JP2007324337A - Linear light emitter and its manufacturing method, and light emitting device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an airtight sealing method which can seal an organic phosphor with a sufficient air-tightness even at the upper temperature limit of the organic phosphor, thereby to provide a linear light emitter which can materialize a white LED, specifically, a white LED with little color variation, and also to provide its manufacturing method. <P>SOLUTION: The linear light emitter includes the organic phosphor for converting the light emitted from a light emitting element into visible light. In the linear light emitter, the organic phosphor are two sheets of plate material, and at least one of the sheets of plate material is put between plates made of a light-transmitting plate material and is air-tightly sealed. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

INDUSTRIAL APPLICABILITY The present invention uses a linear light emitter and a manufacturing method thereof, and a light emitting device using the linear light emitter, in particular, a linear light emitter capable of realizing a white LED, a manufacturing method thereof, and the linear light emitter. The present invention relates to a light emitting device.

Conventionally, as a light emitting device, an LED element is mounted on a lead frame or an insulating substrate (glass epoxy, ceramic, MID) with Ag paste or the like, connected by wire bonding, and sealed with epoxy resin or silicone resin. It was an LED lamp. In the case of a white LED, a GaN-based blue element is used, and a YAG phosphor is mixed in the resin to form an LED lamp, realizing a pseudo white color with yellow as excitation light and blue transmitted through the YAG phosphor. (Patent Document 1).
However, since all of the YAG phosphors are inorganic phosphors, they have a wide excitation spectrum, poor matching with a liquid crystal color filter, and problems such as efficiency and crosstalk.
Therefore, in order to expand the color reproducibility, in addition to the YAG phosphor in the resin, a red phosphor or a red LED has been added.
Among these, the diketone proposed in Patent Documents 2 and 3 or the Eu complex having the carboxylic acid proposed in Patent Document 4 as a ligand has high emission intensity and excellent color rendering. It is a red luminescent material with excellent color reproducibility.
However, these complexes are sensitive to oxygen and humidity and require hermetic sealing.
Conventionally, as a method for performing such sealing, a phosphor layer is formed on the inner wall of the outer cap of the light-emitting device by coating, and the inside is sealed in a vacuum or an inert gas atmosphere. Has been proposed (Patent Document 5). However, in this proposal, there is no disclosure about the material of the cap and the temperature at which the sealing is performed, and the sealing is not actually performed.
In addition, there is also a proposal regarding the use of an organic polymer complex as a light emitter (Patent Document 6), but there is no disclosure regarding a specific sealing method.
JP 2006-49657 A JP 2005-252250 A Japanese Patent Laid-Open No. 2003-81986 JP 2005-8872 A JP 2004-352928 A JP 2002-163902 A

The organic phosphor has a low heat-resistant temperature. For example, the temperature during sealing cannot be increased to about 200 ° C. or higher.
Accordingly, an object of the present invention is to realize a white LED, particularly a white LED with little color variation, by proposing a hermetic sealing method that can sufficiently withstand the heat-resistant temperature in hermetically sealing an organic phosphor. A linear light-emitting body, a manufacturing method thereof, and a light-emitting device using the linear light-emitting body.

An object of the present invention is to provide a linear light-emitting body including an organic phosphor that converts light emitted from a light-emitting element into visible light, the organic phosphor being two plate members, and at least one of them. Is achieved by a linear light emitter characterized by being sandwiched between light-transmitting plates and hermetically sealed.
In this case, the light emitting element is preferably a near ultraviolet LED that emits near ultraviolet light.
Moreover, it is preferable that it is a glass plate as at least one board | plate material of translucency.
The two plate materials are glass plates, and the organic phosphor is preferably hermetically sealed between the glass plates with a fusing agent.
The two glass plates are also preferably hermetically sealed using a fusing agent and a frame member.
The fusion agent is preferably formed from a solder material.
The frame member is preferably formed of a glass material or a thermosetting adhesive.
Furthermore, the organic phosphor is preferably a red phosphor complex.
The red phosphor complex is preferably a Eu diketone or a carboxylic acid complex.
In addition to the organic phosphor, it is preferable to use a blue and / or green phosphor.
Furthermore, it is preferable that one or two or more near-ultraviolet LEDs are arranged in a linear light emitter to constitute a light emitting device.
And, in the manufacturing process of the linear light emitter, it has a step of forming a predetermined frame material pattern and bonding a translucent plate material,
During this pasted process, a space and a gate part are formed,
Further, a step of injecting an organic phosphor in a predetermined atmosphere from the gate portion exposed between the frame material patterns,
Applying a fusion agent to the gate portion to close the gate portion;
And a step of cutting, and it is preferable to obtain a linear light emitter in a collective manner.
In addition, a step of applying an organic phosphor in a predetermined atmosphere to one of the light-transmitting plates among the two light-transmitting plates,
Forming a frame member in a predetermined pattern according to the shape when the organic phosphor is applied to one and / or the other translucent plate;
A step of fusing or sealing these two light-transmitting plate members in a predetermined atmosphere;
And a step of cutting, and it is preferable to obtain a linear light emitter in a collective manner.

According to the present invention, since the organic phosphor can be hermetically sealed without deterioration in characteristics, and the application amount and position of the organic phosphor can be controlled, a white LED with little color variation can be realized. Further, since near-ultraviolet light emitted from the near-ultraviolet LED is converted into excitation light by the phosphor, there is no color coordinate shift due to temperature or long-term deterioration. Further, since the excitation light of the organic phosphor is sharp, color reproducibility and saturation can be increased. Moreover, since a linear light emitter capable of displaying an arbitrary size, for example, an A4 size or larger, can be realized, it is extremely useful in applications such as personal computers.

