KR20190019918A - LIGHT EMITTER, AND SOURCE UNIT, DISPLAY AND LIGHTING DEVICE USING THE SAME - Google Patents

Abstract

A light emitting body having an LED and a color conversion layer, wherein the color conversion layer includes an organic light emitting material, and a resin layer is provided between the LED and the color conversion layer, and is excellent in durability. By using such a light emitting body, a light source unit, a display, and a lighting device excellent in durability can be obtained.

Description

LIGHT EMITTER, AND SOURCE UNIT, DISPLAY AND LIGHTING DEVICE USING THE SAME

The present invention relates to a light emitter, and a light source unit, a display, and a lighting apparatus.

2. Description of the Related Art A light emitting unit using a light emitting diode (LED) as a light source and a color conversion system is used as a member such as a light source unit such as a lighting device and a backlight unit, and a display. Color conversion is to convert light emitted from a light source into light having a longer wavelength. For example, blue light emission is converted into green light emission or red light emission.

Since the emission spectrum of the LED depends on the semiconductor material forming the LED chip, its emission color is limited. Therefore, in order to obtain a white light suitable for a backlight of a liquid crystal display (LCD, liquid crystal display) or a general illumination using an LED, it is necessary to provide a phosphor suitable for each chip on the LED chip and to convert the light emission wavelength . Specifically, there are a method of providing a yellow phosphor on a blue LED chip (hereinafter referred to as a blue LED chip, as appropriate), a method of providing a red phosphor and a green phosphor on a blue LED chip, A method of providing a red phosphor, a green phosphor and a blue phosphor is proposed. Among these methods, a method of installing a yellow phosphor on a blue LED chip and a method of installing a red phosphor and a green phosphor on a blue LED chip are most widely adopted at present from the viewpoint of luminous efficiency and cost of the LED chip.

In recent years, not only inorganic phosphors but also organic light emitting materials have attracted attention as phosphors. Discloses a technique using a pyromethene compound as a color conversion material which has excellent durability, has a high conversion efficiency, absorbs ultraviolet light or visible light and emits light with high luminance in red (see, for example, Patent Documents 1 to 2 ).

Japanese Patent Laid-Open Publication No. 2011-241160 Japanese Patent Application Laid-Open No. 2014-136771

In Patent Documents 1 and 2, it is disclosed that a composition containing a pyromethene compound is molded into a film and used as a color conversion filter. However, a light-emitting body formed by bonding such a wavelength conversion filter directly on a blue LED chip has insufficient durability and can not be used as a backlight light source for illumination or LCD.

Therefore, it is an object of the present invention to provide a light emitting body which is excellent in durability and can be used for a backlight light source such as an illumination or an LCD.

The inventors of the present invention have estimated that the above-described problems of the prior art are caused by deterioration of the pyromethene compound. Then, it has been found that the durability of the luminous body can be improved by examining the configuration of the luminous body, under the idea that such deterioration may be caused by the influence of heat generation accompanying long-time driving of the LED chip.

That is, the present invention is a light emitting device having an LED and a color conversion layer, wherein the color conversion layer includes an organic light emitting material, and a resin layer is provided between the LED and the color conversion layer.

According to the present invention, a light emitting body having excellent durability can be obtained. Further, by using such a light-emitting body, it is possible to obtain a light source unit, a display, and a lighting apparatus excellent in durability.

1 is a side view showing an example of a phosphor according to an embodiment of the present invention;
Fig. 2 is an explanatory diagram of a concave portion formed by a reflector in a light emitting device according to an embodiment of the present invention
3 is a process diagram showing an example of a method of manufacturing a phosphor according to an embodiment of the present invention

Hereinafter, preferred embodiments of a light emitting unit, a light source unit, a display, and a lighting apparatus according to the present invention will be described in detail. However, the present invention is not limited to the following embodiments, .

≪ Light emitting body &

A light emitting device according to an embodiment of the present invention includes an LED and a color conversion layer, wherein the color conversion layer includes an organic light emitting material and has a resin layer between the blue LED and the color conversion layer.

By providing the resin layer between the LED and the color conversion layer, the temperature rise of the color conversion layer can be suppressed even if the LED is driven for a long time. As a result, deterioration of the organic light emitting material can be suppressed, so that a light emitting body having excellent durability can be obtained.

1 is a side view showing an example of a light emitting body according to an embodiment of the present invention. 1 (a), LED 2 emitting blue light is mounted on substrate 1, and LED 2 and substrate 1 are electrically connected by wire 3 , And a reflector 4 is formed around the LED 2. The color conversion layer 5 including the organic light emitting material is disposed in the concave portion formed by the reflector 4 and has the resin layer 6 between the LED 2 and the color conversion layer 5 have.

In the embodiment of FIG. 1 (b), the concave portion formed by the reflector 4 is molded with the resin layer 6, and the color conversion layer 5 is formed thereon.

In the embodiment of FIG. 1 (c), in the embodiment of FIG. 1 (a), the color conversion layer 5 has a laminated structure of the color conversion layer 5a and the color conversion layer 5b have.

The upper surface of the color conversion layer 5 is lower than the upper surface of the reflector 4 in the embodiment of FIG. And a translucent heat-radiating layer 7 on an upper portion of the light-

In the embodiment of FIG. 1 (e), in the embodiment of FIG. 1 (a), the substrate is constituted by the heat-radiating substrate 8.

In the embodiment of FIG. 1 (f), in the embodiment of FIG. 1 (a), a lens 9 is further formed on the reflector 4 and the color conversion layer 5.

In the embodiment of FIG. 1 (g), the reflector 4 is not provided in the embodiment of FIG. 1 (a).

1 (a) to 1 (g) show an example of a light-emitting body on which a wire-bonding type LED is mounted. Even if a flip chip type LED is used, the effect of the present invention is not impaired.

(Color conversion layer)

The color conversion layer in the present invention includes an organic light emitting material. The color conversion layer may contain a resin or other additives as required.

The color conversion layer converts part of the light emitted from the LED, preferably the light whose peak wavelength is observed within a wavelength range of 400 nm to 500 nm (hereinafter referred to as "blue light emission") into a light of a longer wavelength And the like. The converted light is converted into a light having a peak wavelength of 500 nm or more and 580 nm or less (hereinafter referred to as " green light emission ") or a light emission having a peak wavelength of 580 nm or more and 750 nm or less , &Quot; red light emission " In addition, a part of the light emitted from the LED as described above passes through the color conversion layer. By adjusting the wavelengths and intensities of these lights, it is possible to obtain light emission of a desired color such as white light.

(Organic light emitting material)

The organic luminescent material in the present invention refers to a material which emits light having a wavelength different from that of the light when the light is irradiated. The organic luminescent material is an organic luminescent material.

As the organic light emitting material, for example,

Compounds or derivatives thereof having condensed aryl rings such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, triphenylene, perylene, fluoranthene, fluorene, and indene;

Examples of the furan compounds include furan, pyrrole, thiophene, silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, Compounds having a heteroaryl ring such as phosphorus, phosphorus, pyridine, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, and derivatives thereof;

Borane derivatives;

Bis (2- (4-diphenylaminophenyl) ethenyl) biphenyl, 4,4'-bis (N- - phenylamino) stilbene;

Aromatic acetylene derivatives, tetraphenylbutadiene derivatives, aldazine derivatives, pyromethene derivatives, diketopyrrolo [3,4-c] pyrrole derivatives;

Coumarin derivatives such as coumarin 6, coumarin 7 and coumarin 153;

Azole derivatives such as imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole and triazole, and metal complexes thereof;

Cyanine-based compounds such as indocyanine green;

Xanthene compounds and thioxanthene compounds such as fluorescein, eosin, and rhodamine;

Polyphenylene compounds, naphthalimide derivatives, phthalocyanine derivatives and metal complexes thereof, porphyrin derivatives and metal complexes thereof;

An oxazine compound such as Nile Red or Nile Blue;

Helixene compounds;

Aromatic amine derivatives such as N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diphenyl-1,1'-diamine; And

Organometallic complex compounds such as iridium (Ir), ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt), osmium (Os) and rhenium (Re);

And the like, but are not limited thereto.

At least one organic light emitting material may be contained in the color stratum, or two or more kinds of organic light emitting materials may be contained.

The organic light emitting material may be either a fluorescent light emitting material or a phosphorescent light emitting material, but a fluorescent light emitting material is preferable for achieving high color purity.

Among them, a compound having a condensed aryl ring or a derivative thereof is preferable from the viewpoint of high thermal stability and light stability.

Further, the organic luminescent material is preferably a compound having a coordination bond from the viewpoints of solubility and a variety of molecular structures. A compound containing boron such as a boron fluoride complex is also preferable because the half width is small and high-efficiency light emission is possible.

Among them, pyromethene derivatives are preferable because they give a high yield of light emission and good durability. More preferably, it is a compound represented by the general formula (1), that is, a pyromethene compound.

X is CR ⁷ or N; R ¹ to R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a thiol group, an alkoxy group, an alkylthio group, An aryl group, a heteroaryl group, a halogen atom, an aldehyde group, a carbonyl group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxanyl group, a boryl group, A condensed ring formed between the adjacent substituent and the adjacent substituent, and an aliphatic ring.

In all of the above groups, hydrogen may be deuterium. This is also true for the compound described below or a partial structure thereof.

In the following description, for example, the substituted or unsubstituted aryl group having 6 to 40 carbon atoms is 6 to 40, inclusive of the number of carbon atoms contained in the substituent substituted in the aryl group. Other substituents defining the number of carbon atoms are the same.

In the above groups, examples of the substituent in the case of substitution include an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a thiol group, an alkoxy group, an alkylthio group, An aryl group, a heteroaryl group, a halogen atom, an aldehyde group, a carbonyl group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxanyl group, a boryl group or a phosphine oxide group And specific substituents which are preferable in explaining each substituent are preferable. These substituents may be further substituted by the aforementioned substituents.

The term "unsubstituted" in the case of "substituted or unsubstituted" means that a hydrogen atom or a deuterium atom is substituted. In the compound described below or a partial structure thereof, the case of "substituted or unsubstituted" is also the same as described above.

The alkyl group means, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group or a tert-butyl group and may or may not have a substituent. The substituent when it is substituted is not particularly limited and includes, for example, an alkyl group, a halogen, an aryl group, and a heteroaryl group, and this point is common to the following description. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 or more and 20 or less, and more preferably 1 or more and 8 or less from the viewpoints of availability and cost.

The cycloalkyl group refers to a saturated alicyclic hydrocarbon group such as, for example, a cyclopropyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group, which may or may not have a substituent. The number of carbon atoms in the portion of the cycloalkyl group other than the substituent group is not particularly limited, but is preferably 3 or more and 20 or less.

The heterocyclic ring refers to an aliphatic ring having an atom other than carbon in the ring, such as a pyran ring, piperidine ring, or cyclic amide, which may or may not have a substituent. The number of carbon atoms of the heterocyclic group is not particularly limited, but is preferably in the range of 2 or more and 20 or less.

The alkenyl group is, for example, an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group and a butadienyl group, and it may or may not have a substituent. The number of carbon atoms of the alkenyl group is not particularly limited, but is preferably 2 or more and 20 or less.

The cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as, for example, a cyclopentenyl group, a cyclopentadienyl group, and a cyclohexenyl group, which may or may not have a substituent.

The alkynyl group represents, for example, an unsaturated aliphatic hydrocarbon group including a triple bond such as an ethynyl group, which may or may not have a substituent. The carbon number of the alkynyl group is not particularly limited, but is preferably 2 or more and 20 or less.

The alkoxy group refers to a functional group such as a methoxy group, an ethoxy group or a propoxy group bonded to an aliphatic hydrocarbon group via an ether bond, and the aliphatic hydrocarbon group may or may not have a substituent. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 or more and 20 or less.

As the alkylthio group, the oxygen atom of the ether bond of the alkoxy group is substituted with a sulfur atom. The hydrocarbon group of the alkylthio group may or may not have a substituent. The number of carbon atoms of the alkylthio group is not particularly limited, but is preferably 1 or more and 20 or less.

The aryl ether group represents a functional group to which an aromatic hydrocarbon group is bonded through an ether bond such as a phenoxy group, and the aromatic hydrocarbon group may or may not have a substituent. The number of carbon atoms of the aryl ether group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.

In the arylthioether group, the oxygen atom of the ether bond of the aryl ether group is substituted with a sulfur atom. The aromatic hydrocarbon group in the aryl ether group may or may not have a substituent. The number of carbon atoms of the aryl ether group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.

