JP2003064353A - Photochromic material and color dosimeter using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photochromic material for a dosimeter using a photochromic compound usable without being influenced with the environment, having good preservation stability and capable of detecting even a low dose. SOLUTION: This photochromic material is obtained by including at least a luminous element emitting light by exposure to radiations and a diarylethene compound represented by the following general formula (I). The photochromic material is composed so as to make an emission spectrum of the luminous element overlap with an absorption spectrum of a ring opening substance or a cyclized substance of the diarylethene compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic material suitably used for radiation dose measurement, and a color dosimeter using the photochromic material, which can easily measure radiation dose.

[0002]

BACKGROUND ART Irradiation treatments such as X-rays and gamma rays have been conventionally performed for the purpose of sterilizing medical devices, but in recent years, graft-versus-host disease (GVHD) due to blood transfusion.
It is also applied to blood for transfusion to prevent the onset of disease.

In general, in order to check whether or not a required amount of radiation has been applied to an object to be irradiated, an indicator containing a substance that is irreversibly discolored by the radiation is mixed between the objects to be irradiated, and after irradiation, the object is taken out. A method is used to confirm the discoloration.

For example, as an indicator of radiation sterilization of medical devices, one using a redox dye such as a leuco dye and polyvinyl chloride has been put into practical use. This indicator changes color when the radiation dose is 5000 Gy or more. However, the radiation dose to the blood for transfusion is usually 15
Since it is about 50 Gy, the presence or absence of irradiation cannot be detected.

In Japanese Patent Laid-Open No. 2-201440, there is 15
As an indicator that changes color upon irradiation with radiation of up to 50 Gy, a radiation color changing composition in which an alkali halide such as potassium chloride is doped with a metal such as calcium is disclosed. However, it is generally known that alkali metal halides are vulnerable to moisture, which is disadvantageous for use in the medical field where they often come into contact with moisture. Further, there is a drawback that the discolored portion is easily discolored by ambient light such as room light.

Further, Japanese Patent Application Laid-Open No. 2000-65932 discloses a dosimeter composed of an organic compound which exhibits an electron accepting property by radiation and an electron-donating organic compound having a color developability. However, the electron-donating organic substance disclosed is
It is generally known that it is easily affected by moisture and impurities in the air, and a dosimeter using this has a drawback of low storage stability. In addition, such indicators are often erasable and cannot be reused.

[0007]

From such a background, it has been proposed to use a photochromic compound which exhibits radiation sensitivity and is easy to handle in a dosimeter.

For example, Japanese Patent Application Laid-Open No. 2-216493 discloses a radiation-sensitive display sheet comprising a laminate having a layer containing a scintillator which emits fluorescence and a photochromic polymer layer which changes color in response to the fluorescence emitted by the scintillator. It is disclosed. However, the two described in this document
Maleic anhydride-based photochromic compounds such as 4,5-trimethylthienylmaleic anhydride are not sufficiently sensitive to radiation, and the maleic anhydride moiety is hydrolyzed by water, resulting in poor storage stability. was there.

Further, Japanese Laid-Open Patent Publication No. 11-258348 discloses a dosimeter using a heat irreversible photochromic compound. According to this technique, by using a photochromic compound that is thermally stable and reversible,
Although it is possible to accurately measure even a relatively low dose, it is necessary to increase the thickness considerably in order to measure a low dose of about 15 to 50 Gy which is a general irradiation dose for blood for transfusion.

The present invention provides a dosimeter using a photochromic compound and a material thereof, which can be used without being influenced by the environment, has good storage stability, and can detect even a low dose, and a material thereof. The purpose is to provide.

[0011]

Means for Solving the Problems As a result of intensive studies by the present inventors, by using a photochromic compound having a specific skeleton and an inorganic phosphor in combination, the irradiation dose is displayed as a color change by irradiation with radiation. The present invention has been accomplished by finding that it can be suitably used as an indicator and can solve the above problems.

That is, the gist of the present invention is to include at least a light-emitting body which emits light upon irradiation with radiation and a diarylethene compound represented by the following general formula (I), and the emission spectrum of the light-emitting body and the diarylethene compound. The photochromic material is characterized in that the absorption spectrum of the ring-opened material or the absorption spectrum of the ring-closed material overlaps.

[0013]

[Chemical 11]

(In the above general formula (I), the group R ₁ and the group R ₂ each independently represent an alkyl group, a cycloalkyl group or an alkoxy group. The group X ₁ , the group X ₂ , the group Y ₁ and the group Y ₂ are each independently

[Chemical 12] Represents either Group R₃Is a hydrogen atom, substituted
Optionally substituted alkyl group, optionally substituted aryl group
Alternatively, it represents an optionally substituted cycloalkyl group.
Group R_FourIs a hydrogen atom or an optionally substituted alkyl group
Alternatively, it represents an optionally substituted cycloalkyl group.
Ring D is a group X₁, Y₁And the two carbons that bind them
An optionally substituted 5-membered ring formed with the atom
Or a 6-membered aromatic ring, wherein ring E is a group X ₂, Y₂
And with two carbon atoms bonded to them
And optionally substituted 5- or 6-membered aromatic ring
Represents Ring D and Ring E may be further substituted.
A 5-membered or 6-membered aromatic ring may be condensed
Yes. )

Another subject matter of the present invention resides in a color dosimeter characterized by including the photochromic material.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. (1) Structure of Photochromic Material First, at least the photochromic material of the present invention comprises:
It is characterized by having a light-emitting body that emits light upon irradiation with radiation and a diarylethene compound (photochromic compound).

(1-1) Diarylethene Compound The diarylethene compound in the present invention reversibly produces two types of isomers having different optical properties upon irradiation with light or radiation (that is, these isomers are mutually bound to each other). It is reversibly converted into), a kind of so-called photochromic compounds.

The diarylethene compound used in the present invention is specifically a compound represented by the following general formula (I).

[0019]

[Chemical 13]

In the above general formula (I), the groups R ₁ and R ₂ each independently represent an alkyl group, a cycloalkyl group or an alkoxy group.

The group X ₁ , the group X ₂ , the group Y ₁ and the group Y ₂ are each independently,

[Chemical 14] Represents either

The radical R ₃ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted cycloalkyl group.

The group R ₄ represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted cycloalkyl group.

In the above general formula (I), ring D
Represents an optionally substituted 5-membered or 6-membered aromatic ring formed together with the group X ₁ , the group Y ₁ and the two carbon atoms bonded thereto. The ring D may be further condensed with an optionally substituted 5-membered or 6-membered aromatic ring.

Further, ring E represents an optionally substituted 5-membered or 6-membered aromatic ring formed together with group X ₂ , group Y ₂ and two carbon atoms bonded to them. The ring E may be further condensed with an optionally substituted 5-membered or 6-membered aromatic ring.

There are no particular restrictions on the substituents that ring D and ring E may have, but the groups R ₁₃ , R _{16 to} R ₁₈ , and R _{25 to} R ₂₇ are preferred.
And R _{29 includes} each group described later.

When an aromatic ring is further condensed with ring D or ring E, the condensed ring is further condensed with an alkenyl group, an alkoxy group, an alkoxyalkoxy group, an allyloxy group, an aryl group, an aryloxy group. It may have a substituent such as a heteroaryl group, a halogen group, a hydroxy group, a carboxyl group, a carbonyl group, a cyano group and a nitro group.

Specific examples of the compound represented by the above general formula (I) include the following general formula (I-1) or (I-2).
Compounds represented by are preferred.

[0029]

[Chemical 15]

In the above general formula (I-1), the groups R ₁₁ and R ₁₂ each independently represent an alkyl group, a cycloalkyl group or an alkoxy group.

The group X ₁₁ and the group X ₁₂ are each independently

[Chemical 16] Which means either

[Chemical 17] Is preferred.

Furthermore, the group Y ₁₁ and the group Y ₁₂ are each independently

[Chemical 18] Represents either

In each of the above formulas, the group R ₁₃ is
Represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted cycloalkyl group, among which a hydrogen atom, an optionally substituted alkyl group or a substituted An aryl group which may be present is preferred. The group R ₁₆ represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted cycloalkyl group.

The groups R ₁₇ and R ₁₈ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or a substituted group. Represents a cycloalkyl group.

