Patent Application
20240118485
The present invention relates to a plastic wavelength shifting fiber and its manufacturing method.
Scintillators such as liquid organic scintillators, solid (plate-shaped) inorganic scintillators, and plastic scintillators have been widely used for a long time in the field of radiation detection such as particle detection, and are important components in the measurement of radiation. These scintillators contain a fluorescent agent that emits, when the scintillator is irradiated with radiation, blue light having a wavelength of about 430 nm, at which wavelength a photomultiplier tube has the maximum sensitivity. Note that a method in which blue light, which is emitted from a scintillator as it is irradiated with radiation, is not directly detected, but is indirectly detected by shifting the wavelength of the blue light generated by the scintillator into that of green light or the like in an optical fiber and making the obtained green light or the like propagate through the optical fiber has been known.
Such an optical fiber is called a wavelength shifting (WLS) fiber, in which the outer peripheral surface of a core that absorbs blue light generated by a scintillator and shifts its wavelength into that of green light or the like is covered (or coated) with a cladding having a refractive index lower than that of the core. In particular, plastic wavelength shifting fibers made of plastic are inexpensive and easy to process as compared to those made of glass. Therefore, like plastic scintillation fibers in which optical fibers themselves have scintillation properties, plastic wavelength shifting fibers are used in a wide range of applications such as particle physics researches.
As the base material for the core of a plastic wavelength shifting fiber, for example, polystyrene, which is a highly transparent resin material having a relatively high refractive index, is used. By using polystyrene as the base material for the core, a difference between refractive indices can be increased, thus making it possible to increase the total reflection angle with respect to the cladding. Therefore, it is possible to confine green light, which is generated by wavelength shifting inside the core, with a wider angle in the core and to transmit the confined green light to the end face of the fiber. That is, by using polystyrene as the base material for the core, it is possible to realize a wavelength shifting fiber having a high light emitting property.
Further,
Instead of using the PMT shown in
For detectors used in particle physics researches, it is important to distinguish an event(s) to be observed from noise events (background events), so it has long been desired to improve the temporal and position resolutions of detectors. Patent Literature 1 discloses a single-crystal solid scintillator in which the fluorescence lifetime is shortened in order to improve the temporal resolution of the detector. Each of Patent Literatures 2 and 3 discloses an inorganic scintillator that contains inorganic solid crystals and has a high temporal resolution.
Note that Patent Literatures 4 and 5 will be referred to later in descriptions of embodiments according to the present invention.
It has been desired to improve the temporal resolution of a detector by further shortening the fluorescence lifetime in plastic wavelength shifting fibers. An object of the present invention is to provide a plastic wavelength shifting fiber in which the fluorescence lifetime is short.
A plastic wavelength shifting fiber according to an aspect of the present invention includes:
The number of carbonyl bonds in the fluorescent agent is one or smaller.
In this way, it is possible to provide a plastic wavelength shifting fiber in which the fluorescence lifetime is short.
A method for manufacturing a plastic wavelength shifting fiber according to an aspect of the present invention is a method for manufacturing a plastic wavelength shifting fiber which includes:
The method includes:
In this way, it is possible to provide a plastic wavelength shifting fiber in which the fluorescence lifetime is short.
A range of a peak wavelength of a fluorescence spectrum of the fluorescent agent may be 450 to 550 nm.
The fluorescent agent may be a bisstyryl-benzene-based compound, a bisvinylcarbazole-benzene-based compound, or a coumarin-based compound.
Further, an outer diameter of the plastic wavelength shifting fiber may be 0.1 to 3.0 mm.
According to the present invention, it is possible to provide a plastic wavelength shifting fiber in which the fluorescence lifetime is short.
A plastic wavelength shifting fiber according to a first embodiment of the present invention will be described with reference to
The core 11 is made of a transparent resin containing a fluorescent agent that absorbs blue light and emits green light. As the base material for the core, for example, a styrene-based resin, which is inexpensive and easy to use, is used. Details of the base material for the core and the fluorescent agent, which constitute the core 11, will be described later.
The cladding 12, which covers the outer peripheral surface of the core 11, is made of a transparent resin having a refractive index lower than that of the core 11. The base material for the cladding, which constitutes the cladding 12, will be described later.
The outer diameter of the plastic wavelength shifting fiber is, for example, 3.0 mm or smaller, and preferably 2.0 mm or smaller. Further, the outer diameter of the plastic wavelength shifting fiber is, for example, 0.1 mm or larger, and preferably 0.2 mm or larger.
In the plastic wavelength shifting fiber according to this embodiment, the number of carbonyl bonds contained in the fluorescent molecule is controlled. Therefore, in the plastic wavelength shifting fiber according to this embodiment, it is possible to shorten the fluorescence lifetime.
