JP5272343B2 - Novel rare earth complex, rare earth complex phosphor, and phosphor-containing composition, laminate, color conversion film, light emitting device, lighting device, and image display device using the phosphor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rare earth complex fluorescent substance which has high durability to light and oxygen and is excited with blue or near UV light. <P>SOLUTION: This rare earth complex fluorescent substance contains a ligand represented by either of formulas of Figures. Therein, R<SP>1</SP>to R<SP>3</SP>are each a monovalent substituent, provided that at least one of the R<SP>1</SP>to R<SP>3</SP>is represented by -X-A. R<SP>4</SP>, R<SP>5</SP>, R<SP>4'</SP>, and R<SP>5'</SP>are each a monovalent substituent, provided that at least one of them is a group represented by -X-A. R<SP>6</SP>is a divalent bonding group. X is a direct bond or a divalent bonding group. A is a heterocyclic group, wherein the molecular orbital energy of the highest occupied orbital determined by a molecular orbital calculation of a heterocyclic compound forming the heterocyclic group is larger than that of a benzene group. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention is a novel rare earth capable of emitting visible light by being excited using a light source having a light emission maximum in the near ultraviolet to visible light range of 200 nm to 450 nm, represented by organic and inorganic light emitting diodes. The present invention relates to a complex, an organic phosphor composed of the rare earth complex, and a phosphor-containing composition, a laminate, a color conversion film, a light-emitting device, a lighting device, and an image display device using the phosphor.

Rare earth complex phosphors are expected to be used as light-emitting members for fluorescent probes, electronics materials, laser dyes, bioimaging, sensors, lighting, etc. because they exhibit very sharp narrow-band emission resulting from multiple-center transitions at the metal center. ing.
Inorganic phosphors are also known as narrow-band light emitting materials. However, organic phosphors such as rare earth complex phosphors are less expensive to manufacture than inorganic phosphors and have high excitation light absorption efficiency. There is an advantage that it is difficult to escape. Furthermore, the organic phosphor has many advantages such as solubility in an organic solvent and dispersibility in a medium.

  With regard to rare earth complex phosphors, many studies have been made for shift reagents in the 1970s and for fluorescent probes since 1985, respectively. Among these, a europium complex composed of a diketone ligand and a phosphine oxide ligand (Exemplary 1) has high luminous efficiency, and has attracted attention as a luminescent dye for use in organic electroluminescence devices (organic EL) and near-ultraviolet excitation. (See Patent Document 1). In the structural formula below, Ph represents a phenyl group.

In addition, it is also considered that the ligand is a multidentate ligand, and many studies (examples 2 and 3) of connecting two phosphine oxides to form a bidentate ligand have been made so far. (See Non-Patent Document 1 and Patent Documents 2 to 4). In the following structural formula, t-Bu represents a t-butyl group.

JP 2004-179296 A JP 2002-124383 A JP-A-2005-015564 JP 2004-179296 A H. Xu, L.-H. Wang, X.-H. Zhu, K. Yin, G.-Y. Zhong, X.-Y. Hou and W. Huang, J. Phys. Chem. B, 110, 3023 (2006).

However, the rare earth complex phosphor such as Exemplified Example 1 is insufficient for practical use in terms of durability against light and oxygen.
In addition, rare earth complex phosphors such as Exemplified Example 2 and Exemplified Example 3 have a large distortion when bidentately coordinated due to the steric repulsion between substituents on phosphorus. For this reason, they are easy to vibrationally deactivate the excitation energy, and the luminous efficiency may be lowered. Furthermore, since the ligand is easily detached, further improvement has been desired to improve durability.

  The present invention has been made in view of the above-described conventional situation, and when excited using a light source having a light emission maximum in the near ultraviolet to visible region such as a semiconductor light emitting element, the durability is high, A phosphor-containing composition, a laminate, a color conversion film, a light emitting device, a lighting device, and an image capable of obtaining a high-brightness rare-earth complex and a rare-earth complex phosphor and thereby obtaining highly durable and high-brightness light emission An object is to provide a display device.

  As a result of intensive studies to solve the above problems, the present inventors have excited a rare earth complex using a ligand having a specific structure by using a light source having an emission maximum in the near ultraviolet to visible region. The present inventors have found that it emits light with high brightness and exhibits extremely high durability, and has completed the present invention.

（式（１）中、Ｒ¹〜Ｒ³は、それぞれ独立して、芳香族炭化水素基又は−Ｘ−Ａで表される基を示し、かつ、これらのうち少なくとも１つが−Ｘ−Ａで表される基である。
式（２）中、Ｒ⁴、Ｒ⁵、Ｒ⁴’及びＲ⁵’は、それぞれ独立して、芳香族炭化水素基又は−Ｘ−Ａで表される基を示し、かつ、これらのうち少なくとも１つが−Ｘ−Ａで表される基であり、Ｒ⁶は２価の連結基を示す。
ここで、Ｘは直接結合を示し、Ａはピリジル基、キノキサリニル基、イソキノリル基、キノリル基、ピラジニル基、ピリミジニル基、ピリダジニル基から選ばれる含窒素６員環基もしくは６員環で構成される縮合多環基；電子吸引性置換基を有する、ピラゾリル基、イミダゾリル基、オキサゾリル基、チアゾリル基、フリル基、チエニル基から選ばれる５員へテロ環基；ベンゾチエニル基、ジベンゾチエニル基、ジベンゾフラニル基、フェノキサチイニル基から選ばれる縮合環を有する５員ヘテロ環基から選ばれるヘテロ環基であり、かつ、該へテロ環基を構成するヘテロ環化合物の分子軌道計算によって求められる最高被占軌道の分子軌道エネルギーがベンゼン環よりも大きいものを示す。） That is, the gist of the present invention resides in a rare earth complex having a ligand represented by either the following formula (1) or (2) (Claim 1).

(In the formula (1), R ^{1 to} R ³ each independently represents an aromatic hydrocarbon group or a group represented by —XA , and at least one of them is —XA. It is a group represented.
In formula (2), R ⁴ , R ⁵ , R ⁴ ′ and R ⁵ ′ each independently represent an aromatic hydrocarbon group or a group represented by —XA , and at least of these One is a group represented by -X-A, and R ⁶ represents a divalent linking group.
Here, X is shows a direct binding, A is composed of a pyridyl group, a quinoxalinyl group, an isoquinolyl group, a quinolyl group, pyrazinyl group, pyrimidinyl group, 6-membered nitrogen-containing selected from pyridazinyl ring or 6-membered ring Condensed polycyclic group; 5-membered heterocyclic group selected from pyrazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, furyl group and thienyl group having an electron-withdrawing substituent; benzothienyl group, dibenzothienyl group, dibenzofura A heterocyclic group selected from a 5-membered heterocyclic group having a condensed ring selected from a nyl group and a phenoxathiinyl group, and the highest required by molecular orbital calculation of the heterocyclic compound constituting the heterocyclic group The molecular orbital energy of the occupied orbital is larger than that of the benzene ring. )

Further, the rare earth metal element constituting the rare earth complex is preferably an element selected from the group consisting of Eu, Tb, Tm and Ce (Claim 2 ).

（式（３）中、Ｒ⁷及びＲ⁹は、それぞれ独立して、パーフルオロアルキル基、電子吸引性基を有する芳香族炭化水素基、又は、置換基を有していても良い複素環基を示し、Ｒ⁸は、水素原子、重水素原子、アルキル基、置換基を有しても良い芳香族炭化水素基、又は、置換基を有しても良い複素環基を示し、式（４）中、Ｒ¹⁰は、電子吸引性置換基を有する芳香族炭化水素基、又は、置換基を有しても良い複素環基を示す。） Furthermore, rare earth complex of the present invention preferably has an anionic ligand represented by the following formula (3) or (4) (claim 3).

(In Formula (3), R ⁷ and R ⁹ are each independently a perfluoroalkyl group, an aromatic hydrocarbon group having an electron-withdrawing group, or an optionally substituted heterocyclic group. R ⁸ represents a hydrogen atom, a deuterium atom, an alkyl group, an aromatic hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent. ), R ¹⁰ represents an aromatic hydrocarbon group having an electron-withdrawing substituent or a heterocyclic group which may have a substituent.

Another subject of the present invention, there is provided a rare earth complex phosphor having a ligand represented by any of the above formulas (1) or (2) (claim 4).

Still another subject matter of the present invention lies in a phosphor-containing composition comprising the rare earth complex phosphor of the present invention and a liquid medium (Claim 5 ).

Still another subject matter of the present invention lies in a laminate having a phosphor-containing layer containing the rare earth complex phosphor of the present invention (claim 6 ).

Still another subject matter of the present invention lies in a color conversion film comprising the rare earth complex phosphor of the present invention (claim 7 ).

According to still another aspect of the present invention, there is provided a first light emitter and a second light emitter that emits visible light by irradiation of light from the first light emitter, and the second light emitter is the present light emitter. the rare earth complex phosphor of the invention one or more resides in a light-emitting device characterized in that it contains as the first phosphor (claim 8).

At this time, the second luminous body, the first phosphor different phosphor emission peak wavelength 1 or more, preferably contains as the second phosphor (claim 9).

Still another subject matter of the present invention lies in an illuminating device comprising the light emitting device of the present invention (claim 10 ).

Still another subject matter of the present invention lies in an image display device comprising the light emitting device of the present invention (claim 11 ).

The rare earth complex and rare earth complex phosphor of the present invention have high durability and can emit light with high luminance when excited using a light source having a light emission maximum in the near ultraviolet to visible region.
Moreover, the phosphor-containing composition, laminate, color conversion film, light-emitting device, lighting device and image display device of the present invention have high durability and can emit light with high luminance.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the scope of the present invention. .

（式（１）中、Ｒ¹〜Ｒ³は、それぞれ独立して、１価の置換基を示し、かつ、これらのうち少なくとも１つが−Ｘ−Ａで表される基である。式（２）中、Ｒ⁴、Ｒ⁵、Ｒ⁴’及びＲ⁵’は、それぞれ独立して、１価の置換基を示し、かつ、これらのうち少なくとも１つが−Ｘ−Ａで表される基であり、Ｒ⁶は２価の連結基を示す。ここで、Ｘは直接結合又は２価の連結基を示し、Ａはヘテロ環基であり、かつ、Ａを構成するヘテロ環化合物の分子軌道計算によって求められる最高被占軌道の分子軌道エネルギーがベンゼン環よりも大きいものを示す。） [1. Rare earth complex]
The rare earth complex of the present invention is a complex having a rare earth metal as a central metal, and has a ligand represented by either the following formula (1) or (2).

(In formula (1), R ^{1 to} R ³ each independently represents a monovalent substituent, and at least one of these is a group represented by —XA. Formula (2) ), R ⁴ , R ⁵ , R ⁴ ′ and R ⁵ ′ each independently represent a monovalent substituent, and at least one of these is a group represented by —XA. , R ⁶ represents a divalent linking group, wherein X represents a direct bond or a divalent linking group, A is a heterocyclic group, and molecular orbital calculation of the heterocyclic compound constituting A (It indicates that the required molecular orbital energy of the highest occupied orbital is larger than that of the benzene ring.)

[1-1. Central metal]
The central metal element constituting the rare earth complex of the present invention is not particularly limited as long as it is a rare earth metal element. Specific examples thereof include Ce, Pr, Nd, Sm, Eu, Gd, Tb, Er, Tm, Yb, and Lu.
Of these, trivalent metal elements are preferable, Ce, Eu, Tb, Er, and Tm are more preferable, and Eu, Tb, Tm, and Ce are more preferable.
The rare earth complex of the present invention can be a binuclear complex without changing the composition ratio.

[1-2. Ligand]
The rare earth complex of the present invention comprises a neutral ligand (hereinafter referred to as “neutral ligand” as appropriate) and an anionic ligand (hereinafter referred to as “anionic ligand” as appropriate) as ligands. Have As described above, the rare earth complex of the present invention has a ligand represented by either the above formula (1) or (2), but is represented by any one of the above formula (1) or (2). The ligand to be used is usually a neutral ligand.

[1-2-1. Neutral ligand]
The number of neutral ligands is determined according to the coordination number and valence of the central metal element and the type of anionic ligand, but is usually 1 to 5. However, the rare earth complex of the present invention has at least one ligand represented by either the above formula (1) or (2) as a neutral ligand. Specifically, when the central metal element is a trivalent metal, the rare earth complex of the present invention is usually represented by two ligands represented by the above formula (1) or the formula (2). 1 ligand as a neutral ligand.

[1-2-1-1. Ligand represented by formula (1)]
In the above formula (1), R ^{1 to} R ³ each independently represent a monovalent substituent. However, at least one of R ^{1 to} R ³ is a group represented by —XA.
Here, X represents a direct bond or a divalent linking group. Although there is no restriction | limiting in a bivalent coupling group, For example, a linear, branched or cyclic saturated aliphatic, such as a methylene group, ethylene group, propylene group, isopropylene group, cyclopentylene group, cyclohexylene group, etc. Divalent hydrocarbon groups; linear, branched or cyclic unsaturated aliphatic hydrocarbon divalent groups such as vinylene group, propenylene group, cyclohexadienylene group; phenylene group, naphthylene group, etc. A divalent group of an aromatic hydrocarbon; a divalent group obtained by combining a plurality of the above divalent groups such as a benzylene group and a biphenylene group.

  Among these, X is preferably a direct bond or a group having a number of carbons connecting between a phosphorus atom and A (hereinafter referred to as “linked carbon number” as appropriate) of 6 or less, more preferably A group having 3 or less linked carbon atoms, more preferably a group having 2 or less linked carbon atoms, and particularly preferably a group having 1 or less linked carbon atoms. Of these, direct bonding is most preferable.

  In addition, the above divalent group may be optionally substituted as long as it does not adversely affect the stability of the rare earth complex of the present invention. Specific examples of the substituent include a hydrocarbon group and a fluorinated hydrocarbon group. Of these, those having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a trifluoromethyl group are preferable. In addition, as for the said substituent, only 1 type may be substituted and 2 or more types may be substituted by arbitrary combinations and ratios. The number of substituents may be 1 or 2 or more.

Said A shows a heterocyclic group. However, A is the highest occupied orbital (HOMO) calculated | required by the molecular orbital calculation of the heterocyclic compound which comprises the said heterocyclic group (namely, the compound which has the structure which bonded the hydrogen atom to the bond of the said heterocyclic group). ) Has a molecular orbital energy value larger than that of the benzene ring.
As the molecular orbital calculation method, known methods such as an ab initio MO method, an MP3 method, and an HF / 6-31G method can be arbitrarily used, but an ab initio MO method is preferable.

  The molecular orbital energy value of HOMO of the heterocyclic compound is usually −9.3 eV or less, preferably −9.4 eV or less, more preferably −9.5 eV or less, and particularly preferably −9.6 eV or less. The lower limit is usually −15 eV or more, preferably −12 eV or more. If the molecular orbital energy value is too high, it may be decomposed by photooxidation, and if it is too low, energy transfer to the metal may be difficult to occur.

