JP2010095514A - Linear tetraphosphine tetraoxide, rare-earth metal complex comprising the linear tetraphosphine tetraoxide as ligand and use of the complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ligand for achieving a rare-earth metal complex stably exerting high emission intensity and exhibiting high solubility to organic media. <P>SOLUTION: A linear tetraphosphine tetraoxide represented by general formula (1) [wherein, R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>and R<SP>6</SP>represent the same or different (substituted) saturated hydrocarbon, (substituted) aryl, (substituted) heteroaryl or (substituted) aralkyl, or R<SP>1</SP>and R<SP>2</SP>, and R<SP>5</SP>and R<SP>6</SP>on the same phosphorus atom may be bonded to form a ring; and l, m and n each represents the same or different ≥2 integer] is provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a chain tetraphosphine tetraoxide, a rare earth metal complex having the chain tetraphosphine tetraoxide as a ligand, and uses thereof.

  Phosphine oxide is industrially useful fine chemicals, and is further used as a catalyst raw material, functional material, etc. for synthesizing high-value-added fine chemicals. In addition, phosphine oxide can be easily converted into an industrially useful phosphine by a known method (for example, a method using a mixture of chlorosilane and alkylamine, etc.). Yes.

  In particular, in recent years, in the field of electroluminescence and white LED lighting, phosphors containing rare earth metal complexes having phosphine oxide ligands have attracted attention instead of inorganic compound phosphors such as rare earth metal oxides and nitrides. Yes. The said fluorescent substance can provide a light-emitting device by combining with LED or a semiconductor laser, for example (p138-144 of a nonpatent literature 1).

  In recent years, a phosphor containing a rare earth metal complex having a phosphine oxide ligand has attracted attention as a luminescent ink used for security purposes for the purpose of preventing counterfeiting and unauthorized copying ( Patent Document 5).

  Similar to the inorganic compound phosphor, the complex can emit light based on f-orbital electron transition. In addition, by controlling the structure and molecular design of the phosphine oxide ligand, it is possible to precisely control the optical properties. Furthermore, since the complex is uniformly dissolved in an organic solvent and a liquid polymer such as a silicone resin or a fluororesin, a highly transparent phosphor material can be provided. Conventionally used inorganic compound phosphors do not dissolve in the liquid polymer but tend to be dispersed in the liquid polymer. Therefore, the obtained phosphor material has a problem that light extraction efficiency decreases due to light scattering.

  As a rare earth metal complex having a phosphine oxide ligand, for example, Patent Document 1 discloses a complex in which a monodentate phosphine oxide is coordinated to a rare earth metal ion.

  However, the rare earth metal complex of Patent Document 1 cannot realize a phosphor capable of stably exhibiting high emission intensity because the phosphine oxide monodentate ligand easily dissociates from the rare earth metal ion in an organic medium such as a liquid polymer. .

  Therefore, in order to improve the stability of the complex, a complex in which a bidentate bisphosphine dioxide is coordinated to a rare earth metal ion has been proposed (Patent Documents 2 to 5).

  For the purpose of further improving the stability of the complex, Patent Document 6 reports a rare earth metal complex using a macrocyclic tetraphosphine tetraoxide which is a tetradentate ligand as a ligand.

  These rare earth metal complexes having phosphine oxide ligands of Patent Documents 2 to 6 are still insufficient in stability in an organic medium such as a liquid polymer. Moreover, the rare earth metal complex which has the ligand of patent documents 1-6 and nonpatent literature 2 has low solubility with respect to organic media, such as a liquid polymer. For this reason, the rare earth metal complex cannot be sufficiently dissolved in the organic medium, and as a result, there is a disadvantage that a material with high light emission cannot be realized.

  Therefore, development of a novel phosphine oxide ligand that makes it possible to realize a rare earth metal complex that stably exhibits high emission intensity and exhibits high solubility in an organic medium is eagerly desired.

Japanese Patent Laid-Open No. 2003-81986 JP 2004-262909 A JP-A-2005-82529 JP 2005-15564 A JP 2006-77191 A Japanese Patent Laid-Open No. 2007-1880

Supervised by Ginya Adachi, "Functions and Applications of Rare Earths" CMC Publishing (2006) p138-144 M. Vincens, et al., Tetrahedron, 1991, 47, 403.

  The main object of the present invention is to provide a ligand for realizing a rare earth metal complex that stably exhibits high emission intensity and exhibits high solubility in an organic medium.

  As a result of intensive studies to achieve the above object, the present inventor has found that a tetraphosphine tetraoxide having a specific structure can achieve the above object, and has completed the present invention.

That is, the present invention relates to the following tetraphosphine tetraoxide and uses thereof.
1. General formula:

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each may be a saturated hydrocarbon group which may be substituted, an aryl group which may be substituted, or a substituent A heteroaryl group which may be substituted or an aralkyl group which may be substituted, or R ¹ and R ² and R ⁵ and R ⁶ on the same phosphorus atom may be bonded to form a ring Well, l, m and n are the same or different and each represents an integer of 2 or more.)
A linear tetraphosphine tetraoxide represented by
2. In general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each may be a saturated hydrocarbon group which may be substituted, or an aryl which may be substituted Group, an optionally substituted heteroaryl group or an optionally substituted aralkyl group, or R ¹ and R ² and R ⁵ and R ⁶ on the same phosphorus atom are bonded to form a ring. The chain tetraphosphine tetraoxide according to Item 1, wherein l, m and n are the same or different and each represents an integer of 3 to 12.
3. In general formula (1), R ¹ , R ² , R ^5, and R ⁶ are the same or different and each may be a substituted C 3-20 saturated hydrocarbon group or an optionally substituted aryl. A group, a heteroaryl group which may be substituted, or an aralkyl group which may be substituted, wherein R ³ and R ⁴ may be the same or different and each may be a substituted aryl group or a substituted group; Item 3. The chain tetraphosphine tetraoxide according to item 1 or 2, which represents a good heteroaryl group, wherein l, m and n are the same or different and each represents an integer of 3 to 12.
4). In general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each may be an optionally substituted aryl group or an optionally substituted heteroaryl group The chain tetraphosphine tetraoxide according to any one of Items 1 to 3, wherein l, m and n are the same or different and each represents an integer of 3 to 12.
5). In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and may be substituted or substituted aryl groups having 6 to 15 carbon atoms. The chain | strand-shaped tetraphosphine tetraoxide in any one of said claim | item 1-4 which shows the C5-C15 heteroaryl group which may be, and l, m, and n are the same or different, respectively, and show the integer of 3-12. .
6). In general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each represents an optionally substituted aryl group having 6 to 15 carbon atoms; The chain tetraphosphine tetraoxide according to any one of Items 1 to 5, wherein m and n are the same or different and each represents an integer of 3 to 12.
7). In general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each represents an optionally substituted aryl group having 6 to 15 carbon atoms; , M and n are the same or different and each represents 3, 5, 7, 9 or 11, the chain tetraphosphine tetraoxide according to the above items 1 to 6.
8). A rare earth metal complex comprising the chain tetraphosphine tetraoxide according to any one of Items 1 to 7.
9. 9. The rare earth metal complex according to item 8, wherein at least one oxygen atom among the four oxygen atoms of the chain tetraphosphine tetraoxide is coordinated to a rare earth metal ion.
10. Item 10. The rare earth metal complex according to Item 9, wherein the rare earth metal ion is Eu3 ⁺ , Tb3 ⁺ , Er3 ⁺ , Gd3 ^+, or Tm3 ⁺ .
11. Item 10. The rare earth metal complex according to Item 9, wherein the rare earth metal ion is Eu ³⁺ or Tb ³⁺ .
12 Furthermore, the general formula (2)

(In the formula, R ⁸ represents a hydrogen atom, a deuterium atom, a halogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aryl group, or an optionally substituted hetero group. An aryl group or an aralkyl group which may be substituted; R ⁷ and R ⁹ are the same or different and each may be substituted a saturated hydrocarbon group having 1 to 20 carbon atoms or a perfluoro having 1 to 20 carbon atoms; An alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or an optionally substituted aralkyl group is shown.)
The rare earth metal complex according to any one of Items 8 to 11, wherein a β-diketonato ligand represented by the formula is coordinated.
13. The chain tetraphosphine tetraoxide according to any one of Items 1 to 7, and the general formula (3)
LnLp (3)
(In the formula, Ln represents a rare earth metal ion, p represents an integer of 1 to 5, L represents the β-diketonato ligand, and when p is an integer of 2 or more, the β-diketonato coordination The ligands may be the same or different from each other.)
The rare earth metal complex according to claim 12, which is obtained by reacting in a solvent with a β-diketonato rare earth metal complex represented by the formula:
14 The reaction ratio ((1) / (3)) of the chain tetraphosphine tetraoxide (1) and the β-diketonato rare earth metal complex (3) in the reaction is 0.3 to 0.7 in molar ratio. Item 14. The rare earth metal complex according to Item 13.
15. Item 13. The reaction ratio ((1) / (3)) between the chain tetraphosphine tetraoxide (1) and the β-diketonato rare earth metal complex (3) in the reaction is 0.5 in terms of molar ratio. Or the rare earth metal complex of 14.
16. Item 16. The rare earth metal complex according to any one of Items 13 to 15, wherein one or two or more β-diketonato rare earth metal complexes are reacted as the β-diketonato rare earth metal complex (3).
17. A luminescent medium comprising the rare earth metal complex according to any one of Items 8 to 16 dissolved in an organic medium.
18. Item 18. A white LED element having the light emitting medium according to Item 17.
19. Item 17. A fluorescent ink composition comprising the rare earth metal complex according to any one of Items 8 to 16.
20. The organic electroluminescent element which has a light emitting layer containing the rare earth metal complex in any one of said claim | item 8 -16.

  The novel chain tetraphosphine tetraoxide (1) of the present invention can be coordinated to a rare earth metal ion to form a rare earth metal complex composition.

  The rare earth metal complex having the chain tetraphosphine tetraoxide (1) as a ligand 1) has higher emission intensity than conventional luminescent materials, 2) has high solubility in organic media, and 3) in organic media. The chain tetraphosphine tetraoxide (1) has the property of not easily dissociating from rare earth metal ions.

  Therefore, the phosphor containing the complex can stably exhibit high emission intensity. Further, since the complex is easily dissolved in an organic medium (particularly, a liquid polymer), a highly light-emitting material with high transparency can be provided.

  Further, the rare earth metal complex of the present invention is excellent in durability against heat and the like.

  In particular, the complex can be used for a light emitting layer (light emitting medium) of a white LED element, a fluorescent ink composition, and a light emitting layer of an organic electroluminescent element.

FIG. 1 is a cross-sectional view (schematic diagram) of an LED element having a light emitting layer 1 composed of an LED chip 2 and a light emitting medium 3.

Chain tetraphosphine tetraoxide (1)
The chain tetraphosphine tetraoxide (1) of the present invention has the general formula:

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each may be a saturated hydrocarbon group which may be substituted, an aryl group which may be substituted, or a substituent A heteroaryl group which may be substituted or an aralkyl group which may be substituted, or R ¹ and R ² and R ⁵ and R ⁶ on the same phosphorus atom may be bonded to form a ring Well, l, m and n are the same or different and each represents an integer of 2 or more.)
It is represented by

The saturated hydrocarbon group of the saturated hydrocarbon group which may be substituted is not particularly limited, and examples thereof include a C _{1 to} C ₂₀ linear or branched alkyl group and a C _{3 to} C ₁₂ cycloalkyl group. Etc.

Examples of the C _{1 to} C ₂₀ linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, Examples include a hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, icosyl group and the like.

Examples of the C _{3 to} C ₁₂ cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclododecyl group.

  Although it does not specifically limit as a substituent of the saturated hydrocarbon group which may be substituted, For example, a fluoroalkyl group, an alkoxy group, an aryloxy group, a siloxy group, a dialkylamino group etc. are mentioned.

Examples of the fluoroalkyl group include a C _1-6 perfluoroalkyl group. Examples of the C _1-6 perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a tridecafluorohexyl group.

Examples of the alkoxy group include a C _1-6 alkoxy group. Examples of the C _1-6 alkoxy group include a methoxy group, an ethoxy group, and a hexyloxy group.

Examples of the aryloxy group include a C _6-12 aryloxy group. The C _6-12 aryloxy group, a phenoxy group, a naphthyloxy group and the like.

  Examples of the siloxy group include trimethylsiloxy, triethylsiloxy, triisopropylsiloxy, tert-butyldimethylsiloxy and the like.

  Examples of the dialkylamino group include dimethylamino and diethylamino.

  The substitution position of the substituent of the saturated hydrocarbon group which may be substituted and the number of substituents are not particularly limited.

In particular, the saturated hydrocarbon group which may be substituted is preferably a C _3-20 saturated hydrocarbon group which may be substituted, has excellent solubility in an organic medium, and can stably exhibit high emission intensity. The C _4-18 saturated hydrocarbon group which may be substituted is more preferable in that the rare earth metal complex can be obtained more reliably.

The aryl group of the aryl group which may be substituted is not particularly limited, and examples thereof include a C _6-20 aryl group. Examples of the C _6-20 aryl group include phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, anthryl and the like.

The substituent of the aryl group which may be substituted is not particularly limited, and for example, a C _1-6 alkyl group, a C _1-6 perfluoroalkyl group, a C _6-14 aryl group, a 5- to 10-membered aromatic group Heterocyclic group, alkoxy group, aryloxy group, siloxy group, dialkylamino group and the like can be mentioned.

Examples of the C _1-6 alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and the like.

Examples of the C _1-6 perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, tridecafluorohexyl and the like.

Examples of the C _6-14 aryl group include phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, 2-anthryl and the like.

  Examples of the 5- to 10-membered aromatic heterocyclic group include 2- or 3-thienyl, 2-, 3- or 4-pyridyl, 2-, 3-, 4-, 5- or 8-quinolyl, 1-, Examples include 3-, 4- or 5-isoquinolyl, 1-, 2- or 3-indolyl, 2-benzothiazolyl, 2-benzo [b] thienyl, benzo [b] furanyl and the like.

  The alkoxy group, aryloxy group, siloxy group and dialkylamino group are the same as the alkoxy group, aryloxy group, siloxy group and dialkylamino group described as the substituent of the saturated hydrocarbon group.

  The substitution position and the number of substituents of the substituent of the aryl group which may be substituted are not particularly limited.

  In particular, the optionally substituted aryl group is an optionally substituted C6-C6 in that it can more reliably obtain a rare earth metal complex that is excellent in solubility in an organic medium and that can stably exhibit high emission intensity. Fifteen aryl groups are preferred.

  The heteroaryl group of the heteroaryl group which may be substituted is not particularly limited. For example, the heteroaryl group is a condensed ring containing 1 to 3 atoms selected from the group consisting of a sulfur atom, an oxygen atom and a nitrogen atom. There may be mentioned 5 to 14-membered aromatic heterocyclic groups.

  Examples of the aromatic heterocyclic group include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, isothiazolyl, thiazolyl, 1,2,3-oxadiazolyl, triazolyl, tetrazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl , Indazolyl, purinyl, quinolyl, isoquinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinolinyl, pteridinyl, carbazolyl, carbolinyl, phenanthridinyl, acridinyl and the like.

  The substituent of the heteroaryl group which may be substituted is the same as the substituent described for the aryl group which may be substituted.

  The position of the substituent and the number of substituents in the optionally substituted heteroaryl group are not particularly limited.

In particular, the optionally substituted heteroaryl group is an optionally substituted C in that it can more reliably obtain a rare earth metal complex that is excellent in solubility in an organic medium and that can stably exhibit high emission intensity. _5-15 heteroaryl groups are preferred.

  Examples of the aralkyl group of the aralkyl group which may be substituted include a benzyl group, a phenethyl group, and a phenylpropyl group.

  The substituent of the aralkyl group which may be substituted is the same as the substituent described for the aryl group which may be substituted.

  The position of the substituent of the aralkyl group which may be substituted and the number of substituents are not particularly limited.

Examples of the ring formed by combining R ¹ and R ² and R ⁵ and R ⁶ on the same phosphorus atom include a piperidine ring, a pyrrolidine ring, and a morpholine ring.

