JP6903374B2 - Cerium complex composition, manufacturing method and its use - Google Patents

Description

The present invention relates to a cerium complex light emitting material, a cerium complex composition containing the same, a production method, and its use. In particular, it relates to a light emitting material using the cerium complex composition.

Currently, inorganic phosphors such as YAG and phosphorescent materials such as Ir complexes are used as phosphors for LED lighting and organic EL light emitting layer materials.

In LED lighting, high-brightness and high color rendering LED lighting using high-output LED elements such as purple and ultraviolet light source LED elements and blue, green, and red (RGB) phosphors is required.

On the other hand, in organic EL displays and lighting, expensive metals such as Ir are used as phosphorescent dopants for RGB light emitting layers, which are highly durable and do not undergo quenching due to damage to the light emitting layers of oxygen and water vapor invading from the gas barrier layer or in a high current environment. It is hoped that it will be realized without.

Further, since high-power LED elements such as ultraviolet LEDs generate remarkable heat, there is a demand for highly heat-resistant light-emitting materials that can withstand thermal deterioration, and also for organic EL elements that can withstand high-temperature processes such as electrode formation.

A wavelength conversion film made by adding a light emitting material such as a phosphor to EVA, LDPE, and LLDPE has been proposed in order to improve the efficiency of solar cells and the productivity of agricultural facilities. There are many problems in terms of UV resistance, oxidation resistance, moisture resistance, and manufacturing cost, and it has not been put into practical use.

The cerium complex can emit blue, green, and red RGB by controlling the 4f-5d transition with a ligand. For example, in Non-Patent Document 1, the Ce complex having a cyclopentadienyl ligand or a pentamethylcyclopentadienyl ligand becomes purple (408 nm), blue (458 nm), green (544 nm), and red (628 nm). It is reported that it emits light. Further, in Non-Patent Document 2 and Non-Patent Document 3, the Ce complex having a tris (benzimidazol-2-ylmethyl) amine ligand emits blue light (about 450 nm) by ultraviolet excitation. It has been reported that a Ce complex having a trispiridylpyrazolbolate ligand emits green light (529 nm) by ultraviolet excitation. However, there has been no proposal that these Ce complexes are unstable in the atmosphere and have practical performance, durability, life, and manufacturing cost.

That is, in the Ce complex proposed so far, in terms of light resistance (UV resistance), weather resistance, heat resistance, and durability for LEDs, organic EL, films for solar cells, and films for agricultural facilities. Performance is inadequate and improvement is desired.

Japanese Unexamined Patent Publication No. 2012-246230

Organometallics 6,913 (1987) Angew. Chem. Int. Ed. 46,7399 (2007) Chem. Lett. 43,1496 (2014)

The present invention has been made in view of the above problems, and an object of the present invention is a Ce complex suitable for applications such as LED phosphors, organic EL light emitting layer materials, wavelength conversion films for solar cells, and wavelength conversion films for agricultural facilities. It is an object of the present invention to provide a luminescent material and to provide applications such as an LED device, an organic EL device, a solar cell device, and a film for an agricultural facility using the luminescent material.

The present inventors have high light resistance (UV resistance), weather resistance, heat resistance, and durability of a cerium complex light emitting material having a specific structure and a cerium complex composition having the composition, and a phosphor for LED and an organic substance. We have found that it is suitable as an EL light emitting layer material, a wavelength conversion material for solar cells, and a wavelength conversion material for agricultural facilities, and have completed the present invention.

That is, the present invention is a hydrocarbon group-substituted cerium complex monodithiocarbamate light emitting material in which four or more ligands are coordinated with trivalent cerium.

Specifically, a hydrocarbon group-substituted cerium complex monodithiocarbamate light emitting material in which four or more ligands are coordinated to trivalent cerium is the following general formula (1).

（１）
（式中、Ｒ^１，Ｒ^２は炭素数１〜２０の炭化水素基を表し、Ｒ^１，Ｒ^２は、互いに結合しても良い。Ｍ^＋は、アルカリ金属イオン、もしくは、四級ホスホニウムイオンを表す。）
である。

(1)
(In the formula, R ¹ and R ² represent hydrocarbon groups having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other. M ⁺ is an alkali metal ion or a quaternary phosphonium ion. Represents.)
Is.

More specifically, in the above general formula (1), R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms, and M ⁺ is a cerium complex emission of sodium ion, potassium ion, tetraalkylphosphonium ion, and tetraallylphosphonium ion. It is a material.

Furthermore, hydrocarbon group-substituted cerium monodithiocarbamate complex luminescent materials in which four or more ligands are coordinated to trivalent cerium are the following general formulas (2) and (3).

（２）

(2)

（３）
である。

(3)
Is.

In addition, a hydrocarbon group-substituted cerium monodithiocarbamate complex luminescent material in which four or more ligands are coordinated to trivalent cerium is represented by the following general formula (4).

（４）
（式中、Ｒ^１，Ｒ^２は炭素数１〜２０の炭化水素基を表し、Ｒ^１，Ｒ^２は、互いに結合しても良い。Ｌは、窒素原子又はリン原子を含み、電荷が中性である有機配位子を表す。ｎは、１以上の整数を表す）
である。

(4)
(In the formula, R ¹ and R ² represent hydrocarbon groups having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other. L contains a nitrogen atom or a phosphorus atom and has a medium charge. Represents a sex organic ligand; n represents an integer greater than or equal to 1)
Is.

More specifically, in the above general formula (4), R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms, and L is a cerium complex luminescent material of phenanthroline, bipyridine, and triphenylphosphine oxide.

Furthermore, hydrocarbon group-substituted cerium monodithiocarbamate complex luminescent materials in which four or more ligands are coordinated to trivalent cerium are represented by the following general formulas (5) and (6).

（５）

(5)

（６）
である。

(6)
Is.

Further, it is a cerium complex luminescent material composition containing the above-mentioned cerium complex luminescent material and dithiocarbamate of the following general formula (7).

（７）
（式中、Ｒ^１，Ｒ^２は炭素数１〜２０の炭化水素基を表し、Ｒ^１，Ｒ^２は、互いに結合しても良い。Ｍ^＋は、アルカリ金属イオン、もしくは、四級アンモニウムイオンを表す。）
また、紫外光又は可視光により励起し、青色発光する上述のセリウム錯体発光材料もしくはセリウム錯体発光材料組成物である。

(7)
(In the formula, R ¹ and R ² represent hydrocarbon groups having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other. M ⁺ is an alkali metal ion or a quaternary ammonium ion. Represents.)
Further, it is the above-mentioned cerium complex luminescent material or cerium complex luminescent material composition that is excited by ultraviolet light or visible light and emits blue light.

Further, the LED device is characterized by containing the above-mentioned cerium complex light emitting material or cerium complex light emitting material composition.

Further, the organic EL device is characterized by containing the above-mentioned cerium complex luminescent material or cerium complex luminescent material composition.

Further, the solar cell device is characterized by containing the above-mentioned cerium complex luminescent material or cerium complex luminescent material composition.

Further, it is a film for agricultural facilities, which comprises the above-mentioned cerium complex luminescent material or cerium complex luminescent material composition.

Hereinafter, the details of the present invention will be described.

The present invention is a hydrocarbon group-substituted cerium complex monodithiocarbamate light emitting material in which four or more ligands are coordinated with trivalent cerium.

Specifically, a hydrocarbon group-substituted cerium complex monodithiocarbamate light emitting material in which four or more ligands are coordinated to trivalent cerium is the following general formula (1).

（１）
（式中、Ｒ^１，Ｒ^２は炭素数１〜２０の炭化水素基を表し、Ｒ^１，Ｒ^２は、互いに結合しても良い。Ｍ^＋は、アルカリ金属イオン、もしくは、四級ホスホニウムイオンを表す。）
の炭化水素基置換モノジチオカルバミン酸セリウム錯体発光材料であることが好ましい。

(1)
(In the formula, R ¹ and R ² represent hydrocarbon groups having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other. M ⁺ is an alkali metal ion or a quaternary phosphonium ion. Represents.)
It is preferable that the material is a cerium complex luminescent material substituted with a hydrocarbon group.

