WO2021059505A1

WO2021059505A1 - Diarylethene compound, temperature indicator, temperature display device, and package

Info

Publication number: WO2021059505A1
Application number: PCT/JP2019/038273
Authority: WO
Inventors: 誠也小畠; 三本木　法光; 佐藤　義則
Original assignee: 公立大学法人大阪; セイコーインスツル株式会社
Priority date: 2019-09-27
Filing date: 2019-09-27
Publication date: 2021-04-01
Also published as: JPWO2021059505A1; JP7338901B2

Abstract

This diarylethene compound is represented by formula (1). This temperature indicator includes said diarylethene compound. This temperature display device includes said temperature indicator. This package has said temperature display device.

Description

Diarylethene compounds, temperature indicators, temperature display devices and packaging

The present invention relates to a diarylethene compound, a temperature indicator, a temperature display device and a package.

With the development of freezing technology and refrigerating technology, it has become possible to maintain the quality and safety of products such as foods and pharmaceuticals for a long period of time. In addition, with the development and spread of low-temperature transportation technology, various frozen foods and refrigerated foods are becoming available in the market. For this reason, it is important to control the temperature of goods in the distribution process and storage process.

For example, in the equipment infrastructure industry and the industrial world, product temperature control is known as an important control item in the monitoring of facilities and the commercialization process and quality control. At present, temperature control is performed by installing electronic measuring instruments in the equipment where products are managed.
However, the use of electronic measuring instruments for the purpose of temperature control of foods and pharmaceuticals is costly for individual foods and pharmaceuticals because the operating principle is battery-powered, and there is no convenience in handling. It is not suitable for this application due to such reasons.
As another temperature control tool, a thermolabel or the like using a temperature indicating ink material is known. Moreover, although the thermolabel is easy to handle, it does not have a temperature detection start function. Since the color-developing reaction of the temperature-indicating ink material is reversible, the target of temperature detection and the usage status are limited. In addition, thermolabels are difficult to measure with high accuracy.

Therefore, there is a need for indicators, tags, labels, etc. that can easily and accurately detect the storage time and storage temperature of temperature-sensitive products and can display them.
Patent Document 1 discloses an optical functional element containing a photochromic material having a specific structure, and a temperature control technique using photochromism.

Here, photochromism is a phenomenon in which a single chemical species reversibly produces two isomers (A, B) having different absorption spectra by the action of light without changing the molecular weight. In photochromism, when isomer A is irradiated with light of a specific wavelength (for example, ultraviolet rays), the bonding mode or electronic state changes and is converted to isomer B, and as a result, the ultraviolet / visible absorption spectrum changes. It is a phenomenon that the color changes.
The optical functional element described in Patent Document 1 has the following three features. Patent Document 1 discloses that an optical functional element having such a feature is used as a temperature history display material.
(I) It has a switch-on function.
(Ii) Non-renewable decolorization occurs due to heating.
(Iii) The colored state is visible and stable.

Since the technique described in Patent Document 1 using photochromism is based on the principle of utilizing a color change due to an external stimulus, power consumption is zero. In addition, since the temperature of the exposed environment is detected by the color fading characteristic and the difference in color due to the elapsed time, the temperature history can be displayed and recorded, and the evidence can be obtained.
Further, since the technology described in Patent Document 1 can realize a device specification having a small size and a thin film, the place and the target in which the technology described in Patent Document 1 is used are not limited. In addition, since flexibility can be expected, the size of the temperature detection target can be selected.
Further, when a small and thin device is realized by utilizing the technique described in Patent Document 1, disposability, cost reduction, and convenience can be expected, and it is promising as a new temperature indicator.

Japanese Unexamined Patent Publication No. 2014-15552

However, although the photochromic material described in Patent Document 1 is suitable for temperature control in a temperature having a relatively high control temperature, specifically, a temperature range of about 10 to 70 ° C., it is suitable for temperature control in a low temperature environment, particularly refrigeration and freezing. And it is not suitable for temperature control in the ultra-low temperature range.

An object of the present invention is to provide a diarylethene compound, a temperature indicator, a temperature display device and a package suitable for temperature control in a low temperature environment.

The lower the 10-hour half-life temperature of the diarylethene compound, which is a photochromic material, that is, the temperature at which the concentration after 10 hours becomes half of the initial concentration, the more suitable for temperature control in a low temperature environment.
As a result of diligent studies, the present inventors have found that the structure of the diarylethene compound affects the 10-hour half-life temperature. Then, they found the structure of a diarylethene compound having a 10-hour half-life temperature of room temperature or less, and completed the present invention.

That is, the diarylethene compound according to one aspect of the present invention is characterized by being represented by the following general formula (1).

In formula (1), ring A represents a 5-membered ring structure or a 6-membered ring structure.
X is a sulfur atom (S), NR ⁷ or an oxygen atom (O), and R ⁷ is a hydrogen atom (H) or an alkyl group.
Y ¹ and Y ² are independently carbon atoms (C) or nitrogen atoms (N), respectively.
R ¹ and ^{R 2} are each independently an alkyl group, a cycloalkyl group, or ^SiR _{8 3,} in each of the three ^{R 8} independently an alkyl group or an aromatic group, one of ^{R 1} and ^{R 2} are alkyl a group or a cycloalkyl group, the other is ^SiR _{8 3,}
When Y ¹ ^{is a carbon atom (C), R 3} is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R ^{4 to form a ring structure.} When Y ¹ is a nitrogen atom (N), it is an electron pair.
When Y ² ^{is a carbon atom (C), R 5} is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R ^{6 to form a ring structure.} When Y ² is a nitrogen atom (N), it is an electron pair.
R ⁴ is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R ^{3 to form a ring structure.}
R ⁶ is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R ^{5 to form a ring structure.}

The diarylethene compound is preferably represented by the following general formula (1A).

In formula (1A), each of the six Zs is independently a hydrogen atom (H) or a fluorine atom (F).
R ¹ and ^{R 2} are each independently an alkyl group, a cycloalkyl group, or ^SiR _{8 3,} in each of the three ^{R 8} independently an alkyl group or an aromatic group, one of ^{R 1} and ^{R 2} are alkyl a group or a cycloalkyl group, the other is ^SiR _{8 3,}
R ³ is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R ^{4 to form a ring structure.}
R ⁵ is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R ^{6 to form a ring structure.}
R ⁴ is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R ^{3 to form a ring structure.}
R ⁶ is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R ^{5 to form a ring structure.}

In the diarylethene compound, wherein ^{R 1} and ^{R 2} are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or ^SiR _{8 3} 3 to 7 carbon atoms, in each of the three ^{R 8} independently an alkyl group or an aromatic group having 1 to 6 carbon atoms, one of ^{R 1} and ^{R 2} is a cycloalkyl group of an alkyl group or a C 3-7 1 to 10 carbon atoms and the other at ^SiR _{8 3} It is preferable to have.

The temperature indicator according to one aspect of the present invention is characterized by containing the diarylethene compound.
The temperature display device according to one aspect of the present invention is characterized by having the temperature indicator.
It is preferable that the temperature display device has a base material and the temperature indicator is formed on one surface of the base material.
The temperature display device has a time information display unit, and it is preferable that the temperature indicator and the time information display unit are formed side by side in the plane direction on the base material in a plan view.
In the temperature display device, it is preferable that an adhesive layer and a release layer are formed in this order on the other surface of the base material.
The temperature display device preferably has a protective layer formed on the temperature indicator.
In the temperature display device, it is preferable that the temperature indicator has adhesiveness on at least one surface and a release layer is formed on the one surface.
The package according to one aspect of the present invention is characterized by having the temperature indicator.

According to the present invention, it is possible to provide a diarylethene compound, a temperature indicator, a temperature display device and a package suitable for temperature control in a low temperature environment.

It is a top view of the temperature display device of the 3rd aspect of this invention. FIG. 5 is a cross-sectional view taken along the line II-II of FIG. It is a figure which shows an example of the fading characteristic of the temperature indicator in the 3rd aspect of this invention. It is the schematic which shows the issuing apparatus of the temperature display device of the 3rd aspect of this invention. It is sectional drawing of the temperature display device of the 4th aspect of this invention. It is sectional drawing of the temperature display device of the 5th aspect of this invention. It is sectional drawing of the temperature display device of the 6th aspect of this invention. It is a perspective view of the package of the 7th aspect of this invention. It is a figure which shows the relationship between the absorbance at a wavelength of 581 nm and the irradiation time of ultraviolet rays in Example 1. FIG. It is a figure which shows the absorption spectrum in the light steady state (PSS) before irradiation with ultraviolet rays in Example 1. FIG. It is a figure which shows the relationship between the absorbance at a wavelength of 541 nm and the irradiation time of ultraviolet rays in Example 2. FIG. It is a figure which shows the absorption spectrum in the light steady state (PSS) before irradiation with ultraviolet rays in Example 2. FIG. It is a figure which shows the relationship between the absorbance at a wavelength of 591 nm and the irradiation time of ultraviolet rays in Example 3. FIG. It is a figure which shows the absorption spectrum in the light steady state (PSS) before irradiation with ultraviolet rays in Example 3. FIG. It is a figure which shows the relationship between the absorbance at a wavelength of 548 nm and the irradiation time of ultraviolet rays in Example 4. FIG. It is a figure which shows the absorption spectrum in the light steady state (PSS) before irradiation with ultraviolet rays in Example 4. FIG. It is a figure which shows the relationship between the degree of fading (A / A _{0) and the leaving time in Example 5. FIG.} FIG. 5 is a diagram in which the natural logarithm of the degree of fading (A / A ₀ ) in Example 5 is plotted on the vertical axis and the leaving time is plotted on the horizontal axis. FIG. 5 is a diagram in which the natural logarithm of the thermal decomposition rate constant (k) in Example 5 is plotted on the vertical axis, and the reciprocal of each temperature is plotted on the horizontal axis. It is a figure which shows the absorption spectrum before irradiation with ultraviolet rays in Example 12. It is a figure which shows the absorption spectrum in the light steady state (PSS) in Example 12. It is a figure which shows the absorption spectrum after fading in Example 12. It is a figure which shows the absorption spectrum at the time of irradiation with ultraviolet rays again in Example 12. It is a figure which shows the absorption spectrum before irradiation with ultraviolet rays in Example 13. It is a figure which shows the absorption spectrum in the light steady state (PSS) in Example 13. It is a figure which shows the absorption spectrum after fading in Example 13. It is a figure which shows the absorption spectrum at the time of irradiating ultraviolet rays again in Example 13. It is a figure which shows the absorption spectrum before irradiation with ultraviolet rays in Example 14. It is a figure which shows the absorption spectrum in the light steady state (PSS) in Example 14. It is a figure which shows the absorption spectrum after fading in Example 14. It is a figure which shows the absorption spectrum at the time of irradiating ultraviolet rays again in Example 14. It is a figure which shows the absorption spectrum before irradiation with ultraviolet rays in Example 15. It is a figure which shows the absorption spectrum in the light steady state (PSS) in Example 15. It is a figure which shows the absorption spectrum after fading in Example 15. It is a figure which shows the absorption spectrum at the time of irradiating ultraviolet rays again in Example 15.

Hereinafter, the present invention will be described in detail.
However, the embodiments described below are specifically described in order to better understand the gist of the invention, and the contents of the invention are not limited unless otherwise specified. The number, position, size, etc. can be changed, omitted, added, or otherwise changed without departing from the spirit of the present invention.
In addition, in this specification, "under a low temperature environment" means room temperature or less. "Room temperature" means 25 ° C. The low temperature environment can be classified into, for example, constant temperature, refrigeration, freezing, ultra-low temperature and the like. The constant temperature is, for example, a temperature range of about 5 to 25 ° C. Refrigeration is, for example, a temperature range of about -18 to 10 ° C. Freezing refers to a temperature range of, for example, about -40 to -18 ° C. The ultra-low temperature is, for example, a temperature range of about −40 ° C. or lower.
Further, in FIGS. 5 to 8 described later, the same components as those in FIG. 1 are designated by the same reference numerals, and the description thereof will be omitted.

[Diarylethene compound]
The diarylethene compound of the first aspect of the present invention is represented by the following general formula (1).

Ring A shows a 5-membered ring structure or a 6-membered ring structure. In diarylethene compound of this embodiment, coloration by ultraviolet irradiation, excellent stability under visible light of the colored state, and further, the function of decolorizing unreproducible due to the temperature rise in a low-temperature environment, and R ¹ while strongly influenced by the reactivity of the sites with each other and R ² are bonded, the influence of the structure of the ring a is not so large. Therefore, in terms of the three-dimensional structure, the ring A may have either a 5-membered ring structure or a 6-membered ring structure, but a 5-membered ring structure is preferable.

X is a sulfur atom (S), NR ⁷ or an oxygen atom (O).
In NR ⁷ , R ⁷ is a hydrogen atom (H) or an alkyl group. The ^{number of carbon atoms of the alkyl group in R 7} is preferably 1 to 6, and more preferably 1 to 3.
As X, a sulfur atom (S) is preferable.

Y ¹ and Y ² are independently carbon atoms (C) or nitrogen atoms (N), respectively.
As Y ¹ and Y ² , carbon atoms (C) are preferable.

R ¹ and ^{R 2} are each independently an alkyl group, a cycloalkyl group, or ^SiR _{8 3,} one of ^{R 1} and ^{R 2} is an alkyl group or a cycloalkyl group, the other is ^SiR _{8 3.}
The ^{number of carbon atoms of the alkyl group in R 1} and R ² is preferably 1 to 10, more preferably 1 to 7, further preferably 1 to 4, and particularly preferably 1 to 3. The alkyl group in R ¹ and R ² may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group, but a primary alkyl group or a secondary alkyl group is preferable, and a primary alkyl group is preferable. Alkyl groups are more preferred.
The ^{number of carbon atoms of the cycloalkyl group in R 1} and R ² is preferably 3 to 7, and more preferably 3 to 5.
In SiR ⁸ _3, 3 both ^{R 8} are each independently an alkyl group or an aromatic group. The number of carbon atoms in the alkyl group in R ⁸ is preferably 1-6, 1-4 is more preferable. Examples ^{of the aromatic group in R 8} include a phenyl group, a benzyl group, a tolyl group, a xsilyl group and the like, and a phenyl group (Ph) is preferable. Specific examples of SiR ⁸ ₃ include Si (CH ₃ ) ₃ , Si (CH ₂ CH ₃ ) ₃ , Si (CH (CH ₃ ) ₂ ) ₃ , SiC (CH ₃ ) ₃ (CH ₃ ) (CH ₃ ). , SiC (CH ₃ ) ₃ (Ph) (Ph) and the like.