When the groups R ₁₇ and R ₁₈ are an alkyl group, an aryl group, a heteroaryl group or a cycloalkyl group, the substituent which these groups may have is an alkenyl group, an alkoxy group, An alkoxyalkoxy group,
Examples thereof include an allyloxy group, an aryl group, a heteroaryl group, an aryloxy group, a halogen group, a hydroxy group, a carboxyl group, a carbonyl group, a cyano group, and a nitro group.

The group Y ₁₁ and / or the group Y ₁₂ is

[Chemical 19] In the case of, the group R ₁₇ and / or the group R ₁₈ may combine with the group R ₁₆ to form a 5-membered or 6-membered aromatic ring.

The substituent which the aromatic ring may have is, for example, an alkenyl group, an alkoxy group, an alkoxyalkoxy group, an allyloxy group, an aryl group, an aryloxy group, a heteroaryl group, a halogen group, a hydroxy group or a carboxyl group. Group, carbonyl group, cyano group, nitro group and the like.

[0038]

[Chemical 20]

In the above general formula (I-2), the groups R ₂₁ and R ₂₂ each independently represent an alkyl group, a cycloalkyl group or an alkoxy group.

Further, the group Y ₂₁ and the group Y ₂₂ are each independently

[Chemical 21] Represents either

Further, the group X ₂₁ and the group X ₂₂ are each independently

[Chemical formula 22] Represents either

The groups R ₂₅ and R ₂₆ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or a substituted group. Represents an optionally substituted cycloalkyl group. Here, the group X ₂₁ and / or the group X ₂₂ is

[Chemical formula 23] In the case of, the group R ₂₅ and / or the group R ₂₆ may be bonded to the group R ₂₉ to form a 5-membered or 6-membered aromatic ring.

In each of the above formulas, the group R ₂₇ is
Represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted cycloalkyl group, among which a hydrogen atom, an optionally substituted alkyl group or a substituted An aryl group which may be present is preferred. The group R ₂₉ represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted cycloalkyl group.

In the above general formula (I-2), the group R ₂₅ ,
When R ₂₆ is an alkyl group, an aryl group, a heteroaryl group or a cycloalkyl group, the substituent which these groups may have is an alkenyl group, an alkoxy group, an alkoxyalkoxy group, an allyloxy group or an aryl group. Group, heteroaryl group, aryloxy group, halogen group, hydroxy group, carboxyl group, carbonyl group, cyano group, nitro group and the like.

Further, group X _21, X ₂₂ is a carbon atom having a substituent group R _29, the substituents R ₂₉ and group R ₂₅ or a group R ₂₆
In the case where they combine to form a 5- or 6-membered aromatic ring, the aromatic ring is an alkenyl group, an alkoxy group, an alkoxyalkoxy group, an allyloxy group, an aryl group, a heteroaryl group, an aryloxy group, a halogen. It may have a substituent such as a group, a hydroxy group, a carboxyl group, a carbonyl group, a cyano group and a nitro group.

When the groups R ₁₃ , R ₁₆ , R ₂₇ and R _{29 in the} above general formulas (I-1) and (I-2) are alkyl groups, aryl groups or cycloalkyl groups, these groups have As the substituents that may be added, an alkenyl group, an alkoxy group, an alkoxyalkoxy group, an allyloxy group,
Examples thereof include an aryl group, a heteroaryl group, an aryloxy group, a halogen group, a hydroxy group, a carboxyl group, a carbonyl group, a cyano group and a nitro group.

Specific examples of ring D and ring E in the general formula (I) are shown below.

[Chemical formula 24]

[0048]

[Chemical 25]

(In each of the above formulas, the group R ₁₃ has the same meaning as in formula (I-1), and the group R ₂₇ has the same meaning as in formula (I-2).)

Among these, in the above general formula (I-1), a heterocyclic ring containing the group X ₁₁ and the group Y ₁₁ , and the group X ₁₂
The following substituents are preferable as the heterocyclic ring containing and Y ₁₂ .

[Chemical formula 26]

In each of the above formulas, fused to a heterocycle
The benzene ring is₁₇Or group R ₁₈Is the base R₁₆Combine with
It is a ring formed by

Further, in the above general formula (I-2), a heterocyclic ring containing the group X ₂₁ and the group Y ₂₁ , as well as the group X ₂₂ and the group Y _22.
As the heterocycle containing, the following substituents are preferable.

[0053]

[Chemical 27]

In each of the above formulas, fused to a heterocycle
The benzene ring is_{twenty five}Or group R ₂₆Is the base R₂₉Combine with
It is a ring formed by

Specific examples of the compound represented by the general formula (I-1) are shown below, but the invention is not limited thereto.

[Chemical 28]

[0056]

[Chemical 29]

[0057]

[Chemical 30]

[0058]

[Chemical 31]

[0059]

[Chemical 32]

[0060]

[Chemical 33]

Specific examples of the compound represented by the general formula (I-2) are shown below.

[Chemical 34]

[0062]

[Chemical 35]

[0063]

[Chemical 36]

[0064]

[Chemical 37]

[0065]

[Chemical 38]

[0066]

[Chemical Formula 39]

[0067]

[Chemical 40]

[0068]

[Chemical 41]

[0069]

[Chemical 42]

[0070]

[Chemical 43]

[0071]

[Chemical 44]

[0072]

[Chemical formula 45]

[0073]

[Chemical formula 46]

The various photochromic compounds listed above can be appropriately synthesized by using known methods. For example, it can be synthesized by a method appropriately selected from the description in JP-A-9-241625 and the like.

Regarding the diarylethene compound in the photochromic material of the present invention, one selected from the compounds represented by the general formula (I) may be used alone, or two or more kinds may be used in combination. In the latter case, for example, the compound group represented by the general formula (I-1), the compound group represented by the general formula (I-2),
Plural kinds of compounds may be selected from any one of the other compound groups, and one kind or more may be selected from two or more groups of these compound groups and used. Further, one or more compounds selected from the group of compounds represented by the general formula (I) may be used in combination with any other one or more compounds.

The diarylethene compound used in the present invention preferably exhibits thermal irreversibility. In the present invention, “heat irreversible” means that the half-life of the ring-closure product in an environment of 30 ° C. is 10 days or more. If the diarylethene compound does not exhibit heat irreversibility, the ring-closed compound may easily undergo an isomerization reaction at room temperature to be converted into the ring-opened compound, and the discolored state caused by irradiation with radiation may not be maintained stably. Therefore, when the photochromic material of the present invention is used in a color dosimeter, the radiation dose cannot be accurately measured,
There is a risk of problems.

Further, in order to avoid coloring due to ambient light such as room light, it is preferable that the quantum yield of the ring-opening reaction is 10 ⁻³ or less. It is more preferably 10 ^-4 or less, particularly preferably 10 ^-5 or less.

(1-2) Light-Emitting Body The light-emitting body used in the present invention may be of any type as long as it absorbs radiation and emits light. The type of radiation absorbed by the luminescent material used in the present invention is not particularly limited, and includes ultraviolet rays, X-rays, γ rays, α rays, β
There are various types such as rays, electron rays, and neutron rays. Among them, in view of the main application of the color dosimeter in which the photochromic material of the present invention is used, the luminescent material used in the present invention absorbs radiation in the wavelength band of 10 ^{−5 to} 10 nm and emits light. Preferably there is.

With a conventional color dosimeter using a photochromic compound, it is difficult to measure the dose of radiation having a wavelength shorter than that of ultraviolet rays, particularly radiation having strong penetrating power such as γ rays, X rays, and neutron rays. However, in the photochromic material of the present invention, in general, it is possible to efficiently trap radiation by using a light-emitting body containing an atom having a larger atomic weight than the diarylethene compound, and it is also possible to reduce the radiation from the light-emitting body in the excited state. The isomerization reaction of the diarylethene compound is promoted by the energy transfer or the electron transfer, and the sensitivity of the photochromic material to radiation is improved (sensitization effect).

The kind of light emitted by the luminescent material used in the present invention is not particularly limited, but it is necessary to have an emission spectrum which overlaps with the absorption spectrum of the ring-opened or ring-closed diarylethene compound. . Figure 3
In addition, the overlap between the emission spectrum of the luminescent material and the absorption spectrum of the diarylethene compound is schematically shown.

