JP2021195425A - Method for producing photoluminescent material - Google Patents

Abstract

To produce a photoluminescent material in which a content of a silver atom is reduced.SOLUTION: There is provided a method for producing photoluminescent material which emits visible light by being irradiated with light, the method includes acquisition of a photoluminescent material II in which a content of a silver atom is reduced, by extraction of a silver atom from a photoluminescent material I containing the silver atom, in solution containing cation other than a silver ion and ammonia, and the photoluminescent material I is zeolite containing the sliver atom.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a photoluminescent material. Here, the "photoluminescent material" means "a material used for an application utilizing photoluminescence (that is, a phenomenon of emitting visible light by light irradiation)".

Photoluminescent materials that emit visible light when irradiated with light are used in lighting devices, backlights for liquid crystal devices, plasma displays, and the like.

Various photoluminescent materials have been developed so far. For example, Patent Document 1 discloses a photoluminescent material which is a faujasite-type zeolite containing a silver atom (silver ion). Further, Patent Documents 2 to 4 disclose a photoluminescent material which is an A-type zeolite containing a silver atom (silver ion). Further, Patent Document 5 discloses a photoluminescent material which is a sodalite containing a silver atom.

Japanese Unexamined Patent Publication No. 2012-52102 Japanese Unexamined Patent Publication No. 2014-37492 International Publication No. 2017/209033 Japanese Unexamined Patent Publication No. 2018-197296 International Publication No. 2016/190356

In a photoluminescent material containing a silver atom as described in Patent Documents 1 to 5, if the content of the silver atom is large, the obtained mixture is colored when mixed with a resin or rubber. There was a case. The present invention has been made in view of such circumstances, and an object of the present invention is to produce a photoluminescent material having a reduced content of silver atoms.

The present invention that can achieve the above object is as follows.
[1] A method for manufacturing a photoluminescent material that emits visible light by irradiation with light.
In the above method, the content of silver atoms is reduced by extracting silver atoms from the photoluminescent material I containing silver atoms in an aqueous solution containing cations other than silver ions and ammonia. A method comprising obtaining cent material II, as well as the photoluminescent material I being a silver-containing zeolite.
[2] The photoluminescent material I is at least one selected from the group consisting of a faujasite-type zeolite containing a silver atom, an A-type zeolite containing a silver atom, and a sodalite containing a silver atom. The method according to the above [1].
[3] The method according to the above [2], wherein the faujasite-type zeolite containing a silver atom is a faujasite-type zeolite containing 5% by weight or more and 30% by weight or less of silver ions.
[4] The method according to the above [2] or [3], wherein the A-type zeolite containing a silver atom is an A-type zeolite containing 2.5% by weight or more and 40% by weight or less of silver ions.
[5] The method according to any one of the above [2] to [4], wherein the sodalite containing a silver atom is a sodalite containing a silver atom of 0.25% by weight or more and 51% by weight or less.
[6] The method according to any one of the above [1] to [5], wherein the cation other than the silver ion contains an alkali metal ion and / or an alkaline earth metal ion.
[7] Ratio of the silver atom content of the photoluminescent material II to the silver atom content of the photoluminescent material I (silver atom content of the photoluminescent material II / photoluminescent material) The method according to any one of the above [1] to [6], wherein the content of the silver atom of I) is 3/100 to 9/10.
[8] A photoluminescent material produced by the method according to any one of the above [1] to [7].

According to the present invention, it is possible to produce a photoluminescent material having a reduced content of silver atoms.

In the present invention, the content of silver atoms is reduced by extracting silver atoms from the photoluminescent material I containing silver atoms in an aqueous solution containing cations other than silver ions and ammonia. One of the features is to obtain cent material II. By such an operation, silver atoms (silver ions or silver clusters) at sites that do not contribute to light emission in the photoluminescent material I are ammine-complexed and dissolved in the aqueous solution, except for the silver ions in the aqueous solution. It is presumed that the cations of the above are incorporated into the photoluminescent material instead of the dissolved silver atom, resulting in the photoluminescent material II having a reduced silver atom content. However, the present invention is not limited to such an estimation mechanism.

The reduction in the content of silver atoms can be confirmed, for example, by measurement using a wavelength dispersive X-ray fluorescence apparatus, and the inclusion of each atom (each cation) in the photoluminescent material by this apparatus. The amount can be measured.

The mixture obtained by mixing a photoluminescent material having a high content of silver atoms with a resin or rubber has a problem that the color changes to black and the emission intensity is lowered. On the other hand, in a photoluminescent material having a reduced silver atom content, such discoloration and a decrease in emission intensity can be suppressed. Further, if silver dissolved in an aqueous solution can be recovered and used for producing a photoluminescent material by the method of the present invention, a reduction in production cost can be expected.

As shown in Examples and Comparative Examples below, the emission intensity of Photoluminescent Material II obtained by reducing the content of silver atoms in Photoluminescent Material I is surprisingly high. It was equal to or higher than the emission intensity of cent material I. Here, "the light emitting intensity of the photoluminescent material II is equivalent to the light emitting intensity of the photoluminescent material I" means that the light emitting intensity of the photoluminescent material I is calculated as 1. It means that the relative emission intensity of II is in the range of 0.9 to 1.1.

The photoluminescent material I used in the present invention can be produced by ion exchange of zeolite as a raw material. This ion exchange can be performed by stirring and holding the zeolite in a silver ion-containing aqueous solution. Examples of the silver ion-containing aqueous solution include a silver nitrate aqueous solution and the like. If it is necessary to include ions other than silver ions (hereinafter sometimes abbreviated as "other ions") in the photoluminescent material I, other ions are present in the silver ion-containing aqueous solution used for ion exchange. Ion exchange using a silver ion-containing aqueous solution and ion exchange using another ion-containing aqueous solution may be sequentially performed. Examples of the aqueous solution containing other ions include a zinc sulfate aqueous solution, a calcium nitrate aqueous solution, a magnesium sulfate aqueous solution, and a potassium sulfate aqueous solution. Further, the concentration of silver ion and other ions in the aqueous solution can be appropriately adjusted according to the design value of the content of silver ion and other ions of the photoluminescent material I. Ion exchange can be performed at room temperature. The ion exchange time (that is, the stirring and holding time of the zeolite in the ion-containing aqueous solution) is usually 30 minutes or more and 10 hours or less, preferably 5 hours or less.