A principle for these features will be described hereinafter.
A more detailed description will be given with reference to the above-described
Fluorescence is a phenomenon in which molecules of a fluorescent agent absorb energy and are excited, and then emit light having a wavelength longer than that of the absorbed light, and is a phenomenon that is often observed in n-conjugated organic compounds. The π-conjugated organic compound has a repetitive structure of double bonds and single bonds.
The inventors have conducted researches on various π-conjugated organic compounds that emit green fluorescence in a wavelength range of 430 to 550 nm, and in particular, a wavelength range of 450 nm to 550 nm as a preferred range, and found that the number of carbonyl bonds in the chemical structure of the fluorescent molecule has a correlation with the fluorescence lifetime emitted from the fluorescent agent. This is probably because carbon atoms and oxygen atoms are capable of forming double bonds, and greatly contribute to the π-conjugated structure in which double bonds are necessary. As a result of experiments, details of which will be described later, it has been found that the fluorescence lifetime is short when the number of carbonyl bonds is one or smaller. The fluorescence lifetime is preferably 3 ns or shorter.
Note that the term “carbonyl bond” in this specification means a double bond (C═O) between carbon and oxygen, and needless to say, examples of functional groups having carbonyl bonds include an amide group, an aldehyde group, and a ketone group.
As the base material for the core, a transparent resin material having a relatively high refractive index is preferably used. A preferred base material is, for example, a polymer that is obtained by polymerizing one type of monomer selected from a group of monomers consisting of benzyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, chlorobenzyl methacrylate, 1-phenylethyl methacrylate, 1,2-diphenyl ethyl methacrylate, diphenyl ethyl methacrylate, furfuryl methacrylate, 1-phenylcyclohexyl methacrylate, pentachlorophenyl methacrylate, pentabromophenyl methacrylate, 1-naphthyl methacrylate, 2-naphthyl methacrylate, styrene, α-methylstyrene, and vinyltoluene.
Further, another suitable base material is a copolymer that is obtained by copolymerizing at least two types of monomers selected from a group of monomers consisting of methyl methacrylate, benzyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, chlorobenzyl methacrylate, 1-phenylethyl methacrylate, 1,2-diphenyl ethyl methacrylate, diphenyl ethyl methacrylate, furfuryl methacrylate, 1-phenylcyclohexyl methacrylate, pentachlorophenyl methacrylate, pentabromophenyl methacrylate, 1-naphthyl methacrylate, 2-naphthyl methacrylate, styrene, α-methylstyrene, and vinyltoluene. For the polymerization, an ordinary polymerization initiator(s) and an ordinary molecular-weight modifier(s) may be added.
A suitable base material for the cladding is, for example, a polymer that is obtained by polymerizing or copolymerizing at least one type of monomer selected from a group of monomers consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Among them, a polymer of methyl methacrylate or a copolymer of methyl methacrylate and another monomer(s) is preferred. Methyl methacrylate has an advantage that its transparency is high, and it is easy to use because it is easily polymerized. For the polymerization, an ordinary polymerization initiator(s) and an ordinary molecular-weight modifier(s) may be added.
Further, as the base material for the outer cladding, a commercially available material may be used as long as it has a refractive index lower than that of the above-described base material for the cladding. Specifically, examples of suitable base materials include: polymers that are obtained by polymerizing or copolymerizing at least one type of monomer selected from a group of monomers consisting of methyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate, methyl α-fluoroacrylate, and 2-(trifluoromethyl)methyl propenoate; and mixtures of the aforementioned polymers and polyvinylidene fluoride. In particular, a mixture of 2,2,2-trifluoroethyl methacrylate polymer and polyvinylidene fluoride is preferred.
The fluorescent agent has a peak of a fluorescence spectrum in a wavelength range of 430 to 550 nm, preferably 450 to 550 nm, and absorbs blue light and shifts the wavelength of the absorbed blue light into that of green light. There are no restrictions on the above-described fluorescent agent as long as the number of carbonyl bonds is one or smaller. Condensed polycyclic hydrocarbons, hydrocarbon ring assemblies, condensed heterocyclic systems and the like are preferred. In view of solubility in the plastic material of which the core is formed, the molecular weight of the fluorescent agent is preferably 200 to 1,000 and more preferably 300 to 700. For example, bisstyryl-benzene-based compounds, bisvinylcarbazole-benzene-based compounds, coumarin-based compounds and the like are preferred.
Examples of the bisvinylcarbazole-benzene-based compounds include styrylbenzene-based compounds such as 1,4-bis (2-(9-ethylcarbazol-3-yl) vinyl) benzene.