Examples of the aryl group include an aryl group such as phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, An aromatic hydrocarbon group such as a cyclopentyl group, a cyclopentadienyl group, a cyclopentadienyl group, a cyclopentadienyl group, a cyclopentadienyl group, a cyclopentadienyl group, a cyclopentadienyl group,

Among them, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, a fluoranthenyl group and a triphenylenyl group are preferable. The aryl group may or may not have a substituent. The number of carbon atoms of the aryl group is not particularly limited, but is preferably 6 or more and 40 or less, and more preferably 6 or more and 30 or less.

When R ¹ to R ⁹ are a substituted or unsubstituted aryl group, the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group or an anthracenyl group, A phenyl group and a naphthyl group are more preferable, and a phenyl group, a biphenyl group and a terphenyl group are more preferable, and a phenyl group is particularly preferable.

In the substituted aryl group, when the substituent is an aryl group, the aryl group on the substituent is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group or an anthracenyl group, A terphenyl group, and a naphthyl group are more preferable. Particularly preferably a phenyl group.

Examples of the heteroaryl group include a pyridyl group, a furanyl group, a thiophenyl group, a quinolinyl group, an isoquinolinyl group, a pyrazinyl group, a pyrimidyl group, a pyridazinyl group, a triazinyl group, a naphthyridinyl group, , A benzothiophenyl group, an indolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a benzocarbazolyl group, a carbazolyl group, a carbamoyl group, A benzoquinolyl group, an indolocarbazolyl group, a benzofurocarbazolyl group, a benzothienocarbazolyl group, a dihydroindenocarbazolyl group, a benzoquinolinyl group, an acridinyl group, a dibenzoacrylidinyl group, a benzoimidazolyl group A cyclic aromatic group having one or more atoms other than carbon other than carbon such as an imidazopyridyl group, a benzoxazolyl group, a benzothiazolyl group, or a phenanthrolinyl group. The naphthyridinyl group is preferably a 1,5-naphthyridinyl group, a 1,6-naphthyridinyl group, a 1,7-naphthyridinyl group, a 1,8-naphthyridinyl group, a 2,6- Or a 2,7-naphthylidinyl group. The heteroaryl group may or may not have a substituent. The number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably 2 or more and 40 or less, and more preferably 2 or more and 30 or less.

When R ¹ to R ⁹ are substituted or unsubstituted heteroaryl groups, examples of the heteroaryl group include pyridyl, furanyl, thiophenyl, quinolinyl, pyrimidyl, triazinyl, benzothiophenyl, indol A benzoimidazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a phenanthrolinyl group are preferable, and a pyridyl group, a furanyl group, a pyranyl group, , A thiophenyl group, and a quinolinyl group are more preferable. Particularly preferably a pyridyl group.

When each substituent is further substituted with a heteroaryl group, examples of the heteroaryl group include a pyridyl group, a furanyl group, a thiophenyl group, a quinolinyl group, a pyrimidyl group, a triazinyl group, a benzofuranyl group, a benzothiophenyl group, A benzothiophenyl group, a carbazolyl group, a benzoimidazolyl group, an imidazopyridyl group, a benzoxazolyl group, a benzothiazolyl group and a phenanthrolinyl group are preferable, and a pyridyl group, a furanyl group, a thiophenyl group , A quinolinyl group is more preferable, and a pyridyl group is particularly preferable.

Halogen means an atom selected from fluorine, chlorine, bromine and iodine.

The carbonyl group, the carboxyl group, the oxycarbonyl group and the carbamoyl group may or may not have a substituent. Here, examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group, and these substituents may be further substituted.

The amino group is a substituted or unsubstituted amino group. Examples of the substituent in the case of substitution include an aryl group, a heteroaryl group, a straight chain alkyl group and a branched alkyl group. As the aryl group and the heteroaryl group, a phenyl group, a naphthyl group, a pyridyl group and a quinolinyl group are preferable. These substituents may be further substituted. The number of carbon atoms in the substituent portion of the amino group is not particularly limited, but is preferably 2 or more and 50 or less, more preferably 6 or more and 40 or less, particularly preferably 6 or more and 30 or less.

Examples of the silyl group include alkylsilyl groups such as trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, propyldimethylsilyl group and vinyldimethylsilyl group, phenyldimethylsilyl group, tert-butyldiphenylsilyl group, An arylsilyl group such as a triphenylsilyl group and a trinaphthylsilyl group. The substituent on the silicon atom may be further substituted. The number of carbon atoms of the silyl group is not particularly limited, but is preferably 1 or more and 30 or less.

The siloxanyl group represents a silicon compound group through an ether bond, such as, for example, a trimethylsiloxanyl group. The substituent on the silicon atom may be further substituted.

The boryl group is a substituted or unsubstituted boryl group. The substituent when substituted is, for example, an aryl group, a heteroaryl group, a straight-chain alkyl group, a branched alkyl group, an aryl ether group, an alkoxy group or a hydroxyl group, and an aryl group or an aryl ether group is preferable.

Group refers to phosphine oxide, -P (= O) the groups represented by R ¹⁰ R ^11. R ¹⁰ R ¹¹ is selected from the same group as R ¹ to R ⁹ .

The condensed ring formed with the adjacent substituent means that any adjacent bifunctional group (for example, R ¹ and R ^{2 in} the general formula (1)) are bonded to each other to form a conjugated or non-conjugated cyclic skeleton It says. The constituent element of the condensed ring may contain, in addition to carbon, an element selected from nitrogen, oxygen, sulfur, phosphorus and silicon. The condensed ring may be further condensed with another ring.

The compound represented by the general formula (1) exhibits high quantum yield of light emission and has a small peak half value width of the luminescence spectrum, so that efficient color conversion and high color purity can be achieved.

The compound represented by the general formula (1) can be adjusted to various properties and physical properties such as luminous efficiency, color purity, thermal stability, light stability and dispersibility by introducing an appropriate substituent at an appropriate position.

For example, R ^1, R ^3, R ⁴ and R ⁶ are all compared to the case of hydrogen, R ^1, R ^3, R ⁴ and at least one R ⁶ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted Or a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, the higher the thermal stability and the light stability.

When at least one of R ¹ , R ³ , R ⁴ and R ⁶ is a substituted or unsubstituted alkyl group, examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a sec-butyl group, a sec-butyl group, a pentyl group or a hexyl group, Butyl group and tert-butyl group are preferable. In addition, from the viewpoint of preventing concentration quenching and improving the yield of light emission, tert-butyl groups having a large volume are more preferable. From the viewpoint of easiness of synthesis and easiness of obtaining a raw material, a methyl group is also preferably used.

When at least one of R ¹ , R ³ , R ⁴ and R ⁶ is a substituted or unsubstituted aryl group, the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group or a naphthyl group, more preferably a phenyl group or a biphenyl group , And a phenyl group is particularly preferable.

When at least one of R ¹ , R ³ , R ⁴ and R ⁶ is a substituted or unsubstituted heteroaryl group, the heteroaryl group is preferably a pyridyl group, a quinolinyl group or a thiophenyl group, and a pyridyl group or a quinolinyl group More preferably a pyridyl group is particularly preferable.

R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different from each other and are preferably a substituted or unsubstituted alkyl group. In this case, the solubility of the compound represented by the general formula (1) in a resin or a solvent is good. As the alkyl group, a methyl group is preferable in view of easiness of synthesis and easiness of obtaining a raw material.

R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different from each other, and are preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. In these cases, the compound represented by the general formula (1) exhibits higher thermal stability and light stability. R ¹ , R ³ , R ^4, and R ⁶ may be the same or different from each other, and more preferably a substituted or unsubstituted aryl group.

Although there are substituents that improve the properties of a plurality of substituents, substituents that exhibit sufficient performance in all are limited. In particular, it is difficult to achieve both high luminous efficiency and high color purity. Therefore, by introducing a plurality of kinds of substituent groups into the compound represented by the general formula (1), it is possible to obtain a compound balanced in light emission characteristics, color purity, and the like.

In particular, when all of R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different, and when it is a substituted or unsubstituted aryl group, for example, R ¹ ≠ R ⁴ , R ³ ≠ R ⁶ , R ¹ ≠ R ³ or R ⁴ ≠ R ^6, and the like. Here, "?&Quot; indicates that it is a group of another structure. For example, R ¹ ≠ R ⁴ indicates that R ¹ and R ⁴ have different structures. By introducing a plurality of kinds of substituents as described above, an aryl group that affects the color purity and an aryl group that affects the luminous efficiency can be introduced at the same time, so that fine adjustment is possible.

Among them, it is preferable that R ¹ ≠ R ³ or R ⁴ ≠ R ⁶ in terms of improving the luminous efficiency and the color purity to a good balance. In this case, it is possible to introduce at least one aryl group, which affects the color purity into the compound represented by the general formula (1), into each of the pyrrole rings on both sides and to introduce an aryl group influencing the efficiency at other positions , The properties of both sides can be improved as much as possible. When R ¹ ≠ R ³ or R ⁴ ≠ R ⁶ , it is more preferable that R ¹ = R ⁴ and R ³ = R ⁶ from the viewpoint of improving both heat resistance and color purity.

As the aryl group mainly affecting the color purity, an aryl group substituted with an electron-donating group is preferable. The electron donor field is an atomic group that donates electrons to a substituted atomic group by an organic effect or a resonance effect in the organic electron theory. As the electron donating group, a substituent constant (? P (para)) of the Hammet rule is a negative value. The substituent constants (σ p (para)) of the Hammett rule can be quoted from the fifth edition of the Fundamentals of Chemical Handbook (II-380).

Specific examples of the electron donating group include an alkyl group (? P: -0.17 of a methyl group) and an alkoxy group (? P: -0.27 of a methoxy group). Particularly, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms is preferable, and a methyl group, an ethyl group, a tert-butyl group and a methoxy group are more preferable. From the viewpoint of dispersibility, a tert-butyl group and a methoxy group are particularly preferable. When these are the electron donating group, quenching due to aggregation of molecules in the compound represented by the general formula (1) can be prevented . The substitution position of the substituent is not particularly limited. However, in order to enhance the light stability of the compound represented by the general formula (1), it is necessary to suppress the twisting of the bond. Position.

As the aryl group which mainly affects the luminous efficiency, an aryl group having a bulky substituent such as a tert-butyl group, an adamantyl group or a methoxy group is preferable.

R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different from each other, and when they are substituted or unsubstituted aryl groups, R ¹ , R ³ , R ⁴ and R ⁶ may all be the same or different, Or an unsubstituted phenyl group. At this time, they are more preferably selected from the following Ar-1 to Ar-6, respectively. In this case, preferred combinations of R ¹ , R ³ , R ⁴ and R ⁶ include combinations as shown in Tables 1-1 to 1-11, but the present invention is not limited thereto.

[Table 1-1]

[Table 1-2]

[Table 1-3]

[Table 1-4]

[Table 1-5]

[Table 1-6]

[Table 1-7]

[Table 1-8]

[Table 1-9]

[Table 1-10]

[Table 1-11]

R ² and R ⁵ are preferably hydrogen, an alkyl group, a carbonyl group, an oxycarbonyl group or an aryl group. Among them, hydrogen or an alkyl group is preferable from the viewpoint of thermal stability, and hydrogen is more preferable from the viewpoint of obtaining a narrow half band width in the luminescence spectrum.

R ⁸ and R ⁹ are preferably an alkyl group, an aryl group, a heteroaryl group, a fluorine, a fluorine-containing alkyl group, a fluorine-containing heteroaryl group or a fluorine-containing aryl group. In particular, it is more preferable that R ⁸ and R ⁹ are fluorine or fluorine-containing aryl groups since they are stable to the excitation light and higher fluorescence quantum yield can be obtained. Further, for ease of synthesis, it is more preferable that R ⁸ and R ⁹ are fluorine.

Here, the fluorine-containing aryl group is an aryl group containing fluorine, and examples thereof include a fluorophenyl group, a trifluoromethylphenyl group, and a pentafluorophenyl group. The fluorine-containing heteroaryl group is a heteroaryl group containing fluorine, and examples thereof include a fluoropyridyl group, a trifluoromethylpyridyl group, and a trifluoropyridyl group. The fluorine-containing alkyl group is an alkyl group containing fluorine, and examples thereof include a trifluoromethyl group and a pentafluoroethyl group.

In the general formula (1), X is preferably CR ⁷ from the viewpoint of light stability. When X is CR ⁷ , the substituent R ⁷ greatly affects the durability of the compound represented by the general formula (1), that is, the deterioration over time in the luminescence intensity of the compound. Specifically, when R ⁷ is hydrogen, since the reactivity of the hydrogen is high, moisture and oxygen in the air readily react with this site. This causes decomposition of the compound represented by the general formula (1). When R ⁷ is a substituent having a high degree of freedom of movement of a molecular chain such as an alkyl group, for example, the reactivity is surely lowered. However, the compounds are agglomerated with time in the composition, . Therefore, it is preferable that R ⁷ is a group which is rigid, has a small degree of freedom of movement, and is hardly causing aggregation. Specifically, it is preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

It is preferable that X is CR < ⁷ > and R < ⁷ > is a substituted or unsubstituted aryl group from the viewpoints of higher fluorescence quantum yield, less thermal decomposition and from the viewpoint of light stability. As the aryl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group and an anthracenyl group are preferable from the viewpoint of not impairing the emission wavelength.