  Specific examples of the heterocyclic group include a pyridyl group, a quinoxalinyl group, an isoquinolyl group, a quinolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group and the like, or a condensed polycyclic group composed of a nitrogen-containing 6-membered ring group or a 6-membered ring. A 5-membered heterocyclic group having an electron-withdrawing substituent, such as a pyrazolyl group, an imidazolyl group, an oxazolyl group, a thiazolyl group, a furyl group, and a thienyl group; a benzothienyl group, a dibenzothienyl group, a dibenzofuranyl group, a phenoxathi And 5-membered hetero ring group having a condensed ring such as inyl group. Examples of preferred electron-withdrawing substituents include halogen atoms, haloalkyl groups, haloaryl groups, pyridyl groups, nitro groups, cyano groups, carbonyl groups, carboxyl groups, amide groups, and more. Preferred are a fluorine atom, a fluorinated alkyl group and a fluorinated aryl group, and more preferred are a fluorine atom and a trifluoromethyl group.

Among the groups represented by the above -X-A, preferable specific examples include the groups described below. Me represents a methyl group.

In addition, A and X mentioned above and -X-A may each be used only by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
In addition, as the bonding position of A (that is, the position of the bond in the heterocyclic group), the hetero atom is preferably the α position of the carbon bonded to X. This is because a complex stabilization effect due to coordination to metal is expected.

Of R ^{1 to} R ^3, the monovalent substituent other than the group represented by —X—A is not particularly limited as long as it does not adversely affect the rare earth complex. Specific examples thereof include optionally substituted carbon groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. A linear, branched or cyclic saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms; an optionally substituted vinyl group, allyl group, propenyl group, isopropenyl group, etc. A branched or cyclic unsaturated aliphatic hydrocarbon group; an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms such as a phenyl group and a naphthyl group; an optionally substituted methoxy group; Examples thereof include an alkoxy group having 1 to 20 carbon atoms such as an ethoxy group and a propoxy group. Of these, an aromatic hydrocarbon group is preferred.

  In addition, since the types of these substituents and the number of carbons thereof affect the solubility of the rare earth complex of the present invention, the preferred range varies depending on the use and embodiment using the rare earth complex of the present invention, but its fat solubility and dispersibility. In view of the above, an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 6 or more carbon atoms is preferable. Furthermore, as these aliphatic hydrocarbon groups, those having a branch are more preferable, and those having 8 or more carbon atoms are more preferable.

  The above-mentioned saturated aliphatic hydrocarbon group, unsaturated aliphatic hydrocarbon group, aromatic hydrocarbon group and substituent of the alkoxy group are optional as long as the effects of the present invention are not significantly impaired. Specific examples thereof include halogen atoms, alkyl groups, haloalkyl groups, aryl groups, haloaryl groups, nitro groups, cyano groups, carbonyl groups, carboxyl groups, amide groups, and the like. Among these, a fluorine atom, an alkyl group, a fluorinated alkyl group, an aryl group, a fluorinated aryl group and the like are preferable, and a fluorine atom, an alkyl group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, a phenyl group, A fluorinated phenyl group and the like are more preferable, and a fluorine atom and a trifluoromethyl group are particularly preferable. In addition, only 1 type may substitute these substituents and 2 or more types may be substituted by arbitrary combinations and ratios. The number of substituents may be 1 or 2 or more. Further, when a plurality of the substituents are present, two or more substituents may be bonded to each other to form one group.

R ^{1 to} R ³ may be the same or different from each other, but at least two of them are preferably the same group. Moreover, it is convenient and preferable from a synthetic viewpoint that two are the same monovalent substituents and the remaining one is a group represented by -X-A. Two or more of R ^{1 to} R ³ may be bonded to each other to form a ring.

  The molecular weight of the ligand represented by the above formula (1) is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 100 or more, preferably 150 or more, more preferably 200 or more, and usually 1000 or less, preferably 800 or less, more preferably 700 or less. If the molecular weight is too small, the heat resistance may decrease, and if it is too large, purification may be difficult.

Among the ligands represented by the above formula (1), the following can be mentioned as examples of preferable ones.

[1-2-1-2. Ligand represented by formula (2)]
In formula (2), R ⁴ , R ⁵ , R ⁴ ′ and R ⁵ ′ each independently represent a monovalent substituent. However, at least one of R ⁴ , R ⁵ , R ⁴ ′ and R ⁵ ′ is a group represented by —X—A. Here, examples of the monovalent substituent other than -X-A and -X-A include the same groups as those described in the description of R ^{1 to} R ³ in the above formula (1). It is done.

R ⁴ , R ⁵ , R ⁴ ′ and R ⁵ ′ may be the same or different from each other, but at least R ⁴ and R ⁵ are the same group or R ⁴ ′ and R ⁵ are the same. ⁵ ′ is preferably the same group, and R ⁴ , R ⁵ , R ⁴ ′ and R ⁵ ′ are more preferably all the same group. R ⁴ and R ⁵ , or R ⁴ ′ and R ⁵ ′ may be bonded to form a ring.

R ⁶ represents a divalent linking group. Specific examples include the same groups as the divalent linking groups described in the above description of X.

  The molecular weight of the compound represented by the formula (2) is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 200 or more, preferably 300 or more, more preferably 400 or more, and usually 2000 or less. , Preferably 1600 or less, more preferably 1400 or less. If the molecular weight is too small, the heat resistance may decrease, and if it is too large, purification may be difficult.

Of the ligands represented by the above formula (2), the following can be given as examples of preferable ones.

[1-2-1-3. Method for producing ligand represented by formula (1) or (2)]
The ligand represented by the formula (1) or (2) can be arbitrarily produced according to a known method.
Especially, the synthetic route described as a following formula (a)-(c) is mentioned as a preferable example among the manufacturing methods of the ligand represented by Formula (1). The following formula (a) is an example of the production method in the case where R ¹ , R ² and R ³ are all the same group R. The following formula (b) is an example of a production method in the case where ^two of R ¹ , R ² and R ³ are the same group R and one is another group R ′. Furthermore, the following formula (c) is an example of the production method in the case where ^one of R ¹ , R ² and R ³ is a group R and two are other groups R ′. In the following formulas (a) to (c) and formulas (d) to (g) described later, M represents a metal atom.

That is, a metal compound RM is prepared by reacting a halide R—X ′ of a compound corresponding to a substituent of R ^{1 to} R ³ with an alkyl lithium such as butyl lithium or a Grignard reagent, and various phosphine halides. (In Formula (a), PCl ₃ , in Formula (b) R′PCl ₂ , in Formula (c) R ′ ₂ PCl), various phosphine compounds (in Formula (a), PR ₃ , Formula (b ) To obtain PR ₂ R ′, in formula (c) to PRR ′ ₂ ), and subsequently react with an oxidizing agent such as hydrogen peroxide to form a ligand (PR ₃ O in formula (a), formula (b) And PR ₂ R′O, and in the formula (c), PRR ′ ₂ O) is obtained.

Specific operation and reaction conditions are arbitrary as long as the target ligand can be obtained. For example, the reaction can be performed as follows. That is, a halide of a compound corresponding to a substituent of R ^{1 to} R ³ and an organic solvent such as dehydrated diethyl ether or THF are mixed and cooled to −78 ° C. to 0 ° C. under inert gas conditions. 1.0 to 1.2 equivalents of an alkyl lithium and a Grignard reagent are mixed and reacted at room temperature under reflux conditions for 1 to 10 hours to prepare a metal compound in the system. And after cooling to -78 degreeC-0 degreeC again, the quantity corresponding to this metal compound (the quantity used as 0.8-1 equivalent in terms of the number of halogen atoms in a phosphine) is mixed, and room temperature- By reacting under reflux conditions for 0.5 to 10 hours, an intermediate phosphine derivative is obtained. Thereafter, after removing the inorganic salt from the reaction system, the phosphine derivative is purified by recrystallization. This phosphine derivative is dissolved in a solvent such as acetone, ethanol, THF, etc., 1 to 10 equivalents of 30% aqueous hydrogen peroxide is mixed at 0 ° C. to room temperature, and stirred at room temperature for 1 to 10 hours. Can be obtained. The purification can be performed by, for example, column chromatography or recrystallization.

For example, as shown in the following formula (d), if a disubstituted phosphinic acid chloride is used instead of the halogenated phosphine, the final oxidation reaction can be simplified.

Further, when a phosphine oxide compound in which R ^{1 to} R ³ are all different is produced as a ligand, it corresponds to each of trichlorophosphine and substituents R ^{1 to} R ³ as described in the following formula (e). It can be obtained by stepwise reaction with metal compounds (R ¹ -M, R ² -M, R ³ -M).

On the other hand, as a preferable example of the method for producing the ligand represented by the formula (2), as described in the following (f) and (g), the halide corresponding to the starting material corresponds to R ⁶ . The method of manufacturing according to the manufacturing method of the compound represented by the said Formula (1) except using a bifunctional thing is mentioned.

[1-2-1-4. Other neutral ligands]
The rare earth complex of the present invention may have a neutral ligand other than the ligand represented by either the above formula (1) or (2) unless the effects of the present invention are significantly impaired. .
However, from the viewpoint of more effectively demonstrating the effects of the present invention, it is preferable to use only the ligand represented by either the above formula (1) or (2) as the neutral ligand.

[1-2-2. Anionic ligand]
The number of anionic ligands is determined according to the valence of the central metal element. For example, when the central metal element is a trivalent metal, the valence of the anionic ligand coordinated to the central metal is set to -3. If a specific example is given, if the said anionic ligand is a monoanionic ligand, the rare earth complex of this invention will have three said anionic ligands.

  The type of the anionic ligand is not particularly limited as long as it can be coordinated to the central metal, and any known ligand for the rare earth complex can be appropriately selected. For example, examples of the monoanionic ligand include diketone compounds, compounds having a carboxylic acid group, compounds having a phosphonic acid group, and compounds having a sulfonic acid group.

（式（３）中、Ｒ⁷及びＲ⁹は、それぞれ独立して、パーフルオロアルキル基、電子吸引性基を有する芳香族炭化水素基、又は、置換基を有していても良い複素環基を示し、Ｒ⁸は、水素原子、重水素原子、アルキル基、置換基を有しても良い芳香族炭化水素基、又は、置換基を有しても良い複素環基を示し、式（４）中、Ｒ¹⁰は、電子吸引性置換基を有する芳香族炭化水素基、又は、置換基を有しても良い複素環基を示す。） Among these, preferable ligands include diketone compounds, compounds having a carboxylic acid group, or compounds having a phosphonic acid group, more preferably a diketone compound or a compound having a carboxylic acid group, and even more preferable. What is represented by following formula (3) or (4) is mentioned.

(In Formula (3), R ⁷ and R ⁹ are each independently a perfluoroalkyl group, an aromatic hydrocarbon group having an electron-withdrawing group, or an optionally substituted heterocyclic group. R ⁸ represents a hydrogen atom, a deuterium atom, an alkyl group, an aromatic hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent. ), R ¹⁰ represents an aromatic hydrocarbon group having an electron-withdrawing substituent or a heterocyclic group which may have a substituent.

In the above formula (3), R ⁷ and R ⁹ are each independently a perfluoroalkyl group, an aromatic hydrocarbon group having an electron-withdrawing group, or an optionally substituted heterocyclic group. Indicates.

Of the groups constituting R ⁷ and R ⁹ , examples of the perfluoroalkyl group include linear, branched or cyclic groups such as a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group. Can be mentioned. Of these, linear ones are preferred.
The carbon number of the perfluoroalkyl group is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 1 or more, and usually 8 or less, preferably 6 or less.

Of the aromatic hydrocarbon groups having an electron-withdrawing group among the groups constituting R ⁷ and R ⁹ , examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group having an electron-withdrawing group described later, Examples thereof include a phenanthrenyl group, a triphenylene group, and a biphenylene group. Among these, a phenyl group and a naphthyl group are preferable, and a naphthyl group is more preferable.
Examples of the electron-withdrawing group possessed by the aromatic hydrocarbon group include a halogen atom, a haloalkyl group, a haloaryl group, a pyridyl group, a nitro group, a cyano group, a carbonyl group, a carboxyl group, and an amide group. Among these, a fluorine atom, a fluorinated alkyl group, and a fluorinated aryl group are preferable, and a fluorine atom and a perfluoroalkyl group are more preferable. In addition, the aromatic hydrocarbon group may have only one type of electron withdrawing group, and may have two or more types in any combination and ratio. The number of electron-withdrawing groups may be 1 or 2 or more.
Of the aromatic ring groups having an electron withdrawing group, preferred examples include a fluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a nitrophenyl group, and a cyanophenyl group.

In the heterocyclic group which may have a substituent among the groups constituting R ⁷ and R ⁹ , examples of the heterocyclic group include a pyridyl group, a quinoxalinyl group, an isoquinolyl group, a quinolyl group, a pyrazinyl group, and a pyrimidinyl group. Groups, nitrogen-containing 6-membered cyclic groups such as pyridazinyl groups or condensed polycyclic groups composed of 6-membered rings; 5-membered heterocyclic groups such as pyrazolyl groups, imidazolyl groups, oxazolyl groups, thiazolyl groups, furyl groups, thienyl groups A 5-membered heterocyclic group having a condensed ring such as a benzothienyl group, a dibenzothienyl group, a dibenzofuranyl group, or a phenoxathiinyl group; Among these, a nitrogen-containing 6-membered cyclic group and a condensed polycyclic group composed of a 6-membered ring are preferable.
The substituent that may be substituted on the heterocyclic group is not limited as long as the effects of the present invention are not significantly impaired. Examples thereof include a halogen atom, an alkyl group, and the above-described electron-withdrawing group. In addition, as for a substituent, only 1 type may be substituted and 2 or more types may be substituted by arbitrary combinations and ratios. The number of substituents may be 1 or 2 or more.

In the above formula (3), R ⁸ represents a hydrogen atom, a deuterium atom, an alkyl group, an aromatic hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent. .
Of the groups constituting R ⁸ , the carbon number of the alkyl group is arbitrary as long as the effects of the present invention are not significantly impaired, but it is usually 1 or more and usually 6 or less. The alkyl group is preferably a chain. Among these, the alkyl group is preferably a methyl group.

Among the groups constituting R ⁸ , examples of the aromatic hydrocarbon group which may have a substituent include a phenyl group and a tolyl group. In addition, examples of the substituent that the aromatic hydrocarbon group may have include the same groups as the substituent that the heterocyclic group constituting R ⁷ and R ⁹ may have.

Among the groups constituting R ⁸ , examples of the heterocyclic group which may have a substituent include the same groups as the heterocyclic groups which may have a substituent described in the paragraphs of R ⁷ and R ^9. Can be mentioned.

In said formula (4), R < ¹⁰ > shows the aromatic hydrocarbon group which has an electron withdrawing substituent, or the heterocyclic group which may have a substituent.
Among the groups constituting R ¹⁰ , the aromatic hydrocarbon group having an electron-withdrawing substituent and the heterocyclic group which may have a substituent have been described in the above R ⁷ and R ⁹ sections. The same groups as those mentioned above can be mentioned.

Preferable specific examples of the anionic ligand represented by the above formula (3) or (4) include those shown below. Of these, diketone compounds are particularly preferred.

