ratio of the resistance values at 25 ° C. and 60 ° C. at this time was as high as R25 / R60 = 2.1. Further, no hysteresis was observed in the temperature change of the resistance value even in the temperature change of 7 reciprocations from FIG.
In addition, FIG. 3 shows a change in resistance value depending on the temperature when the temperature of the hot plate is changed between −5 ° C. and 100 ° C. in a glove box in which dry air is flowed (humidity <10%). It was confirmed that a wide range of temperature changes could be detected.

(Example 2)
In the same manner as in Example 1, by using 4-Isopropyl-4′-methyldiphenyliodonium Tetrakis (pentafluorophenyl) borate (I-TePFB: manufactured by Tokyo Chemical Industry) instead of C ₆₀ F ₃₆ , π-conjugated polymer compounds A and I -A 2% by mass tetralin solution of Composition B containing 3% by mass of I-TePFB is made for a total amount of 100% by mass of TePFB, and the temperature sensor device B is prepared in the same manner as in Example 1 using this solution. Created.
Using the temperature sensor device B, in the same manner as in Example 1, the resistance value and temperature at 25 ° C. and 10 V were repeatedly changed between 20 ° C. and 65 ° C., and the resistance value and temperature change when a pulse voltage was applied. Was measured. The results are summarized in Table 1.

(Example 3)
[Creation of composition]
Repeating unit A having a condensed ring by the method described in Example 54 of WO2011 / 052709 (5,5-di-3,7-dimethyloctyl-5H-Dithieno [3,2-b: 2 ′, 3′-d] π-conjugated polymer compound B having pyran) and repeating unit C (Difluorobenzothiadiazole) was synthesized. The HOMO level of the π-conjugated polymer compound B was 5.2 eV. The π-conjugated polymer compound B was dissolved in tetralin to prepare a 1.5 mass% tetralin solution. Separately, fluorinated fullerene C ₆₀ F ₃₆ was dissolved in tetralin to prepare a 1.5 mass% tetralin solution. Subsequently, the prepared π-conjugated polymer compound B and a C ₆₀ F ₃₆ tetralin 1.5% solution are mixed at a mass ratio of 90:10, and 10 mass% of C ₆₀ F ₃₆ is added to the π-conjugated polymer compound B. The 1.5 mass% tetralin solution of the composition C containing this was created.
A temperature sensor device C was produced in the same manner as in Example 1 except that the composition C was used in place of the composition A.
Using the temperature sensor device C, similarly to Example 1, the resistance value and temperature at 25 ° C. and 10 V were repeatedly changed between 20 ° C. and 65 ° C., and the resistance value and temperature change when a pulse voltage was applied. Was measured. The results are summarized in Table 1.

Example 4
In the same manner as in Example 3, except that 4-Isopropyl-4′-methyldiphenyliodonium Tetrakis (pentafluorophenyl) borate (I-TePFB: manufactured by Tokyo Chemical Industry Co., Ltd.) is used instead of C ₆₀ F ₃₆ , the π-conjugated polymer compounds B and I A 1.5 mass% tetralin solution of composition D containing 3 mass% of I-TePFB is prepared for 100 mass% of the total amount of TePFB, and a temperature sensor device is prepared in the same manner as in Example 1 using this solution. D was created.
Using the temperature sensor device D, in the same manner as in Example 1, the resistance value and temperature at 25 ° C. and 10 V were repeatedly changed between 25 ° C. and 65 ° C., and the resistance value and temperature change when a pulse voltage was applied. Was measured. The results are summarized in Table 1.

(Example 5)
The π-conjugated polymer compound B used in Example 3 was dissolved in o-dichlorobenzene (ODCB) to prepare a 0.4 mass% ODCB solution. Separately, 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ, manufactured by Tokyo Chemical Industry) was dissolved in ODCB to prepare a 0.4 mass% ODCB solution. Next, the prepared π-conjugated polymer compound B and ODCB 0.4% solution of F4-TCNQ were mixed at a mass ratio of 80:20, and the total amount of π-conjugated polymer compound B and F4-TCNQ was 100% by mass. The 0.4 mass% ODCB solution of the composition E containing 20 mass% of F4-TCNQ was created. Using this solution of composition E, a temperature sensor device E was produced in the same manner as in Example 1.
Using the temperature sensor device E, in the same manner as in Example 1, the resistance value and temperature at 25 ° C. and 10 V were repeatedly changed between 20 ° C. and 65 ° C., and the resistance value and temperature change when a pulse voltage was applied. Was measured. The results are summarized in Table 1.