The linear light-emitting body in this embodiment is characterized in that it is hermetically sealed by sandwiching an organic phosphor between two glass plates, more preferably as a light-transmitting substrate, particularly as a light-transmitting substrate. As shown in FIGS. 1 and 2, the basic structure of the light-emitting device 100 is an injection-molded substrate having an upper opening, more preferably a molded substrate 1 made of ceramic such as alumina, and the molded substrate. Two plate members facing a light emitting diode element (not shown) mounted on the bottom of the substrate and a molded substrate 1 facing, for example, a reflection frame (not shown) provided integrally with the molded substrate 1 In particular, a line made of a translucent substrate, preferably a long glass plate 311, 315 and a container having a layer of organic phosphor 40 sandwiched therebetween and hermetically sealed therein A light emitter 10 is disposed. In addition, although the board | substrate made from a ceramic was illustrated in the above, it can be used without a restriction | limiting in particular. Further, in the illustrated example, two molded substrates 1 incorporating LED elements are provided on both sides of the linear light emitter, but only one may be used. In addition, a plurality of the light emitters 10 can be arranged below the linear light emitter 10. Moreover, as a translucent board, the board | plate material of various plastic materials which gave glass gas barrier property other than a glass plate can also be used, for example. In addition, as a light emitting element, near ultraviolet LED which light-emits near ultraviolet light is preferable.
In this case, sealing hermetically may be performed in a vacuum or in an inert gas atmosphere such as nitrogen or Ar, and hermetically sealed in an atmosphere having an oxygen gas concentration of 100 ppm, preferably 20 ppm or less. Say to stop. Moreover, you may seal using inert liquids, such as a silicone oil.

The two glass plates 311 and 315 constituting the linear light-emitting body 10 are linear and usually have a thickness of about 0.1 to 2 mm, a width of about 1 to 5 mm, particularly about 2 to 3 mm, and a length. Is a length that matches the length in the short or long direction of the display. Therefore, for example, in the case of a display of 10 to 500 mm, particularly A4 size, the length in the longitudinal direction of the display is about 300 mm. The two glass plates 311 and 315 may be formed of the same material or may be formed of different materials. However, both are preferably transparent in the visible range and high in strength.
The Young's modulus of the glass material is about 50 to 80 MPa, the density is 2 to ³ g / cm ³ , the refractive index is about 1.4 to 1.6, and the softening point is an arbitrary value of 600 to 1600 ° C. If it is in range. Note that the transmittance in the visible region is 400 nm or more, preferably 80% or more, and particularly preferably 85% or more.
The transmittance in the near ultraviolet region of 350 nm or less is preferably 40% or less.
Such a glass material may be any of white plate glass, high silicate glass, zinc borosilicate glass and the like. For example, as white plate glass, SiO ₂ 60-80%, Al ₂ O ₃ 1-5%, B ₂ O ₃ 2-5%, NaO, K ₂ O, CaO total 20-30%, high silicic acid The glass is preferably SiO ₂ 80% or more, particularly 90% or more, and the zinc borosilicate glass is preferably a composition such as SiO ₂ 70 to 90%, residual ZnO.
One of the plate materials may be a plate material that reflects or scatters alumina, ceramics, or the like. In particular, as shown in the figure, for example, when the molded substrate 1 on which the LED is mounted is provided at both ends of the linear light emitter 10 to form a backlight, a reflecting member or the like is separately provided on any plate material. There is no need to provide it, and the manufacturing process can be simplified. However, even in such a case, one of the plate materials is a translucent plate material. Note that the linear shape of the linear light emitter is a linear shape, but is not necessarily a linear shape, and may be a curved shape as necessary.

A sealing material is used to fuse or seal the two glass plates 311 and 315 with each other. Various adhesives such as an ultraviolet curable resin can be used as the sealing material, but it is particularly preferable to use an Sn-based low-melting-point solder material from the viewpoint of hermetic sealing. In the example shown in FIGS. 1 and 2, fusion agents 51 and 55 (55 is a frame member) are formed as sealing materials. As a result, hermetic sealing can be performed at a temperature lower than the heat resistant temperature of the organic phosphor to be used, thereby preventing deterioration of characteristics due to heat.
In this case, the Sn-based solder is preferably an alloy containing 58% of eutectic Bi in Sn, and the melting point is preferably about 110 to 140 ° C. At this time, flux or the like may be used as necessary.

3 and 4 show a more efficient method for hermetic sealing by such fusion or sealing.
In the example shown in FIGS. 3 and 4, on one side of the long glass plate 311, for example, screen printing, a dispenser, etc., and other methods, a sealant for spacers for determining the gap is predetermined in the X direction. The frame member 55 having a plurality of patterns 555 is formed by coating or applying a glass material such as glass frit. This pattern 555 is based on two linear portions according to the shape of the light emitter. The two strip-shaped linear portions arranged in parallel to each other are connected to each other with a gap so that one end thereof is connected and the other end has a gate portion 552. . And the thickness is about 50-100 micrometers.
Thereafter, another long glass plate 315 is placed thereon and subjected to a predetermined fusing process. The fusing temperature is, for example, 400 to 600 ° C. Thereafter, in this case, since the gate portion 552 is exposed to the aggregate, the organic phosphor is applied from the exposed gate portion 552 as, for example, a paste. Then, a fusion agent 51 of a low melting point solder material such as Sn is applied to the gate portion 552 and is locally heated at a temperature of 200 ° C. or lower, for example, 140 to 170 ° C., to perform fusion. Then, it is cut in one direction, that is, the Y direction in FIG. 3 using, for example, a carbide chip scriber to obtain a single linear light emitter 10 shown in FIG. Thus, the linear light-emitting body 10 is obtained by a set. As a result, manufacturing efficiency and manufacturing time can be reduced.
Before applying the phosphor and sealing the gate portion 552, cut it into single pieces, and then inject an organic phosphor from the exposed gate portion 552 to seal the gate portion 552. You may stop and obtain the linear light-emitting body 10. FIG. In the illustrated example, the gate portion 552 is already exposed after the glass plates 311 and 315 are fused. However, before injection and fusion, cutting in the Y direction may be performed, and thereafter, cutting may be performed from the aggregate into a single body to expose the gate portion 552, and then injection and fusion may be performed.
In the case where a plurality of patterns 555 are provided in the XY direction, the gate portions 552 may be formed at both ends facing each other in the Y direction, for example. As shown in the drawing, when a plurality of rows of patterns 555 are formed only in the X direction, an organic phosphor can be applied to all the recesses 553 without cutting. In the case where a plurality of patterns 555 are provided in both the XY directions, the gate portion is exposed after cutting, and then an organic phosphor is injected.