Further, in order to increase the light stability of the compound represented by the general formula (1), it is necessary to appropriately suppress the twisting of the carbon-carbon bond of R ⁷ and the pyromethene skeleton. This is because, if the twist is excessively large, the light stability is lowered, for example, the reactivity to the excitation light is increased. In this respect, examples of R ⁷ include a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, and a substituted or unsubstituted naphthyl group, preferably a substituted or unsubstituted phenyl group, a substituted Or an unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group. Particularly preferably a substituted or unsubstituted phenyl group.

It is also preferred that R ⁷ is a suitably bulky substituent. By having a certain large volume of R ⁷ , aggregation of molecules can be prevented. As a result, the luminous efficiency and durability of the compound represented by the general formula (1) are further improved.

A more preferred example of such a bulky substituent is a structure represented by the following general formula (2).

R ¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a thiol group, an alkoxy group, an alkylthio group, an arylether group, an arylthioether group, Is selected from the group consisting of halogen, cyano, aldehyde, carbonyl, carboxyl, oxycarbonyl, carbamoyl, amino, nitro, silyl, siloxanyl, boryl and phosphine oxide groups. k is an integer of 1 to 3; When k is 2 or more, r ¹ may be the same or different from each other.

From the viewpoint of giving higher fluorescence quantum yield, it is preferable that r ¹ is a substituted or unsubstituted aryl group. Of these aryl groups, a phenyl group and a naphthyl group are particularly preferable. When r ¹ is an aryl group, k in the general formula (2) is preferably 1 or 2. Among them, k is preferably 2 from the viewpoint of further preventing aggregation of molecules. When k is 2 or more, it is preferable that at least one of r ¹ is substituted with an alkyl group. As the alkyl group in this case, a methyl group, an ethyl group and a tert-butyl group are particularly preferable examples from the viewpoint of thermal stability.

From the viewpoint of controlling the fluorescence wavelength or the absorption wavelength or enhancing compatibility with the solvent, r ¹ is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a halogen, and a methyl group, an ethyl group , a tert-butyl group, and a methoxy group are more preferable. From the viewpoint of dispersibility, a tert-butyl group and a methoxy group are particularly preferable. It is more effective for r ¹ to be a tert-butyl group or a methoxy group to prevent quenching due to aggregation of molecules.

In the compound represented by the general formula (1), all of R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different and more preferably a group represented by the following general formula (3). Thereby, both the light emission efficiency and the color purity can be achieved.

r ² is selected from the group consisting of an alkyl group, a cycloalkyl group, an alkoxy group and an alkylthio group. m is an integer of 1 to 3; When m is 2 or more, each r ² may be the same or different. Provided that R ¹ ≠ R ³ or R ⁴ ≠ R ⁶ . Where < RTI ID = 0.0 > denotes < / RTI > R ⁷ is an aryl group or a heteroaryl group.

As another form of the compound represented by the general formula (1), it is preferable that at least one of R ¹ to R ⁷ is an electron withdrawing group. (1) at least one of R ¹ to R ⁶ is an electron withdrawing group, (2) R ⁷ is an electron withdrawing group, or (3) at least one of R ¹ to R ⁶ is an electron withdrawing group and R ⁷ is preferably an electron-attracting device. By introducing an electron-withdrawing group into the pyrromethene skeleton, the electron density of the pyromethene skeleton can be greatly lowered. As a result, the stability of the compound against oxygen is further improved, and as a result, the durability of the compound can be further improved.

The electron donor group is also referred to as an electron accepting group and is an atom group that attracts electrons from a substituted atom group by an organic effect or a resonance effect in the organic electron theory. As the electronic bulletin popularity, a substituent constant (? P (para)) of the Hammet rule is taken as a positive value. The substituent constants (σ p (para)) of the Hammett rule can be quoted from the fifth edition of the Fundamentals of Chemical Handbook (II-380).

The phenyl group also has such a positive value as described above, but the phenyl group is not included in the electron withdrawing group in the present invention.

As an example of a popular electronic, obtain, for example, -F (σp: +0.06), -Cl (σp: +0.23), -Br (σp: +0.23), -I (σp: +0.18), -CO 2 R ¹² (σp: ethyl date when _{^{R 12 +0.45), -CONH 2 (}} σp: +0.38), -COR 12 (σp: when the R ¹² group _{+0.49), -CF 3 (σp:} +0.50), -SO ₂ R ¹² (σp: +0.69 when R ¹² is methyl), -NO ₂ (σp: +0.81), and the like. R ¹² each independently represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring-forming carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring-forming atoms, a substituted or unsubstituted C1- An alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms. Specific examples of these groups include the same examples as described above.

Preferable examples of the electron donor include fluorine, a fluorine-containing aryl group, a fluorine-containing heteroaryl group, a fluorine-containing alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted amide group, A substituted sulfonyl group or a cyano group. This is because they are difficult to decompose chemically.

As a more preferable electron emitter, there may be mentioned a fluorine-containing alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted ester group or a cyano group. This is because they are connected to the effect of preventing concentration quenching and improving the quantum yield of light emission. Particularly preferred electron-withdrawing groups are substituted or unsubstituted ester groups.

R ¹ , R ³ , R ⁴ and R ⁶ may all be the same or different and are each a substituted or unsubstituted alkyl group, and when X is CR ⁷ , And R ⁷ is a group represented by the general formula (2), particularly preferably a group represented by the general formula (2) in which r is a substituted or unsubstituted phenyl group.

R ¹ , R ³ , R ⁴ and R ⁶ may all be the same or different from each other, and it is also possible to use a compound represented by the general formula (1) And X is CR < ⁷ > and R < ⁷ > is a group represented by the general formula (2). In this case, R ⁷ is preferably a group represented by the general formula (2) contained as a tert-butyl group or a methoxy group and more preferably a group represented by the general formula (2) in which r is included as a methoxy group Particularly preferred.

One example of the compound represented by the general formula (1) is shown below, but the compound is not limited thereto.

The compound represented by the general formula (1) can be synthesized by the method described in, for example, Japanese Patent Application Laid-Open Nos. 8-509471 and 2000-208262. That is, the desired pyromethene metal complex is obtained by reacting the pyromethene compound and the metal salt in the presence of a base.

For the pyromethene-boron fluoride complexes, see J. Org. Chem., Vol.64, No.21, pp.7813-7819 (1999), Angew. Chem., Int. Ed. Engl., Vol. 36, pp. 1333-1335 (1997), the compound represented by the general formula (1) can be synthesized. For example, the compound represented by the following general formula (3) and the compound represented by the general formula (4) are heated in 1,2-dichloroethane in the presence of phosphorus oxychloride, In the presence of triethylamine in 1,2-dichloroethane, thereby obtaining a compound represented by the general formula (1). However, the present invention is not limited to this. Here, R ¹ to R ⁹ are the same as described above. J represents halogen.

In the introduction of an aryl group or a heteroaryl group, a coupling reaction of a halogenated derivative with a boronic acid or a boronic acid esterified derivative is used to produce a carbon-carbon bond, but the present invention is limited to this It is not. Similarly, a method for producing a carbon-nitrogen bond by using a coupling reaction of a halogenated derivative with an amine or a carbazole derivative in the presence of a metal catalyst such as palladium, for example, even when an amino group or a carbazolyl group is introduced , But the present invention is not limited thereto.

The color conversion layer may suitably contain other compounds as necessary in addition to the compound represented by the general formula (1). For example, an assist dopant such as rubrene may be contained in order to further increase the energy transfer efficiency from the excited light to the compound represented by the general formula (1). When it is desired to add a luminescent color other than the luminescent color of the compound represented by the general formula (1), a desired organic luminescent material, for example, an organic luminescent material such as a coumarin-based pigment and a rhodamine-based pigment may be added. In addition to these organic luminescent materials, known luminescent materials such as inorganic phosphors, fluorescent pigments, fluorescent dyes and quantum dots can be added in combination.

Hereinafter, examples of the organic luminescent material other than the compound represented by the general formula (1) are shown below, but the present invention is not particularly limited to these.

The color conversion layer preferably contains the following light-emitting material (A) and light-emitting material (B). The light-emitting material (A) is an organic light-emitting material exhibiting light emission (i.e., green light emission) observed in a region where the peak wavelength is 500 nm or more and 580 nm or less by using excitation light having a wavelength in a range of 400 nm to 500 nm. The light emitting material (B) is excited by at least one of the excitation light in the wavelength range of 400 nm to 500 nm and the light emission from the organic light emitting material (A), whereby the light emission in the range of the peak wavelength of 580 nm to 750 nm Emitting material).

In the case of a light emitting body in which a color conversion layer containing an organic light emitting material (A) and an organic light emitting material (B) and a blue LED light source whose sharpening peak is sharp, light emitted from the light emitting body is reflected by blue Shows a sharp emission spectrum in color. Therefore, white light having good color purity can be obtained. As a result, in particular, in the display, the color region becomes larger, and more clear color display becomes possible.

In order to enlarge the color region and improve the color reproducibility, it is preferable that the overlapping of the emission spectra of the respective colors of blue, green and red is small.

When blue light having a wavelength of 400 nm or more and 500 nm or less having suitable excitation energy is used as the excitation light, it is preferable to use the light emission observed in the region having the peak wavelength of 500 nm or more as green light emission. This is because overlapping of the spectra of the blue light and the green light is reduced and the color reproducibility is improved. In making the effect larger, the lower limit value of the peak wavelength of the organic light-emitting material (A) is more preferably 510 nm or more, still more preferably 515 nm or more, and particularly preferably 520 nm or more.

Further, in order to reduce the overlap of the spectrum of the green light and the red light, it is preferable to use the light emission observed in the region having the peak wavelength of 580 nm or less as the green light emission. In making the effect larger, the upper limit value of the peak wavelength of the organic light-emitting material (A) is more preferably 550 nm or less, still more preferably 540 nm or less, particularly preferably 530 nm or less.

When luminescence observed in a region having a peak wavelength of 500 nm or more and 580 nm or less is used as green luminescence, it is preferable to use luminescence observed in a region having a peak wavelength of 580 nm or more as red luminescence. This is because overlapping of the spectra of the green light and the red light is reduced and the color reproducibility is improved. To make the effect larger, the lower limit value of the peak wavelength of the organic light-emitting material (B) is more preferably 620 nm or more, still more preferably 630 nm or more, particularly preferably 635 nm or more.

The upper limit of the peak wavelength of the red light may be 750 nm or less near the upper boundary of the visible region, but it is more preferable that the peak wavelength is 700 nm or less. In making the effect larger, the upper limit value of the peak wavelength of the organic light-emitting material (B) is more preferably 680 nm or less, particularly preferably 660 nm or less.

In order to reduce the overlap of the emission spectrum and improve the color reproducibility, it is preferable that the half-width of the emission spectrum of each color of blue, green and red is small. Particularly, it is effective for improving the color reproducibility that the half width of the emission spectrum of the green light and the red light is small.

The half width of the emission spectrum of the green light is preferably 50 nm or less, more preferably 40 nm or less, still more preferably 35 nm or less, particularly preferably 30 nm or less.

The half width of the emission spectrum of the red light is preferably 80 nm or less, more preferably 70 nm or less, further preferably 60 nm or less, particularly preferably 50 nm or less.

The shape of the luminescence spectrum is not particularly limited, but a single peak is preferable. This is because energy can be efficiently utilized and color purity is increased. Here, a single peak indicates a state in which there is no peak having a strength of 5% or more of the intensity with respect to a peak having the highest intensity in a certain wavelength region.

The color conversion layer may be a single layer or a plurality of layers may be laminated. The number of layers in the case where a plurality of layers are stacked is not particularly limited, but two layers are preferable. When a plurality of layers are stacked, it is preferable that at least two of them are a layer including the organic light-emitting material (A) and a layer b including the organic light-emitting material (B). The organic light-emitting materials (A) and (B) are contained in different layers, respectively, so that the interaction between the respective light-emitting materials is suppressed. Therefore, they exhibit light emission with higher color purity than when they are dispersed in the same layer. Further, since the mutual action between the respective light emitting materials is suppressed, the organic light emitting materials (A) and (B) emit light independently from each other in the respective layers, so that adjustment of the emission peak wavelength and emission intensity of green and red is easy.