From the viewpoint of easily controlling the 10-hour half-life temperature of the diarylethene compound to a temperature suitable for temperature control in a low temperature environment, R ¹ and R ² are independently alkyl groups having 1 to 10 carbon atoms and 3 carbon atoms, respectively. ~ 7 cycloalkyl group, or ^SiR _{8 3} of each of the three ^{R 8} independently an alkyl group or an aromatic group having 1 to 6 carbon atoms, ^{R 1} and one having 1 to 10 carbon atoms ^{R 2} an alkyl group or a cycloalkyl group having 3 to 7 carbon atoms, it is preferred the other is SiR ⁸ _3.
The combination of R ¹ and R ² may be determined according to the use (operating temperature) of the diarylethene compound. As the number of carbon atoms in the alkyl group or cycloalkyl group increases, the 10-hour half-life temperature of the diarylethene compound tends to decrease.
Preferred combinations of R ¹ and ^{R 2,} one of ^{R 1} and ^{R 2} is an alkyl group having 1 to 10 carbon atoms and the other as combinations is ^SiR _{8 3.} In particular, when ^{R 1} is a ^SiR _{8 3,} 10-hour half-life temperature of the diarylethene compound tends to be low.

Optimal diarylethene compound in that can be easily obtained in the temperature management in refrigerated or frozen temperature range, R ¹ is an alkyl group having 2 to 10 carbon atoms, a combination wherein R ² is SiR ⁸ _3, or R ¹ is a SiR ⁸ _3, the combination ^{R 2} is an alkyl group having 1 to 10 carbon atoms are preferred. In particular, R ¹ is a primary alkyl group or a secondary alkyl group having 2 to 4 carbon atoms, and R ² is a trimethylsilyl group (Si (CH ₃ ) ₃ ) or a triethylsilyl group (Si (CH ₂ CH ₃ )). ₃ ), or a combination in which R ¹ is a trimethylsilyl group or a triethylsilyl group and R ² is a primary alkyl group having 1 to 2 carbon atoms is more preferable.
In terms of easily optimal diarylethene compound temperature control is obtained at extremely low temperatures in the temperature range, R ¹ is SiR ⁸ _3, the combination R ² is an alkyl group having 3 to 10 carbon atoms are preferred. In particular, a combination in which R ¹ is a trimethylsilyl group or a triethylsilyl group and R ² is a primary alkyl group or a secondary alkyl group having 3 to 7 carbon atoms is more preferable.

^{R 1} is a methyl group or an isopropyl group in that it has a function of non-reproducible decolorization, that is, it is easy to obtain a diarylethene compound that does not easily recolor even if it is irradiated with light such as ultraviolet rays again after decolorization. , R ² is a trimethylsilyl group, or R ¹ is a trimethylsilyl group and R ² is a methyl group or an isopropyl group.

When Y ¹ is a carbon atom (C), R ³ is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R ^{4 to form a ring structure.} The ^{number of carbon atoms of the alkyl group in R 3} is preferably 1 to 6, and more preferably 1 to 3. The number of carbon atoms of the alkoxy group in R ³ is preferably 1 to 6, 1 to 3 more preferred.
If Y ¹ is a nitrogen atom (N), then R ³ is an electron pair.
It ^{is preferable that Y 1} is a carbon atom (C), R ³ is a hydrogen atom (H) or an alkyl group, and R ³ is a hydrogen atom (H) or an alkyl group having 1 to 3 carbon atoms. More preferred.

When Y ² is a carbon atom (C), R ⁵ is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R ^{6 to form a ring structure.} The number of carbon atoms of the alkyl group in R ⁵ is preferably 1-6, is 1-3 and more preferably. The number of carbon atoms of the alkoxy group in R ⁵ is preferably 1-6, is 1-3 and more preferably.
If Y ² is a nitrogen atom (N), then R ⁵ is an electron pair.
It ^{is preferable that Y 2} is a carbon atom (C), R ⁵ is a hydrogen atom (H) or an alkyl group, and R ³ is a hydrogen atom (H) or an alkyl group having 1 to 3 carbon atoms. More preferred.

The phenyl group, alkyl group, and alkoxy group in R ³ and R ^{5 may each have a substituent.} The substituent is not particularly limited, and examples thereof include a cyano group, an alkyl group, an alkoxy group, a chloro group, and a bromo group.

R ⁴ is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R ^{3 to form a ring structure.} The number of carbon atoms in the alkyl group for R ⁴ is preferably 1 to 10, 1 to 5 and more preferable. The number of carbon atoms of the alkoxy group for R ⁴ is preferably 1 to 10, 1 to 5 and more preferable.
The R ^4, a hydrogen atom (H), a alkyl group of the phenyl group or C 1-5 is preferred.
R ⁶ is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R ^{5 to form a ring structure.} The ^{number of carbon atoms of the alkyl group in R 6} is preferably 1 to 10, and more preferably 1 to 5. The ^{number of carbon atoms of the alkoxy group in R 6} is preferably 1 to 10, and more preferably 1 to 5.
As R ⁶ , a hydrogen atom (H), a phenyl group, or an alkyl group having 1 to 5 carbon atoms is preferable.
Among these, ^{it is particularly preferable that R 4} and R ⁶ are phenyl groups, respectively. The phenyl group, alkyl group, and alkoxy group in R ⁴ and R ^{6 may each have a substituent.} The substituent is not particularly limited, and examples thereof include a cyano group, an alkyl group, an alkoxy group, a chloro group, and a bromo group.

Preferred structures of the ring A include, for example, a structure represented by the following general formula (a1), the following general formula (a2), the following general formula (a3), or the following general formula (a4).

In these structures, the six Zs are each independently a hydrogen atom (H) or a fluorine atom (F). It is preferable that all six Z's are fluorine atoms (F) or hydrogen atoms (H). It is more preferable that all six Z's are fluorine atoms (F) because they are excellent in stability under visible light.
R ^c, ^{R d} and ^{R e} are each independently phenyl group or an alkyl group. R ^c, the number of carbon atoms in the alkyl group in ^{R d} and ^{R e} is preferably 1 to 10, 1 to 5 and more preferable. The phenyl group and alkyl group in R ^c , R ^d and ^{Re may each have a substituent.} The substituent is not particularly limited, and examples thereof include a cyano group, an alkyl group, an alkoxy group, a chloro group, and a bromo group.
As R ^c , R ^d, and ^Re , alkyl groups having 1 to 5 carbon atoms, which may have substituents, are preferable.

From the viewpoint of effectively exerting the functions of coloring by ultraviolet light irradiation, excellent stability of the colored state under visible light, and non-reproducible decolorization due to temperature rise in a low temperature environment, the above general formula is used. In (1), X is preferably a sulfur atom (S). From the same viewpoint, ^{it is preferable that Y 1} and Y ² are carbon atoms (C), respectively. Further, R ³ and R ⁴ are independently hydrogen atoms (H), phenyl groups, or alkyl groups having 1 to 5 carbon atoms, or R ³ and R ⁴ are bonded to each other to form a 6-membered ring structure. It is preferable to do so. Further, R ⁵ and R ⁶ are independently hydrogen atoms (H), phenyl groups or alkyl groups having 1 to 5 carbon atoms, or R ⁵ and R ⁶ are bonded to each other to form a 6-membered ring structure. It is preferable to do so. It is preferable that R ³ and R ⁴ are independently hydrogen atoms (H) or alkyl groups having 1 to 5 carbon atoms. Further, ^{it is particularly preferable that R 5} and R ⁶ are phenyl groups, respectively.

The ^{6-membered ring structure in which R 3} and R ⁴ are bonded to each other and the 6-membered ring structure in which R ⁵ and R ⁶ are bonded to each other are not particularly limited, but from the viewpoint of effectively exerting the above functions, the structure is not particularly limited. A benzene ring skeleton is preferable.

From the viewpoint of effectively exerting the functions of coloring by ultraviolet light irradiation, excellent stability of the colored state under visible light, and non-reproducible decolorization due to temperature rise in a low temperature environment, the present embodiment is used. The diarylethene compound is preferably represented by the following general formula (1A).

^R 1 in the general formula ^{^{(1A), R 2, R}} 3, R 4, R 5 and ^{R 6,} ^R 1 of each of the general formulas ^{^{^{(1), R 2, R 3, R}}} 4, R 5 and is the same as R ^6.
In the general formula (1A), it is preferable that R ³ and R ⁵ are independently hydrogen atoms (H) or alkyl groups having 1 to 5 carbon atoms. It is preferable that R ⁴ and R ⁶ are phenyl groups, respectively. Further, R ³ and R ⁴ may be bonded to each other to form a benzene ring. Similarly, R ⁵ and R ⁶ may be bonded to each other to form a benzene ring. In the general formula (1A), all 6 Zs are preferably fluorine atoms or hydrogen atoms (H), and since they are excellent in stability under visible light, all 6Zs are fluorine atoms (F). Is particularly preferable.

More specifically, from the viewpoint of effectively exerting the above functions, the diarylethene compound of the present embodiment is more preferably represented by the following general formula (1B).

In formula (1B), each of the six Zs is independently a hydrogen atom (H) or a fluorine atom (F).
R ¹ and ^{R 2} are each independently an alkyl group, a cycloalkyl group, or ^SiR _{8 3,} in each of the three ^{R 8} independently an alkyl group or an aromatic group, one of ^{R 1} and ^{R 2} are alkyl a group or a cycloalkyl group, the other is ^SiR _{8 3,}
R ³ is a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group.
R ⁵ is a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group.

^R ^1, R 2, ^{R 3} and ^{R 5} in the general formula (1B) is the same as ^R ^1, R 2, ^{R 3} and ^{R 5} of each of the general formula (1).
In the general formula (1B), ^{it is preferable that R 3} and R ⁵ are independently hydrogen atoms (H) or methyl groups, respectively. In the general formula (1B), all 6 Zs are preferably fluorine atoms or hydrogen atoms (H), and since they are excellent in stability under visible light, all 6Zs are fluorine atoms (F). Is particularly preferable.

Among the diarylethene compounds represented by the general formula (1), the viewpoint of effectively exerting the above functions while controlling the 10-hour half-life temperature of the diarylethene compound to a temperature suitable for temperature control in a low temperature environment. Therefore, it is particularly preferable that the diarylethene compound is represented by the following general formula (1C).

Wherein (1C), ^{R 1} and ^{R 2} are each independently an alkyl group, a cycloalkyl group, or ^SiR _{8 3,} the three ^{R 8} each independently represent an alkyl group or an aromatic group, ^{R 1} and one of R ² is an alkyl group or a cycloalkyl group, the other is ^SiR _{8 3.}

^{R 1} and ^{R 2} in the general formula (1C) is the same as ^{R 1} and ^{R 2} of each of the general formula (1).

The method for producing the diarylethene compound represented by the general formula (1) is not particularly limited, and a known production method can be adopted. For example, first, a precursor of a diarylethene compound represented by the following general formula (2) (hereinafter, also referred to as “precursor (2)”) is produced. Next, the diarylethene compound represented by the general formula (1) is produced by oxidizing the sulfur atom (S) in the 5-membered ring skeleton (thiophene) _{and converting it into a sulfonyl group (SO 2).} Can be done.

The method of oxidizing S in the 5-membered ring skeleton of the precursor (2) _{to convert it into a sulfonyl group (SO 2} ) is not particularly limited, and for example, the precursor (2) is converted into m-chloroperbenzoic acid. Examples thereof include a method of oxidizing with a peracid such as an acid.

When X in the general formula (2) is a sulfur atom (S), the diarylethene compound is represented by the following general formula (1-1) when the precursor represented by the following general formula (2A) is oxidized. It is obtained in the form of a mixture of the diarylethene compound and the diarylethene compound represented by the following general formula (1-2). These may be used isolated or in the form of a mixture.

^{Rings A, X, Y 1} , Y ² , R ¹ , R ² , R ³ , R in the general formula (2), general formula (2A), general formula (1-1) and general formula (1-2). ⁴ , R ⁵ and R ⁶ are the same as rings A, X, Y ¹ , Y ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 in the general formula (1), respectively.} ..

In the production of the diarylethene compound, the reaction conditions such as the starting material, the amount and ratio thereof used, the temperature, time, pressure, the atmosphere and the type and amount of the solvent should be appropriately set according to the structure of the diarylethene compound to be produced. Just do it. Further, the fact that the produced compound is the desired diarylethene compound (1) can be determined by a general organic analysis method such as nuclear magnetic resonance spectrum method (NMR) or mass spectrometry, as shown in Examples described later. You can check.

Here, an example of the method for producing the precursor (2) will be described. The following description, X in the general formula (2) is a sulfur atom (S), R ¹ is SiR ⁸ _3, to produce the precursor R ² is an alkyl group or a cycloalkyl group Although it is a method, this does not limit the present invention.

First, as shown in Examples described later, compound (3) and compound (4) are reacted to obtain compound (5).
Next, the compound (5) is reacted with the cyclic compound (A) from which the ring A is derived to obtain the compound (6). For example, when the ring A has a structure represented by the general formula (a1), the cyclic compound (A) includes cyclopentene, octafluorocyclopentene and the like.

Separately, as shown in Examples described later, compound (7) is reacted with bromine to obtain compound (8). ^{R 9} in compound (7) is an alkyl group or a cycloalkyl group.

^{When R 9} in the compound (7) is a primary alkyl group, a commercially available product can be used as the compound (7), for example.
When R ⁹ in the compound (7) is other than the primary alkyl group, the compound (7) is prepared by reacting, for example, the compound (9) with the ketone compound (B) to obtain the compound (10), and then the compound. (10) is reduced to obtain compound (7). ^{R 9} in the compound (10) is an alkyl group or a cycloalkyl group other than the primary alkyl group.