[1-3. Method for producing rare earth complex of the present invention]
The rare earth complex of the present invention can be arbitrarily produced according to a known method. An example of the production method is as follows: an anionic ligand corresponding to the valence of the central metal element and a ligand represented by the above (1) or (2) in an organic solvent under basic conditions. Thus, it can be obtained by reacting with a rare earth metal salt.

As a specific example, when the rare earth metal salt is Eu halide, 3.0 to 3.1 equivalents of an anionic ligand and 1 to 6 equivalents of the ligand are mixed with ethanol or isopropanol. After dissolving in an organic solvent and mixing a base such as triethylamine in a range of usually 3 to 6 equivalents, a solution of EuCl ₃ · 6H ₂ O in ethanol or the like is added dropwise and stirred at room temperature for 1 to 4 hours to produce a crude product You can get things. For the purification, after removing the solvent, the inorganic salt is washed away with water and recrystallized using methanol or the like.

[1-4. Advantages of rare earth complex of the present invention]
The rare earth complex of the present invention has a heterocycle having a specific structure in the partial structure -XA of the ligand. This allows the ligand to coordinate to the central metal in the molecule or between the molecules other than the phosphine oxide portion. For this reason, the strong durability accompanying coordination stabilization is maintained.

[2. Rare earth complex phosphor of the present invention]
The rare earth complex of the present invention functions as a rare earth complex phosphor that emits fluorescence using light in the near ultraviolet to visible region as an excitation light source (hereinafter referred to as “phosphor of the present invention” as appropriate).

  When the excitation wavelength range of the phosphor of the present invention is given, it is usually 200 to 450 nm when the central metal of the phosphor of the present invention is Eu, and is usually 200 to 440 nm when the central metal is Tb. When the central metal is Tm or Ce, it is usually 200 to 400 nm.

  The maximum emission peak wavelength of the phosphor of the present invention varies depending on the type of rare earth element which is the central metal of the complex. For example, when the central metal is Eu, it is usually 600 to 630 nm, when the central metal is Tb, it is 530 to 550 nm, and when the central metal is Tm or Ce, it is 440 to 460 nm. .

The phosphor of the present invention is irradiated with excitation light at an excitation light intensity of 500 mW / cm ² in a nitrogen atmosphere at room temperature, and the emission peak area determined from the emission spectrum after 90 minutes is immediately after irradiation (after 0 minutes). The value obtained by dividing the light emission peak area (referred to as “luminance maintenance ratio”) is usually 95% or more, preferably 97% or more, more preferably 98% or more, still more preferably 99% or more, particularly preferably 100. %.

  The phosphor of the present invention has a thermal decomposition temperature (TG) determined by a differential thermal balance / mass spectrometry simultaneous measurement apparatus (TG-DTA apparatus) of usually 70 ° C. or higher, preferably 80 ° C. or higher, more preferably 90 ° C. or higher. It is.

The phosphor of the present invention has an external quantum efficiency of usually 20% or more, preferably 25% or more, more preferably 30% or more, still more preferably 35% or more, according to the measurement method described later (see Examples). Particularly preferably, it is 40% or more.
The internal quantum efficiency of the phosphor of the present invention is usually 50% or more, preferably 60% or more, more preferably 70% or more, still more preferably 80% or more, and particularly preferably 85% or more.
The absorption efficiency of the phosphor of the present invention is usually 40% or more, preferably 50% or more, more preferably 55% or more.

  The phosphor of the present invention is excited with light in the above-mentioned wavelength range, and particularly preferably excited with light from a light source having an emission maximum in the wavelength range of 380 nm to 450 nm. No bright emission. Moreover, in the partial structure -X-A of the ligand, by having a heterocycle having a specific structure, the ligand can be coordinated to the central metal within the molecule or between the molecules other than the phosphine oxide portion. And has high durability (particularly durability against light and oxygen) associated with coordination stabilization.

  For this reason, the phosphor of the present invention using such a rare earth complex can be effectively used in a light emitting device using a light emitting diode having a light emission maximum in the near ultraviolet to visible range. It is possible to achieve high-efficiency light emission by light-emitting diode excitation and suppression of light degradation while ensuring the features, that is, the manufacturing cost and high dispersibility in the medium due to the low specific gravity.

The phosphor of the present invention can be used not only as a monochromatic light-emitting device but also as a white light-emitting device using a combination of RGB. By using the light emitting device, it can be expected to be applied to illumination, a backlight for liquid crystal, a headlight for automobile, general illumination and the like.
Furthermore, since the phosphor of the present invention has a high absorption efficiency of near-ultraviolet light (NUV) and does not leak NUV to the outside, it is useful for protecting liquid crystals when used in a liquid crystal backlight for NUVLED.
The phosphor of the present invention can also be used as an NUV cut film or sheet. These can be combined with organic EL and used as a color conversion material for organic EL.

[3. Phosphor-containing composition]
The phosphor of the present invention can be mixed with a liquid medium and used as a composition containing the phosphor of the present invention and a liquid medium. The phosphor of the present invention dispersed in a liquid medium will be referred to as “the phosphor-containing composition of the present invention” as appropriate.

[3-1. Phosphor]
There is no restriction | limiting in the kind of fluorescent substance of this invention contained in the fluorescent substance containing composition of this invention, It can select arbitrarily from what was mentioned above. Moreover, the fluorescent substance of this invention contained in the fluorescent substance containing composition of this invention may be only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
Furthermore, you may make the fluorescent substance containing composition of this invention contain fluorescent substances other than the fluorescent substance of this invention, unless the effect of this invention is impaired remarkably.

[3-2. Liquid medium]
The liquid medium used in the phosphor-containing composition of the present invention is not particularly limited as long as the performance of the phosphor is not impaired within the intended range. For example, any inorganic material and / or organic material may be used as long as it exhibits liquid properties under the desired use conditions, suitably disperses the phosphor of the present invention, and does not cause an undesirable reaction. it can.

  As the inorganic material, for example, a solution obtained by hydrolytic polymerization of a solution containing a metal alkoxide, a ceramic precursor polymer or a metal alkoxide by a sol-gel method, or a combination thereof is solidified (for example, a siloxane bond). Inorganic materials having

  Examples of organic materials include thermoplastic resins, thermosetting resins, and photocurable resins. Specific examples include methacrylic resins such as polymethylmethacrylate; styrene resins such as polystyrene and styrene-acrylonitrile copolymers; polycarbonate resins; polyester resins; phenoxy resins; butyral resins; polyvinyl alcohols; Cellulose-based resins such as cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins.

Among these, in particular, when the phosphor of the present invention is used in a light-emitting device having a high output such as illumination, it is preferable to use a silicon-containing compound as a liquid medium for the purpose of improving heat resistance, light resistance and the like.
The silicon-containing compound refers to a compound having a silicon atom in the molecule, for example, an organic material (silicone material) such as polyorganosiloxane, an inorganic material such as silicon oxide, silicon nitride, silicon oxynitride, and borosilicate, Examples thereof include glass materials such as phosphosilicate and alkali silicate. Among these, silicone materials are preferable from the viewpoint of ease of handling.

The silicone material generally refers to an organic polymer having a siloxane bond as a main chain, and examples thereof include a compound represented by the general composition formula (i) and / or a mixture thereof.
(R ^1a R ^2a R ^3a SiO _1/2 ) _Q1 (R ^4a R ^5a SiO _2/2 ) _Q2 (R ^6a SiO _3/2 ) _Q3 (SiO _4/2 ) _Q4 Formula (i)
In general formula (i), R ^1a ~R ^6a represents one selected organic functional group, hydroxyl group, from the group consisting of a hydrogen atom. R ^{1a to} R ^6a may be the same or different.
In the above formula (i), Q1, Q2, Q3, and Q4 are numbers that are 0 or more and less than 1, respectively, and satisfy Q1 + Q2 + Q3 + Q4 = 1.
When used for sealing a semiconductor light emitting device, the silicone material can be used after being sealed with a liquid silicone material and then cured by heat or light.

  When silicone materials are classified according to the curing mechanism, silicone materials such as an addition polymerization curing type, a condensation polymerization curing type, an ultraviolet curing type, and a peroxide vulcanization type can be generally cited. Among these, addition polymerization curing type (addition type silicone material), condensation curing type (condensation type silicone material), and ultraviolet curing type are preferable. Hereinafter, the addition type silicone material and the condensation type silicone material will be described.

  The addition-type silicone material refers to a material in which a polyorganosiloxane chain is crosslinked by an organic addition bond. Typical examples include compounds having a Si—C—C—Si bond at the crosslinking point obtained by reacting vinylsilane and hydrosilane in the presence of an addition catalyst such as a Pt catalyst. As these, commercially available products can be used. Specific examples of addition polymerization curing type trade names include “LPS-1400”, “LPS-2410”, and “LPS-3400” manufactured by Shin-Etsu Chemical Co., Ltd.

  On the other hand, examples of the condensation-type silicone material include compounds obtained by hydrolysis and polycondensation of alkylalkoxysilane and having a Si—O—Si bond at a crosslinking point. Specific examples thereof include polycondensates obtained by hydrolysis and polycondensation of compounds represented by the following general formula (ii) and / or (iii) and / or oligomers thereof. In addition, only 1 type may be used for these compounds and / or its oligomer, and 2 or more types may be used together by arbitrary combinations and a ratio.

M ^{1m +} X ¹ _n Y ¹ _mn General formula (ii)
(In the general formula (ii), M ¹ represents at least one element selected from silicon, aluminum, zirconium, and titanium, X ¹ represents a hydrolyzable group, and Y ¹ represents a monovalent group. Represents an organic group, m represents an integer of 1 or more representing the valence of M ¹ , and n represents an integer of 1 or more representing the number of X ¹ groups, where m ≧ n.

(M ^{1s +} X ¹ _t Y ¹ _st-1 ) _u Y ² general formula (iii)
(In general formula (iii), M ¹ represents at least one element selected from silicon, aluminum, zirconium and titanium, X ¹ represents a hydrolyzable group, and Y ¹ represents a monovalent group. Y ² represents an u-valent organic group, s represents an integer of 1 or more representing the valence of M ¹ , t represents an integer of 1 or more and s−1 or less, u Represents an integer of 2 or more.)

  Further, the condensation type silicone material may contain a curing catalyst. As this curing catalyst, for example, a metal chelate compound or the like can be suitably used. The metal chelate compound preferably contains one or more of Ti, Ta, and Zr, and more preferably contains Zr. In addition, only 1 type may be used for a curing catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of such condensation type silicone materials include members for semiconductor light emitting devices described in JP-A Nos. 2007-112973 to 112975, JP-A No. 2007-19459, and Japanese Patent Application No. 2006-176468. Is preferred.

Of the condensed silicone materials, particularly preferred materials will be described below.
Silicone-based materials generally have a problem of poor adhesion to semiconductor light-emitting elements, substrates on which the elements are arranged, packages, and the like, but as silicone-based materials having high adhesion, the following features [1] to A condensation type silicone material having one or more of [3] is preferred.
[1] The silicon content is 20% by weight or more.
[2] The solid Si-nuclear magnetic resonance (NMR) spectrum measured by the method described in detail later has at least one peak derived from Si in the following (a) and / or (b).
(A) A peak whose peak top position is in a region where the chemical shift is −40 ppm or more and 0 ppm or less with respect to tetramethoxysilane, and the half width of the peak is 0.3 ppm or more and 3.0 ppm or less.
(B) A peak whose peak top position is in a region where the chemical shift is −80 ppm or more and less than −40 ppm with respect to tetramethoxysilane, and the half width of the peak is 0.3 ppm or more and 5.0 ppm or less.
[3] The silanol content is 0.1% by weight or more and 10% by weight or less.

  In the present invention, among the above features [1] to [3], a silicone material having the feature [1] is preferable. More preferably, a silicone material having the above features [1] and [2] is preferable. Particularly preferably, a silicone material having all of the above features [1] to [3] is preferable. Hereinafter, the above features [1] to [3] will be described.

[Feature [1] (Silicon content)]
The silicon content of the silicone material suitable for the present invention is usually 20% by weight or more, preferably 25% by weight or more, and more preferably 30% by weight or more. On the other hand, the upper limit is usually in the range of 47% by weight or less because the silicon content of the glass composed solely of SiO ₂ is 47% by weight.

  Note that the silicon content of the silicone-based material is calculated based on the results of performing inductively coupled plasma spectroscopy (hereinafter abbreviated as “ICP” where appropriate) using, for example, the following method. be able to.

{Measurement of silicon content}
Silicone material is baked in a platinum crucible in the air at 450 ° C. for 1 hour, then at 750 ° C. for 1 hour, and at 950 ° C. for 1.5 hours to remove the carbon component, and then a small amount of residue is obtained. Add more than 10 times the amount of sodium carbonate and heat with a burner to melt, cool this, add demineralized water, and adjust the pH to neutral with hydrochloric acid to a few ppm as silicon. ICP analysis is performed.

[Feature [2] (Solid Si-NMR spectrum)]
When a solid Si-NMR spectrum of a silicone-based material suitable for the present invention is measured, at least one peak in the peak region of (a) and / or (b) derived from a silicon atom to which a carbon atom of an organic group is directly bonded, Preferably, a plurality of peaks are observed.

When organized by chemical shift, in the silicone-based material suitable for the present invention, the half width of the peak described in (a) is generally the case of the peak described in (b) described later because molecular motion is less restricted. It is smaller, usually 3.0 ppm or less, preferably 2.0 ppm or less, and usually 0.3 ppm or more.
On the other hand, the full width at half maximum of the peak described in (b) is usually 5.0 ppm or less, preferably 4.0 ppm or less, and usually 0.3 ppm or more, preferably 0.4 ppm or more.

If the half-value width of the peak observed in the chemical shift region is too large, the molecular motion is constrained and strain is large, cracks are likely to occur, and the member may be inferior in heat resistance and weather resistance. For example, when a large amount of tetrafunctional silane is used, or when a large internal stress is accumulated by rapid drying in the drying process, the half width range becomes larger than the above range.
In addition, if the half width of the peak is too small, Si atoms in the environment will not be involved in siloxane crosslinking, and heat resistance is higher than substances formed mainly from siloxane bonds, such as examples where trifunctional silane remains in an uncrosslinked state. -It may be a member inferior in weather resistance.
However, in a silicone material containing a small amount of Si component in a large amount of organic component, good heat resistance / light resistance and coating performance can be obtained even if the peak of the above-mentioned half width range is observed at -80 ppm or more. There may not be.

  The value of the chemical shift of the silicone material suitable for the present invention can be calculated based on the results of solid Si-NMR measurement using the following method, for example. In addition, analysis of measurement data (half-width or silanol amount analysis) is performed by a method of dividing and extracting each peak by, for example, waveform separation analysis using a Gaussian function or a Lorentz function.

{Solid Si-NMR spectrum measurement and silanol content calculation}
When a solid Si-NMR spectrum is measured for a silicone material, solid Si-NMR spectrum measurement and waveform separation analysis are performed under the following conditions. Further, from the obtained waveform data, the half width of each peak is determined for the silicone material. In addition, from the ratio of the peak area derived from silanol to the total peak area, the ratio (%) of silicon atoms that are silanols in all silicon atoms is obtained, and the silanol content is determined by comparing with the silicon content analyzed separately. Ask.