There is no particular limitation on the order of lamination of the a-layer and the b-layer. The layer a and the layer b may be in contact with each other or may be spaced apart from each other. When the organic light-emitting material (B) is excited by light emission from the organic light-emitting material (A) to emit light, it is preferable that a layer (b) is formed on the layer (a).

The content of the organic light-emitting material in the color conversion layer differs depending on the molar extinction coefficient of the compound, the quantum yield of fluorescent light, the absorption intensity at the excitation wavelength, and the thickness or transmissivity of the sheet to be produced. Usually, of with respect to 100 parts by weight of 1.0 × 10 ^{- 4} parts by weight, preferably to 30 parts by weight. The content of the organic light-emitting material is based on 100 parts by weight of the resin component 1.0 × 10 ^- and ³ parts by weight to 10 parts by weight, more preferably, 1.0 × 10 ^{- 2} parts by weight is particularly preferred to 5 weight parts.

In the case where both the organic light-emitting material (A) exhibiting green light emission and the organic light-emitting material (B) exhibiting red light emission are contained in the color conversion layer, a part of the green light emission is converted into red light emission preferably, the content of w ₂ of the organic light emitting material (a) and the content of w _1, the organic light emitting material (B) of a, w ₁ of the parties ≥w _2. The content ratio of the materials of the light emitting material (A) and the light emitting material (B) is preferably w ₁ : w ₂ = 1000: 1 to 1: 1, more preferably 500: 1 to 2: 1 , And particularly preferably from 200: 1 to 3: 1. W ₁ and w ₂ are weight percentages of the organic light emitting material with respect to the weight of the resin component.

(The resin contained in the color conversion layer)

The color conversion layer may contain a resin. This resin forms a continuous phase and may be any material having excellent molding processability, transparency, heat resistance, and the like. Examples of the resin include a photo-curable resist material having reactive vinyl groups such as acrylic, methacrylic, polyvinyl cinnamate, polyimide, and cyclic rubber, epoxy resin, silicone resin (such as silicone rubber, Polyolefin resin, polystyrene resin, polystyrene resin, polystyrene resin, polycarbonate resin, polycarbonate resin, polycarbonate resin, polycarbonate resin, Known resins such as urethane resin, melamine resin, polyvinyl resin, polyamide resin, phenol resin, polyvinyl alcohol resin, cellulose resin, aliphatic ester resin, aromatic ester resin, aliphatic polyolefin resin and aromatic polyolefin resin can be used. As the resin, these copolymer resins may also be used.

Among these resins, an epoxy resin, a silicone resin, an acrylic resin, an ester resin, or a mixture thereof can be suitably used from the viewpoint of transparency, and a silicone resin is preferably used from the viewpoint of heat resistance.

The silicone resin may be either a thermosetting silicone resin or a thermoplastic silicone resin. The thermosetting silicone resin is cured at room temperature or at a temperature of 50 to 200 占 폚, and is excellent in transparency, heat resistance, and adhesion.

The thermosetting silicone resin is formed, for example, by a hydrosilylation reaction of a compound containing an alkenyl group bonded to a silicon atom and a compound having a hydrogen atom bonded to a silicon atom. Examples of such a material include a silane coupling agent such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, propenyltrimethoxysilane, norbornenyltrimethoxysilane, and octenyltrimethoxysilane; A compound having a hydrogen atom bonded to a silicon atom such as methylhydrogenpolysiloxane, dimethylpolysiloxane-CO-methylhydrogenpolysiloxane, ethylhydrogenpolysiloxane, methylhydrogenpolysiloxane-CO-methylphenylpolysiloxane and the like , And those formed by a hydrosilylation reaction. Further, as the thermosetting silicone resin, there can be used, for example, those known in Japanese Patent Application Laid-Open No. 159411/1990.

As the thermosetting silicone resin, it is also possible to use a commercially available silicone sealant for general LED applications, for example. Specific examples thereof include OE-6630A / B and OE-6336A / B manufactured by Toray / Dow Corning Corporation, and SCR-1012A / B and SCR-1016A / B manufactured by Shinetsu Chemical Industry Co., .

The thermosetting silicone resin is preferably mixed with a hydrosilylation reaction retarding agent such as acetylene alcohol in order to suppress curing at room temperature and to increase the usable time.

The thermoplastic silicone resin is a resin that is softened by heating to a glass transition temperature or melting point and exhibits fluidity. Since the thermoplastic silicone resin does not undergo a chemical reaction such as a curing reaction even if it is softened by heating once, it becomes solid again when it is returned to room temperature.

Examples of the thermoplastic silicone resin include commercially available RSN series such as RSN-0805 and RSN-0217 manufactured by Doray Dow Corning Corporation.

(Other additives)

The color conversion layer may contain additives insofar as the effect of the present invention is not impaired. Specific examples of the additives include adhesion stabilizers such as a dispersion stabilizer, a leveling agent, an antioxidant, a flame retardant, a defoaming agent, a plasticizer, a crosslinking agent, a curing agent, a light stabilizer such as an ultraviolet absorber, and a silane coupling agent.

Further, for the purpose of increasing the light extraction efficiency from the color conversion layer, the color conversion layer may contain inorganic particles. Specific examples of the inorganic particles include microparticles composed of glass, titania, silica, alumina, silicon, zirconia, ceria, aluminum nitride, silicon carbide, silicon nitride, barium titanate and the like. These may be used alone or in combination of two or more. From the viewpoint of availability, silica, alumina, titania and zirconia are preferable.

(Resin layer)

In the light emitting device according to the embodiment of the present invention, the resin layer included between the LED and the color conversion layer is not particularly limited as long as it includes a resin and transmits the emitted light of the LED.

Since the color conversion layer and the LED do not directly contact each other due to the presence of the resin layer, the heat generated during driving the LED is hardly transmitted to the color conversion layer, and the durability of the color conversion layer is improved.

At this time, the color conversion layer and the resin layer may be in direct contact with each other or may not be in contact with each other. However, from the viewpoint of making it difficult to transmit heat generated in the LED to the color conversion layer, It is more preferable that they are not in direct contact with each other.

As the resin contained in the resin layer, the same resin as that contained in the color conversion layer can be used. Specific examples of the resin include a photocurable resist material having reactive vinyl groups such as acrylic, methacrylic, polypyrinamic acid vinyl, polyimide, and cyclic rubber, epoxy resins, silicone resins (such as silicone rubber and silicone gel) (Including a crosslinked product), urethane resin, fluororesin, polycarbonate resin, acrylic resin, methacrylic resin, polyimide resin, cyclic olefin, polyethylene terephthalate resin, polypropylene resin, polystyrene Known resins such as resins, urethane resins, melamine resins, polyvinyl resins, polyamide resins, phenol resins, polyvinyl alcohol resins, cellulose resins, aliphatic ester resins, aromatic ester resins, aliphatic polyolefin resins and aromatic polyolefin resins . As the resin, these copolymer resins may also be used.

Among these resins, an epoxy resin, a silicone resin, an acrylic resin, an ester resin, or a mixture thereof can be suitably used from the viewpoint of transparency. Among them, a silicone resin and an acrylic resin are preferable, and a silicone resin is more preferably used from the viewpoint of heat resistance.

The silicone resin may be either a thermosetting silicone resin or a thermoplastic silicone resin. The thermosetting silicone resin is cured at room temperature or at a temperature of 50 to 200 占 폚, and is excellent in transparency, heat resistance, and adhesion.

As specific examples of the thermosetting silicone resin, commercially available ones, for example, a silicone sealing material for general LED applications, may be used. Specific examples thereof include OE-6630A / B and OE-6336A / B manufactured by Toray / Dow Corning Corporation, and SCR-1012A / B and SCR-1016A / B manufactured by Shinetsu Chemical Industry Co., .

The thermosetting silicone resin is preferably mixed with a hydrosilylation reaction retarding agent such as acetylene alcohol in order to suppress curing at room temperature and to increase the usable time.

The thermoplastic silicone resin is a resin exhibiting fluidity by being softened by heating to a glass transition temperature or melting point. Since the thermoplastic silicone resin does not undergo a chemical reaction such as a curing reaction even if it is softened by heating once, it becomes solid again when it is returned to room temperature.

Specific examples of the thermoplastic silicone resin include commercially available ones such as RSN series such as RSN-0805 and RSN-0217 manufactured by Doray Dow Corning.

The thickness of the resin layer is preferably 50 占 퐉 or more, more preferably 100 占 퐉 or more, and even more preferably 150 占 퐉 or more from the viewpoint of enhancing the heat insulating property. The upper limit of the thickness of the resin layer is not particularly limited, but is preferably 500 탆 or less from the viewpoint of thinning.

From the viewpoint of further improving the heat insulation property, it is preferable that the resin layer further comprises a heat insulating material. The heat insulating material in the present invention is a material whose thermal conductivity is lower than that of the resin contained in the resin layer.

Specific examples of the heat insulating material include foamed plastics such as urethane foam, phenol foam and polystyrene foam, and porous particles and hollow particles. These materials have a low thermal conductivity and excellent heat insulating properties because they have an air layer on the surface or inside of the particles. By including these heat insulating materials in the resin layer, voids can be included in the resin layer, and the heat insulating property of the resin layer can be improved. From the viewpoint of excellent light resistance, the heat insulating material is preferably hollow particles or porous particles.

From the viewpoint of further improving the heat insulation property, the porosity of the resin layer is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more. From the viewpoint of not lowering the transmittance of the resin layer, the void ratio in the resin layer is preferably 90% or less. The porosity referred to herein is a ratio of voids in the resin layer, and is a value measured by the following method. Polishing is performed so that the cross section of the color conversion layer is observed by any one of the mechanical polishing method, the microtome method, the cross-section polisher (CP) method, and the focused ion beam (FIB) method. The obtained cross section is observed with a scanning electron microscope (SEM), and the porosity is obtained from the obtained two-dimensional image.

More specifically, the porosity is calculated by the following procedure. First, an image obtained by SEM observation is read by image processing software such as ImageJ, and the image is converted to gray scale. Subsequently, the void is divided into black by the binarization treatment, and the portion other than the cavity is divided into white, and the area of the black portion and the area of the white portion are calculated. At this time, binarization processing may be performed by automatic processing or by eye. (Area of black portion) / (area of black portion + area of white portion), porosity can be obtained.

Examples of the matrix of porous particles and hollow particles include ceramics such as glass, titania, silica, alumina, silicon, zirconia, ceria, aluminum nitride, silicon carbide, silicon nitride, and barium titanate; A photo-curable resist material having reactive vinyl groups such as acrylic, methacrylic, vinyl polycinnamate, polyimide, and cyclic rubber; An epoxy resin, a silicone resin (including an organopolysiloxane cured product (crosslinked product) such as silicone rubber or silicone gel), urea resin, fluororesin, polycarbonate resin, acrylic resin, methacrylic resin, polyimide resin, A polyolefin resin, a polyamide resin, a phenol resin, a polyvinyl alcohol resin, a cellulose resin, an aliphatic ester resin, an aromatic ester resin, an aliphatic polyolefin resin Resins, and aromatic polyolefin resins, but are not limited thereto.

The material of the matrix is preferably a silica or a resin, and an acrylic resin is more preferable among the resins because the thermal conductivity of the matrix is small and the heat insulation is excellent. From the viewpoint of heat resistance and light resistance, silica is more preferable as the material of the matrix. The term "silica" as used herein refers to a glass containing 50% by weight or more of silicon dioxide.

The content of the heat insulating material in the resin layer is preferably 10 vol% or more, more preferably 30 vol% or more, further preferably 50 vol% or more, from the viewpoint of further improving the heat insulating property. Further, in relation to not lowering the light transmittance, the content of the heat insulating material is preferably 90% by volume or less. When the transmittance of light in the resin layer is lowered, the luminance of the light emitting body is lowered. From the viewpoint of suppressing lowering of the luminance of the light emitting body, the transmittance of light in the resin layer is preferably 70% or more.

Here, the transmittance of the resin layer refers to the transmittance of the resin layer at a wavelength of 450 nm. The transmittance can be measured by the following procedure. First, a resin liquid containing a resin and a heat insulating material is prepared. It is coated on quartz glass with a slit die coater or the like, and then heated in an oven at 150 DEG C for 1 hour to prepare a sample for measuring the transmittance. The transmittance at a wavelength of 450 nm can be obtained by measuring the transmittance of a sample for measurement of transmittance by using a basic constitution using an integrating sphere attached to a spectrophotometer (U-4100 Spectrophotomater (Hitachi Seisakusho)).

Further, the light emitted from the organic light emitting material contained in the light emitting body is refracted or reflected at the interface between the layers included in the light emitting body. The light reflected in the light emitting body repeats reflection in the light emitting body and is eventually taken out of the light emitting body. However, in the process of reflecting light in the light emitting body, since light is partially absorbed, attenuation of light occurs.