  L, m and n in the formula (1) are the same or different and may be an integer of 2 or more, preferably an integer of 3 to 12. In particular, l, m, and n are the same or different from each other in that they are excellent in solubility in an organic medium and can more reliably obtain a rare earth metal complex that can stably exhibit high emission intensity. Or 11 is more preferable, and 3 or 5 is even more preferable.

In particular, as the chain tetraphosphine tetraoxide of the present invention, in general formula (1), R ¹ , R ² , R ⁵ and R ⁶ are the same or different and each may be substituted. 20 saturated hydrocarbon groups, an optionally substituted aryl group, an optionally substituted heteroaryl group, or an optionally substituted aralkyl group, wherein R ³ and R ⁴ are the same or different; A linear tetraphosphine tetraoxide, which represents an optionally substituted aryl group or an optionally substituted heteroaryl group, wherein l, m and n are the same or different and each represents an integer of 3 to 12, wherein ^{(1), R 1, R} 2, R 3, R 4, R 5 and ^{R 6} are the same or different, an aryl group or a location of a good 6 to 15 carbon atoms which may be substituted A chain tetraphosphine tetraoxide, which is an optionally substituted heteroaryl group having 5 to 15 carbon atoms, wherein l, m and n are the same or different and each represents an integer of 3 to 12, is more preferred. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each represents an optionally substituted aryl group having 6 to 15 carbon atoms, wherein l, m and n are A linear tetraphosphine tetraoxide which is the same or different and represents an integer of 3 to 12 is more preferred, and in general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same. Alternatively, a linear tetraphosphine tetraoxide which represents an optionally substituted aryl group having 6 to 15 carbon atoms, wherein l, m and n are the same or different and each represents 3, 5, 7, 9 or 11 Is most preferred.

Manufacturing method of chain | strand tetraphosphine tetraoxide (1) The manufacturing method of the chain | strand tetraphosphine tetraoxide of this invention is not specifically limited, For example, it can manufacture by combining a well-known method suitably. For example, the chain tetraphosphine tetraoxide (1) in which l, m, and n are integers of 3 or more can be produced according to a synthetic route shown in the following reaction formula 1 or a synthetic route to which this is applied. The chain tetraphosphine tetraoxide (1) in which l and n are 2 and m is an integer of 2 or more can be produced according to the synthesis route shown in the following reaction formula 2 or a synthesis route to which this is applied.

  Hereinafter, the production method of the chain tetraphosphine tetraoxide of the present invention will be specifically described by using the following reaction formulas 1 and 2 as representative examples.

  <Reaction Formula 1>

First Step In the first step, a phosphonium salt (6) is obtained by reacting bisphosphine (4) with a leaving group-containing unsaturated hydrocarbon (5).

R ³ and R ⁴ in the general formula (4) are the same as the above R ³ and R ⁴ . In particular, each of R ³ and R ⁴ is preferably an aryl group which may be the same or different, or an optionally substituted heteroaryl group, and an optionally substituted aryl group having 6 to 15 carbon atoms or An optionally substituted heteroaryl group having 5 to 15 carbon atoms is more preferable, and an optionally substituted aryl group having 6 to 15 carbon atoms is more preferable. R ³ and R ⁴ may be the same as or different from each other.

  M in the general formula (4) is preferably an integer of 3 to 12, and more preferably 3, 5, 7, 9 or 11.

  The bisphosphine (4) can be easily obtained by manufacturing it according to a commercially available product or a known method.

  In general formula (5), X is a leaving group. Examples of the leaving group include a toluenesulfonyloxy group (OTs group), a methanesulfonyloxy group (OMs group), a halogen atom, and the like. Examples of the halogen atom include F, Cl, Br, and I. Among these, in particular, a halogen atom is preferable and Br is more preferable because the phosphonium salt (6) can be obtained in a high yield and the compound (5) can be obtained at a low cost.

  In the general formula (5), l and n are each preferably an integer of 3 to 12.

  A leaving group containing unsaturated hydrocarbon (5) can be obtained easily by manufacturing according to a commercial item or a well-known method.

  Although the usage-amount of a leaving group containing unsaturated hydrocarbon (5) in a 1st process is not specifically limited, About 2-4 mol is preferable with respect to 1 mol of bisphosphine (4), and about 2-3 mol is more preferable.

  The reaction of bisphosphine (4) with the leaving group-containing unsaturated hydrocarbon (5) is preferably carried out in a solvent.

  The solvent is not particularly limited, and examples thereof include amide solvents such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide and N, N-dibutylformamide; nitro solvents such as nitromethane and nitrobenzene; acetonitrile Nitrile solvents such as propionitrile, benzonitrile; sulfoxide solvents such as dimethyl sulfoxide (DMSO); alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, diethylene glycol; diisopropyl ether, dibutyl ether, Tetrahydrofuran (THF), cyclopentyl methyl ether, dihydropyran, 1,4-dioxane, t-butyl methyl ether, 1,2-dimethoxyethane (DME), diethylene Ether solvents such as recall dimethyl ether, diethylene glycol dibutyl ether, ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, propylene glycol methyl ether acetate, anisole; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone; Ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate; aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, n-heptane and n-octane Is mentioned. These solvents can be used alone or as a mixed solvent of two or more. Among these, N, N-dimethylformamide (DMF), methanol, ethanol, and isopropanol are particularly preferable.

  The reaction may be performed in either a batch type or a continuous type.

The reaction pressure is not particularly limited, it may be a normal pressure to 100 kg / cm ² approximately.

  The reaction temperature may be appropriately set according to the progress of the reaction and the like, but is usually about -20 to 300 ° C, preferably about 0 to 200 ° C.

  The reaction time is not particularly limited and may be appropriately set according to the reaction temperature and the progress of the reaction, but is usually about 1 to 24 hours, preferably about 2 to 12 hours.

  When the phosphorus compound (4) and the compound (5) are reacted in a solvent, the charged molar concentration of the phosphorus compound (4) and the compound (5) in the reaction solution is as follows. Although it will not be limited if it is the density | concentration which a compound (5) melt | dissolves, Preferably it is 0.1 mol / kg or more respectively, and 0.2-2 mol / kg is more preferable.

  After the reaction, the phosphonium salt (6) may be isolated and purified from the obtained crude phosphonium salt, if necessary. As an isolation method, a known method may be employed as appropriate. Examples of the method for isolating the phosphonium salt (6) include filtration and centrifugation. Examples of the method for isolating the phosphonium salt (6) dissolved in the solvent include recrystallization and reprecipitation. In addition, you may isolate by concentrating and drying the liquid mixture obtained after completion | finish of reaction. As a method for purifying the obtained phosphonium salt (6), a known method may be appropriately employed. Examples thereof include recrystallization and reprecipitation.

  Moreover, you may transfer to a 2nd process, without isolating and refine | purifying a phosphonium salt (6). That is, the reaction of the following second step may be directly performed on the phosphonium salt (6) obtained in the first step.

Second Step In the second step, the phosphonium salt (8) is obtained by reacting the phosphonium salt (6) with the phosphine oxide (7) in the presence of a catalyst.

Wherein ^{R 1,} R 2, ^{R 5} and ^{R 6} in the phosphorus compound (7) is the same as ^{R 1,} R 2, ^{R 5} and ^{R 6.}

  The phosphorus compound (7) exists in an equilibrium state with the tautomeric phosphorus compound (7 ') as shown in the following formula.

The phosphorus compounds (7) and (7 ′) can be easily obtained by manufacturing them according to commercially available products or known methods. For example, the method described in R. Hays, J. Org. Chem., 1968, 33, 3691. That is, by reacting 1 mol of diethyl phosphite with 3 mol of Grignard reagent, R ¹ , R ² , R ⁵ and ^{R 6} can be prepared by the same said phosphorus compound (7). Also, GM Kosolapoff, et al., J. Chem. Soc. (C), 1967, to produce the R ^1, R ^2, R ⁵ and R ⁶ are different from each other phosphorus compounds (7) according to the method described in 1789. be able to.

In particular, R ¹ , R ² , R ⁵ and R ⁶ may be the same or different and each may be substituted with a C 3-20 saturated hydrocarbon group, an optionally substituted aryl group, or a substituted group. An optionally substituted heteroaryl group or an optionally substituted aralkyl group is preferred, and an optionally substituted aryl group having 6 to 15 carbon atoms or an optionally substituted heteroaryl group having 5 to 15 carbon atoms is More preferably, an optionally substituted aryl group having 6 to 15 carbon atoms is more preferable.

  Examples of the catalyst include a radical initiator type catalyst, a transition metal complex catalyst, and a basic catalyst. These can be used alone or in combination of two or more. Among these, a radical initiator catalyst is particularly preferable. By using a radical initiator catalyst, the target phosphonium salt (8) can be produced in a better yield.

  Examples of the radical initiator catalyst include azo compounds, organic peroxides, and trialkylboranes. Examples of the azo compound include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile (AMVN). ), 1,1′-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4′-azobis-4-cyanovaleric acid, 1,1′- Azobis (1-acetoxy-1-phenylethane) and the like can be exemplified. Examples of the organic peroxide include dibenzoyl peroxide (BPO), di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dilauroyl peroxide, diisobutyl peroxide, and t-butylperoxy-2- Examples include ethylhexanoate (perbutyl-O), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxyneodecanate, etc. it can. Examples of the trialkylborane include trialkylboranes such as triethylborane and tributylborane. These radical initiator catalysts can be used singly or in combination of two or more.

Examples of the transition metal complex catalyst include Fe complex, Ni complex, Pd complex and the like. Examples of the Fe complex include [CpFe (CO) ₂ ] ₂ and Fe (CO) ₅ . Examples of Ni complexes include NiCl ₂ (PPh ₃ ) ₂ and NiBr ₂ (PPh ₃ ) ₂ . Examples of the Pd complex include PdCl ₂ (PPh ₃ ) ₂ , PdCl ₂ (PhCN) ₂ , PdCl ₂ (CH ₃ CN) _{2 and the} like. These transition metal complex catalysts can be used singly or in combination of two or more.

  Examples of the basic catalyst include sodium methoxide, sodium ethoxide, potassium-t-butoxide, isopropylmagnesium isoporopoxide, t-butylmagnesium methoxide, and the like. These basic catalysts can be used singly or in combination of two or more.

  In particular, the catalyst is preferably a radical initiator catalyst, and is preferably an azo compound, an organic peroxide, or a trialkylborane.

  The amount of the catalyst used is not limited, but is usually about 0.01 to 5 mol, preferably about 0.02 to 3 mol, more preferably about 0.05 to 1 mol, with respect to 1 mol of the phosphonium salt (6). is there.

  Although the usage-amount of the phosphorus compound (7) in a 2nd process is not specifically limited, About 2-6 mol is preferable with respect to 1 mol of phosphonium salts (6), and about 2-3 mol is more preferable.

  The reaction between the phosphonium salt (6) and the phosphorus compound (7) is preferably performed in a solvent in the presence of the catalyst.

  The solvent is not particularly limited as long as it effectively exhibits a catalytic function. Examples include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ether solvents, ester solvents, alcohol solvents, amide solvents, sulfoxide solvents, and the like. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like. Examples of the aliphatic hydrocarbon solvent include n-hexane, cyclohexane, n-heptane, n-octane, and decalin. Examples of the ether solvent include diisopropyl ether, dibutyl ether, THF, DME, cyclopentyl methyl ether, dihydropyran, 1,4-dioxane, t-butyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, ethylene glycol monoalkyl ether, ethylene Examples include glycol monoalkyl ether acetate, propylene glycol methyl ether acetate, and anisole. Examples of the ester solvent include ethyl acetate, butyl acetate, isopropyl acetate and the like. Examples of the alcohol solvent include methanol, ethanol, isopropanol and the like. Examples of the amide solvent include dimethylformamide and diethylformamide. Examples of the sulfoxide solvent include dimethyl sulfoxide. These solvents can be used alone or as a mixed solvent of two or more. Among these, alcohol solvents such as methanol, ethanol and isopropanol are particularly preferable.

  It is preferable that the phosphonium salt (6), the phosphorus compound (7) and the catalyst are completely dissolved in a solvent from the viewpoint of reaction efficiency. The phosphonium salt (6) may be dissolved while reacting.

  The reaction may be performed in either a batch type or a continuous type.

The reaction pressure is not particularly limited, it may be a normal pressure to 100 kg / cm ² approximately.

  The reaction temperature may be appropriately set according to the progress of the reaction and the like, but is usually about -20 to 200 ° C, preferably about 0 to 150 ° C. For example, when reacting at normal pressure, the range of 0 ° C. to the reflux temperature of the solvent is preferred.

  The reaction time is not particularly limited and may be appropriately set according to the reaction temperature and the progress of the reaction, but is usually about 15 minutes to 72 hours, preferably about 1 to 36 hours.

  After the reaction, the phosphonium salt (8) may be isolated and purified from the obtained crude phosphonium salt, if necessary. As an isolation method, a known method may be employed as appropriate. Examples of the method for isolating the phosphonium salt (8) include recrystallization and reprecipitation. In addition, you may isolate by drying the liquid mixture obtained after completion | finish of reaction. As a method for purifying the obtained phosphonium salt (8), a known method may be appropriately employed. Examples thereof include recrystallization and reprecipitation.

  Moreover, you may transfer to a 3rd process, without isolating and refine | purifying a phosphonium salt (8). That is, the following alkaline hydrolysis may be directly performed on the phosphonium salt (8) obtained in the second step.

Third Step In the third step, the chain phosphine tetraoxide (1) is obtained by alkaline hydrolysis of the phosphonium salt (8) obtained in the second step.

  Specifically, the hydrolysis reaction is carried out by adding the phosphonium salt (8) and the base to water alone or a mixed solvent system of water and a co-solvent.

  The co-solvent is not particularly limited, but alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, and diethylene glycol are preferable.

  The content of water in the mixed solvent is preferably 5% by weight or more, and more preferably 20% by weight or more.

As the base, for example, NaOH, KOH, Ca (OH) ₂ or the like can be used. These bases can be used alone or in combination of two or more.

  About the usage-amount of a base, it is preferable to set so that it may become 2 equivalent or more with respect to 1 molecule of the said phosphonium salt (8). In particular, in order to increase the reaction rate, it is preferable to add 4 bases or more, and more preferably 4 to 20 equivalents, to one molecule of the phosphonium salt (8).

  The concentration of the phosphonium salt (8) in water or the mixed solvent is preferably 0.01 mol / kg or more, more preferably 0.05 to 2 mol / kg. When the concentration of the phosphonium salt (8) is 0.01 mol / kg or more, the hydrolysis reaction can be efficiently performed, and the chain tetraphosphine tetraoxide (1) can be easily obtained in a high yield.

  The hydrolysis reaction in the third step is preferably a homogeneous reaction from the viewpoint of reaction efficiency. When the hydrolysis reaction is a heterogeneous system, a surfactant or a phase transfer catalyst may be further added to accelerate the reaction.

  The hydrolysis reaction may be performed in either a batch type or a continuous type.

The reaction pressure may range from normal pressure to 100 kg / cm ² .

  Although reaction temperature is not specifically limited, Usually, 0-300 degreeC, Preferably it is 25-200 degreeC. For example, the reaction temperature when the reaction is carried out at normal pressure is preferably 60 ° C. to the reflux temperature of the reaction solvent.

  The reaction time is not limited as long as it is appropriately set according to the progress of the reaction. After the reaction, the obtained chain tetraphosphine tetraoxide (1) may be isolated and purified as necessary. As an isolation and purification method, a known method may be appropriately employed. For example, a method of extracting and separating the chain tetraphosphine tetraoxide (1) by adding an organic solvent to the mixed solution obtained after completion of the reaction, concentrating the mixed solution, and then adding an organic solvent to the resulting concentrated solution or concentrated residue. Examples include a method of extracting and separating the chain tetraphosphine tetraoxide (1) by adding a solvent. The obtained extract may be isolated by concentration and drying as it is, or may be purified by recrystallization, reprecipitation, column chromatography or the like, if necessary.

  <Reaction Formula 2>

First Step In the first step, bisphosphine (10) is obtained by dealkylation reaction of bisphosphine (9).