When the zeolite used as the raw material of the photoluminescent material I is a faujasite type zeolite or an A type zeolite, the zeolite after ion exchange may be collected by filtration from an ion-containing aqueous solution, washed with water, and then dried. preferable. Drying can be performed in an air atmosphere, an inert gas (for example, nitrogen gas) atmosphere, or a reduced pressure atmosphere. Among these, drying in an air atmosphere is preferable because the operation can be easily performed. The drying time is usually 1 hour or more and 30 hours or less, preferably 20 hours or less. The drying temperature is preferably 300 ° C. or lower, more preferably 200 ° C. or lower, preferably 50 ° C. or higher, and more preferably 100 ° C. or higher. This drying condition can be appropriately adjusted according to the type of zeolite used.

The dried A-type zeolite may be further subjected to a heat treatment such as calcination. The heat treatment can be performed in an atmospheric atmosphere, an inert gas (for example, nitrogen gas) atmosphere, or a reduced pressure atmosphere. Heat treatment in an air atmosphere is preferable because the operation can be easily performed. The heat treatment temperature is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, preferably 300 ° C. or lower, and more preferably 250 ° C. or lower. The heat treatment time is preferably 1 hour or more, more preferably 2 hours or more, preferably 10 hours or less, and more preferably 5 hours or less.

When the zeolite which is the raw material of the photoluminescent material I is sodalite, it is preferable to remove the sodalite after ion exchange from the ion-containing aqueous solution, wash it with water, and then heat-treat it. The heat treatment may be carried out in an atmosphere of an inert gas (for example, nitrogen gas) or in an atmosphere of air. The heat treatment temperature is preferably 50 ° C. or higher and 850 ° C. or lower, more preferably 150 ° C. or higher and 600 ° C. or lower, and can be appropriately adjusted depending on the type of photoluminescent material I produced from sodalite. The heat treatment time at this time is preferably 1 hour or more and 24 hours or less, and more preferably 2 hours or more and 24 hours or less.

The photoluminescent material I used in the present invention is preferably a faujasite-type zeolite containing a silver atom (hereinafter, may be abbreviated as “photoluminescent material I-1”).
A-type zeolite containing a silver atom (hereinafter abbreviated as "photoluminescent material I-2") and sodalite containing a silver atom (hereinafter abbreviated as "photoluminescent material I-3"). May do)
At least one selected from the group consisting of. Hereinafter, the photoluminescent material I-1 to the photoluminescent material I-3 will be described in order.

First, examples of the photoluminescent material I-1 containing a faujasite-type zeolite include those described in Patent Document 1. Examples of the faujasite-type zeolite include X-type zeolite and Y-type zeolite, which are synthetic zeolites, and Faujasite, which is a natural zeolite. Among these, X-type zeolite is preferable.

The average particle size of the photoluminescent material I-1 obtained from the faujasite-type zeolite, the photoluminescent material I-1 obtained from the faujasite-type zeolite, and the photoluminescent material II obtained from the photoluminescent material I-1 is preferable, respectively. Is 0.1 μm or more and 2 μm or less, more preferably 0.5 μm or more and 1.5 μm or less. These average particle sizes can be measured by laser diffraction and laser scattering methods.

Faujasite-type zeolites (faujasite, X-type zeolite and Y-type zeolite) are commercially available and easily available.

The photoluminescent material I-1 is a faujasite-type zeolite containing preferably 5% by weight or more and 30% by weight or less of silver ions, and the silver ion content thereof is more preferably 7% by weight or more and 20% by weight. % Or less.

In the present invention, the content of silver atoms in the photoluminescent material I or II is a value based on the entire photoluminescent material I or II. The same applies to the content of other atoms or ions.

The photoluminescent material I-1 may contain ions other than silver ions (hereinafter, may be abbreviated as "other ions"). Only one type of other ion may be used, or two or more types may be used in combination.

Other ions contained in the photoluminescent material I-1 can be introduced into the photoluminescent material I-1 by ion exchange using an aqueous metal salt solution containing the other ions.

Examples of other ions contained in the photoluminescent material I-1 include alkali metal ions such as sodium ion and potassium ion, alkaline earth metal ions such as calcium ion and magnesium ion, and zinc ion. Be done. Among these, the photoluminescent material I-1 containing calcium ions is preferable because the emission intensity is increased.

When the photoluminescent material I-1 contains other ions, the content of each of them is preferably 1% by weight or more and 10% by weight or less.

Next, the photoluminescent material I-2 containing the A-type zeolite will be described.
The average particle size of the photoluminescent material I-2 obtained from the A-type zeolite, the photoluminescent material I-2 obtained from the A-type zeolite, and the photoluminescent material II obtained from the photoluminescent material I-2 is preferably 0.1 μm, respectively. It is 20 μm or less, more preferably 0.5 μm or more and 15 μm or less.
Type A zeolite is commercially available and can be easily obtained.

The photoluminescent material I-2 is preferably an A-type zeolite containing 2.5% by weight or more and 40% by weight or less of silver ions, and more preferably contains silver ions and zinc ions, and has a silver ion content. Is 2.5% by weight or more and 30% by weight or less, the zinc ion content is 0.5% by weight or more and 15% by weight or less, and the total content of silver ions and zinc ions is 5% by weight or more and 35% by weight or less. The following type A zeolite (hereinafter sometimes abbreviated as "photoluminescent material I-2a"),
The total content of at least one selected from the group consisting of cesium ion and rubidium ion and at least one selected from the group consisting of silver ion and zinc ion and consisting of cesium ion and rubidium ion is 1% by weight or more and 25% by weight. A type zeolite having a silver ion content of 2.5% by weight or more and 30% by weight or less and a zinc ion content of 0.5% by weight or more and 15% by weight or less (hereinafter referred to as "photolumi"). Nescent Material I-2b ”), and contains silver and ammonium ions, the silver ion content is 5% by weight or more and 40% by weight or less, and the ammonium ion content is 0.1. A-type zeolite containing 50% by weight or more and 25% by weight or less (excluding A-type zeolite containing zinc ions) (hereinafter, may be abbreviated as "photoluminescent material I-2c"),
At least one selected from the group consisting of. Hereinafter, the photoluminescent material I-2a to the photoluminescent material I-2c will be described in order.

Examples of the photoluminescent material I-2a include those described in Patent Document 2. The silver ion content in the photoluminescent material I-2a is more preferably 3.5% by weight or more and 20% by weight or less.

The zinc ion content in the photoluminescent material I-2a is more preferably 5% by weight or more and 7% by weight or less.

The total content of silver ions and zinc ions in the photoluminescent material I-2a is more preferably 10% by weight or more and 25% by weight or less.

The molar ratio of silver ion: zinc ion in the photoluminescent material I-2a is preferably 1:45 to 8: 1, more preferably 1: 5 to 2: 1.