Of these, a phosphor (ultraviolet emitting phosphor) having an emission peak in the ultraviolet wavelength region, that is, having a level of excitation energy higher than that of the diarylethene compound is preferable. Especially 10 to 400 nm
It is preferable that it emits light in the ultraviolet wavelength band. Further, the light emitting body used in the present invention is preferably an inorganic compound.

Further, in view of the purpose of the photochromic material of the present invention, it is preferable that the luminescent material used in the present invention has a high sensitivity to radiation and a sufficiently large amount of light emission. Among them, since an atom having a larger atomic number (heavy atom) is generally more sensitive to radiation, a light-emitting body containing such a heavy atom, which emits light upon irradiation with radiation, can be preferably used. Specifically, a light-emitting body containing an element having an atomic number of 19 or more is preferable, and a light-emitting body containing an element having an atomic number of 37 or more is more preferable.

Specific examples of the luminescent material used in the present invention
Is 3Ca₃(PO_Four)₂・ Ca (F, Cl)₂: Sb³⁺,
3Ca₃(PO_Four)₂・ Ca (F, Cl)₂: Sb³⁺, Mn
²⁺, Sr_Ten(PO_Four)₆Cl₂: Eu²⁺, (Sr, Ca)
_Ten(PO_Four)₆Cl₂: Eu²⁺, (Sr, Ca)_Ten(P
O_Four)₆Cl₂・ NB₂O₃: Eu²⁺, (Ba, Ca, M
g)_{1 0}(PO_Four)₆Cl₂: Eu²⁺Halophosphate fluorescence of etc.
Body, Sr₂P₂O₇: Sn²⁺, Ba₂P₂O₇: Ti⁴⁺, (S
r, Mg)₃(PO_Four)₂: Sn²⁺, Ca₃(PO_Four)₂: T
l⁺, (Ca, Zn)₃(PO_Four)₂: Tl⁺, Sr₂P
₂O₇: Eu²⁺, SrMgP ₂O₇: Eu²⁺, Sr₃(P
O_Four)₂: Eu²⁺2SrO 0.84P₂O_Five・ 0.16
B₂O₃: Eu²⁺, LaPO_Four: Ce³⁺, Tb³⁺, La₂O
₃・ 0.2SiO₂・ 0.9P₂O_Five: Ce³⁺, Tb³⁺, Z
n₃(PO_Four)₂: Mn²⁺, (Sr, Mg)₃(PO_Four)₂:
Cu⁺Phosphate phosphors such as Zn₂SiO_Four: Mn²⁺, C
aSiO₃: Pb ²⁺, Mn²⁺, (Ba, Sr, Mg)₃S
i₂O₇: Pb²⁺, (Ba, Mg, Zn)₃Si₂O₇: P
b²⁺, BaSi₂O_Five: Pb²⁺, Sr₂Si₃O₈・ 2Sr
Cl₂: Eu ²⁺, Ba₃MgSi₂O₈: Eu²⁺, (Sr,
Ba) Al₂Si₂O₈: Eu²⁺, Y₂SiO_Five: Ce³⁺，
Tb³⁺Silicate phosphors such as CaWO_Four, CaWO_Four: P
b²⁺, MgWO_FourTungstate phosphor such as LiA
10₂: Fe³⁺, BaAl₈O_{1 3}: Eu²⁺, BaMgAl
_TenO₁₇: Eu²⁺, BaMgAl_TenO₁₇: Eu²⁺, M
n^{2 +}, Sr_FourAl₁₄O_{twenty five}: Eu²⁺, SrMgAl
_TenO₁₇: Eu²⁺, CeMgAl₁₁O ₁₉: Tb³⁺, CeM
gAl₁₁O₁₉, (Ce, Gd) (Mg, Ba) Al₁₁O
₁₉, Y₂O₃・ Al₂O₃: Tb³⁺, Y₃Al_FiveO₁₂: Ce³⁺
Aluminate phosphor such as Y₂O₃: Eu³⁺, YV
O_Four: Eu³⁺, Y (P, V) O_Four: Eu³⁺, YVO_Four: D
y³⁺, Cd₂B₂O_Five: Mn²⁺, SrB_FourO₇: Eu²⁺, S
rB_FourO₇F: Eu²⁺, GdMgB_FiveO_Ten: Ce³⁺, Tb
³⁺, 6MgO · As₂O_Five: Mn⁴⁺, 3.5MgO.0.
5MgF₂・ GeO₂: Mn⁴⁺, MgGa₂O_Four: Mn²⁺,
ZnS: Ag, (Zn, Cd) S: Ag, (Zn, C
d) S: Cu, Al, ZnS: Ag, ZnS: Cu, A
1, ZnS: Au, Cu, Al, CsI: Na, Cs
I: Tl, BaSO_Four: Eu²⁺, Gd₂O₂S: Tb³⁺,
La₂O₂S: Tb³⁺, Y₂O₂S: Tb^{3 +}, Y₂O₂S: E
u³⁺, LaOBr: Tb³⁺, LaOBr: Tm³⁺, Ba
FCl: Eu²⁺, BaFBr: Eu²⁺, HfP₂O₇, L
iF, Li₂B_FourO₇: Mn²⁺, CaF₂: Mn²⁺, CaS
O_Four: Mn²⁺, CaSO_Four: Dy³⁺, Mg₂SiO_Four: Tb
³⁺, CaF₂: Eu²⁺, LiI: Eu²⁺, TlCl: B
e, I, CsF, BaF₂, Bi_FourGe₃O₁₂, Kl: T
l, CaWO_Four, CdWO_FourUsed as a practical phosphor, etc.
There are various luminescent materials that have been used. In addition, this
Properly synthesize these luminescent materials using known methods.
Is possible. Many of these phosphors are mentioned above.
Elements with atomic number 19 or more and atomic number 37 or more
Since it contains these elements, it has high sensitivity to radiation.
In addition, the amount of light emitted is sufficiently large.

Among these, especially Ca₃(PO_Four)₂:
Tl⁺, (Ca, Zn)₃(PO_Four)₂: Tl⁺, SrMg
P₂O₇: Eu²⁺, SrB_FourO₇F: Eu²⁺, (Ba, S
r, Mg)₃Si₂O₇: Pb²⁺, (Ba, Mg, Zn)₃
Si₂O₇: Pb²⁺, BaSi₂O_Five: Pb²⁺, (Sr, B
a) Al₂Si₂O₈: Eu²⁺, CeMgAl₁₁O₁₉,
(Ce, Gd) (Mg, Ba) Al₁₁O₁₉, SrB
_FourO₇: Eu²⁺, CsF, BaF ₂, BaSO_Four: Eu²⁺,
BaFCl: Eu²⁺, BaFBr: Eu²⁺, HfP
₂O₇, UV light emitting phosphors such as LiF are preferred. In addition,
The luminescent materials typified by the above-mentioned various phosphors should not be used alone.
May be used in combination.

The fluorescent substance used in the present invention is preferably one having a high luminous efficiency with respect to irradiation light. That is, for example, when the photochromic material of the present invention is used in a color dosimeter described later, it is preferable that the photochromic material has high luminous efficiency with respect to stimulation by light having a wavelength to be detected. Further, the higher the density of the phosphor, the higher the ability to make the light to be detected thin, which is preferable.

(1-3) Combination of Diarylethene Compound and Light-Emitting Body In the photochromic material of the present invention, a part or all of the emission spectrum of the light-emitting body overlaps with the absorption spectrum of the ring-opened or closed ring of the diarylethene compound. In addition, it is characterized in that the above-mentioned diarylethene compound and a light emitting body are selected and combined. With this configuration,
When the photochromic material of the present invention is used for a color dosimeter, the electrons of the luminescent material are brought into an excited state by irradiation with radiation, and energy or electrons are transferred from the excited state to the excited state of the diarylethene compound, thereby producing a diarylethene compound. Since the isomerization reaction occurs and the color is changed, the irradiated radiation can be efficiently detected, and the dose can be measured with high sensitivity.

For example, in order to efficiently cause the isomerization reaction of the diarylethene compound from the ring-opened form to the ring-closed form,
The UV wavelength band from 10 to 400 nm is preferred. Therefore, it is preferable that the luminescent material used in combination with this diarylethene compound has an luminescent wavelength band mainly in this ultraviolet wavelength band (that is, the ultraviolet luminescent phosphors listed above).