{Device conditions}
Equipment: Chemagnetics Infinity CMX-400 Nuclear Magnetic Resonance Spectrometer
²⁹ Si resonance frequency: 79.436 MHz
Probe: 7.5 mmφ CP / MAS probe Measurement temperature: room temperature Sample rotation speed: 4 kHz
Measurement method: Single pulse method
¹ H decoupling frequency: 50 kHz
²⁹ Si flip angle: 90 °
²⁹ Si 90 ° pulse width: 5.0μs
Repeat time: 600s
Integration count: 128 Observation width: 30 kHz
Broadening factor: 20Hz
Reference Sample Tetramethoxysilane For silicone-based materials, 512 points are taken as measurement data, zero-filled to 8192 points, and Fourier transformed.

{Waveform separation analysis method}
For each peak of the spectrum after Fourier transform, optimization calculation is performed by a non-linear least square method with the center position, height, and half width of the peak shape created by Lorentz waveform and Gaussian waveform or a mixture of both as variable parameters.
For peak identification, refer to AIChE Journal, 44 (5), p.1141, 1998, etc.

[Feature [3] (silanol content)]
The silicone material suitable for the present invention has a silanol content of usually 0.1% by weight or more, preferably 0.3% by weight or more, and usually 10% by weight or less, preferably 8% by weight or less, more preferably The range is 5% by weight or less. By reducing the silanol content, the silanol-based material has excellent performance with little change over time, excellent long-term performance stability, and low moisture absorption and moisture permeability. However, since a member containing no silanol is inferior in adhesion, there exists an optimum range for the silanol content as described above.

  The silanol content of the silicone-based material can be obtained by, for example, using the method described in the section of [Feature [2] (Solid Si-NMR spectrum)] {Solid Si-NMR spectrum measurement and silanol content calculation}. Si-NMR spectrum measurement is performed, and the ratio (%) of silicon atoms that are silanols in all silicon atoms is determined from the ratio of the peak area derived from silanol to the total peak area, and is compared with the separately analyzed silicon content. This can be calculated.

In addition, since the silicone-based material suitable for the present invention contains an appropriate amount of silanol, the silanol usually bonds with hydrogen at the polar portion present on the device surface, thereby exhibiting adhesion. Examples of the polar part include a hydroxyl group and a metalloxane-bonded oxygen.
In addition, the silicone material suitable for the present invention is usually heated in the presence of an appropriate catalyst to form a covalent bond by dehydration condensation with the hydroxyl group on the device surface, thereby exhibiting stronger adhesion. can do.
On the other hand, if there is too much silanol, the inside of the system will thicken and it will be difficult to apply, or it will become more active and solidify before the light-boiling components volatilize by heating, resulting in increased foaming and internal stress It may occur and induce cracks.

[Content of liquid medium]
The content of the liquid medium is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 50% by weight or more, preferably 75% by weight or more, based on the entire phosphor-containing composition of the present invention. It is 99 weight% or less, Preferably it is 95 weight% or less. When the amount of the liquid medium is large, no particular problem occurs. However, in order to obtain a desired chromaticity coordinate, color rendering index, luminous efficiency, etc. in the case of a semiconductor light emitting device, it is usually at a blending ratio as described above. It is desirable to use a liquid medium. On the other hand, if the amount of the liquid medium is too small, there is a possibility that it is difficult to handle due to lack of fluidity.

  The liquid medium mainly serves as a binder in the phosphor-containing composition of the present invention. Although only 1 type may be used for a liquid medium, you may use 2 or more types together by arbitrary combinations and a ratio. For example, when a silicon-containing compound is used for the purpose of heat resistance, light resistance, etc., other thermosetting resins such as an epoxy resin may be contained to the extent that the durability of the silicon-containing compound is not impaired. In this case, the content of the other thermosetting resin is usually 25% by weight or less, preferably 10% by weight or less based on the total amount of the liquid medium as the binder.

[3-3. Other ingredients]
The phosphor-containing composition of the present invention may contain other components in addition to the phosphor and the liquid medium as long as the effects of the present invention are not significantly impaired. Moreover, only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio.

[4. Laminate]
The laminate of the present invention comprises a layer containing the above-described phosphor of the present invention (hereinafter appropriately referred to as “the phosphor-containing layer of the present invention”). In addition, the laminate of the present invention is usually configured by including the phosphor-containing layer of the present invention on a substrate such as a substrate or a carrier. In addition, another constituent layer such as an adhesive layer, a surface coat layer, or an antireflection layer is provided between the substrate and the phosphor-containing layer of the present invention and / or on the phosphor-containing layer of the present invention. May be. Moreover, there is no restriction | limiting in the lamination | stacking order of these layers, What is necessary is just to set arbitrarily according to the various uses of the laminated body of this invention.

  There is no restriction | limiting in the material which comprises a base | substrate, For example, arbitrary materials, such as wood, resin, glass, can be mentioned. Further, the shape of the substrate is not limited, and may be appropriately selected from a spherical shape, a sheet / film shape, and the like according to various uses.

  The phosphor-containing layer of the present invention is not limited as long as it is formed containing at least the phosphor of the present invention. Usually, the phosphor-containing layer contains a binder such as the above-described liquid medium, and the phosphor is formed by this binder. It is intended to be retained in the layer.

  The concentration of the phosphor in the phosphor-containing layer of the present invention can be arbitrarily set according to the use of the laminate of the present invention, but is usually 1% by weight or more, preferably 5% by weight or more, more preferably It is 10% by weight or more, and is usually 90% by weight or less, preferably 85% by weight or less, more preferably 80% by weight or less. If the concentration of the phosphor is too low, the luminance may decrease, and if it is too high, uneven coloring due to crystallization may occur.

The thickness of the phosphor-containing layer can be arbitrarily set according to the use of the laminate of the present invention, but is usually 10 ⁻² μm or more, preferably 10 ⁻¹ μm or more, more preferably ¹ μm or more. Also, it is usually 10 ⁴ μm or less, preferably 10 ³ μm or less, more preferably 10 ² μm or less. If the film thickness is too thin, the excitation light may be leaked, and if it is too thick, the brightness may be reduced due to light scattering.

  In addition, arbitrary additives, a heat-resistant deterioration preventing agent, a lubricant, an antistatic agent, a dispersing agent, etc. can be mix | blended with the fluorescent substance containing layer and base | substrate mentioned above as needed.

  There is no restriction | limiting in the manufacturing method of the laminated body of this invention. For example, the phosphor-containing composition of the present invention can be produced by molding and filming using a molding technique such as injection molding, T-die molding, calendar molding, or compression molding, and then bonding to a substrate. Further, for example, the phosphor-containing composition of the present invention can be directly dyed on a substrate. Furthermore, for example, the phosphor-containing composition of the present invention can be coated and dried on a substrate. For example, it can also be produced by directly laminating the phosphor of the present invention directly on the substrate via an adhesive layer as necessary. Among these, the manufacturing method of applying and drying on a substrate is preferable.

Hereinafter, as an example of the laminate of the present invention, a projector screen will be described with reference to the drawings.
FIG. 1 is a diagram schematically showing a projector screen as an example of the laminate of the present invention. The screen 1 includes a sheet 2 as a base and a phosphor-containing layer 3 formed on the surface of the sheet 2. Here, the phosphor-containing layer 3 is formed by applying and drying the phosphor-containing composition of the present invention on the surface of the sheet 2. When the phosphor-containing layer 3 is irradiated with light in the ultraviolet to near-ultraviolet wavelength range, The phosphor in the body-containing layer 3 emits light.

When the screen 1 is used, an image is projected from the projector 4 toward the screen 1. At this time, since the light used for projecting the image is mainly visible light, the phosphor in the phosphor-containing layer 3 does not emit light, and the image quality of the image does not deteriorate.
Further, during use of the screen 1, ultraviolet or near ultraviolet laser is irradiated from the laser pointer 5 to the screen 1 as necessary. Thereby, the phosphor emits light at the spot 6 irradiated with the laser, and the spot 6 pointed to by the laser pointer 5 can be clearly recognized.

  In this regard, a conventional laser pointer uses a visible light laser (usually a red laser) and uses the reflection of the visible light laser on the screen surface to point to the desired spot. In this case, since the phosphor emits light on the surface of the screen 1, the spot 6 shines brighter than before, so that it becomes easier to visually recognize. Furthermore, if the phosphor is used, the spot 6 can be emitted in green or blue with high visibility, so that the visibility can be further improved as compared with the conventional red laser reflection.

Moreover, since the organic phosphor is used as the phosphor, the screen 1 can be manufactured by a simple method called a coating method, and the manufacturing cost can be suppressed.
Furthermore, the conventional organic phosphor has low resistance to light having a wavelength of ultraviolet to near ultraviolet and oxygen, and easily deteriorates with use. However, the screen 1 of the present example suppresses the deterioration of the fluorescence of the present invention. Since the body is used, it can be used sufficiently stably for practical use.

  However, the screen 1 is not limited to the above configuration. For example, other layers such as a protective layer may be provided in addition to the sheet 2 and the phosphor-containing layer 3. Further, for example, the phosphor of the present invention may be fixed to the surface of the sheet 2 without using a binder such as a liquid medium, and the phosphor-containing layer 3 may be formed only by the phosphor of the present invention. In addition, a phosphor that emits light when excited by light in the visible region may be included in the phosphor-containing layer 3 to exhibit some visual effect.

[5. Color conversion film]
The color conversion film of the present invention comprises the phosphor of the present invention. The specific configuration is not limited, and the phosphor of the present invention can be arbitrarily applied to a known color conversion film.

For example, the color conversion film of this invention can be comprised as one form of said laminated body which laminated | stacked the fluorescent substance containing layer containing the fluorescent substance of this invention on the transparent substrate.
The transparent substrate may be arbitrarily selected depending on the use of the color conversion film. Usually, a substrate formed of a material that is substantially transparent and does not significantly absorb and scatter is used. Here, “substantially transparent” means that there is little or no coloration, and the light transmittance in the visible light region (420 nm to 700 nm or less) is usually 80% or more, preferably 90% or more. Means.

Specific examples of transparent substrate materials include glass, polyolefin resin, amorphous polyolefin resin, polyester resin, polycarbonate resin, poly (meth) acrylate resin, polystyrene, polyvinyl chloride, polyvinyl acetate, and polyarylate resin. And polyether sulfone resin. In addition, these materials may use only 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
The transparent substrate may contain additives, heat aging inhibitors, lubricants, antistatic agents and the like as necessary in addition to the above-described materials such as resins.

  There is no restriction | limiting in the thickness of a transparent substrate, Although it can set arbitrarily according to the objective, Usually, it is the range of 10 micrometers or more and 5 mm or less.

  The transparent substrate can be produced, for example, by molding the above material by a method such as injection molding, T-die molding, calendar molding, compression molding or the like. In addition, for example, the above materials can be produced by melting in a solvent such as an organic solvent and casting. Thereby, a transparent substrate can be obtained by film or sheet (plate).

  The base material constituting such a transparent substrate may be unstretched or stretched. Moreover, you may laminate | stack with another base material. Further, the transparent substrate is subjected to surface treatment by a conventionally known method such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, surface roughening treatment, chemical treatment or the like, or coating with an anchor coating agent or a primer. May be.

  Further, for example, the color conversion film of the present invention may be formed into a film by casting the above-described phosphor-containing composition, and the molded body itself may be used as the color conversion film.

  Further, for example, the color conversion film of the present invention is formed into a film shape by a method such as injection molding, T-die molding, calendar molding, compression molding, etc. by kneading the phosphor of the present invention into a binder using a dispersant as necessary. And the molded body may be used as a color conversion film.

  Examples of the dispersant used as necessary include polyvinyl butyral resin, phenoxy resin, rosin-modified phenol resin, petroleum resin, cured rosin, rosin ester, maleated rosin, and polyurethane resin. In addition, only 1 type may be used for a dispersing agent and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the binder used include acrylate resins such as polymethyl methacrylate resin and polyethyl acrylate resin, polycarbonate resin, ethylene-vinyl alcohol copolymer resin, ethylene-vinyl acetate copolymer resin, polyacrylonitrile styryl resin ( AS resin), polyester resin, polychlorovinyl acetate resin (vinyl acetate resin), polyvinyl butyral resin, polyvinyl resin (PVPA), polystyrene resin, phenol resin, phenoxy resin, polysulfone, nylon, cellulose resin, acetic acid Cellulose-type resin etc. are mentioned. In addition, only 1 type may be used for a binder and it may use 2 or more types together by arbitrary combinations and a ratio.
The amount of the binder used is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 10 times by weight or more, preferably 50 times by weight or more, and usually 500 times by weight or less, preferably 350 weight times or less.

There is no restriction | limiting in the dimension of a color conversion film, According to the use, it can set arbitrarily. However, the thickness is usually 10 ⁻² μm or more, preferably 10 ⁻¹ μm or more, more preferably ¹ μm or more, and usually 5 mm or less, preferably 1 mm or less, more preferably 0.5 mm or less. If the thickness is too thin, the excitation light may be leaked to the outside, and if it is too thick, the luminance may be reduced due to light scattering.

[6. Light emitting device]
The light-emitting device of the present invention (hereinafter referred to as “light-emitting device” as appropriate) includes a first light-emitting body (excitation light source), and a second light-emitting body that emits visible light when irradiated with light from the first light-emitting body. The second light emitter contains at least one phosphor of the present invention as the first phosphor.

  Specifically, the light-emitting device of the present invention uses an excitation light source as will be described later as the first light emitter, adjusts the type and proportion of the phosphor used as the second light emitter, and is a known device configuration By arbitrarily taking, a light emitting device that emits light in any color can be manufactured. For example, a white light emitting device is manufactured by combining an excitation light source that emits blue light, a phosphor that emits green fluorescence (green phosphor), and a phosphor that emits orange or red fluorescence (orange or red phosphor). be able to. In this case, the emission color of the light emitting device can be changed to a desired emission color by adjusting the emission wavelength of the phosphor of the present invention or the combined orange or red phosphor. For example, an emission spectrum similar to the emission spectrum of so-called pseudo white (for example, the emission color of a light emitting device combining a blue LED and a yellow phosphor) can be obtained. Furthermore, combining this white light-emitting device with a phosphor that emits red fluorescence (red phosphor) realizes a light-emitting device that excels in red color rendering and a light-emitting device that emits light bulb color (warm white). can do. Also, a white light emitting device can be manufactured by combining an excitation light source that emits near-ultraviolet light with a phosphor that emits blue fluorescence (blue phosphor), a green phosphor, and a red phosphor.

  Here, the white color of the white light emitting device means all of (yellowish) white, (greenish) white, (blueish) white, (purple) white and white defined by JIS Z 8701 Of these, white is preferred.

Furthermore, if necessary, yellow phosphors (phosphors that emit yellow fluorescence), blue phosphors, orange to red phosphors, other types of green phosphors, etc. It is also possible to manufacture a light emitting device that adjusts and emits light in an arbitrary color.
Any one of the phosphors of the present invention may be used, or two or more may be used in any combination and ratio.