Examples of the ketone compound (B) include acetone, methyl ethyl ketone, 2-pentanone, diethyl ketone, 3-hexanone, 4-heptanone, 2,4-dimethyl-3-pentanone, cyclopentanone, cyclohexanone and the like.
Compound (10) can be reduced using, for example, aluminum chloride (AlCl ₃ ) and lithium aluminum hydride (LiAlH _4).

If there is no commercially available compound (7) in which R ⁹ is a primary alkyl group, the compound (9) is lithiated with an organic lithium compound, and then the obtained reaction product and an alkyl halide are used. (R ^9- X) is reacted to obtain compound (7).
Examples of the organic lithium compound include butyllithium and the like.
The alkyl halide (R ^9- X) is ^{not particularly limited as long as it has R 9} ^{as an alkyl group, and is, for example, an alkyl iodide (R 9-} I) such as methyl iodide, ethyl iodide, and propyl iodide. ^{); Alkyl bromide (R 9-} Br) such as methyl bromide, ethyl bromide, propyl bromide and the like can be mentioned.

When ^{the compound (8) in which R 6} is a phenyl group is obtained, for example ^{, the compound (7) in which R 6} is a hydrogen atom (H) is reacted with bromine, and then further reacted with an aromatic halogen compound. Just do it. Examples of the aromatic halogen compound include iodobenzene, bromobenzene, m-substituted iodobenzene, p-substituted iodobenzene and the like.

Next, the compound (6) and the compound (8) are reacted to obtain the compound (2B).

The diarylethene compound of the present embodiment is colored by forming (closing) a ring between two thiophene rings to which ^{R 1} and R ² are bonded by irradiation with ultraviolet light, for example, as represented by the following formula. (Switching function). This coloring is stable under visible light and below a predetermined temperature (Δ), but is decomposed into by-products by being exposed (heated) to conditions above the predetermined temperature (Δ). Therefore, it is decolorized (faded). This decoloring (fading) state is stable under ultraviolet light and visible light, and decolorization from coloring is irreversible.

After the diarylethene compound of the present embodiment forms a ring structure by ultraviolet light irradiation to become the compound represented by the general formula (11), the temperatures at which it is decomposed into by-products are R ¹ and R. Affected by ^{two types.} As described above, the ^{larger the number of carbon atoms in the alkyl group or cycloalkyl group of R 1} or R ² , the lower the 10-hour half-life temperature of the diarylethene compound tends to be. That is, it is decomposed at a lower temperature and decolorized. Therefore, ^{by adjusting the types of R 1} and R ² , the 10-hour half-life temperature of the diarylethene compound can be controlled, and the coloring can be decolorized at a desired temperature.

The 10-hour half-life temperature of the diarylethene compound of the present embodiment is preferably room temperature or lower, more preferably 15 ° C. or lower, and even more preferably 0 ° C. or lower. The lower limit of the 10-hour half-life temperature is not particularly limited, but when the diarylethene compound is used for temperature control in a refrigerated or frozen region, the 10-hour half-life temperature is preferably −40 ° C. or higher, more preferably −20 ° C. or higher.
The method for measuring the 10-hour half-life temperature of the diarylethene compound is as described in Examples described later.

As described above, since the diarylethene compound of the present embodiment has a specific structure, it is suitable for temperature control in a low temperature environment. When the diarylethene compound of the present embodiment is used for a temperature sensor, the operating temperature (functional temperature) can be changed. The diarylethene compound of the present embodiment can be used as a photochromic material because it has a P-type photochromism performance capable of setting a desired operating temperature.

The diarylethene compound of the present embodiment may be microencapsulated in order to exhibit stable properties in a solvent.
Here, "microencapsulation" is to process a diarylethene compound diffused in a solvent into minute capsules containing a melted solution.
Examples of the solvent include organic solvents and water. Examples of the organic solvent include hydrocarbons such as hexane and toluene; alcohols such as methanol and ethanol; and ketones such as acetone.
Examples of the microencapsulation method include known interfacial polymerization methods, in-situ polymerization methods, in-liquid curing coating methods, phase separation methods from aqueous solutions, phase separation methods from organic solvents, melt-dispersion cooling methods, and air suspensions. Examples include a turbid coating method and a spray drying method.
The average particle size of the microcapsules is preferably 0.1 to 100 μm, more preferably 1 to 50 μm, and even more preferably 5 to 15 μm.

[Temperature indicator]
The temperature indicator of the second aspect of the present invention comprises the diarylethene compound of the first aspect of the present invention described above.
The temperature indicator has a function of initiating temperature detection by irradiation with light. The temperature indicator is initialized by, for example, being irradiated with light of a specific wavelength, and the color intensity changes. By recognizing the color information, it is possible to confirm the temperature at which the temperature indicator was exposed and the elapsed time at the temperature at which the temperature indicator was exposed.

The diarylethene compound of the first aspect of the present invention is irreversibly discolored (colored) when irradiated with light of a specific wavelength, and irreversibly faded (decolorized) by heat. Therefore, the temperature indicator can be initialized by irradiating the temperature indicator with light having a specific wavelength to discolor it.
That is, the temperature indicator is initialized by irradiating the temperature indicator with light just before the temperature indicator is actually used. Therefore, there are few restrictions on the temperature environment in which the temperature indicator is stored, that is, the temperature environment before the temperature indicator is initialized. For example, even a temperature indicator for temperature control in a low temperature environment can be stored at room temperature.

The content of the diarylethene compound contained in the temperature indicator is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass (total mass) of the temperature indicator. When the content of the diarylethene compound is 0.1% by mass or more, the initialization concentration does not become too thin and can be recognized well, so that the temperature detection accuracy can be maintained. When the content of the diarylethene compound is 20% by mass or less, the reaction rate of the diarylethene compound is unlikely to decrease during initialization by light irradiation, and uninitialized portions are unlikely to occur. Therefore, light such as ultraviolet rays is irradiated again. However, it becomes more difficult for the color to recur.

The temperature indicator may include a binder in addition to the diarylethene compound.
Examples of the binder include polyvinyl acetal resin, silicone resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, polyurethane resin, polyester, epoxy resin, nitrocellulose (nitrified cotton), ethyl cellulose, polyamide, isoprene rubber and the like. Examples thereof include cyclized rubber, chlorinated polyolefin, maleic acid resin, phenol resin, ketone resin, xylene resin, petroleum resin, melamine resin, urea resin, polyisocyanate and the like.

The content of the binder contained in the temperature indicator is preferably 80 to 99.9% by mass, more preferably 90 to 99% by mass, based on the total mass (total mass) of the temperature indicator. When the binder content is 80% by mass or more, the temperature indicator can be easily formed. When the binder content is 99.9% by mass or less, the amount of the diarylethene compound in the temperature indicator becomes sufficient, the initialization concentration does not become too thin, and it can be recognized well, so that the temperature detection accuracy can be maintained.

The shape of the temperature indicator is not particularly limited, but a film shape is preferable.
When the temperature indicator is in the form of a film, its thickness is preferably 100 nm to 50 μm, more preferably 500 nm to 20 μm. When the thickness of the temperature indicator is 100 nm or more, the initialization concentration does not become too thin and can be recognized well, so that the temperature detection accuracy can be maintained. When the thickness of the temperature indicator is 50 μm or less, the light can sufficiently reach the inside of the temperature indicator at the time of initialization by light irradiation. Therefore, the reaction rate of the diarylethene compound is unlikely to decrease, and uninitialized portions are unlikely to occur, so that recoloring is less likely to occur even if light such as ultraviolet rays is irradiated again.

[Temperature display device]
<Third aspect>
The temperature display device according to the third aspect of the present invention will be described with reference to FIGS. 1 and 2.
FIG. 1 is a plan view showing a temperature display device 20 according to a third aspect of the present invention. FIG. 2 is a cross-sectional view taken along the line II-II of the temperature display device 20 of FIG.

As shown in FIGS. 1 and 2, the temperature display device 20 of the present embodiment includes a base material 21, a reference unit 22, a temperature indicator 23, and a time information display unit 24. The temperature indicator 23 is formed on one surface of the base material 21. In a plan view, the reference unit 22, the temperature indicator 23, and the time information display unit 24 are formed side by side in the plane direction on the base material 21.

The temperature display device 20 is attached to a package or the like of an object (for example, food, pharmaceutical product, etc.) such as a product to be temperature-controlled.
It is assumed that the temperature display device 20 is used by being attached to an object subject to temperature control. Therefore, the shape and size of the base material 21 are selected based on the specifications, size, usage, and the like of the product of the object.

Examples of the material of the base material 21 include glass, plastic, synthetic paper, woodfree paper, and metal (for example, aluminum). The base material 21 is preferably synthetic paper or high-quality paper. When the temperature display device 20 is used at a low temperature and dew condensation may occur, it is preferable to use synthetic paper as the base material 21. When synthetic paper is used as the base material 21, moisture does not easily permeate into the base material 21 and the strength is maintained.

The base material 21 may be plate-shaped, foil-shaped, or the like. The base material 21 preferably has flexibility. The base material 21 may be transparent or non-transparent to the light (for example, ultraviolet rays) irradiated to the temperature indicator 23. The base material 21 may be, for example, a card shape having a substantially rectangular shape in a plan view.

The thickness of the base material 21 is not particularly limited as long as it can support the reference portion 22 and the temperature indicator 23, but is preferably 10 μm to 1.0 mm, more preferably 50 μm to 0.5 mm.

As the material of the base material 21, a material that is easy to print may be selected. The material of the base material 21 may be selected in consideration of the formation of the temperature indicator 23, ink adhesion, pattern arrangement such as printing, etc., regardless of the recording method. For example, when at least a part of the surface region of the base material 21 is made of thermal paper, the region becomes a thermal paper region that develops color by heating. When a thermal recording type printing recording device is adopted, printing can be performed on the thermal paper area.
Further, a heat-sensitive recording layer (not shown) may be provided between the base material 21, the reference unit 22, and the temperature indicator 23. From the viewpoint of improving print quality, the thickness of the heat-sensitive recording layer is preferably 0.1 to 50 μm, more preferably 0.1 to 10 μm.

The reference unit 22 presents a reference color as an index for specifying the color of the temperature indicator 23. The color of the temperature indicator 23 can be determined by visually comparing the temperature indicator 23 with the reference unit 22.
The configuration of the reference unit 22 is not particularly limited, but includes a material (for example, a pigment) that can maintain a desired color intensity without discoloration due to the influence of the external environment (temperature, light, etc.) and has excellent water resistance and light resistance. It is preferable to have.
The shape and size of the reference unit 22 are appropriately selected based on the specifications, size, usage method, and the like of the target product that is expected to be used by being attached to the target object for temperature detection.

The temperature indicator 23 is the temperature indicator of the second aspect of the present invention described above. That is, the temperature display device of the present embodiment has the temperature indicator of the second aspect of the present invention.

The time information display unit 24 is an area on which time information is printed. The time information is, for example, character information (printed as characters), a bar code, a two-dimensional code, or the like. The time information is time information indicating the time when the temperature display device 20 is started to be used. When the time information display unit 24 is a bar code, a two-dimensional code, or the like, it may include information about an object on which the temperature display device 20 is mounted. The information about the object is, for example, a product name, identification information for identifying the object, and the like.

The time information display unit 24 may print the time information before the temperature display device 20 is initialized, or may print the time information when the temperature indicator 23 is initialized.
The shape and size of the time information display unit 24 are appropriately selected based on the specifications, size, usage method, and the like of the target product that is expected to be used by being attached to the target object for temperature detection.
In the temperature display device 20 shown in FIG. 1, time information is printed on the time information display unit 24.

The temperature display device 20 of the present embodiment can be manufactured, for example, as follows.
The reference portion 22 is formed on the base material 21. Examples of the method of forming the reference portion 22 include a method of preparing a solution containing a pigment and a solvent having a desired color intensity, printing the solution on a part of the base material 21, and then drying the solution.
Examples of the printing method include screen printing, letterpress printing, flexo printing, dry offset printing, gravure printing, gravure offset printing, pad printing, offset printing, silk printing, and printing using a bar coater.

A temperature indicator 23 is formed on the base material 21. Examples of the method for forming the temperature indicator 23 include a method of preparing a solution containing a diarylethene compound, a binder, and a solvent, printing the solution on a part of the base material 21, and then drying the solution.
The solvent used to form the temperature indicator 23 depends on the material of the temperature indicator 23 and the substrate 21, such as mineral spirit, petroleum naphtha, terepine oil, n-butyl, toluene, xylene, cyclohexane. , Tetraline, acetic acid, methoxybutyl acetate, acetone, methyl isobutyl ketone (MIBK), isophorone, diacetone alcohol, isopropyl alcohol (IPA), n-butanol, ethylene glycol monomethyl ether (methyl cellosolve), 2-ethoxyethanol (ethyl cellosolve) ), Ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoethyl ether acetate (cellosolve acetate), ethylene glycol monobutyl ether acetate (butyl cellosolve acetate), diethylene glycol monobutyl ether (butyl carbitol) and the like. Two or more of these materials may be mixed and used as a solvent. Of these, toluene and acetone are preferable as the solvent.

The content of the diarylethene compound contained in the solution containing the diarylethene compound, the binder, and the solvent is such that the solution has appropriate viscosity and is less likely to bleed during printing, and the diarylethene compound is uniformly dispersed in the solution. Is set as appropriate so that
Examples of the printing method include a method similar to the printing method used when forming the reference portion 22.
The drying temperature is preferably determined between 20 and 100 ° C. in consideration of productivity and damage to the temperature indicator 23.

If a solvent-free resin such as a thermosetting resin or a water-based paint is used as the binder, the temperature indicator 23 can be formed without using a solvent. That is, the temperature indicator 23 is formed by mixing the solvent-free resin and the diarylethene compound, printing the obtained mixture on the base material 21, and then curing the solvent-free resin by heating or drying. With this method, the emission of VOC (volatile organic compounds) can be suppressed.

When a microencapsulated diarylethene compound is used, for example, microcapsules of the diarylethene compound are mixed with screen ink to a desired concentration, and then partially printed on the substrate 21 by screen printing. , The temperature indicator 23 may be formed. The printing method is not limited to screen printing, and a method similar to the printing method used when forming the reference portion 22 may be used.