In this way, after injecting a phosphor paste or the like into the recess 553 formed between the patterns 555 of the frame member 55 in a predetermined atmosphere, the Sn-based material is dispensed in the same atmosphere by, for example, a dispenser. What is necessary is just to melt | fuse with the melt | fusion agent 51 (refer FIG. 1) of low melting-point solder materials, such as solder. If fused at a predetermined temperature, the linear light emitter 10 is obtained. In this case, the phosphor may be provided as a rectangular straight line as illustrated, or may be provided in various shapes such as a curved line or a circle.
In such a case, the frame member 55 may be made of a glass material such as a glass frit made of the same or different material as the two glass plates 311 and 315, or a filler for determining a gap as necessary. Alternatively, various adhesives with added may be applied, or the adhesive 51 itself may be applied and applied. In this case, the fusing agent 51 may be applied by plating or other methods. In that case, there is no particular limitation on the material of the fusion solder. Further, in the above, an example in which a plurality of pairs and a plurality of patterns 555 of the frame member and the organic phosphor are provided in one direction, for example, the X direction, respectively, but in addition, in the XY direction, A plurality of pairs and a plurality of pairs may be provided, and firstly cut in one direction, for example, the X direction to expose the gate portion 552 of each pattern 555, and thereafter, injection and fusion of organic phosphors may be performed. Good. In this case, in order to obtain a single linear light emitter 10, cutting in the other direction, the Y direction, is required, but this cutting may be performed at any time before or after fusion and injection. Good. In the case where a plurality of patterns 555 provided in the X direction are provided in two rows in the Y direction, the gate portions 552 of the patterns 555 in each row are directed to the end of the glass. According to this, since the phosphor can be injected into the concave portions 553 of all the patterns 555 without cutting in the X direction, the manufacturing efficiency and the manufacturing time can be shortened.

Next, a different method for producing the linear light emitter 10 will be described with reference to FIGS.
In the example shown in FIGS. 5, 6, and 7, an organic phosphor paste or the like is first formed on one surface of a long glass plate 311 in a predetermined atmosphere, for example, in a rectangular pattern by screen printing or the like. To do. In this case as well, in the illustrated example, a plurality are provided in the X direction, but it is needless to say that a plurality may also be provided in the Y direction. Then, corresponding to this organic phosphor pattern, a seal material pattern 555 is formed as a frame member 55 on one surface of the other glass plate 315, for example, by screen printing to a thickness of about 50 to 100 μm. To do. As the sealing material, for example, an epoxy thermosetting adhesive can be used. Then, the two glass plates 311 and 315 are overlapped and bonded at a predetermined temperature of about 120 to 180 ° C., for example. Then, it cut | disconnects to a Y direction, for example, a UV hardening type adhesive agent and a low melting-point solder material may be provided to the gate part 552 in nitrogen atmosphere, and a UV hardening process may be performed. Also in this case, the order of cutting, injection and fusion is not limited.
Note that the linear light emitter can be manufactured by forming the pattern 555 of the sealing material on one or both of the glass plates 311 and 315.

Next, the organic phosphor will be described.
In the present invention, an organic fluorescent complex is used as the phosphor. In addition, organic phosphors such as polymers containing various phosphor portions in the main chain can also be used. Although it does not specifically limit as a fluorescent complex, Usually, the rare earth ion complex which is a complex of the 1 type (s) or 2 or more types of ligand anion and the ion of a trivalent rare earth element is used. Examples of rare earth elements include Sm, Eu, Tb, Ey, Tm and the like. Of these, an Eu (europium) element is preferable as the red phosphor, a Tm (thulium) element as the blue phosphor, and an ion complex of Tb (terbium) element as the green phosphor.
Examples of such fluorescent complexes include JP-A-2005-8872, JP-A-2004-356358, JP-A-2004-352928, JP-A-2005-41941, JP-A-2005-41942, JP 2005-112923 A, JP 2005-252250 A, JP 2003-81986 A, JP 3668966 A, JP 2003-147346 A, International Publication No. 2004/104136 Pamphlet, International Publication No. 2004. / 107459 pamphlet, the international publication 2005/75598 pamphlet, etc. can be illustrated.

In particular, a europium complex which is a red fluorescent complex is preferably used. In the present invention, a polymer containing a phosphor substance in the main chain can be used, but in terms of luminous efficiency, it is preferable to use a diketone or a europium complex having a carboxylic acid as a ligand as the red phosphor. . In addition to the red phosphor, the above-mentioned various organic phosphors may be used, or inorganic phosphors may be used.
As a preferable example of such a complex, first, a complex having a specific β-diketone anion represented by the following formula (1) as a ligand is exemplified.

  In the formula (1), p is 1 or 2, and q is 1, 2, 3 or 4. X may be the same or different and each is a hydrogen atom, deuterium atom, halogen atom (fluorine, chlorine, bromine, iodine), group having 1 to 20 carbon atoms, hydroxyl group, nitro group, amino group, sulfonyl Represents a group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, or a mercapto group. Y may be the same or different and each represents a group having 1 to 20 carbon atoms, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, or a mercapto group. To express. Z represents a hydrogen atom or a deuterium atom.