In particular, it is preferable that the emission spectrum of the luminescent material and the absorption band including the maximum absorption wavelength of the ring-opened or ring-closed material of the diarylethene compound overlap as much as possible.

The emission spectrum of the luminescent material preferably overlaps with the absorption spectrum of the ring-opened product of the diarylethene compound. The reason is that the ring-opened product usually has absorption in the radiation wavelength region, the ring-closing reaction often has a higher quantum yield than the ring-opening reaction, and Since many compounds are darker in color, it is easier to detect exposure by forming a ring-closed body.

The light-emitting body used in the photochromic material of the present invention may be one kind or a combination of two or more kinds. In particular, when the absorption spectrum peak of the diarylethene compound is sharp, strong emission in a specific wavelength region can be obtained by using an illuminant having an emission spectrum close to the peak wavelength alone, and radiation detection The sensitivity can be increased. Further, when the absorption spectrum peak of the diarylethene compound is broad, by using two or more light-emitting substances that emit light in different wavelength regions in combination, light emission can be obtained in a wide wavelength region and radiation can be efficiently emitted. It becomes possible to detect.

(2) Aspects of Photochromic Material and Color Dosimeter The photochromic material of the present invention is not particularly limited as long as it is an aspect in which the above-mentioned diarylethene compound and the luminous body interact with each other. It is preferable to form a composition containing a phosphor and a luminescent material, or a laminated body including a layer containing the above-mentioned diarylethene compound and a layer containing a luminescent material. Here, the former composition broadly refers to solids and liquids that are contained in a state in which the above-mentioned diarylethene compound and the luminescent material are mixed. Specifically, a solution / dispersion solution of a diarylethene compound in which the above diarylethene compound is dissolved or dispersed and a light emitter is dispersed therein, or a resin composition containing the above diarylethene compound and a light emitter,
Alternatively, a molded body or the like formed by mixing a solid diarylethene compound and a light emitting body may be used.

The photochromic material of the present invention configured as each of the above aspects can be used as a color dosimeter by a method according to the aspect. Hereinafter, aspects of the photochromic material of the present invention and a method of using the photochromic material as a color dosimeter will be described in detail for each aspect.

(2-1) Solution or Dispersion The solution / dispersion of the diarylethene compound, which is one embodiment of the photochromic material of the present invention, dissolves or disperses the above-mentioned diarylethene compound in a solvent or a dispersion medium, and emits the above-mentioned light. It can be prepared by dispersing the body in the above solvent or dispersion medium.

As the solvent (dispersion medium), the above-mentioned diarylethene compound is preferably dissolved or dispersed, and when used as a color dosimeter, detection of the discolored state of the diarylethene compound due to radiation exposure is performed. There is no particular limitation as long as it does not interfere. In particular,
Examples of the organic solvent include aromatic solvents such as benzene and toluene, aliphatic solvents such as hexane, ether solvents such as tetrahydrofuran (THF), chlorine solvents such as chloroform, and the like. Of these, aromatic solvents such as benzene and toluene are preferable.

A solution / dispersion solution of the diarylethene compound is prepared by dissolving or dispersing the above-mentioned diarylethene compound in the above-mentioned solvent (dispersion medium) and dispersing the above-mentioned luminescent material. The amount of the diarylethene compound added is 10 ⁻⁵ to 10 mo with respect to the solution or dispersion.
It is preferably in the range of 1 / l, and the addition amount of the luminescent material is preferably in the range of 0.5 to 100% by weight based on the solution or dispersion. When the above-mentioned diarylethene compound and the luminescent material are dispersed, a known dispersant or the like may be added in order to uniformly disperse this in the solution or the dispersion liquid.

A color dosimeter can be obtained by enclosing the solution or dispersion of the diarylethene compound thus prepared in a quartz cell containing no impurities. When the prepared cell is exposed to radiation, the color tone of the solution or dispersion changes depending on the radiation dose. The radiation dose can be estimated by measuring the absorption, transmission or reflection spectrum and measuring the amount of change in the absorbance, the transmittance or the reflectance.

(2-2) Resin Composition The resin composition which is one aspect of the photochromic material of the present invention includes, for example, (a) the above-mentioned diarylethene compound and the luminescent material dissolved in a solvent (dispersion medium) together with the base resin ( Or (b) directly dissolving (dispersing) the above-mentioned diarylethene compound and luminescent material in the base resin.

The base resin is not particularly limited as long as it can suitably dissolve or disperse the above-mentioned diarylethene compound. Specific examples thereof include acrylic resin, methacrylic resin, vinyl acetate resin, vinyl chloride resin, polyethylene resin, polypropylene resin, polystyrene resin, polynaphthalene resin, polycarbonate resin, polyethylene terephthalate resin, polyvinyl butyral resin and the like.

When the method (a) is used, as the solvent (dispersion medium), the above-mentioned diarylethene compound is preferably dissolved or dispersed, and the above-mentioned base resin is preferably dissolved or dispersed, and There is no particular limitation as long as it does not hinder the film forming process. Specific examples thereof include various organic solvents such as aromatic solvents such as benzene and toluene, aliphatic solvents such as hexane, ether solvents such as THF and chlorine solvents such as chloroform.

The above-mentioned diarylethene compound is dissolved or dispersed in this solvent (dispersion medium), and then the above-mentioned luminescent material is added and dispersed to prepare a resin composition. The addition amount of the diarylethene compound is preferably in the range of 0.2 to 200 parts by weight with respect to 100 parts by weight of the base resin, and the addition amount of the luminescent material is 1 to 20 parts with respect to 100 parts by weight of the base resin.
The range of 00 parts by weight is preferable, and the range of 5 to 2000 parts by weight is more preferable. Incidentally, known dispersants, antioxidants,
You may add an oxygen trap agent, a plasticizer, etc.

On the other hand, in the case of the method (b), the above-mentioned diarylethene compound and the luminescent material are directly kneaded into the above-mentioned base resin to prepare a resin composition.

A color dosimeter can be obtained by molding the resin composition thus prepared into a film shape, a rod shape or the like by a known method such as injection molding, extrusion molding, or heat pressing. In particular, in the case of processing into a film, the film can be processed by using various known techniques such as a casting method, a spin coating method, a bar coater method and a die casting method. The thickness of the film is not particularly limited as long as it does not deviate from the purpose of the color dosimeter, but is 0.01 to
A range of 10 mm is preferred.

When the molded resin composition is exposed to radiation, the color tone changes depending on the radiation dose. The radiation dose can be estimated by measuring the absorption, transmission or reflection spectrum and measuring the amount of change in the absorbance, the transmittance or the reflectance.

(2-3) Molded Product A molded product, which is one embodiment of the photochromic material of the present invention, is prepared by mixing the above-mentioned diarylethene compound and the luminescent material, and compressing this mixture into a solid product having a specific shape. Can be created.

Specifically, the median particle diameter is 10 nm to 50 μm.
Luminescent powder whose particle size is adjusted to about 10 nm, median particle size
After thoroughly mixing the above-mentioned diarylethene compound having a particle size adjusted to about 100 μm and, if necessary, a binder, the mixed powder is filled in a molding die and compression-molded to a pressure of 1 MPa to 1 GPa. The median particle size of the luminous body is 10
If it is smaller than nm, the powder may be aggregated, so that it may not be sufficiently mixed with the diarylethene compound. On the other hand, if the median particle size exceeds 50 μm, it may be difficult to maintain the shape of the molded body.

The median particle diameter of the diarylethene compound is usually about 10 nm to 100 μm, but it is more preferable if it is a particle diameter that can enter the gap of the light emitting body. Therefore, it is preferably about 10 nm to 50 μm.

The binder to be added is not particularly limited as long as it is generally known as a binder used for inorganic powders. Specifically, water-soluble substances such as water glass, sol-like substances such as silica sol and alumina sol, inorganic binders such as various cements that cause a hydration reaction, nitrification cotton, cellulose acetate, ethyl cellulose, polyvinyl butyral, wire Polyester, polyvinyl acetate, vinylidene chloride-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, polyalkyl- (meth) acrylate, polycarbonate, polyurethane, cellulose acetate butyrate, polyvinyl alcohol, gelatin, polysaccharides such as dextrin, Arabic, Examples include organic binders such as rubber.