(Example 6)
In the same manner as in Example 3 except that Tris (pentafluorophenyl) borane (TPFB: manufactured by Tokyo Chemical Industry Co., Ltd.) is used instead of C ₆₀ F ₃₆ , TPFB is used with respect to 100 mass% of the total amount of π-conjugated polymer compound B and TPFB The 1.5 mass% tetralin solution of the composition F containing 20 mass% was created.
A pair of Au electrode patterns having a width of 100 μm and a channel length of 20 μm were formed on a glass substrate by vacuum deposition. A temperature sensor device F was produced in the same manner as in Example 1 by using the solution of the composition F on this electrode.
Using the temperature sensor device F, in the same manner as in Example 1, the resistance value and temperature at 25 ° C. and 10 V were repeatedly changed between 20 ° C. and 65 ° C., and the resistance value and temperature change when a pulse voltage was applied. Was measured. The results are summarized in Table 1.

(Example 7)
In the same manner as in Example 6, except that Molybdenum tris (1,2-bis (trifluoromethyl) ethane-1,2-dithiolene) (Mo (tfd) ₃ : manufactured by Sigma-Aldrich) is used instead of TPFB, A 1.5% by mass tetralin solution of a composition G containing 10% by mass of Mo (tfd) ₃ is prepared for 100% by mass of the total amount of the molecular compound B and Mo (tfd) _3. A temperature sensor device G was prepared in the same manner as in Example 6.
Using the temperature sensor device G, in the same manner as in Example 1, the resistance value and temperature at 25 ° C. and 10 V were repeatedly changed between 20 ° C. and 65 ° C., and the resistance value and temperature change when a pulse voltage was applied. Was measured. The results are summarized in Table 1.

(Comparative Example 1)
Total of π-conjugated polymer compound B and I-HFP in the same manner as in Example 5 except that Bis (4-tert-butylphenyl) iodonium Hexafluorophosphate (I-HFP: manufactured by Tokyo Chemical Industry) is used instead of F4-TCNQ. A 0.4% by mass ODCB solution of composition H containing 10% by mass of I-HFP was produced with respect to the amount of 100% by mass, and a temperature sensor device H was produced in the same manner as in Example 6 using this solution. .
Using the temperature sensor device H, in the same manner as in Example 1, the resistance value and temperature at 25 ° C. and 10 V were repeatedly changed between 20 ° C. and 65 ° C., and the resistance value and temperature change when a pulse voltage was applied. As a result, the change in resistance with time gradually increased and became unstable (FIG. 4). At this time, R25 / R60 was 1.4 at the maximum.

(Example 8)
Poly (3-hexylthiophene-2,5-diyl) (P3HT: manufactured by Tokyo Chemical Industry Co., Ltd., HOMO level 4.8 eV) was dissolved in tetralin to prepare a 1% by mass tetralin solution. Separately, fluorinated fullerene C ₆₀ F ₃₆ was dissolved in tetralin to prepare a 1% by mass tetralin solution. Subsequently, the prepared P3HT and 1-% tetralin solution of I-TePFB were mixed at a mass ratio of 95: 5, and a composition containing 5% by mass of I-TePFB with respect to 100% by mass of the total amount of P3HT and I-TePFB. A 1 mass% tetralin solution of I was prepared, and using this solution, a temperature sensor device I was prepared in the same manner as in Example 1.
Using the temperature sensor device I, in the same manner as in Example 1, the resistance value and temperature at 25 ° C. and 10 V were repeatedly changed between 20 ° C. and 65 ° C., and the resistance value and temperature change when a pulse voltage was applied. Was measured. The results are summarized in Table 1.

Example 9
Synthesis of a π-conjugated polymer compound C having a repeating unit D (9,9-dioctylfluorene) having a condensed ring and a repeating unit E (N, N-diphenyl-4-sec-butylphenylamine) by the method described in WO2000 / 55927 did. The HOMO level of the π-conjugated polymer compound C was 5.4 eV. Except for using π-conjugated polymer compound C instead of π-conjugated polymer compound B, in the same manner as in Example 4, for a total amount of 100 mass% of π-conjugated polymer compound C and I-TePFB, I -A 1.5 mass% tetralin solution of composition J containing 15 mass% of TePFB was prepared, and using this solution, a temperature sensor device J was produced in the same manner as in Example 6.
Using the temperature sensor device J, in the same manner as in Example 1, the resistance value and temperature at 25 ° C. and 10 V were repeatedly changed between 20 ° C. and 65 ° C., and the resistance value and temperature change when a pulse voltage was applied. Was measured. The results are summarized in Table 1.