  In the emission spectrum of the light emitting device of the present invention, the emission peak in the blue region preferably has an emission peak in the wavelength range of 400 nm to 480 nm, and the emission peak in the green region has an emission peak in the wavelength range of 500 nm to 550 nm. What has it is preferable, and what has a light emission peak in the wavelength range of 600 nm-650 nm as a light emission peak of a red area | region is preferable.

  Note that the emission spectrum of the light emitting device is measured by energizing 20 mA with a color / illuminance measurement software and USB2000 series spectroscope (integral sphere specification) manufactured by Ocean Optics in a room maintained at a temperature of 25 ± 1 ° C. It can be carried out. Chromaticity values (x, y, z) can be calculated as chromaticity coordinates in the XYZ color system defined by JIS Z8701 from data in the wavelength region of 380 nm to 780 nm of the emission spectrum. In this case, the relational expression x + y + z = 1 holds. In the present specification, the XYZ color system may be referred to as an XY color system, and is usually expressed as (x, y).

  The luminous efficiency is obtained by obtaining the total luminous flux from the result of the emission spectrum measurement using the light emitting device as described above, and dividing the lumen (lm) value by the power consumption (W). The power consumption is obtained by measuring a voltage using a True RMS Multimeters Model 187 & 189 manufactured by Fluke in a state in which 20 mA is energized, and obtaining the product of the current value and the voltage value.

[6-1. Configuration of Light Emitting Device (Light Emitter)]
(First luminous body)
The 1st light-emitting body in the light-emitting device of this invention light-emits the light which excites the 2nd light-emitting body mentioned later.

  The light emission wavelength of the first light emitter is not particularly limited as long as it overlaps with the absorption wavelength of the second light emitter described later, and a light emitter having a wide light emission wavelength region can be used. Usually, an illuminant having an emission wavelength from the ultraviolet region to the blue region is used, and it is particularly preferable to use an illuminant having an emission wavelength from the near ultraviolet region to the blue region.

  As a specific numerical value of the emission peak wavelength of the first illuminant, 200 nm or more is usually desirable. Among these, when using near-ultraviolet light as excitation light, it is desirable to use a light emitter having a peak emission wavelength of usually 300 nm or more, preferably 330 nm or more, more preferably 360 nm or more, and usually 420 nm or less. When blue light is used as excitation light, it is desirable to use a light emitter having an emission peak wavelength of usually 420 nm or more, preferably 430 nm or more, and usually 500 nm or less, preferably 480 nm or less. Both are from the viewpoint of color purity of the light emitting device.

  As the first light emitter, a semiconductor light emitting element is generally used, and specifically, a light emitting LED, a semiconductor laser diode (hereinafter abbreviated as “LD” as appropriate), or the like can be used. In addition, as a light-emitting body which can be used as a 1st light-emitting body, an organic electroluminescent light emitting element, an inorganic electroluminescent light emitting element, etc. are mentioned, for example. However, what can be used as a 1st light-emitting body is not restricted to what is illustrated by this specification.

Among these, as the first light emitter, a GaN LED or LD using a GaN compound semiconductor is preferable. This is because GaN-based LEDs and LDs have significantly higher light emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and are extremely bright with very low power when combined with the phosphor. This is because light emission can be obtained. For example, for a current load of 20 mA, GaN-based LEDs and LDs usually have a light emission intensity 100 times or more that of SiC-based. GaN-based LEDs and LDs preferably have an Al _x Ga _y N light emitting layer, a GaN light emitting layer, or an In _x Ga _y N light emitting layer. Among GaN-based LEDs, those having an In _X Ga _Y N light-emitting layer are particularly preferable because of their very high emission intensity. In GaN-based LEDs, a multiple quantum well structure of In _X Ga _Y N layers and GaN layers is preferred. Is particularly preferable because the emission intensity is very strong.

  In the above, the value of X + Y is usually a value in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics.

A GaN-based LED has these light-emitting layer, p-layer, n-layer, electrode, and substrate as basic components, and the light-emitting layer is composed of n-type and p-type Al _x Ga _y N layers, GaN layers, or In _x. Those having a heterostructure sandwiched between Ga _Y N layers and the like are preferable because of high light emission efficiency, and those having a heterostructure having a quantum well structure are more preferable because of high light emission efficiency.
Note that only one first light emitter may be used, or two or more first light emitters may be used in any combination and ratio.

(Second light emitter)
The second light emitter in the light emitting device of the present invention is a light emitter that emits visible light when irradiated with light from the first light emitter described above, and contains the phosphor of the present invention described above as the first phosphor. In addition, a second phosphor (a red to orange phosphor, a green phosphor, a blue phosphor, a yellow phosphor, or the like), which will be described later, is appropriately contained depending on the application. Further, for example, the second light emitter is configured by dispersing the first and second phosphors in a sealing material.

There is no restriction | limiting in particular in the composition of fluorescent substance other than the fluorescent substance of this invention used in the said 2nd light-emitting body. For example, metal oxides represented by Y ₂ O ₃ , YVO ₄ , Zn ₂ SiO ₄ , Y ₃ Al ₅ O ₁₂ , Sr ₂ SiO _4, etc., which become the crystal matrix, Sr ₂ Si ₅ N ₈ Metal nitrides typified by, etc., phosphates typified by Ca ₅ (PO ₄ ) ₃ Cl, etc. and sulfides typified by ZnS, SrS, CaS, etc., Y ₂ O ₂ S, La ₂ O ₂ S Examples of oxysulfides such as Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb, ions of rare earth metals, Ag, Cu, Au, Al, Mn , Sb and other metal ions combined as an activator element or a coactivator element.

Preferred examples of the crystal matrix include, for example, sulfides such as (Zn, Cd) S, SrGa ₂ S ₄ , SrS, ZnS; oxysulfides such as Y ₂ O ₂ S; (Y, Gd) ₃ Al ₅ O ₁₂ , YAlO ₃ , BaMgAl ₁₀ O ₁₇ , (Ba, Sr) (Mg, Mn) Al ₁₀ O ₁₇ , (Ba, Sr, Ca) (Mg, Zn, Mn) Al ₁₀ O ₁₇ , BaAl ₁₂ O ₁₉ , CeMgAl Aluminates such as ₁₁ O ₁₉ , (Ba, Sr, Mg) O.Al ₂ O ₃ , BaAl ₂ Si ₂ O ₈ , SrAl ₂ O ₄ , Sr ₄ Al ₁₄ O ₂₅ , Y ₃ Al ₅ O ₁₂ ; Y Silicates such as ₂ SiO ₅ and Zn ₂ SiO ₄ ; Oxides such as SnO ₂ and Y ₂ O ₃ ; Borates such as GdMgB ₅ O ₁₀ and (Y, Gd) BO ₃ ; Ca ₁₀ (PO ₄ ) ₆ ( _{F, Cl) 2, (Sr} , Ca, Ba, Mg) 10 (PO 4) 6 halophosphate of ₂ such as Cl; Sr ₂ P _{2 7,} it may be mentioned (La, Ce) phosphate PO _4, etc. and the like.

  However, the above-mentioned crystal matrix, activator element and coactivator element are not particularly limited in element composition, and can be partially replaced with elements of the same family, and the obtained phosphor is light in the near ultraviolet to visible region. Any material that absorbs and emits visible light can be used.

Specifically, the following phosphors can be used, but these are merely examples, and phosphors that can be used in the present invention are not limited to these.
In the composition formula of the phosphors in this specification, each composition formula is delimited by a punctuation mark (,). In addition, when a plurality of elements are listed separated by commas (,), one or two or more of the listed elements may be included in any combination and composition. However, the total of the elements shown in parentheses is 1 mol. For example, the composition formula “(Ba, Sr, Ca) Al ₂ O ₄ : Eu” is expressed by “BaAl ₂ O ₄ : Eu”, “SrAl ₂ O ₄ : Eu”, and “CaAl ₂ O ₄ : Eu”. “Ba _1-x Sr _x Al ₂ O ₄ : Eu”, “Ba _1-x Ca _x Al ₂ O ₄ : Eu”, “Sr _1-x Ca _x Al ₂ O ₄ : Eu”, _{"Ba 1-xy Sr x Ca y} Al 2 O 4: Eu " and all assumed to generically indicated (in the above formula, 0 <x <1,0 <y <1,0 <x + y <1.)

(First phosphor)
The second light emitter in the light emitting device of the present invention contains at least the above-described phosphor of the present invention as the first phosphor. Any one of the phosphors of the present invention may be used, or two or more may be used in any combination and ratio.

  In addition to the phosphor of the present invention, a phosphor that emits fluorescence of the same color as the phosphor of the present invention (same color combined phosphor) may be used as the first phosphor. For example, when the phosphor of the present invention is a green phosphor, another type of green phosphor can be used together with the phosphor of the present invention as the first phosphor. In the case of a red phosphor, other types of orange or red phosphor can be used together with the phosphor of the present invention as the first phosphor, and when the phosphor of the present invention is a blue phosphor, As the first phosphor, other types of blue phosphors can be used in combination with the phosphor of the present invention. Any phosphor can be used as long as the effects of the present invention are not significantly impaired.

  However, the first phosphor used in the light-emitting device of the present invention has an emission peak half-width in the above-described emission spectrum (hereinafter referred to as “FWHM” where appropriate), usually 10 nm or more. The thickness is preferably 20 nm or more, more preferably 25 nm or more, and it is usually 85 nm or less, particularly 75 nm or less, and more preferably 70 nm or less. If the full width at half maximum FWHM is too narrow, the emission intensity may decrease, and if it is too wide, the color purity may decrease.

Hereinafter, green phosphors, orange to red phosphors, and blue phosphors will be described as examples of phosphors that can be used in combination with the phosphor of the present invention.
(Green phosphor)
When the green phosphor is used, any green phosphor can be used as long as the effect of the present invention is not significantly impaired. At this time, the emission peak wavelength of the green phosphor is usually larger than 500 nm, preferably 510 nm or more, more preferably 515 nm or more, and usually 550 nm or less, especially 540 nm or less, and further preferably 535 nm or less. If this emission peak wavelength λ _p is too short, it tends to be bluish, while if it is too long, it tends to be yellowish, and there is a possibility that the characteristics as green light will deteriorate.

Specifically, the green phosphor is composed of, for example, fractured particles having a fractured surface, and emits a green region (Mg, Ca, Sr, Ba) with europium represented by (Si ₂ O ₂ N ₂ : Eu). Examples include active alkaline earth silicon oxynitride phosphors.

Other green phosphors include Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) Al ₂ O ₄ : Eu, and (Sr, Ba) Al _{2. Si 2 O 8: Eu, (} Ba, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca) 2 (Mg, Zn) Si 2 O 7 : Eu, (Ba, Ca, Sr, Mg) ₉ (Sc, Y, Lu, Gd) ₂ (Si, Ge) ₆ O ₂₄ : Eu-activated silicate phosphor such as Eu, Y ₂ SiO ₅ : Ce, Ce, Tb activated silicate phosphor such as Tb, Sr ₂ P ₂ O ₇ —Sr ₂ B ₂ O ₅ : Eu activated borate phosphate phosphor such as Eu, Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu-activated halo silicate phosphor such as Eu, Zn ₂ SiO _4: Mn-activated silicate phosphors such as _{Mn, CeMgAl 11 O 19: Tb} , ₃ Al ₅ O _12: Tb-activated aluminate phosphors such as _{Tb, Ca 2 Y 8 (SiO} 4) 6 O 2: Tb, La 3 Ga 5 SiO 14: Tb -activated silicate phosphors such as Tb, (Sr, Ba, Ca) Ga ₂ S ₄ : Eu, Tb, Sm activated thiogallate phosphors such as Eu, Tb, Sm, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce activated silicate phosphor such as Ce, Ce activated oxide phosphor such as CaSc ₂ O ₄ : Ce, Eu activated oxynitride phosphor such as Eu activated β sialon _{, BaMgAl 10 O 17: Eu,} Eu such as Mn, Mn-activated aluminate phosphor, SrAl ₂ O _4: Eu such as Eu Activated aluminate phosphors, (La, Gd, Y) 2 O 2 S: Tb Tsukekatsusan sulfide phosphor such as Tb, LaPO _4: Ce, Ce and Tb such, Tb-activated phosphate phosphor, Sulfide phosphors such as ZnS: Cu, Al, ZnS: Cu, Au, Al, (Y, Ga, Lu, Sc, La) BO ₃ : Ce, Tb, Na ₂ Gd ₂ B ₂ O ₇ : Ce, Tb (Ba, Sr) ₂ (Ca, Mg, Zn) B ₂ O ₆ : Ce, Tb activated borate phosphors such as K, Ce, Tb, Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu, Mn Eu, Mn activated halosilicate phosphors such as (Sr, Ca, Ba) (Al, Ga, In) ₂ S ₄ : Eu activated thioaluminate phosphors and thiogallate phosphors such as Eu, (Ca, Sr) ₈ (Mg, Zn) (SiO ₄ ) ₄ Cl ₂ : Eu, Mn activated halosilicate phosphor such as Eu, Mn, M ₃ S i ₆ O ₉ N ₄ : Eu, M ₃ Si ₆ O ₁₂ N ₂ : Eu (where M represents an alkaline earth metal element). It is also possible to use Eu-activated oxynitride phosphors such as

In addition, as the green phosphor, it is also possible to use a pyridine-phthalimide condensed derivative, a benzoxazinone-based, a quinazolinone-based, a coumarin-based, a quinophthalone-based, a naltalimide-based fluorescent pigment, or an organic phosphor such as a terbium complex. is there.
Any one of the green phosphors exemplified above may be used, or two or more may be used in any combination and ratio.

(Orange to red phosphor)
When an orange or red phosphor is used, any orange or red phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the orange to red phosphor is usually in the wavelength range of 570 nm or more, preferably 580 nm or more, more preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less, more preferably 680 nm or less. Is preferred.

Examples of such orange to red phosphors are europium expressed by (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu, which is composed of broken particles having a red fracture surface and emits light in the red region. The activated alkaline earth silicon nitride phosphor is composed of growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the red region (Y, La, Gd, Lu) ₂ O ₂ S: Eu And europium activated rare earth oxychalcogenide phosphors represented by the formula:

  Furthermore, an oxynitride and / or an acid containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo described in JP-A No. 2004-300247 A phosphor containing a sulfide and containing an oxynitride having an alpha sialon structure in which a part or all of the Al element is substituted with a Ga element can also be used in the present invention. These are phosphors containing oxynitride and / or oxysulfide.