The shape of the molded body may be any shape in accordance with the shape used as the color dosimeter. For example, when the color dosimeter is used in a flat plate shape, it is compressed into a flat plate shape by using a uniaxial molding machine or a biaxial molding machine after filling the mold with the mixed powder. Also,
When molding into a complicated shape, after filling the rubber powder of the complicated shape with the mixed powder, it is compressed using a hydrostatic press,
Mold into complex shapes. Compression molding pressure is 1MPa-1G
It is preferable that the surface pressure be Pa. Pressure is 1M
If it is less than Pa, sufficient mechanical strength is not imparted, and the molded body may not be able to maintain its shape. On the other hand, if the pressure is higher than 1 GPa, more equipment than is necessary for molding is required, which may result in extra cost.

On the other hand, a sintered body obtained by molding and firing the phosphor powder may be impregnated or coated with the above-mentioned diarylethene compound to form a molded body of a sintered body having high strength. In this case, the phosphor powder adjusted to the above particle size and, if necessary, the above-mentioned binder are sufficiently mixed, compression-molded, and then fired the molded body under firing conditions suitable for the type of the phosphor. The surface of the obtained dense sintered body is coated with the above diarylethene compound, or the inside of the obtained porous sintered body is impregnated with the above diarylethene compound. When applying or impregnating, the above-mentioned diarylethene compound is dissolved or dispersed in a satisfactorily solvent and then carried out. Further, the firing conditions suitable for the type of the luminescent material are preferably those close to the calcination temperature, holding time, and atmosphere adopted when synthesizing the luminescent material powder. The preferable firing temperature range is 500 to 1900 ° C., the holding time is 10 minutes to 48 hours, and the atmosphere is adjusted to an oxidizing atmosphere, a reducing atmosphere, a sulfurizing atmosphere, or the like depending on the composition of the luminescent material and the type of luminescent ions.

The molded body thus molded into a desired shape such as a film shape, a rod shape, or a plate shape can be used as it is as a color dosimeter. When the formed body produced is exposed to radiation, the color tone of the formed body changes depending on the radiation dose. The radiation dose can be estimated by measuring the absorption, transmission or reflection spectrum and measuring the amount of change in the absorbance, the transmittance or the reflectance.

(2-4) Laminated Body A laminated body which is one embodiment of the photochromic material of the present invention is characterized by having at least a layer containing the above-mentioned diarylethene compound and a layer containing a light emitting body.

Here, an example of the layer structure of the laminate, which is one embodiment of the photochromic material of the present invention, will be described with reference to FIGS. 1 and 2, but of course the invention is not limited thereto. It should be noted that both FIG. 1 and FIG. 2 are cross-sectional views schematically showing an example of the layer structure of the laminate.

In the example of the layer structure shown in FIG. 1, the light emitting layer 2 containing the above-mentioned light emitting material is provided on the support 1, and the photochromic layer 3 containing the above diarylethene compound is further provided on the light emitting layer 2. After that, the laminated body 10 is created. In addition, two laminated bodies 10 thus prepared are prepared, and the surfaces of the respective supports 1 are opposed to each other to form two laminated bodies 10.
May be brought into close contact with each other and bonded to form a single laminated body (not shown).

In the example of the layer structure shown in FIG. 2, a laminate having a layer structure of a support 1, a light emitting layer 2 and a photochromic layer 3 is prepared as in the example shown in FIG. Another light emitting layer 2 ′ is further provided on the above to form another laminated body. The former photochromic layer 3 and the latter light emitting layer 2 '
And 2 are opposed to each other to bring these two laminated bodies into close contact with each other, and adhere to each other to form a new laminated body 11.

The materials of the supports 1 and 1'can ensure the stability of the shapes of the light emitting layers 2 and 2'and the photochromic layer 3 and do not impair the purpose of the color dosimeter of the present invention. However, it is not particularly limited. Specifically, resins such as polyesters such as cellulose acetate, cellulose propionate, cellulose acetate butyrate, polyethylene terephthalate, polystyrene, polymethylmethacrylate, polyamide, polyimide, vinyl chloride-vinyl acetate copolymer, and polycarbonate are formed into a film shape. , Baryta paper, resin-coated paper, ordinary paper, aluminum alloy foil and the like. Among these, when materials such as resin film and paper are used, light absorbing substances such as carbon black and light reflecting substances such as titanium dioxide and calcium carbonate are directly kneaded into these materials in advance. It may be mixed.

For the light-emitting layers 2 and 2 ', an appropriate amount of the luminescent material is mixed with a binder, and an organic solvent is added to this to prepare a luminescent material coating solution having an appropriate viscosity, and this coating solution is used for a knife coater or a roll. It is applied on the support 1 or 1'by a coater or the like,
Created by drying. If necessary, a dispersant such as phthalic acid or stearic acid or a plasticizer such as triphenyl phosphate or diethyl phthalate may be added to the phosphor coating solution. The binder is not particularly limited as long as it is generally known as a binder for luminescent materials. Specifically, nitrified cotton, cellulose acetate, ethyl cellulose, polyvinyl butyral, linear polyester, polyvinyl acetate, vinylidene chloride-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, polyalkyl- (meth) acrylate, polycarbonate, polyurethane, Examples thereof include cellulose acetate butyrate, polyvinyl alcohol, gelatin, polysaccharides such as dextrin, and gum arabic. The organic solvent is not particularly limited as long as it can disperse the luminescent material. Examples thereof include alcohol solvents such as ethanol, ether solvents such as methyl ethyl ether, ketone solvents such as methyl ethyl ketone, ester solvents such as butyl acetate and ethyl acetate, aromatic solvents such as xylene. The final weight of the luminescent material coated on the support 1 or 1'is generally preferably 30 to 200 mg / cm ² . Coating weight is 3
When it is less than 0 mg / cm ² , the sensitivity of the dosimeter tends to decrease because the sensitivity to radiation decreases, and conversely, when it exceeds 200 mg / cm ² , the sensitivity to radiation saturates and the sensitivity of the dosimeter decreases. There is a risk that improvement will reach a ceiling.

The photochromic layer 3 is prepared by dissolving a diarylethene compound in an organic solvent together with a base resin and the like, if necessary, and processing it into a film by a known technique such as a casting method and a spin coating method.
When a base resin is used, this base resin can dissolve or disperse a diarylethene compound,
There is no particular limitation. Specifically, any of the base resins mentioned in the section of (2-2) Resin composition such as polystyrene resin and polycarbonates can be mentioned. The content of the diarylethene compound is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the base resin. The organic solvent is not particularly limited as long as it dissolves or disperses the diarylethene compound and dissolves the base resin. In particular,
Any of those listed in the section of (2-2) resin composition such as toluene and THF can be mentioned. Alternatively, it may be prepared by directly kneading a diarylethene compound into a base resin and processing it into a film using a conventionally known technique such as an extrusion molding method or an injection molding method. The layer thickness is preferably in the range of 0.01 to 10 mm.

The support 1 or 1'and the light emitting layer 2 or 2 '
A light-reflecting layer, a light-absorbing layer, a metal foil layer, or the like may be provided between and. In this case, the support 1
Alternatively, a light-reflecting layer, a light-absorbing layer or a metal foil layer is provided on 1 ', and the phosphor coating solution is applied and dried on the light-reflecting layer to form the light-emitting layer 2 or 2'.

A protective film may be formed on the surface of the light emitting layer 2 or 2'contacting the photochromic layer 3 if necessary. The protective film is cellulose acetate, nitrocellulose,
Cellulose derivatives such as cellulose acetate butyrate, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polycarbonate, polyvinyl butyral, polymethylmethacrylate, polyvinyl formal, polyurethane, etc. A protective film coating solution is prepared, and this is applied onto the previously formed light emitting layer 2 or 2 ′ and dried, or a preformed protective film such as polyethylene terephthalate, polyethylene, polyvinylidene chloride, polyamide, etc. It is formed by laminating the transparent film of (1) on the light emitting layer 2 or 2'formed above.