The photoluminescent material I-2a may contain ions other than silver ions and zinc ions (hereinafter, may be abbreviated as "other ions"). The photoluminescent material I-2a may contain one type of other ion or may contain two or more types of other ions.

Other ions contained in the photoluminescent material I-2a can be introduced into the photoluminescent material I-2a by ion exchange using an aqueous solution of a salt containing the other ions.

Examples of other ions contained in the photoluminescent material I-2a include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion and the like. .. Of these, ammonium ions are preferred.

When the photoluminescent material I-2a contains other ions (for example, ammonium ions), the content thereof is preferably 1% by weight or more and 10% by weight or less.

Examples of the photoluminescent material I-2b include those described in Patent Document 3. The photoluminescent material I-2b contains at least one ion selected from the group consisting of cesium ion and rubidium ion, and preferably contains cesium ion.

The total content of at least one (if only one of these, the content thereof) selected from the group consisting of cesium ions and rubidium ions in the photoluminescent material I-2b is more preferably 2 weights. % Or more and 23% by weight or less.

The silver ion content in the photoluminescent material I-2b is more preferably 3.5% by weight or more and 28% by weight or less.

The zinc ion content in the photoluminescent material I-2b is more preferably 5% by weight or more and 13% by weight or less.

The photoluminescent material I-2b may contain ions other than cesium ion, rubidium ion, silver ion and zinc ion (hereinafter, may be abbreviated as "other ions"). The photoluminescent material I-2b may contain one type of other ion or may contain two or more types of other ions.

Other ions contained in the photoluminescent material I-2b can be introduced into the photoluminescent material I-2b by ion exchange using an aqueous solution containing the other ions.

Examples of other ions contained in the photoluminescent material I-2b include ammonium ion, sodium ion, potassium ion, calcium ion, magnesium ion and the like.

Examples of the photoluminescent material I-2c include those described in Patent Document 4. The silver ion content in the photoluminescent material I-2c is more preferably 7% by weight or more and 35% by weight or less.

The ammonium ion content in the photoluminescent material I-2c is preferably 0.1% by weight or more and 25% by weight or less, and more preferably 1% by weight or more and 15% by weight or less.

The total content of silver ions and ammonium ions in the photoluminescent material I-2c is preferably 6% by weight or more and 40% by weight or less, and more preferably 10% by weight or more and 35% by weight or less.

The photoluminescent material I-2c may contain ions different from silver ions and ammonium ions (excluding zinc ions) (hereinafter, may be abbreviated as "other ions"). The photoluminescent material I-2c may contain one type of other ion or may contain two or more types of other ions.

Other ions contained in the photoluminescent material I-2c can be introduced into the photoluminescent material I-2c by ion exchange using an aqueous solution containing the other ions.

Other ions contained in the photoluminescent material I-2c include, for example, alkali metal ions such as sodium ion, potassium ion and cesium ion; alkaline earth metal ion such as calcium ion, strontium ion and barium ion; nickel. Examples thereof include other metal ions such as ions, copper ions, manganese ions and aluminum ions. Of these, cesium ions are preferred.

When the photoluminescent material I-2c contains other ions, the content thereof (or the total content of the other ions when two or more other ions are contained) is preferably 0.1 weight by weight. % Or more and 40% by weight or less.

Examples of the photoluminescent material I-3 containing sodalite include those described in Patent Document 5. The photoluminescent material I-3 is subjected to ion exchange by stirring and holding sodalite in a silver ion-containing aqueous solution, then collected by filtration, washed with water, and then the obtained ion exchange sodalite is heat-treated. Can be manufactured by. The heat treatment conditions vary depending on the content of silver atoms and, if zinc atoms are required, their content. In the production of the photoluminescent material I-3, drying at a temperature higher than room temperature is included in the heat treatment. Sodalite can be easily obtained as a by-product of type A zeolite, which is currently mass-produced at low cost.

The average particle size of the photoluminescent material I-3 obtained from sodalite and sodalite, and the photoluminescent material II obtained from the photoluminescent material I-3 is preferably 0.05 μm or more and 500 μm, respectively. Below, it is more preferably 0.5 μm or more and 50 μm or less.

The photoluminescent material I-3 is preferably sodalite containing 0.25% by weight or more and 51% by weight or less of silver atoms, and more preferably 0.25% by weight or more and 10% by weight or less of silver atoms. Sodalite contained (hereinafter sometimes abbreviated as "photoluminescent material I-3a"),
Sodalite containing 12% by weight or more and 18% by weight or less of silver atoms (hereinafter, may be abbreviated as "photoluminescent material I-3b"), which is produced by heat treatment at a temperature of less than 300 ° C.
Sodalite containing 20% by weight or more and 31% by weight or less of silver atoms and 7% by weight or more and 17% by weight or less of zinc atoms (hereinafter sometimes abbreviated as "photoluminescent material I-3c"), and 300. Sodalite containing 33% by weight or more and 51% by weight or less of silver atoms and 0.5% by weight or more and 11% by weight or less of zinc atoms produced by heat treatment at a temperature of ° C. or higher and 850 ° C. or lower (hereinafter referred to as "photo"). Luminous material I-3d "may be abbreviated)
At least one selected from the group consisting of. It is preferable that neither the photoluminescent material I-3a nor the photoluminescent material I-3b contains an oxalate anion. Hereinafter, the photoluminescent material I-3a to the photoluminescent material I-3d will be described.

The photoluminescent material I-3b (silver atom content: 12% by weight or more and 18% by weight or less) needs to be produced through heat treatment at a temperature of less than 300 ° C. On the other hand, the photoluminescent material I-3d (silver atom content: 33% by weight or more and 51% by weight or less) needs to be produced through heat treatment at a temperature of 300 ° C. or higher. When the content of silver atoms is 0.25% by weight or more and 10% by weight or less (photoluminescent material I-3a) and when the content of silver atoms is 20% by weight or more and 31% by weight or less (). The photoluminescent material I-3c) can be produced after being heat-treated at either a temperature of 300 ° C. or higher or lower than 300 ° C.

It is presumed that the difference in the heat treatment temperature for producing the photoluminescent material I-3 is due to the difference in the morphology of the silver atom required for light emission due to the difference in the content of the silver atom in the sodalite. Will be done. In sodalite obtained by low temperature heat treatment, silver atoms are present in the form of silver ions, and in sodalite obtained by high temperature heat treatment, silver atoms are in the form of silver ions or silver clusters, or the like thereof. It is presumed that some are in the form of silver ions and the rest are in the form of silver clusters.