In the above general formula (1), R ¹ and R ² are hydrocarbon groups having 1 to 20 carbon atoms, and the hydrocarbon groups may be saturated or unsaturated, and may be linear or branched. It may have any annular structure. R ¹ and R ² may be the same or different.

R ¹ and R ² are hydrocarbon groups having 1 to 20 carbon atoms, preferably alkyl groups having 1 to 10 carbon atoms, aryl groups, arylalkyl groups, alkylaryl groups, vinyl groups and other alkenyl groups, and acetylynyl. Examples thereof include an alkynyl group such as a group.

Specific examples of R ¹ and R ² include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl, n-pentyl, tert. -Amil, cyclopentyl, n-hexyl, cyclohexyl, methylcyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecylic, n-eicocil,
Cyclobutenyl, cyclopentadienyl, cyclohexenyl, cyclooctenyl, cyclooctadienyl, 1-adamantyl,
Phenyl, toluyl, xylenyl, ethylphenyl, isopropylphenyl, butylphenyl, naphthyl, anthracenyl, benzyl,
And so on.

R ¹ and R ² are, among other things, economically, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl, n-pentyl, tert. -Amil, cyclopentyl, n-hexyl, cyclohexyl, methylcyclohexyl, n-heptyl, cyclobutenyl, cyclopentadienyl, cyclohexenyl, phenyl, toluyl, etc. Linear alkyl group with 7 or less carbon atoms, branched chain alkyl group, cyclic Alkyl groups and cyclic aryl groups are preferable, and methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert. -Alkyl group having 4 or less carbon atoms such as butyl.

Examples of M ⁺ include alkali metal ions such as lithium, sodium, potassium, rubidium, and cesium, and quaternary phosphonium ions of the following general formula (8).

（８）
（式中、Ｒ^３，Ｒ^４，Ｒ^５，Ｒ^６は、炭素数１〜２０の炭化水素基、アルコキシ置換炭化水素基を表し、Ｒ^３，Ｒ^４，Ｒ^５，Ｒ^６は、互いに結合しても良い。Ｒ^３，Ｒ^４，Ｒ^５，Ｒ^６は、同一であっても、異なってもよい。）
Ｒ^３，Ｒ^４，Ｒ^５，Ｒ^６としては、炭素数１〜２０の炭化水素基又はアルコキシ置換炭化水素基であり、好ましくは炭素数１〜１０のアルキル基、アリール基、アリールアルキル基、アルキルアリール基、ビニル基等のアルケニル基、アセチニル基等のアルキニル基、アルコキシアルキル基、アルコキシアリール基等を挙げることができる。

(8)
(In the formula, R ³ , R ⁴ , R ⁵ , and R ⁶ represent hydrocarbon groups having 1 to 20 carbon atoms and alkoxy-substituted hydrocarbon groups, and R ³ , R ⁴ , R ⁵ , and R ⁶ are bonded to each other. R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different.)
Examples of R ³ , R ⁴ , R ⁵ , and R ⁶ are hydrocarbon groups having 1 to 20 carbon atoms or alkoxy-substituted hydrocarbon groups, preferably alkyl groups having 1 to 10 carbon atoms, aryl groups, and arylalkyl groups. Examples thereof include an alkenyl group such as an alkylaryl group and a vinyl group, an alkynyl group such as an acetylynyl group, an alkoxyalkyl group and an alkoxyaryl group.

Specific examples of R ³ , R ⁴ , R ⁵ , and R ⁶ include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl, n-pentyl, tert. -Amil, cyclopentyl, n-hexyl, cyclohexyl, methylcyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecylic, n-eicocil,
Cyclobutenyl, cyclopentadienyl, cyclohexenyl, cyclooctenyl, cyclooctadienyl, 1-adamantyl,
Phenyl, toluyl, xylenyl, ethylphenyl, isopropylphenyl, butylphenyl, naphthyl, anthracenyl, benzyl, phenylethyl,
Methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl,
And so on.

R ³ , R ⁴ , R ⁵ , and R ⁶ are, among other things, economically methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl, n-pentyl, tert. -Amil, cyclopentyl, n-hexyl, cyclohexyl, methylcyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, 1-adamantyl, phenyl, toluyl, xylenyl, ethylphenyl, isopropylphenyl, Hydrocarbon groups having 10 or less carbon atoms such as butylphenyl, naphthyl, benzyl, and phenylethyl or alkoxy-substituted hydrocarbon groups are preferable, and phenyl, toluyl, xylenyl, ethylphenyl, isopropylphenyl, butylphenyl, naphthyl, benzyl, and the like are particularly preferable. It is an aryl group having 10 or less carbon atoms such as phenylethyl.

Specific examples of the quaternary phosphonium ion of the above general formula (8) include, for example, tetramethylphosphonium ion, trimethyl-n-hexylphosphonium ion, tetraethylphosphonium ion, triethyl-n-pentylphosphonium ion, and triethyl-n-octylphosphonium ion. , Triethyl-n-dodecylphosphonium ion, triethyl (methoxymethyl) phosphonium ion, triethyl (methoxyethyl) phosphonium ion, tetra-n-butylphosphonium ion, tetra-isobutylphosphonium ion, tetra-tert. -Butylphosphonium ion, tri-n-butylmethylphosphonium ion, triisobutylmethylphosphonium ion, tri-tert. -Butylmethylphosphonium ion, tri-n-butyl-n-octylphosphonium ion, triisobutyl-n-octylphosphonium ion, tri-tert. -Butyl-n-octylphosphonium ion, tri-n-butyl-n-dodecylphosphonium ion, triisobutyl-n-dodecylphosphonium ion, tri-tert. -Butyl-n-dodecylphosphonium ion, tri-n-butyl (methoxyethyl) phosphonium ion, triisobutyl (methoxyethyl) phosphonium ion, tri-tert. -Butyl (methoxyethyl) phosphonium ion, tetra-n-pentylphosphonium ion, tri-n-pentyl-n-tetradecylphosphonium ion, tetracyclopentylphosphonium ion, tricyclopentyl-n-tetradecylphosphonium ion, tetra-n-hexyl Phosphonium ion, tri-n-hexyl-n-tetradecylphosphonium ion, tetracyclohexylphosphonium ion, tricyclohexyl-n-tetradecylphosphonium ion, tetra (2-ethylhexyl) phosphonium ion tetraphenylphosphonium ion, triphenylmethylphosphonium ion, Triphenylethylphosphonium ion, triphenyl-n-butylphosphonium ion, triphenyl-n-hexylphosphonium ion, triphenylcyclohexylphosphonium ion, triphenyl-n-octylphosphonium ion, triphenyl (2-ethylhexyl) phosphonium ion, tri Phenyl-n-dodecylphosphonium ion, triphenyl (methoxymethyl) phosphonium ion, triphenyl (methoxyethyl) phosphonium ion, triphenyl (ethoxymethyl) phosphonium ion, triphenyl (ethoxyethyl) phosphonium ion, triphenyltoluylphosphonium ion, Tetratoluyl phosphonium ion, tritoluyl phenyl phosphonium ion, tetraxylenyl phosphonium ion, trixylenyl phenyl phosphonium ion, tetraethyl phenyl phosphonium ion, tetranaphthyl phosphonium ion, tetraanthrasenyl phosphonium ion and the like can be mentioned. Tetraphenylphosphonium ion, triphenyltoluylphosphonium ion, tetratoluylphosphonium ion, tritoluylphenylphosphonium ion, tetraxylenylphosphonium ion, trixylenylphenylphosphonium ion, tetraethylphenylphosphonium ion, tetranaphthylphosphonium ion and the like are preferable, and particularly It is preferably tetraphenylphosphonium ion or the like.

M ⁺ may be single or mixed.