R ³ and R ⁴ in the general formulas (9) and (10) are the same as the above R ³ and R ⁴ . In particular, each of R ³ and R ⁴ is preferably an aryl group which may be the same or different, or an optionally substituted heteroaryl group, and an optionally substituted aryl group having 6 to 15 carbon atoms or An optionally substituted heteroaryl group having 5 to 15 carbon atoms is more preferable, and an optionally substituted aryl group having 6 to 15 carbon atoms is more preferable. R ³ and R ⁴ may be the same as or different from each other.

  M in the general formula (9) is preferably an integer of 3 to 12, and more preferably 3, 5, 7, 9 or 11.

The bisphosphine (10) can be synthesized from bisphosphine (9) by the method described in, for example, Dickson et al. (Ron. S. Dickson, et. Al. Organometallics 1999, 18, 2912-2914.). That is, the bisphosphine (10) in which R ³ and R ⁴ may be the same or different can be produced by allowing 10 mol of lithium wire to act on 1 mol of bisphosphine (9) in THF.

  The said bisphosphine (9) is obtained by manufacturing according to a commercial item or a well-known method.

Second Step In the second step, phosphine oxide (13) is obtained by reacting phosphinic acid chloride (11) with vinylmagnesium chloride (12).

R ¹ , R ² , R ⁵ and R ⁶ in the general formula (11) are the same as the above R ¹ , R ² , R ⁵ and R ⁶ . In particular, each of R ¹ , R ² , R ⁵ and R ⁶ is the same or different and may be substituted with a saturated hydrocarbon group having 3 to 20 carbon atoms, an optionally substituted aryl group, or a substituted group. A heteroaryl group which may be substituted or an aralkyl group which may be substituted is preferable, and an aryl group having 6 to 15 carbon atoms which may be substituted or a heteroaryl group having 5 to 15 carbon atoms which may be substituted is more preferred. Preferably, an optionally substituted aryl group having 6 to 15 carbon atoms is more preferable.

  The phosphinic acid chloride (11) and the vinylmagnesium chloride (12) can be easily obtained by manufacturing them according to commercially available products or known methods.

  When the phosphinic acid chloride (11) and the vinylmagnesium chloride (12) are reacted, it is preferable that the phosphinic acid chloride (11) and the vinylmagnesium chloride (12) are dissolved in a solvent. The concentration of the phosphinic acid chloride (11) and the vinylmagnesium chloride (12) in the solution is not particularly limited as long as it is within the range in which the reaction proceeds suitably.

  The solvent is not particularly limited as long as the reaction between the phosphinic acid chloride (11) and the vinylmagnesium chloride (12) is not hindered. For example, an aromatic hydrocarbon solvent such as benzene, toluene, xylene, etc .; n-hexane Aliphatic hydrocarbon solvents such as cyclohexane, n-heptane and n-octane; diisopropyl ether, dibutyl ether, THF, DME, cyclopentyl methyl ether, dihydropyran, 1,4-dioxane, t-butyl methyl ether, diethylene glycol And ether solvents such as dimethyl ether, diethylene glycol dibutyl ether, and anisole. These solvents can be used alone or as a mixed solvent of two or more. Of these, THF is particularly preferable.

  In particular, in the reaction, it is preferable to add dropwise a solution of vinylmagnesium chloride (12) to the phosphinic acid chloride (11).

  The dropwise addition is desirably performed under conditions where the temperature of the reaction solution to be obtained is usually about -20 to 60 ° C, preferably about -10 to 40 ° C, more preferably 0 to 20 ° C.

  The dropping speed is not particularly limited as long as it is within the above dropping temperature range, but the solution of the vinylmagnesium chloride (12) is usually dropped over about 15 minutes to 12 hours, preferably over about 30 minutes to 6 hours. It is desirable to set to.

  After completion of dropping, it may be further reacted at a temperature of usually about 0 to 30 ° C, preferably about 5 to 25 ° C, if necessary.

  After the reaction, the obtained phosphine oxide (13) may be isolated and purified as necessary. The isolation and purification method is not limited as long as a known method is appropriately employed. For example, after completion of the reaction, a small amount of phosphinic acid chloride (11 ) And vinylmagnesium chloride (12) are deactivated, and then an organic solvent is added to the resulting mixed solution to extract and separate phosphine oxide (13), and the mixed solution is concentrated and obtained. Examples thereof include a method of extracting and separating phosphine oxide (13) by adding an organic solvent to the concentrated liquid or the concentrated residue.

  The obtained extract may be isolated by concentration and drying as it is, or may be purified by recrystallization, reprecipitation, column chromatography or the like, if necessary.

Third Step In the third step, phosphine oxide (14) is obtained by reacting bisphosphine (10) with phosphine oxide (13) in the presence of a catalyst.

  As the catalyst, for example, the radical initiator catalyst, the transition metal complex catalyst, the basic catalyst, or the like can be used. These can be used alone or in combination of two or more. Among these, a radical initiator type catalyst is preferable, and an azo compound, an organic peroxide, and a trialkylborane are more preferable in that the target phosphine oxide (14) can be produced in a better yield.

  The amount of the catalyst used is not limited, but is usually about 0.01 to 5 mol, preferably about 0.02 to 3 mol, more preferably about 0.05 to 1 mol, with respect to 1 mol of the bissulfine (10). .

  Although the usage-amount of the phosphine oxide (13) in a 2nd process is not specifically limited, About 2-6 mol is preferable with respect to 1 mol of bisphosphine (10), and about 2-3 mol is more preferable.

  The reaction of bisphosphine (10) and phosphine oxide (13) is preferably carried out in a solvent in the presence of the catalyst.

  The solvent is not particularly limited as long as it effectively exhibits a catalytic function. For example, the aromatic hydrocarbon solvent, the aliphatic hydrocarbon solvent, the ether solvent, the ester solvent, the alcohol solvent, the amide solvent, the sulfoxide solvent, and the like can be used. These solvents can be used alone or as a mixed solvent of two or more. Of these, alcohol solvents such as methanol, ethanol and isopropanol, and aromatic hydrocarbon solvents such as benzene, toluene, xylene and mesitylene are particularly preferable.

  It is preferable that bisphosphine (10), phosphine oxide (13) and the catalyst are completely dissolved in a solvent from the viewpoint of reaction efficiency. Bisphosphine (10) and phosphine oxide (13) may be dissolved while reacting.

  The reaction may be performed in either a batch type or a continuous type.

The reaction pressure is not particularly limited, and may usually be about normal pressure to about 100 kg / cm ² .

  The reaction temperature may be appropriately set according to the progress of the reaction and the like, but is usually about -20 to 200 ° C, preferably about 0 to 150 ° C. For example, when reacting at normal pressure, the range of 0 ° C. to the reflux temperature of the solvent is preferred.

  The reaction time is not particularly limited and may be appropriately set according to the reaction temperature and the progress of the reaction, but is usually about 15 minutes to 72 hours, preferably about 1 to 36 hours.

  After the reaction, the obtained phosphine oxide (14) may be isolated and purified as necessary. As an isolation method, a known method may be adopted as appropriate, and the mixture obtained after completion of the reaction may be isolated by drying. As a method for purifying the obtained phosphine oxide (14), a known method may be appropriately employed. Examples of known methods include recrystallization, reprecipitation, column chromatography and the like.

Fourth Step In the fourth step, the chain phosphine tetraoxide (1) is obtained by oxidizing the phosphine moiety of the phosphine oxide (14) obtained in the third step. For example, according to the method described in Patent Document 2, after dissolving the phosphine oxide (14) in a solvent, a linear tetraphosphine tetraoxide (1) is obtained by allowing a commercially available 35% hydrogen peroxide solution to act. Can do.

  The solvent used for the reaction is not particularly limited. For example, the aromatic hydrocarbon solvent, the aliphatic hydrocarbon solvent, the ether solvent, the ester solvent, the alcohol solvent, the amide solvent, the sulfoxide solvent, and the like can be used. These solvents can be used alone or as a mixed solvent of two or more. Among these, ether solvents such as THF, 1,4-dioxane, diisopropyl ether, dibutyl ether, t-butyl methyl ether, 1,2-dimethoxyethane, methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, diethylene glycol Alcohol solvents such as are preferred.

  The phosphine oxide (14) is preferably completely dissolved in the solvent from the viewpoint of reaction efficiency. The phosphine oxide (14) may be dissolved while reacting.

  The reaction temperature may be appropriately set, but is usually about -20 ° C to 100 ° C, preferably about -10 ° C to 30 ° C.

  The reaction time is not particularly limited and may be appropriately set depending on the reaction temperature and the progress of the reaction, but is usually about 1 to 50 hours, preferably about 1 to 4 hours.

  After the reaction, after removing the remaining peroxide completely with an aqueous sodium thiosulfate solution or the like, the obtained crude chain tetraphosphine tetraoxide (1) may be isolated and purified. As an isolation and purification method, a known method may be appropriately employed. For example, a method of extracting and separating the chain tetraphosphine tetraoxide (1) by adding an organic solvent and water to the mixed solution obtained after completion of the reaction can be mentioned. The obtained extract may be isolated by concentration and drying as it is, or may be purified by recrystallization, reprecipitation, column chromatography or the like, if necessary.

Rare earth metal complex The rare earth metal complex of the present invention is a complex containing the chain tetraphosphine tetraoxide (1). Specifically, in the rare earth metal complex of the present invention, the oxygen atom of the chain tetraphosphine tetraoxide (1) is coordinated to a rare earth metal ion (central metal ion). That is, the chain tetraphosphine tetraoxide (1) of the present invention can be used as a ligand for a rare earth metal complex.

  The rare earth metal complex having the chain tetraphosphine tetraoxide (1) as a ligand 1) has higher emission intensity than conventional luminescent materials, 2) has high solubility in organic media, and 3) in organic media. The chain tetraphosphine tetraoxide (1) has the property of not easily dissociating from rare earth metal ions.

  Therefore, the phosphor containing the complex can stably exhibit high emission intensity. Further, since the complex is easily dissolved in an organic medium (particularly, a liquid polymer), a highly light-emitting material with high transparency can be provided.

  Further, the rare earth metal complex of the present invention is excellent in durability against heat and the like.

In particular, as the chain tetraphosphine tetraoxide (1) coordinated to the rare earth metal complex of the present invention, in the general formula (1), R ¹ , R ² , R ⁵ and R ⁶ are the same or different, R ³ represents a saturated hydrocarbon group having 3 to 20 carbon atoms that may be substituted, an aryl group that may be substituted, a heteroaryl group that may be substituted, or an aralkyl group that may be substituted; And R ⁴ are the same or different and each represents an optionally substituted aryl group or an optionally substituted heteroaryl group, and l, m and n are the same or different and each represents an integer of 3 to 12 chain tetra phosphine tetraoxide is preferably, in the general formula ^{(1), R 1, R} 2, R 3, R 4, R 5 and ^{R 6} are the same or different, may charcoal substituted A linear tetraphosphine tetraoxide which represents an aryl group of 6 to 15 or an optionally substituted heteroaryl group of 5 to 15 carbon atoms, wherein l, m and n are the same or different and each represents an integer of 3 to 12 In general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each may be substituted and an aryl group having 6 to 15 carbon atoms. In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , and more preferably a linear tetraphosphine tetraoxide in which l, m and n are the same or different and each represents an integer of 3 to 12. R ⁵ and R ⁶ are the same or different and each represents an optionally substituted aryl group having 6 to 15 carbon atoms, and l, m and n are the same or different and are 3, 5, 7, 9 or 11; Showing chain Tetraphosphine tetraoxide is most preferred.

  The rare earth metal complex is not particularly limited as long as it has the rare earth metal ion as a central metal ion and the chain tetraphosphine tetraoxide (1) as a ligand.

  Of the four oxygen atoms of the chain tetraphosphine tetraoxide (1), at least one oxygen atom may be coordinated to the rare earth metal ion. For example, when one oxygen atom of a chain tetraphosphine tetraoxide (1) is coordinated as a coordination atom to one rare earth metal ion, and the rare earth metal complex has two rare earth metal ions, Two oxygen atoms of the chain tetraphosphine tetraoxide (1) are coordinated with the rare earth metal ion, and the remaining oxygen atoms of the chain tetraphosphine tetraoxide (1) are two with respect to the other rare earth metal ion. The form which one coordinates is mentioned.

Examples of the rare earth metal ions include Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Tb, Dy, Ho, Er, Tm, Yb, and Lu + 2. And cations such as +3 valence. In particular, as Ln, Eu ³⁺ , Tb ³⁺ , Gd ³⁺ , Tm ³⁺ or Er ³⁺ is preferable, Eu ³⁺ is more preferable in that the rare earth metal complex exhibits high red emission intensity, and the rare earth metal complex has high green emission. Tb ³⁺ is more preferable in view of strength. When the rare earth metal complex contains a plurality of rare earth metal ions, the rare earth metal ions are preferably the same as each other.

  A ligand other than the chain tetraphosphine tetraoxide (1) may be coordinated with the rare earth metal complex. The ligand other than the chain tetraphosphine tetraoxide (1) is not particularly limited. For example, β-diketonato ligand, sulfonylimide ligand, carboxylate ligand, alkoxy ligand, aryl Examples thereof include an oxy ligand, an ether ligand, an amine ligand, a crown ether ligand, and an azacrown ether ligand. These ligands may be coordinated to the rare earth metal ion alone or in combination of two or more. Among these, a β-diketonato ligand is particularly preferable.

  As the β-diketonato ligand, the general formula (2)

(In the formula, R ⁸ represents a hydrogen atom, a deuterium atom, a halogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aryl group, or an optionally substituted hetero group. An aryl group or an aralkyl group which may be substituted; R ⁷ and R ⁹ are the same or different and each may be substituted a saturated hydrocarbon group having 1 to 20 carbon atoms or a perfluoro having 1 to 20 carbon atoms; An alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or an optionally substituted aralkyl group is shown.)
The β-diketonato ligand represented by

Regarding R ⁸ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

With respect to R ⁷ , R ⁸ and R ⁹ , the saturated hydrocarbon group of a saturated hydrocarbon having 1 to 20 carbon atoms which may be substituted is not particularly limited, and for example, C _{1 to} C ₂₀ linear or branched Examples thereof include a chain alkyl group and a C _{3 to} C ₁₂ cycloalkyl group.

Examples of the C _{1 to} C ₂₀ linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, Examples include a hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, icosyl group and the like.

Examples of the C _{3 to} C ₁₂ cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclododecyl group.

  Although it does not specifically limit as a substituent of the saturated hydrocarbon group which may be substituted, For example, a fluoroalkyl group, an alkoxy group, an aryloxy group, a siloxy group, a dialkylamino group etc. are mentioned.

Examples of the fluoroalkyl group include a C _1-6 perfluoroalkyl group. Examples of the C _1-6 perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a tridecafluorohexyl group.

Examples of the alkoxy group include a C _1-6 alkoxy group. Examples of the C _1-6 alkoxy group include a methoxy group, an ethoxy group, and a hexyloxy group.

Examples of the aryloxy group include a C _6-12 aryloxy group. Examples of the C _6-12 aryloxy group include a phenoxy group and a naphthyloxy group.

  Examples of the siloxy group include trimethylsiloxy, triethylsiloxy, triisopropylsiloxy, tert-butyldimethylsiloxy and the like.

  Examples of the dialkylamino group include dimethylamino and diethylamino.

  The substitution position of the substituent of the saturated hydrocarbon group which may be substituted and the number of substituents are not particularly limited.

It relates R ^{7, R 8} and ^{R 9,} as the aryl group of the aryl group which may be substituted is not particularly _limited, and examples thereof include _{C 6-14} aryl groups. Examples of the C _6-14 aryl group include phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, anthryl and the like.

The substituent of the aryl group which may be substituted is not particularly limited, and for example, a C _1-6 alkyl group, a C _1-6 perfluoroalkyl group, a C _6-14 aryl group, a 5- to 10-membered aromatic group Heterocyclic group, alkoxy group, aryloxy group, siloxy group, dialkylamino group and the like can be mentioned.

Examples of the C _1-6 alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and the like.

As the C _1-6 perfluoroalkyl group, for example, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, tridecafluorohexyl and the like.

Examples of the C _6-14 aryl group include phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, 2-anthryl and the like.