As the group having 1 to 20 carbon atoms;
A linear or branched alkyl group (C _n H _{2n + 1} ; n = 1 to 20), a perfluoroalkyl group (C _n F _{2n + 1} ; n = 1 to 20), a perchloroalkyl group (C a perhalogenated alkyl group having a straight chain or a branch, such as _n Cl _{2n + 1} ; n = 1 to 20);
Straight or branched alkenyl groups (vinyl group, allyl group, butenyl group), perfluoroalkenyl groups (perfluorovinyl group, perfluoroallyl group, perfluorobutenyl group), perchloroalkenyl groups, etc. A perhalogenated alkenyl group having a chain or a branch;
Cycloalkyl group _{(C n H 2n-1;} n = 3~20), and perfluoro cycloalkyl group _{(C n F 2n-1;} n = 3~20), perchlorethylene alkyl group _{(C n Cl 2n-1} A perhalogenated alkyl group having a straight chain or a branch, such as n = 3 to 20);
A cycloalkenyl group (cyclopenten-yl group, cyclohexen-yl group and the like), and a perhalogenated alkenyl group such as a perfluorocycloalkenyl group and a perchloroalkenyl group;
Aromatic groups such as phenyl, naphthyl and biphenyl, and perhalogenated aromatics such as perfluorophenyl, perfluoronaphthyl, perfluorobiphenyl, perchlorophenyl, perchloronaphthyl and perchlorobiphenyl Group;
Heteroaromatic groups such as pyridyl groups and perhalogenated heteroaromatic groups such as perfluoropyridyl groups;
Aralkyl groups such as benzyl group and phenethyl group, and perhalogenated aralkyl groups such as perfluorobenzyl group;
Etc.

The group having 1 to 20 carbon atoms represented by X and Y is a deuterium atom, a halogen atom (fluorine, chlorine, bromine, iodine), a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, if necessary. It may be substituted with a substituent such as a silyl group, a phosphonic acid group, a diazo group, or a mercapto group.
Further, an ether, ester, or ketone structure may be formed by interposing one or more —O—, —COO—, or —CO— between C—C single bonds at arbitrary positions of a group having 1 to 20 carbon atoms. Good.

The europium complex of the formula (1) in which X and Y are alkenyl groups may be polymerized with an olefin such as ethylene and propylene and a halogenated olefin as necessary to form a high-molecular europium complex.

  In the compound represented by the formula (1), the above-mentioned compounds can be used as Y. In particular, in view of the stability and emission intensity of a solid support containing a europium complex or a europium complex, the number of carbon atoms 1-4 alkyl groups, perhalogenated alkyl groups, aromatic groups, perhalogenated aromatic groups, heteroaromatic groups, perhalogenated heteroaromatic groups are preferred, among which perfluoroalkyl groups, aromatic groups, Heteroaromatic groups are most preferred.

  p is 1 or 2, but is preferably 2. q is any one of 1 to 4, and is preferably 3.

A complex represented by the formula (1) in which Z is a deuterium atom D is a deuterium substitution reaction between the complex represented by the formula (1) in which Z is a hydrogen atom and a deuterating agent. Is obtained. Examples of the deuterating agent used include deuterium-containing protic compounds, specifically, deuterated alcohols such as deuterated water, deuterated methanol, and deuterated ethanol, deuterated hydrogen chloride, and deuterated alkali. It is done. In order to accelerate the reaction, a base agent or additive such as trimethylamine or triethylamine may be added. The deuterium substitution reaction is obtained by mixing the complex represented by the formula (1) in which Z is a hydrogen atom and a deuterating agent, but an aprotic solvent may be added during the reaction. Examples of aprotic solvents include ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as diethyl ether and tetrahydrofuran, halogen solvents such as chloroform and methylene chloride, dimethyl sulfoxide (DMSO), and dimethylformamide (DMF). It is done. Among these, a solvent in which the formula (1) is soluble and soluble is preferable.

Moreover, as a quantity of the deuterating agent to be used, about 1-100 mass parts is illustrated with respect to the total amount (it is set as 1 mass part) of the complex represented by Formula (1), Preferably it is 1-20 mass parts Degree.

  The mixing method is not particularly limited, and is performed at a temperature of room temperature to 150 ° C., preferably at a temperature of 30 ° C. to 100 ° C., with stirring as necessary for 0.1 to 100 hours, preferably 0 to 20-20. Mix for hours.

  After the stirring, the deuterating agent and the solvent are distilled off to obtain a deuterated complex. Moreover, it can further refine | purify by methods, such as recrystallization, column chromatography, and sublimation, as needed.

As a specific example of the complex represented by the formula (1), according to the notation of the formula (1),
A compound represented by a combination of X = H, Y = CF ₃ , Z = H, p = 2 and q = 3 (complex compound 1-1),
A compound represented by a combination of X = H, Y = CF ₃ , Z = D, p = 2, q = 3 (complex compound 1-2),
Etc.

Moreover, as a preferable example of a europium complex, the complex which uses the anion of (beta) -diketone which has a substituent containing an aromatic ring, or the carboxylate ion which has a substituent containing an aromatic group as a ligand is mentioned.

Examples of the complex having a β-diketone anion having a substituent containing an aromatic ring as a ligand include a europium complex represented by the following formula (2), (3) or (4).
(R ₁ ) ₃ Eu (2)
(R ₁ ) ₃ Eu (R ₂ ) ₂
(3)
[(R ₁ ) ₄ Eu] ⁻ R ₃ ⁺
(4)
In the formulas (2), (3) and (4), R ₁ is an anion of a β-diketone having a substituent containing an aromatic ring, R ₂ is an auxiliary ligand composed of a Lewis base, and R ₃ ⁺ Is a quaternary ammonium ion.