As a specific example of the above general formula (1), for example

等が挙げられ、その中でも１−２〜１−１５、１−３１〜１−３７、１−４２〜１−４７等が好ましく、特に好ましくは１−２〜１−１５、１−３１〜１−３３、１−３５〜１−３７等である。

Among them, 1-2-1-15, 1-31-37, 1-42-1-47 and the like are preferable, and 1-2-1-15, 1-31-1 are particularly preferable. -33, 1-35 to 1-37 and the like.

Further, as a preferable specific example of the hydrocarbon group-substituted cerium complex monodithiocarbamate light emitting material in which four or more ligands are coordinated to trivalent cerium, the following general formula (4) is used.

（４）
（式中、Ｒ^１，Ｒ^２は炭素数１〜２０の炭化水素基を表し、Ｒ^１，Ｒ^２は、互いに結合しても良い。Ｌは、窒素原子又はリン原子を含み、電荷が中性である有機配位子を表す。ｎは、１以上の整数を表す）
が挙げられる。

(4)
(In the formula, R ¹ and R ² represent hydrocarbon groups having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other. L contains a nitrogen atom or a phosphorus atom and has a medium charge. Represents a sex organic ligand; n represents an integer greater than or equal to 1)
Can be mentioned.

^R 1, ^{R 2} in the general formula (4) is ^R 1, it can be the same as the ^{R 2} L in the general formula (1) contains a nitrogen atom or a phosphorus atom, the charge is neutral It is an organic ligand.

Specifically, as the nitrogen atom-containing charged neutral organic ligand, for example, 1,10-phenanthroline, 2-methyl-1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2,9-dimethyl- 1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 2,9-dibutyl-1,10-phenanthroline, 3,4,7,8- Tetramethyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 4,7-distyryl-1,10-phenanthroline ,
2-Bromo-1,10-phenanthroline, 3-bromo-1,10-phenanthroline, 5-bromo-1,10-phenanthroline, 3,5,6,8-tetrabromo-1,10-phenanthroline, 2-chloro- 1,10-Phenanthroline, 3-chloro-1,10-phenanthroline, 5-chloro-1,10-phenanthroline, 3,8-dibromo-1,10-phenanthroline, 4,7-dibromo-1,10-phenanthroline, 2,9-dichloro-1,10-phenanthroline, 4,7-dichloro-1,10-phenanthroline, 1,10-phenanthroline-5,6-dione, 5-nitro-1,10-phenanthroline, 4,7- Dihydroxy-1,10-phenanthroline,
Dipyrid [3,2-a: 2', 3'-c] Phenanthroline 1,10-phenanthroline-4,7-di (phenylsulfonic acid) disodium, 2,9-dimethyl-1,10-phenanthroline-4, Phenanthroline compounds such as 7-di (phenylsulfonic acid) disodium 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 5,5'-dimethyl-2,2'-bipyridyl, 6 , 6'-dimethyl-2,2'-bipyridyl, 4,4'-di-tert. -Butyl-2,2'-bipyridyl, 4,4'-di-n-nonyl-2,2'-bipyridyl, 6-bromo-2,2'-bipyridyl, 4,4'-dibromo-2,2' -Bipyridyl, 5,5'-dibromo-2,2'-bipyridyl, 6,6'-dibromo-2,2'-bipyridyl, 6-cyano-2,2'-bipyridyl, 6,6'-dicyano-2 , 2'-bipyridyl, 3,3'-dihydroxy-2,2'-bipyridyl, 6,6'-dihydroxy-2,2'-bipyridyl, 4,4'-bis (hydroxymethyl) -2,2'- Bipyridyl, 4-hydroxymethyl-4'-methyl-2,2'-bipyridyl, 4,4'-bis (chloromethyl) -2,2'-bipyridyl, 6,6'-bis (chloromethyl) -2, 2'-bipyridyl, 4- (chloromethyl) -4'-methyl-2,2'-bipyridyl, 4- (bromomethyl) -4'-methyl-2,2'-bipyridyl, 6-bromo-4,4'-Dimethyl-2,2'-bipyridyl,4,4'-dimethoxy-2,2'-bipyridyl,4,4'-dimethoxycarbonyl-2,2'-bipyridyl,6,6'-dimethoxycarbonyl-2,2'-Bipiridyl,4,4'-diamino-2,2'-bipyridyl,6,6'-diamino-2,2'-bipyridyl,2,2'-bipyridine-3,3'-dicarboxylic acid, 2,2 '-Bipyridine-4,4'-dicarboxylic acid, 2,2'-bipyridine-5,5'-dicarboxylic acid, 2,2'-bipyridine-6,6'-dicarboxylic acid, 4,4'-bis (5) -Hexyl-2-chenyl) -2,2'-bipyridyl compounds such as bipyridyl a, a'a''-tripyridyl, 4'-chloro-a, a'a''-tripyridyl, 4'-bromo-a, a'a''-tripyridyl, 4'-methoxycarbonyl-a, a'a''-tripyridyl, 4'-(4-bromophenyl) -a, a'a''-tripyridyl, 2,2': 6 ', 2''-terpyridine-4'-diethylphosphonate, 2,2': 6', 2''-terpyridine-4,4', 4''-, 1,4-[[2,2': 6', 2''-terpyridine] -4'-yl] benzene, 4'-(4-pyridyl) -2,2': 6', 2''-terpyridine, 4,4', 4''-tri Terpyridine compounds such as methoxycarbonyl-2,2': 6', 2''-terpyridine, 4'-(4-methoxycarbonylphenyl) -2,2': 6', 2''-terpyridine,
2,2'-biquinoline, 4,4'-dimethyl-2,2'-biquinoline, 2,2'-biquinoline-4,4'-dipotassium dicarboxylic acid, 2,2'-biquinoline-4,4'- Quinoline compounds such as disodium dicarboxylic acid,
2,2'-(1,8-naphthylidine), 1,2-bis (4'-methyl-2,2'-bipyridine-4-yl) ethane, 2,6-bis (2-pyridyl) -4 ( 1H) -pyridone, 4,5-diazafluorene-9-on-o-tosyloxime, 2,2'-dipyrimidyl, 2,2'-bipyrazine and the like, among which 1,10-phenanthroline and 2-methyl -1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline, 5,6-dimethyl-1,10 -Phenanthroline, 2,9-dibutyl-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl- 4,7-Diphenyl-1,10-phenanthroline, 4,7-dystyryl-1,10-phenanthroline, 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 5,5'- Dimethyl-2,2'-bipyridyl, 6,6'-dimethyl-2,2'-bipyridyl, 4,4'-di-tert. -Butyl-2,2'-bipyridyl, 4,4'-di-n-nonyl-2,2'-bipyridyl, 4,4'-dimethoxy-2,2'-bipyridyl, 4,4'-dimethoxycarbonyl- 2,2'-bipyridyl, 6,6'-dimethoxycarbonyl-2,2'-bipyridyl, 4,4'-diamino-2,2'-bipyridyl, 6,6'-diamino-2,2'-bipyridyl, 2,2'-Bipyridine-3,3'-dicarboxylic acid, 2,2'-bipyridine-4,4'-dicarboxylic acid, 2,2'-bipyridine-5,5'-dicarboxylic acid, 2,2'- Bipyridine-6,6'-dicarboxylic acid, 4,4'-bis (5-hexyl-2-chenyl) -2,2'-bipyridyl, a, a'a''-tripyridyl, 2,2'-biquinolin, 4,4'-dimethyl-2,2'-biquinolin, 2,2'-(1,8-naphthylidine), 1,2-bis (4'-methyl-2,2'-bipyridine-4-yl) ethane Etc., and particularly preferably 1,10-phenanthroline, 2-methyl-1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 4,7-dimethyl. -1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 2,9-dibutyl-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 4, 7-Diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 5 , 5'-dimethyl-2,2'-bipyridyl, 6,6'-dimethyl-2,2'-bipyridyl, 4,4'-di-tert. -Butyl-2,2'-bipyridyl, a, a'a''-tripyridyl, 2,2'-biquinolin and the like.