Next, an example of how to use the temperature display device 20 will be described. FIG. 3 is a diagram showing an example of the fading characteristic of the temperature indicator 23. The vertical axis of FIG. 3 is the color intensity of the temperature indicator 23 (for example, the absorption amount of the light intensity of the light absorption wavelength and the color difference when the color difference before color development is used as the reference color), and the larger the color intensity, the darker the color. The horizontal axis shows the elapsed time from the time of initialization of the temperature indicator 23.

As shown in FIG. 3, the temperature indicator 23 fades (decolorizes) with time after being irradiated with light of a specific wavelength and becoming colored. In FIG. 3, the reference numeral a indicates the change over time of the color at the first temperature. Reference numeral b indicates a change in color over time at a second temperature higher than the first temperature. Reference numeral c indicates a change in color over time at a third temperature higher than the second temperature. As described above, the higher the temperature of the temperature indicator 23, the faster the fading (decoloring) becomes. Since the color intensity is a value corresponding to the temperature, the temperature of the environment in which the temperature display device 20 is placed can be known based on the color intensity.

As for the color intensity in the reference unit 22, the change in color intensity from the time when the diarylethane compound contained in the temperature indicator 23 is colored (that is, initialized) is measured in advance under a predetermined temperature condition, and a predetermined process is obtained. It can be determined based on the color intensity over time. For example, the color intensity of the reference unit 22 is defined as the color intensity obtained after a predetermined elapsed time from the initialization of the temperature display device 20 under the assumed temperature environment. Here, the color intensity obtained when the temperature display device 20 is held at 5 ° C. for 10 hours from the initialization is used.

Next, an example of a method of controlling the temperature of an object using the temperature display device 20 will be described.
First, the temperature indicator 23 of the temperature display device 20 is initialized by using the issuing device described later, and the initialized time is printed on the time information display unit 24. In the present embodiment, the temperature display device 20 in which the temperature indicator 23 is initialized and the initialized time and the like are printed on the time information display unit 24 is defined as the temperature history management label.

The issuing device is provided with a temperature display device 20 in advance. The temperature indicator 23 of the temperature display device 20 provided in the issuing device is irradiated with light from a light source provided in the issuing device, and the temperature indicator 23 is initialized. The time information display unit 24 is printed with the time when the temperature indicator 23 is initialized by the print recording unit of the issuing device. Information such as the time may be coded and printed on the time information display unit 24. The temperature indicator 23 is initialized, and the initialized time is printed on the time information display unit 24 to generate a temperature history management label. The temperature history control label is taken out of the issuing device and immediately affixed to the product subject to temperature detection.

Ten hours after the temperature indicator 23 is initialized, the color intensity of the reference unit 22 and the color intensity of the temperature indicator 23 are visually compared. If it is determined that the color intensity of the temperature indicator 23 is higher than the color intensity of the reference unit 22, it is presumed that the object was held at a temperature lower than 5 ° C. If the color intensity of the temperature indicator 23 is determined to be the same as the color intensity of the reference unit 22, it is estimated that the object was held at about 5 ° C. When the color intensity of the temperature indicator 23 is lower than the color intensity of the reference portion 22, it is presumed that the object was held at a temperature higher than 5 ° C.

As described above, by visually comparing the color intensity of the reference unit 22 with the color intensity of the temperature indicator 23 after a lapse of a predetermined time after the temperature display device 20 is initialized, the object to which the temperature history management label is attached is attached. Can be estimated whether or not the temperature environment was as expected. The temperature display device 20 in the present embodiment is effective when the temperature control time of the object is set in advance.

As the issuing device of the temperature display device, for example, the issuing device 50 of FIG. 4 can be used. The issuing device 50 includes a base material supply unit 55, a print recording unit 52, an irradiation unit 53, and a control unit 51. Further, the issuing device 50 includes a moving mechanism unit (not shown).

The base material supply unit 55 can include, for example, a roll 551 (for example, roll paper) around which a long temperature display device 20A is wound. The temperature display device 20A is a form before the temperature display device 20 is cut, and a plurality of temperature display devices 20 are connected in a row.
The base material supply unit 55 may adopt a method (single-wafer type) capable of supplying a temperature display device cut to a predetermined size in advance.

The print recording unit 52 has various print recording methods such as a thermal recording type using a thermal head, an ink ribbon type, an inkjet type, an electrophotographic type, and a laser marking type (a method of irradiating a laser beam to perform surface processing). It can be adopted. Of these, a thermal printer using a thermal recording type is particularly preferable. Thermal printers have the advantages of extremely low operating noise, a relatively simple structure suitable for small size and light weight, and low cost. Further, since the thermal printer does not use inks such as ink ribbons and ink cartridges, the only consumable item is thermal paper, which has the advantage of being simple and reducing running costs.
The print recording unit 52 prints display information such as time and information on an object to which the temperature history management label 40 is attached on the temperature display device 20A on the time information display unit of the temperature display device.

The irradiation unit 53 includes a light source of irradiation light that irradiates the temperature indicator. The wavelength of the irradiation light by the irradiation unit 53 is, for example, an ultraviolet light region (for example, 250 to 400 nm). Ultraviolet rays can color temperature indicators in a wide range from short wavelengths to long wavelengths close to the visible light region. It is desirable that the irradiation unit 53 has a configuration in which the wavelength of the irradiation light to be used can be selected based on the absorption spectra of the ring-opened body and the ring-closed body of the diarylethene compound.

There are LED type, lamp type, etc. as the light source. The light source can be selected according to the specifications of the temperature display device and the specifications of the issuing device 50. In the small issuing device 50, it is preferable to use an ultraviolet LED as a light source. Since the ultraviolet LED has a narrow wavelength band, it is preferable to select a wavelength from the photochromic absorption spectrum of the temperature indicator portion of the temperature display device and select an ultraviolet LED capable of irradiating light of that wavelength. When a light source having a wide wavelength band such as a lamp type is used, it is possible to adjust the color development characteristics of the irradiation light by a filter according to the absorption spectrum of the temperature indicator unit.

It is preferable that the irradiation unit 53 does not leak the irradiation light to the outside of the issuing device 50 when the light is irradiated. The irradiation unit 53 is provided on the downstream side of the print recording unit 52 (downstream side in the transport direction of the temperature display device 20A) and close to the outlet of the issuing device 50 (the carry-out outlet from which the temperature display device 20A is carried out). It may have been printed. Since the temperature indicator unit of the temperature display device 20A starts temperature detection by light irradiation, if the irradiation unit 53 is located near the outlet of the issuing device 50, the temperature display device can be displayed on the target product in a short time from the start of temperature detection. This is because it can be pasted. Further, since the print recording unit 52 is on the upstream side of the irradiation unit 53 in the transport direction, the temperature detection is not started at the time of printing. Therefore, the heating during printing does not affect the temperature history of the temperature indicator. Therefore, it is possible to display an accurate temperature history.

The control unit 51 includes, for example, a CPU (Central Processing Unit), a ROM (Read Only Memory), and a RAM (Random Access Memory) that are connected to each other. For example, the control unit 51 executes a pre-stored program by the CPU.

Further, the control unit 51 includes an irradiation control unit, a print control unit, an information acquisition unit, a timekeeping unit, and a position control unit (all of which are not shown).
The irradiation control unit controls the irradiation of light to the temperature display device 20A by the irradiation unit 53. The print control unit controls printing of display information on the temperature display device 20A by the print recording unit 52. The display information is, for example, time information that is the start time of temperature detection of the temperature display device 20A, that is, time information that initializes the temperature display device 20A by irradiating the temperature indicator 23 with light, product information, or the like. ..
The information acquisition unit acquires time information and product information. The timekeeping unit measures the irradiation time at which the temperature indicator is irradiated with light in the irradiation unit 53, and outputs time information (irradiation time). According to this configuration, an accurate time can be printed on the temperature display device 20A.
The position control unit controls, for example, the transfer of the temperature display device 20A supplied from the base material supply unit 55. The position control unit outputs a control signal to the irradiation control unit and the print control unit according to the position of the temperature display device 20A, and operates the print recording unit 52 and the irradiation unit 53.

The moving mechanism unit feeds out the long temperature display device 20A from the roll 551 by a driving unit (not shown) such as a motor, and sends out the temperature display device via the print recording unit 52 and the irradiation unit 53. This issues a temperature display device.

By using the issuing device 50 having the above configuration, it is possible to both initialize the temperature display device of the present invention and print the initialized time and the like.

The temperature display device 20 according to the third aspect of the present invention is not limited to the above. For example, a part of the temperature indicator 23 may soak into a part of the base material 21.
The degree to which the temperature indicator 23 soaks into a part of the base material 21 depends on the method of forming the temperature indicator 23. Therefore, in order to obtain the desired form of the temperature indicator 23, the method for forming the temperature indicator 23 may be appropriately selected. For example, in order to control the position of the temperature indicator 23, the viscosity of the solution containing the diarylethene compound, the binder and the solvent may be specified.

The temperature display device 20 may have a blocking layer (not shown) between the temperature indicator 23 and the base material 21. The area of the barrier layer is larger than the area of the temperature indicator 23. The barrier layer is arranged so as to prevent the temperature indicator 23 from coming into direct contact with the base material 21. By arranging the blocking layer, it is possible to prevent the base material 21 from being discolored due to the solvent or binder for forming the temperature indicator 23 permeating into the base material 21. Further, by arranging the blocking layer, it is possible to suppress the influence of the base material 21 on the color development characteristics of the temperature indicator 23.
As the material of the barrier layer, cyclized rubber such as vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, polyurethane resin, polyester, epoxy resin, nitrocellulose (nitrified cotton), ethylcellulose resin, polyamide, isoprene rubber, etc. , Chlorinated polyolefin, maleic acid resin, phenol resin, ketone resin, xylene resin, petroleum resin, melamine resin, urea resin, polyisocyanate and the like. The above material may be a photocurable resin such as ultraviolet curable. Acrylic resin is preferable as the material of the barrier layer.
Examples of the method for forming the blocking layer include the following methods. First, a solution containing the above-mentioned barrier layer material and solvent is prepared. The barrier layer is formed by printing a solution containing the material and solvent of the barrier layer on the base material 21 and drying it before forming the temperature indicator 23. Examples of the printing method include a method similar to the printing method used when forming the reference portion 22.

The temperature display device 20 may have a reference unit 22 having a plurality of color intensities. It may also have a plurality of temperature indicators 23.
If it has a plurality of reference parts and a plurality of temperature indicators, it is possible to easily visually determine how much the object to which the temperature display device 20 is attached deviates from the controlled temperature range. This is useful when you need to know how much you deviate from the temperature range to be controlled.

As another method of using the temperature display device 20, a temperature detection method using a reading processing device can be mentioned. The temperature display device 20 in this embodiment does not need to be provided with the reference unit 22.
The reading processing device is, for example, a smartphone, a tablet terminal, a dedicated device, or the like having an imaging function. The reading processing device reads the information of the temperature history management label (the image including the temperature indicator 23 and the time information display unit 24) through the imaging means, and based on the read information, the temperature history management label (temperature display device 20). Find the temperature and elapsed time that the object to which is affixed was exposed. The reading processing device causes the display unit to display the temperature at which the obtained object was exposed, the elapsed time from the initialization of the temperature history management label, and the like.
In this way, by reading the information on the temperature history management label using the reading processing device and performing temperature detection, the temperature history can be easily and more accurately performed at an arbitrary elapsed time after the temperature history management label is initialized. It is possible to control the temperature of the object to which the control label is affixed.

<Fourth aspect>
The temperature display device according to the fourth aspect of the present invention will be described with reference to FIG.
FIG. 5 is a cross-sectional view of the temperature display device 20B according to the fourth aspect of the present invention.
The temperature display device 20B of the present embodiment has a surface (base material) opposite to the surface (one surface of the base material) on which the reference portion 22, the temperature indicator 23, and the time information display unit 24 of the base material 21 are located. The temperature display device of the third aspect is the same as that of the temperature display device of the third aspect, except that the adhesive layer 31 and the release layer 32 are provided on the other surface).

The adhesive layer 31 is located between the base material 21 and the release layer 32. That is, the adhesive layer 31 and the release layer 32 are formed on the other surface of the base material 21 in this order.
The material of the adhesive layer 31 is not particularly limited as long as the temperature display device 20B can be attached to the temperature detection object.
The material of the release layer 32 is not particularly limited as long as it can be easily separated from the adhesive layer 31.
Immediately before using the temperature display device 20B, the release layer 32 can be peeled off from the adhesive layer 31, and the temperature display device 20B from which the release layer 32 has been peeled off can be attached to an object for use.

<Fifth aspect>
The temperature display device according to the fifth aspect of the present invention will be described with reference to FIG.
FIG. 6 is a cross-sectional view of the temperature display device 20C according to the fifth aspect of the present invention.
The temperature display device 20C of the present embodiment is the same as the temperature display device of the third aspect except that the protective layer 33 is provided on the temperature indicator 23.

The protective layer 33 is formed on the temperature indicator 23 (the surface of the temperature indicator 23 opposite to the surface on which the base material 21 is located). The area of the protective layer 33 is larger than the area of the temperature indicator 23. The protective layer 33 is preferably arranged so as to cover the entire temperature indicator 23. By providing the protective layer 33, the influence of temperature, humidity, chemicals, etc. on the temperature indicator 23 can be suppressed. Further, the protective layer 33 prevents the temperature indicator 23 from being heated when printing on the time information display unit 24. By providing the protective layer 33 on the temperature display device 20C, it is possible to suppress the influence of heat on the temperature indicator 23 even when the printing position accuracy of a printing device such as a thermal printer used for printing is low. The protective layer 33 may cover not only the temperature indicator 23 but also the entire surface of the temperature display device 20C.

The protective layer 33 is preferably a thermally and chemically stable silicone-coated layer, but is not particularly limited as long as it is a thermally and chemically stable layer. For example, examples of the protective layer 33 include an aqueous emulsion coating layer made of polyvinyl alcohol and the like, a laminated layer made of a transparent film made of an olefin resin such as polyethylene and polypropylene, and the like.
As a method for forming the protective layer 33, for example, when a silicone coating layer is used as the protection layer 33, it is formed by applying a solution for forming the silicone coating layer so as to cover the entire temperature indicator 23 and drying it. Can be done. As another method, when a laminated layer is used as the protective layer 33, the protective layer 33 can be formed by arranging the laminated layer so as to cover the entire temperature indicator 23 and fixing the laminated layer by crimping.