The β-diketone having a substituent containing an aromatic ring in the formulas (2), (3) and (4) preferably has at least one aromatic group. And a group derived from an aromatic hydrocarbon compound or an aromatic heterocyclic (heterocyclic) compound which may have a group.
Examples of the aromatic hydrocarbon compound include benzene, naphthalene, phenanthrene, and the like. Examples of the aromatic heterocyclic compound include heterocyclic compounds containing oxygen, nitrogen, and sulfur atoms such as furan, thiophene, pyrazoline, pyridine, carbazole, dibenzofuran, and dibenzothiophene.

  Examples of the substituent of these aromatic hydrocarbon compounds or aromatic heterocyclic compounds include alkyl groups such as methyl, ethyl, propyl, and butyl; fluoroalkyl groups such as trifluoromethyl and pentafluoromethyl; methoxy, Alkoxy groups such as ethoxy; aryloxy groups such as benzyl and phenethyl; hydroxyl groups; allyl groups; acyl groups such as acetyl and propionyl; acyloxy groups such as acetoxy, propionyloxy and benzoyloxy; alkoxycarbonyls such as methoxycarbonyl and ethoxycarbonyl Group; aryloxycarbonyl group such as phenoxycarbonyl; carboxyl group; carbamoyl group; amino group; substituted dimethylamino, diethylamino, methylbenzylamino, diphenylamino, acetylmethylamino, etc. Amino group; methylthio, ethylthio, phenylthio, substituted thio group such as benzylthio; a mercapto group; ethylsulfonyl, substituted sulfonyl groups such as phenylsulfonyl; cyano group; fluoro, chloro, bromo, and the like halogen groups iodine and the like. These substituents may be bonded to each other to form a ring.

  Examples of the substituent other than the aromatic group constituting the β-diketone include the same substituents as those of the aromatic hydrocarbon compound or aromatic heterocyclic compound described above (however, the halogen group is excluded). Specific examples (1 to 19) of β-diketone having a substituent containing an aromatic ring are shown below, but the present invention is not limited thereto.

  Specific examples (1 to 7) of the europium complex represented by the formula (2) are shown below, but the present invention is not limited thereto.

Next, the europium complex represented by Formula (3) will be described. Is not particularly limited as consisting Lewis base auxiliary ligand (R ₂₎ in formula (3) it is generally selected from a Lewis base compound having capable of coordinating nitrogen atom or an oxygen atom in the europium ions. Examples thereof include amines, amine oxides, phosphine oxides, sulfoxides and the like which may have a substituent. The two Lewis base compounds used as auxiliary ligands may be different from each other, or two compounds may form one compound.

  Specifically, for example, amines include pyridine, pyrazine, quinoline, isoquinoline, phenanthridine, 2,2'-bipyridine, 1,10-phenanthroline, and the like. Examples of the amine oxide include N-oxides of the above amines such as pyridine-N-oxide and 2,2'-bipyridine-N, N'-dioxide. Examples of the phosphine oxide include triphenylphosphine oxide, trimethylphosphine oxide, and trioctylphosphine oxide. Examples of the sulfoxide include diphenyl sulfoxide and dioctyl sulfoxide. Examples of the substituent that substitutes for these include the substituents described above. Among these, an alkyl group, an aryl group, an alkoxyl group, an aralkyl group, an aryloxy group, a halogen group and the like are particularly preferable.

  Among these Lewis base compounds, when two atoms coordinated in the molecule, such as a nitrogen atom, such as bipyridine and phenanthroline, are present, two auxiliary ligands can be combined with one Lewis base compound. You may do the same work. In addition, as a substituent substituted by these Lewis base compounds, the substituent mentioned above is illustrated. Among these, an alkyl group, an aryl group, an alkoxyl group, an aralkyl group, an aryloxy group, a halogen group and the like are particularly preferable.

Specific examples (1 to 23) of the Lewis base compound (R ₂ ) used as the auxiliary ligand are exemplified below, but the present invention is not limited thereto.

  Specific examples (1 to 13) of the europium complex represented by the formula (3) are shown below, but the present invention is not limited thereto.

  Next, the europium complex represented by Formula (4) will be described. Examples of ammonium ions in formula (4) include quaternary ammonium salts derived from alkylamines, arylamines, and aralkyl ions. Examples of amine substituents include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl and octyl; substituted alkyl groups such as hydroxyethyl and methoxyethyl; aryl groups such as phenyl and tolyl; arylalkyls such as benzyl and phenethyl groups Groups and the like.

  Specific examples (1-5) of the europium complex represented by the formula (4) are shown below, but the present invention is not limited thereto.

On the other hand, examples of the complex having a carboxylate ion having a substituent containing an aromatic group as a ligand include a europium complex represented by the formula (5).
_{(R 4 - (X 1)} n -COO) 3 Eu (R 5) 2
(5)
In Formula (5), R ₄ is a group containing at least one aromatic hydrocarbon ring or aromatic heterocyclic ring which may have a substituent, X ₁ is a divalent linking group, and n is 0 or 1 and R ₅ is an auxiliary ligand comprising a Lewis base.

  The ligand represented by the formula (5) includes at least one aromatic ring, has 8 or more π electrons, and uses a carboxylate ion constituting a π electron conjugated system as a ligand. This is preferable from the viewpoint of the absorption wavelength region. The number of aromatic rings is not particularly limited as long as the triplet energy of the carboxylate ion matrix compound is higher than the europium ion excited state energy level. It is preferable to use a group heterocycle. When the number of aromatic rings is 4 or more, for example, a compound such as pyrene having 4 or more aromatic rings has low triplet energy excited by absorbing light from a semiconductor light emitting device or the like, The europium complex may not emit light.