  Examples of the 5- to 10-membered aromatic heterocyclic group include 2- or 3-thienyl, 2-, 3- or 4-pyridyl, 2-, 3-, 4-, 5- or 8-quinolyl, 1-, Examples include 3-, 4- or 5-isoquinolyl, 1-, 2- or 3-indolyl, 2-benzothiazolyl, 2-benzo [b] thienyl, benzo [b] furanyl and the like.

  The alkoxy group, aryloxy group, siloxy group and dialkylamino group are the same as the alkoxy group, aryloxy group, siloxy group and dialkylamino group described as the substituent of the saturated hydrocarbon group.

  The substitution position and the number of substituents of the substituent of the aryl group which may be substituted are not particularly limited.

With respect to R ⁷ , R ⁸ and R ⁹ , the heteroaryl group of the optionally substituted heteroaryl group is not particularly limited, and for example, 1 atom selected from the group consisting of a sulfur atom, an oxygen atom and a nitrogen atom 5 to 14-membered aromatic heterocyclic group which may contain -3 and may be condensed is mentioned.

  Examples of the aromatic heterocyclic group include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, isothiazolyl, thiazolyl, 1,2,3-oxadiazolyl, triazolyl, tetrazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolyl , Indazolyl, purinyl, quinolyl, isoquinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinolinyl, pteridinyl, carbazolyl, carbolinyl, phenanthridinyl, acridinyl and the like.

  The substituent of the heteroaryl group which may be substituted is the same as the substituent described for the aryl group which may be substituted.

Regarding R ⁷ , R ⁸ and R ⁹ , examples of the aralkyl group of the aralkyl group which may be substituted include a benzyl group, a phenethyl group, and a phenylpropyl group.

  The substituent of the aralkyl group which may be substituted is the same as the substituent described for the aryl group which may be substituted.

  The position of the substituent of the aralkyl group which may be substituted and the number of substituents are not particularly limited.

Regarding R ⁷ and R ⁹ , the perfluoroalkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic. For example, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, pentafluorocyclopropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, heptafluorocyclobutyl, undecafluoropentyl, undecafluoroisopentyl, nonafluorocyclopentyl , Tridecafluorohexyl, tridecafluoroisohexyl, undecafluorocyclohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, nonadecafluorononyl, henicosafluorodecyl, tricosafluoroundecyl, pentacosafluorododecyl, hepta Examples include a cosafluorotridecyl group.

In particular, as the β-diketonato ligand, R ⁷ and R ⁹ are the same or different from each other and may be substituted with a C 1-20 saturated hydrocarbon group, an optionally substituted aryl group, a substituted A β-diketonato ligand in which R ⁸ is a hydrogen atom, a deuterium atom or a halogen atom, preferably a heteroaryl group which may be substituted, a perfluoroalkyl group having 1 to 20 carbon atoms, and R ⁷ and R ⁹ is a saturated hydrocarbon group having 1 to 20 carbon atoms which may be the same or different from each other, an aryl group which may be substituted, a peroalkyl group having 1 to 20 carbon atoms, and R ⁸ is A β-diketonato ligand which is a hydrogen atom or a deuterium atom is more preferable.

  Examples of the method for producing the rare earth metal complex include a method of reacting at least one selected from rare earth metal ions and rare earth metal salts with the chain tetraphosphine tetraoxide (1) in a solvent.

  Examples of the rare earth metal ions include the rare earth metal ions described above.

  Examples of rare earth metal salts include rare earth metal halides, rare earth metal nitrates, rare earth metal carboxylates, rare earth metal alkoxides, rare earth metal aryloxides, β-diketonato rare earth metal complexes, sulfonylimide rare earth metal complexes, and the like.

  In particular, it is preferable to react a β-diketonato rare earth metal complex with the chain tetraphosphine tetraoxide (1).

  Examples of the solvent include halogen solvents such as chloroform and dichloromethane; ketone solvents such as acetone and methyl isobutyl ketone; aromatic solvents such as toluene, xylene and nitrobenzene; methanol, ethanol, propanol, isopropanol, octanol and the like. Alcohol solvent; water etc. are mentioned. These solvents can be used alone or as a mixed solvent of two or more. Of these solvents, halogen solvents and aromatic solvents are particularly preferable.

  The reaction format may be either batch type or continuous type.

The reaction pressure is not particularly limited, and may usually be about normal pressure to about 100 kg / cm ² .

  The reaction temperature may be appropriately set, but is usually about -20 to 200 ° C, preferably 20 to 150 ° C. For example, when reacting at normal pressure, the range of 20 ° C. to the reflux temperature of the solvent is preferred.

  The reaction time is not particularly limited and may be appropriately set according to the reaction temperature and the like, but is usually about 15 minutes to 24 hours, preferably about 30 minutes to 12 hours.

  You may refine | purify by a well-known purification method as needed after reaction. Examples of known purification methods include recrystallization and column chromatography.

  Whether or not the chain tetraphosphine tetraoxide (1) is coordinated to the rare earth metal ion can be confirmed by a fluorescence intensity measurement test or the like described later.

In particular, the rare earth metal complex of the present invention includes the chain tetraphosphine tetraoxide (1) and the general formula (3).
LnLp (3)
(In the formula, Ln represents a rare earth metal ion, p represents an integer of 1 to 5, L represents the β-diketonato ligand, and when p is an integer of 2 or more, the β-diketonato coordination The ligands may be the same or different from each other.)
What is obtained by making the (beta) -diketonato rare earth metal complex (3) represented by these react with the said solvent is preferable. The reaction is performed, for example, by mixing the chain tetraphosphine tetraoxide (1) and the β-diketonato rare earth metal complex (3) in the solvent. The charge molar ratio of the chain tetraphosphine tetraoxide (1) and the β-diketonato rare earth metal complex (3) is not particularly limited, and may be appropriately set, for example, to be a reaction ratio described later.

  The chain tetraphosphine tetraoxide (1) is reacted alone or in combination of two or more.

  The β-diketonato rare earth metal complex (3) is reacted alone or in combination of two or more.

  The reaction ratio ((1) / (3)) of the chain tetraphosphine tetraoxide (1) and the β-diketonato rare earth metal complex (3) in the reaction is 0.3 to 0.7 in molar ratio. Preferably, there is 0.5, and more preferably 0.5. When the reaction ratio ((1) / (3)) is 0.3 to 0.7 in terms of molar ratio, the obtained rare earth metal complex suitably acts as a light emitting source such as a light emitting medium described later. In particular, when the reaction ratio ((1) / (3)) is 0.5 in terms of molar ratio, a rare earth metal complex that can stably exhibit high emission intensity can be obtained more reliably.

  When the reaction ratio ((1) / (3)) of the chain tetraphosphine tetraoxide and the β-diketonato rare earth metal complex is 0.5 in molar ratio, for example, the following rare earth metal complex is used alone: Or as a mixture of two or more.

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , l, m, n, p, Ln and L are the same as described above, and q, r, s, t, u, v and w each represent an integer of 1 or more, and * means that the structural formula in [] is repeated via Ln.)
Use of Rare Earth Metal Complex The rare earth metal complex of the present invention (rare earth metal complex coordinated with the chain tetraphosphine tetraoxide (1) of the present invention) is disclosed in Patent Documents 2 to 6, as shown in Examples described later. Compared with a rare earth metal complex having a phosphine oxide ligand as shown in FIG. 1, it exhibits high solubility unprecedented in organic media and can stably exhibit high emission intensity. It can be used for a light emitting layer (light emitting medium) of an LED element, a fluorescent ink composition, and a light emitting layer of an organic electroluminescent element.

  When the rare earth metal complex is used in these applications, the rare earth metal complex can be used alone or in combination of two or more.

  Moreover, it can also be used as a mixture containing the rare earth metal complex as an essential component and further containing ions, compounds and the like other than the complex. The mixture only needs to contain the rare earth metal complex, and the rare earth metal ion, the rare earth metal complex in which the chain tetraphosphine tetraoxide is not coordinated, and the like within a range not impairing the effects of the present invention. Further, it may be included.

(1) White LED element The white LED element of this invention can employ | adopt the structure similar to a well-known LED element except making the said rare earth metal complex contain in the light emitting medium (phosphor) which comprises a light emitting layer.

  For example, the LED element which has the light emitting layer 1 which consists of LED chip 2 and the light emission medium 3 as shown in FIG. 1 is mentioned.

  The LED chip 2 receives electric energy from an electrode (not shown), emits light, and emits light. The light emitting medium (phosphor) 3 that has absorbed the light emitted from the LED chip 2 emits light having a wavelength different from that of the absorbed light. At this time, a new color of light is formed by combining the light emitted from the LED chip 2 and the light emitted from the phosphor. In the present invention, white light can be emitted by including the rare earth metal complex in the phosphor. Moreover, since the rare earth metal complex is suitably dissolved in an organic medium and basically does not precipitate in the organic medium, it can emit white light efficiently (with high light extraction efficiency).

  The LED chip 2 is not particularly limited as long as it is an element that emits light in the ultraviolet, near ultraviolet, visible, and near infrared regions. For example, blue LED, near ultraviolet LED, etc. are mentioned.

The luminescent medium 3 is obtained by dissolving the rare earth metal complex in an organic medium. In the present invention, the color of light emitted from the light emitting medium 3 can be controlled by appropriately selecting a rare earth metal ion (central metal ion) in the rare earth metal complex. For example, a light-emitting medium including a rare earth metal complex whose central metal ions are all Eu ³⁺ can emit red light. In addition, a light-emitting medium including a rare earth metal complex whose central metal ions are all Tb ³⁺ can emit green light. Furthermore, a light emitting medium including a rare earth complex whose rare earth metal ions are other than Eu ³⁺ and Tb ³⁺ (for example, all of the central metal ions are Tm ³⁺ ) can emit blue light.

  The light emitting medium 3 may contain two or more kinds of the rare earth metal complexes. From the viewpoint of reducing light extraction efficiency, the luminescent medium 3 should not contain known fluorescent inorganic compound particles. However, the particles may be added as necessary as long as the effects of the present invention are not hindered. You may make it contain.

Examples of the particles include inorganic compound particles that emit yellow light, such as particles obtained by activating Ce to Y ₃ Al ₅ O ₁₂ (YAG); Eu to Sr ₁₀ (PO ₄ ) ₆ Cl ₂ Particles, particles formed by activating Eu to Ca ₁₀ (PO ₄ ) ₆ Cl ₂ , particles formed by activating Eu to Ba ₁₀ (PO ₄ ) ₆ Cl ₂ , and particles activating Eu to BaMgAl ₁₀ O ₁₇ Inorganic compound particles that emit blue light, such as particles formed by activating Eu to Ba ₃ MgSi ₂ O ₈ ; particles formed by activating Eu to SrGa ₂ S ₄ , CaAl ₂ O ₄ Inorganic compound particles that emit green light, such as particles activated by Eu, particles activated by Eu in BaAl ₂ O ₄ , particles activated by Eu in SrAl ₂ O ₄ ; Eu in SrS Activating Eu into particles, CaS Comprising particles, the particles comprising activated by Eu in CaAlSiN _3, the Ba 3 MgSi ₂ O ₈ Eu, inorganic compound particles or the like that emits red light such as particles comprising activated with Mn and the like. These particles can be used singly or in combination of two or more.

For example, in the case of the combination of the following LED chip 2 and the light emitting medium 3, white light can be suitably obtained.
(1) LED chip 2: blue LED (for example, InGaN), luminescent medium 3: rare earth metal complex that emits red light + inorganic compound particles that emit yellow light (for example, Y ₃ Al ₅ O ₁₂ (YAG) crystal with Ce) Activated particles)
(2) LED chip 2: blue LED (for example, InGaN), luminescent medium 3: rare earth metal complex that emits red light + rare earth metal complex that emits green light (3) LED chip 2: near-ultraviolet LED (for example, InGaN), Luminescent medium 3: Inorganic compound particles emitting blue light (for example, particles obtained by activating Eu to Sr ₁₀ (PO ₄ ) ₆ Cl ₂ , Eu being activated to Ca ₁₀ (PO ₄ ) ₆ Cl ₂ Particles, particles formed by activating Eu to Ba ₁₀ (PO ₄ ) ₆ Cl ₂ ) + rare earth metal complex emitting red light + rare earth metal complex emitting green light (4) LED chip 2: near ultraviolet LED (for example, InGaN), luminescent medium 3: rare earth metal complex that emits red light + rare earth metal complex that emits green light + rare earth metal complex that emits blue light Examples of the organic medium include: Examples include organic solvents and liquid polymers.

  Examples of the organic solvent include a fluorine-based solvent. These organic solvents can be used alone or as a mixed solvent composed of two or more.

  Examples of the liquid polymer include fluorine resins and silicone resins. Commercially available products can be suitably used as the fluororesin and the silicone resin. Examples of commercially available fluororesins include Teflon (registered trademark) AF (manufactured by DuPont) and Cytop (manufactured by Asahi Glass). Examples of commercially available silicone resins include polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane.

  In particular, the organic medium is preferably a liquid polymer, and more preferably a fluororesin. Since the fluororesin has characteristics such as a high glass transition point, high moisture resistance, and low gas permeability, the use of the fluororesin as the organic medium allows the light emission characteristics, light emission lifetime, durability, and the like of the light emitting medium 3. Can be improved.

  The content of the rare earth metal complex in the luminescent medium 3 is not particularly limited, but is preferably about 5 to 90% by weight.

  The content of the fluorescent inorganic compound particles in the luminescent medium 3 is not particularly limited as long as it does not interfere with the present invention.

  The white LED element of the present invention can be used for various LEDs such as a bullet-type LED and a surface-mounted LED. The specific configuration of the LED may be the same as that of a known LED except that the white LED element is arranged.

(2) Luminescent ink composition The fluorescent ink composition of the present invention contains the rare earth metal complex.

  The rare earth metal complex emits substantially no color under natural light.

  On the other hand, when the rare earth metal complex is irradiated with ultraviolet light, since the complex emits colored light, the emitted light can be observed. Therefore, by printing the ink composition in which the rare earth metal complex is dissolved on various substrates, the printed contents can be visually recognized only under ultraviolet irradiation using black light or the like. For example, by printing the ink composition on a base material such as banknotes, documents, documents, cards, etc., it is possible to have a security function that can prevent forgery, unauthorized copying, and the like.

The color of the emitted light varies depending on the type of central metal ion of the rare earth metal complex. For example, when the central metal ion is Eu ³⁺ , the complex emits strong red light, and when the central metal ion is Tb ³⁺ , the complex emits strong green light. When the rare earth metal complex has a plurality of central metal ions, it is preferable that the plurality of rare earth metal ions are all the same.

  Two or more kinds of the rare earth metal complex compositions may be contained in the ink composition.

For example, the rare earth metal complex composition of the present invention in which the central metal ion that exhibits strong green light emission when irradiated with a black light lamp that emits ultraviolet rays having wavelengths of 365 nm and 254 nm is Tb ³⁺ is applied to the first phosphor. A rare earth element according to the present invention, in which a central metal ion is composed of Eu ³⁺ that emits strong red light by irradiation with a black light lamp that emits ultraviolet light having a wavelength of 365 nm, and hardly emits red light by irradiation with black light lamp that emits ultraviolet light having a wavelength of 254 nm. A two-color mixed ink in which a metal complex is mixed can be prepared.

  When the ink composition is irradiated with a black light lamp that emits ultraviolet light having a wavelength of 365 nm, the first phosphor and the second phosphor emit light of a color close to yellow, which is a mixed color of green and red, respectively.

  On the other hand, when a black light lamp that emits ultraviolet light having a wavelength of 254 nm is irradiated, the second phosphor hardly emits light and only the first phosphor green emits light.

  In this way, since different hues are discriminated using the two wavelength regions, authenticity discrimination can be further improved.

  The content of the rare earth metal complex in the fluorescent ink composition of the present invention may be appropriately set according to the type of the base material, but is preferably about 0.001 to 30% by weight, About 3% by weight is more preferable.

  You may make the fluorescent ink composition of this invention contain additives, such as a solvent, resin (binder), a penetrating agent, an antifoamer, a dispersing agent, and a coloring agent, as needed.

  In particular, the ink composition of the present invention is preferably one in which the rare earth metal complex is dissolved in a solvent.