Specifically, as a phosphorus atom-containing charge neutral organic ligand,
The phosphine compound of the following general formula (9) and the phosphine oxide compound of the following general formula (10) are preferable.

（９）

(9)

（１０）
（式中、Ｒ^７，Ｒ^８，Ｒ^９は、炭素数１〜２０の炭化水素基、酸素原子又は窒素原子又はハロゲン含有炭化水素基を表し、Ｒ^７，Ｒ^８，Ｒ^９は、直接もしくは、炭素数１〜２０の炭化水素基、酸素原子又は窒素原子含有炭化水素基や酸素原子、窒素原子を介して、互いに結合しても良い。Ｒ^７，Ｒ^８，Ｒ^９は、同一であっても、異なってもよい。）
Ｒ^７，Ｒ^８，Ｒ^９としては、炭素数１〜２０の炭化水素基、酸素原子又は窒素原子又はハロゲン含有炭化水素基であり、好ましくは炭素数１〜１０のアルキル基、アリール基、アリールアルキル基、アルキルアリール基、ビニル基等のアルケニル基、アセチニル基等のアルキニル基、アルコキシアルキル基、アルコキシアリール基等を挙げることができる。

(10)
(In the formula, R ⁷ , R ⁸ , R ⁹ represent a hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom, or a halogen-containing hydrocarbon group, and R ⁷ , R ⁸ , R ⁹ are direct or , hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom-containing hydrocarbon group or oxygen atom through a nitrogen atom, be combined with good .R ^{7, R 8, R 9} are each, there in the same It may be different.)
Examples of R ⁷ , R ⁸ and R ⁹ are hydrocarbon groups having 1 to 20 carbon atoms, oxygen atoms or nitrogen atoms or halogen-containing hydrocarbon groups, preferably alkyl groups having 1 to 10 carbon atoms, aryl groups and aryl groups. Examples thereof include an alkenyl group such as an alkyl group, an alkylaryl group and a vinyl group, an alkynyl group such as an acetylynyl group, an alkoxyalkyl group and an alkoxyaryl group.

Specific examples of R ⁷ , R ⁸ and R ⁹ include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl, n-pentyl, tert. -Amil, cyclopentyl, n-hexyl, cyclohexyl, methylcyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, adamantyl, n-undecyl, n-dodecyl, n-tridecyl, n- Tetradecyl, n-pentadecylic, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecylic, n-eicocil,
Cyclobutenyl, cyclopentadienyl, cyclohexenyl, cyclooctenyl, cyclooctadienyl, 1-adamantyl,
Phenyl, trill, xylyl, ethylphenyl, isopropylphenyl, butylphenyl, naphthyl, anthracenyl, benzyl, phenylethyl,
Phenoxy, phenyldioxy, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, 2,6-dimethoxyphenyl, 2-furyl, o-fluorophenyl, m-fluorophenyl, p-fluorophenyl, pentafluorophenyl , O-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-bromophenyl, m-bromophenyl, p-bromophenyl, o-iodophenyl, m-iodophenyl, p-iodophenyl, 3,5-bis (tri) Fluoromethyl) phenyl, o-dimethylaminophenyl, m-dimethylaminophenyl, p-dimethylaminophenyl,
Methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl,
And so on.

R ⁷ , R ⁸ , and R ⁹ are, among other things, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl, n-pentyl, tert. -Amil, cyclopentyl, n-hexyl, cyclohexyl, methylcyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, 1-adamantyl, phenyl, toluyl, xylenyl, ethylphenyl, isopropylphenyl, Hydrocarbon groups having 10 or less carbon atoms such as butylphenyl, naphthyl, benzyl, and phenylethyl or alkoxy-substituted hydrocarbon groups are preferable, and phenyl, toluyl, xylenyl, ethylphenyl, isopropylphenyl, butylphenyl, naphthyl, benzyl, and the like are particularly preferable. It is an aryl group having 10 or less carbon atoms such as phenylethyl.