Even when the temperature display device 20C is not provided with the protective layer 33, the dimensions of the temperature display device 20C and the layout of the temperature indicator 23 and the time information display unit 24 are stored in the printing device in advance, and the temperature indicator is stored. The print range may be set so as to avoid the position of 23. By doing so, it is possible to print the time and other information without directly heating the temperature indicator 23 at the time of printing and without affecting the temperature characteristics of the temperature indicator 23.
Further, in the present embodiment, the adhesive layer and the peeling layer (both are) on the surface opposite to the surface on which the reference portion 22, the temperature indicator 23, the time information display portion 24 and the protective layer 33 of the base material 21 are located. (Not shown) may be provided in this order.

<Sixth aspect>
The temperature display device according to the sixth aspect of the present invention will be described with reference to FIG.
FIG. 7 is a cross-sectional view of the temperature display device 20D according to the sixth aspect of the present invention.
The temperature display device 20D of the present embodiment has a peeling layer 32, a temperature indicator 23D on the peeling layer 32, and a transparent base material 34 on the temperature indicator 23D.

The temperature indicator 23D is a thin layer containing the diarylethene compound of the first aspect of the present invention and a binder, and has adhesiveness on at least one surface.
Examples of the binder include an adhesive capable of attaching the temperature display device 20D to the temperature detection object and having a hardness of the temperature indicator 23D measured using a nanoindenter of 60 MPa or less. By using an adhesive as the binder, the temperature indicator 23D has adhesiveness not only on one surface but also on a portion other than the one surface.
Examples of such an adhesive include an acrylic adhesive, a urethane adhesive, and a silicone adhesive.

The content of the diarylethene compound and the binder contained in the temperature indicator 23D is the same as that of the temperature indicator of the second aspect of the present invention.

The release layer 32 is formed on one surface of the temperature indicator 23D.
The material of the release layer 32 is not particularly limited as long as it can be easily separated from the temperature indicator 23D.

The transparent substrate 34 is formed on the other surface of the temperature indicator 23D.
The transparent base material 34 does not interfere with light irradiation when initializing the temperature indicator 23D, and does not interfere with visually confirming the color change after a lapse of a predetermined time or by checking with a reading processing apparatus. The substrate is not particularly limited as long as it is a base material made of a material that transmits light.
Examples of the transparent base material 34 include a glass base material and a transparent resin base material. Examples of the resin forming the transparent resin base material include polyester resins such as polyethylene terephthalate (PET), methacrylic resins, acrylic resins, polycarbonate resins, vinyl chloride resins, and polyolefin resins.

The temperature display device 20D can be manufactured, for example, by forming the temperature indicator 23D on the release layer 32 and then forming the transparent base material 34 on the temperature indicator 23D.
The method of forming the temperature indicator 23D is the same as the method of forming the temperature indicator on the base material in the third aspect of the present invention.
As a method for forming the transparent base material 34, a method of attaching a separately prepared transparent base material 34 to the temperature indicator 23D, and a method of applying a solution containing a resin and a solvent for forming the transparent resin base material and drying the transparent base material 34. And so on.
Further, the temperature indicator 23D may be formed on the transparent base material 34, and the release layer 32 may be attached on the temperature indicator 23D.

Since the binder constituting the temperature indicator 23D has adhesiveness, the peeling layer 32 is peeled off from the temperature indicator 23D immediately before using the temperature display device 20D, and the temperature display device 20D from which the peeling layer 32 is peeled off is an object. It can be used by pasting it on.
Examples of the method of using the temperature display device 20D include a temperature detection method using the reading processing device described in the third aspect of the present invention.

[Packaging]
The packaging body of the seventh aspect of the present invention will be described with reference to FIG.
FIG. 8 is a perspective view of the package 60 according to the seventh aspect of the present invention.
The package 60 of the present embodiment has a packaging material 61 for packaging an object (for example, food, pharmaceutical product, etc.) such as a product to be temperature-controlled, a reference unit 22, and a temperature indicator 23. In a plan view, the reference portion 22 and the temperature indicator 23 are formed side by side in the plane direction on the packaging material 61.

The form of packaging is not particularly limited, and may be individual packaging, interior packaging, or exterior packaging.
Examples of the packaging material 61 include corrugated cardboard, styrofoam, bags, boxes, cans, bottles, barrels, and the like.
Examples of the material of the packaging material 61 include paper, plastic, vinyl, cloth, metal, glass, wood and the like.
The packaging material 61 and its material are determined according to the form of the packaging.

The reference unit 22 presents a reference color as an index for specifying the color of the temperature indicator 23.
Examples of the reference unit 22 include the reference unit exemplified above in the description of the third aspect of the present invention.

The temperature indicator 23 is the temperature indicator of the second aspect of the present invention described above. That is, the package 60 of the present embodiment has the temperature indicator of the second aspect of the present invention.

The package 60 of the present embodiment can be manufactured, for example, as follows.
The reference portion 22 is formed on the packaging material 61. The method for forming the reference portion 22 is the same as the method for forming the reference portion exemplified above in the description of the third aspect of the present invention.

A temperature indicator 23 is formed on the packaging material 61. As a method for forming the temperature indicator 23, for example, a solution containing the diarylethene compound of the first aspect of the present invention, a binder, and a solvent was prepared, and this solution was printed or applied to a part on the packaging material 61. After that, a method of drying can be mentioned. Examples of the binder include the binder exemplified above in the description of the second aspect of the present invention. Examples of the solvent include the solvents exemplified above in the description of the third aspect of the present invention.

Examples of the printing method include inkjet printing, screen printing, letterpress printing, flexo printing, dry offset printing, gravure printing, gravure offset printing, pad printing, offset printing, silk printing, and printing using a bar coater.
Examples of the coating method include a spray coating method, a brush coating method, a roller coating method and the like.
The drying temperature is preferably determined between 20 and 100 ° C. in consideration of productivity and damage to the temperature indicator 23.

If a solvent-free resin such as a thermosetting resin or a water-based paint is used as the binder, the temperature indicator 23 can be formed without using a solvent. That is, the temperature indicator 23 is formed by mixing the solvent-free resin and the diarylethene compound, printing or applying the obtained mixture on the packaging material 61, and then curing the solvent-free resin by heating or drying.

When a microencapsulated diarylethene compound is used, for example, microcapsules of the diarylethene compound are mixed with screen ink to a desired concentration, and then partially printed on the packaging material 61 by screen printing. , The temperature indicator 23 may be formed. The printing method is not limited to screen printing, and the printing method exemplified above may be used.

After packaging the object with the package 60 thus obtained, the temperature indicator 23 is irradiated with light to initialize the temperature indicator 23, and the temperature of the object is controlled.
After packaging the object with the packaging material 61, the reference portion 22 and the temperature indicator 23 may be formed on the packaging material 61.

The package 60 of the seventh aspect of the present invention is not limited to the above. For example, the package 60 may have a reference portion 22 having a plurality of color intensities. It may also have a plurality of temperature indicators 23.
Further, when the temperature is detected by using the reading processing device, the package 60 does not need to be provided with the reference portion 22. Examples of the reading processing device include the reading processing device exemplified above in the description of the third aspect of the present invention.

Other aspects of the present invention are as follows.
<1> A diarylethene compound represented by the general formula (1).
<2> The diarylethene compound of <1> represented by the general formula (1A).
<3> The diarylethene compound of <2> represented by the general formula (1B).
<4> The diarylethene compound of <3> represented by the general formula (1C).
<5> to ^{R 1} and ^{R 2} are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or ^SiR _{8 3} 3 to 7 carbon atoms, in each of the three ^{R 8} independently, carbon atoms a 1-6 alkyl group or an aromatic group, one of ^{R 1} and ^{R 2} is a cycloalkyl group of an alkyl group or a C 3-7 1 to 10 carbon atoms, and the other is ^SiR _{8 3,} The diarylethene compound according to any one of <1> to <4>.
<6> is an alkyl group of ^{R 1} and one has 1 to 10 carbon atoms ^{R 2,} the other is ^SiR _{8 3,} wherein the diarylethene compound of <5>.
<7> wherein ^{R 1} is an alkyl group having 2 to 10 carbon atoms, wherein ^{R 2} is ^SiR _{8 3,} wherein <5> or diarylethene compound of <6>.
<8> The R ¹ is a primary alkyl group or a secondary alkyl group having 2 to 4 carbon atoms, and the R ² is a trimethylsilyl group (Si (CH ₃ ) ₃ ) or a triethylsilyl group (Si (CH _2)). CH ₃ ) The diarylethene compound of <7> according to _3).
<9> wherein ^{R 1} is ^SiR _{8 3,} wherein ^{R 2} is an alkyl group having 1 to 10 carbon atoms, wherein <5> or diarylethene compound of <6>.
<10> ^{The diarylethene compound of <9>, wherein R 1} is a trimethylsilyl group or a triethylsilyl group, and R ² is a primary alkyl group having 1 to 2 carbon atoms.
<11> wherein ^{R 1} is ^SiR _{8 3,} wherein ^{R 2} is an alkyl group having 3-10 carbon atoms, wherein <5> or diarylethene compound of <6>.
<12> ^{The diarylethene compound of <11>, wherein R 1} is a trimethylsilyl group or a triethylsilyl group, and R ² is a primary alkyl group or a secondary alkyl group having 3 to 7 carbon atoms.
<13> The diarylethene compound of <5> or <6>, ^{wherein R 1} is a methyl group or an isopropyl group and R ^{2 is a trimethylsilyl group.}
<14> The diarylethene compound of <5> or <6>, ^{wherein R 1} is a trimethylsilyl group and R ^{2 is a methyl group or an isopropyl group.}
<15> A temperature indicator comprising any one of the diarylethene compounds <1> to <14>.
<16> The temperature indicator of <15>, further including a binder.
<17> A temperature display device having the temperature indicator of <15> or <16>.
<18> The temperature display device according to <17>, which has a base material and has the temperature indicator formed on one surface of the base material.
<19> The temperature display device according to <18>, which has a time information display unit, and the temperature indicator and the time information display unit are formed side by side in a plane direction on the base material in a plan view.
<20> The temperature display device according to <18> or <19>, wherein an adhesive layer and a release layer are formed on the other surface of the base material in this order.
<21> The temperature display device according to any one of <17> to <20>, wherein a protective layer is formed on the temperature indicator.
<22> The temperature display device according to <17>, wherein the temperature indicator has adhesiveness on at least one surface and a release layer is formed on the one surface.
<23> A package having the temperature indicator of <15> or <16>.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.
For the identification of the diarylethene compound and its intermediate compound, ^{one or more of the following 1} H-NMR, ¹³ C-NMR, and mass spectrometry was used.

< ^{1 1} H-NMR, ¹³ C-NMR>
An intermediate compound and a diallylethene compound were identified using a nuclear magnetic resonance spectrum apparatus (Bruker BioSpin KK, model "AV-300N"). Deuterated chloroform was used as the solvent, and tetramethylsilane (TMS) was used as the reference substance.

<Mass spectrometry>
As a mass spectrometer, use the model "FT-ICR / solariX (MALDI)" manufactured by Bruker BioSpin KK or the model "JMS-700 / 700S (FAB)" manufactured by Nippon Denshi Co., Ltd. Used to identify intermediate compounds and diarylethene compounds. For ionization, 3-nitrobenzyl alcohol was used in the matrix.

<Manufacturing example 1>
(Synthesis of 1- (2-trimethylsilyl-5-phenyl-3-thienyl) heptafluorocyclopentene)
Compound (5-1) was reacted with cyclic compound (A-1) to obtain compound (6-1). TMS is a trimethylsilyl group.
The compound (5-1), 3-bromo-2-trimethylsilyl-5-phenylthiophene, is described in S.I. Kobatake et al. , New J. Chem. , 2009, 33 (6), 1362-1637.

2 g (6.4 mmol) of the compound (5-1) 3-bromo-2-trimethylsilyl-5-phenylthiophene was placed in a four-necked flask in an argon atmosphere and dissolved in 50 mL of anhydrous ether. 5 mL (8 mmol) of a 1.6 M n-BuLi hexane solution was slowly added dropwise at −78 ° C., and the mixture was stirred for 1.5 hours. 5 mL of anhydrous ether containing 2 mL (15 mmol) of octafluorocyclopentene as the cyclic compound (A-1) was quickly added dropwise, and the mixture was stirred for 5 hours. It was returned to room temperature, quenched with water and extracted with ether. The organic layer was taken out, salted out, dried over magnesium sulfate, filtered, and the remaining solvent was distilled off. Then, it was separated and purified by silica gel column chromatography (eluent: n-hexane) and further purified by recycle preparative HPLC to obtain 1.9 g (4.5 mmol) of compound (6-1) in a yield of 70%. It was.
^{By 1} H-NMR and ¹³ C-NMR and mass spectrometry, it was confirmed that the obtained compound (6-1) was 1- (2-trimethylsilyl-5-phenyl-3-thienyl) heptafluorocyclopentene. ..
^{1 1} H-NMR (300 MHz, CDCl ₃ , TMS): δ = 0.339 and 0.342 (s, 9H), 7.3-7.5 (m, 4H), 7.5-7.5 (m) , 2H). ¹³ C-NMR (75 MHz, CDCl ₃ , TMS) δ = -0.054, 125.0, 126.3, 128.3, 128.5, 129.2, 133.2, 143.6, 150.7 .. HR-MS (MALDI): m / z = 424.0546 (M ⁺ ). Calcd for C ₁₈ H ₁₅ F ₇ SSi ⁺ = 424.0547.

(Synthesis of 1- (2-trimethylsilyl-5-phenyl-3-thienyl) -2- (2-methyl-5-phenyl-3-thienyl) perfluorocyclopentene)
Compound (6-1) and compound (8-1) were reacted to obtain compound (2-1). Me is a methyl group.
The compound (8-1), 3-bromo-2-methyl-5-phenylthiophene, was prepared from M. Irie et al. , J. Am. Chem. Soc. , 2000, 122 (20), 4871-4876.