(Comparative Example 2)
A π-conjugated polymer compound D having a repeating unit D (9,9-dioctylfluorene) having a condensed ring and a repeating unit F (Bithiophene) was synthesized by the method described in US5777070. The HOMO level of the π-conjugated polymer compound D was 5.5 eV. Except for using π-conjugated polymer compound D instead of π-conjugated polymer compound B, in the same manner as in Example 4, for a total amount of π-conjugated polymer compound D and I-TePFB of 100% by mass, I -A 1.5 mass% tetralin solution of composition K containing 15 mass% of TePFB was prepared, and a temperature sensor device K was fabricated in the same manner as in Example 6 using this solution.
Using the temperature sensor device K, the resistance value at 25 ° C. and 10 V was measured in the same manner as in Example 1. As a result, the resistance value was not sufficiently low at 2.5 × 10 ⁹ Ω.

(Example 10)
A π-conjugated polymer compound E having a repeating unit G (Diketopyrrolopyrrole) having a condensed ring and a repeating unit H (Quaterthiophene) was synthesized by the method described in Journal of American Chemical Society Vol.133 (2011) p.2198. The HOMO level of the π-conjugated polymer compound E was 5.0 eV. The π-conjugated polymer compound E was dissolved in o-dichlorobenzene (ODCB) to prepare a 0.4 mass% ODCB solution. Separately, I-TePFB was dissolved in ODCB to prepare a 0.4 mass% ODCB solution. Next, the prepared π-conjugated polymer compound E and I-TePFB 0.4 mass% ODCB solution were mixed at a mass ratio of 99: 1, and the total amount of π-conjugated polymer compound E and I-TePFB was 100 mass%. On the other hand, a 0.4 mass% ODCB solution of composition L containing 1 mass% of I-TePFB was prepared. Using the solution of the composition L, a temperature sensor device L was produced in the same manner as in Example 6.
Using the temperature sensor device L, in the same manner as in Example 1, the resistance value and temperature at 25 ° C. and 10 V were repeatedly changed between 20 ° C. and 65 ° C., and the resistance value and temperature change when a pulse voltage was applied. Was measured. The results are summarized in Table 1.

(Example 11)
Total of π-conjugated polymer compound B and N-TePFB in the same manner as in Example 4 except that N, N-dimethylanilinium Tetrakis (pentafluorophenyl) borate (N-TePFB: manufactured by Tokyo Chemical Industry) is used instead of I-TePFB. A 0.4% by mass ODCB solution of composition M containing 1% by mass of N-TePFB with respect to 100% by mass was prepared, and a temperature sensor device M was prepared in the same manner as in Example 6 using this solution. .
Using the temperature sensor device M, in the same manner as in Example 1, the resistance value and temperature at 25 ° C. and 10 V were repeatedly changed between 20 ° C. and 65 ° C., and the resistance value and temperature change when a pulse voltage was applied. Was measured. The results are summarized in Table 1.

  As described above, as shown in the Examples, a device capable of increasing the change in resistance value due to temperature was obtained by producing a temperature sensor device using the temperature sensor composition according to the present invention.

Claims (5)

The composition for temperature sensors containing following (a) and (b).
(A) π-conjugated polymer compound having a HOMO level of 4.8 eV or more and less than 5.5 eV (b) a fluorine-substituted conjugated low-molecular compound that further satisfies any of the following requirements: B, N, Has any atom of S ・ Has fullerene skeleton   The temperature sensor composition according to claim 1, wherein (b) is a fluorine-substituted conjugated low molecular compound having a B atom.   The temperature sensor composition according to claim 1 or 2, wherein (a) is a π-conjugated polymer compound further having a condensed ring as a structural unit.   A temperature sensor device comprising the temperature sensor composition according to claim 1 between a pair of electrodes.   A temperature sensor array comprising a plurality of temperature sensor devices according to claim 4.

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