In the case where an organic light emitting material is used as in the present invention, a decrease in luminance due to the attenuation of such light is conspicuous. It is for the following reasons. In order to suppress the attenuation of the light, it is necessary to change the proceeding direction of the light from the direction of reflection in the light emitting body to the direction to be taken out of the light emitting body. However, unlike the inorganic phosphor such as the YAG-base phosphor, the organic light emitting material has no function of scattering light, and it is difficult to change the traveling direction of the light as described above.

However, in the case of the light emitting body having the heat insulating particles in the resin layer, the heat insulating particles can also serve as the light scattering particles. That is, light is scattered by the heat insulating particles contained in the resin layer, and the traveling direction of light is changed, whereby the light extraction efficiency outside the light emitting body is improved. Thus, the luminance of the light emitting body can be prevented from being lowered.

From the viewpoints of improving the light scattering property and suppressing the deterioration of the extraction efficiency of light, the average particle diameter of the heat insulating material is preferably 0.01 占 퐉 or more, more preferably 0.1 占 퐉 or more.

From the viewpoint of uniformly dispersing the heat insulating material in the resin and obtaining uniform light emission, the average particle diameter of the heat insulating material is preferably 50 占 퐉 or less, more preferably 10 占 퐉 or less, and further preferably 5 占 퐉 or less.

In the present invention, the average particle diameter of the heat insulating material is the median diameter represented by D50. Here, D50 refers to the particle diameter measured by the following method. Polishing is performed so that the cross section of the resin layer is observed by any one of mechanical polishing, microtome method, cross-section polisher (CP) method and focused ion beam (FIB) method. The obtained cross-section is observed with an SEM, and the "individual particle diameter of the particle" defined below is measured from the obtained two-dimensional image. Among the arbitrary straight lines intersecting with the outer edge of the particle at two points, the distance between the two intersection points is selected to be maximum, and the distance is defined as " individual particle diameter of particles ". The particle size distribution was determined from the individual particle diameters of all the observed particles, and the particle diameter of 10% of the passing particle size distribution from the small particle diameter side was D10, the particle diameter of 50% of the passing particle size distribution was D50, The particle diameter of 90% is referred to as D90.

The hollow particle, which is one of preferable forms of the heat insulating material, is not particularly limited, and examples thereof include hollow silica particles, hollow alumina particles, hollow zirconia particles, hollow carbon particles, and hollow acrylic particles. Those commercially available can be used.

Specific examples of the hollow silica particles include XG series such as XG40 and XG100 manufactured by Glandex, Syriacus manufactured by Nittsu High School, Glass Bubbles S60-HS made by 3M, Glass Bubbles S22, Glass Bubbles S38, K20 and the like, HSC-110C manufactured by Potaz-Baratini Co., Sphericel 60P18, Fuji Balloon H-40 manufactured by Fuji Silicia Chemical Co., and Fuji Balloon Series such as Fuji Balloon H-35 . Specific examples of the hollow alumina particles include BW of Showa Denko Co., Ltd. Specific examples of the hollow zirconia particles include HOLLOW ZIRCONIUM SPHEES made by ZIRCOA. Specific examples of the hollow carbon particles include Gureka spearhead manufactured by Kureha Chemical Industry Co., Ltd., and Gabobeare manufactured by GENERAL TECHNOLOGIES. Specific examples of the hollow acrylic particles include ADVANCELL HB-2051 manufactured by Sekisui Chemical Co., Ltd. Of these, hollow silica particles and hollow acrylic particles are more preferable, and hollow silica particles are particularly preferable in that the thermal conductivity of the base material is small in the heat insulating property.

The porous particle, which is one of preferable forms of the heat insulating material, is not particularly limited, and examples thereof include porous silica particles and porous titania particles. Those commercially available can be used.

Specific examples of the porous silica particles include NIPGEL series and NIPSIL series such as NIPGEL AY-603, NIPGEL BY-001, NIPGEL ER-100, NIPGEL AZ-260 and NIPSIL SS50F, 436, Sarisia 446, Sarisia 476, Sarisia 430, and Sarisia 450, and San Sphere Series such as SanSphere H31, SanSphere H51, and SanSphere H121 manufactured by AGC Esotech . Specific examples of the porous titania particles include TITAN MICRO BEAD AA-1515 manufactured by NIKKISO CO., LTD. And the like. Of these, porous silica particles are preferable because the thermal conductivity of the base material is small in terms of excellent heat insulating properties.

From the viewpoint of enhancing the heat insulating property of the resin layer, the resin layer may contain a foamable material. Examples of the foamable material include thermoexpandable fine particles such as Ad Bansel EM series manufactured by Sekisui Chemical Co., Ltd., and X-Pansel manufactured by Nippon Ferrite Co., These foamable materials may be used alone or in combination of two or more.

(LED)

The luminescent color of the LED included in the phosphor according to the embodiment of the present invention is not particularly limited, but it is preferable that the peak of the luminescence wavelength is blue with a range of 400 nm or more and 500 nm or less.

The blue LED may have one type of emission peak, or two or more types of emission peak. From the viewpoint of improving the color reproduction range of the display or illumination, it is preferable that the blue LED has one kind of light emission peak.

Further, a plurality of LEDs having different emission peaks may be arbitrarily combined and used as an aggregate of luminous bodies. Further, a plurality of LEDs may be mounted on one luminous body.

In order to increase the color purity of blue light, the lower limit value of the luminescence peak wavelength is more preferably 430 nm or more, still more preferably 440 nm or more, and particularly preferably 445 nm or more.

In order to reduce the overlap of the spectra of the blue light and the green light, it is preferable to use the light emission observed in the region where the emission peak wavelength is 500 nm or less as blue light emission. In making the effect larger, the upper limit value of the emission peak wavelength of the LED is more preferably 480 nm or less, still more preferably 470 nm or less, and particularly preferably 465 nm or less.

Further, in order to increase the color purity of the blue light, the half width of the peak wavelength of the blue light is preferably 30 nm or less, more preferably 25 nm or less.

(Board)

The substrate usable in the light emitting device according to the embodiment of the present invention is not particularly limited and a substrate including a known material such as a glass epoxy resin, a metal material, and a ceramic material can be used.

The LED of the light emitting body in the present invention is preferably mounted on a heat-dissipating substrate. Since the LED is mounted on the heat-dissipating substrate, it is possible to efficiently dissipate the heat generated by the LED, and the temperature rise of the color conversion layer can be suppressed.

The material of the heat-radiating substrate is not particularly limited as long as heat radiation can be obtained. Specific examples of the heat-radiating substrate include, for example, aluminum, aluminum alloys, copper, copper alloys, and ceramics substrates. Aluminum alloys include Al-Zn-Mg-Cu duralumin alloys. In addition, there are aluminum alloys containing 1% or less of silicon, iron, copper, manganese, magnesium, chromium, zinc, titanium and the like. Examples of copper alloys include guiding metal, single copper, brass, phosphor bronze, mang metal, aluminum bronze, beryllium copper, copper copper, white copper, and gold. Examples of ceramics include alumina, zirconia, zinc oxide, barium titanate, hydroxyapatite, silicon carbide, silicon nitride, fluorite, lead zirconium titanate, and stearate. Of these, aluminum substrates are preferred.

The LED is preferably face-up mounted or face-down mounted on a heat-dissipating substrate. According to the face-down mounting, each electrode of the LED is connected to the conductive region of the substrate without using a wire.

A heat sink is preferably used for the light emitting body according to the embodiment of the present invention for the purpose of further improving heat dissipation. Specifically, for example, it is preferable to use a heat sink which is in contact with the back surface of the substrate. It is preferable that substantially all of the back surface of the substrate is in contact with the heat sink since a higher heat radiation effect can be obtained as the contact area between the substrate and the heat sink is larger. The heat sink is required to have a large heat capacity. A specific example of the material of the heat sink is, for example, copper or aluminum.

(Light-transmitting heat-radiating layer)

It is preferable that the luminous body according to the embodiment of the present invention further has a translucent heat-radiating layer on the color conversion layer. The light-transmitting heat-radiating layer is a layer mainly containing resin and thermally conductive particles, and is a layer having a property of transmitting 50% or more of light having a wavelength of 450 nm. A part of the blue light irradiated to the color conversion layer is absorbed by the organic light emitting material and is converted into light having a longer wavelength. At this time, since a part of the absorbed energy is converted into heat, the temperature of the color conversion layer rises. In order to efficiently dissipate the heat generated in the color conversion layer, it is preferable to form a heat dissipation layer on the color conversion layer. It is preferable that the transmittance of light having a wavelength of 450 nm is 50% or more so that the layer is located above the color conversion layer so as not to lower the luminance of the light emitting body.

As the translucent heat-radiating layer, the same resin as that used for the color conversion layer can be used. Of these, a silicone resin is preferable. As the thermally conductive material, a material having a high thermal conductivity such as alumina, titania, zirconia, boron nitride, aluminum nitride, silicon carbide, or the like can be used. Of these, alumina, titania and aluminum nitride are preferable.

(Reflector)

It is preferable that the light emitting body according to the embodiment of the present invention has a reflector, and the LED and the color conversion layer are disposed in the concave portion formed by the reflector. It is preferable that the reflector constituting the concave portion is inclined so as to widen to the opening side (the side far from the LED mounting surface) in order to efficiently reflect light. In this case, the angle of inclination is not particularly limited, and may be about 90 to 45 degrees with respect to the upper surface of the substrate on which the LED is mounted.

Preferable materials for constituting the reflector include resins such as a thermosetting resin and a thermoplastic resin. Specific examples thereof include epoxy resin, silicone resin, polyimide resin, modified polyimide resin, polyphthalamide resin, polycarbonate resin, polyphenylene sulfide resin, liquid crystal polymer, ABS resin, phenol resin, acrylic resin, PBT resin .

When the reflector is made of a thermosetting resin, a light emitting device having excellent durability can be obtained, which is more preferable. As the thermosetting resin, an epoxy resin, a modified epoxy resin, a silicone resin, a modified silicone resin and the like are preferable.

Further, in order to improve the reflectance, the reflector may contain inorganic particles such as titanium dioxide. The reflectance of the reflector is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more.

The concave portion formed by the reflector is an area from the substrate surface on which the LED is mounted to the upper surface of the reflector, and also refers to an area other than the reflector.

The shape of the concave portion formed by the reflector is not particularly limited and may be any of a circle shape, a circle shape, a cone shape, a polygonal shape, a polygonal shape, a polygonal shape, In particular, from the viewpoint of downsizing, the side view type light emitting device is preferably a shape in which the concave portion extends in the long side direction. Particularly, it is preferable that the shape of the concave portion is a quadrangle, a polygon approximate to a quadrangle, It is more preferable that it is a crucible subject to be widened toward the front side.

2 (a) and 2 (b) are a cross-sectional view and a top view of an example of a light-emitting body in the present invention. In the concave portion formed by the reflector of the luminous body, the uppermost surface of the reflector is called the opening portion 14 of the concave portion. The length in the long side direction of the opening 14 of the concave portion is referred to as the length 10 of the concave portion and the length in the short side direction of the opening portion 14 of the concave portion is referred to as the width 11 of the concave portion.

The length of the concave portion may be different along the short side direction. In this case, it is preferable that the width is increased toward the center in the short side direction, and the longest portion in the short side direction is called the length of the recess.

The width of the concave portion may be different along the long side direction. In this case, it is preferable that the width is increased toward the center in the long side direction, and the longest length in the short side direction is called the width of the concave portion.

The bottom portion of the concave portion refers to the substrate surface portion of the concave portion. The longest portion of the length of the recessed portion in the long side direction is referred to as the bottom portion length 12 and the longest portion of the length in the short side direction of the bottom portion is referred to as the bottom portion width 13. [

The length and width of the concave portion are not particularly limited. However, for a side-edge type display LED, a length sufficient to mount the LED on the substrate is sufficient. Specifically, the length of the concave portion is preferably 0.5 mm or more and 10 mm or less. The width of the concave portion is preferably 1 mm or less, more preferably 0.5 mm or less, and still more preferably 0.3 mm or less, from the viewpoint of thinning of the display. The width of the concave portion is not particularly limited as long as it is a size into which the needle of the dispenser is inserted, and is preferably 0.05 mm or more from the viewpoint of productivity. The depth of the concave portion can be appropriately adjusted by the thickness of the mounted LED, the bonding method and the like, and is preferably 0.1 mm or more and 3 mm or less.

In the direct-type display, the length of the concave portion is preferably 0.5 mm or more and 10 mm or less in the same manner as for the side-edge type display. As for the width of the concave portion, it is not necessary to be thin in contrast to the side edge type, but it is preferably 10 mm or less from the viewpoint of light extraction efficiency. The width of the concave portion is not particularly limited as long as it is a size into which the needles of the dispenser are inserted, and is preferably 0.05 mm or more from the viewpoint of productivity.