290 mg (1.1 mmol) of the compound (8-1) 3-bromo-2-methyl-5-phenylthiophene was placed in a three-necked flask in an argon atmosphere and dissolved in 10 mL of anhydrous THF. 0.9 mL (1.4 mmol) of a 1.6 M n-BuLi hexane solution was slowly added dropwise at −78 ° C., and the mixture was stirred for 1 hour. 480 mg (1.1 mmol) of 1- (2-trimethylsilyl-5-phenyl-3-thienyl) heptafluorocyclopentene, which is a compound (6-1) dissolved in 5 mL of anhydrous THF, was added, and the mixture was stirred for 3 hours. Then, the temperature was returned to room temperature, the mixture was quenched with water, THF was distilled off, and the mixture was extracted with ether. The organic layer was taken out, salted out, dried over magnesium sulfate, filtered, and the remaining solvent was distilled off. Then, it is separated and purified by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 95: 5), and further reclaimed preparative HPLC and HPLC using a normal phase silica gel column (eluent: n-hexane: ethyl acetate). Purification was carried out in 95: 5) to obtain 440 mg (0.76 mmol) of compound (2-1) in a yield of 69%.
^{1 The} compound (2-1) obtained by 1 H-NMR is 1- (2-trimethylsilyl-5-phenyl-3-thienyl) -2- (2-methyl-5-phenyl-3-thienyl) perfluorocyclopentene. I confirmed that there was.
^{1 1} H-NMR (300 MHz, CDCl ₃ , TMS): δ = 0.06 (s, 9H), 2.02 (s, 3H), 7.19 (s, 1H), 7.2-7.7 ( m, 11H).

(Oxidation reaction of 1- (2-trimethylsilyl-5-phenyl-3-thienyl) -2- (2-methyl-5-phenyl-3-thienyl) perfluorocyclopentene)
Compound (2-1) was oxidized to obtain compound (1-11) and compound (1-12).

Compound (2-1) 1- (2-trimethylsilyl-5-phenyl-3-thienyl) -2- (2-methyl-5-phenyl-3-thienyl) perfluorocyclopentene 110 mg (0.19 mmol) and dichloromethane 70% by mass of m-chloroperbenzoic acid (110 mg, 0.45 mmol) was added to a eggplant-shaped flask containing 5 mL, and the mixture was stirred overnight in the dark. After neutralization with an aqueous sodium hydrogen carbonate solution, extraction with dichloromethane and salting out, the solvent was distilled off. After passing through a short column (eluent: n-hexane: ethyl acetate = 8: 2), recycle preparative HPLC and HPLC using a normal phase silica gel column (eluent: n-hexane: ethyl acetate = 9: 1) The compound (1-11) was obtained in 18 mg (0.029 mmol) with a yield of 15%. Similarly, compound (1-12) was obtained in 42 mg (0.069 mmol) in 36% yield.
^{1 The} compound (1-11) and compound (1-12) obtained by 1 H-NMR are 1- (2-trimethylsilyl-5-phenyl-3-thienyl) -2- (2-methyl-5-phenyl-). It was confirmed that it was an oxide of 3-thienyl) perfluorocyclopentene.
¹ H-NMR (300 MHz, CDCl ₃ , TMS) of compound (1-11): δ = 0.26 (s, 9H), 2.13 (s, 3H), 6.56 (s, 1H), 7 .3-7.7 (m, 9H), 7.6-7.7 (m, 2H).
¹ H-NMR (300 MHz, CDCl ₃ , TMS) of compound (1-12): δ = 0.14 (s, 9H), 2.36 (s, 3H), 6.81 (s, 1H), 7 .24 (s, 1H), 7.3-7.6 (m, 8H), 7.7-7.8 (m, 2H).

<Manufacturing example 2>
(Synthesis of 1- (2-trimethylsilyl-5-phenyl-3-thienyl) -2- (2-ethyl-5-phenyl-3-thienyl) perfluorocyclopentene)
Compound (6-1) and compound (8-2) were reacted to obtain compound (2-2). Et is an ethyl group.
The compound (8-2), 3-bromo-2-ethyl-5-phenylthiophene, is described in S.I. Kobatake et al. , J. Am. Chem. Soc. , 2000, 122 (49), 121351-12141.

400 mg (1.5 mmol) of the compound (8-2) 3-bromo-2-ethyl-5-phenylthiophene was placed in a three-necked flask in an argon atmosphere and dissolved in 10 mL of anhydrous THF. 1.0 mL (1.6 mmol) of a 1.6 M n-BuLi hexane solution was slowly added dropwise at −78 ° C., and the mixture was stirred for 1.5 hours. 650 mg (1.5 mmol) of 1- (2-trimethylsilyl-5-phenyl-3-thienyl) heptafluorocyclopentene, which is a compound (6-1) dissolved in 5 mL of anhydrous THF, was added, and the mixture was stirred for 2.5 hours. Then, the temperature was returned to room temperature, the mixture was quenched with water, THF was distilled off, and the mixture was extracted with ether. The organic layer was taken out, salted out, dried over magnesium sulfate, filtered, and the remaining solvent was distilled off. Then, it was separated and purified by silica gel column chromatography (eluent: n-hexane) and further purified by recycle preparative HPLC to obtain 550 mg (0.93 mmol) of compound (2-2) in a yield of 62%.
^{1 The} compound (2-2) obtained by 1 H-NMR is 1- (2-trimethylsilyl-5-phenyl-3-thienyl) -2- (2-ethyl-5-phenyl-3-thienyl) perfluorocyclopentene. I confirmed that there was.
^{1 1} H-NMR (300MHz, CDCl ₃ , TMS): δ = 0.07 (s, 9H), 0.95 (t, J = 7.5Hz, 3H), 2.37 (q, J = 7.5Hz) , 2H), 7.2-7.7 (m, 12H).

(Oxidation reaction of 1- (2-trimethylsilyl-5-phenyl-3-thienyl) -2- (2-ethyl-5-phenyl-3-thienyl) perfluorocyclopentene)
Compound (2-2) was oxidized to obtain compound (1-21) and compound (1-22).

Compound (2-2) 1- (2-trimethylsilyl-5-phenyl-3-thienyl) -2- (2-ethyl-5-phenyl-3-thienyl) perfluorocyclopentene 140 mg (0.24 mmol) and dichloromethane To a eggplant-shaped flask containing 5 mL, 140 mg (0.57 mmol) of 70% by mass of m-chloroperbenzoic acid was added, and the mixture was stirred overnight in the dark. After neutralization with an aqueous sodium hydrogen carbonate solution, extraction with dichloromethane and salting out, the solvent was distilled off. After passing through a short column (eluent: n-hexane: ethyl acetate = 8: 2), recycle preparative HPLC and HPLC using a normal phase silica gel column (eluent: n-hexane: ethyl acetate = 9: 1) The compound (1-21) was obtained in 20 mg (0.032 mmol) with a yield of 13%. Similarly, compound (1-22) was obtained in 60 mg (0.096 mmol), yield 40%.
^{1 The} compound (1-21) and compound (1-22) obtained by 1 H-NMR are 1- (2-trimethylsilyl-5-phenyl-3-thienyl) -2- (2-ethyl-5-phenyl-). It was confirmed that it was an oxide of 3-thienyl) perfluorocyclopentene.
¹ H-NMR (300 MHz, CDCl ₃ , TMS) of compound (1-21): δ = 0.28 (s, 9H), 1.04 (t, J = 7.5 Hz, 3H), 2.54 ( q, J = 7.5Hz, 2H), 6.58 (s, 1H), 7.3-7.7 (m, 11H).
¹ H-NMR (300 MHz, CDCl ₃ , TMS) of compound (1-22): δ = 0.14 (s, 9H), 1.27 (t, J = 7.5 Hz, 3H), 2.64 ( q, J = 7.5Hz, 2H), 6.80 (s, 1H), 7.22 (s, 1H), 7.3-7.6 (m, 8H), 7.7-7.8 ( m, 2H).

<Manufacturing example 3>
(Synthesis of 2- (2-hydroxy-2-propyl) thiophene)
Compound (9-3) was reacted with a ketone compound (B-3) to obtain compound (10-3).

Under an argon atmosphere, 9.3 g (110 mmol) of thiophene as compound (9-3) and 100 mL of ether were added to a four-necked flask. At 0 ° C., 83 mL (130 mmol) of a 1.6 M n-BuLi hexane solution was slowly added dropwise. Then, the mixture was refluxed for 1 hour, 9.8 mL (130 mmol) of anhydrous acetone was added dropwise as a ketone compound (B-3) at 0 ° C., and the mixture was stirred at room temperature for 1 hour. Then, water was added, acidified with dilute hydrochloric acid, extracted with ether, and dried over magnesium sulfate. Then, it was separated and purified by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 7: 3) to obtain 11 g (77 mmol) of compound (10-3) in a yield of 70%.
¹ It was confirmed by 1 H-NMR that the obtained compound (10-3) was 2- (2-hydroxy-2-propyl) thiophene.
^{1 1} H-NMR (300 MHz, CDCl ₃ , TMS): δ = 1.67 (s, 6H), 2.06 (s, 1H), 6.92-6.98 (m, 2H), 7.19 ( dd, J = 4.7, 1.5Hz, 1H).

(Synthesis of 2-isopropylthiophene)
Compound (10-3) was reduced to give compound (7-3).

36 g (270 mmol) of aluminum chloride was placed in a flask under an argon atmosphere, and 80 mL of anhydrous ether was slowly added dropwise while cooling with ice. Then, 5 g (130 mmol) of lithium aluminum hydride was added, and a 100 mL solution of 11 g (77 mmol) of 2- (2-hydroxy-2-propyl) thiophene as compound (10-3) was slowly added dropwise. Then, the mixture was refluxed for 1.5 hours and treated with 20% by mass of dilute sulfuric acid. Then, it was extracted with ether, washed with saturated brine, dried over magnesium sulfate, and the solvent was evaporated. Then, it was purified by vacuum distillation (55 C / 3.9 kPa) to obtain 2.2 g (17 mmol) of compound (7-3) in a yield of 23%.
¹ It was confirmed by 1 H-NMR that the obtained compound (7-3) was 2-isopropylthiophene.
^{1 1} H-NMR (300 MHz, CDCl ₃ , TMS): δ = 1.34 (d, J = 6.9 Hz, 6H), 3.19 (sep, J = 6.9 Hz, 1H), 6.80 (d) , J = 3.6Hz, 1H), 6.92 (dd, J = 5.1, 3.6Hz, 1H), 7.11 (d, J = 5.1Hz, 1H).

(Synthesis of 3-bromo-2-isopropyl-5-phenylthiophene)
After reacting compound (7-3) with bromine, the obtained intermediate was reacted with an aromatic halogen compound to obtain compound (8-3).

15 mL of acetic acid, 1 mL of water, and 2.2 g (17 mmol) of 2-isopropylthiophene as a compound (7-3) were placed in a flask, and 6 g (38 mmol) of bromine was slowly added dropwise while cooling with ice. Then, it was stirred in a water bath overnight. Then, it was neutralized with an aqueous sodium hydroxide solution and extracted with ether. After washing with an aqueous sodium thiosulfate solution and a saturated brine, the mixture was dried over magnesium sulfate and the solvent was distilled off. Then, it was separated and purified by column chromatography (eluent: n-hexane) to obtain 3 g (11 mmol) of the intermediate in a yield of 61%.
¹ It was confirmed by 1 H-NMR that the obtained intermediate was 3,5-dibromo-2-isopropylthiophene.
^{1 1} H-NMR (300 MHz, CDCl ₃ , TMS): δ = 1.27 (d, J = 6.8 Hz, 6H), 3.30 (sep, J = 6.8 Hz, 1H), 6.85 (s) , 1H).

Next, 1.1 g (3.9 mmol) of the intermediate 3,5-dibromo-2-isopropylthiophene was placed in 20 mL of anhydrous THF in a four-necked flask in an argon atmosphere, and 1.6 M n-BuLi at −78 ° C. 2.6 mL (4.2 mmol) of the hexane solution was slowly added dropwise. After stirring for 1 hour, 2.2 mL (8 mmol) of tri-n-butyl borate was further added dropwise, and the mixture was stirred. After stirring for 1 hour, quenched with quenched with water, and 20 wt% aqueous solution of sodium carbonate 7 _mL, and _{Pd (PPh 3) 4 84mg (} 0.074mmol), and iodobenzene 0.75 g (3.7 mmol) Was added, and the mixture was heated under reflux for 9 hours. Then, it was neutralized with dilute hydrochloric acid, extracted with ether, dried over magnesium sulfate, and the solvent was distilled off. Then, it was separated and purified by column chromatophy (eluent: n-hexane) to obtain 730 mg (2.6 mmol) of compound (8-3) in a yield of 67%.
¹ It was confirmed by 1 H-NMR that the obtained compound (8-3) was 3-bromo-2-isopropyl-5-phenylthiophene.
^{1 1} H-NMR (300 MHz, CDCl ₃ , TMS): δ = 1.33 (d, J = 6.8 Hz, 6H), 3.34 (sep, J = 6.8 Hz, 3H), 7.10 (s) , 1H), 7.20-7.55 (m, 5H).

(Synthesis of 1- (2-trimethylsilyl-5-phenyl-3-thienyl) -2- (2-isopropyl-5-phenyl-3-thienyl) perfluorocyclopentene)
Compound (6-1) and compound (8-3) were reacted to obtain compound (2-3).
IPr is an isopropyl group.