Specifically, as phosphorus atom-containing charged neutral organic ligands, for example, trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, tri-tert. -Butylphosphine, tri-n-pentylphosphine, tri-tert. -Amilphosphine, tricyclopentylphosphine, tri-n-hexylphosphine, tricyclohexylphosphine, tri-n-heptylphosphine, tri-n-octylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine , Tri-p-trilphosphine, trichenylphosphine, tris (2-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2,6-dimethoxyphenyl) phosphine, tris (2-furyl) phosphine, Tris (4-dimethylaminophenyl) phosphine,
Diethylphenylphosphine, di-tert. -Butylphenylphosphine, dicyclohexylphenylphosphine, dicyclohexylphenylphosphine, diphenylmethylphosphine, diphenylethylphosphine, diphenylisopropylphosphine, diphenylcyclohexylphosphine, diphenyl-2-pyridylphosphine, diphenyl-1-pyrenylphosphine, di-tert. -Butyl (dimethylaminophenyl) phosphine, di-tert. -Butyl (3-methyl-2-butenyl) phosphine, (4-fluorophenyl) diphenylphosphine, tris (4-fluorophenyl) phosphine, (2-bromophenyl) diphenylphosphine, (pentafluorophenyl) diphenylphosphine, bis ( Pentafluorophenyl) phenylphosphine, tris (pentafluorophenyl) phosphine, tris [(3,5-bis (trifluoromethyl) phenyl] phosphine,
Monophosphine compounds such as 2- (di-tert.-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl,
Bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,5-bis ( Diphenylphosphino) pentane, 1,6-bis (diphenylphosphino) hexane, 1,2-bis [bis (pentafluorophenyl) phosphino] ethane,
1,4-bis (diphenylphosphino) benzene, 2,2'-bis (diphenylphosphino) biphenyl, 4,4'-bis (diphenylphosphino) biphenyl, trans-1,2-bis (diphenylphosphino) Ethylene, (±) -2,2'-bis (diphenylphosphino) -1,1'-binaphthyl, (S)-(-)-2,2'-bis (diphenylphosphino) -1,1'- Binaphthyl, (R)-(+)-2,2'-bis (diphenylphosphino) -1,1'-binaphthyl, 4,5-bis (diphenylphosphino) -9,9'-dimethylxanthene, 4, 6-bis (diphenylphosphino) phenoxazine, bis [2- (diphenylphosphino) phenyl) ether, (R, R) -1,2-bis [(2-methoxyphenyl) phenylphosphino] ethane, (S) , S) -1,2-bis [(2-methoxyphenyl) phenylphosphino] ethane,
Bis (dimethylphosphino) methane, 1,2-bis (dimethylphosphino) ethane, 1,3-bis (dimethylphosphino) propane, 1,4-bis (dimethylphosphino) butane, 1,5-bis ( Dimethylphosphino) pentane, 1,6-bis (dimethylphosphino) hexane,
1,4-bis (dimethylphosphino) benzene, 2,2'-bis (dimethylphosphine) biphenyl, 4,4'-bis (dimethylphosphino) biphenyl, trans-1,2-bis (dimethylphosphine) Diphosphane compounds such as ethylene,
Trimethylphosphine oxide, triethylphosphine oxide, tri-n-propylphosphine oxide, triisopropylphosphine oxide, tri-n-butylphosphine oxide, tri-tert. -Butylphosphine oxide, tri-n-pentylphosphine oxide, tri-tert. -Amilphosphine oxide, tricyclopentylphosphine oxide, tri-n-hexylphosphine oxide, tricyclohexylphosphine oxide, tri-n-heptylphosphine oxide, tri-n-octylphosphine oxide, triphenylphosphine oxide, tri-o-trilphosphine Oxide, tri-m-tolylphosphine oxide, tri-p-tolylphosphine oxide, trichenylphosphine oxide, tris (2-methoxyphenyl) phosphine oxide, tris (4-methoxyphenyl) phosphine oxide, tris (2,6- Dimethoxyphenyl) phosphine oxide, tris (2-furyl) phosphine oxide, tris (4-dimethylaminophenyl) phosphine oxide,
Diethylphenylphosphine oxide, di-tert. -Butylphenylphosphine oxide, dicyclohexylphenylphosphine oxide, dicyclohexylphenylphosphine oxide, diphenylmethylphosphine oxide, diphenylethylphosphine oxide, diphenylisopropylphosphine oxide, diphenylcyclohexylphosphine oxide, diphenyl-2-pyridylphosphine oxide, diphenyl-1-pyrenyl Phosphine oxide, di-tert. -Butyl (dimethylaminophenyl) phosphine oxide, di-tert. -Butyl (3-methyl-2-butenyl) phosphine oxide, (4-fluorophenyl) diphenylphosphine oxide, tris (4-fluorophenyl) phosphine oxide, (2-bromophenyl) diphenylphosphine oxide, (pentafluorophenyl) diphenyl Phosphine oxide, bis (pentafluorophenyl) phenylphosphine oxide, tris (pentafluorophenyl) phosphine oxide, tris [(3,5-bis (trifluoromethyl) phenyl] phosphine oxide, 2- (di-tert.-butylphosphine) Monophosphine oxide compounds such as fino) biphenyl oxide and 2- (dicyclohexylphosphoryl) biphenyl,
Bis (diphenylphosphoryl) methane, 1,2-bis (diphenylphosphoryl) ethane, 1,3-bis (diphenylphosphoryl) propane, 1,4-bis (diphenylphosphoryl) butane, 1,5-bis (diphenylphosphoryl) pentane , 1,6-bis (diphenylphosphoryl) hexane, 1,2-bis [bis (pentafluorophenyl) phosphoryl] ethane,
1,4-bis (diphenylphosphoryl) benzene, 2,2'-bis (diphenylphosphoryl) biphenyl, 4,4'-bis (diphenylphosphoryl) biphenyl, trans-1,2-bis (diphenylphosphoryl) ethylene, (± ) -2,2'-bis (diphenylphosphoryl) -1,1'-binaphthyl, (S)-(-)-2,2'-bis (diphenylphosphoryl) -1,1'-binaphthyl, (R)- (+) -2,2'-bis (diphenylphosphoryl) -1,1'-binaphthyl, 4,5-bis (diphenylphosphoryl) -9,9'-dimethylxanthene, 4,6-bis (diphenylphosphoryl) phenoki Saddin, bis [2- (diphenylphosphoryl) phenyl) ether, (R, R) -1,2-bis [(2-methoxyphenyl) phenylphosphoryl] ethane, (S, S) -1,2-bis [( 2-methoxyphenyl) phenylphosphoryl] ethane,
Bis (dimethylphosphoyl) methane, 1,2-bis (dimethylphosphoyl) ethane, 1,3-bis (dimethylphosphoyl) propane, 1,4-bis (dimethylphosphoyl) butane, 1,5-bis (dimethylphosphoryl) pentane , 1,6-bis (dimethylphosphoyl) hexane,
Diphosphines such as 1,4-bis (dimethylphosphoryl) benzene, 2,2'-bis (dimethylphosphoryl) biphenyl, 4,4'-bis (dimethylphosphoryl) biphenyl, trans-1,2-bis (dimethylphosphoryl) ethylene, etc. Oxide compounds can be mentioned, and among them, phosphine oxide compounds are preferable, and trimethylphosphine oxide, triethylphosphine oxide, tri-n-propylphosphine oxide, triisopropylphosphine oxide, tri-n-butylphosphine oxide, and tri are particularly preferable. -Tert. -Butylphosphine oxide, tri-n-pentylphosphine oxide, tri-tert. -Amilphosphine oxide, tricyclopentylphosphine oxide, tri-n-hexylphosphine oxide, tricyclohexylphosphine oxide, tri-n-heptylphosphine oxide, tri-n-octylphosphine oxide, triphenylphosphine oxide, tri-o-trilphosphine Oxide, tri-m-tolylphosphine oxide, tri-p-tolylphosphine oxide, trichenylphosphine oxide, tris (2-methoxyphenyl) phosphine oxide, tris (4-methoxyphenyl) phosphine oxide, tris (2,6- Dimethoxyphenyl) phosphine oxide, diethylphenylphosphine oxide, di-tert. -Butylphenylphosphine oxide, dicyclohexylphenylphosphine oxide, dicyclohexylphenylphosphine oxide, diphenylmethylphosphine oxide, diphenylethylphosphine oxide, diphenylisopropylphosphine oxide, diphenylcyclohexylphosphine oxide, (pentafluorophenyl) diphenylphosphine oxide, bis (pentafluorophenyl) ) Monophosphine oxide compounds such as phenylphosphine oxide and tris (pentafluorophenyl) phosphine oxide,
Bis (diphenylphosphoryl) methane, 1,2-bis (diphenylphosphoryl) ethane, 1,3-bis (diphenylphosphoryl) propane, 1,4-bis (diphenylphosphoryl) butane, 1,5-bis (diphenylphosphoryl) pentane , 1,6-bis (diphenylphosphoryl) hexane, 1,2-bis [bis (pentafluorophenyl) phosphoryl] ethane, 1,4-bis (diphenylphosphoryl) benzene, 2,2'-bis (diphenylphosphoryl) biphenyl , 4,4'-bis (diphenylphosphoryl) biphenyl, trans-1,2-bis (diphenylphosphoryl) ethylene, bis (dimethylphosphoryl) methane, 1,2-bis (dimethylphosphoryl) ethane, 1,3-bis ( Dimethylphosphoryl) propane, 1,4-bis (dimethylphosphoryl) butane, 1,5-bis (dimethylphosphoryl) pentane, 1,6-bis (dimethylphosphoryl) hexane, 1,4-bis (dimethylphosphoryl) benzene, 2 , 2'-bis (dimethylphosphoryl) biphenyl, 4,4'-bis (dimethylphosphoryl) biphenyl, trans-1,2-bis (dimethylphosphoryl) ethylene and other diphosphine oxide compounds.

As a specific example of the above general formula (4), for example

等が挙げられ、その中でも４−１〜４−３１、４−５２〜４−７１等が好ましく、特に好ましくは４−１〜４−２５、４−２７〜４−３１、４−５２、４−５８、４−５９、４−６２〜４−７１等である。

Among them, 4-1 to 4-31, 4-52 to 4-71 and the like are preferable, and 4-1 to 4-25, 4-27 to 4-31, 4-52, 4 are particularly preferable. -58, 4-59, 4-62 to 4-71 and the like.

The hydrocarbon group-substituted cerium complex monodithiocarbamate luminescent material in which four or more ligands are coordinated to trivalent cerium, and the compounds of the above general formula (1) and the above general formula (4) are used alone or in combination of two or more. Used as a mixture of. Further, a mixture of the compounds of the above general formula (1) and the above general formula (4) also falls within the scope of the present invention.

Further, a hydrocarbon group-substituted cerium complex monodithiocarbamate luminescent material in which four or more ligands are coordinated to trivalent cerium, compounds of the above general formula (1) and the above general formula (4), and the following general formula (7). ) Dithiocarbamic acid compounds are also included in the scope of the present invention.

（７）
（式中、Ｒ^１，Ｒ^２は炭素数１〜２０の炭化水素基を表し、Ｒ^１，Ｒ^２は、互いに結合しても良い。Ｍ^＋は、アルカリ金属イオン、もしくは、四級アンモニウムイオンを表す。）
上記一般式（７）のＲ^１、Ｒ^２は、一般式（１）のＲ^１、Ｒ^２と同じものを挙げることできる。

(7)
(In the formula, R ¹ and R ² represent hydrocarbon groups having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other. M ⁺ is an alkali metal ion or a quaternary ammonium ion. Represents.)
Said ^R 1, ^{R 2} of the general formula (7) can be generalized formula (1) ^R 1, it exemplified the same as ^{R 2} of.