R ₄ in formula (5) is preferably a monovalent group derived from a tricyclic or lower aromatic ring which may have a substituent, or a heteroaromatic ring. Examples of the aromatic ring include aromatic monocyclic hydrocarbons or aromatic condensed polycyclic hydrocarbons such as benzene, naphthalene, indene, biphenylene, acenaphthene, fluorene, phenanthrene, tetralin, indane, and indene; benzoquinone, naphthoquinone, And compounds derived from aromatic hydrocarbons such as anthraquinone. Heteroaromatic rings include aromatic monocyclic heterocycles such as furan, pyrrole, thiophene, oxazole, isoxazole, thiazole, imidazole, pyridine, benzofuran, benzothiophene, coumarin, benzopyran, carbazole, xanthene, quinoline, and triazine. Examples thereof include a ring or an aromatic condensed polycyclic heterocycle.

Examples of the substituent that R ₄ may have include alkyl groups such as methyl, ethyl, propyl and butyl; fluoroalkyl groups such as trifluoromethyl and pentafluoroethyl; cycloalkyl groups such as cyclohexyl group; ethynyl Groups; arylethynyl groups such as phenylethynyl, pyridylethynyl and thienylethynyl; alkoxy groups such as methoxy and ethoxy; aryl groups such as phenyl and naphthyl; aralkyl groups such as benzyl and phenethyl; aryloxy such as phenoxy, naphthoxy and biphenyloxy Hydroxyl group; allyl group; acyl groups such as acetyl, propionyl, benzoyl, toluoyl, biphenylcarbonyl; acyloxy groups such as acetoxy, propionyloxy, benzoyloxy; methoxycarbonyl, ethoxycarbonyl An alkoxy group such as phenoxycarbonyl; a carboxyl group; a carbamoyl group; an amino group; a substituted amino group such as dimethylamino, diethylamino, methylbenzylamino, diphenylamino, acetylmethylamino; methylthio, ethylthio, phenylthio; And substituted thio groups such as benzylthio; mercapto groups; substituted sulfonyl groups such as ethylsulfonyl and phenylsulfonyl groups; cyano groups; halogen groups such as fluoro, chloro, bromo and iodo. Among these, an alkyl group, an alkoxy group, an aryl group, a cycloalkyl group, a cycloalkyl group, an aryloxy group, an aralkyl group, an ethynyl group, and a halogen group are preferable. R ₄ is not limited to these substituents. Moreover, these substituents may further have a substituent.

Next, the carboxylate ion in Formula (5) is divided into a case where it does not have X ₁ which is a divalent linking group (n = 0) and a case where it has (n = 1). Furthermore, when having X ₁ is a divalent linking group (n = 1), X ₁ is a case of having a carbonyl group, are divided into two types of case no. For this reason, the carboxylate ion in Formula (5) is further represented by Formula (5-1) having no carbonyl group and Formula (5-2) having a carbonyl group. The europium complex may have any of complex structures having these carboxylate ions as ligands.
^{_{R 4 -R 6 -COO - (5-1}} )
_{R 4 - (CO) - (} R 6) m -COO - (5-2)

In the formula (5-1) and the formula (5-2), R ₆ may be any divalent linking group, and for example, a divalent linking derived from an alkylene group or a ring-assembled hydrocarbon. And a divalent linking group derived from a group, an aliphatic ring, an aromatic ring, or a heterocyclic ring. In Formula (5-2), m is 0 or 1. Examples of the alkylene group for R ₆ include methylene and ethylene. Examples of the ring assembly hydrocarbon include biphenyl, terphenyl, binaphthyl, cyclohexylbenzene, and phenylnaphthalene. Examples of the aliphatic ring include cyclopentane, cyclohexane, cycloheptane, norbornane, bicyclohexyl and the like. Examples of the aromatic ring include the same compounds as the specific examples of the aromatic ring described above. Examples of the heterocyclic ring include aliphatic heterocyclic rings such as pyrazoline, piperazine, imidazolidine, and morpholine in addition to the aromatic heterocyclic ring described above. Other examples include thioalkylene such as —SCH ₂ —; oxyalkylene such as —OCH ₂ —; vinylene (—C═C—) and the like. R ₆ is not limited to these divalent substituents. Moreover, these divalent substituents may further have a substituent.

  Specific examples of the carboxylic acid from which the carboxylic acid ion in formula (5) is derived are illustrated below, but the present invention is not limited thereto. The following carboxylic acid (1-10) is mentioned as a compound in case n is 0 in Formula (5).

In the formula (5), when n is 1 and X is R ₆ (formula (5-1)), the following carboxylic acids (11 to 15) may be mentioned.

  In the formula (5-2), examples of the compound when m is 0 include the following carboxylic acids (16, 17).

In the formula (5-2), the following carboxylic acids (18 to 30) are exemplified as a compound in which m is 1 and R ₄ is a phenyl group and R ₆ is a phenyl group.

In the formula (5-2), the following carboxylic acids (31 to 34) may be mentioned as a compound when m is 1 and R ₄ is a phenyl group and R ₆ is a naphthyl group.

In the formula (5-2), when m is 1, R ₄ is a phenyl group, and R ₆ is another group, the following carboxylic acids (35 to 37) are exemplified.

In the formula (5-2), the following carboxylic acids (38 to 41) may be mentioned as a compound when m is 1 and R ₄ is a naphthyl group and R ₆ is an aromatic ring.

In the formula (5-2), examples of the compound in which m is 1 and R ₄ is a naphthyl group and R ₆ is another group include the following carboxylic acids (42 to 44).

In the formula (5-2), examples of the compound in which m is 1 and R ₄ is an acenaphthyl group, R ₆ is a phenyl group or the like include the following carboxylic acids (45 to 48).

In the formula (5-2), the following carboxylic acids (49 to 55) may be mentioned as compounds in which m is 1 and R ₄ is a fluorenyl group and R ₆ is a phenyl group.

In the formula (5-2), examples of the compound in which m is 1 and R ₄ is a phenanthrenyl group, R ₆ is a phenyl group or the like include the following carboxylic acids (56 to 59).

In the formula (5-2), when m is 1, R ₄ is a heterocyclic group, and R ₆ is a phenyl group, the compound has the following carboxylic acid (60, 61, I-1 to I— 21).