The temperature of the heat treatment for producing the photoluminescent material I-3a is preferably 50 ° C. or higher and 850 ° C. or lower, more preferably 100 ° C. or higher and 700 ° C. or lower, and further preferably 150 ° C. or higher and 600 ° C. or lower. The heat treatment time for producing the photoluminescent material I-3a is preferably 1 hour or more and 24 hours or less, and more preferably 2 hours or more and 24 hours or less.

The temperature of the heat treatment for producing the photoluminescent material I-3b needs to be less than 300 ° C., preferably 50 ° C. or higher and lower than 300 ° C., more preferably 100 ° C. or higher and 270 ° C. or lower, still more preferable. Is 150 ° C. or higher and 250 ° C. or lower. The heat treatment time for producing the photoluminescent material I-3b is preferably 1 hour or more and 24 hours, more preferably 2 hours or more and 16 hours or less.

The temperature of the heat treatment for producing the photoluminescent material I-3c is preferably 50 ° C. or higher and 850 ° C. or lower, more preferably 100 ° C. or higher and 700 ° C. or lower, and further preferably 150 ° C. or higher and 600 ° C. or lower. The heat treatment time for producing the photoluminescent material I-3c is preferably 1 hour or more and 24 hours or less, and more preferably 2 hours or more and 24 hours or less.

The temperature of the heat treatment for producing the photoluminescent material I-3d needs to be 300 ° C. or higher and 850 ° C. or lower, preferably 300 ° C. or higher and 700 ° C. or lower, and more preferably 350 ° C. or higher and 650 ° C. or lower. More preferably, it is 400 ° C. or higher and 600 ° C. or lower. The heat treatment time for producing the photoluminescent material I-3d is preferably 1 hour or more and 12 hours or less, and more preferably 2 hours or more and 8 hours or less.

In the photoluminescent material I-3a and the photoluminescent material I-3b having a silver atom content of 18% by weight or less, zinc atoms are not required for light emission. However, the photoluminescent material I-3a and the photoluminescent material I-3b may also contain a zinc atom. On the other hand, in the photoluminescent material I-3c and the photoluminescent material I-3d having a silver atom content of 20% by weight or more, a zinc atom is required in addition to the silver atom for light emission. The reason why zinc atoms are required when the content of silver atoms is high is that the morphology of silver atoms required for light emission differs in sodalite due to the difference in the content of silver atoms as described above. Presumed.

The photoluminescent material I-3 may contain atoms other than silver and zinc atoms (hereinafter referred to as "other atoms") and / or ions (hereinafter referred to as "other ions"). Examples of other atoms include transition metal atoms other than silver and zinc, alkali metal atoms, alkaline earth metal atoms, halogen atoms and the like. Examples of other ions include ammonium ion, halide ion and the like. However, it is preferable that the photoluminescent material I-3a and the photoluminescent material I-3b do not contain an oxalate anion.

The content of silver atoms in the photoluminescent material I-3a is preferably 2.5% by weight or more and 10% by weight or less, and more preferably 3.5% by weight or more and 8% by weight or less. The photoluminescent material I-3a may contain a zinc atom. The content of zinc atoms in the photoluminescent material I-3a is preferably 25% by weight or less, more preferably 5% by weight or more and 25% by weight or less.

The content of silver atoms in the photoluminescent material I-3b is preferably 12% by weight or more and 18% by weight or less, and more preferably 13% by weight or more and 17% by weight or less. The photoluminescent material I-3b may contain a zinc atom. The content of zinc atoms in the photoluminescent material I-3b is preferably 0% by weight or more and 21% by weight or less, and more preferably 5% by weight or more and 21% by weight or less.

The content of silver atoms in the photoluminescent material I-3c is preferably 20% by weight or more and 31% by weight or less, and more preferably 22% by weight or more and 31% by weight or less. The content of zinc atoms in the photoluminescent material I-3c is preferably 7% by weight or more and 17% by weight or less, and more preferably 8.5% by weight or more and 17% by weight or less.

The content of silver atoms in the photoluminescent material I-3d is preferably 33% by weight or more and 50.5% by weight or less, and more preferably 35% by weight or more and 49% by weight or less. The content of zinc atoms in the photoluminescent material I-3d is preferably 0.5% by weight or more and 11% by weight or less, and more preferably 0.8% by weight or more and 11% by weight or less.

The aqueous solution for extracting a silver atom from the photoluminescent material I (hereinafter, may be abbreviated as "extracted aqueous solution") contains cations other than silver ions and ammonia. The cation other than the silver ion may be a non-metal ion such as an ammonium ion, or may be a metal ion such as an alkali metal ion, an alkaline earth metal ion, or a zinc ion.

The cations other than silver ions preferably include alkali metal ions and / or alkaline earth metal ions. As the alkali metal ion, lithium ion, sodium ion, potassium ion and cesium ion are preferable. As the alkaline earth metal ion, strontium ion and barium ion are preferable. The cation other than the silver ion more preferably contains at least one selected from the group consisting of lithium ion, sodium ion, potassium ion, cesium ion, strontium ion and barium ion, and more preferably sodium ion, potassium ion and cesium ion. , At least one selected from the group consisting of strontium ion and barium ion, particularly preferably at least one selected from the group consisting of sodium ion, potassium ion, and strontium ion, most preferably sodium ion and / or. Contains strontium ions.

As the cation other than the silver ion, only one kind may be used, or two or more kinds may be used. For example, as the cation other than the silver ion, two or more kinds of alkali metal ions may be used, or the alkali metal ion and other cations (for example, zinc ion) may be used.

In the photoluminescent material I-2a or I-2b containing silver and zinc, when zinc ions are extracted together with silver ions, the emission intensity may decrease. Therefore, when the photoluminescent material I-2a or I-2b is used, it is preferable that the cation other than the silver ion contains a zinc ion. By using zinc ions, it is possible to suppress a decrease in the emission intensity of the photoluminescent material II obtained from the photoluminescent material I-2a or I-2b.

By using a cation having a small atomic weight (for example, sodium ion) as a cation other than the silver ion, the density of the photoluminescent material II can be made lower than the density of the photoluminescent material I. The low-density photoluminescent material can maintain a better dispersed state in a mixture with a resin, rubber, a solvent, etc., as compared with the high-density photoluminescent material.

Further, the operation of extracting silver atoms from the photoluminescent material I by using the extraction aqueous solution (hereinafter referred to as “extraction operation”) may be performed only once or twice or more. The extraction operation may be performed twice or more using one type of extraction aqueous solution (for example, an extraction aqueous solution containing sodium ions and ammonia). Further, the extraction operation may be performed twice or more by using two or more different kinds of extraction aqueous solutions. For example, an extraction operation may be performed using an extraction aqueous solution containing sodium ions and ammonia, and then an extraction operation may be performed using an extraction aqueous solution containing potassium ions and ammonia.