Specific examples of the above general formula (7) include, for example, lithium dimethyldithiocarbamate, sodium dimethyldithiocarbamate, potassium dimethyldithiocarbamate, rubidium dimethyldithiocarbamate, cesium dimethyldithiocarbamate, ethylammonium dimethyldithiocarbamate, diethylammonium dimethyldithiocarbamate, Triethylammonium dimethyldithiocarbamate, tetraethylammonium dimethyldithiocarbamate,
Lithium diethyldithiocarbamate, sodium diethyldithiocarbamate, potassium diethyldithiocarbamate, rubidium diethyldithiocarbamate, cesium diethyldithiocarbamate, ethylammonium diethyldithiocarbamate, diethylammonium diethyldithiocarbamate, triethylammonium diethyldithiocarbamate, tetraethylammonium diethyldithiocarbamate,
Lithium di-n-propyldithiocarbamate, sodium di-n-propyldithiocarbamate, potassium di-n-propyldithiocarbamate, rubidium di-n-propyldithiocarbamate, cesium di-n-propyldithiocarbamate, di-n-propyl Ethylammonium dithiocarbamate, diethylammonium di-n-propyldithiocarbamate, triethylammonium di-n-propyldithiocarbamate, tetraethylammonium di-n-propyldithiocarbamate,
Lithium diisopropyldithiocarbamate, sodium diisopropyldithiocarbamate, potassium diisopropyldithiocarbamate, rubidium diisopropyldithiocarbamate, cesium diisopropyldithiocarbamate, ethylammonium diisopropyldithiocarbamate, diethylammonium diisopropyldithiocarbamate, triethylammonium diisopropyldithiocarbamate, tetraethylammonium diisopropyldithiocarbamate,
Lithium dicyclopropyldithiocarbamate, sodium dicyclopropyldithiocarbamate, potassium dicyclopropyldithiocarbamate, rubidium dicyclopropyldithiocarbamate, cesium dicyclopropyldithiocarbamate, ethylammonium dicyclopropyldithiocarbamate, diethylammonium dicyclopropyldithiocarbamate , Triethylammonium dicyclopropyldithiocarbamate, Tetraethylammonium dicyclopropyldithiocarbamate,
Lithium di-n-butyldithiocarbamate, sodium di-n-butyldithiocarbamate, potassium di-n-butyldithiocarbamate, rubidium di-n-butyldithiocarbamate, cesium di-n-butyldithiocarbamate, di-n-butyl Ethylammonium dithiocarbamate, diethylammonium di-n-butyldithiocarbamate, triethylammonium di-n-butyldithiocarbamate, tetraethylammonium di-n-butyldithiocarbamate,
Lithium diisobutyldithiocarbamate, sodium diisobutyldithiocarbamate, potassium diisobutyldithiocarbamate, rubidium diisobutyldithiocarbamate, cesium diisobutyldithiocarbamate, ethylammonium diisobutyldithiocarbamate, diethylammonium diisobutyldithiocarbamate, triethylammonium diisobutyldithiocarbamate
The tert. -Lithium butyl dithiocarbamate, di-tert. -Sodium butyldithiocarbamate, di-tert. -Potassium butyl dithiocarbamate, di-tert. -Rubidium butyldithiocarbamate, di-tert. -Cesium butyldithiocarbamate, di-tert. -Ethylammonium butyldithiocarbamate, di-tert. -Diethylammonium butyldithiocarbamate, di-tert. -Triethylammonium butyldithiocarbamate, di-tert. -Tetraethylammonium butyldithiocarbamate,
Lithium di-n-pentyl dithiocarbamate, sodium di-n-pentyl dithiocarbamate, potassium di-n-pentyl dithiocarbamate, rubidium di-n-pentyl dithiocarbamate, cesium di-n-pentyl dithiocarbamate, di-n-pentyl Ethylammonium dithiocarbamate, diethylammonium di-n-pentyldithiocarbamate, triethylammonium di-n-pentyldithiocarbamate, tetraethylammonium di-n-pentyldithiocarbamate,
The tert. -Lithium amyldithiocarbamate, di-tert. -Sodium amyldithiocarbamate, di-tert. -Potassium amyldithiocarbamate, di-tert. -Rubidium amyldithiocarbamate, di-tert. -Cesium amyldithiocarbamate, di-tert. -Ethylammonium amyldithiocarbamate, di-tert. -Diethylammonium amyldithiocarbamate, di-tert. -Triethylammonium amyldithiocarbamate, di-tert. -Tetraethylammonium amyldithiocarbamate,
Lithium dicyclopentyl dithiocarbamate, sodium dicyclopentyl dithiocarbamate, potassium dicyclopentyl dithiocarbamate, rubidium dicyclopentyl dithiocarbamate, cesium dicyclopentyl dithiocarbamate, ethylammonium dicyclopentyl dithiocarbamate, diethylammonium dicyclopentyl dithiocarbamate, triethylammonium dicyclopentyldithiocarbamate. , Tetraethylammonium dicyclopentyldithiocarbamate,
Lithium di-n-hexyldithiocarbamate, sodium di-n-hexyldithiocarbamate, potassium di-n-hexyldithiocarbamate, rubidium di-n-hexyldithiocarbamate, cesium di-n-hexyldithiocarbamate, di-n-hexyl Ethylammonium dithiocarbamate, diethylammonium di-n-hexyldithiocarbamate, triethylammonium di-n-hexyldithiocarbamate, tetraethylammonium di-n-hexyldithiocarbamate,
Lithium dicyclohexyldithiocarbamate, sodium dicyclohexyldithiocarbamate, potassium dicyclohexyldithiocarbamate, rubidium dicyclohexyldithiocarbamate, cesium dicyclohexyldithiocarbamate, ethylammonium dicyclohexyldithiocarbamate, diethylammonium dicyclohexyldithiocarbamate, triethylammonium dicyclohexyldithiocarbamate, tetraethylammonium dicyclohexyldithiocarbamate,
Lithium ethylphenyldithiocarbamate, sodium ethylphenyldithiocarbamate, potassium ethylphenyldithiocarbamate, rubidium ethylphenyldithiocarbamate, cesium ethylphenyldithiocarbamate, ethylammonium ethylphenyldithiocarbamate, diethylammonium ethylphenyldithiocarbamate, triethylammonium ethylphenyldithiocarbamate , Tetraethylammonium ethylphenyldithiocarbamate,
Lithium diphenyldithiocarbamate, sodium diphenyldithiocarbamate, potassium diphenyldithiocarbamate, rubidium diphenyldithiocarbamate, cesium diphenyldithiocarbamate, ethylammonium diphenyldithiocarbamate, diethylammonium diphenyldithiocarbamate, triethylammonium diphenyldithiocarbamate, tetraethylammonium diphenyldithiocarbamate,
Lithium dibenzyldithiocarbamate, sodium dibenzyldithiocarbamate, potassium dibenzyldithiocarbamate, rubidium dibenzyldithiocarbamate, cesium dibenzyldithiocarbamate, ethylamethylene dibenzyldithiocarbamate, diethylamethylene dibenzyldithiocarbamate, triethylamammamdibenzyldithiocarbamate , Tetraethylamthiocarbamate dibenzyldithiocarbamate, etc., among which sodium dimethyldithiocarbamate, potassium dimethyldithiocarbamate, tetraethylammonium dimethyldithiocarbamate, etc.
Sodium diethyldithiocarbamate, potassium diethyldithiocarbamate, tetraethylammonium diethyldithiocarbamate,
Sodium di-n-propyldithiocarbamate, potassium di-n-propyldithiocarbamate, tetraethylammonium di-n-propyldithiocarbamate,
Sodium diisopropyldithiocarbamate, potassium diisopropyldithiocarbamate, tetraethylammonium diisopropyldithiocarbamate,
Sodium dicyclopropyldithiocarbamate, potassium dicyclopropyldithiocarbamate, tetraethylammonium dicyclopropyldithiocarbamate,
Sodium di-n-butyldithiocarbamate, potassium di-n-butyldithiocarbamate, tetraethylammonium di-n-butyldithiocarbamate,
Sodium diisobutyldithiocarbamate, potassium diisobutyldithiocarbamate, tetraethylammonium diisobutyldithiocarbamate,
The tert. -Sodium butyldithiocarbamate, di-tert. -Potassium butyl dithiocarbamate, di-tert. -Tetraethylammonium butyldithiocarbamate,
Sodium di-n-pentyldithiocarbamate, potassium di-n-pentyldithiocarbamate, tetraethylammonium di-n-pentyldithiocarbamate,
The tert. -Sodium amyldithiocarbamate, di-tert. -Potassium amyldithiocarbamate, di-tert. -Tetraethylammonium amyldithiocarbamate,
Sodium dicyclopentyl dithiocarbamate, potassium dicyclopentyl dithiocarbamate, tetraethylammonium dicyclopentyl dithiocarbamate,
Sodium di-n-hexyldithiocarbamate, potassium di-n-hexyldithiocarbamate, tetraethylammonium di-n-hexyldithiocarbamate,
Sodium dicyclohexyldithiocarbamate, potassium dicyclohexyldithiocarbamate, tetraethylammonium dicyclohexyldithiocarbamate, etc. are preferred.
Particularly preferred are sodium dimethyldithiocarbamate, potassium dimethyldithiocarbamate, tetraethylammonium dimethyldithiocarbamate,
Sodium diethyldithiocarbamate, potassium diethyldithiocarbamate, tetraethylammonium diethyldithiocarbamate,
Sodium di-n-propyldithiocarbamate, potassium di-n-propyldithiocarbamate, tetraethylammonium di-n-propyldithiocarbamate,
Sodium diisopropyldithiocarbamate, potassium diisopropyldithiocarbamate, tetraethylammonium diisopropyldithiocarbamate,
Sodium dicyclopropyldithiocarbamate, potassium dicyclopropyldithiocarbamate, tetraethylammonium dicyclopropyldithiocarbamate,
Sodium di-n-butyldithiocarbamate, potassium di-n-butyldithiocarbamate, tetraethylammonium di-n-butyldithiocarbamate,
Sodium diisobutyldithiocarbamate, potassium diisobutyldithiocarbamate, tetraethylammonium diisobutyldithiocarbamate,
The tert. -Sodium butyldithiocarbamate, di-tert. -Potassium butyl dithiocarbamate, di-tert. -Tetraethylammonium butyldithiocarbamate and the like.