  The solvent is not particularly limited as long as it can dissolve the rare earth metal complex. Examples thereof include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; fats such as n-hexane, cyclohexane, n-pentane, and n-heptane. Aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether; methanol, Alcohol solvents such as ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, propylene glycol, glycerin; ester solvents such as ethyl acetate and butyl acetate, 2-pyro Don, N- methyl-2-pyrrolidone. These solvents may be appropriately selected according to the use of the fluorescent ink composition, and can be used alone or as a mixed solvent of two or more.

  The resin (binder) is preferably one that can satisfactorily fix the rare earth metal complex on the substrate and that dissolves well in the solvent. The resin may be optically transparent or opaque. Examples thereof include polyvinyl resins, phenol resins, amino resins, polyamide resins, nylon resins, polyolefin resins, acrylic resins, epoxy resins, urethane resins, cellulose resins, polyester resins, silicone resins, and fluorine resins. These resins may be appropriately selected according to the use of the fluorescent ink composition, and may be used alone or in combination of two or more.

  The penetrating agent is added for the purpose of accelerating the penetration of the ink composition into paper or the like and increasing the apparent drying property. Examples of the penetrant include glycol ether, alkylene glycol, sodium lauryl sulfate, sodium oleate, sodium dodecylbenzenesulfonate, sodium dioctylsulfosuccinate and the like. These penetrants can be used singly or in combination of two or more.

  The antifoaming agent is added for the purpose of preventing the movement of the ink composition and the generation of bubbles during the production of the ink composition. As the antifoaming agent, anionic, nonionic, cationic and amphoteric surfactants can be used. Examples of the anionic surfactant include fatty acid salt, alkyl sulfate ester salt, alkyl phosphate salt, alkyl ether phosphate ester salt and the like. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkyl. Examples include amines, fluorine-based materials, and silicon-based materials. Examples of the cationic surfactant include quaternary ammonium salts and alkylpyridinium salts. Examples of amphoteric surfactants include alkylbetaines, alkylamine oxides, phosphatidylcholines, and the like. These surfactants can be used singly or in combination of two or more.

  Examples of the dispersant include stearic acid soap, oleic acid soap, rosin acid soap, Na-di-β-naphthylmethane disulfate, Na-lauryl sulfate, Na-diethylhexyl sulfosuccinate, Na-dioctyl sulfosuccinate And the like. These surfactants can be used singly or in combination of two or more.

  As the colorant, known pigments and dyes can be used. For example, organic dyes such as azo, azomethine, quinacdrine, anthraquinone, dioxazine, quinoline, perylene, isoindolinone, and quinophthalone can be used. These colorants can be used singly or in combination of two or more.

  The content of the various additives in the fluorescent ink composition of the present invention is not particularly limited, and may be set as appropriate according to the type and use of the substrate, but in the fluorescent ink composition of the present invention. The content of the resin (binder) in is preferably about 0.5 to 30% by weight, more preferably about 1 to 10% by weight. When the content of the resin is less than 0.5% by weight, the rare earth metal complex cannot be sufficiently fixed to the non-permeable base material. Further, when the content of the resin exceeds 30% by weight, the resin (binder) is thickly covered around the rare earth metal complex in the fluorescent ink composition, so that the emission of the rare earth metal complex is reduced. There is a fear.

(3) Organic electroluminescence (EL) element The organic EL element of this invention has a light emitting layer containing the said rare earth metal complex.

  The organic electroluminescence device usually has a structure in which a substrate, an anode, a charge (hole) transport layer, the light emitting layer, a charge (electron) transport layer, and a cathode are sequentially stacked.

  The content of the rare earth metal complex in the light emitting layer is preferably about 5 to 100% by weight.

  The light emitting layer may be formed of the rare earth metal complex of the present invention alone or may further contain a compound other than the rare earth complex of the present invention. For example, the following charge (hole) transport layer material or charge (electron) transport layer material may be contained as a host compound.

  The thickness of the light emitting layer needs to be at least such that no pinholes are generated. However, if the thickness is too large, the resistance of the element increases and a high driving voltage is required, which is not preferable. Therefore, the thickness of the light emitting layer is about 0.0005 to 10 μm, preferably about 0.001 to 1 μm, and more preferably about 0.005 to 0.2 μm.

  The method for forming the light emitting layer is not particularly limited. For example, the rare earth metal complex is deposited on the hole transport layer, or the light emitting ink composition is printed by a printing method such as a spin coating method or an ink jet method. The method of apply | coating is mentioned.

  The substrate may be transparent, for example, glass, quartz, light transmissive plastic film (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polycarbonate ( PC) etc.). The thickness of the substrate is not particularly limited as long as it does not interfere with the effects of the present invention.

  As the material of the anode, for example, ITO (indium tin oxide) which is a conductive material having a large work function can be used. The thickness of the anode is preferably about 0.1 to 0.3 μm.

  As the material for the charge (hole) transport layer, for example, arylamine compounds such as triarylamine are used. The said material can be used individually by 1 type or in combination of 2 or more types.

  Examples of the material for the charge (electron) transporting layer include tris (8-hydroxyquinolinol) aluminum, triazoles, phenanthrolines, oxadiazoles, and the like. The said material can be used individually by 1 type or in combination of 2 or more types.

  The thickness of these charge transport layers is usually about 0.0005 μm to 10 μm, preferably about 0.001 to 1 μm.

  As the material of the cathode, aluminum, magnesium, indium, aluminum-lithium alloy, magnesium-silver alloy, or the like, which is a metal having a small work function, is used. The thickness of the cathode is preferably about 0.01 to 0.5 μm.

  The anode, the hole transport layer, the electron transport layer, and the cathode can be formed using the various materials according to a known method such as resistance heating deposition, vacuum deposition, or sputtering.

  The organic EL element of the present invention can be used for an illuminator such as a backlight of a color liquid crystal display, a display, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to the following Example.

Synthesis of chain tetraphosphine tetraoxide (1) Chain tetraphosphine tetraoxide (1) in which l, m and n are integers of 3 or more was produced according to the following reaction formula 1 (Examples A-1 to A- 14).

  <Reaction Formula 1>

Example A-1
(I) First step Under a nitrogen atmosphere, 4.0 g (9.7 mmol) of 1,3-bisdiphenylphosphinopropane (4), N, N was added to a 200 ml four-necked flask equipped with a stirrer, a thermometer, and a condenser. -10 ml of dimethylformamide (DMF) was charged, and 2.0 ml (23.2 mmol) of allyl bromide (5) was added with stirring. Then, it heated for 2.5 hours, maintaining internal temperature at 45-50 degreeC. The obtained reaction solution was cooled, 100 ml of toluene was added, and the mixture was stirred for 30 minutes to obtain a white precipitate. The resulting white precipitate was collected by suction filtration. The white solid (residue) obtained by filtration was dried at 45 ° C. under reduced pressure for about 3 hours. As a result, 5.4 g (yield 85%) of phosphonium salt (6) was obtained.

(Ii) Second step Under a nitrogen atmosphere, in a 100 ml four-necked flask equipped with a stirrer, a thermometer and a condenser, 5.4 g (8.3 mmol) of the phosphonium salt (6) obtained above, diphenylphosphine oxide (7) 3.7 g (18.3 mmol) and 20 ml of methanol were added. Then, after cooling to 0 ° C. in an ice bath, 1.1 ml of 1M hexane solution of triethylborane was added, and further 6 ml of air was blown. The mixture was gradually warmed to room temperature and stirred for about 12 hours. Next, the concentrate residue obtained by evaporating the solvent under reduced pressure was dissolved in chloroform, and the chloroform solution was transferred to a dropping funnel.

  Next, while adding 200 ml of toluene to a 500 ml eggplant type flask and stirring, the chloroform solution transferred to the dropping funnel was dropped over 15 minutes, and then stirred for 1 hour to obtain a white precipitate. The resulting white precipitate was collected by suction filtration. The white solid (residue) obtained by filtration was dried at 60 ° C. under reduced pressure for about 6 hours, whereby 4.37 g (yield 50%) of phosphonium salt (8) could be obtained.

(Iii) Third Step 3.88 g (3.66 mmol) of the phosphonium salt (8) obtained above was added to a 100 ml four-necked flask equipped with a stirrer, a thermometer and a condenser. Subsequently, 10 ml of ethanol and 3 ml of water were added, and then 9.2 ml of 4M aqueous sodium hydroxide solution was added and heated to reflux for 6 hours. After heating under reflux (after reaction), extraction was performed 3 times using 30 ml of chloroform. The obtained organic layer was dehydrated and dried over magnesium sulfate, filtered with suction, and further concentrated under reduced pressure. Thereafter, the residue was purified by silica gel column chromatography (eluent: ethyl acetate, methanol) to obtain 2.5 g (yield 88%) of chain tetraphosphine tetraoxide (1). The results are shown in Table 1.

Examples A-2 to A-14
According to the method of Example A-1, chain tetraphosphine tetraoxide (1) was produced as shown in Tables 1 to 3.

  In Examples A-13 and A-14, ethanol was used instead of methanol in the second step, and AMVN was used instead of the 1M hexane solution of triethylborane. The results are shown in Tables 1, 2 and 3.

  Moreover, the chain | strand-shaped tetraphosphine tetraoxide (1) whose l and n are 2, and m is an integer greater than or equal to 2 was manufactured according to following Reaction formula 2 (Example A-15).

  <Reaction Formula 2>

Example A-15
(I) First Step 1,2-bis (phenylphosphino) ethane (10) is prepared as follows according to Dickson et al. (Ron. S. Dickson, et. Al. Organometallics 1999, 18, 2912-2914.). And synthesized.

  Under a nitrogen atmosphere, in a 500 ml SUS reaction vessel equipped with a stirrer, a thermometer and a condenser, 1,2-bisdiphenylphosphinoethane (9) 10 g (25.1 mmol), THF 250 ml, lithium wire 1.75 g (251 mmol) ). Next, an ultrasonic cleaner was prepared, and a reaction solution was obtained by irradiating ultrasonic waves while stirring for about 5 hours while maintaining the internal temperature at 10 ° C.

  Separately, 60 ml of degassed water was placed in a 1000 ml four-necked flask equipped with a stirrer, a thermometer and a cooler in a nitrogen atmosphere, and the internal temperature was brought to 0 ° C. in an ice bath (flask 1).

  Subsequently, using the cannula, the reaction solution was dropped into the flask 1 so that the internal temperature of the flask 1 was kept within the range of 0 ° C to 10 ° C while leaving an excessive amount of lithium.

  Further, 80 ml of diethyl ether that had been degassed and cooled in advance under a nitrogen atmosphere was added to the previous flask 1 in an ice bath using an addition funnel while maintaining the internal temperature at 0 ° C. After stirring for about 30 minutes under ice cooling, the reaction solution was allowed to stand to separate into two layers. The aqueous layer was extracted using a 10 ml pipette under a nitrogen atmosphere.

  Next, 30 ml of 2M hydrochloric acid that had been degassed and cooled in advance was added to the previous flask 1 in an ice bath using an addition funnel while maintaining the internal temperature at 0 ° C. After stirring for about 30 minutes under ice cooling, the reaction solution was allowed to stand to separate into two layers. The obtained aqueous layer portion was extracted using a 10 ml pipette under a nitrogen atmosphere.

  Next, 50 ml of water that had been degassed and cooled in advance was added to the flask 1 using an addition funnel while maintaining the internal temperature at 0 ° C. in an ice bath. After stirring for about 30 minutes under ice cooling, the reaction solution was allowed to stand to separate into two layers. The obtained aqueous layer portion was extracted using a 10 ml pipette under a nitrogen atmosphere. This operation was performed two more times. The obtained organic layer was dried over sodium carbonate under a nitrogen atmosphere, filtered, and the solvent was distilled off.

  The resulting crude 1,2-bis (phenylphosphino) ethane (10) is purified using a Kugelrohr distillation apparatus under a reduced pressure of 1 torr (boiling point 161 ° C.), and 1,2-bis (phenylphosphino) is obtained. ) 4.33 g (70% yield) of ethane (10) was obtained.

(Ii) Second step Under a nitrogen atmosphere, a 200 ml four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 10 ml of THF and 3.00 g (12.7 mmol) of diphenylphosphinic chloride (11) up to 0 ° C. Cooled down. Subsequently, 12.7 ml (12.7 mmol) of a 1.0 M THF solution of vinylmagnesium chloride (12) was dropped in a temperature range of 0 ° C. to 5 ° C. over 15 minutes with a dropping funnel. After stirring at 0 ° C. for 30 minutes, 20 ml of saturated aqueous ammonium chloride solution was added, followed by extraction three times using 20 ml of ethyl acetate. The obtained organic layer was dehydrated and dried over magnesium sulfate, filtered with suction, and further concentrated under reduced pressure. Thereafter, the residue was purified by silica gel column chromatography (eluent: ethyl acetate, methanol) to obtain 2.35 g (yield 81%) of diphenylvinylphosphine oxide (13).

(Iii) Third Step In a 100 ml four-necked flask equipped with a stirrer, a thermometer and a cooler under a nitrogen atmosphere, 1.21 g of 1,2-bis (phenylphosphino) ethane (10) obtained above (4.9 mmol), 2.30 g (10.2 mmol) of diphenylvinylphosphine oxide (13), 4 ml of toluene and 0.15 g (0.93 mmol) of AIBN were added and stirred at 80 ° C. for 12 hours. Then, after distilling off the solvent under reduced pressure, the obtained solid was purified by silica gel column chromatography (eluent: ethyl acetate, methanol) to obtain 2.41 g (yield 70%) of phosphine oxide (14). It was.

(Iv) Fourth Step 2.33 g (3.3 mmol) of the phosphine oxide (14) obtained above was placed in a 100 ml four-necked flask and dissolved in 10 ml of tetrahydrofuran (THF). Under ice cooling, 2.0 ml of 35% aqueous hydrogen peroxide was added dropwise little by little, and the mixture was stirred at room temperature for 4 hours. After stirring (after reaction), 5 ml of 30% aqueous thiosulfuric acid solution was added and stirred for 30 minutes. The resulting mixture was extracted 3 times using 30 ml of chloroform. The obtained organic layer was dehydrated and dried over magnesium sulfate, filtered with suction, and further concentrated under reduced pressure. Thereafter, the residue was purified by silica gel column chromatography (eluent: ethyl acetate, methanol) to obtain 1.58 g (yield 65%) of chain tetraphosphine tetraoxide (1). The results are shown in Table 4.

Synthesis of rare earth metal complex coordinated with linear tetraphosphine tetraoxide (1) ligand and emission intensity of the complex <Synthesis of complex>
Example B-1
As a β-diketonato rare earth metal complex, 1.17 g (1.5 mmol) of the chain tetraphosphine tetraoxide (1) synthesized in Example A-1 was added to a 100 ml flask equipped with a stirrer, a thermometer and a cooler in a nitrogen atmosphere. Europium (III) -tris (1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionate) (hereinafter abbreviated as “EuFOD”) 3.11 g (3 mmol) and 18 ml of chloroform were charged and reacted at room temperature for 4 hours with stirring. After the reaction, the reaction mixture was transferred to a 100 ml eggplant type flask, concentrated as it was under reduced pressure with an evaporator, and dried under reduced pressure with a vacuum pump.

  By the above method, 4.23 g (99% yield) of a rare earth metal complex in which chain tetraphosphine tetraoxide (1) and EuFOD were coordinated at a molar ratio of 1: 2.

The obtained rare earth metal complex has two Eu ³⁺ as central metal ions, each oxygen atom of phosphine oxide is coordinated to each Eu ^3+, and three β-diketonato ligands are coordinated. Is. The results of the infrared absorption spectrum are shown in Table 5.

<Confirmation of whether or not the oxygen atom of the chain tetraphosphine tetraoxide (1) is coordinated to Eu ³⁺ of EuFOD>
First, ESI ⁺ -MS of the complex synthesized in this example was measured using a mass spectrometer (manufactured by JEOL). As a result, a molecular ion peak of chain tetraphosphine tetraoxide synthesized in Example 1 and a molecular ion peak of EuFOD were confirmed. This means that a complex is formed by chain tetraphosphine tetraoxide and EuFOD even after the complex synthesis reaction.

Whether or not the oxygen atom of the chain tetraphosphine tetraoxide (1) was coordinated to Eu ³⁺ of EuFOD was confirmed by the following experiment.