(Other layer)

The light emitting body according to the embodiment of the present invention may further include an auxiliary layer having a light diffusing function, a polarization function, a coloring function, a refractive index matching function and the like in accordance with a required function.

≪ Method of producing luminous body &

Next, a method of manufacturing a phosphor according to an embodiment of the present invention will be described with reference to Fig. In addition, the following description is only an example and the manufacturing method is not limited thereto.

First, as shown in Fig. 3A, the LED 2 is disposed on the recess formed by the reflector 4 of the substrate 1 on which the reflector 4 is formed, which is manufactured by a known method , And is connected to the substrate 1 by wiring. 3A shows an example of wire bonding in which wires on the upper surface electrode of the LED 2 and the wires in the circuit included in the substrate 1 are connected by the wires 3. Fig. In the case of a flip chip type in which the LED has an electrode pad on the opposite side of the light emitting surface, the electrode surface of the LED is connected to the wiring of the circuit board by a lumped connection.

3 (b), the resin composition is injected into the concave portion formed by the reflector 4 to form the resin layer 6. Next, as shown in Fig. Fig. 3B shows a case where a part of the concave portion formed by the reflector 4 is filled with the resin composition, but the present invention is not limited to this, and the entire concave portion may be filled with the resin composition.

The resin composition can be produced as follows. A predetermined amount of a resin, a solvent, a heat insulating material, an additive and the like are mixed and homogeneously mixed and dispersed with a stirring / kneading machine such as a homogenizer, a self-ball type stirrer, three rollers, a ball mill, a planetary ball mill and a bead mill. After the mixed dispersion, or in the course of mixed dispersion, it may be defoamed under vacuum or reduced pressure. It is also possible to mix any specific component in advance, or to subject the mixture to treatment such as aging. Part or all of the solvent in the mixture may be removed by an evaporator to obtain a desired solid content concentration.

The solvent is not particularly limited as long as it can adjust the viscosity of the resin in a flowing state. Examples of the solvent include toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol, texanol, methyl cellosolve, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether acetate and the like have. It is also possible to use a mixture of two or more of these solvents.

By drying or thermosetting the resin composition injected into the concave portion, the resin layer 6 is formed. Drying and thermosetting can be performed using a general heating apparatus such as a hot air dryer or an infrared dryer. In this case, the drying and heat curing conditions are usually from 40 to 200 ° C for 1 minute to 3 hours, preferably from 80 to 150 ° C for 2 minutes to 1 hour.

Before the step of drying or thermosetting the resin composition, the resin composition may be left in a vacuum atmosphere in order to remove water, oxygen, and the like dissolved in the resin composition.

3 (c), the color conversion layer 5 is formed on the resin layer 6. Then, as shown in Fig. The color conversion layer 5 may be formed using a composition in a solution state (hereinafter, a composition for forming a color conversion layer is referred to as a "color conversion composition" as appropriate), or a color conversion composition (Hereinafter referred to as " color conversion sheet " as appropriate) of a color conversion composition.

The color conversion composition can be prepared as follows. After mixing a predetermined amount of a compound represented by the general formula (1), a resin, a solvent, and an additive, the mixture is homogenized by a homogenizer, a self-ball type stirrer, three rollers, a ball mill, a planetary ball mill, . After the mixed dispersion, or in the course of mixed dispersion, it may be defoamed under vacuum or reduced pressure. It is also possible to mix any specific component in advance, or to subject the mixture to treatment such as aging. Part or all of the solvent in the mixture may be removed by an evaporator to obtain a desired solid content concentration.

The solvent is not particularly limited as long as it can adjust the viscosity of the resin in a flowing state and does not affect the deterioration of the compound represented by the general formula (1). Examples of the solvent include toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol, texanol, methyl cellosolve, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether acetate and the like have. It is also possible to use a mixture of two or more of these solvents. Among these solvents, toluene is suitably used because it does not affect the deterioration of the compound represented by the general formula (1) and has a small amount of residual solvent after drying.

When the color conversion composition in a solution state is injected onto the resin layer 6 by a dispenser or the like, the color conversion layer 5 can be formed by drying or thermosetting it. Drying and thermosetting can be performed using a general heating apparatus such as a hot air dryer or an infrared dryer. In this case, the drying and heat curing conditions are usually from 40 to 200 ° C for 1 minute to 3 hours, preferably from 80 to 150 ° C for 2 minutes to 1 hour.

The color conversion layer may be formed by a sheet method. The sheet method is a method of adhering a color conversion sheet onto a resin layer.

The color conversion sheet can be produced by applying the color conversion composition onto a substrate and drying. The application may be carried out by a roll coater, a blade coater, a lip coater, a slit die coater, a direct gravure coater, an offset gravure coater, a kiss coater, a screen printing, a natural roll coater, an air knife coater, A wire bar coater, an applicator, a dip coater, a curtain coater, a spin coater, a knife coater and the like. In order to make the film thickness of the color conversion sheet uniform, it is preferable to coat it with a slit die coater. Drying of the color conversion sheet can be performed using a general heating apparatus such as a hot-air dryer or an infrared dryer. In this case, the heat curing is usually carried out at 40 to 200 ° C for 1 minute to 3 hours, preferably at 80 to 150 ° C for 2 minutes to 1 hour. The configuration of the color conversion sheet is not limited as long as it includes a layer obtained by curing the color conversion composition.

The thickness of the color conversion sheet is preferably 500 탆 or less, more preferably 300 탆 or less, and further preferably 200 탆 or less from the viewpoint of enhancing heat resistance. The film thickness measurement method refers to the film thickness (average film thickness) measured on the basis of the method A for measuring the thickness by mechanical scanning in the method of measuring the thickness of plastic film and sheet in JIS K7130 (1999).

The substrate used for the color conversion sheet is not particularly limited, and known metals, films, glasses, ceramics, paper, and the like can be used. In the case where the base material is a metal plate, the surface may be plated with chromium, nickel, or the like or subjected to a ceramic treatment.

Of these, glass or a resin film is preferably used because of the ease of production and molding of the color conversion sheet. Further, a film having high strength is preferably used so that there is no possibility of breakage or the like when handling a film-like base material. (PET), polyethylene naphthalate (PEN), polyphenylene sulfide and polycarbonate, poly (ethylene terephthalate), and poly (ethylene terephthalate) are preferable from the viewpoints of their required characteristics and economical efficiency. And a propylene-based plastic film.

Further, the color conversion sheet may be subjected to compression molding at a high temperature of 200 ° C or higher by an extruder. The substrate in this case is preferably a polyimide film in terms of heat resistance. When the color conversion sheet is peeled off from the base material, the surface of the base material may be subjected to a releasing treatment beforehand in order to facilitate peeling. When the color conversion sheet is used without peeling from the substrate, the substrate is preferably a film containing PET, PEN, polycarbonate in terms of transparency.

The thickness of the base material is not particularly limited, but is preferably 25 占 퐉 or more and more preferably 38 占 퐉 or more as the lower limit. The upper limit is preferably 5000 탆 or less, more preferably 3000 탆 or less.

The base film may be provided with a barrier layer for the purpose of improving the gas barrier property with respect to the color conversion layer. Examples of the barrier layer include metal oxide thin films obtained by adding silicon oxide, aluminum oxide, tin oxide, indium oxide, yttrium oxide, magnesium oxide, etc., or a mixture thereof or other elements thereto, or metal oxide thin films such as polyvinylidene chloride, A film containing various resins such as a resin, a silicone resin, a melamine resin, a urethane resin, and a fluorine resin, but is not limited thereto. Examples of the film having a barrier function against moisture include various kinds of films such as polyethylene, polypropylene, nylon, polyvinylidene chloride, copolymers of vinylidene chloride and vinyl chloride, vinylidene chloride and acrylonitrile, and fluorine resins A film containing a resin, and the like.

In addition, according to the function required for the color conversion sheet, the antireflection function, the antiglare function, the antireflection function, the hard coating function (anti-friction function), the antistatic function, the antifouling function, the electromagnetic shielding function, An auxiliary layer having a function, a polarization function, and a toning function may be additionally provided.

The color conversion sheet preferably has a storage elastic modulus at 25 DEG C of from 0.1 MPa to 2 GPa. Within the above range, it is possible to easily perform cutting processing such as discretization on the color conversion sheet. When the storage elastic modulus at 25 캜 is 0.1 MPa or more, it is possible to secure the hardness for carrying out stable cutting processing. In addition, since the storage elastic modulus at 25 DEG C is 2 GPa or less, it is possible to prevent cracks from occurring in the color conversion sheet at the time of cutting

Here, the storage elastic modulus is a storage elastic modulus determined by dynamic viscoelasticity measurement. The dynamic viscoelasticity means that the shear stress that appears when a material undergoes shear deformation at a sinusoidal frequency and reaches a steady state is defined as a material having a phase and a phase corresponding to each other (elastic component) A viscous component) and analyzing the dynamic dynamics of the material. Here, the storage modulus G 'obtained by dividing the stress component in phase with the shear strain by the shear strain indicates the deformation and follow-up of the material with respect to the dynamic deformation at each temperature. Therefore, .

In the case of using the sheet method for forming the color conversion layer, the color conversion sheet is separated into the size required for each light emitting body, and the separated color conversion sheet is picked up and adhered to the resin layer 6, Layer 5 is formed. A known adhesive may be used to bond the resin layer 6 and the color conversion sheet, or the resin layer 6 itself may be used as an adhesive. When the resin layer 6 is used as an adhesive, the resin layer 6 is completely cured at the time of forming the resin layer 6, but is made semi-cured, and the resin layer 6 is completely cured after attaching the color conversion sheet, Both can be bonded.

The method for separating the color conversion sheet is not particularly limited, and methods such as punching by a mold, processing by a laser, and cutting by a blade are used.

In the processing by the laser, it is very difficult to avoid the burden of the resin and deterioration of the fluorescent material because high energy is applied, and cutting by the blade is preferable.

As a method of cutting with a blade, there are a method of cutting a simple blade by press-fitting and a method of cutting by a rotating blade, all of which can be suitably used.

When a light-transmitting heat-radiating layer is provided in a light-emitting body as required, a method of using a resin composition as a material for the light-transmitting heat-radiating layer can be mentioned. A predetermined amount of resin, solvent, thermally conductive material and the like are mixed and homogeneously mixed and dispersed by a homogenizer, a self-ball type stirrer, three rollers, a ball mill, a planetary ball mill and a bead mill, A resin composition for fabrication is obtained. After the mixed dispersion, or in the course of mixed dispersion, it may be defoamed under vacuum or reduced pressure. It is also possible to mix any specific component in advance, or to subject the mixture to treatment such as aging. Part or all of the solvent in the mixture may be removed by an evaporator to obtain a desired solid content concentration.

The solvent is not particularly limited as long as it can adjust the viscosity of the resin in a flowing state. Examples of the solvent include toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol, texanol, methyl cellosolve, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether acetate and the like . It is also possible to use a mixture of two or more of these solvents.

The transparent resin layer can be formed by dispensing the obtained resin composition onto the color conversion layer 5 and drying or thermosetting it.

Other methods of forming the light-transmitting heat-radiating layer include a method of manufacturing a laminate of a color conversion sheet and a light-transmitting heat-radiating layer, and attaching the laminate to the resin layer 6. In this case, a resin composition for forming a light-transmitting heat-radiating layer is coated on the color conversion sheet, and the laminate is dried or cured.

<Light source unit>

The light source unit according to the embodiment of the present invention includes at least the above-described light emitting body. Specific examples of the light source unit include a backlight unit used for a display or the like. The light source unit may be configured to include an optical film such as a prism sheet, a polarized-light reflective film, or a micro-lens film for the purpose of increasing the brightness. The light source unit may be further provided with a color filter for the purpose of increasing color purity.

<Display, lighting device>

The display according to the embodiment of the present invention includes at least the above-described light emitting body. For example, in a display such as a liquid crystal display, the above-described light emitting unit is used as a backlight unit. Further, a lighting apparatus according to an embodiment of the present invention includes at least the above-described light emitting body. For example, the lighting apparatus is configured to emit white light by combining a blue LED light source as a light source and a color conversion layer for converting blue light from the blue LED light source into light having a longer wavelength than the blue LED light source.

Example

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples. The materials used in each of the Examples and Comparative Examples are as follows.

<Resin>

Acrylic resin: Oricox KC-7000 (manufactured by Kyoe Sagaku Kogyo Co., Ltd.)

Silicone resin: OE6630A / B (manufactured by Toray Dow Corning).

&Lt; Organic light emitting material &

In the following Examples and Comparative Examples, the compounds G-1 and R-1 are shown below.