In this case, the light emitting layer 2 or 2'can be manufactured by a method different from the above-described manufacturing method. That is, after forming a protective film on a smooth support substrate in advance and forming a light emitting layer 2 or 2'on it, this is peeled off from the support substrate together with the protective film, and then on the support 1 or 1 '. Transfer to. In the case of the layer structure shown in FIG.
The light emitters used for the light emitting layers 2 and 2'may be the same or different.

Further, in the layer structure shown in FIG. 2, in order to allow the discoloration of the photochromic layer 3 due to radiation exposure to be visually recognized and measured from the outside of the laminated body 11, at least one of the supports 1 and 1 '. It is preferable to use a colorless and transparent material. In that case, it is preferable to subject the transparent support to a treatment for preventing ultraviolet rays, which will be described later.

The layer structure of the laminates 10 and 11 described with reference to FIGS. 1 and 2 is merely a preferable example, and the other layers (the illustrated support 1,
1 ', the light emitting layer 2, 2', and the photochromic layer 3, a light reflecting layer, a light absorbing layer, a metal foil layer, a protective layer, etc.) are laminated in any combination and order, and a new layer is added in some cases. By doing so, an infinite number of layer configurations are possible in principle.

The laminated bodies 10 and 11 thus produced can be used as they are or after being molded as required, as a color dosimeter. When the produced laminated bodies 10 and 11 are exposed to radiation, the color tone changes depending on the radiation dose. The radiation dose can be estimated by measuring the absorption, transmission or reflection spectrum and mechanically or visually measuring the amount of change in the absorbance, transmittance or reflectance.

[0124] Instead of adhering the layers of the laminates 10 and 11 to each other, the layers can be separated from each other. Specifically, in the layer structure of FIG. 2, if the light emitting layers 2 and 2 ′ and the photochromic layer 3 are configured without being adhered to each other, the laminated body 11 has a portion including the support 1 and the light emitting layer 2. Thus, the portion composed of the support 1 ′ and the light emitting layer 2 ′ and the portion composed of the photochromic layer 3 can be separated. If the configuration is such that after exposing all of these portions to radiation in a laminated state and then measuring only the portion formed of the photochromic layer 3 to measure the discolored state, the discolored state of the photochromic layer 3 present in the center of the laminated body 11 is Since it is not necessary to measure from the outside, the supports 1 and 1'and the light emitting layers 2 and 2'can be configured to be sufficiently thick, and consequently the radiation detection sensitivity can be further enhanced.

Among the above-described embodiments of the photochromic material of the present invention, from the viewpoint of easy energy transfer or electron transfer from the luminescent material excited by radiation to the diarylethene compound, (2-1) to (2-
The composition typified by 3) is preferable, and from the viewpoint of easiness of production and handling when used as a color dosimeter, (2)
-2) The resin composition or (2-3) molded body is preferable. Most preferred is (2-2) resin composition.

The photochromic material of the present invention may further contain an ultraviolet absorber. Specifically, when the photochromic material is a composition represented by the above (2-1) to (2-3), it may be contained as one component of the composition, or the composition is used. An ultraviolet ray blocking layer may be provided on the surface of the color dosimeter formed as described above. When the photochromic material is a laminated body, an ultraviolet absorber may be contained in any of the layers constituting the laminated body, and an ultraviolet ray blocking layer may be provided on the radiation incident side for detection in the laminated body. It may be further laminated.

The ultraviolet ray blocking layer has a wavelength of 10 to 450 nm.
What cuts the light of is preferable. In the present invention, “cutting” light having a wavelength of 10 to 450 nm means
It means that the light transmittance in the wavelength region is 5% or less, preferably 3% or less.

By providing such a layer or containing an ultraviolet absorber, it is possible to prevent the compound from reacting with ultraviolet rays contained in ambient light in addition to the reaction due to ionizing radiation to be detected, The accuracy of dose detection is improved.

In order to absorb light having a wavelength of about 380 nm to 450 nm contained in ambient light, it is preferable to use a dye having absorption in the wavelength region, that is, a yellow dye together. Such dyes are not particularly limited, but for example, Orient Chemical Co., Ltd. OILYELLOW 3G, BASF Neptun
Examples include e (TM) Gelb 075 and BAYEL LTD's MACROLEX YELLOW 6G. These dyes are
An oil-soluble resin that is easily compatible with organic solvents and resins is preferable.

In order to prevent the influence of ambient light on the accuracy of dose detection and the deterioration of performance, light in the wavelength region exceeding the wavelength of 450 nm may be cut to some extent. However, since the layer is colored by cutting the light in the visible light wavelength region, it may be difficult to determine the color change of the display portion in the color dosimeter. More preferably, with respect to many diarylethene-based photochromic compounds, it is preferable to provide a layer that blocks light having a wavelength of 230 to 420 nm at which the maximum absorption wavelength of the ring-opened product exists.

The method for forming the ultraviolet cut layer is not particularly limited and may be appropriately formed depending on the form of the color dosimeter. For example, it may be formed by coating, drying, and curing a composition containing a known ultraviolet absorber on the surface of the color dosimeter, or by forming a film containing the ultraviolet absorber in advance and attaching it to the surface of the dosimeter. You may attach it.

As the ultraviolet absorber contained in the ultraviolet cut layer and the ultraviolet absorber contained in the composition which is one form of the photochromic material of the present invention, benzophenone type, benzotriazole type, aryl ester type, etc. are known. Compounds of

Specifically, for example, UVINUL D-4 manufactured by BASF
9, UVINUL D-50; Kemisorb1011, manufactured by Chemipro Kasei Co., Ltd.
Kemisorb1001 ； MARK LA- by Adeka Argus Chemical Co., Ltd.
51, MARKLA-31; Sumitomo Chemical Co., Ltd. Sumisorb250; Takemoto Yushi Co., Ltd. UVA101; Ciba Specialty Chemicals Tinuvin213, Tinuvin327, Tinuvin1577, Sandoz S
andouvor3206 and so on.

As a method of forming the ultraviolet ray blocking layer, a method of attaching a commercially available or previously formed ultraviolet ray cutting film can also be mentioned.

Examples of the UV cut film include a polyimide film and a film obtained by coating or kneading a UV absorber. For example, Fuji Photo Film Co., Ltd.
UVGard manufactured by 3M Company Scotchtint (TM) Super Layer SCLARL150, SCLARL400, SCLARL600, ULTRA600, Musiclear Eco RE80CLIS; Mitsubishi Kagaku Polyester Film Co., Ltd. Hello Wind-TK Clear, commercially available UV such as BZA-50K Cut film can be used.

Further, the ultraviolet cut film can be properly manufactured by itself. A film is formed by a known method using the composition obtained by adding an oil-soluble dye (the above-mentioned yellow dye) in addition to the binder resin and the ultraviolet absorber described above. It can be prepared by dissolving the composition in a suitable solvent and then applying it by a known method such as a bar coater or a die coater. Alternatively, it can be formed by mixing a binder resin, an ultraviolet absorber, and an appropriate oil-soluble dye, kneading the resin with heat and kneading into the resin, and processing into a film by a known technique such as an extrusion molding machine. As the binder resin, polymethylmethacrylate, polystyrene, polycarbonate, polyethylene,
Examples include polypropylene and polyvinyl chloride. The content of the ultraviolet absorber is preferably 1 to 30% by weight of the solid content.

The oil-soluble dye may be appropriately selected from commercially available products including the compounds described above as the yellow dye. The amount of the dye added is preferably 0.01 to 20% by weight of the solid content.

Any solvent can be used as long as it can dissolve the binder resin, the ultraviolet absorber, the oil-soluble dye and the like. For example, an ether solvent such as tetrahydrofuran,
Examples thereof include aromatic solvents such as toluene, ketone solvents such as methyl ethyl ketone, methyl amyl ketone, and propylene glycol solvents such as propylene glycol monomethyl ether-2-acetate.

The thickness of the ultraviolet cut film is 0.01
The range of about μm to 500 μm is preferable.

Two or more kinds of the ultraviolet absorber and the yellow dye may be mixed and used. It is preferable to use a plurality of types in combination because a wider range of light rays can be efficiently absorbed.

When the photochromic material of the present invention is a composition represented by the above (2-1) to (2-3), the composition may contain an ultraviolet absorber as described above. Good. Examples of the ultraviolet absorber include compounds similar to the above-mentioned compounds contained in the ultraviolet cut layer.