  First, when the rare earth metal complex synthesized in Example B-1 was irradiated with a simple UV lamp (ultraviolet light having a wavelength of 365 nm), strong red light emission was observed. On the other hand, even when EuFOD was irradiated with the UV lamp, almost no light emission was observed.

Next, a fluorescence intensity measurement test was performed according to the following method. From Table 8, it can be seen that the rare earth metal complex synthesized in Example B-1 has a red emission intensity five times or more stronger than EuFOD alone (Reference Example 1). This result is due to the coordination of the oxygen atom of the phosphine oxide of the chain tetraphosphine tetraoxide to Eu ³⁺ of EuFOD.

From these measurement results, the substance (complex) obtained by reacting the chain tetraphosphine tetraoxide (1) synthesized in Example B-1 with EuFOD at a molar ratio of 1: 2 is the structure of EuFOD. It can be seen that the phosphine oxide part of the chain tetraphosphine tetraoxide (1) is coordinated to Eu ^{3+ of the} central metal ion.

Examples B-2 to B-8
<Synthesis of complex>
Rare earth metal complexes were synthesized using the chain tetraphosphine tetraoxide (1) listed in Tables 1 to 4 according to the method of Example B-1. Each of the obtained rare earth metal complexes has two Eu ³⁺ as central metal ions, and each Eu ³⁺ is coordinated with two oxygen atoms of phosphine oxide, and three β-diketonate ligands are coordinated. It is what was ranked. The results of the infrared absorption spectrum are shown in Table 5.

<Confirmation of whether or not the oxygen atom of the chain tetraphosphine tetraoxide (1) is coordinated to Eu ³⁺ of EuFOD>
ESI ⁺ -MS was measured by the same method as in Example B-1. As a result, a molecular ion peak of chain tetraphosphine tetraoxide and a molecular ion peak of EuFOD were confirmed. This means that a complex is formed by chain tetraphosphine tetraoxide and EuFOD even after the complex synthesis reaction.

  Next, when the rare earth metal complexes synthesized in Examples B-2 to B-8 were irradiated with a simple UV lamp (ultraviolet light having a wavelength of 365 nm), strong red light emission was observed. On the other hand, even when EuFOD was irradiated with the UV lamp, almost no light emission was observed.

Next, a fluorescence intensity measurement test was performed according to the following method. From Table 8, it can be seen that the rare earth metal complexes synthesized in Examples B-2 to B-8 have a red emission intensity five times or more stronger than EuFOD alone (Reference Example 1). This result is due to the coordination of the oxygen atom of the phosphine oxide of the chain tetraphosphine tetraoxide to Eu ³⁺ of EuFOD.

From these measurement results, a substance (complex) obtained by reacting the chain tetraphosphine tetraoxide (1) synthesized in Examples B-2 to B-8 with EuFOD at a molar ratio of 1: 2 was obtained. It can be seen that the structure of EuFOD is retained and the phosphine oxide portion of the chain tetraphosphine tetraoxide (1) is coordinated to Eu ³⁺ of the central metal.

Comparative Examples 1-3
Using the phosphine oxide and β-diketonato rare earth metal complex shown in Table 8 in the proportions shown in Table 8, a rare earth metal complex was synthesized according to the method of Example B-1. The rare earth metal complexes obtained in Comparative Examples 1 and 2 each have one Eu ³⁺ as a central metal ion, two oxygen atoms of phosphine oxide are coordinated to Eu ³⁺ , and a β-diketonato ligand Are coordinated three times. In addition, the rare earth complex obtained in Comparative Example 3 has two Eu ³⁺ as central metal ions, and each Eu ³⁺ is coordinated with two oxygen atoms of phosphine oxide, and further a β-diketonato ligand is present. Three-coordinated. The phosphine oxide used in Comparative Example 2 was obtained by the method described in Japanese Patent Application Laid-Open No. 2007-308411 and Japanese Patent Application Laid-Open No. 2007-308412, and the macrocyclic tetraphosphine tetramer used in Comparative Example 3 was used. The oxide is obtained by the method described in Non-Patent Document 2.

Examples B-9 to B-13
Using the linear tetraphosphine tetraoxide (1) described in Tables 1 to 4, instead of EuFOD, europium (III) -tris (1,1,1-trifluoro-5,5-dimethyl-2,4- A rare earth metal complex was synthesized in the same manner as in Example B-1, except that (hexane dionate) (hereinafter abbreviated as “Eu (tfdh)”) was used. The results of the infrared absorption spectrum are shown in Table 5.

<The oxygen atom of the chain tetraphosphine tetraoxide (1) is coordinated to Eu ³⁺ of europium (III) -tris (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate) Check whether or not>
ESI ⁺ -MS was measured by the same method as in Example B-1. As a result, a molecular ion peak of chain tetraphosphine tetraoxide and a molecular ion peak of Eu (tfdh) were confirmed. This means that a complex is formed by chain tetraphosphine tetraoxide and Eu (tfdh) even after the complex synthesis reaction.
Next, when the rare earth metal complexes synthesized in Examples B-9 to B-13 were irradiated with a simple UV lamp (ultraviolet light having a wavelength of 365 nm), strong red light emission was observed. On the other hand, even when Eu (tfdh) was irradiated with the UV lamp, almost no light emission was observed.
Next, a fluorescence intensity measurement test was performed according to the following method. From Table 9, it can be seen that the rare earth metal complexes synthesized in Examples B-9 to B-13 have a red emission intensity that is about 10 times or more stronger than Eu (tfdh) alone (Reference Example 2). This result is due to the coordination of the oxygen atom of the phosphine oxide of the chain tetraphosphine tetraoxide to Eu ³⁺ of Eu (tfdh).
From these measurement results, the substance (complex) obtained by reacting the chain tetraphosphine tetraoxide (1) synthesized in Tables 1 to 4 with Eu (tfdh) in a molar ratio of 1: 2 It can be seen that the structure of (tfdh) is maintained and the phosphine oxide part of the chain tetraphosphine tetraoxide (1) is coordinated to Eu ³⁺ of the central metal.

Comparative Example 4
Using the phosphine oxide and β-diketonato rare earth metal complex shown in Table 9 in the proportions shown in Table 9, a rare earth metal complex was synthesized according to the method of Example B-1.

Examples B-14 to B-17
The linear tetraphosphine tetraoxide (1) described in Tables 1 to 4 was used, and instead of EuFOD, europium (III) -tris (4, 4, 5, 5, 6, 6, 6-heptafluoro-1- A rare earth metal complex was synthesized by the same method as in Example B-1, except that (2-naphthyl) -1,3-hexanedionate (hereinafter abbreviated as “Eu (hnhd)”) was used. The results of the infrared absorption spectrum are shown in Table 6.

<The oxygen atom of the chain tetraphosphine tetraoxide (1) is europium (III) -tris (4,4,5,5,6,6,6-heptafluoro-1- (2-naphthyl) -1,3- Confirmation of Coordination to Eu ³⁺ of Hexanedionate)
ESI ⁺ -MS was measured by the same method as in Example B-1. As a result, a molecular ion peak of chain tetraphosphine tetraoxide and a molecular ion peak of Eu (hnhd) were confirmed. This means that a complex is formed by chain tetraphosphine tetraoxide and Eu (hnhd) even after the complex synthesis reaction.
Next, when the rare earth metal complex synthesized in Examples B-14 to B-17 was irradiated with a simple UV lamp (ultraviolet light having a wavelength of 365 nm), strong red light emission was observed. On the other hand, even when Eu (hnhd) was irradiated with the UV lamp, almost no light emission was observed.
Next, a fluorescence intensity measurement test was performed according to the following method. From Table 10, it can be seen that the rare earth metal complexes synthesized in Examples B-14 to B-17 have a red emission intensity about twice or more higher than Eu (hnhd) alone (Reference Example 3). This result is due to the coordination of the oxygen atom of the phosphine oxide of the chain tetraphosphine tetraoxide to Eu ³⁺ of Eu (hnhd).
From these measurement results, a substance (complex) obtained by reacting the chain tetraphosphine tetraoxide (1) synthesized in Tables 1 to 4 with Eu (hnhd) at a molar ratio of 1: 2 was obtained as Eu. It can be seen that the structure of (hnhd) is retained and the phosphine oxide part of the chain tetraphosphine tetraoxide (1) is coordinated to Eu ^{3+ of the} central metal ion.

Examples B-18 to B-20
Using the linear tetraphosphine tetraoxide (1) listed in Tables 1 to 4, instead of EuFOD, europium (III) -tris (1,1,1,5,5,5-hexafluoro-2,4- A rare earth metal complex was synthesized in the same manner as in Example B-1, except that pentanedionate (hereinafter abbreviated as “Eu (hfpd)”) was used. The results of the infrared absorption spectrum are shown in Table 6.

<Coordination of Eu atom of chain tetraphosphine tetraoxide (1) to Eu ³⁺ of europium (III) -tris (1,1,1,5,5,5-hexafluoro-2,4-pentanedionate) Check whether or not>
When the rare earth metal complexes synthesized in Examples B-18 to B-20 were irradiated with a simple UV lamp (ultraviolet light having a wavelength of 365 nm), strong red light emission was observed. On the other hand, even when Eu (hfpd) was irradiated with the UV lamp, almost no light emission was observed.

Next, a fluorescence intensity measurement test was performed according to the following method. From Table 11, it is found that the rare earth metal complexes synthesized in Examples B-18 to B-20 have a red emission intensity that is about 5 to 6 times higher than that of Eu (hfpd) alone (Reference Example 4). Recognize. This result is due to the coordination of the oxygen atom of the phosphine oxide of the chain tetraphosphine tetraoxide to Eu ³⁺ of Eu (hfpd).
From these measurement results, a substance (complex) obtained by reacting the chain tetraphosphine tetraoxide (1) synthesized in Tables 1 to 4 with Eu (hfpd) at a molar ratio of 1: 2 was obtained as Eu. It can be seen that the structure of (hfpd) is retained and the phosphine oxide moiety of the chain tetraphosphine tetraoxide (1) is coordinated to Eu ^{3+ of the} central metal ion.

Example B-21
<Synthesis of complex>
Instead of EuFOD, terbium (III) -tris (1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionate) (hereinafter referred to as “TbFOD”) A rare earth metal complex was synthesized by the same method as in Example B-1, except that (abbreviated) was used. The obtained rare earth metal complex has the same structure as the rare earth metal complex obtained in Example B-1, except that the central metal ion is Tb ³⁺ . The results of the infrared absorption spectrum are shown in Table 7.

<Confirmation of whether or not the oxygen atom of the chain tetraphosphine tetraoxide (1) is coordinated to Tb ³⁺ of TbFOD>
ESI ⁺ -MS was measured by the same method as in Example B-1. As a result, a molecular ion peak of chain tetraphosphine tetraoxide and a molecular ion peak of TbFOD were confirmed. This means that a complex is formed by chain tetraphosphine tetraoxide and TbFOD even after the complex synthesis reaction.

  Next, when the rare earth metal complex synthesized in Example B-21 was irradiated with a simple UV lamp (ultraviolet light having a wavelength of 365 nm), strong green light emission was observed. On the other hand, even when TbFOD was irradiated with the UV lamp, almost no light emission was observed.

Next, a fluorescence intensity measurement test was performed according to the following method. From Table 12, it can be seen that the rare earth metal complex synthesized in Example B-21 has a green emission intensity that is 18 times higher than that of TbFOD alone (Reference Example 5).
This result is due to the coordination of the oxygen atom of the phosphine oxide of the chain tetraphosphine tetraoxide to Tb ³⁺ of TbFOD.

From these measurement results, the substance (complex) obtained by reacting the chain tetraphosphine tetraoxide (1) synthesized in Example B-21 with TbFOD at a molar ratio of 1: 2 is the structure of TbFOD. It can be seen that the phosphine oxide site of the chain tetraphosphine tetraoxide (1) is coordinated to the central metal ion Tb ³⁺ .

Comparative Example 5
Using the phosphine oxide and β-diketonato rare earth metal complex shown in Table 12 in the proportions shown in Table 12, a rare earth metal complex was synthesized according to the method of Example B-1.

Examples B-22 and B-23
<Synthesis of complex>
Using chain tetraphosphine tetraoxide (1) listed in Tables 1 to 4, instead of Eu (tfdh), terbium (III) -tris (1,1,1-trifluoro-5,5-dimethyl-2 , 4-hexanedionate) (hereinafter abbreviated as “Tb (tfdh)”), a rare earth metal complex was synthesized by the same method as in Example B-1. The obtained rare earth metal complex has the same structure as the rare earth metal complex obtained in Example B-9 or B-13 except that the central metal ion is Tb ³⁺ . The results of the infrared absorption spectrum are shown in Table 7.

<Confirmation of whether or not the oxygen atom of the chain tetraphosphine tetraoxide (1) is coordinated to Tb ³⁺ of Tb (tfdh)>
ESI ⁺ -MS was measured by the same method as in Example B-1. As a result, a molecular ion peak of chain tetraphosphine tetraoxide and a molecular ion peak of Tb (tfdh) were confirmed. This means that a complex is formed with chain tetraphosphine tetraoxide and Tb (tfdh) after the complex synthesis reaction.
Next, when the rare earth metal complex synthesized in Examples B-22 and B-23 was irradiated with a simple UV lamp (ultraviolet light having a wavelength of 365 nm), strong green light emission was observed. On the other hand, even when Tb (tfdh) was irradiated with the UV lamp, almost no light emission was observed.
Next, a fluorescence intensity measurement test was performed according to the following method. Table 13 shows that the rare earth metal complex synthesized in this example has a green emission intensity that is 10 to 17 times higher than that of Tb (tfdh) alone (Reference Example 6). This result is due to the fact that the oxygen atom of the phosphine oxide of the chain tetraphosphine tetraoxide is coordinated to Tb ³⁺ of Tb (tfdh).
From these measurement results, the substance (complex) obtained by reacting the chain tetraphosphine tetraoxide (1) synthesized in Tables 1 to 4 with Tb (tfdh) at a molar ratio of 1: 2 It can be seen that the structure of (tfdh) is retained, and the phosphine oxide part of the chain tetraphosphine tetraoxide (1) is coordinated to the central metal Tb ³⁺ .

Comparative Example 6
Using the phosphine oxide and β-diketonato rare earth metal complex shown in Table 13 in the ratio shown in Table 13, a rare earth metal complex was synthesized according to the method of Example B-1.

Examples B-24 to B-26
Using the linear tetraphosphine tetraoxide (1) described in Tables 1 to 4, instead of EuFOD, terbium (III) -tris (2,2,6,6-tetramethyl-3,5-heptanedionate) (Hereinafter abbreviated as “Tb (tmhd)”), a rare earth metal complex was synthesized by the same method as in Example B-1. The results of the infrared absorption spectrum are shown in Table 7.

<Whether the oxygen atom of the chain tetraphosphine tetraoxide (1) is coordinated to Tb ³⁺ of terbium (III) -tris (2,2,6,6-tetramethyl-3,5-heptanedionate) Confirmation>
ESI ⁺ -MS was measured by the same method as in Example B-1. As a result, a molecular ion peak of chain tetraphosphine tetraoxide and a molecular ion peak of Tb (tmhd) were confirmed. This means that a complex is formed with chain tetraphosphine tetraoxide and Tb (tmhd) even after the complex synthesis reaction.
Next, when the rare earth metal complex synthesized in Examples B-24 to B-26 was irradiated with a simple UV lamp (ultraviolet light having a wavelength of 365 nm), strong green light emission was observed. On the other hand, when the UV lamp was irradiated to Tb (tmhd), the luminescence was almost equal to that of the complex as observed.
Next, a fluorescence intensity measurement test was performed according to the following method. Table 14 shows that the rare earth metal complexes synthesized in Examples B-24 to B-26 have a green emission intensity that is about 3 times higher than that of Tb (tmhd) alone (Reference Example 7). This result is due to the coordination of the oxygen atom of the phosphine oxide of the chain tetraphosphine tetraoxide to Tb ³⁺ of Tb (tmhd).
From these measurement results, the substance (complex) obtained by reacting the chain tetraphosphine tetraoxide (1) synthesized in Tables 1 to 4 and Tb (tmhd) at a molar ratio of 1: 2 It can be seen that the structure of (tmhd) is retained, and the phosphine oxide portion of the chain tetraphosphine tetraoxide (1) is coordinated to Tb ³⁺ of the central metal.