In order to efficiently extract silver atoms from the photoluminescent material I, the concentration of cations other than silver ions in the extraction aqueous solution (when two or more cations are used, the sum of their concentrations) is preferable. Is 0.3% by weight or more and 20% by weight or less, more preferably 0.45% by weight or more and 20% by weight or less. For the same reason, the concentration of ammonia in the extracted aqueous solution is preferably 0.12% by weight or more and 30% by weight or less, more preferably 0.18% by weight or more and 30% by weight or less.

When only alkali metal ions are used as cations other than silver ions, the preferable range of the concentration of alkali metal ions in the extracted aqueous solution is the same as the preferable range of the concentration of cations other than silver ions in the above-mentioned extracted aqueous solution. When a cation other than the alkali metal ion and an alkali metal ion are used in combination as a cation other than the silver ion, the concentration of the alkali metal ion in the extraction aqueous solution (when two or more kinds of alkali metal ions are used, their concentration). Is preferably 0.05% by weight or more and 10% by weight or less, and more preferably 0.1% by weight or more and 5% by weight or less.

When only alkaline earth metal ions are used as cations other than silver ions, the preferable range of the concentration of alkaline earth metal ions in the extracted aqueous solution is the preferable range of the concentration of cations other than silver ions in the above-mentioned extracted aqueous solution. It is the same. When a cation other than alkaline earth metal ion and an alkaline earth metal ion are used in combination as a cation other than silver ion, the concentration of alkaline earth metal ion in the extraction aqueous solution (two or more kinds of alkaline earth metal ion). When used, the total concentration thereof) is preferably 0.05% by weight or more and 10% by weight or less, and more preferably 0.1% by weight or more and 5% by weight or less.

When only zinc ion is used as the cation other than silver ion, the preferable range of the concentration of zinc ion in the extracted aqueous solution is the same as the preferable range of the concentration of the cation other than silver ion in the above-mentioned extracted aqueous solution. When a cation other than zinc ion and zinc ion are used in combination as the cation other than silver ion, the concentration of zinc ion in the extracted aqueous solution is preferably 0.15% by weight or more and 0.30% by weight or less, more preferably. It is 0.20% by weight or more and 0.26% by weight or less.

The extracted aqueous solution may contain an organic solvent that is miscible with water. Examples of the organic solvent include alcohols such as methanol and ethanol, and ketones such as acetone. The content of the organic solvent is preferably 50% by weight or less, more preferably 20% by weight or less of the entire extracted aqueous solution from the viewpoint of dissolving silver ions in the extracted aqueous solution. The content of the organic solvent is a value based on the entire extracted aqueous solution. Most preferably, the extraction aqueous solution does not contain an organic solvent.

In order to efficiently extract silver atoms from the photoluminescent material I, the amount of the extraction aqueous solution used is preferably 5 to 500 mL, more preferably 7.5 to 5 per 1 g of the photoluminescent material I. It is 300 mL, more preferably 10 to 100 mL.

The temperature of the extracted aqueous solution in the extraction operation is preferably 0 to 30 ° C., more preferably 5 to 25 ° C. from the viewpoint of cation solubility and ammonia volatility. The time of the extraction operation is preferably 5 minutes to 24 hours, more preferably 10 minutes to 16 hours, from the viewpoint of the volatility of ammonia and the reaction time required for the ammine complexation of silver.

When the photoluminescent material I-1 is used as the photoluminescent material I, the silver atom content of the photoluminescent material II obtained by the above-mentioned extraction operation is preferably 0.9% by weight or more 18 It is 1% by weight or less, more preferably 1.2% by weight or more and 15% by weight or less.

When the photoluminescent material I-2a is used as the photoluminescent material I, the silver atom content of the photoluminescent material II obtained by the above-mentioned extraction operation is preferably 0.3% by weight or more 18 By weight% or less, more preferably 0.4% by weight or more and 16% by weight or less.

When the photoluminescent material I-2b is used as the photoluminescent material I, the content of silver atoms in the photoluminescent material II obtained by the above-mentioned extraction operation is preferably 0.3% by weight or more. It is 25% by weight or less, more preferably 0.4% by weight or more and 22% by weight or less.

When the photoluminescent material I-2c is used as the photoluminescent material I, the silver atom content of the photoluminescent material II obtained by the above-mentioned extraction operation is preferably 0.3% by weight or more. It is 31% by weight or less, more preferably 0.4% by weight or more and 28% by weight or less.

When the photoluminescent material I-3a is used as the photoluminescent material I, the content of the silver atom of the photoluminescent material II obtained by the above-mentioned extraction operation is preferably 0.1% by weight or more 7 It is .2% by weight or less, more preferably 0.2% by weight or more and 6.4% by weight or less.

When the photoluminescent material I-3b is used as the photoluminescent material I, the silver atom content of the photoluminescent material II obtained by the above-mentioned extraction operation is preferably 0.39% by weight or more. It is 15% by weight or less, more preferably 0.52% by weight or more and 14% by weight or less.

When the photoluminescent material I-3c is used as the photoluminescent material I, the content of silver atoms in the photoluminescent material II obtained by the above-mentioned extraction operation is preferably 0.66% by weight or more. It is 27% by weight or less, more preferably 0.88% by weight or more and 25% by weight or less.

When the photoluminescent material I-3d is used as the photoluminescent material I, the content of the silver atom of the photoluminescent material II obtained by the above-mentioned extraction operation is preferably 1.05% by weight or more. It is 44% by weight or less, more preferably 1.4% by weight or more and 39% by weight or less.

The ratio of the silver atom content of the photoluminescent material II obtained by the method of the present invention to the silver atom content of the photoluminescent material I (silver atom content of the photoluminescent material II / The content of silver atoms in the photoluminescent material I) is preferably 3/100 to 9/10, more preferably 1/25 to 3/4, and even more preferably 1/20 to 1/2. Here, the unit of the content used in the above ratio is "% by weight".

The present invention provides a photoluminescent material produced by the method described above (ie, a photoluminescent material II with a reduced silver atom content). As the photoluminescent material II, only one kind may be used, or two or more kinds may be used in combination. Further, the photoluminescent material II may be used in combination with other photoluminescent materials. The photoluminescent material II can be used, for example, in a lighting device, a light emitting paint, a light emitting fiber, a resin molded product, a rubber molded product, a light emitting element, a sensor and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, and is carried out with appropriate modifications to the extent that it can meet the above gist. It is also possible, all of which are within the technical scope of the invention.