In the color dosimeter of the present invention, as a means for preventing deterioration by ultraviolet rays, a method of providing an ultraviolet ray cut layer is more preferable.

As described in (2-1), the color dosimeter of the present invention is one in which a solution or dispersion liquid is enclosed in a cell or the resin composition described in (2-2) is formed into a desired shape. Examples include molded products, molded products described in (2-3) into desired shapes, and (2-4) laminated products. Of these, from the viewpoint of use in medical devices such as blood for transfusion, tag-like or seal-like products using these are preferred.

Specifically, cells or molded articles containing these photochromic materials are attached to a part or the whole of a film-shaped or plate-shaped base material to form the base material in a tag shape,
A method of using it by tying it to a blood bag for transfusion or a medical device can be mentioned. A photochromic material may be sandwiched between two base materials and formed into a tag shape. Further, (2-4) a method in which the support layer of the laminate is formed in a tag shape, and is similarly used in association with a blood bag or a medical device is used. There is no particular limitation on the method of tying, and it may be appropriately selected depending on the shape of the blood bag or the medical concern.

Similarly, as a seal-like color dosimeter, a layer made of a photochromic material is provided on a part or the whole surface of a base material, or a cell or a molded article containing the photochromic material is attached, and an adhesive is applied to the back surface. After forming the layer or the pressure-sensitive adhesive layer, a method of attaching the layer or the pressure-sensitive adhesive layer to a blood bag or a medical device and using it can be mentioned.

A photochromic material may be sandwiched between two base materials to form a seal. Also (2-4)
An adhesive layer or a pressure-sensitive adhesive layer may be provided on the back surface of the support layer itself of the laminate to form a seal. The adhesive layer and the pressure-sensitive adhesive layer may be formed by applying an adhesive or a pressure-sensitive adhesive, or a commercially available double-sided tape or the like may be used.

FIGS. 4 (I) to (III) are all diagrams showing an example of a seal type color dosimeter using the photochromic material of the present invention. In each of (I) to (III), (a) is a front view of a color dosimeter and (b) is a sectional view.

The color dosimeter shown in FIG. 4 (I) is constituted by sandwiching the photochromic material 4 between the light-shielding base material 5 and the ultraviolet absorbing transparent base material 5'and adhering it. Further, an adhesive layer or a double-sided tape 6 is provided on the surface of the light-shielding base material 5 opposite to the surface in contact with the photochromic material 4, and this is covered with a release paper 7 for protection. When the color dosimeter is used, the release paper 7 is peeled off to expose the adhesive layer or the double-sided tape 6, and the color paper is attached to a desired place such as clothes or articles for use.

The color dosimeter shown in FIG. 4 (II) is shown in FIG.
Instead of using the transparent ultraviolet absorbing substrate 5'of (I), the transparent ultraviolet absorbing film 8 is adhered to the light shielding substrate 5 from above the photochromic material 4 to cover the photochromic material 4. And is fixed to the light-shielding base material 5. The surface portion of the light-shielding base material 5 to which the ultraviolet absorbing transparent film 8 is not adhered can be used for entering necessary information such as date and time and name.

The color dosimeter shown in FIG.
In the constitution of (II), a transparent film 8 which absorbs ultraviolet rays
From above, a light-shielding base material 5 is further adhered to enhance the strength. An opening or a transparent portion 9 containing an ultraviolet absorber is provided in a portion of the light-shielding base material 5 located on the photochromic material 4 to enhance the visibility at the time of exposure.

FIG. 5 shows an example of a tag-shaped color dosimeter. The tag-shaped color dosimeter 20, 20 ′ provided with the photochromic material 4 of the present invention is partially folded back and attached to the handle portion of the blood bag 30 (reference numeral 20).
It is configured so that it can be attached (reference numeral 20 ') using a string or the like.

Of course, the color dosimeter using the photochromic material of the present invention is not limited to the forms shown in FIGS. 4 and 5 and the forms described with reference to these drawings. Within the scope of
It can be configured in various forms.

[0153]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1

[Chemical 47]

The above diarylethene compound (photochromic compound; quantum yield of ring-opening reaction is 1.3 × 10 ^-2 )
(1) 0.02 g and polystyrene resin 0.2 g are dissolved in toluene 0.51 g to obtain an ultraviolet light emitting phosphor (light emitting body).
After adding 0.1 g of CeMgAl ₁₁ O ₁₉ and stirring,
A white film having a thickness of 0.5 mm was prepared by the casting method. The prepared film was irradiated with γ-rays at 100 Gy using ⁶⁰ Co as a radiation source, and absorption spectra in the visible region before and after irradiation were measured. "Shimadzu automatic spectrophotometer UV-3100PC" (manufactured by Shimadzu Corporation) was used for the measurement.
The change in absorbance at a wavelength of 600 nm, which is the maximum absorption wavelength of compound (1), was measured. The results are shown in Table 1.

Example 2 Ultraviolet light emitting phosphor (emitter) CeMgAl of Example 1₁₁O
₁₉To SrB_FourO₇: Eu ²⁺The same as Example 1 except that
The experiment was carried out under the condition. The results are shown in Table 1 below.

Example 3 4 g of ultraviolet light emitting phosphor (light emitting body) CeMgAl ₁₁ O ₁₉ and 0.5 g of polyvinyl butyral were added to 5 ml of ethanol and stirred, and then aluminum foil was provided as a reflector on transparent polyethylene terephthalate. Coating and film formation were performed on the support by using a bar coater method to form a light emitting layer having a thickness of 0.1 mm. On top of that, polystyrene resin 0.2
g, the compound (1) (photochromic compound) 0.
A solution of 02 g dissolved in toluene was cast to form a photochromic layer having a thickness of 0.3 mm. For the film made, ⁶⁰ Co was used as the radiation source and 100 gamma rays were used.
Gy irradiation was performed, and absorption spectra in the visible region of the photochromic layer before and after irradiation were measured. Changes in absorbance at a wavelength of 600 nm before and after irradiation with γ-ray are shown in Table 1 described later.

Comparative Example 1 Ultraviolet light-emitting phosphor (emitter) CeMgAl ₁₁ O of Example 1
_A film was prepared under the same conditions as in Example 1 except that ₁₉ , and the same experiment as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 2 Ultraviolet-Emitting Phosphor (Emitter) CeMgAl ₁₁ O of Example 1
_A film was prepared under the same conditions as in Example 1 except that ₁₉ was replaced with HfO ₂ , and the same experiment as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 3 Ultraviolet light-emitting phosphor (emitter) CeMgAl ₁₁ O of Example 1
_A film was prepared under the same conditions as in Example 1 except that ₁₉ was changed to Bi ₂ O ₃ , and the same experiment as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 4 Ultraviolet-Emitting Phosphor (Emitter) CeMgAl ₁₁ O of Example 3
_A film was prepared under the same conditions as in Example 3 except that the light emitting layer containing ₁₉ was removed, and the same experiment as in Example 1 was performed. The results are shown in Table 1.

Examples 4 to 6 Films were prepared by the same casting method as in Example 1 except that the phosphors shown in Table 1 were used instead of CeMgAl ₁₁ O ₁₉ . For these, the change in absorbance at a wavelength of 600 nm before and after γ-ray irradiation was measured in the same manner as in Example 1. The results are shown in Table 1.

[0163]

[Table 1]

In Table 1, it is considered that the larger the relative value of the amount of change in absorbance (rightmost column), the higher the radiation (γ-ray) detection sensitivity. The relative value of the absorbance change amount of the film containing the photochromic material of the present invention (Examples 1 to 6) is larger than the relative value of the absorbance change amount of the film not containing the photochromic material of the present invention (Comparative Examples 1 to 4). Therefore, it can be seen that the film containing the photochromic material of the present invention has high radiation detection sensitivity.

Next, the change in absorbance of the sample due to X-ray irradiation was examined. -Example 7 The soft X-ray irradiation device "SOFTEX M-80W special type" made by Softex Co., Ltd. was added to the sample prepared in Example 1.
Upon irradiation with 45 Gy of X-rays using (50 kV, 4 mA), the sample turned blue. Regarding the absorption spectra of the sample before and after irradiation, the change in absorbance at a wavelength of 600 nm was measured. The results are shown in Table 2.