Examples of the bisstyryl-benzene-based compounds include 1,4-bis (4-(di-p-tolylamino) styryl) benzene.
Examples of the coumarin-based compounds include 3-(2-benzimidazolyl)-7-(diethylamino) coumarin.
When selecting a wavelength shifting fluorescent agent, it is preferred that its solubility in a monomer used as the raw material for the base material for the core, and in its polymer be high. The concentration of the fluorescent agent is preferably 30 to 10,000 mass ppm, more preferably, 50 to 1,000 mass ppm, and still more preferably 100 to 500 mass ppm is suitable. A preferred indicator for the concentration is the molar absorption coefficient of the fluorescent agent. For example, in the case of a wavelength shifting fiber having a diameter of 1 mm, the concentration of the fluorescent agent is adjusted so that it can absorb, while blue light emitted from the scintillator crosses (i.e., travels) a length of 1 mm inside the fiber, 70 to 99% of that blue light.
There are no restrictions on the method for manufacturing a wavelength shifting fiber. For example, a preform rod is manufactured by inserting a transparent rod-shaped polymer for a core (a rod for a core) made of a base material having a high refractive index into a transparent cylindrical polymer for cladding (a cylinder for cladding) made of a base material having a low refractive index. After that, the tip of the manufactured preform is heated and thereby finely drawn.
The outer diameter, the length, and the like of the fiber are selected as appropriate according to the use conditions.
A rod for a core can be manufactured by putting a monomer in a cylindrical polymerization container and performing thermal polymerization. As the polymerization method, a spontaneous polymerization that is performed by just heating the monomer without adding any initiator is preferred. However, a minimal amount of a thermal cleavage-type radical initiator may be added. Further, a photo cleavable-type radical initiator may be used in combination with the thermal cleavage-type radical initiator. Further, if the molecular weight of the rod for the core is too low, its mechanical strength and reliability required as an optical fiber may not be ensured. On the other hand, if the molecular weight is too high, the heating temperature needs to be raised because the viscosity of the molten material increases, thus possibly causing problems such as coloring caused by thermal degradation and thermal decomposition. Therefore, a molecular-weight modifier(s) may be added as required.
A cylinder for cladding can be manufactured by charging thermoplastic resin pellets into a melt extruder equipped with a circular die and extruding them into a cylindrical shape. Alternatively, a method in which a monomer is pressed onto a side surface of a rotating cylindrical container by a centrifugal force, so that the monomer is polymerized and solidified while forming a hollow part, may be used. Alternatively, a method in which a hollow part is formed by drilling a hole at the axial center of a cylindrical polymer may be used.
As described above, the concentration of the fluorescent agent is adjusted so that 70 to 99% of blue light can be absorbed at the outer diameter of the fiber. In the case of a single-cladding structure having an outer diameter of 1 mm, as an optical property of the fiber, the attenuation length AL is preferably longer than 300 cm (Attenuation Length AL>300 cm). The attenuation length AL can be adjusted by changing the structure of the cladding, the type of the fluorescent agent, the concentration of the fluorescent agent, and/or the outer diameter of the fiber.
The present invention will be described hereinafter in a more detailed manner by using examples, but is not limited by those examples at all.
In Table 1, molecular structures, molecular weights, classifications, molecular formulas, numbers of carbonyl bonds, and lifetimes of fluorescence (ns) of fluorescent agents according to Examples 1 to 3 are summarized.
Note that the fluorescence lifetime was obtained by performing measurement on a solvent in which a fluorescent agent having a dilute concentration of about 10 ppm was dissolved in a styrene monomer by using a compact fluorescence-lifetime measuring apparatus Quantaurus-Tau manufactured by Hamamatsu Photonics K.K. As the excitation wavelength, light having a wavelength close to the peak wavelength was selected according to the absorption spectrum of the fluorescent agent-containing solvent.
A bisvinylcarbazole-benzene-based fluorescent agent listed in Table 1 was used. The number of carbonyl bonds was zero and the fluorescence lifetime was 0.9 ns.
A bisstyryl-benzene-based fluorescent agent listed in Table 1 was used. The number of carbonyl bonds was zero and the fluorescence lifetime was 1.1 ns.
A coumarin-based fluorescent agent listed in Table 1 was used. The number of carbonyl bonds was one and the fluorescence lifetime was 2.4 ns.
In Table 2, molecular structures, molecular weights, classifications, molecular formulas, numbers of carbonyl bonds, and lifetimes of fluorescence (ns) of fluorescent agents according to Comparative Examples 1 and 2 are summarized.
A perylene-based fluorescent agent listed in Table 1 was used. The number of carbonyl bonds was two and the fluorescence lifetime was 3.8 ns.