Unless otherwise specified, the raw materials (for example, A-type zeolite) used in the following Examples and Comparative Examples are the same ones obtained from the same manufacturer (for example, Union Showa Co., Ltd.).

In addition, the properties of the obtained photoluminescent material were evaluated as follows.
The composition of the photoluminescent material was measured by a scanning fluorescent X-ray analyzer ZSX Primus III + manufactured by Rigaku Corporation, and the mass (A) per mole of the photoluminescent material was calculated based on the measurement. Next, the lattice constant of the photoluminescent material is measured by the fully automated multipurpose X-ray diffractometer SmartLab manufactured by Rigaku, and the lattice constant is squared to the cube of the volume per molecule of the photoluminescent material (B, unit: cm). ³ ) was calculated. From these values, the density of the photoluminescent material (unit: g / cm ³ ) was calculated by the following formula.
Density (g / cm ³ ) = A (g) / Avogadro constant (6.02 × ^10-23 ) / B (cm ³ )
Further, the emission intensity of this photoluminescent material was measured by a fluorescence spectrophotometer FluoroMax-4 manufactured by HORIBA, Ltd.

Example 1
(1) Manufacture of photoluminescent material I (type A zeolite containing silver atom) Type A zeolite (manufactured by Union Showa Co., Ltd., average particle size 5 μm, containing 11% by weight of sodium ion as an exchangeable cation) 5.00 g , Silver nitrate (manufactured by Inuijo Kikinzoku Co., Ltd., purity 99.8% by weight) 0.93 g, zinc nitrate hexahydrate (manufactured by Kishida Chemical Co., Ltd., purity 99% by weight) 2.85 g and ion-exchanged water 30 mL are mixed to obtain. The resulting mixture was stirred and retained at room temperature for 1 hour. After that, stirring is stopped, the solid is recovered by suction filtration, and the recovered solid is dried at 105 ° C. for 16 hours and then fired at 230 ° C. for 16 hours to obtain a photoluminescent material (A-type zeolite containing a silver atom). 5.95 g was obtained.

(2) Production of photoluminescent material II with reduced silver atom content Sodium nitrate (manufactured by Nakaraitesk Co., Ltd., purity 99% by weight) 0.28 g, zinc nitrate hexahydrate 0.33 g, ammonia water (2) Kishida Chemical Co., Ltd., 1.5 mL of ammonia concentration 28.7% by weight) and 30 mL of ion-exchanged water were mixed to obtain an extracted aqueous solution (sodium ion concentration 0.24% by weight in the extracted aqueous solution, zinc ion. Concentration 0.23% by weight, concentration of ammonia 1.20% by weight).

1.00 g of the photoluminescent material (type A zeolite containing a silver atom) obtained in (1) above was added to the obtained aqueous extraction solution, and the obtained mixture was stirred at room temperature for 1 hour. Then, the solid was collected by suction filtration and dried at 105 ° C. for 16 hours to obtain 0.98 g of a photoluminescent material having a reduced silver atom content.

Comparative Example 1: Photoluminescent material (A-type zeolite containing a silver atom)
The photoluminescent material (type A zeolite containing a silver atom) produced in Example 1 (1) was used as Comparative Example 1.

Comparative Example 2: Production of photoluminescent material (A-type zeolite containing silver atom) 5.00 g of A-type zeolite, 0.093 g of silver nitrate, 2.85 g of zinc nitrate hexahydrate and 30 mL of ion-exchanged water are mixed. The resulting mixture was stirred and retained at room temperature for 1 hour. After that, stirring is stopped, the solid is recovered by suction filtration, and the recovered solid is dried at 105 ° C. for 16 hours and then fired at 230 ° C. for 16 hours to obtain a photoluminescent material (A-type zeolite containing a silver atom) 5. .60 g was obtained.

The composition and density of the photoluminescent materials obtained in Example 1 (2) and Comparative Examples 1 and 2 are shown in Table 1. Further, the relative emission intensities of the photoluminescent materials obtained in Example 1 (2) and Comparative Examples 1 and 2, which were calculated with the emission intensity of the photoluminescent material obtained in Comparative Example 1 as 1, are shown in the table. Shown in 1.

The photoluminescent material obtained in Example 1 (2) has a lower silver atom content than that obtained in Comparative Example 1, but the photo obtained in Example 1 (2). The emission intensity of the luminescent material was higher than that of the photoluminescent material obtained in Comparative Example 1.

The silver atom content of the photoluminescent material obtained in Example 1 (2) and Comparative Example 2 is the same, but the emission intensity of the photoluminescent material obtained in Example 1 (2) is , It was higher than that of the photoluminescent material obtained in Comparative Example 2 which did not include the step of reducing silver atoms.

Example 2
(1) Production of photoluminescent material I (sodalite containing silver atom) 10.00 g of type A zeolite, 25.60 g of sodium hydroxide (manufactured by Nacalai Tesque, purity 97% by weight) and ion-exchanged water 38. 40 g was mixed and the resulting mixture was allowed to stand at 95 ° C. for 16 hours. Then, the solid was collected by suction filtration and dried at 105 ° C. for 16 hours to obtain 10.00 g of sodalite (average particle size 3 μm, containing 12% by weight of sodium ion as an exchangeable cation).

Obtained by mixing 5.00 g of the obtained sodalite, 0.070 g of silver nitrate, 1.85 g of zinc nitrate hexahydrate, 2.51 g of potassium nitrate (manufactured by Nacalai Tesque, purity 99% by weight) and 30 mL of ion-exchanged water. The mixture was stirred at room temperature for 1 hour. Then, the solid was collected by suction filtration, dried at 105 ° C. for 16 hours, and then baked at 230 ° C. for 16 hours to obtain 5.57 g of a photoluminescent material (sodalite containing a silver atom).

(2) Production of Photoluminescent Material II with Reduced Silver Atomic Concentration 0.28 g of sodium nitrate, 0.25 g of potassium nitrate, 0.4 mL of ammonia water and 30 mL of ion-exchanged water are mixed to obtain an extracted aqueous solution. (Sodium ion concentration 0.25% by weight, potassium ion concentration 0.31% by weight, ammonia concentration 0.33% by weight in the extracted aqueous solution).

1.00 g of the photoluminescent material (sodalite containing a silver atom) obtained in (1) above was added to the obtained aqueous extraction solution, and the obtained mixture was stirred at room temperature for 1 hour. Then, the solid was collected by suction filtration and dried at 105 ° C. for 16 hours to obtain 0.99 g of a photoluminescent material having a reduced silver atom content.