Example 8 A sample was prepared in the same manner as in Example 1 except that the phosphor was changed from CeMgAl ₁₁ O ₁₉ to BaFCl: Eu ²⁺ , and X-ray irradiation was performed in the same manner as in Example 7. The sample turned blue. Regarding the absorption spectra of the sample before and after irradiation, the change in absorbance at a wavelength of 600 nm was measured.
The results are shown in Table 2. This sample is 100 Gy
It did not discolor even when it was irradiated with X-rays.

Comparative Example 5 A sample was prepared in the same manner as in Example 7 except that the photochromic compound was changed to the following compound (2), and the sample was not irradiated with X-rays. It was Regarding the absorption spectra of the sample before and after irradiation, the change in absorbance at a wavelength of 600 nm was measured.

[0168]

[Chemical 48]

The results are shown in Table 2. The sample using the compound (2) showed no change in absorbance even when irradiated with 100 Gy of X-ray.

Comparative Example 6 The sample prepared in Comparative Example 1 was irradiated with X-rays in the same manner as in Example 7. Regarding the absorption spectra of the sample before and after irradiation, the change in absorbance at a wavelength of 600 nm was measured. The results are shown in Table 2.

[0171]

[Table 2]

As shown in Table 2, when the diarylethene compound represented by the general formula (I) was not used, discoloration was not exhibited by irradiation with X-rays having an intensity which is usually used for blood for transfusion.

Example 9

[Chemical 49]

The above-mentioned diarylethene compound (3) (photochromic compound. The quantum yield of the ring-opening reaction is 1.7 × 1.
0 ^-5) to 0.02g and polystyrene resin 0.2g were dissolved in toluene 0.51 g, UV-emitting phosphor as (light emitter) BaFCl: After stirring added Eu ²⁺ 0.1 g, a film thickness by casting A 0.3 mm white film was created.

The prepared film was irradiated with X-rays for 15 Gy using the same X-ray apparatus as in Example 7, and the reflection spectra in the visible light wavelength region before and after irradiation were measured. The integral-class accessory "ISR-3100" (manufactured by Shimadzu Corporation) was used for the measurement, and the reflectance at 645 nm, which is the maximum absorption wavelength of the compound (3), was measured. The results are shown in Table 3.

Comparative Example 7 Except that the phosphor BaFCl: Eu ²⁺ was not used,
A white film was prepared in the same manner as in Example 9, and the wavelength was 645n.
The change in reflectance at m was measured. The results are shown in Table 3 below.

[0177]

[Table 3]

[0178]

According to the photochromic material of the present invention and the color dosimeter using the same, in addition to the diarylethene compound which is converted into a color-change isomer by irradiation with light of a specific wavelength, the above-mentioned wavelength band by absorbing radiation is obtained. By using a light-emitting body that emits light in overlapping wavelength bands, irradiation radiation can be efficiently detected, and the dose can be measured with high sensitivity.

[Brief description of drawings]

FIG. 1 is a cross-sectional view schematically showing an example of the layer structure of a laminate as a color dosimeter of the present invention.

FIG. 2 is a cross-sectional view schematically showing another example of the layer structure of the laminate as the color dosimeter of the present invention.

FIG. 3 is a diagram illustrating overlap between an emission spectrum of a light emitting body and an absorption spectrum of a diarylethene compound.
The solid line shows the absorption spectrum of the diarylethene compound, and the dotted line shows the emission spectrum of the luminescent material.

4 (A) to (III) are diagrams showing an example of the seal-type color dosimeter of the present invention. In each (a)
Is a front view and (b) is a sectional view.

FIG. 5 is a diagram showing an example of a tag-shaped color dosimeter of the present invention.

[Explanation of symbols]

1,1 'support layer 2,2 'light emitting layer 3 Photochromic layer 4 Photochromic material 5 Light-shielding base material 5'UV absorbing transparent substrate 6 Adhesive layer or double-sided tape 7 Release paper 8 UV absorbing transparent film 9 Opening part or transparent part containing UV absorber 10,11 Laminate (color dosimeter) 20, 20 'Tag-shaped color dosimeter 30 blood bags

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinichiro Nakamura             1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa             Within Mitsubishi Chemical Corporation (72) Inventor Masahiro Irie             24-25 Muromi, Sawara-ku, Fukuoka City, Fukuoka Prefecture             No. 706 (72) Inventor Setsuko Irie             35-22-6 Oikedai, Sakai City, Osaka Prefecture

Claims (12)

[Claims] 1. A light-emitting body that emits light when irradiated with radiation,
Diarylethene compounds represented by the following general formula (I)
And at least the content of
Opened or closed ring of kuttle and the diarylethene compound
Is characterized by overlapping with the absorption spectrum of
Photochromic material. [Chemical 1] (In the above general formula (I), the group R₁And the group R₂Each is German
Vertically, alkyl group, cycloalkyl group or alkoxy group
Represents Group X₁, Group X₂, Y₁And group Y₂Are each independent
To [Chemical 2] Represents either Group R₃Is a hydrogen atom, substituted
Optionally substituted alkyl group, optionally substituted aryl group
Alternatively, it represents an optionally substituted cycloalkyl group.
Group R_FourIs a hydrogen atom or an optionally substituted alkyl group
Alternatively, it represents an optionally substituted cycloalkyl group.
Ring D is a group X₁, Y₁And the two carbons that bind them
An optionally substituted 5-membered ring formed with the atom
Or a 6-membered aromatic ring, wherein ring E is a group X ₂, Y₂
And with two carbon atoms bonded to them
And optionally substituted 5- or 6-membered aromatic ring
Represents Ring D and Ring E may be further substituted.
A 5-membered or 6-membered aromatic ring may be condensed
Yes. ) 2. The diarylethene compound is represented by the following general formula (I-1):
The described photochromic material. [Chemical 3] (In the general formula (I-1), the groups R ₁₁ and R ₁₂ each independently represent an alkyl group, a cycloalkyl group or an alkoxy group. The groups X ₁₁ and X ₁₂ are each independently ] And each of the group Y ₁₁ and the group Y ₁₂ independently represents Represents either The group R ₁₇ and the group R ₁₈ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or an optionally substituted cyclo group. Represents an alkyl group. The group Y ₁₁ and / or the group Y ₁₂ is In the case of, the group R ₁₇ and / or the group R ₁₈ may combine with the group R ₁₆ to form a 5-membered or 6-membered aromatic ring. The group R ₁₃ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted cycloalkyl group. The groups R ₁₆ each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted cycloalkyl group. ) 3. The diarylethene compound is represented by the following general formula (I-2): 1.
The described photochromic material. [Chemical 7] (In the above general formula (I-2), the group R ₂₁ and the group R ₂₁
Each ₂₂ independently represents an alkyl group, a cycloalkyl group or an alkoxy group. The group Y ₂₁ and the group Y ₂₂ are each independently And the group X ₂₁ and the group X ₂₂ each independently represent Represents either The group R ₂₅ and the group R ₂₆ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or an optionally substituted cyclo group. Represents an alkyl group. The group X ₂₁ and / or the group X ₂₂ is In the case of, the group R ₂₅ and / or the group R ₂₆ may be bonded to the group R ₂₉ to form a 5-membered or 6-membered aromatic ring. The group R ₂₇ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted cycloalkyl group. The group R ₂₉ represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted cycloalkyl group. ) 4. The photochromic material according to claim 1, wherein the diarylethene compound is thermally irreversible. 5. The photochromic material according to claim 1, wherein a quantum yield of a ring-opening reaction of the diarylethene compound is 10 ⁻³ or less. 6. The photochromic material according to claim 1, wherein the light emitting body is an ultraviolet light emitting phosphor. 7. A composition containing the luminescent material and the diarylethene compound, according to claim 1.
6. The photochromic material according to any one of 6 above. 8. The photochromic material according to claim 7, wherein the composition further contains an ultraviolet absorber. 9. The photochromic material according to claim 1, wherein the photochromic material is a laminate having a layer containing the luminescent material and a layer containing the diarylethene compound. 10. A color dosimeter comprising the photochromic material according to any one of claims 1 to 9. 11. The color dosimeter according to claim 10, wherein the color dosimeter has a seal shape. 12. The color dosimeter according to claim 10, wherein the color dosimeter has a tag shape.