The content of the cerium complex luminescent material and the dithiocarbamate of the general formula (7) in the cerium complex luminescent material composition containing the cerium complex luminescent material of the present invention and the dithiocarbamate of the general formula (7) is the cerium complex luminescence. The amount of dithiocarbamate of the general formula (7) is preferably 0.0001 to 1,000,000 mol, particularly preferably 0.001 to 100,000 mol, based on 1 mol of cerium as a material.

A method for producing a hydrocarbon group-substituted cerium monodithiocarbamate complex luminescent material in which four or more ligands are coordinated with trivalent cerium will be described.

The conditions for producing a hydrocarbon group-substituted cerium monodithiocarbamate complex luminescent material in which four or more ligands are coordinated with trivalent cerium are not particularly limited, but the following conditions should be used. Can be done.

By dissolving or suspending a trivalent cerium salt in an inert solvent and reacting with the dithiocarbamate of the above general formula (7), carbonization in which four or more ligands are coordinated with trivalent cerium. A hydrogen group-substituted cerium complex monodithiocarbamate light emitting material can be synthesized. During or after this synthesis reaction, the quaternary phosphonium ion of the above general formula (8), the above nitrogen atom-containing charged neutral organic ligand, the phosphine compound of the above general formula (9) and the above general formula By adding the phosphine oxide compound of (10), the compound of the general formula (1) and the compound of the general formula (4) can be synthesized.

Examples of the trivalent cerium salt include cerium fluoride (III), cerium chloride (III), cerium bromide (III), cerium iodide (III), cerium sulfate (III), cerium nitrate (III), and phosphoric acid. Cerium (III), cerium carbonate (III), cerium perchlorate (III), cerium acetate (III), cerium 2-ethylhexanoate (III), cerium stearate (III), cerium oxalate (III), 2 , 4-Pentandionatocerium (III), Trifluoroacetylacetonatocerium (III), 6,6,7,7,8,8,8-Heptafluoro-2,2-dimethyl-3,5-octanedio Use anhydrides and hydrates such as cerium (III), cerium trifluoromethanesulfonate (III), 1,2,3,4-tetramethyl-2,4-cyclopentadienylcerium (III). Can be done.

The inert solvent that can be used as the reaction medium is not particularly limited as long as it is used in the art, and is, for example, n-pentane, i-pentane, n-hexane, cyclohexane, n-heptane, n. -Saturated hydrocarbons such as decane; unsaturated hydrocarbons such as toluene, xylene and decene-1; diethyl ether, dipropyl ether, tert. -Ethers such as butyl methyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran; methanol, ethanol, isopropanol, n-butanol, sec-butanol, tert. -Alcohols such as butanol, 2-ethylhexanol; nitriles such as acetonitrile, octanonitrile, decanonitrile, pentadecanonitrile; dimethyl sulfoxide, N, N-dimethylformamide, N, N, N', N'-tetra Heteroatom-containing solvents such as methylethylenediamine and hexamethylphosphoric acid triamide can be used. Moreover, these mixed solvents can also be used.

The reaction temperature at the time of producing the cerium complex luminescent material is usually preferably in the range of -100 to 200 ° C, which is an industrially used temperature, and particularly preferably in the range of −85 to 150 ° C. The pressure conditions for the reaction can be any of pressure, normal pressure, and reduced pressure.

Further, when the trivalent cerium salt is reacted with the dithiocarbamate of the general formula (7), the amount of the dithiocarbamate of the general formula (7) is 0 with respect to the cerium content of 1 mol in the trivalent cerium salt. It is preferably .0001 mol to 1,000,000 mol, and particularly preferably in the range of 0.001 mol to 100,000 mol. If it is out of this range, the emission intensity may decrease, and the durability and emission life may decrease.

The method for producing a hydrocarbon group-substituted cerium complex monodithiocarbamate luminescent material in which four or more ligands are coordinated to the trivalent cerium of the present invention and a method thereof are not particularly limited, but are as follows. The production method shown in the above can be particularly preferably used.

After reacting the trivalent cerium salt with the dithiocarbamate of the general formula (7), the quaternary phosphonium ion of the general formula (8) and the nitrogen atom-containing charge-neutral organic ligand of the general formula (8) are ligands. A method of adding and reacting the phosphine compound of the above general formula (9) and the phosphine oxide compound of the above general formula (10), and the dithiocarbamine of the general formula (7) after mixing the trivalent cerium salt and the ligand. Any mixing method can be used, including the method of reacting the acid salt.

The produced cerium complex luminescent material and its composition may be used as it is, and may be used as it is, for filtration using a glass filter, sintered porous body, etc., sublimation, recrystallization, or column separation using silica, alumina, polymer gel, etc. It can also be purified by using the purification means of. At this time, these means may be used in combination as needed.

The hydrocarbon group-substituted cerium complex monodithiocarbamate light-emitting material in which four or more ligands are coordinated with the trivalent cerium of the present invention and its composition can be used as a light-emitting material, a wavelength conversion material, and the like, and are light-resistant. It is possible to provide LED devices, organic EL devices, solar cell devices, films for agricultural facilities, etc., which have good properties (UV resistance), weather resistance, heat resistance, durability, and the like.

Examples are shown below, but the present invention is not limited to these examples.

Fluorescence emission measurement was performed using FP-6500 manufactured by JASCO Corporation.

Example 1
[Synthesis of cerium complex luminescent material (1-2) of the above general formula (2)]
Under a nitrogen stream, a solution of 2.97 g (7.97 mmol) of cerium (III) chloride heptahydrate in 15 ml of methanol was placed in a 100 mL Schlenk tube equipped with a stirrer, and sodium diethyldithiocarbamate 7. A solution prepared by dissolving 20 ml of methanol in 22 g (32.0 mmol) was added dropwise from a dropping filter. After completion of the dropping, the mixture was stirred at room temperature for 1 hour.