Comparative Example 3: Photoluminescent material (sodalite containing a silver atom)
The photoluminescent material (sodalite containing a silver atom) produced in Example 2 (1) was used as Comparative Example 3.

Comparative Example 4: Production of photoluminescent material (sodalite containing silver atom) 5.00 g of sodalite, 0.018 g of silver nitrate, 1.85 g of zinc nitrate hexahydrate, 2.51 g of potassium nitrate and 30 mL of ion-exchanged water. Was mixed, and the obtained mixture was stirred at room temperature for 1 hour. Then, the solid was collected by suction filtration, dried at 105 ° C. for 16 hours, and then baked at 230 ° C. for 16 hours to obtain 5.58 g of a photoluminescent material (sodalite containing a silver atom).

Table 2 shows the composition and density of the photoluminescent materials obtained in Example 2 (2) and Comparative Examples 3 and 4. Further, the relative emission intensities of the photoluminescent materials obtained in Example 2 (2) and Comparative Examples 3 and 4, which were calculated with the emission intensity of the photoluminescent material obtained in Comparative Example 3 as 1, are shown in the table. Shown in 2.

The photoluminescent material obtained in Example 2 (2) has a lower silver atom content than that obtained in Comparative Example 3, but the photo obtained in Example 2 (2). The emission intensity of the luminescent material was higher than that of the photoluminescent material obtained in Comparative Example 3.

The silver atom content of the photoluminescent material obtained in Example 2 (2) and Comparative Example 4 is the same, but the emission intensity of the photoluminescent material obtained in Example 2 (2) is , It was higher than that of the photoluminescent material obtained in Comparative Example 4 which did not include the step of reducing silver atoms.

Example 3
(1) Production of Photoluminescent Material I (X-type Zeolite Containing Silver Atom) 0.60 g of silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in ion-exchanged water to prepare a 100 mL aqueous solution. To the obtained aqueous solution, 3.00 g of X-type zeolite (manufactured by Tosoh Corporation, average particle size 5 μm, containing 8% by weight of sodium ion as an exchangeable cation) was added, and the obtained mixture was stirred at 25 ° C. for 2 hours. Then, the solid was collected by suction filtration and dried at 70 ° C. for 24 hours to obtain 4.05 g of a photoluminescent material (X-type zeolite containing a silver atom).

(2) Production of photoluminescent material with reduced silver atom content 2.19 g of sodium nitrate and 3.6 mL of ammonia water were mixed with ion-exchanged water to obtain 100 mL of an extracted aqueous solution (in the extracted aqueous solution). Sodium ion concentration 0.56% by weight, ammonia concentration 0.88% by weight).

3.00 g of the photoluminescent material (X-type zeolite containing a silver atom) obtained in (1) above was added to the obtained aqueous extraction solution, and the obtained mixture was stirred at room temperature for 2 hours. Then, the solid was collected by suction filtration and dried at 70 ° C. for 24 hours to obtain 2.36 g of a photoluminescent material having a reduced silver atom content.

Comparative Example 5: Photoluminescent material (X-type zeolite containing a silver atom)
The photoluminescent material (X-type zeolite containing a silver atom) produced in Example 3 (1) was used as Comparative Example 5.

Comparative Example 6: Production of Photoluminescent Material (X-type Zeolite Containing Silver Atom) 0.033 g of silver nitrate was dissolved in ion-exchanged water to prepare a 100 mL aqueous solution. 0.95 g of X-type zeolite was added to the obtained aqueous solution, and the obtained mixture was stirred at 25 ° C. for 2 hours. Then, the solid was collected by suction filtration and dried at 70 ° C. for 24 hours to obtain 1.00 g of a photoluminescent material (X-type zeolite containing a silver atom).

The composition and density of the photoluminescent materials obtained in Example 3 (2) and Comparative Examples 5 and 6 are shown in Table 3. Further, the relative emission intensities of the photoluminescent materials obtained in Example 3 (2) and Comparative Examples 5 and 6, which were calculated with the emission intensity of the photoluminescent material obtained in Comparative Example 5 as 1, are shown in the table. Shown in 3.

The photoluminescent material obtained in Example 3 (2) has a lower silver atom content than that obtained in Comparative Example 5, but the photo obtained in Example 3 (2). The emission intensity of the luminescent material was equivalent to that of the photoluminescent material obtained in Comparative Example 5.

The silver atom content of the photoluminescent material obtained in Example 3 (2) and Comparative Example 6 is the same, but the emission intensity of the photoluminescent material obtained in Example 3 (2) is It was higher than that of the photoluminescent material obtained in Comparative Example 6 which did not include the step of reducing silver atoms.

Example 4
(1) Production of photoluminescent material I (A-type zeolite containing silver atom) 5.00 g of A-type zeolite, 0.47 g of silver nitrate, 2.49 g of zinc nitrate hexahydrate, ammonium nitrate (manufactured by Kanto Chemical Co., Ltd., 1.97 g of purity 99% by weight), 2.67 g of cesium nitrate (manufactured by Mitsuwa Chemical Co., Ltd., purity 99% by weight) and 30 mL of ion-exchanged water were mixed, and the obtained mixture was stirred at room temperature for 1 hour. Then, the solid was collected by suction filtration, dried at 105 ° C. for 16 hours, and then fired at 150 ° C. for 16 hours to obtain 6.30 g of a photoluminescent material (A-type zeolite containing a silver atom).

(2) Production of photoluminescent material II with reduced silver atom content 0.58 g of strontium nitrate (manufactured by Kishida Chemical Co., Ltd., purity 98% by weight), 0.4 mL of ammonia water and 30 mL of ion-exchanged water are mixed. Then, an aqueous solution of strontium was obtained (concentration of strontium ion in the aqueous solution of extraction was 0.76% by weight, concentration of ammonia was 0.33% by weight).

1.00 g of the photoluminescent material (type A zeolite containing a silver atom) obtained in (1) above was added to the obtained aqueous extraction solution, and the obtained mixture was stirred at room temperature for 1 hour. Then, the solid was collected by suction filtration and dried at 105 ° C. for 16 hours to obtain 0.82 g of a photoluminescent material having a reduced silver atom content.

Comparative Example 7: Photoluminescent material (A-type zeolite containing a silver atom)
The photoluminescent material I-2b (A-type zeolite containing a silver atom) produced in Example 4 (1) was used as Comparative Example 7.