In addition, examples of red phosphors include Eu-activated oxysulfide phosphors such as (La, Y) ₂ O ₂ S: Eu, Y (V, P) O ₄ : Eu, Y ₂ O ₃ : Eu, and the like. Eu-activated oxide phosphors of (Ba, Mg) ₂ SiO ₄ : Eu, Mn, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Mn-activated silicate phosphors such as Eu and Mn, Eu-activated tungstate phosphors such as LiW ₂ O ₈ : Eu, LiW ₂ O ₈ : Eu, Sm, Eu ₂ W ₂ O ₉ , Eu ₂ W ₂ O ₉ : Nb, Eu ₂ W ₂ O ₉ : Sm Eu-activated sulfide phosphors such as (Ca, Sr) S: Eu, Eu-activated aluminate phosphors such as YAlO ₃ : Eu, Ca ₂ Y ₈ (SiO ₄ ) ₆ O ₂ : Eu, LiY _{9 (SiO 4) 6 O 2:} Eu, (Sr, Ba, Ca) 3 SiO 5: Eu, Sr 2 BaSiO 5: Eu -activated silicate phosphors such as Eu, _{Y, Gd) 3 Al 5 O} 12: Ce, (Tb, Gd) 3 Al 5 O 12: Ce -activated aluminate phosphor such as Ce, (Mg, Ca, Sr , Ba) 2 Si 5 (N, Eu-activated oxides such as O) ₈ : Eu, (Mg, Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Mg, Ca, Sr, Ba) AlSi (N, O) ₃ : Eu , Nitride or oxynitride phosphor, (Mg, Ca, Sr, Ba) AlSi (N, O) ₃ : Ce activated oxide such as Ce, nitride or oxynitride phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn-activated halophosphate phosphor such as Eu, Mn, Ba ₃ MgSi ₂ O ₈ : Eu, Mn, (Ba, Sr, Ca, Mg) ₃ (Zn, Mg) Si ₂ O ₈ : Eu, Mn activated silicate phosphor such as Eu, Mn, 3.5MgO.0.5MgF ₂ .GeO ₂ : Mn Mn-activated germanate phosphor such as Eu-activated α-sialon phosphor such as Eu-activated α-sialon, (Gd, Y, Lu, La) ₂ O ₃ : Eu, Bi-activated Eu, Bi, etc. Oxide phosphor, (Gd, Y, Lu, La) ₂ O ₂ S: Eu, Bi activated oxysulfide phosphor such as Eu, Bi, (Gd, Y, Lu, La) VO ₄ : Eu, Bi Eu, Bi activated vanadate phosphors such as SrY ₂ S ₄ : Eu, Ce activated sulfide phosphors such as Eu, Ce, Ce activated sulfide phosphors such as CaLa ₂ S ₄ : Ce, ( Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Mn activated phosphate phosphor such as Eu, Mn, (Y _{, Lu) 2 WO 6: Eu} , Eu such as Mo, Mo-activated tungstate phosphor, (Ba, Sr, Ca) x Si y N z: Eu, Ce However, x, y, z are an integer of 1 or more. Eu, Ce-activated nitride phosphors such as (Ca, Sr, Ba, Mg) ₁₀ (PO ₄ ) ₆ (F, Cl, Br, OH): Eu, Mn-activated halophosphoric acid such as Eu, Mn Ce phosphors such as salt phosphors, ((Y, Lu, Gd, Tb) _1-xy Sc _x Ce _y ) ₂ (Ca, Mg) _1-r (Mg, Zn) _{2 + r} Si _zq Ge _q O _{12 + δ} It is also possible to use an activated silicate phosphor or the like.

  Examples of red phosphors include β-diketonates, β-diketones, aromatic carboxylic acids, red organic phosphors composed of rare earth element ion complexes having an anion such as Bronsted acid as a ligand, and perylene pigments (for example, Dibenzo {[f, f ′]-4,4 ′, 7,7′-tetraphenyl} diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene), anthraquinone pigment, Lake pigments, azo pigments, quinacridone pigments, anthracene pigments, isoindoline pigments, isoindolinone pigments, phthalocyanine pigments, triphenylmethane basic dyes, indanthrone pigments, indophenol pigments, It is also possible to use a cyanine pigment or a dioxazine pigment.

Among these, as red phosphors, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Ca, Sr , Ba) AlSi (N, O) ₃ : Eu, (Ca, Sr, Ba) AlSi (N, O) ₃ : Ce, (Sr, Ba) ₃ SiO ₅ : Eu, (Ca, Sr) S: Eu, It is preferable to contain (La, Y) ₂ O ₂ S: Eu or Eu complex, more preferably (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) Si. (N, O) ₂ : Eu, (Ca, Sr, Ba) AlSi (N, O) ₃ : Eu, (Ca, Sr, Ba) AlSi (N, O) ₃ : Ce, (Sr, Ba) ₃ SiO _{5: Eu, (Ca, Sr} ) S: Eu or _{(La, Y) 2 O 2} S: Eu or Eu (dibenzoylmethane) ₃ · 1, Preferably comprises a β- diketone Eu complex or carboxylic acid type Eu complex such as 10-phenanthroline complex, (Ca, Sr, Ba) 2 Si 5 (N, O) 8: Eu, (Sr, Ca) AlSiN 3 : Eu or (La, Y) ₂ O ₂ S: Eu is particularly preferred.

Of the above examples, (Sr, Ba) ₃ SiO ₅ : Eu is preferable as the orange phosphor.
Any one of the orange to red phosphors exemplified above may be used, or two or more may be used in any combination and ratio.

(Blue phosphor)
When using blue fluorescent substance, the said blue fluorescent substance can use arbitrary things, unless the effect of this invention is impaired remarkably. At this time, the emission peak wavelength of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 490 nm or less, preferably 480 nm or less, more preferably 470 nm or less, and further preferably 460 nm or less. It is preferable to be in the wavelength range.

Such a blue phosphor is composed of growing particles having a substantially hexagonal shape as a regular crystal growth shape, and europium represented by (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu that emits light in a blue region. The activated barium magnesium aluminate-based phosphor is composed of growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the blue region (Mg, Ca, Sr, Ba) ₅ (PO ₄ ) ₃ (Cl , F): a europium activated calcium halophosphate phosphor represented by Eu, and a growth crystal having a substantially cubic shape as a regular crystal growth shape, and emits light in a blue region (Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: europium-activated alkaline earth aluminate phosphor represented by Eu, which is constituted by fractured particles having a fractured surface, blue-green Emission at a region (Sr, Ca, Ba) Al 2 O 4: Eu or _{(Sr, Ca, Ba) 4} Al 14 O 25: europium-activated alkaline earth represented by Eu aluminate-based phosphor, and the like .

In addition, as the blue phosphor, Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, (Sr, Ca, Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, Tb, Sm, BaAl ₈ O ₁₃ : Eu attached Active aluminate phosphor, Ce-activated thiogallate phosphor such as SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce, Eu, Mn such as (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn Active aluminate phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): Eu, Mn, Eu-activated halophosphate phosphors such as Sb, BaAl ₂ Si _{2 8: Eu, (Sr, Ba} ) 3 MgSi 2 O 8: Eu -activated silicate phosphors such as _{Eu, Sr 2 P 2 O 7} : Eu -activated phosphate phosphor such as Eu, ZnS: Ag, ZnS : Sulfide phosphors such as Ag and Al, Y ₂ SiO ₅ : Ce activated silicate phosphors such as Ce, Tungsten phosphors such as CaWO ₄ , (Ba, Sr, Ca) BPO ₅ : Eu, Mn _{, (Sr, Ca) 10 (} PO 4) 6 · nB 2 O 3: Eu, 2SrO · 0.84P 2 O 5 · 0.16B 2 O 3: Eu such as Eu, Mn-activated borate phosphate phosphors Sr ₂ Si ₃ O ₈ .2SrCl ₂ : Eu-activated halosilicate phosphor such as Eu, SrSi ₉ Al ₁₉ ON ₃₁ : Eu-activated oxynitride phosphor such as Eu and EuSi ₉ Al ₁₉ ON ₃₁ , La _{1-x Ce x Al (Si} 6-z Al z) (N 10-z O z) ( here, x, and y are each 0 ≦ x ≦ A number satisfying 0 ≦ z ≦ 6.), La 1-xy Ce x Ca y Al (Si 6-z Al z) (N 10-z O z) ( here, x, y, and z Ce-activated oxynitride phosphors such as 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, and 0 ≦ z ≦ 6) can also be used.

  In addition, as the blue phosphor, for example, naphthalic acid imide-based, benzoxazole-based, styryl-based, coumarin-based, pyrarizone-based, triazole-based compound fluorescent dyes, organic phosphors such as thulium complexes, and the like can be used. .

Among the above examples, as the blue phosphor, (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu or It is preferable to contain (Ba, Ca, Mg, Sr) ₂ SiO ₄ : Eu, and (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ ( Cl, F) ₂ : Eu or (Ba, Ca, Sr) ₃ MgSi ₂ O ₈ : Eu is more preferable, and BaMgAl ₁₀ O ₁₇ : Eu, Sr ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : More preferably, Eu or Ba ₃ MgSi ₂ O ₈ : Eu is included. Of these, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu or (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu is particularly preferred for illumination and display applications.
Any one of the blue phosphors exemplified above may be used, or two or more may be used in any combination and ratio.

(Second phosphor)
The second light emitter in the light emitting device of the present invention may contain a phosphor (that is, a second phosphor) in addition to the first phosphor described above, depending on the application. This second phosphor is a phosphor having an emission peak wavelength different from that of the first phosphor. Usually, since these second phosphors are used to adjust the color tone of light emitted from the second light emitter, the second phosphor emits fluorescence having a color different from that of the first phosphor. Often phosphors are used. Therefore, when a green phosphor is used as the first phosphor, the second phosphor is a phosphor other than a green phosphor, such as an orange to red phosphor, a blue phosphor, or a yellow phosphor. Use. When an orange or red phosphor is used as the first phosphor, examples of the second phosphor include fluorescent materials other than orange or red phosphors such as a green phosphor, a blue phosphor, and a yellow phosphor. Use the body. Further, when a blue phosphor is used as the first phosphor, the second phosphor is a phosphor other than a blue phosphor such as a green phosphor, an orange to red phosphor, or a yellow phosphor. Use.

Examples of the green phosphor, orange to red phosphor, and blue phosphor include the same phosphors as described in the first phosphor section.
Examples of the yellow phosphor include those described below.

(Yellow phosphor)
When using a yellow phosphor, any can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the yellow phosphor is usually in the wavelength range of 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. Is preferred.

Examples of such yellow phosphors include various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors.
In particular, RE ₃ M ² ₅ O ₁₂ : Ce (where RE represents at least one element selected from the group consisting of Y, Tb, Gd, Lu, and Sm, and M ² represents Al, Ga, And M ^a ₃ M ^b ₂ M ^c ₃ O ₁₂ : Ce (where M ^a is a divalent metal element, M ^b is a trivalent element). A garnet-based phosphor having a garnet structure represented by a metal element, M ^c represents a tetravalent metal element, etc., AE ₂ M ^d O ₄ : Eu (where AE is Ba, Sr, Ca, Mg) And at least one element selected from the group consisting of Zn, M ^d represents Si and / or Ge), etc., and constituent elements of the phosphors of these systems AEA, an oxynitride-based phosphor in which part of oxygen is substituted with nitrogen SiN _3: Ce (., Where, AE is, Ba, Sr, Ca, Mg and represents at least one element selected from the group consisting of Zn) of the nitride-based fluorescent material or the like having a CaAlSiN ₃ structure, such as Ce And the phosphor activated in step (b).

Other examples of yellow phosphors include sulfide-based fluorescence such as CaGa ₂ S ₄ : Eu, (Ca, Sr) Ga ₂ S ₄ : Eu, (Ca, Sr) (Ga, Al) ₂ S ₄ : Eu. Body, Ca _x (Si, Al) ₁₂ (O, N) ₁₆ : Eu-activated phosphor such as oxynitride-based phosphor having a SiAlON structure such as Eu, (M ³ _1-ab Eu _a Mn _b ) ₂ (BO ₃ ) _1-p (PO ₄ ) _p X ² (M ³ represents one or more elements selected from the group consisting of Ca, Sr, and Ba, and X ² represents F, Cl And one or more elements selected from the group consisting of Br, and a, b, and p are 0.001 ≦ a ≦ 0.3, 0 ≦ b ≦ 0.3, and 0 ≦ p ≦ 0, respectively. It is also possible to use Eu-activated or Eu / Mn co-activated halogenated borate phosphors.

Examples of yellow phosphors include brilliant sulfoflavine FF (Color Index Number 56205), basic yellow HG (Color Index Number 46040), eosine (Color Index Number 45Gd), 45G Etc. can also be used.
Any one of the yellow phosphors exemplified above may be used, or two or more may be used in any combination and ratio.

  The weight median diameter of the second phosphor used in the light emitting device of the present invention is usually in the range of 10 μm or more, especially 12 μm or more, and usually 30 μm or less, especially 25 μm or less. When the weight median diameter is too small, the luminance decreases and the phosphor particles tend to aggregate. On the other hand, if the weight median diameter is too large, there is a tendency for coating unevenness and blockage of the dispenser to occur.

(Combination of second phosphors)
As the second phosphor, only one kind of phosphor may be used, or two or more kinds of phosphors may be used in any combination and ratio. Further, the ratio between the first phosphor and the second phosphor is also arbitrary as long as the effects of the present invention are not significantly impaired. Therefore, the usage amount of the second phosphor, the combination and ratio of the phosphors used as the second phosphor, and the like may be arbitrarily set according to the use of the light emitting device.

  In addition, the phosphor of the present invention is mixed with other phosphors (here, mixing does not necessarily mean that the phosphors need to be mixed with each other, but means that different types of phosphors are combined). ) Can be used. In particular, when phosphors are mixed in the combination described above, a preferable phosphor mixture is obtained. In addition, there is no restriction | limiting in particular in the kind and the ratio of the fluorescent substance to mix.

(Sealing material)
In the light emitting device of the present invention, the first and / or second phosphors are usually used by being dispersed in a liquid medium that is a sealing material.
Examples of the liquid medium are the same as those described in the section of the phosphor-containing composition.

  The liquid medium can contain a metal element that can be a metal oxide having a high refractive index in order to adjust the refractive index of the sealing member. Examples of metal elements that give a metal oxide having a high refractive index include Si, Al, Zr, Ti, Y, Nb, and B. These metal elements may be used alone or in combination of two or more in any combination and ratio.

The presence form of such a metal element is not particularly limited as long as the transparency of the sealing member is not impaired. For example, even if a uniform glass layer is formed as a metalloxane bond, the metal element is present in a particulate form in the sealing member. It may be. When present in the form of particles, the structure inside the particles may be either amorphous or crystalline, but is preferably a crystalline structure in order to provide a high refractive index. Further, the particle diameter is usually not more than the emission wavelength of the semiconductor light emitting device, preferably not more than 100 nm, more preferably not more than 50 nm, particularly preferably not more than 30 nm so as not to impair the transparency of the sealing member. For example, by mixing particles of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, yttrium oxide, niobium oxide, etc. with a silicone-based material, the metal element can be present in the sealing member in the form of particles. .
The liquid medium may further contain known additives such as a diffusing agent, a filler, a viscosity modifier, and an ultraviolet absorber.

[6-2. Configuration of light emitting device (others)]
The other configurations of the light emitting device of the present invention are not particularly limited as long as the first light emitting body and the second light emitting body described above are provided. Usually, the first light emitting body described above is formed on an appropriate frame. And a second light emitter. At this time, the second light emitter is excited by the light emission of the first light emitter (that is, the first and second phosphors are excited) to emit light, and the first light emitter emits light. And / or it arrange | positions so that light emission of a 2nd light-emitting body may be taken out outside. In this case, the first phosphor and the second phosphor are not necessarily mixed in the same layer. For example, the second phosphor is contained on the layer containing the first phosphor. For example, the phosphor may be contained in a separate layer for each color development of the phosphor, such as by stacking layers.