450 mg (1.6 mmol) of the compound (8-3) 3-bromo-2-isopropyl-5-phenylthiophene was placed in a three-necked flask in an argon atmosphere and dissolved in 10 mL of anhydrous THF. 1.2 mL (1.9 mmol) of a 1.6 M n-BuLi hexane solution was slowly added dropwise at −78 ° C., and the mixture was stirred for 1 hour. 680 mg (1.6 mmol) of 1- (2-trimethylsilyl-5-phenyl-3-thienyl) heptafluorocyclopentene, which is a compound (6-1) dissolved in 5 mL of anhydrous THF, was added, and the mixture was stirred for 5 hours. Then, the temperature was returned to room temperature, the mixture was quenched with water, THF was distilled off, and the mixture was extracted with ether. The organic layer was taken out, salted out, dried over magnesium sulfate, filtered, and the remaining solvent was distilled off. Then, it was separated and purified by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 95: 5), further purified by recycle preparative HPLC, and the compound (2-3) was collected in 750 mg (1.2 mmol). Obtained at a rate of 75%.
^The compound (2-3) obtained by 1 H-NMR and ¹³ C-NMR and mass spectrometry is 1- (2-trimethylsilyl-5-phenyl-3-thienyl) -2- (2-isopropyl-5). -Phenyl-3-thienyl) It was confirmed that it was perfluorocyclopentene.
^{1 1} H-NMR (300 MHz, CDCl ₃ , TMS): δ = 0.09 (s, 9H), 0.92 (d, J = 6.7 Hz, 6H), 2.84 (sep, J = 6.7 Hz) , 1H), 7.21 (s, 1H), 7.2-7.7 (m, 1H). ¹³ C-NMR (75 MHz, CDCl ₃ , TMS) δ = 0.03, 25.4, 30.0, 122.6, 122.9, 125.7, 125.9, 126.3, 128.0, 128.4, 129.1, 129.2, 133.5, 133.8, 134.3, 142.0, 150.3, 156.4. MS (MALDI): m / z = 606.1300 (M ⁺ ). Calcd for C ₃₁ H ₂₈ F ₆ S ₂ Si ⁺ = 606.1300.

(Oxidation reaction of 1- (2-trimethylsilyl-5-phenyl-3-thienyl) -2- (2-isopropyl-5-phenyl-3-thienyl) perfluorocyclopentene)
Compound (2-3) was oxidized to obtain compound (1-31) and compound (1-32).

Compound (2-3) 1- (2-trimethylsilyl-5-phenyl-3-thienyl) -2- (2-isopropyl-5-phenyl-3-thienyl) perfluorocyclopentene 120 mg (0.20 mmol) and dichloromethane 70% by mass of m-chloroperbenzoic acid (120 mg, 0.49 mmol) was added to a eggplant-shaped flask containing 5 mL, and the mixture was stirred overnight in the dark. After neutralization with an aqueous sodium hydrogen carbonate solution, extraction with dichloromethane and salting out, the solvent was distilled off. After passing through a short column (eluent: n-hexane: ethyl acetate = 9: 1), recycle preparative HPLC and HPLC using a normal phase silica gel column (eluent: n-hexane: ethyl acetate = 9: 1) The compound (1-31) was obtained in 23 mg (0.036 mmol) with a yield of 18%. Similarly, compound (1-32) was obtained in 46 mg (0.072 mmol) in 36% yield.
^{1 The} compound (1-31) and compound (1-32) obtained by 1 H-NMR are 1- (2-trimethylsilyl-5-phenyl-3-thienyl) -2- (2-isopropyl-5-phenyl-). It was confirmed that it was an oxide of 3-thienyl) perfluorocyclopentene.
¹ H-NMR (300 MHz, CDCl ₃ , TMS) of compound (1-31): δ = 0.30 (s, 9H), 1.15 (d, J = 7.0 Hz, 6H), 2.88 ( sep, J = 7.0Hz, 1H), 6.79 (s, 1H), 7.24 (s, 1H), 7.3-7.7 (m, 10H).
¹ H-NMR (300 MHz, CDCl ₃ , TMS) of compound (1-32): δ = 0.16 (s, 9H), 1.23 (d, J = 6.7 Hz, 6H), 2.95 ( sep, J = 6.7Hz, 1H), 6.78 (s, 1H), 7.16 (s, 1H), 7.3-7.6 (m, 8H), 7.7-7.8 ( m, 2H).

<Manufacturing example 4>
(Synthesis of 1- (2-triethylsilyl-5-phenyl-3-thienyl) -2- (2-methyl-5-phenyl-3-thienyl) perfluorocyclopentene)
Compound (6-4) and compound (8-1) were reacted to obtain compound (2-4). TES is a triethylsilyl group.
The compound (6-4) 1- (2-triethylsilyl-5-phenyl-3-thienyl) heptafluorocyclopentene is described in D.I. Kitagawa et al. , J. Mater. Chem. It was synthesized by the method described in C, 2017, 5 (25), 6210-6215.

410 mg (1.6 mmol) of the compound (8-1) 3-bromo-2-methyl-5-phenylthiophene was placed in a three-necked flask in an argon atmosphere and dissolved in 10 mL of anhydrous THF. 1.1 mL (1.8 mmol) of a 1.6 M n-BuLi hexane solution was slowly added dropwise at −78 ° C., and the mixture was stirred for 1 hour. 760 mg (1.6 mmol) of 1- (2-triethylsilyl-5-phenyl-3-thienyl) heptafluorocyclopentene, which is a compound (6-4) dissolved in 5 mL of anhydrous THF, was added, and the mixture was stirred for 1 hour. Then, the temperature was returned to room temperature, the mixture was quenched with water, THF was distilled off, and the mixture was extracted with ether. The organic layer was taken out, salted out, dried over magnesium sulfate, filtered, and the remaining solvent was distilled off. Then, it was separated and purified by silica gel column chromatography (eluent: n-hexane) to obtain 490 mg (0.79 mmol) of compound (2-4) in a yield of 49%.
^{1 The} compound (2-4) obtained by 1 H-NMR is 1- (2-triethylsilyl-5-phenyl-3-thienyl) -2- (2-methyl-5-phenyl-3-thienyl) perfluorocyclopentene. I confirmed that.
^{1 1} H-NMR (300 MHz, CDCl ₃ , TMS): δ = 0.55 (br, 6H), 0.81 (br, 9H), 2.04 (s, 3H), 7.18 (s, 1H) , 7.2-7.5 (m, 9H), 7.6-7.7 (m, 2H).

(Oxidation reaction of 1- (2-triethylsilyl-5-phenyl-3-thienyl) -2- (2-methyl-5-phenyl-3-thienyl) perfluorocyclopentene)
Compound (2-4) was oxidized to obtain compound (1-41) and compound (1-42).

Compound (2-4) 1- (2-triethylsilyl-5-phenyl-3-thienyl) -2- (2-methyl-5-phenyl-3-thienyl) perfluorocyclopentene 120 mg (0.19 mmol) and To a eggplant-shaped flask containing 5 mL of dichloromethane, 120 mg (0.49 mmol) of 70% by mass of m-chloroperbenzoic acid was added, and the mixture was stirred overnight in the dark. After neutralization with an aqueous sodium hydrogen carbonate solution, extraction with dichloromethane and salting out, the solvent was distilled off. After passing through a short column (eluent: n-hexane: ethyl acetate = 9: 1), recycle preparative HPLC and HPLC using a normal phase silica gel column (eluent: n-hexane: ethyl acetate = 9: 1) The compound (1-41) was obtained in 37 mg (0.057 mmol) with a yield of 30%. Similarly, compound (1-42) was obtained in 24 mg (0.037 mmol) in 19% yield.
^{1 The} compound (1-41) and compound (1-42) obtained by 1 H-NMR are 1- (2-triethylsilyl-5-phenyl-3-thienyl) -2- (2-methyl-5-phenyl). It was confirmed that it was an oxide of -3-thienyl) perfluorocyclopentene.
¹ H-NMR (300 MHz, CDCl ₃ , TMS) of compound (1-41): δ = 0.73 (q, J = 7.7 Hz, 6H), 0.90 (t, J = 7.7 Hz, 9H). ), 2.16 (s, 3H), 6.53 (s, 1H), 7.3-7.5 (m, 9H), 7.6-7.7 (m, 2H).
¹ H-NMR (300 MHz, CDCl ₃ , TMS) of compound (1-42): δ = 0.67 (q, J = 7.7 Hz, 6H), 0.84 (t, J = 7.7 Hz, 9H). ), 2.39 (s, 3H), 6.83 (s, 1H), 7.21 (s, 1H), 7.3-7.5 (m, 8H), 7.7-7.8 ( m, 2H).

<Manufacturing example 5>
(Synthesis of 1- (1,1-dioxide-2-isopropyl-5-phenyl-3-thienyl) -2- (2-isopropyl-5-phenyl-3-thienyl) perfluorocyclopentene)
1- (1,1-dioxide-2-isopropyl-5-phenyl-3-thienyl) -2- (2-isopropyl), which is compound (1-5), by the method described in JP-A-2014-15552. -5-Phenyl-3-thienyl) Perfluorocyclopentene was obtained.

<Manufacturing example 6>
(Synthesis of 1- (1,1-dioxide-2-cyclohexyl-5-phenyl-3-thienyl) -2- (2-cyclohexyl-5-phenyl-3-thienyl) perfluorocyclopentene)
1- (1,1-dioxide-2-cyclohexyl-5-phenyl-3-thienyl) -2- (2-cyclohexyl), which is compound (1-6), by the method described in JP-A-2014-15552. -5-Phenyl-3-thienyl) perfluorocyclopentene was obtained.

<Example 1>
At -60 ° C, an n-hexane solution (concentration: about ^10-5 mol / L) of the compound (1-11) obtained in Production Example 1 was placed in a quartz cell, sealed, and then ultraviolet rays (wavelength 313 nm). ), And the absorption spectrum was measured using an absorptiometer (manufactured by JASCO Corporation, model "V-560"). The relationship between the absorbance at a wavelength of 581 nm and the irradiation time of ultraviolet rays is shown in FIG. 9A. Further, the absorption spectra before irradiation with ultraviolet rays and in the light steady state (PSS) are shown in FIG. 9B.
It was confirmed that when the compound (1-11) was irradiated with ultraviolet rays, it was colored. This means that, as shown below, the two thiophene rings of compound (1-11) form a ring (ring closure) by irradiation with ultraviolet rays.

As shown in FIG. 9B, the ring-opened body, that is, the compound (1-11) had an absorption spectrum at a wavelength of 285 nm, and the ring-closed body, that is, the compound in the light steady state had an absorption spectrum at a wavelength of 581 nm.

<Example 2>
At -60 ° C, an n-hexane solution (concentration: about ^10-5 mol / L) of the compound (1-12) obtained in Production Example 1 was placed in a quartz cell, sealed, and then ultraviolet rays (wavelength 313 nm). ), And the absorption spectrum was measured using an absorptiometer (manufactured by JASCO Corporation, model "V-560"). The relationship between the absorbance at a wavelength of 541 nm and the irradiation time of ultraviolet rays is shown in FIG. 10A. Further, the absorption spectra before irradiation with ultraviolet rays and in the light steady state (PSS) are shown in FIG. 10B.
It was confirmed that when the compound (1-12) was irradiated with ultraviolet rays, it was colored. This means that the two thiophene rings of compound (1-12) formed a ring (ring closure) by irradiation with ultraviolet rays, as shown below.

As shown in FIG. 10B, the ring-opened body, that is, the compound (1-12) had an absorption spectrum at a wavelength of 284 nm, and the ring-closed body, that is, the compound in the light steady state had an absorption spectrum at a wavelength of 541 nm.

<Example 3>
At -80 ° C, an n-hexane solution (concentration: about ^10-5 mol / L) of the compound (1-31) obtained in Production Example 3 was placed in a quartz cell, sealed, and then ultraviolet rays (wavelength 313 nm). ), And the absorption spectrum was measured using an absorptiometer (manufactured by JASCO Corporation, model "V-560"). The relationship between the absorbance at a wavelength of 591 nm and the irradiation time of ultraviolet rays is shown in FIG. 11A. Further, the absorption spectra before irradiation with ultraviolet rays and in the light steady state (PSS) are shown in FIG. 11B.
It was confirmed that when the compound (1-31) was irradiated with ultraviolet rays, it was colored. This means that the two thiophene rings of compound (1-31) formed a ring (ring closure) by irradiation with ultraviolet rays, as shown below.

As shown in FIG. 11B, the ring-opened body, that is, the compound (1-31) had an absorption spectrum at a wavelength of 284 nm, and the ring-closed body, that is, the compound in the light steady state had an absorption spectrum at a wavelength of 591 nm.

<Example 4>
At -60 ° C, an n-hexane solution (concentration: about ^10-5 mol / L) of the compound (1-32) obtained in Production Example 3 was placed in a quartz cell, sealed, and then ultraviolet rays (wavelength 313 nm). ), And the absorption spectrum was measured using an absorptiometer (manufactured by JASCO Corporation, model "V-560"). The relationship between the absorbance at a wavelength of 548 nm and the irradiation time of ultraviolet rays is shown in FIG. 12A. Further, the absorption spectra before irradiation with ultraviolet rays and in the light steady state (PSS) are shown in FIG. 12B.
It was confirmed that when the compound (1-32) was irradiated with ultraviolet rays, it was colored. This means that, as shown below, the two thiophene rings of compound (1-32) form a ring (ring closure) by irradiation with ultraviolet rays.

As shown in FIG. 12B, the ring-opened body, that is, the compound (1-32) had an absorption spectrum at a wavelength of 283 nm, and the ring-closed body, that is, the compound in the light steady state had an absorption spectrum at a wavelength of 548 nm.

<Example 5>
At each temperature of 30 ° C., 35 ° C., 40 ° C., and 45 ° C., a toluene solution (concentration: about ^10-5 mol / L) of the compound (1-12) obtained in Production Example 1 was placed in a quartz cell. After sealing, it was colored by irradiating with ultraviolet rays (wavelength 313 nm) for about 30 seconds. Then, the cells were allowed to stand at each temperature, the change in color in the cell was confirmed over time, and the absorption spectrum was measured using an absorptiometer (manufactured by JASCO Corporation, model "V-560"). FIG. 13A shows the relationship between the _{degree of fading (A / A 0} ) and the leaving time in terms of absorbance at a wavelength of 541 nm. Further, FIG. 13B shows a graph in which the natural logarithm of the degree of fading (A / A ₀ ) is plotted on the vertical axis and the leaving time is plotted on the horizontal axis.
In addition, "A ₀ " is the absorbance at a wavelength of 541 nm at 0 seconds after irradiation with ultraviolet rays, and "A" is the absorbance at a wavelength of 541 nm at each standing time. Moreover, the measurement under each temperature was performed twice.