Comparative Example 7
Using the phosphine oxide and β-diketonato rare earth metal complex shown in Table 14 in the proportions shown in Table 14, a rare earth metal complex was synthesized according to the method of Example B-1.

<Fluorescence intensity measurement test>
Examples C-1 to C-8
The rare earth metal complexes obtained in Examples B-1 to B-8 and Comparative Examples 1 to 3 were each fluorinated solvent (trade name “VertrelXF”) so that the Eu concentration was 2 × 10 ⁻⁵ mol / l. And Mitsui DuPont Fluorochemical Co., Ltd.). The red emission intensity in the vicinity of 614 to 616 nm of each sample when excited with light having a wavelength of 395 nm was measured. For the measurement, a spectrofluorometer (trade name “Hitachi spectrofluorometer F-7000”, manufactured by Hitachi High-Technologies Corporation) was used.

The emission intensity of each sample is shown as a relative value with the red emission intensity of a sample (Eu concentration 2 × 10 ⁻⁵ mol / l) in which only EuFOD (Reference Example 1) is dissolved in the solvent as 100. . The results are shown in Table 8.

Examples C-9 to C-13
The rare earth metal complexes obtained in Examples B-9 to B-13 and Comparative Example 4 were each dissolved in hexane (manufactured by Kishida Chemical Co., Ltd.) so that the Eu concentration was 2 × 10 ⁻⁵ mol / l. . The red emission intensity in the vicinity of 614 to 616 nm of each sample when excited with light having a wavelength of 395 nm was measured. For the measurement, a spectrofluorometer (trade name “Hitachi spectrofluorometer F-7000”, manufactured by Hitachi High-Technologies Corporation) was used.

The emission intensity of each of the samples is a relative value where the red emission intensity of a sample (Eu concentration 2 × 10 ⁻⁵ mol / l) in which only Eu (tfdh) (Reference Example 2) is dissolved in the solvent is 100. It showed in. The results are shown in Table 9.

Examples C-14 to C-17
The rare earth metal complexes obtained in Examples B-14 to B-17 were dissolved in a toluene solvent (manufactured by Kishida Chemical Co., Ltd.) so that the Eu concentration was 2 × 10 ⁻⁴ mol / l. The red emission intensity around 614 to 616 nm of the sample when excited with light having a wavelength of 395 nm was measured. For the measurement, a spectrofluorometer (trade name “Hitachi spectrofluorometer F-7000”, manufactured by Hitachi High-Technologies Corporation) was used.

The luminescence intensity of each sample is a relative value where the red luminescence intensity of a sample (Eu concentration 2 × 10 ⁻⁴ mol / l) in which only Eu (hnhd) (Reference Example 3) is dissolved is 100. It showed in. The results are shown in Table 10.

Examples C-18 to C-20
The rare earth metal complexes obtained in Examples B-18 to B-20 were dissolved in a toluene solvent (manufactured by Kishida Chemical Co., Ltd.) so that the Eu concentration was 2 × 10 ⁻⁴ mol / l. The red emission intensity around 614 to 616 nm of the sample when excited with light having a wavelength of 395 nm was measured. For the measurement, a spectrofluorometer (trade name “Hitachi spectrofluorometer F-7000”, manufactured by Hitachi High-Technologies Corporation) was used.

The emission intensity of each of the samples is a relative value where the red emission intensity of a sample (Eu concentration 2 × 10 ⁻⁴ mol / l) in which only Eu (hfpd) (Reference Example 4) is dissolved is 100. It showed in. The results are shown in Table 11.

Example C-21
The rare earth metal complexes obtained in Example B-21 and Comparative Example 5 were mixed with a fluorinated solvent (trade name “Vertrel XF”, manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) so that the Tb concentration was 2 × 10 ⁻⁵ mol / l. ). When the sample was excited with light having a wavelength of 395 nm, the green emission intensity around 542 to 545 nm of the sample was measured. For the measurement, a spectrofluorometer (trade name “Hitachi spectrofluorometer F-7000”, manufactured by Hitachi High-Technologies Corporation) was used.

The luminescence intensity of each sample was expressed as a relative value with the green luminescence intensity of a sample (Tb concentration 2 × 10 ⁻⁵ mol / l) in which only TbFOD (Reference Example 5) was dissolved in the solvent as 100. . The results are shown in Table 12.

Examples C-22 and C-23
Further, the rare earth metal complexes obtained in Examples B-22 and B-23 and Comparative Example 6 were dissolved in hexane (manufactured by Kishida Chemical Co., Ltd.) so that the Tb concentration was 2 × 10 ⁻⁵ mol / l. I let you. When the sample was excited with light having a wavelength of 395 nm, the green emission intensity around 542 to 545 nm of the sample was measured. For the measurement, a spectrofluorometer (trade name “Hitachi spectrofluorometer F-7000”, manufactured by Hitachi High-Technologies Corporation) was used.

The luminescence intensity of each sample is a relative value where the green luminescence intensity of a sample (Tb concentration 2 × 10 ⁻⁵ mol / l) in which only Tb (tfdh) (Reference Example 6) is dissolved in the solvent is 100. It showed in. The results are shown in Table 13.

Examples C-24 to C-26
The rare earth metal complexes obtained in Examples B-24 to B-26 and Comparative Example 7 were dissolved in a toluene solvent (manufactured by Kishida Chemical Co., Ltd.) so that the Tb concentration was 2 × 10 ⁻⁴ mol / l. . When the sample was excited with light having a wavelength of 395 nm, the green emission intensity around 542 to 545 nm of the sample was measured. For the measurement, a spectrofluorometer (trade name “Hitachi spectrofluorometer F-7000”, manufactured by Hitachi High-Technologies Corporation) was used.

The luminescence intensity of each sample is a relative value where the green luminescence intensity of a sample (Tb concentration 2 × 10 ⁻⁴ mol / l) in which only Tb (tmhd) (Reference Example 7) is dissolved in the solvent is 100. It showed in. The results are shown in Table 14.

<Saturated solubility measurement test>
Examples C-1 to C-8
A predetermined amount of Vertrel XF (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) was weighed out, the rare earth metal complexes obtained in Examples B-1 to B-8 and Comparative Examples 1 to 3 were added in large excess, and then stirred at room temperature for 2 hours. The insoluble part was removed by suction filtration. About the melt | dissolved part, after depressurizingly distilling a solvent, it dried and measured the weight. The saturation solubility per gram of solvent (mg / solvent 1 g) was calculated by dividing the weight of each rare earth metal complex obtained from the dissolved portion by the weight of Vertrel XF initially weighed. The results are shown in Table 8.

Examples C-9 to C-13
A predetermined amount of decamethyltetrasiloxane (silicon solvent: Aldrich, USA) was weighed out and stirred while adding the rare earth metal complexes of Examples B-9 to B-13 and Comparative Example 4 little by little. I stopped adding it when it became hazy. The saturation solubility per gram of solvent (mg / solvent 1 g) was calculated by dividing the weight of each rare earth metal complex added up to the time of hazing by the weight of the decamethyltetrasiloxane solvent weighed first. The results are shown in Table 9.

Examples C-14 to C-17
A predetermined amount of toluene (manufactured by Kishida Chemical Co., Ltd.) was weighed out and stirred while adding the rare earth metal complexes of Examples B-14 to B-17 and Reference Example 3 little by little. The saturation solubility per gram of solvent (mg / solvent 1 g) was calculated by dividing the weight of each rare earth metal complex added up to the time of hazing by the weight of the toluene solvent weighed first. The results are shown in Table 10.

Examples C-18 to C-20
A predetermined amount of toluene (manufactured by Kishida Chemical Co., Ltd.) was weighed out and stirred while adding the rare earth metal complexes of Examples B-18 to B-20 and Reference Example 4 little by little. The saturation solubility per gram of solvent (mg / solvent 1 g) was calculated by dividing the weight of each rare earth metal complex added up to the time of hazing by the weight of the toluene solvent weighed first. The results are shown in Table 11.

Example C-21
A predetermined amount of Vertrel XF (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) was weighed out, and the rare earth metal complex obtained in Example B-21 and Comparative Example 5 was added in large excess, followed by stirring at room temperature for 2 hours, and suction filtration of the insoluble portion. Removed. About the melt | dissolved part, after depressurizingly distilling a solvent, it dried and measured the weight. The saturation solubility per gram of solvent (mg / solvent 1 g) was calculated by dividing the weight of each rare earth metal complex obtained from the dissolved portion by the weight of Vertrel XF initially weighed. The results are shown in Table 12.

Examples C-22 and C-23
A predetermined amount of decamethyltetrasiloxane (silicon solvent: Aldrich, USA) was weighed out and stirred while gradually adding the rare earth metal complexes of Examples B-22 and B-23 and Comparative Example 6. I stopped adding it when it became hazy. The saturation solubility per gram of solvent (mg / solvent 1 g) was calculated by dividing the weight of each rare earth metal complex added up to the time of hazing by the weight of the decamethyltetrasiloxane solvent weighed first. The results are shown in Table 13.

Examples C-24 to C-26
A predetermined amount of toluene (manufactured by Kishida Chemical Co., Ltd.) is weighed out and stirred while adding rare earth metal complexes of Examples B-24 to B-26, Comparative Example 7 and Reference Example 7 little by little. Stopped. The saturation solubility per gram of solvent (mg / solvent 1 g) was calculated by dividing the weight of each rare earth metal complex added up to the time of hazing by the weight of the toluene solvent weighed first. The results are shown in Table 14.

<Thermal stability test>
Examples C-1 to C-26
5 mg each of the rare earth metal complexes obtained in Examples B-1 to B-26, Comparative Examples 1 to 7 and Reference Examples 1 to 7 were weighed, and a differential thermothermal weight (TG / DTA) simultaneous measurement device (trade name “ The decomposition temperature of the rare earth metal complex was measured using TG / DTA220 (manufactured by Seiko Denshi Kogyo). The results are shown in Tables 8-14.

  From the results of Tables 8 to 14, the rare earth metal complex of the present invention (the rare earth metal complex coordinated with the chain tetraphosphine tetraoxide (1) of the present invention has a higher fluorescence intensity and fluorine than the conventional rare earth metal complex). It can be seen that the solubility in an organic solvent such as a system solvent or a silicon-based solvent is very excellent, in particular, regarding the solubility, l, m and n in the general formula (1) are all odd numbers (l, m And n is 3 or 5), the solubility is remarkably excellent, and it can be seen that the saturation solubility is 2 to 30 times higher than that of the conventional rare earth metal complex.

  Regarding the thermal stability, the rare earth metal complex of the present invention has a decomposition temperature equal to or higher than that of the conventional rare earth metal complex. That is, it can be seen that the rare earth metal complex of the present invention is excellent in durability against heat and the like.

  From these results, the rare earth metal complex of the present invention has high emission intensity, high solubility in an organic medium, the chain tetraphosphine tetraoxide (1) is not easily dissociated from the rare earth metal ion in the organic medium, heat, etc. It can be seen that it is excellent in durability.

  Therefore, the rare earth metal complex of the present invention is suitable for the rare earth metal complex of the present invention when a fluorinated solvent, a fluorinated resin, a silicon resin, or the like is used, for example, in forming a luminescent medium in a light emitting layer of a white LED element. can do.

  For example, a solution prepared by dissolving the rare earth metal complex of the present invention in a fluorine-based solvent such as Vertrel XF (fluorine solvent: manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) and a fluorine-based polymer is prepared in the same manner as in Examples of Patent Document 4 and the like. If the light emitting layer of the LED element is housed and a light emitting medium is prepared after heating and drying, an LED element capable of emitting red, white or the like can be manufactured.

Fluorescent Light-Emitting Ink Composition The rare earth metal complex of the present invention (the rare earth metal complex coordinated with the chain tetraphosphine tetraoxide (1) of the present invention) is not only dissolved in a fluorine-based solvent or silicon-based solvent but also various solvents. And can be used as a fluorescent ink composition. An example is shown below.

<Preparation of red luminescent ink composition>
Example D-1
Using the rare earth metal complex exhibiting red luminescence obtained in Example B-1, the weight ratio of the rare earth metal complex of Example B-1: N-methyl-2-pyrrolidone: ethylene glycol: ethanol is 1: 4. : The ink composition which is 5:90 was created. The results are shown in Table 15.

Examples D-2 to D-8
In accordance with the method of Example D-1, the weight ratio of rare earth metal complex: N-methyl-2-pyrrolidone: ethylene glycol: ethanol showing red luminescence of Examples B-2 to B-8 was 1: 4: 5: 90. An ink composition was prepared. The results are shown in Table 15.

Comparative Examples 1 and 2 and Reference Example 1
According to the method of Example D-1, the weight ratio of rare earth metal complex: N-methyl-2-pyrrolidone: ethylene glycol: ethanol showing red luminescence of Comparative Examples 1, 2 and Reference Example 1 is 1: 4: 5: 90. An ink composition was prepared. The results are shown in Table 15.

Examples D-9 to D-13
According to Example D-1, using the rare earth metal complex showing red emission obtained in Examples B-9 to B-13, the rare earth metal complex of Examples B-9 to B-13: N-methyl-2 An ink composition having a weight ratio of pyrrolidone: ethylene glycol: ethanol of 1: 4: 5: 90 was prepared. The results are shown in Table 16.

Comparative Example 4 and Reference Example 2
According to the method of Example D-1, the weight ratio of the rare earth metal complex: N-methyl-2-pyrrolidone: ethylene glycol: ethanol showing red light emission of Comparative Example 4 and Reference Example 2 is 1: 4: 5: 90. An ink composition was prepared. The results are shown in Table 16.

Examples D-14 to D-17
In accordance with Example D-1, using the rare earth metal complex showing red emission obtained in Examples B-14 to B-17, the rare earth metal complex of Examples B-14 to B-17: N-methyl 2- An ink composition having a weight ratio of pyrrolidone: ethylene glycol: ethanol of 1: 4: 5: 90 was prepared. The results are shown in Table 17.

Reference example 3
According to the method of Example D-1, an ink composition in which the weight ratio of the rare earth metal complex showing the red color in Reference Example 3: N-methyl-2-pyrrolidone: ethylene glycol: ethanol is 1: 4: 5: 90 is prepared. did. The results are shown in Table 17.

Examples D-18 to D-20
According to Example D-1, using the rare earth metal complex showing red emission obtained in Examples B-18 to B-20, the rare earth metal complex of Examples B-18 to B-20: N-methyl-2 An ink composition having a weight ratio of pyrrolidone: ethylene glycol: ethanol of 1: 4: 5: 90 was prepared. The results are shown in Table 18.

Reference example 4
According to the method of Example D-1, an ink composition in which the weight ratio of the rare earth metal complex showing the red color in Reference Example 4: N-methyl-2-pyrrolidone: ethylene glycol: ethanol is 1: 4: 5: 90 is prepared. did. The results are shown in Table 18.

<Red light emission and visual inspection of ink compositions of Examples D-1 to D-20, Comparative Examples 1, 2, 4 and Reference Examples 1-4>
Using the obtained ink composition immediately after preparation, it was applied on the paper surface and irradiated with a black light lamp (ultraviolet light with a wavelength of 365 nm) for the state of light emission of the ink when left at room temperature for 1 week. I investigated.

  At the same time, as for the ink state, the state of the ink was examined immediately after preparation and after being left at room temperature for 1 week.

  Further, for Examples D-1 to D-20, the inks after being left at room temperature for 1 week were respectively applied on the paper surface, and the state of light emission of the inks when left at room temperature for 1 week was also examined. The results are shown in Tables 15, 16, 17, and 18.

Note that the criteria for determining the light emission condition are represented by the following symbols.
A very strong light emission was confirmed.
○... Light emission sufficient for visual recognition was confirmed.
Δ: Although visible, light emission is weak.
X: Visible, but luminescence is very weak.
In addition, the ink state is represented by the following symbols.
◎ ... Since the rare earth complex is completely dissolved without precipitation, there is no haze. Furthermore, there is no color change.
○ ... Haze or precipitation occurs because part of the rare earth metal complex does not dissolve.
X: The haze is very intense with almost no dissolution of the complex.