Comparative Example 8: Production of photoluminescent material (A-type zeolite containing silver atom) 5.00 g of A-type zeolite, 0.33 g of silver nitrate, 2.85 g of zinc nitrate hexahydrate, 1.97 g of ammonium nitrate, cesium nitrate 0.53 g, 2.90 g of strontium nitrate and 30 mL of ion-exchanged water were mixed, and the obtained mixture was stirred at room temperature for 1 hour. Then, the solid was collected by suction filtration, dried at 105 ° C. for 16 hours, and then fired at 150 ° C. for 16 hours to obtain 5.98 g of a photoluminescent material (A-type zeolite containing a silver atom).

The composition and density of the photoluminescent materials obtained in Example 4 (2) and Comparative Examples 7 and 8 are shown in Table 4. Further, the relative emission intensities of the photoluminescent materials obtained in Example 4 (2) and Comparative Examples 7 and 8, which were calculated with the emission intensity of the photoluminescent material obtained in Comparative Example 7 as 1, are shown in the table. Shown in 4.

The photoluminescent material obtained in Example 4 (2) has a lower silver atom content than that obtained in Comparative Example 7, but the photo obtained in Example 4 (2). The emission intensity of the luminescent material was equivalent to that of the photoluminescent material obtained in Comparative Example 7.

The silver atom content of the photoluminescent material obtained in Example 4 (2) and Comparative Example 8 is the same, but the emission intensity of the photoluminescent material obtained in Example 4 (2) is It was higher than that of the photoluminescent material obtained in Comparative Example 8 which did not include the step of reducing silver atoms.

Example 5
(1) Production of Photoluminescent Material I (Sodalite Containing Silver Atoms) 5.00 g of sodalite, 0.070 g of silver nitrate, and zinc nitrate hexahydration produced by the same method as in Example 2 (1). 2.46 g of the product and 30 mL of ion-exchanged water were mixed, and the obtained mixture was stirred at 80 ° C. for 3 hours. Then, the solid was collected by suction filtration, dried at 105 ° C. for 16 hours, and then baked at 230 ° C. for 16 hours to obtain 5.81 g of a photoluminescent material (sodalite containing a silver atom).

(2) Production of photoluminescent material II with reduced silver atom content 0.75 g of sodium nitrate, 0.4 mL of ammonia water, 24 mL of ion-exchanged water and methanol (manufactured by Kanto Chemical Co., Ltd., purity 99.8% by weight) ) 6 mL was mixed to obtain an aqueous extraction solution (sodium ion concentration 0.68% by weight, ammonia concentration 0.44% by weight, methanol concentration 15.9% by weight).

1.00 g of the photoluminescent material (sodalite containing a silver atom) obtained in (1) above was added to the obtained aqueous extraction solution, and the obtained mixture was stirred at room temperature for 1 hour. Then, the solid was collected by suction filtration and dried at 105 ° C. for 16 hours to obtain 0.99 g of a photoluminescent material having a reduced silver atom content.

Comparative Example 9: Photoluminescent material (sodalite containing a silver atom)
The photoluminescent material (sodalite containing a silver atom) produced in Example 5 (1) was used as Comparative Example 9.

The composition and density of the photoluminescent materials obtained in Example 5 (2) and Comparative Example 9 are shown in Table 5. Further, Table 5 shows the relative emission intensities of the photoluminescent material obtained in Example 5 (2) and Comparative Example 9, which were calculated with the emission intensity of the photoluminescent material obtained in Comparative Example 9 as 1. show.

The photoluminescent material obtained in Example 5 (2) has a lower silver atom content than that obtained in Comparative Example 9, but the photo obtained in Example 5 (2). The emission intensity of the luminescent material was equivalent to that of the photoluminescent material obtained in Comparative Example 9.

Experimental example: Measurement of emission intensity of cured product containing photoluminescent material 0.75 g of liquid A and 0.75 g of liquid B of silicone rubber for two-component LED ("SCR-1012" manufactured by Shin-Etsu Chemical Co., Ltd.), In addition, 0.05 g of the photoluminescent material obtained in Example 1 (2) or the photoluminescent material of Comparative Example 1 (that is, the photoluminescent material obtained in Example 1 (1)) is mixed. did. The emission intensity immediately after preparation of the obtained mixture was measured by a fluorescence spectrophotometer FluoroMax-4 manufactured by HORIBA, Ltd. Then, these mixtures were allowed to stand in a blower dryer at 105 ° C. for 1 hour to prepare a cured product, and the emission intensity of the obtained cured product was measured in the same manner as described above. Table 6 shows the relative luminescence intensity of the cured product calculated with the luminescence intensity of the mixture immediately after production as 1.

The cured product obtained by using the photoluminescent material of Comparative Example 1 was visually discolored, and its luminescence intensity was significantly lower than that of the mixture immediately after production. On the other hand, the cured product obtained by using the photoluminescent material obtained in Example 1 (2) had no discoloration, and its luminescence intensity was almost changed as compared with the luminescence intensity of the mixture immediately after production. There was no.

The photoluminescent material obtained by the production method of the present invention can be used, for example, in a lighting device, a light emitting paint, a light emitting fiber, a resin molded product, a rubber molded product, a light emitting element, a sensor and the like.

Claims (8)

A method for manufacturing a photoluminescent material that emits visible light when irradiated with light.
In the above method, the content of silver atoms is reduced by extracting silver atoms from the photoluminescent material I containing silver atoms in an aqueous solution containing cations other than silver ions and ammonia. A method comprising obtaining cent material II, as well as the photoluminescent material I being a silver-containing zeolite. Claim 1 in which the photoluminescent material I is at least one selected from the group consisting of a faujasite-type zeolite containing a silver atom, an A-type zeolite containing a silver atom, and a sodalite containing a silver atom. The method described in. The method according to claim 2, wherein the faujasite-type zeolite containing a silver atom is a faujasite-type zeolite containing 5% by weight or more and 30% by weight or less of silver ions. The method according to claim 2 or 3, wherein the A-type zeolite containing a silver atom is an A-type zeolite containing 2.5% by weight or more and 40% by weight or less of silver ions. The method according to any one of claims 2 to 4, wherein the sodalite containing a silver atom is a sodalite containing a silver atom of 0.25% by weight or more and 51% by weight or less. The method according to any one of claims 1 to 5, wherein the cation other than the silver ion contains an alkali metal ion and / or an alkaline earth metal ion. The ratio of the silver atom content of the photoluminescent material II to the silver atom content of the photoluminescent material I (silver atom content of the photoluminescent material II / silver of the photoluminescent material I). The method according to any one of claims 1 to 6, wherein the content of the atom) is 3/100 to 9/10. A photoluminescent material produced by the method according to any one of claims 1 to 7.