Then, from FIG. 13B, the thermal decomposition rate constant (k) at each temperature was obtained. FIG. 13C shows a graph in which the natural logarithm of the pyrolysis rate constant (k) is plotted on the vertical axis and the reciprocal of each temperature is plotted on the horizontal axis.
Then, the 10-hour half-life was determined as follows.
First, assuming that the thermal decomposition reaction is a primary reaction equation, the following equation (i) holds.
ln (C ₀ / C _t ) = kt ・・・ (i)
In formula (i), "C ₀ " is the initial concentration of the compound, "C _t " is the concentration of the compound after t hours, "k" is the thermal decomposition rate constant, and t is the reaction time.

The half-life is the time at which the concentration of the compound is reduced to half of the initial concentration, that is, the time at which C _t = C _0/2 . Therefore, the half-life and the thermal decomposition rate constant (k) have the relationship of the following equation (ii).
t _1/2 = ln2 / k ・・・ (ii)

On the other hand, since the temperature dependence of the rate constant is expressed by the Arrhenius equation, the following equation (iii) holds.
k = A ・ exp (−E _a / RT) ・・・ (iii)
In formula (iii), "A" is a frequency factor, "E _a " is activation energy, "R" is a gas constant (8.314 J / mol · K), and “T” is absolute temperature (K).

Seeking activation energy (E _a) of the compound from the slope of the straight line shown in FIG. 13C, was determined frequency factor (A) from the y-intercept. By substituting these into the formula (iii), the temperature (10-hour half-life temperature T) when _{t 1/2 = 10 h in the formula (ii) was obtained.} The results are shown in Table 1. Furthermore, activation energy (E _a) and the frequency factor and (A), Table 1 shows the half-life at 0 ° C..
Incidentally, ^{R 1} and ^{R 2} in Table 1 correspond to ^{R 1} and ^{R 2} in the general formula (1C).

<Example 6>
Using the compound (1-22) obtained in Production Example 2, absorption was carried out in the same manner as in Example 5 except that the temperatures at the time of ultraviolet irradiation and standing were changed to 15 ° C, 20 ° C, 25 ° C and 30 ° C. The spectrum was measured and the 10-hour half-life temperature and the like were determined. However, when determining the 10-hour half-life temperature and the like, the same graphs as in FIGS. 13A to 13C were created based on the absorbance at a wavelength of 553 nm. The results are shown in Table 1.

<Example 7>
Using the compound (1-32) obtained in Production Example 3, absorption was carried out in the same manner as in Example 5 except that the temperatures at the time of irradiation with ultraviolet rays and when left to stand were changed to 0 ° C., 5 ° C., 10 ° C. and 15 ° C. The spectrum was measured and the 10-hour half-life temperature and the like were determined. However, when determining the 10-hour half-life temperature and the like, the same graphs as in FIGS. 13A to 13C were created based on the absorbance at a wavelength of 548 nm. The results are shown in Table 1.

<Example 8>
Using the compound (1-11) obtained in Production Example 1, absorption was carried out in the same manner as in Example 5 except that the temperatures during ultraviolet irradiation and standing were changed to 0 ° C, 5 ° C, 10 ° C and 15 ° C. The spectrum was measured and the 10-hour half-life temperature and the like were determined. However, when determining the 10-hour half-life temperature and the like, the same graphs as in FIGS. 13A to 13C were created based on the absorbance at a wavelength of 581 nm. The results are shown in Table 1.

<Example 9>
Using the compound (1-41) obtained in Production Example 4, the same procedure as in Example 5 except that the temperatures at the time of ultraviolet irradiation and standing were changed to −5 ° C., 0 ° C., 5 ° C., and 10 ° C. The absorption spectrum was measured to determine the 10-hour half-life temperature and the like. However, when determining the 10-hour half-life temperature and the like, the same graphs as in FIGS. 13A to 13C were created based on the absorbance at a wavelength of 584 nm. The results are shown in Table 1.

<Example 10>
Example 5 and Example 5 except that the compound (1-21) obtained in Production Example 2 was used and the temperatures at the time of ultraviolet irradiation and standing were changed to −20 ° C., −15 ° C., −10 ° C., and −5 ° C. The absorption spectrum was measured in the same manner, and the 10-hour half-life temperature and the like were determined. However, when determining the 10-hour half-life temperature and the like, the same graphs as in FIGS. 13A to 13C were created based on the absorbance at a wavelength of 581 nm. The results are shown in Table 1.

<Example 11>
Using the compound (1-31) obtained in Production Example 3, absorption was carried out in the same manner as in Example 5 except that the temperatures during ultraviolet irradiation and standing were changed to −50 ° C., −45 ° C., and −40 ° C. The spectrum was measured and the 10-hour half-life temperature and the like were determined. However, when determining the 10-hour half-life temperature and the like, the same graphs as in FIGS. 13A to 13C were created based on the absorbance at a wavelength of 591 nm. The results are shown in Table 1.

<Comparative example 1>
Using the compound (1-5) obtained in Production Example 5, absorption was carried out in the same manner as in Example 5 except that the temperatures at the time of ultraviolet irradiation and standing were changed to 60 ° C, 70 ° C, 80 ° C and 90 ° C. The spectrum was measured and the 10-hour half-life temperature and the like were determined. However, when determining the 10-hour half-life temperature and the like, the same graphs as in FIGS. 13A to 13C were created based on the absorbance at a wavelength of 550 nm. The results are shown in Table 1.

<Comparative example 2>
Using the compound (1-6) obtained in Production Example 6, the absorption spectrum was measured in the same manner as in Example 5 except that the temperatures at the time of ultraviolet irradiation and standing were changed to 60 ° C, 70 ° C, and 80 ° C. Then, the 10-hour half-life temperature and the like were determined. However, when determining the 10-hour half-life temperature and the like, the same graphs as in FIGS. 13A to 13C were created based on the absorbance at a wavelength of 554 nm. The results are shown in Table 1.

As shown in Table 1, the compounds used in Examples 6 to 11 had a 10-hour half-life temperature of 22 ° C. or lower.
On the other hand, the compounds used in Comparative Examples 1 and 2 had a high 10-hour half-life temperature of 60 ° C. or higher.
Therefore, the diarylethene compound of the present invention is suitable for temperature control in a low temperature environment.

<Example 12>
At -60 ° C, an n-hexane solution (concentration: about ^10-5 mol / L) of the compound (1-11) obtained in Production Example 1 was placed in a quartz cell, sealed, and then ultraviolet rays (wavelength 313 nm). ) Was irradiated for 120 seconds to color it, and the absorption spectrum was measured using an absorptiometer (manufactured by JASCO Corporation, model "V-560"). The absorption spectrum before irradiation with ultraviolet rays is shown in FIG. 14A, and the absorption spectrum in the light steady state (PSS) is shown in FIG. 14B.
Then, after leaving it at 40 ° C. until discoloration, the absorption spectrum was measured at −60 ° C. The results are shown in FIG. 14C.
Then, ultraviolet rays (wavelength 313 nm) were irradiated for 480 seconds, and the absorption spectrum was measured. The results are shown in FIG. 14D.

As shown in FIG. 14B, the light steady state (PSS) compound, the ring closure, had an absorption spectrum at a wavelength of 581 nm.
On the other hand, in FIG. 14D, the absorption spectrum could not be confirmed in the vicinity of the wavelength of 581 nm. That is, it was shown that the compound (1-11) did not recolor even if it was irradiated with ultraviolet rays again after fading.

<Example 13>
At -60 ° C, an n-hexane solution (concentration: about ^10-5 mol / L) of the compound (1-12) obtained in Production Example 1 was placed in a quartz cell, sealed, and then ultraviolet rays (wavelength 313 nm). ) Was irradiated for 300 seconds to color it, and the absorption spectrum was measured using an absorptiometer (manufactured by JASCO Corporation, model "V-560"). The absorption spectrum before irradiation with ultraviolet rays is shown in FIG. 15A, and the absorption spectrum in the light steady state (PSS) is shown in FIG. 15B.
Then, after leaving it at 55 ° C. until discoloration, the absorption spectrum was measured at −60 ° C. The results are shown in FIG. 15C.
Then, ultraviolet rays (wavelength 313 nm) were irradiated for 600 seconds, and the absorption spectrum was measured. The results are shown in FIG. 15D.

As shown in FIG. 15B, the light steady state (PSS) compound, the ring closure, had an absorption spectrum at a wavelength of 541 nm.
On the other hand, in FIG. 15D, the absorption spectrum could not be confirmed in the vicinity of the wavelength of 541 nm. That is, it was shown that the compound (1-12) did not recolor even if it was irradiated with ultraviolet rays again after fading.

<Example 14>
At -80 ° C, an n-hexane solution (concentration: about ^10-5 mol / L) of the compound (1-31) obtained in Production Example 3 was placed in a quartz cell, sealed, and then ultraviolet rays (wavelength 313 nm). ) Was irradiated for 180 seconds for coloring, and the absorption spectrum was measured using an absorptiometer (manufactured by JASCO Corporation, model "V-560"). The absorption spectrum before irradiation with ultraviolet rays is shown in FIG. 16A, and the absorption spectrum in the light steady state (PSS) is shown in FIG. 16B.
Then, after leaving it at 0 ° C. until discoloration, the absorption spectrum was measured at −80 ° C. The results are shown in FIG. 16C.
Then, ultraviolet rays (wavelength 313 nm) were irradiated for 600 seconds, and the absorption spectrum was measured. The results are shown in FIG. 16D.

As shown in FIG. 16B, the light steady state (PSS) compound, the ring closure, had an absorption spectrum at a wavelength of 591 nm.
On the other hand, in FIG. 16D, the absorption spectrum could not be confirmed in the vicinity of the wavelength of 591 nm. That is, it was shown that the compound (1-31) did not recolor even if it was irradiated with ultraviolet rays again after fading.

<Example 15>
At -60 ° C, an n-hexane solution (concentration: about ^10-5 mol / L) of the compound (1-32) obtained in Production Example 3 was placed in a quartz cell, sealed, and then ultraviolet rays (wavelength 313 nm). ) Was irradiated for 360 seconds for coloring, and the absorption spectrum was measured using an absorptiometer (manufactured by JASCO Corporation, model "V-560"). The absorption spectrum before irradiation with ultraviolet rays is shown in FIG. 17A, and the absorption spectrum in the light steady state (PSS) is shown in FIG. 17B.
Then, after leaving it at 40 ° C. until discoloration, the absorption spectrum was measured at −60 ° C. The results are shown in FIG. 17C.
Then, ultraviolet rays (wavelength 313 nm) were irradiated for 780 seconds, and the absorption spectrum was measured. The results are shown in FIG. 17D.

As shown in FIG. 17B, the light steady state (PSS) compound, the ring closure, had an absorption spectrum at a wavelength of 548 nm.
On the other hand, in FIG. 17D, the absorption spectrum could not be confirmed in the vicinity of the wavelength of 548 nm. That is, it was shown that the compound (1-32) did not recolor even if it was irradiated with ultraviolet rays again after fading.

The diarylethene compound, temperature indicator, temperature display device and package of the present invention are suitable for temperature control in a low temperature environment.

20, 20A, 20B, 20C, 20D ... Temperature display device, 21 ... Base material, 22 ... Reference part, 23, 23D ... Temperature indicator, 24 ... Time information display part, 31 ... Adhesive layer, 32 ... Peeling layer, 33 ... Protective layer, 34 ... transparent substrate, 40 ... temperature history control label, 60 ... package, 61 ... packaging material.

Claims

A diarylethene compound represented by the following general formula (1).

(In the formula (1), the ring A shows a 5-membered ring structure or a 6-membered ring structure.
X is a sulfur atom (S), NR 7 or an oxygen atom (O), and R 7 is a hydrogen atom (H) or an alkyl group.
Y 1 and Y 2 are independently carbon atoms (C) or nitrogen atoms (N), respectively.
R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, or SiR 8 3, in each of the three R 8 independently an alkyl group or an aromatic group, one of R 1 and R 2 are alkyl a group or a cycloalkyl group, the other is SiR 8 3,
When Y 1 is a carbon atom (C), R 3 is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R 4 to form a ring structure. When Y 1 is a nitrogen atom (N), it is an electron pair.
When Y 2 is a carbon atom (C), R 5 is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R 6 to form a ring structure. When Y 2 is a nitrogen atom (N), it is an electron pair.
R 4 is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R 3 to form a ring structure.
R 6 is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R 5 to form a ring structure. )
The diarylethene compound according to claim 1, which is represented by the following general formula (1A).

(In the formula (1A), each of the six Zs is independently a hydrogen atom (H) or a fluorine atom (F).
R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, or SiR 8 3, in each of the three R 8 independently an alkyl group or an aromatic group, one of R 1 and R 2 are alkyl a group or a cycloalkyl group, the other is SiR 8 3,
R 3 is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R 4 to form a ring structure.
R 5 is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R 6 to form a ring structure.
R 4 is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R 3 to form a ring structure.
R 6 is bonded to each other with a hydrogen atom (H), a phenyl group, an alkyl group, an alkoxy group or a cyano group, or R 5 to form a ring structure. )
Wherein R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or SiR 8 3 3 to 7 carbon atoms, in each of the three R 8 independently, 1 to 6 carbon atoms an alkyl group or an aromatic group, one of R 1 and R 2 is a cycloalkyl group of an alkyl group or a C 3-7 1 to 10 carbon atoms, and the other is SiR 8 3, claim 1 Or the diarylethene compound according to 2.
A temperature indicator comprising the diarylethene compound according to any one of claims 1 to 3.
A temperature display device having the temperature indicator according to claim 4.
The temperature display device according to claim 5, which has a base material and has the temperature indicator formed on one surface of the base material.
The temperature display device according to claim 6, further comprising a time information display unit, wherein the temperature indicator and the time information display unit are formed side by side in a plane direction on the base material in a plan view.
The temperature display device according to claim 6 or 7, wherein an adhesive layer and a release layer are formed on the other surface of the base material in this order.
The temperature display device according to any one of claims 5 to 8, wherein a protective layer is formed on the temperature indicator.
The temperature display device according to claim 5, wherein the temperature indicator has adhesiveness on at least one surface and a peeling layer is formed on the one surface.
A package having the temperature indicator according to claim 4.