Synthesis Example 1

Synthesis of Compound G-1

(3.0 g), 4-t-butylphenylboronic acid (5.3 g), tetrakis (triphenylphosphine) palladium (0) (0.4 g) and potassium carbonate The flask was purged with nitrogen. Degassed toluene (30 mL) and degassed water (10 mL) were added, and the mixture was refluxed for 4 hours. The reaction solution was cooled to room temperature, the organic layer was separated, and then washed with saturated brine. The organic layer was dried with magnesium sulfate, filtered, and the solvent was distilled off. The obtained reaction product was purified by silica gel chromatography to obtain 3,5-bis (4-t-butylphenyl) benzaldehyde (3.5 g) as a white solid.

(1.5 g) and 2,4-dimethylpyrrole (0.7 g) were added to the reaction solution, and dehydrated dichloromethane (200 mL) and trifluoroacetic acid (1 drop) And the mixture was stirred under a nitrogen atmosphere for 4 hours. To this was added a dehydrated dichloromethane solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.85 g) and further stirred for 1 hour. After completion of the reaction, boron trifluoride diethyl ether complex (7.0 mL) and diisopropylethylamine (7.0 mL) were added and stirred for 4 hours. Then, water (100 mL) was further added and stirred, and the organic layer was separated. The organic layer was dried with magnesium sulfate, filtered, and the solvent was distilled off. The obtained reaction product was purified by silica gel chromatography to obtain 0.4 g of the following compound G-1 (yield: 18%).

_{^{1 H-NMR (CDCl 3,}} ppm): 7.95 (s, 1H), 7.63-7.48 (m, 10H), 6.00 (s, 2H), 2.58 (s, 6H), 1.50 (s, 6H), 1.37 ( s, 18H).

This compound also exhibited light absorption characteristics in a blue excitation light source and a sharp emission peak in a green region.

Synthesis Example 2

Method for synthesizing compound R-1

A mixed solution of 300 mg of 4- (4-t-butylphenyl) -2- (4-methoxyphenyl) pyrrole, 201 mg of 2-methoxybenzoyl chloride and 10 ml of toluene was heated at 120 占 폚 for 6 hours under a nitrogen stream. After cooling to room temperature, the solvent was removed by evaporation. The residue was washed with 20 ml of ethanol and dried under vacuum to obtain 260 mg of 2- (2-methoxybenzoyl) -3- (4-t-butylphenyl) -5- (4-methoxyphenyl) pyrrole.

Subsequently, 260 mg of 4- (4-t-butylphenyl) -2- (4-t-butylphenyl) -Methoxyphenyl) pyrrole, 206 mg of methanesulfonic anhydride and 10 ml of degassed toluene was heated at 125 占 폚 for 7 hours under a nitrogen stream. After cooling to room temperature, 20 ml of water was poured and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water and evaporated to remove the solvent and vacuum dried.

Subsequently, 305 mg of diisopropylethylamine and 670 mg of boron trifluoride diethyl ether complex were added to a mixed solution of the resulting pyromethene and 10 ml of toluene, and the mixture was stirred at room temperature for 3 hours. 20 ml of water was poured, and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, dried over magnesium sulfate and evaporated to remove the solvent. The residue was purified by silica gel column chromatography and vacuum-dried to obtain 0.27 g of red purple powder. The results of ¹ H-NMR analysis of the obtained powder were as follows, and it was confirmed that the red purple powder obtained in the above was R-1.

_{^{1 H-NMR (CDCl 3,}} ppm): 1.19 (s, 18H), 3.42 (s, 3H), 3.85 (s, 6H), 5.72 (d, 1H), 6.20 (t, 1H), 6.42-6.97 ( m, 16H), 7.89 (d, 4H).

This compound exhibited light absorption characteristics in blue and green excitation light sources and a sharp emission peak in the red region.

&Lt; Heat insulating material &

(Hollow silica particles)

Hollow silica particles 1: XG40 (manufactured by GLANDEX) Average particle diameter 0.4 탆

Hollow silica particles 2: XG100 (manufactured by GLANDEX) Average particle diameter 0.7 탆

Hollow silica particles 3: XG200 (manufactured by GLANDEX) Average particle diameter 1.0 占 퐉.

The hollow silica particles 4 were prepared in the following manner. Average particle diameter 5.0 mu m

800 g of water was placed in a reaction tank having a jacket made of SUS304 of 2 L and adjusted to 10 캜. This was called liquid A. 267 g of methanol (manufactured by Wako Pure Chemical Industries, Ltd.), 16 g of hexane (manufactured by Wako Pure Chemical Industries, Ltd.) and 25 mass% aqueous solution of tetramethylammonium hydroxide (manufactured by Tokyo Kasei Kogyo K.K.) And 18 g of a 30 mass% aqueous solution of lauryltrimethylammonium chloride (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and the mixture was adjusted to 7 캜 by immersing in ice water. This was called liquid B.

While stirring the solution A, the solution B was added at an addition rate of 10 g / sec. After the addition was completed, the mixture was further stirred for 20 seconds, and further 34 g of tetramethoxysilane (manufactured by Tokyo Kasei Kogyo K.K.) was added and stirred for 10 minutes.

The obtained aqueous solution of white liquor was separated by filtration using a filter paper (Kiriyama Seisakusho Co., Ltd.) of 5C and dried at 100 占 폚 in a dryer to obtain a white powder of composite silica particles containing hexane inside the particles. The white powder of the obtained composite silica particles was heated to 1100 占 폚 over 11 hours in a sintering furnace (Superbay Co., Ltd., Motoyama Co., Ltd.) and then held at 1100 占 폚 for 1 hour to completely remove hexane therein, White powder of hollow silica particles 4 was obtained.

0.1 g of the obtained hollow silica particles 4 was weighed into a test tube, 10 ml of isopropyl alcohol was added, and the mixture was subjected to dispersion treatment using ultrasonic waves. The obtained dispersion was subjected to particle size distribution measurement using a laser diffraction scattering type particle size distribution analyzer Micro Trac HRA 9320-X100 (manufactured by Nikkiso Co., Ltd.).

The hollow silica particles 5 were prepared in the following manner. Average particle diameter 10 mu m

Except that 200 g of water to be added to the reaction tank in the preparation of the liquid A was added and the liquid A was added to the liquid B and after stirring for a further 20 seconds, 600 g of water was added and tetramethoxysilane was added. A white powder of the hollow silica particles 5 was obtained in the same manner as in the preparation of the particles 4. The particle size distribution of the hollow silica particles 4 was measured in the same manner as the hollow silica particles 4.

Porous silica particles 1: Sanpearl H31 (manufactured by AGC SAI TECH) Average particle diameter 3 m

Porous silica particles 2: SanSphere H51 (manufactured by AGC SAI TECH CO., LTD.) Average particle diameter 5 탆

Porous silica particles 3: SAN SPEAR H121 (manufactured by AGC SAI TECH CO., LTD.) Average particle diameter 12 탆

Hollow acrylic particles: ADVANCELL HB-2051 (manufactured by Sekisui Chemical Co., Ltd.) average particle diameter 20 탆

<Heat-radiating material>

Alumina particles: AKP3000 (manufactured by Sumitomo Chemical Co., Ltd.)

Titania particles: JR301 (Teika)

Aluminum nitride particles: E grade (manufactured by Tokuyama).

<Inorganic Phosphor>

Green Inorganic Phosphor: GR-MW540K (manufactured by Denka Co.)

Red inorganic phosphor: BR-301 (manufactured by Mitsubishi Chemical).

The various methods of measurement in each of the examples and comparative examples are as follows.

<Measurement of transmittance>

In each of the examples, a part of the sample for measuring transmittance was cut by a focused ion beam (FIB) processing method, and the cross section of the resin layer was observed by SEM. From the obtained SEM image, the thickness of the resin layer was randomly measured at five points, and the average value was determined as the film thickness of the resin layer.

The transmittance at a wavelength of 450 nm was obtained by measuring the transmittance measurement sample produced in each Example in a basic configuration using an integrating sphere attached to a spectrophotometer (U-4100 Spectrophotomater (Hitachi Seisakusho)).

&Lt; Measurement of porosity &

The luminous body produced in each example was cut by a focused ion beam (FIB) processing method, and the cross section of the resin layer was observed by SEM. 10 cross sections were observed, and the images obtained by SEM observation were read by the image processing software ImageJ on the obtained two two-dimensional images. Subsequently, the area of the black part and the area of the white part were calculated by dividing the space other than the cavity with white by filling the space with black by the binarization processing of converting the image into gray scale. At this time, binarization processing was performed by automatic processing. (Area of the black portion) / (area of the black portion + area of the white portion), the porosity was obtained.

&Lt; Measurement of content of heat insulating material &

The luminous body produced in each of the Examples and Comparative Examples was cut by a focused ion beam (FIB) processing method, and the cross section of the resin layer was observed by SEM. 10 sections were observed, and the sum of the cross-sectional areas corresponding to the heat insulating materials of the obtained 10 two-dimensional images was calculated. The total of the cross sectional areas corresponding to the heat insulating material was divided by the sum of the cross sectional areas of the ten two-dimensional images to obtain the content of the heat insulating material in the resin layer. At this time, the void portion included in the heat insulating material was also made a part of the heat insulating material.

<Measurement of Film Thickness of Resin Layer>

The luminous body produced in each of the Examples and Comparative Examples was cut by a focused ion beam (FIB) processing method, and the cross section of the resin layer was observed by SEM. The length from the interface between the LED and the resin layer to the interface between the resin layer and the color conversion layer was measured at 10 points and the average value of 10 points was defined as the film thickness of the resin layer.

<Measurement of film thickness of color conversion layer>

The luminous body produced in each of the Examples and Comparative Examples was cut by a focused ion beam (FIB) processing method, and the cross section of the color conversion layer was observed by SEM. The length from the interface between the resin layer and the color conversion layer to the interface between the color conversion layer and the air layer or the heat dissipation layer was measured at 10 points and the average value of 10 points was defined as the film thickness of the color conversion layer.

&Lt; Measurement of film thickness of heat dissipation layer &

The luminous body produced in each of the examples and the comparative examples was cut by a focused ion beam (FIB) processing method, and the cross section of the heat radiation layer was observed by SEM. The length from the interface between the color conversion layer and the heat dissipation layer to the interface between the heat dissipation layer and the air layer was measured at 10 points and the average value of 10 points was defined as the thickness of the heat dissipation layer.

<Chromaticity, Total luminous flux measurement>

The LEDs were lighted by applying 1 W of power to the luminous bodies produced in the examples and the comparative examples, and the chromaticity (x, y) of the CIE1931 XYZ color system was measured using an entire luminous flux measuring system (HM-3000, manufactured by Otsuka Electric) And the total luminous flux (lm) were measured. At this time, the luminescence spectrum was also obtained at the same time. In each of the following examples and comparative examples described later, the luminous body produced in Comparative Example 1 was evaluated as a relative value to the total luminous flux.

<Measurement of Luminous Maintenance Rate>

Electric power of 1 W was applied to the luminous body produced in each of the examples and the comparative examples, and the total luminous flux after 1,000 hours passed was measured while the LED device was lit in an environment of 25 캜. The durability was evaluated by calculating the total luminous flux holding ratio by the following formula. The higher the total luminous flux holding ratio is, the better the durability is.

Total luminous flux holding ratio (%) = (total luminous flux after 1000 hours passed / total luminous flux immediately after start of test) 100)

<Calculation of Color Reproduction Range>

The color area in the (u ', v') color space when the color purity was improved by the color filter was calculated from the emission spectrum data obtained at the time of chromaticity and total luminous flux measurement and the spectral data of the transmittance of the color filter. The area of the color area in the calculated (u ', v') color space was evaluated by the ratio (color reproduction range (%)) when the area of the color area of the BT.2020 standard was taken as 100% . The higher the ratio, the better the color reproducibility.

<Temperature Measurement>

Electric power of 1 W was applied to the luminous body produced in each of the Examples and Comparative Examples, and the surface temperature of the color conversion layer after one hour had passed was measured using a radiation thermometer FT3701 (manufactured by Hioki Denki K.K.).

<Measurement of Average Particle Diameter of Heat Insulating Material>

Polishing was performed so that the cross section of the resin layer was observed by a focused ion beam (FIB) method using the luminous body obtained in each example. The resulting cross-section was observed with an SEM. From the obtained two-dimensional image, one of the arbitrary straight lines intersecting with the outer edge of the particle at two points was selected so that the distance between the two intersection points became the maximum, Particle diameter &quot;. The particle size distribution was obtained from the individual particle diameters of all the observed particles, and the particle diameter of 50% of the passing particle size distribution from the small particle diameter side in the distribution was calculated to obtain an average particle diameter (D50).