  The carboxylic acid from which the carboxylate ion as the ligand in formula (5) is derived can be synthesized by a known synthesis method. Regarding the synthesis method, for example, New Experimental Chemistry Course Vol. 14 “Synthesis and Reaction of Organic Compounds (II)”, page 921 (1977), edited by The Chemical Society of Japan, or 4th edition Experimental Chemistry Course Volume 22 “Organic Synthesis”. IV ", page 1 (1992) edited by the Chemical Society of Japan. Typical examples of the synthesis method include oxidation reaction of the corresponding primary alcohol or aldehyde, hydrolysis reaction of ester or nitrile, Friedel-Crafts reaction with acid anhydride, and the like.

In particular, cyclic anhydrides of dicarboxylic acids such as phthalic anhydride, naphthalic anhydride, succinic anhydride, diphenic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 2,3-pyridazine dicarboxylic anhydride were used. In the Friedel-Crafts reaction, a carboxylic acid having a carbonyl group in the molecule can be synthesized. For example, according to the Friedel-Crafts reaction using an aromatic hydrocarbon or aromatic heterocycle and phthalic anhydride, a carboxylic acid having a carbonyl group bonded to the ortho position of the benzene ring is represented by the following reaction formula. Easy to synthesize. A carboxylic acid having a carbonyl group bonded to the ortho position of the benzene ring is preferable because a complex having higher luminance than that of the para-substituted product can be easily obtained. In the formula, Ar represents an aromatic hydrocarbon or an aromatic heterocyclic ring.

Examples of the auxiliary ligand (R ₅ ) composed of the Lewis base in Formula (5) include the same compounds as the auxiliary ligand (R ₂ ) composed of the Lewis base in Formula (3) described above.

  The following can be illustrated as a europium complex which coordinated such carboxylic acid.

In the present invention, as the blue phosphor and the green phosphor used together with the europium complex which is a red fluorescent complex, known phosphors can be used in addition to the above-described fluorescent complexes. Examples of such phosphors include inorganic phosphors such as ZnS: Ag, Sr ₅ (PO ₄ ) ₃ Cl: Eu, BaMgAl ₁₀ O ₁₇ : Eu as blue phosphors. In addition, examples of the green phosphor include inorganic phosphors such as ZnS: Cu, ZnS: CuAl, BaMgAl ₁₀ O ₁₇ : Eu, Mn.
In order to emit white light, these phosphors may be used in combination.

The LED (light emitting diode) used in the present invention is a near-ultraviolet LED, and the emission peak wavelength is preferably in the range of 360 nm to 470 nm, and particularly preferably has a peak wavelength in the range of 380 nm to 470 nm. In particular, it is preferable to use an LED having an emission peak wavelength of 405 ± 10 nm.
If the peak wavelength is excessively short, organic compounds such as complexes are likely to be photodegraded. If the peak wavelength is excessively long, photoexcitation energy necessary for the emission of the fluorescent complex can be obtained. Therefore, the phosphor cannot emit light.

The molded substrate 1 on which the near ultraviolet LED GU35S400T (center wavelength: 400 nm) manufactured by Showa Denko KK was mounted on both ends of the linear light emitter 10 to assemble the light emitting device 100.
Two pieces of glass of the linear light emitter 10 are special thin glass (white plate glass) D263No. 2 ((thermal expansion coefficient: 73 × 10 ⁻⁷ / ° C.). The size was about Amm size of about 300 mm, width 400 mm, thickness 0.5 mm. These were washed with an aqueous detergent. The glass material to be the top glass substrate 315 was printed with a frit glass paste and dried at 300 ° C. The paste thickness after drying was 50 μm. A frit glass paste was printed (see FIGS. 3 and 4.) Printing was performed by screen printing using a 400 mesh stainless steel screen plate and held in a wet state. # 4017C was used.
Next, the upper glass substrate 315 and the lower glass substrate 311 were stacked and baked. The substrate interval at the time of superposition was 100 μm. Firing was performed at 100 ° C. for 30 minutes (solvent drying), at 350 ° C. for 45 minutes, and at 480 ° C. for 1 hour, for a total of 3 hours. At this time, a pressure of 20 to 30 g per 1 cm ² was applied. The distance between the substrates after firing and fusing was 70 μm.
Subsequently, it cut | disconnected in strip shape to width 2.0mm. That is, only the Y direction was cut from the front and back of the two bonded sheets using a carbide chip scriber.
Multi-layer deposition of Cr, Ni, and Ag metal was performed on the injection port (gate portion 552) surface of the complex phosphor paste.
Europium complex compound 1-1 [combination of X = H, Y = CF ₃ , Y = H, p = 2, q = 3 in formula (1)] is used as the complex phosphor, and this is used as a silicate resin. To prepare a paste. The material for preparing the paste may be silicone resin or polyvinyl alcohol.
Subsequently, the prepared paste was injected from the gate portion 552 into the recess 553, and after the injection, the paste was cured by heating at 150 ° C. Thereafter, the injection port (gate portion 552) was sealed with solder. The solder used was a low melting point solder. Specifically, an eutectic alloy of 58 mass% Bi of Sn solder (manufactured by Senju Metal Co., Ltd .: solder temperature 139 ° C.) was used. The sealing operation temperature was 160 ° C.
Thereafter, cutting in the Y direction was performed to obtain a single linear light emitter having a length of 300 mm, a width of 2.0 mm, and a thickness of 1.07 mm.
About these, the stain | pollution | contamination at the time of a cutting | disconnection and injection | pouring was wash | cleaned with the ultrasonic cleaner which used acetone as a washing | cleaning liquid.

Airtightness was checked with a red check solution. After 6 hours of immersion in this solution, the appearance was judged by visual inspection. As a result, it turned out that it is excellent in airtightness.
In this product, red light emission with high color reproducibility was observed in a linear form.