A thioxanthene-based fluorescent agent listed in Table 1 was used. The number of carbonyl bonds was two and the fluorescence lifetime was 7.0 ns.
Here,
Fibers using the fluorescent agents according to the Examples 1 to 3 and the Comparative Examples 1 and 2, respectively, were manufactured, and their attenuation lengths AL were evaluated.
The absorption spectrum was obtained by performing measurement on a solvent in which a fluorescent agent having a dilute concentration of about 10 ppm was dissolved in a styrene monomer by using a UV-Visible-IR Spectrophotometer UV3600 manufactured by Shimadzu Corporation. The measurement range of the spectrum was 300 to 700 nm.
The fluorescence spectrum was obtained by performing measurement on a solvent in which a fluorescent agent having a dilute concentration of about 10 ppm was dissolved in a styrene monomer by using a fluorescence spectrophotometer FluoroMax-4 manufactured by HORIBA, Ltd. In the measurement, the excitation wavelength was set to a wavelength at which the absorption by the respective fluorescent agent was maximized. The measurement range of the spectrum was 300 to 700 nm.
When the concentration of the fluorescent agent is high, the fluorescence spectrum of the fluorescent agent itself cannot be properly measured due to the reabsorption by the fluorescent agent. Therefore, the concentration of the fluorescent agent was set to 10 ppm.
The quantum yield QE was obtained by performing measurement on a solvent in which a fluorescent agent having a dilute concentration of about 10 ppm was dissolved in a styrene monomer by using an absolute PL quantum yield measuring apparatus Quantaurus-QY manufactured by Hamamatsu Photonics K.K. In the measurement, the excitation wavelength was set to a wavelength at which the absorption by the respective fluorescent agent was maximized.
Fibers containing the fluorescent agents according to the Examples 1 to 3 and the Comparative Examples 1 and 2, respectively, were manufactured in accordance with the methods disclosed in Patent Literatures 4 and 5. Each fiber had an outer diameter of 1 mm and a single-cladding structure. The concentration of the fluorescent agent was adjusted so that the fluorescent agent absorbs, while blue light crosses (i.e., travels) a length of 1 mm inside the fiber, 70 to 99% of that blue light.
The attenuation lengths AL of the fibers were measured by using the apparatus shown in
As shown in
In Table 3, results of the evaluations of the fluorescent agents and fibers using them according to the Examples 1 to 3 and the Comparative Examples 1 and 2, respectively, are summarized. In Table 3, from the top, concentrations (ppm) of the fluorescent agents, lifetimes (ns) of the fluorescent agents, quantum yields QE, absorption peak wavelengths (nm) of the fluorescent agents, emission peak wavelengths (nm), and attenuation lengths AL (cm) of the fibers are listed.
The quantum yield QE was 0.93 (QE=0.93), and the absorption peak wavelength was 396 nm. Further, the fluorescence peak wavelength was 438 nm. Under that condition that the concentration of the fluorescent agent was 150 ppm, the attenuation length AL of the fiber was 393 cm, which was longer than the target of 300 cm and hence was excellent.
The quantum yield QE was 0.89 (QE=0.89), and the absorption peak wavelength was 420 nm. Further, the fluorescence peak wavelength was 470 nm. Under that condition that the concentration of the fluorescent agent was 200 ppm, the attenuation length AL of the fiber was 416 cm, which was longer than the target of 300 cm and hence was excellent.
The quantum yield QE was 0.79 (QE=0.79), and the absorption peak wavelength was 436 nm. Further, the fluorescence peak wavelength was 484 nm. Under that condition that the concentration of the fluorescent agent was 100 ppm, the attenuation length AL of the fiber was 170 cm, which was shorter than the target of 300 cm.
The quantum yield QE was 0.77 (QE=0.77), and the absorption peak wavelength was 470 nm. Further, the fluorescence peak wavelength was 512 nm. Under that condition that the concentration of the fluorescent agent was 250 ppm, the attenuation length AL of the fiber was 205 cm, which was shorter than the target of 300 cm.
The quantum yield QE was 0.81 (QE=0.81), and the absorption peak wavelength was 456 nm. Further, the fluorescence peak wavelength was 508 nm. Under that condition that the concentration of the fluorescent agent was 100 ppm, the attenuation length AL of the fiber was 287 cm, which was shorter than the target of 300 cm.
The present invention is not limited to the above-described embodiments, and they may be modified as desired without departing from the scope and spirit of the present invention.
This application is based upon and claims the benefit of priority from Japanese patent application No. 2021-004762, filed on Jan. 15, 2021, the disclosure of which is incorporated herein in its entirety by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-004762 | Jan 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/001038 | 1/14/2022 | WO |