The precipitated white solid was filtered off by a glass filter to obtain a green solution. The obtained green solution was recharged into a 100 ml Schlenk tube equipped with a stirrer, and a solution prepared by dissolving 3.40 g (8.11 mmol) of tetraphenylphosphonium bromide in 20 ml of methanol was added dropwise from a dropping filter. After completion of the dropping, the mixture was stirred at room temperature for 1 hour, the precipitated orange solid was filtered off, washed with ethanol, and dried under reduced pressure. The yield of the obtained tetrakis (diethyldithiocarbamic acid) cerium (tetraphenylphosphonium) complex luminescent material of the general formula (1) was 0.49 g, and the yield was 5.8%.
[Measurement of fluorescence emission of cerium complex luminescent material of the above general formula (2)]
The obtained tetrakis (diethyldithiocarbamic acid) cerium (tetraphenylphosphonium) complex luminescent material of the general formula (2) was dissolved in oleylamine, and the luminescence behavior was observed using a spectrofluorometer FP-6500 manufactured by JASCO Corporation. did. It was found that the cerium complex light emitting material emits blue light having a peak of 451 nm by excitation with 390 nm.

Example 2
[Synthesis of cerium complex luminescent material (1-31) of the above general formula (3)]
Under a nitrogen stream, a solution of 3.00 g (8.30 mmol) of cerium (III) chloride heptahydrate in 16 ml of methanol was placed in a 100 mL Schlenck tube equipped with a stirrer, and sodium diethyldithiocarbamate 7. A solution prepared by dissolving 20 ml of methanol in 50 g (33.2 mmol) was added dropwise from a dropping filter. After completion of the dropping, the mixture was stirred at room temperature for 1 hour. 20 ml of 1,2-dichloroethane was added to the reaction solution, and the precipitated white solid was filtered off by a glass filter to obtain a yellow solution. Methanol and 1,2-dichloroethane were distilled off from the obtained container and dried under reduced pressure to obtain a brown tetrakis (diethyldithiocarbamic acid) cerium sodium complex luminescent material.
[Measurement of fluorescence emission of cerium complex luminescent material of the above general formula (3)]
The obtained tetrakis (diethyldithiocarbamic acid) cerium sodium complex luminescent material of the general formula (3) was dissolved in oleylamine, and the luminescence behavior was observed using a spectrofluorometer FP-6500 manufactured by JASCO Corporation. It was found that this cerium complex light emitting material emits blue light having a peak of 505 nm by excitation at 435 nm.

Example 3
[Synthesis of cerium complex luminescent material (4-1) of the above general formula (5)]
Under a nitrogen stream, a solution prepared by dissolving 1.73 g (4.60 mmol) of cerium (III) chloride heptahydrate in a mixed solvent of 80 ml of acetonitrile and 10 ml of ethanol was charged into a 200 mL Schlenck tube equipped with a stirrer, and diethyldithio. A solution prepared by dissolving 3.07 g (13.5 mmol) of diethylammonium caribamate and 0.829 g (4.60 mmol) of phenanthroline in 50 ml of acetonitrile was added dropwise from a dropping filter. After completion of the dropping, the mixture was stirred at room temperature for 4 hours.

The precipitated orange solid was separated by filtration, washed with acetonitrile, and dried under reduced pressure to obtain a tris (diethyldithiocarbamic acid) cerium (phenanthroline) complex luminescent material.
[Measurement of fluorescence emission of cerium complex luminescent material of the above general formula (5)]
The obtained tris (diethyldithiocarbamic acid) cerium (phenanthroline) complex luminescent material of the general formula (5) was dissolved in oleylamine, and the luminescence behavior was observed using a spectrofluorometer FP-6500 manufactured by JASCO Corporation. It was found that the cerium complex light emitting material emits blue light having a peak of 510 nm when excited at 435 nm.

Example 4
[Synthesis of cerium complex luminescent material (4-52) of the above general formula (6)]
Under a nitrogen stream, a solution prepared by dissolving 1.71 g (4.58 mmol) of cerium (III) chloride heptahydrate in a mixed solvent of 100 ml of acetonitrile and 10 ml of ethanol was charged into a 200 mL Schlenck tube equipped with a stirrer, and diethyldithio. A solution prepared by dissolving 3.11 g (14.0 mmol) of diethylammonium caribamate and 2.56 g (9.21 mmol) of triphenylphosphine oxide in 60 ml of acetonitrile was added dropwise from a dropping filter. After completion of the dropping, the mixture was stirred at room temperature for 4 hours.

The resulting reaction mixture was subjected to 1350 rpm / 10 min. Centrifugation under the conditions of (1) to obtain a brown solid. The brown solid was washed with methanol and dried under reduced pressure to obtain a tris (diethyldithiocarbamic acid) cerium (triphenylphosphine oxide) complex luminescent material.
[Measurement of fluorescence emission of cerium complex luminescent material of the above general formula (6)]
The obtained tris (diethyldithiocarbamic acid) cerium (triphenylphosphine oxide) complex luminescent material of the general formula (6) was dissolved in oleylamine, and the luminescence behavior was observed using a spectrofluorometer FP-6500 manufactured by JASCO Corporation. Observed. It was found that the cerium complex light emitting material emits blue light having a peak of 491 nm when excited at 425 nm.

Claims (12)

A hydrocarbon group-substituted cerium monodithiocarbamate complex luminescent material in which four or more ligands are coordinated to trivalent cerium is the following general formula (1).

(1)
(In the formula, R ¹ and R ² represent hydrocarbon groups having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other. M ⁺ is an alkali metal ion or a quaternary phosphonium ion. Represents.)
Cerium complex luminescent material. R ^1, R ² is an alkyl group having 1 to 6 carbon atoms, M ⁺ is sodium ion, potassium ion, a tetraalkylphosphonium ion, tetra allyl phosphonium ion ion, cerium complex luminescent material according to claim 1. Hydrocarbon group-substituted cerium monodithiocarbamate complex luminescent material in which four or more ligands are coordinated to trivalent cerium is the following general formulas (2) and (3).

(2)

(3)
The cerium complex luminescent material according to claim 1 or 2. A hydrocarbon group-substituted cerium monodithiocarbamate complex luminescent material in which four or more ligands are coordinated to trivalent cerium is the following general formula (4).

(4)
(.N ^wherein, R 1, ^{R 2} is a table to .L a hydrocarbon group having 1 to 20 carbon atoms, a nitrogen atom, include a phosphorus atom, represent an organic ligand charge is neutral, Represents an integer of 1 or more.)
Cerium complex luminescent material. The cerium complex luminescent material according to claim 4 , wherein R ¹ and R ² are alkyl groups having 1 to 6 carbon atoms, and L is phenanthroline, bipyridine, and triphenylphosphine oxide. Hydrocarbon group-substituted cerium monodithiocarbamate complex luminescent materials in which four or more ligands are coordinated to trivalent cerium are the following general formulas (5) and (6).

(5)

(6)
The cerium complex luminescent material according to claim 4 or 5. A cerium complex luminescent material composition comprising the cerium complex luminescent material according to any one of claims 1 to 6 and the dithiocarbamate of the following general formula (7).

(7)
(In the formula, R ¹ and R ² represent hydrocarbon groups having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other. M ⁺ is an alkali metal ion or a quaternary ammonium ion. Represents.) The cerium complex luminescent material or cerium complex luminescent material composition according to any one of claims 1 to 7 , which is excited by ultraviolet light or visible light and emits blue light. An LED device comprising the cerium complex light emitting material or the cerium complex light emitting material composition according to any one of claims 1 to 8. An organic EL device comprising the cerium complex luminescent material or the cerium complex luminescent material composition according to any one of claims 1 to 8. A solar cell device comprising the cerium complex luminescent material or the cerium complex luminescent material composition according to any one of claims 1 to 8. A film for agricultural facilities, which comprises the cerium complex luminescent material or the cerium complex luminescent material composition according to any one of claims 1 to 8.