(result)
The surface of the paper coated with the inks of Examples, Comparative Examples, and Reference Examples was colorless under natural light, but when irradiated with ultraviolet light (ultraviolet light having a wavelength of 365 nm) by a black light lamp, The luminescence was confirmed.

  On the surface of the paper coated with ink immediately after the preparation of Examples D-1 to D-20, the light emission can be confirmed sufficiently even when left at room temperature for one week, and at the same time, the complex is deposited in an obvious manner. It never happened.

  Further, the ink was allowed to stand at room temperature for 1 week, and then the ink was applied to the paper surface in the same manner and the state was observed. Even after one week had passed, it was possible to confirm the light emission enough to be visually recognized as described above. In addition, the complex did not deposit on the paper.

  Therefore, it can be seen that the rare earth metal complex of the present invention does not precipitate at all and is excellent in stability.

  It can be seen that the ink state is excellent in storage stability with no change over time such as coloring or partial complex precipitation even immediately after preparation or when left at room temperature for 1 week.

  On the other hand, the paper surface coated with the rare earth metal complex compositions of Comparative Examples 1 to 3 and Reference Examples 1 to 4 was colorless under natural light, but was irradiated with ultraviolet light (ultraviolet light having a wavelength of 365 nm) by a black light lamp. Then, although red light emission was observed in the coated part as before, the light emission was weaker from the beginning than in the inks of Examples D-1 to D-20, or the light emission gradually weakened. Some rare earth metal complexes were clearly deposited and lacked stability.

  As for the state of the ink, in Comparative Examples 1 to 3 and Reference Examples 1 to 4, there was no change over time such as coloring, but a portion of the rare earth metal complex or almost all did not dissolve, and a haze occurred and the stability was improved. You can see that it is missing.

  Therefore, from the results of Tables 15 to 18, the rare earth metal complex of the present invention (the rare earth metal complex coordinated with the chain tetraphosphine tetraoxide (1) of the present invention) is more ink-like than the conventional rare earth metal complex. It can be seen that even in the case of coating, the stability at the time of coating and the storage stability are excellent.

<Preparation of green luminescent ink composition>
Examples D-22 and D-23
According to the method of Example D-1, the weight ratio of the rare earth metal complex: N-methyl-2-pyrrolidone: ethylene glycol: ethanol of Examples B-22 and B-23 that emits green light is 1: 4: 5: 90. An ink composition was prepared. The results are shown in Table 19.

Comparative Example 6 and Reference Example 6
According to the method of Example D-1, ink having a weight ratio of rare earth metal complex: N-methyl-2-pyrrolidone: ethylene glycol: ethanol of Comparative Example 6 and Reference Example 6 of 1: 4: 5: 90 A composition was prepared. The results are shown in Table 19.

Examples D-24 to D-26
According to the method of Example D-1, the weight ratio of the rare earth metal complex showing the green color of Examples D-24 to D-26: N-methyl-2-pyrrolidone: ethylene glycol: ethanol is 1: 4: 5: 90 An ink composition was prepared. The results are shown in Table 20.

Comparative Example 7 and Reference Example 7
According to the method of Example D-1, ink having a weight ratio of rare earth metal complex: N-methyl-2-pyrrolidone: ethylene glycol: ethanol of Comparative Example 7 and Reference Example 7 of 1: 4: 5: 90 A composition was prepared. The results are shown in Table 20.

<Green emission and visual examination of ink compositions of Examples D-22 to D-26, Comparative Examples 6 and 7, and Reference Examples 6 and 7>
Apply the black ink lamp (ultraviolet light with a wavelength of 365 nm) on the light emission condition of the ink when applied to the paper surface using the ink composition immediately after preparation and left at room temperature for 1 week. I examined it.

  At the same time, as for the ink state, the state of the ink was examined immediately after preparation and after being left at room temperature for 1 week.

  Furthermore, for the inks of Examples D-22 to D-26, the inks after being left to stand at room temperature for 1 week were respectively applied on the paper surface and the light emission of the ink when left at room temperature for 1 week. I also checked the condition. The results are shown in Tables 19 and 20.

Note that the criteria for determining the light emission condition are represented by the following symbols.
A very strong light emission was confirmed.
○... Light emission sufficient for visual recognition was confirmed.
Δ: Although visible, light emission is weak.
X: Visible, but luminescence is very weak.
In addition, the ink state is represented by the following symbols.
◎ ... Since the rare earth complex is completely dissolved without precipitation, there is no haze. Furthermore, there is no color change.
○ ... Haze or precipitation occurs because part of the rare earth metal complex does not dissolve.
X: The haze is very intense with almost no dissolution of the complex.

(result)
The surface of the paper coated with the inks of Examples, Comparative Examples and Reference Examples was colorless under natural light, but when irradiated with ultraviolet light (ultraviolet light having a wavelength of 365 nm) by a black light lamp, The luminescence was confirmed.

  In the paper surface coated with ink immediately after the preparation of Examples D-22 to D-26, the light emission was sufficiently observable even when left at room temperature for one week, and at the same time the complex was partially on the paper surface. It did not precipitate.

  Further, when the ink was allowed to stand at room temperature for 1 week, the ink was applied and the state was observed. It can be seen that even after one week has passed, green light emission that can be sufficiently visually recognized can be confirmed as described above, and at the same time, the rare earth metal complex of the present invention does not precipitate and is excellent in stability.

  It can be seen that the ink state is excellent in storage stability with no change over time such as coloring or partial complex precipitation even immediately after preparation or when left at room temperature for 1 week.

  On the other hand, the ink compositions having the rare earth metal complex compositions of Comparative Examples 6 and 7 and Reference Examples 6 and 7 are slightly hazy with some ink compositions or emit light from the beginning when applied on paper. Was weak or the luminescence gradually weakened.

  Therefore, from the results of Tables 19 and 20, the rare earth metal complex of the present invention (the rare earth metal complex coordinated with the chain tetraphosphine tetraoxide (1) of the present invention) is more ink-like than the conventional rare earth metal complex. It can be seen that even in the case of coating, the stability at the time of coating and the storage stability are excellent.

  Furthermore, a red light emitting ink or a green light emitting ink is prepared in advance, and a two-color mixed ink can be prepared by mixing these inks. Since the obtained ink emits different colors when irradiated with ultraviolet rays having different wavelengths, the security can be further improved. An example is shown below.

<Preparation of red luminescent ink>
Example D-27
Using the rare earth metal complex showing red emission obtained in Example B-1, the weight ratio of the rare earth metal complex of Example B-1: polyvinyl butyral (manufactured by Aldrich, USA): ethylene glycol: ethanol is 1 An ink composition of 4: 5: 90 was prepared and applied on the paper surface. After drying, when irradiated with a black light lamp (ultraviolet light having a wavelength of 365 nm), a bright red light was emitted.

Example D-28
Using the rare earth metal complex showing red light emission obtained in Example B-13, the weight ratio of the rare earth metal complex of Example B-13: polyvinyl butyral (Aldrich, USA): ethylene glycol: ethanol is 1 An ink composition of 4: 5: 90 was prepared and applied on the paper surface. After drying, when irradiated with a black light lamp (ultraviolet light having a wavelength of 365 nm), a bright red light was emitted.

Example D-29
Using the rare earth metal complex showing red light emission obtained in Example B-17, the weight ratio of the rare earth metal complex of Example B-17: polyvinyl butyral (Aldrich, USA): ethylene glycol: ethanol is 1 An ink composition of 4: 5: 90 was prepared and applied on the paper surface. After drying, when irradiated with a black light lamp (ultraviolet light having a wavelength of 365 nm), a bright red light was emitted.

  In any case, the ink was colorless, and no phenomenon such as haze or precipitation was observed immediately after preparation or after standing at room temperature for a week. The results are shown in Table 21.

<Preparation of green luminescent ink>
Example D-30
Using the rare earth metal complex exhibiting green light emission obtained in Example B-22, the weight ratio of the rare earth metal complex of Example B-22: polyvinyl butyral (manufactured by Aldrich, USA): ethylene glycol: ethanol is 1 An ink composition of 4: 5: 90 was prepared and applied on the paper surface. After drying, when irradiated with a black light lamp (wavelength 365 nm ultraviolet light), it showed clear green light emission.

Example D-31
Using the rare earth metal complex exhibiting green luminescence obtained in Example B-23, the weight ratio of the rare earth metal complex of Example B-23: polyvinyl butyral (manufactured by Aldrich, USA): ethylene glycol: ethanol is 1 An ink composition of 4: 5: 90 was prepared and applied on the paper surface. After drying, when irradiated with a black light lamp (ultraviolet light with a wavelength of 365 nm), it showed a clear green light emission.

  In any case, the ink was colorless, and no phenomenon such as haze or precipitation was observed immediately after preparation or after standing at room temperature for a week. The results are shown in Table 21.

<Preparation of dichroic mixed ink>
Example D-32
The red luminescent ink obtained in Example D-27 and the green luminescent ink obtained in Example D-31 were mixed at a weight ratio of 5: 9 to prepare a dichroic ink. When it was applied onto a paper surface and dried, and then irradiated with a black light lamp (ultraviolet light having a wavelength of 365 nm), it showed a clear yellow color. On the other hand, when irradiated with a black light lamp (ultraviolet light having a wavelength of 254 nm), it showed a clear green light emission.

Example D-33
A dichroic ink was prepared by mixing the red luminescent ink obtained in Example D-28 and the green luminescent ink obtained in Example D-31 at a weight ratio of 5: 9. When it was applied onto a paper surface and dried, and then irradiated with a black light lamp (ultraviolet light having a wavelength of 365 nm), it showed a clear yellow color. On the other hand, when irradiated with a black light lamp (ultraviolet light having a wavelength of 254 nm), it showed a clear green light emission.

Example D-34
A dichroic ink was prepared by mixing the red luminescent ink obtained in Example D-29 and the green luminescent ink obtained in Example D-30 at a weight ratio of 1:25. When it was applied onto a paper surface and dried, and then irradiated with a black light lamp (ultraviolet light having a wavelength of 365 nm), it showed a clear yellow color. On the other hand, when irradiated with a black light lamp (ultraviolet light having a wavelength of 254 nm), it showed a clear green light emission.

  These two-color mixed inks were colorless and were found to be excellent in storage stability without any phenomenon such as being hazy immediately after preparation or after being left at room temperature for a week, or formation of precipitates.

  As shown in the results of Tables 15 to 21 of the examples, the fluorescent ink composition containing the rare earth metal complex of the present invention having the above characteristics has a clear red color when irradiated with a black light lamp (ultraviolet light having a wavelength of 365 nm, etc.). Stable emission of colors such as green. Furthermore, it turns out that it is excellent in stability with time or storage stability.

  From the results of all these examples, the rare earth metal complex of the present invention has high emission intensity and high solubility in an organic medium, and the chain tetraphosphine tetraoxide (1) is hardly dissociated from the rare earth metal ion in the organic medium. It can be seen that it is excellent in durability against heat and the like.

  Therefore, the rare earth metal complex coordinated with the chain tetraphosphine tetraoxide (1) of the present invention is used for a light emitting material for white LEDs, a light emitting material used for a light emitting layer of an organic EL element, or security applications such as forgery prevention. It can be applied and developed for the intended fluorescent ink.

DESCRIPTION OF SYMBOLS 1 Light emitting layer 2 LED chip 3 Light emitting medium

Claims (20)

General formula:

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each may be a saturated hydrocarbon group which may be substituted, an aryl group which may be substituted, or a substituent A heteroaryl group which may be substituted or an aralkyl group which may be substituted, or R ¹ and R ² and R ⁵ and R ⁶ on the same phosphorus atom may be bonded to form a ring Well, l, m and n are the same or different and each represents an integer of 2 or more.)
A linear tetraphosphine tetraoxide represented by In general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each may be a saturated hydrocarbon group which may be substituted, or an aryl which may be substituted Group, an optionally substituted heteroaryl group or an optionally substituted aralkyl group, or R ¹ and R ² and R ⁵ and R ⁶ on the same phosphorus atom are bonded to form a ring. The linear tetraphosphine tetraoxide according to claim 1, wherein l, m and n are the same or different and each represents an integer of 3 to 12. In general formula (1), R ¹ , R ² , R ^5, and R ⁶ are the same or different and each may be a substituted C 3-20 saturated hydrocarbon group or an optionally substituted aryl. A group, a heteroaryl group which may be substituted, or an aralkyl group which may be substituted, wherein R ³ and R ⁴ may be the same or different and each may be a substituted aryl group or a substituted group; The chain | strand-shaped tetraphosphine tetraoxide of Claim 1 or 2 which shows a good heteroaryl group and l, m, and n are the same or different, respectively, and show the integer of 3-12. In general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each may be an optionally substituted aryl group or an optionally substituted heteroaryl group The chain tetraphosphine tetraoxide according to any one of claims 1 to 3, wherein l, m and n are the same or different and each represents an integer of 3 to 12. In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and may be substituted or substituted aryl groups having 6 to 15 carbon atoms. The chain | strand-shaped tetraphosphine tetraoxide in any one of Claims 1-4 which shows the C5-C15 heteroaryl group which may be shown, and l, m, and n are the same or different, respectively, and show the integer of 3-12. . In general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each represents an optionally substituted aryl group having 6 to 15 carbon atoms; , M and n are the same or different and each represents an integer of 3 to 12, and the chain tetraphosphine tetraoxide according to any one of claims 1 to 5. In general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each represents an optionally substituted aryl group having 6 to 15 carbon atoms; , M and n are the same or different and each represents 3, 5, 7, 9 or 11, chain tetraphosphine tetraoxide according to claim 1. The rare earth metal complex containing the chain | strand-shaped tetraphosphine tetraoxide in any one of Claims 1-7. The rare earth metal complex according to claim 8, wherein at least one oxygen atom among the four oxygen atoms of the chain tetraphosphine tetraoxide is coordinated to a rare earth metal ion. The rare earth metal complex according to claim 9, wherein the rare earth metal ion is Eu ³⁺ , Tb ³⁺ , Er ³⁺ , Gd ³⁺ or Tm ³⁺ . The rare earth metal complex according to claim 9, wherein the rare earth metal ion is Eu ³⁺ or Tb ³⁺ . Furthermore, the general formula (2)

(In the formula, R ⁸ represents a hydrogen atom, a deuterium atom, a halogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aryl group, or an optionally substituted hetero group. An aryl group or an aralkyl group which may be substituted; R ⁷ and R ⁹ are the same or different and each may be substituted a saturated hydrocarbon group having 1 to 20 carbon atoms or a perfluoro having 1 to 20 carbon atoms; An alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or an optionally substituted aralkyl group is shown.)
The rare earth metal complex according to any one of claims 8 to 11, wherein a β-diketonato ligand represented by the formula is coordinated. The chain tetraphosphine tetraoxide according to any one of claims 1 to 7, and the general formula (3) LnLp (3)
(In the formula, Ln represents a rare earth metal ion, p represents an integer of 1 to 5, L represents the β-diketonato ligand, and when p is an integer of 2 or more, the β-diketonato coordination The ligands may be the same or different from each other.)
The rare earth metal complex according to claim 12, which is obtained by reacting in a solvent with a β-diketonato rare earth metal complex represented by the formula: The reaction ratio ((1) / (3)) of the chain tetraphosphine tetraoxide (1) and the β-diketonato rare earth metal complex (3) in the reaction is 0.3 to 0.7 in molar ratio. The rare earth metal complex according to claim 13. The reaction ratio ((1) / (3)) of the chain tetraphosphine tetraoxide (1) and the β-diketonato rare earth metal complex (3) in the reaction is 0.5 in terms of molar ratio. Or the rare earth metal complex of 14. The rare earth metal complex according to any one of claims 13 to 15, wherein one or two or more β-diketonato rare earth metal complexes are reacted as the β-diketonato rare earth metal complex (3). A luminescent medium comprising the rare earth metal complex according to any one of claims 8 to 16 dissolved in an organic medium. A white LED element comprising the light emitting medium according to claim 17. A fluorescent ink composition comprising the rare earth metal complex according to claim 8. The organic electroluminescent element which has a light emitting layer containing the rare earth metal complex in any one of Claims 8-16.

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