  In the light emitting device of the present invention, members other than the above-described excitation light source (first light emitter), phosphor (second light emitter), and frame may be used. Examples thereof include the aforementioned sealing materials. In addition to the purpose of dispersing the phosphor (second light emitter) in the light emitting device, the sealing material is provided between the excitation light source (first light emitter), the phosphor (second light emitter), and the frame. It can be used for the purpose of bonding.

[6-3. Embodiment of Light Emitting Device]
Hereinafter, the light-emitting device of the present invention will be described in more detail with reference to specific embodiments. However, the present invention is not limited to the following embodiments, and does not depart from the gist of the present invention. It can be implemented with arbitrary modifications.

  FIG. 2 is a schematic perspective view showing a positional relationship between a first light emitter serving as an excitation light source and a second light emitter configured as a phosphor-containing portion having a phosphor in an example of the light emitting device of the present invention. Shown in In FIG. 2, reference numeral 11 denotes a phosphor-containing portion (second light emitter), reference numeral 12 denotes a surface-emitting GaN-based LD as an excitation light source (first light emitter), and reference numeral 13 denotes a substrate. In order to create a state in which they are in contact with each other, the LD (12) and the phosphor-containing portion (second light emitter) (11) are separately manufactured, and their surfaces are brought into contact with each other by an adhesive or other means. Alternatively, the phosphor-containing portion (second light emitter) may be formed (molded) on the light emitting surface of the LD (12). As a result, the LD (12) and the phosphor-containing part (second light emitter) (11) can be brought into contact with each other.

  When such an apparatus configuration is employed, the light loss is such that light from the excitation light source (first light emitter) is reflected by the film surface of the phosphor-containing portion (second light emitter) and oozes out. Therefore, the light emission efficiency of the entire device can be improved.

  FIG. 3A is a typical example of a light emitting device of a form generally referred to as a shell type, and has a light emission having an excitation light source (first light emitter) and a phosphor-containing portion (second light emitter). It is typical sectional drawing which shows one Example of an apparatus. In the light emitting device (14), reference numeral 15 is a mount lead, reference numeral 16 is an inner lead, reference numeral 17 is an excitation light source (first light emitter), reference numeral 18 is a phosphor-containing resin portion, reference numeral 19 is a conductive wire, reference numeral Reference numeral 20 denotes a mold member.

  FIG. 3B is a representative example of a light-emitting device of a form called a surface-mount type, and light emission having an excitation light source (first light emitter) and a phosphor-containing portion (second light emitter). It is typical sectional drawing which shows one Example of an apparatus. In the figure, reference numeral 21 is an excitation light source (first light emitter), reference numeral 22 is a phosphor-containing resin part as a phosphor containing part (second light emitter), reference numeral 23 is a frame, reference numeral 24 is a conductive wire, Reference numerals 25 and 26 indicate electrodes.

[6-4. Application of light emitting device]
The application of the light-emitting device of the present invention is not particularly limited and can be used in various fields where ordinary light-emitting devices are used. However, since the color reproduction range is wide and the color rendering property is high, illumination is particularly important. It is particularly preferably used as a light source for a device or an image display device.

(Lighting device)
When the light-emitting device of the present invention is applied to a lighting device, the above-described light-emitting device may be appropriately incorporated into a known lighting device. For example, a surface emitting illumination device (27) incorporating the above-described light emitting device (14) as shown in FIG.

  FIG. 4 is a cross-sectional view schematically showing an embodiment of the illumination device of the present invention. As shown in FIG. 4, the surface-emitting illumination device has a large number of light-emitting devices (29) (described above) on the bottom surface of a rectangular holding case (28) whose inner surface is light-opaque such as a white smooth surface. The light emitting device (14) corresponds to the lid portion of the holding case (28) by arranging a power source and a circuit (not shown) for driving the light emitting device (29) on the outside thereof. A diffuser plate (30) such as a milky white acrylic plate is fixed to the spot for uniform light emission.

  Then, the surface emitting illumination device (27) is driven to apply light to the excitation light source (first light emitter) of the light emitting device (29) to emit light, and a part of the light emission is converted into the phosphor. The phosphor in the phosphor-containing resin part as the containing part (second light emitter) absorbs and emits visible light, while having high color rendering due to color mixing with blue light or the like that is not absorbed by the phosphor. Luminescence is obtained, and this light is transmitted through the diffusion plate (30) and emitted upward in the drawing, so that illumination light with uniform brightness can be obtained within the surface of the diffusion plate (30) of the holding case (28). Become.

(Image display device)
When the light emitting device of the present invention is used as a light source of an image display device, the specific configuration of the image display device is not limited, but it is preferably used together with a color filter. For example, when the image display device is a color image display device using color liquid crystal display elements, the light emitting device is used as a backlight, a light shutter using liquid crystal, and a color filter having red, green, and blue pixels; By combining these, an image display device can be formed.

[7. Others]
The present invention is not limited to the above-described embodiment, examples, and the like, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

For example, the phosphor of the present invention may be used as sand for hourglasses. An example of such an hourglass is schematically shown in FIG.
As shown in FIG. 5, the hourglass 31 includes a transparent container 35 between upper and lower pedestals 33 and 34 connected by a support column 32. The transparent container 35 is partitioned into two chambers 37 and 38 by an orifice 36 provided at the center thereof, and sand 39 is enclosed in the chambers 37 and 38. For the sand 39, the phosphor of the present invention may be used as it is, but particles encapsulated in any binder may be used as the sand 39.

  As described above, when the phosphor of the present invention is used for the sand 39 in the hourglass 31, an hourglass that is easy to visually recognize and excellent in practicality, decoration, and playability can be realized. In addition, the conventional organic phosphor has a problem in durability against light and oxygen. However, since the phosphor of the present invention has sufficient durability, the luminance of light emitted from the sand 39 can be kept high. is there.

For example, the phosphor of the present invention may be used as a snow material for a snow globe (snow glove). An example of such a snow dome is schematically shown in FIG.
As shown in FIG. 6, this snow dome 40 is configured by installing a transparent container 42 on a pedestal 41 and providing a miniature 43 such as a building in the transparent container 42. Further, a liquid 44 such as water is sealed in the transparent container 42, and the snow material 45 is dispersed in this liquid. For the snow material 45, the phosphor of the present invention may be used as it is, but particles encapsulated in any binder may be used as the snow material 45.

  Thus, if the phosphor of the present invention is used for the snow material 45 in the snow dome 40, a snow dome that is easy to visually recognize and excellent in decorativeness and playability can be realized. Further, the conventional organic phosphors have problems in durability such as light resistance and water resistance. However, since the phosphors of the present invention have sufficient durability, the luminance of light emitted from the snow material 45 is kept high. It is possible.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless departing from the gist thereof.

[Measurement and evaluation method of phosphor]
In each of Examples and Comparative Examples described later, various evaluations of the phosphor were performed by the following methods.

[1. Measurement method of emission spectrum]
The emission spectrum was measured using FP-6500 manufactured by JASCO Corporation.

  Further, the emission peak wavelength and the half width were read from the obtained emission spectrum. The emission intensity was expressed as a relative value with a peak value of BR-101A manufactured by Mitsubishi Chemical Corporation at the time of excitation at a wavelength of 455 nm as a reference value of 100. A higher relative emission peak intensity is preferred.

[2. Measurement method of chromaticity coordinates]
Chromaticity coordinates CIEx and CIEy in the XYZ color system defined by JIS Z8701 were calculated from data in the wavelength region of 480 nm to 800 nm (in the case of excitation wavelength of 455 nm) of the emission spectrum by a method according to JIS Z8724.

[3. Luminance maintenance rate measurement method]
About 8 mg of measurement sample powder (complex phosphor) was packed in a powder holder having a diameter of 8 mm, and set in a phosphor load test apparatus (manufactured by Koyo Electronics Co., Ltd.). The attached vacuum pump was operated for 25 minutes, and the sample chamber was evacuated. Next, after the vacuum pump was stopped, the pressure was restored with pure nitrogen, and nitrogen was continuously supplied at 2.5 L / min to make the sample chamber a nitrogen atmosphere. As an excitation light source, a near ultraviolet laser diode (emission wavelength: 407 nm) manufactured by Nichia Corporation was used, and the sample powder in the sample chamber in a nitrogen atmosphere was irradiated with an excitation light intensity of 500 mW / cm ² . The time change of the emission spectrum from the sample powder was measured using MCPD-3000 manufactured by Otsuka Electronics. The evaluation was performed at room temperature.

  The emission peak area is calculated from the emission spectrum, and the ratio of the peak area at time t = 90 minutes to the peak area at time t = 0 minutes in the change over time (the peak area at time t = 0 minutes is 1). The peak area at t = 90 minutes when normalized) was defined as the luminance maintenance rate (%).

[4. Internal quantum efficiency, external quantum efficiency, and absorption efficiency]
The absorption efficiency αq, internal quantum efficiency ηi, and external quantum efficiency ηo of the phosphor were determined as follows.
First, the phosphor sample to be measured was packed in a cell with a sufficiently smooth surface so that the measurement accuracy was maintained, and was attached to an integrating sphere.

  Light was introduced into this integrating sphere from an emission light source (150 W Xe lamp) for exciting the phosphor using an optical fiber. The emission peak wavelength of light from the light emission source was adjusted using a monochromator (diffraction grating spectrometer) or the like so as to be monochromatic light of 455 nm. Using this monochromatic light as excitation light, the phosphor sample to be measured was irradiated, and the spectrum was measured for the emission (fluorescence) and reflected light of the phosphor sample using a spectrometer (MCPD7000 manufactured by Otsuka Electronics Co., Ltd.). The light in the integrating sphere was guided to a spectroscopic measurement device using an optical fiber.

The absorption efficiency αq is a value obtained by dividing the number of photons _Nabs of excitation light absorbed by the phosphor sample by the total number of photons N of excitation light.

The total number of photons N of the latter excitation light is proportional to the numerical value obtained by the following (formula A). Therefore, a “Spectralon” manufactured by Labsphere (having a reflectance R of 98% with respect to the excitation light having a wavelength of 450 nm), which is a reflector having a reflectance R of almost 100% with respect to the excitation light, is measured. A reflection spectrum I _ref (λ) was measured by attaching to the integrating sphere with the same arrangement as the phosphor sample, irradiating with excitation light, and measuring with a spectroscopic measurement device, and the following value (Equation A) was obtained. .

Here, the integration interval was 410 nm to 480 nm.
The number N _abs of the photons in the excitation light that is absorbed in the phosphor sample is proportional to the amount calculated by the following equation (B).

Therefore, the reflection spectrum I (λ) was obtained when the phosphor sample for which the absorption efficiency αq is to be obtained was attached. The integration range of (Formula B) was the same as the integration range defined in (Formula A). Since the actual spectrum measurement value is generally obtained as digital data divided by a certain finite bandwidth with respect to λ, the integration of (Equation A) and (Equation B) was obtained by the sum based on the bandwidth. .
From the above, αq = _Nabs / N = (Formula B) / (Formula A) was calculated.

Next, the internal quantum efficiency ηi was determined as follows. Internal quantum efficiency ηi is a value obtained by dividing the number N _abs of photons number N _PL of photons originating from the fluorescence phenomenon absorbed by the phosphor sample.
Here, N _PL is proportional to the amount obtained by the following (formula C). Therefore, the amount required by the following (formula C) was determined.

The integration interval was 481 nm to 800 nm.
As described above, ηi = (formula C) / (formula B) was calculated, and the internal quantum efficiency ηi was obtained.

It should be noted that the integration from the spectrum that was converted to digital data was performed in the same manner as when the absorption efficiency αq was obtained.
And the external quantum efficiency (eta) o was calculated | required by taking the product of absorption efficiency (alpha) q calculated | required as mentioned above and internal quantum efficiency (eta) i.

[Example 1]

  Dissolve 2.1 g of diphenylpyridylphosphine (manufactured by Aldrich) in 30 mL of ethanol (Pure Chemical) and slowly drop 2.0 mL of an aqueous solution of 30 wt% hydrogen peroxide (Wako Pure Chemical Industries) at 0 ° C for 5 hours at room temperature. Stir. Thereafter, 50 mL of water was added to the reaction solution, extraction was performed with methylene chloride, magnesium sulfate (Kanto Chemical) was added to the organic layer, dried, and concentrated by filtration. The obtained solid was recrystallized from hexane to obtain 1.1 g of a white solid (phosphine oxide).

The obtained phosphine oxide and 686 mg of hexafluoroacetylacetone (manufactured by Aldrich) are dissolved in 5 mL of isopropanol, 404 mg of triethylamine (Junsei) is added, and then a solution of 366 mg of europium chloride hydrate EuCl ₃ / 6H ₂ O in ethanol (5 mL) is added. The solution was added dropwise and stirred at room temperature for 2 hours. After completion of the reaction, the mixture was concentrated, water was added, the crude product was washed and filtered, and recrystallized with hexane to obtain 2.0 g of the target complex 1.

The emission spectrum of the complex 1 is measured, and the target complex is obtained from the maximum emission peak wavelength (616 nm) and chromaticity (CIE (x, y) = (0.65, 0.31)). Confirmed that.
Moreover, about this complex 1, the brightness | luminance maintenance factor, the quantum efficiency, and the absorption efficiency were measured. The results are shown in Table 1.

[Comparative Example 1]
For the following complex A, which is a known complex, the luminance maintenance factor, quantum efficiency, and absorption efficiency were measured in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
With respect to the following complex B, which is a known complex, the luminance maintenance factor, quantum efficiency, and absorption efficiency were measured in the same manner as in Example 1. The results are shown in Table 1.

[Example 2]

6 mL of deuterated methanol was added to the complex 1 obtained in Example 1 and refluxed for 4 hours. Thereafter, 824 mg of the target complex 2 could be obtained by recrystallization.
About this complex 2, the emission spectrum was measured like Example 1, and it confirmed that the target complex was obtained from the maximum light emission peak wavelength and chromaticity.
Moreover, about this complex 2, the luminance maintenance factor, the quantum efficiency, and the absorption efficiency were measured. The results are shown in Table 2.

[Comparative Example 3]
With respect to the following complex C, which is a known complex, the luminance maintenance rate, quantum efficiency, and absorption efficiency were measured in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 4]
For the following complex D, which is a known complex, the luminance maintenance ratio, quantum efficiency, and absorption efficiency were measured in the same manner as in Example 1. The results are shown in Table 2.

[Example 3]

  6.3 g (Tokyo Kasei) of bromopyridine was dissolved in 50 mL of dehydrated diethyl ether (Kanto Chemical), and 26 mL of butyl lithium (Kanto Chemical) was added at −78 ° C. under nitrogen, followed by stirring for 30 minutes while raising the temperature to 0 ° C. . Thereafter, 3.2 g of dichlorophenylphosphine was added, and the mixture was further stirred at room temperature for 2 hours. After adding 100 mL of methylene chloride and filtering the inorganic salt, the solution was concentrated and purified by column chromatography (developing solvent: dichloromethane / methanol 10/1) to obtain 1.7 g of dipyridylphenylphosphine.