Two pieces of borosilicate glass-based shot glass D263 (plate thickness 0.5 mm) were prepared, washed with an aqueous detergent, and steam-dried. One glass substrate to be the lower glass substrate 311 was printed by screen printing using a paste in which the same organic phosphor as in Example 1 was dispersed (see FIGS. 5, 6, and 7). The paste thickness was 50 μm. Screen printing was performed using a 350 mesh stainless steel screen plate. The other glass substrate to be the upper glass substrate 315 was printed as shown in the figure by screen printing using struct bond HC-1413FP (manufactured by Mitsui Chemicals), which is an epoxy thermosetting adhesive, as a sealing material. . Screen printing was performed using a 250 mesh stainless steel screen plate. After printing the sealing material, it was temporarily dried at 90 ° C. for 10 minutes.
Next, the upper glass substrate 315 and the lower glass substrate 311 were stacked and baked. The substrate interval at the time of superposition was 100 μm. Firing was performed at 150 ° C. for 1 hour. At this time, a pressure of 200 to 300 g per 1 cm ² was applied. The substrate interval after baking and bonding was 60 μm.
Next, from the front and back of the two sheets, using a carbide chip scriber, cutting is performed between the patterns, which are portions where the pattern is not printed, that is, cutting from the Y direction shown in the drawing, and a single unit having the same size as that of Example 1 Got.
This complex phosphor paste was cured, and then sealed by applying an ultraviolet curing treatment in a nitrogen atmosphere using ThreeBond 3051 (manufactured by Sumitomo 3M) with the inlet as a sealing material.
About these, the stain | pollution | contamination at the time of a cutting | disconnection and injection | pouring was wash | cleaned with the ultrasonic cleaner which used acetone as a washing | cleaning liquid.
Airtightness was checked with a red check solution. After 6 hours of immersion in this solution, the appearance was judged by visual inspection. As a result, it turned out that it is excellent in airtightness.
When this was used as a linear light emitter 10 and a light emitting device was assembled in the same manner as in Example 1, linear red light emission with high color reproducibility was observed.

In Examples 1 and 2, as pastes to be injected, BaMgAl ₁₀ O ₁₇ : Eu (blue phosphor), ZnS: Cu (green phosphor), and the same europium complex compound 1-1 (red phosphor) as in Example 1 A light emitting device was assembled in the same manner as in Examples 1 and 2 except that a mixture of the above was dispersed in polyvinyl alcohol and the same operation was performed. White light emission was observed that emitted linear light with reproducibility.

In Examples 1 to 3, when the same operation was performed except that the europium complex (red phosphor) was changed to the above-described various exemplary compounds, similarly, good results were obtained.

A linear light emitter capable of realizing a white LED, a manufacturing method thereof, and a light emitting device using the linear light emitter are obtained.

It is a front view which shows the structure of embodiment of a linear light-emitting body. It is a schematic cross section which shows the structure of embodiment of a linear light-emitting body. FIG. 5 is an explanatory diagram of a first fusion sealing method in the production of a linear light emitter. FIG. 5 is an explanatory diagram of a first fusion sealing method in the production of a linear light emitter. It is explanatory drawing of the 2nd fusion sealing method in manufacture of a linear light-emitting body. It is explanatory drawing of the 2nd fusion sealing method in manufacture of a linear light-emitting body. It is explanatory drawing of the 2nd fusion sealing method in manufacture of a linear light-emitting body.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Light-emitting device 10 Linear light-emitting body 1 Molding board | substrate 311,315 Glass substrate 40 Organic fluorescent substance 51 Fusion agent 55 Frame member

Claims (13)

A linear light-emitting body including an organic phosphor that converts light emitted from a light-emitting element into visible light, the organic phosphor being two plate members, at least one of which is a light-transmitting plate member A linear light-emitting body characterized by being sandwiched between two plates and hermetically sealed. The linear light-emitting body according to claim 1, wherein the light-emitting element is a near-ultraviolet LED that emits near-ultraviolet light. The linear light-emitting body according to claim 1 or 2, wherein at least one of the translucent plates is a glass plate. The linear light emitter according to any one of claims 1 to 3, wherein the two plate members are glass plates, and the organic phosphor is hermetically sealed between the glass plates with a fusing agent. The linear light-emitting body according to claim 4, wherein the two glass plates are hermetically sealed using a fusing agent and a frame member. The linear light-emitting body according to claim 1, wherein the fusion agent is formed of a solder material. The linear light emitter according to claim 5 or 6, wherein the frame member is formed of a glass material or a thermosetting adhesive. The linear light emitter according to claim 1, wherein the organic phosphor is a red phosphor complex. The linear light emitter according to claim 8, wherein the red phosphor complex is a diketone or carboxylic acid complex of Eu. The linear light emitter according to any one of claims 1 to 9, wherein a blue and / or green phosphor is further used in addition to the organic phosphor. The light-emitting device which has arrange | positioned 1 or 2 or more near ultraviolet LED in the linear light-emitting body in any one of Claims 1-10. A step of forming a predetermined frame material pattern and attaching a light-transmitting plate material;
During this pasted process, a space and a gate part are formed,
Further, a step of injecting an organic phosphor in a predetermined atmosphere from the gate portion exposed between the frame material patterns,
Applying a fusion agent to the gate portion to close the gate portion;
The manufacturing method of the linear light-emitting body which has the process of cut | disconnecting and obtains the linear light-emitting body in any one of Claims 1-10 in multiple. A step of applying an organic phosphor in a predetermined atmosphere to one of the light-transmitting plate materials among the two light-transmitting plate materials;
Forming a frame member in a predetermined pattern according to the shape when the organic phosphor is applied to one and / or the other translucent plate;
A step of fusing or sealing these two light-transmitting plate members in a predetermined atmosphere;
The manufacturing method of the linear light-emitting body which has the process of cut | disconnecting and obtains the linear light-emitting body in any one of Claims 1-10 in multiple.

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