  1.0 g of the obtained phosphine was dissolved in 50 mL of ethanol (Pure Chemical), 1.0 mL of an aqueous solution of 30% by weight of hydrogen peroxide (Wako Pure Chemical Industries) was slowly added dropwise at 0 ° C., and the mixture was stirred for 1 hour at room temperature. Thereafter, 50 mL of water was added to the reaction solution, extraction was performed with methylene chloride, magnesium sulfate (Kanto Chemical) was added to the organic layer, dried, and concentrated by filtration. The obtained solid was washed with hexane to obtain 1.0 g of a white solid (phosphine oxide).

560 mg of the obtained phosphine oxide and 686 mg of hexafluoroacetylacetone (manufactured by Aldrich) are dissolved in 5 mL of isopropanol. After adding 404 mg (Pure Chemical) of triethylamine, a solution of 366 mg of europium chloride hydrate EuCl ₃ / 6H ₂ O in ethanol (5 mL) Was added dropwise and stirred at room temperature for 2 hours. After completion of the reaction, the mixture was concentrated, water was added, the crude product was washed and filtered, and recrystallized from hexane, whereby 880 mg of the target complex 3 could be obtained.

The complex 3 was measured for its emission spectrum, and it was confirmed from the maximum emission peak wavelength and chromaticity that the desired complex was obtained.
Moreover, about this complex 3, the brightness | luminance maintenance factor, the quantum efficiency, and the absorption efficiency were measured. The results are shown in Table 3.

[Example 4]

  Dissolve 2.58 g of 2-bromo-5-methylpyridine (Tokyo Kasei) in 20 mL of dehydrated diethyl ether (Kanto Chemical), add 10.3 mL of butyllithium (Kanto Chemical) at -78 ° C under nitrogen, and raise the temperature to 0 ° C. The mixture was stirred for 30 minutes. Thereafter, 3.75 g of chlorodiphenylphosphine was added, and the mixture was further stirred at room temperature for 2 hours. After adding 50 mL of methylene chloride and filtering the inorganic salt, the solution was concentrated and purified by column chromatography (developing solvent: dichloromethane / methanol 10/1) to obtain 3.0 g of 5-methyl-2-pyridylphenylphosphine.

  3.0 g of the obtained phosphine was dissolved in 40 mL of tetrahydrofuran (Pure Chemical), and 4 mL of an aqueous solution of 30 wt% hydrogen peroxide (Wako Pure Chemical Industries) was slowly added dropwise at 0 ° C. and stirred for 1 hour at room temperature. Thereafter, 100 mL of water was added to the reaction solution, extraction was performed with methylene chloride, magnesium sulfate (Kanto Chemical) was added to the organic layer, dried, and concentrated by filtration. The obtained solid was washed with hexane to obtain 3.2 g of a white solid (phosphine oxide).

587 mg of the obtained phosphine oxide and 686 mg of hexafluoroacetylacetone (manufactured by Aldrich) are dissolved in 5 mL of isopropanol. After adding 404 mg (Pure Chemical) of triethylamine, a solution of 366 mg of europium chloride hydrate EuCl ₃ / 6H ₂ O in ethanol (5 mL) Was added dropwise and stirred at room temperature for 2 hours. After completion of the reaction, the mixture was concentrated, water was added, the crude product was washed and filtered, and recrystallized with methanol, whereby 1.0 g of the desired complex 4 could be obtained.

The complex 4 was measured for its emission spectrum, and it was confirmed from the maximum emission peak wavelength and chromaticity that the desired complex was obtained.
Moreover, about this complex 4, the brightness | luminance maintenance factor, the quantum efficiency, and the absorption efficiency were measured. The results are shown in Table 3.

[Example 5]

  Dissolve 1.65 mL of 2-bromo-6-methylpyridine (Aldrich) in 29 mL of dehydrated THF (Kanto Chemical), add 9.25 mL of butyl lithium (Kanto Chemical) at −78 ° C. under nitrogen, and increase the temperature to 0 ° C. Stir for minutes. Thereafter, 2.7 mL of chlorodiphenylphosphine (Wako Pure Chemical Industries) was added, and the mixture was further stirred at room temperature for 2 hours. 50 mL of methylene chloride was added for extraction, and after concentration by drying filtration with magnesium sulfate, purification was performed by column chromatography (developing solvent: dichloromethane / methanol 10/1) to obtain 4.2 g of 6-methyl-2-pyridylphenylphosphine.

  The obtained phosphine was dissolved in 73 mL of THF (Pure Chemical), and 1.5 mL of an aqueous solution of 30% by weight of hydrogen peroxide (Wako Pure Chemical Industries, Ltd.) was slowly added dropwise at 0 ° C. and stirred for 40 minutes at room temperature. Thereafter, 100 mL of water was added to the reaction solution, followed by extraction with methylene chloride. Magnesium sulfate (Kanto Chemical) was added to the organic layer, dried, and concentrated by filtration. The obtained solid was washed with hexane to obtain 4.5 g of a white solid (phosphine oxide).

587 mg of the obtained phosphine oxide and 686 mg of hexafluoroacetylacetone (manufactured by Aldrich) are dissolved in 5 mL of isopropanol. After adding 404 mg (Pure Chemical) of triethylamine, a solution of 366 mg of europium chloride hydrate EuCl ₃ / 6H ₂ O in ethanol (5 mL) Was added dropwise and stirred at room temperature for 2 hours. After completion of the reaction, the mixture was concentrated, water was added, the crude product was washed and filtered, and recrystallized with methanol, whereby 1.1 g of the target complex 5 could be obtained.

The complex 5 was measured for its emission spectrum, and it was confirmed from the maximum emission peak wavelength and chromaticity that the desired complex was obtained.
Moreover, about this complex 5, the brightness | luminance maintenance factor, the quantum efficiency, and the absorption efficiency were measured. The results are shown in Table 3.

[Example 6]

  Dissolve 6.32 g of 3-bromopyridine (Tokyo Kasei) in 50 mL of dehydrated diethyl ether (Kanto Chemical), add 26.3 mL of butyllithium (Kanto Chemical) at -78 ° C under nitrogen, and raise the temperature to 0 ° C for 30 minutes. Stirring was performed. Thereafter, 9.7 g of chlorodiphenylphosphine was added, and the mixture was further stirred at room temperature for 2 hours. After adding 100 mL of methylene chloride and filtering the inorganic salt, the solution was concentrated and purified by column chromatography (developing solvent: dichloromethane / methanol = 10/1) to obtain 3-pyridylphenylphosphine.

  The obtained phosphine was dissolved in 100 mL of acetone (Pure Chemical), and 2.0 mL of an aqueous solution of 30% by weight of hydrogen peroxide (Wako Pure Chemical Industries) was slowly added dropwise at 0 ° C. and stirred at room temperature for 1 hour. Thereafter, 100 mL of water was added to the reaction solution, followed by extraction with methylene chloride. Magnesium sulfate (Kanto Chemical) was added to the organic layer, dried, and concentrated by filtration. The obtained solid was washed with hexane to obtain 3.3 g of a white solid (phosphine oxide).

559 mg of the obtained phosphine oxide and 686 mg of hexafluoroacetylacetone (manufactured by Aldrich) are dissolved in 5 mL of isopropanol. After adding 404 mg (Pure Chemical) of triethylamine, a solution of 366 mg of europium chloride hydrate EuCl ₃ / 6H ₂ O in ethanol (5 mL) Was added dropwise and stirred at room temperature for 2 hours. After completion of the reaction, the mixture was concentrated, water was added, the crude product was washed and filtered, and recrystallized with methanol, whereby 724 mg of the target complex 6 could be obtained.

The complex 6 was measured for its emission spectrum, and it was confirmed from the maximum emission peak wavelength and chromaticity that the desired complex was obtained.
Moreover, about this complex 6, the brightness | luminance maintenance factor, the quantum efficiency, and the absorption efficiency were measured. The results are shown in Table 3.

[Example 7]

  Dissolve 1.5 g of trifurylphosphine (WAKO) in 32 mL of THF (Pure Chemical), slowly add 0.66 mL of 30 wt% hydrogen peroxide aqueous solution (Wako Pure Chemical Industries) at 0 ° C and stir at room temperature for 5 hours. did. Thereafter, 60 mL of water was added to the reaction solution, extraction was performed with methylene chloride, magnesium sulfate (Kanto Chemical) was added to the organic layer, dried, and concentrated by filtration. The obtained solid was recrystallized from hexane to obtain 1.1 g of a white solid (phosphine oxide).

The obtained phosphine oxide and 686 mg of hexafluoroacetylacetone (manufactured by Aldrich) are dissolved in 5 mL of isopropanol, and after adding 480 mg of triethylamine (Pure Chemical), a solution of 366 mg of europium chloride hydrate EuCl ₃ / 6H ₂ O in ethanol (5 mL) Was added dropwise and stirred at room temperature for 2 hours. After completion of the reaction, the mixture was concentrated, water was added, the crude product was washed and filtered, and recrystallized with methanol, whereby 836 mg of the target complex 7 was obtained.

With respect to the complex 7, the emission spectrum was measured, and it was confirmed that the target complex was obtained from the maximum emission peak wavelength and chromaticity.
Moreover, about this complex 7, the brightness | luminance maintenance factor, the quantum efficiency, and the absorption efficiency were measured. The results are shown in Table 3.

  The present invention relates to a novel rare earth complex phosphor having high durability and high luminance, and the phosphor is particularly suitable for use in light such as illumination and image display devices.

It is a figure which shows typically about the screen for projectors as an example of the laminated body of this invention. It is a typical perspective view which shows the positional relationship of an excitation light source (1st light emission body) and a fluorescent substance containing part (2nd light emission body) in an example of the light-emitting device of this invention. 3 (a) and 3 (b) are schematic views showing an embodiment of a light emitting device having an excitation light source (first light emitter) and a phosphor containing portion (second light emitter). It is sectional drawing. It is sectional drawing which shows typically one Embodiment of the illuminating device of this invention. It is a figure which shows typically the hourglass as an example of the use of the fluorescent substance of this invention. It is a figure which shows typically the snow dome as an example of the use of the fluorescent substance of this invention.

Explanation of symbols

1: Screen 2: Sheet 3: Phosphor-containing layer 4: Projector 5: Laser pointer 6: Spot 11: Second light emitter 12: Surface-emitting GaN-based LD
13: Substrate 14: Light emitting device 15: Mount lead 16: Inner lead 17: First light emitter 18: Phosphor-containing resin part 19: Conductive wire 20: Mold member 21: Excitation light source 22: Phosphor containing part 23: Frame 24: Conductive wire 25, 26: Electrode 27: Surface emitting illumination device 28: Holding case 29: Light emitting device 30: Diffusion plate 31: Hourglass 32: Support 33, 34: Base 35: Transparent container 36: Orifice 37, 38 : Room 39: Sand 40: Snow dome 41: Pedestal 42: Transparent container 43: Miniature 44: Liquid 45: Snow material

Claims (11)

A rare earth complex having a ligand represented by any one of the following formulas (1) and (2).

(In the formula (1), R ^{1 to} R ³ each independently represents an aromatic hydrocarbon group or a group represented by —XA , and at least one of them is —XA. It is a group represented.
In formula (2), R ⁴ , R ⁵ , R ⁴ ′ and R ⁵ ′ each independently represent an aromatic hydrocarbon group or a group represented by —XA , and at least of these One is a group represented by -X-A;
R ⁶ represents a divalent linking group.
here,
X represents a direct binding,
A represents a pyridyl group, a quinoxalinyl group, an isoquinolyl group, a quinolyl group, a pyrazinyl group, a pyrimidinyl group or a pyridazinyl group, a nitrogen-containing 6-membered cyclic group or a condensed polycyclic group composed of a 6-membered ring; A 5-membered heterocyclic group selected from a pyrazolyl group, an imidazolyl group, an oxazolyl group, a thiazolyl group, a furyl group, and a thienyl group; selected from a benzothienyl group, a dibenzothienyl group, a dibenzofuranyl group, and a phenoxathiinyl group The molecular orbital energy of the highest occupied orbital obtained from the molecular orbital calculation of the heterocyclic compound which is a heterocyclic group selected from 5-membered heterocyclic groups having a condensed ring and which constitutes the heterocyclic group is higher than that of the benzene ring. Indicates a large one. ) 2. The rare earth complex according to claim 1, wherein the rare earth metal element constituting the rare earth complex is an element selected from the group consisting of Eu, Tb, Tm and Ce. The rare earth complex according to claim 1 or 2 , which has an anionic ligand represented by the following formula (3) or (4).

(In Formula (3), R ⁷ and R ⁹ are each independently a perfluoroalkyl group, an aromatic hydrocarbon group having an electron-withdrawing group, or an optionally substituted heterocyclic group. Indicate
R ⁸ represents a hydrogen atom, a deuterium atom, an alkyl group, an aromatic hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent,
In formula (4), R ¹⁰ represents an aromatic hydrocarbon group having an electron-withdrawing substituent or a heterocyclic group which may have a substituent. ) A rare earth complex phosphor having a ligand represented by either the following formula (1) or (2).

(In the formula (1), R ^{1 to} R ³ each independently represents an aromatic hydrocarbon group or a group represented by —XA , and at least one of them is —XA. It is a group represented.
In formula (2), R ⁴ , R ⁵ , R ⁴ ′ and R ⁵ ′ each independently represent an aromatic hydrocarbon group or a group represented by —XA , and at least of these One is a group represented by -X-A;
R ⁶ represents a divalent linking group.
here,
X represents a direct binding,
A represents a pyridyl group, a quinoxalinyl group, an isoquinolyl group, a quinolyl group, a pyrazinyl group, a pyrimidinyl group or a pyridazinyl group, a nitrogen-containing 6-membered cyclic group or a condensed polycyclic group composed of a 6-membered ring; A 5-membered heterocyclic group selected from a pyrazolyl group, an imidazolyl group, an oxazolyl group, a thiazolyl group, a furyl group, and a thienyl group; selected from a benzothienyl group, a dibenzothienyl group, a dibenzofuranyl group, and a phenoxathiinyl group The molecular orbital energy of the highest occupied orbital obtained by the molecular orbital calculation of the heterocyclic compound that is a heterocyclic group selected from a 5-membered heterocyclic group having a condensed ring and that constitutes the heterocyclic group is higher than that of the benzene ring. Indicates the big one. ) A phosphor-containing composition comprising the rare earth complex phosphor according to claim 4 and a liquid medium. A laminate comprising a phosphor-containing layer containing the rare earth complex phosphor according to claim 4 . A color conversion film comprising the rare earth complex phosphor according to claim 4 . A first light emitter, and a second light emitter that emits visible light by irradiation of light from the first light emitter,
The light emitting device, wherein the second light emitter contains at least one rare earth complex phosphor according to claim 4 as the first phosphor. 9. The light emitting device according to claim 8 , wherein the second phosphor includes at least one phosphor having a light emission peak wavelength different from that of the first phosphor as the second phosphor. Lighting apparatus comprising: a light-emitting device according to claim 8 or 9. The image display apparatus comprising: a light-emitting device according to claim 8 or 9.

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