(Examples 1 to 6)

A glass epoxy substrate on which an electrode was previously formed was fitted with a mold for transfer molding, and a thermosetting resin &quot; TA112 &quot; (manufactured by Kuraray Co., Ltd.) was introduced into the mold and cured to form a reflector. At this time, the shape of the concave portion of the reflector was designed such that the concave portion had a length and width of 3 mm, a bottom portion having a length and width of 2 mm, and a depth of 1 mm. Subsequently, a flip chip type blue LED having a thickness of 300 mu m was disposed in the concave portion formed by the reflector, and the LED electrode and the substrate were electrically connected.

A silicone resin was charged into a polyethylene container having a volume of 300 ml and stirred and deaerated at 1000 rpm for 20 minutes using a planetary stirring and defoaming device &quot; Mazerusta KK-400 &quot; (Kurabo) Respectively. Using the dispenser, the resulting resin layer-forming resin liquid was injected into the recess formed by the reflector and heated at 150 캜 for 3 hours to form a resin layer. At this time, in each of Examples 1 to 6, the thickness of the resin layer was changed by changing the injection amount of the resin liquid for forming the resin layer.

Next, 100 parts by weight of an acrylic resin, 0.22 parts by weight of a compound G-1 and 0.02 parts by weight of a compound R-1 were mixed in a 300-ml polyethylene container. 200 parts by weight of toluene was added to 100 parts by weight of the acrylic resin, and the mixture was stirred and defoamed at 1000 rpm for 60 minutes using a planetary stirring and defoaming device &quot; Mazerusta KK-400 &quot; (Kurabo) Thereby obtaining a composition for producing a color conversion layer. Using a dispenser, a color conversion layer composition was injected onto the resin layer and heated at 150 캜 for 2 hours to dry the color conversion composition to obtain a light emitting body.

The film thickness of the resin layer and the porosity of the resin layer of the light emitting body fabricated in Examples 1 to 6 were measured by the method described above. The results are shown in Table 2.

The resin solution for forming a resin layer was coated on quartz glass with a blade coater and then heated in an oven at 150 DEG C for 3 hours to obtain a resin film having the same film thickness as that of the resin layer in the light emitting bodies of Examples 1 to 6 And a sample for measuring the transmittance was prepared. The transmittance of this sample was measured by the method described above.

(Comparative Example 1)

In Comparative Example 1, the same operation as in Example 1 was carried out except that a resin layer was not provided between the LED and the color conversion layer to prepare a light emitting body.

The surface temperature, the total luminous flux, the luminous flux maintenance ratio, and the color reproduction range of the color conversion layer of the luminous body prepared in Examples 1 to 6 and Comparative Example 1 were measured by the methods described above. The results are shown in Table 2.

It was found that the presence of the resin layer between the LED and the color conversion layer suppresses the surface temperature rise of the color conversion layer and improves the light flux retention rate.

[Table 2]

(Examples 7 to 12)

In Examples 7 to 12, by the same operation as in Example 3 except that the silicone resin and the hollow silica particles 1 as the heat insulating material were mixed at the weight ratios shown in Table 3 at the time of making the resin liquid for forming the resin layer, A sample for measuring the transmittance was prepared. The film thickness of the resin layer of the luminous body produced in Examples 7 to 12, the content of the heat insulating material in the resin layer, the porosity of the resin layer, the surface temperature of the color conversion layer, the total luminous flux, the luminous flux maintenance rate, and the color reproduction range were measured by the above- .

A sample for measuring transmittance was prepared by the same procedure as in Example 3 except that the resin liquid for resin layer formation prepared in Examples 7 to 12 was used and the transmittance was measured. The results are shown in Table 3. Also, the results of Example 3 are posted again.

It has been found that the surface temperature of the color conversion layer is further lowered and the light flux retention ratio is further improved by including the heat insulating material in the resin layer.

[Table 3]

(Examples 13 to 16)

In Examples 13 to 16, the same operations as in Example 9 were carried out except that kinds of the heat insulating material were changed as shown in Table 4, to prepare a light emitting body. The film thickness of the resin layer of the luminous body produced in Examples 13 to 16, the content of the heat insulating material in the resin layer, the porosity of the resin layer, the D50 of the heat insulating material, the surface temperature of the color conversion layer, the total luminous flux, Was measured by the method described above. Further, the D50 of the heat insulating material in the resin layer was measured for the phosphor prepared in Example 9 as well.

A sample for measurement of transmittance was prepared in the same manner as in Example 9 except that the resin liquid for resin layer formation prepared in Examples 13 to 16 was used and the transmittance was measured. The results are shown in Table 4. Also, the results of Example 9 are posted again.

It was found that the surface temperature of the color conversion layer was lowered by including the heat insulating material regardless of the kind of the hollow silica particles and the light flux retention ratio was improved.

[Table 4]

(Examples 17 to 22)

Examples 17 to 22 were prepared in the same manner as in Example 3 except that the silicone resin and the porous silica particles 1 as the heat insulating material were mixed at the weight ratios shown in Table 5 at the time of preparing the resin liquid for forming the resin layer, A sample for measurement was prepared. The film thickness of the resin layer of the luminous body fabricated in Examples 17 to 22, the content of the heat insulating material in the resin layer, the porosity of the resin layer, the surface temperature of the color conversion layer, the total luminous flux, the luminous flux maintenance ratio and the color reproduction range were measured by the above- .

A sample for measuring the transmittance was prepared by the same procedure as in Example 3 except that the resin liquid for resin layer formation prepared in Examples 17 to 22 was used and the transmittance was measured. The results are shown in Table 5. Also, the results of Example 3 are posted again.

It has been found that the surface temperature of the color conversion layer is lowered and the luminous flux retention ratio is improved, as in the case of the hollow silica particles, even if the heat insulating material is porous silica particles.

[Table 5]

(Examples 23 and 24)

In Examples 23 and 24, the same operation as in Example 19 was performed except that kinds of the heat insulating material were changed as shown in Table 6, to prepare a light emitting body. The film thickness of the resin layer of the luminous body produced in Examples 23 and 24, the content of the heat insulating material in the resin layer, the porosity of the D50 resin layer of the heat insulating material, the surface temperature of the color conversion layer, the total luminous flux, Was measured by the above-mentioned method. The D50 of the heat insulating material in the resin layer was also measured for the phosphor prepared in Example 19. [

A sample for measurement of transmittance was prepared by the same procedure as in Example 19 except that the resin solution for resin layer formation prepared in Examples 23 and 24 was used and the transmittance was measured. The results are shown in Table 6. Also, the results of Example 19 are published again.

It has been found that the surface temperature of the color conversion layer is reduced and the light flux retention ratio is improved by including the heat insulating material regardless of the kind of the porous silica particles.

[Table 6]

(Example 25)

A luminous body was fabricated in the same manner as in Example 9 except that hollow acrylic particles were used as a heat insulating material. The film thickness of the resin layer, the content of the heat insulating material in the resin layer, the porosity of the resin layer, the surface temperature of the color conversion layer, the total luminous flux, the luminous flux maintenance ratio and the color reproduction range of the prepared luminous body were measured by the methods described above.

A sample for measurement of transmittance was prepared by the same operation as in Example 9 except that the resin liquid for resin layer formation prepared in Example 25 was used and the transmittance was measured. The results are shown in Table 7. In addition, the results of Example 3 and Example 9 are published again.

When the hollow acrylic particles were used, the surface temperature of the color conversion layer was the same as that in the case of using the hollow silica particles 1, but the result was that the light flux retention was low. It is considered that the hollow acrylic particles themselves are photodegraded. However, the constraining retention ratio in Example 25 was improved as compared with Example 3 in which the heat insulating material was not used.

[Table 7]

(Example 26)

A light emitting body was fabricated in the same manner as in Example 9 except that the substrate was changed to an aluminum substrate. The film thickness of the resin layer, the content of the heat insulating material in the resin layer, the porosity of the resin layer, the surface temperature of the color conversion layer, the total luminous flux, the luminous flux maintenance ratio and the color reproduction range of the prepared luminous body were measured by the methods described above. The results are shown in Table 8. Also, the results of Example 9 are posted again.

It has been found that the surface temperature of the color conversion layer is further lowered and the light flux retention ratio is further improved by using a substrate made of aluminum having high heat dissipation property.

[Table 8]

(Examples 27 to 29)

In Example 27, a luminous body was first fabricated in the same manner as in Example 9. [ Then, 100 parts by weight of the silicone resin and 5 parts by weight of the alumina particles were mixed in a 300-ml polyethylene container. This mixture was stirred and deprived at 1000 rpm for 20 minutes using a planetary stirring / defoaming device &quot; Mazerstar KK-400 &quot; (Kurabo), to prepare a resin solution for forming a heat radiation layer. Using the dispenser, the obtained resin liquid for forming the heat dissipation layer was injected onto the color conversion layer of the light emitting body and heated at 150 占 폚 for 3 hours to form a heat dissipation layer.

In Example 28, a luminous body was fabricated in the same manner as in Example 27 except that titania particles were used instead of alumina particles.

In Example 29, a luminous body was fabricated in the same manner as in Example 27 except that aluminum nitride particles were used instead of alumina particles.

The film thickness of the resin layer of the luminous body prepared in Examples 27 to 29, the content of the heat insulating material in the resin layer, the porosity of the resin layer, the surface temperature of the color conversion layer, the total luminous flux, the luminous flux maintenance ratio, . The results are shown in Table 9. Also, the results of Example 9 are posted again.

It has been found that the light flux retention rate is further improved by forming the heat dissipation layer on the color conversion layer.

[Table 9]

(Example 30)

The shape of the recess formed by the reflector was designed such that the recess was formed into a rectangular shape with a length of 1 mm, a recess width of 0.3 mm, a bottom length of 0.8 mm, a bottom width of 0.25 mm, and a depth of 0.5 mm Except for this, the same operation as in Example 9 was carried out.

The film thickness of the resin layer of the obtained luminous body, the content of the heat insulating material in the resin layer, the porosity of the resin layer, the surface temperature of the color conversion layer, the total luminous flux, the luminous flux retention rate and the color reproduction range were measured by the methods described above. The results are shown in Table 10. Also, the results of Example 9 are posted again.

Good light flux retention was exhibited regardless of the shape of the concave portion formed by the reflector.

[Table 10]

(Examples 31 and 32)

In Example 31, first, 100 parts by weight of an acrylic resin, 0.22 parts by weight of a compound G-1 and 0.02 parts by weight of a compound R-1 were mixed in a 300-ml polyethylene container. 200 parts by weight of toluene was added to 100 parts by weight of the acrylic resin and the mixture was stirred and defoamed at 1000 rpm for 60 minutes using a planetary stirring and defoaming device &quot; Mazerusta KK-400 &quot; (Kurabo) Thereby obtaining a composition for color conversion.

Subsequently, using a slit die coater, the composition for color conversion layer formation was applied on "Loomirror" U48 (thickness: 50 μm, manufactured by Toray Industries, Inc.), heated at 120 ° C. for 20 minutes, To prepare a color conversion sheet.

A color conversion sheet was used as the color conversion layer and the shape of the concave portion formed by the reflector was designed such that the concave portion had a rectangular shape with a length and width of 3 mm and a bottom length of 2 mm and a depth of 0.4 mm , And a luminous body was fabricated in the same manner as in Example 3.

In Example 32, a luminous body was fabricated in the same manner as in Example 31 except that the hollow silica particles 1 were mixed in a ratio of 20 parts by weight to 100 parts by weight of the silicone resin when the resin solution for resin layer formation was produced.

The film thickness of the resin layer, the content of the heat insulating material in the resin layer, the porosity of the resin layer, the surface temperature of the color conversion layer, the total luminous flux, the luminous flux maintenance ratio and the color reproduction range of the prepared luminous body were measured by the methods described above. The results are shown in Table 11. Also, the results of Example 3 are posted again.

It was found that even when a color conversion sheet was used for the color conversion layer, a good light flux retention ratio was obtained. Further, it has been found that the surface temperature of the color conversion layer is lowered and the light flux retention ratio is improved by including the heat insulating material in the resin layer.

[Table 11]

(Comparative Examples 2 to 7)

In Comparative Example 2, 100 parts by weight of a silicone resin, 30 parts by weight of a green inorganic fluorescent substance and 20 parts by weight of a red inorganic fluorescent substance were mixed in a polyethylene container having a capacity of 300 ml. Subsequently, the mixture was stirred and defoamed at 1000 rpm for 60 minutes using a planetary stirring / defoaming device &quot; Mazerusta KK-400 &quot; (Kurabo) to obtain a composition for producing a color conversion layer.

A luminous body was produced in the same manner as in Comparative Example 1 except that the color conversion layer-forming composition thus obtained was used for the production of a color conversion layer.

In Comparative Example 3, the same operation as in Example 3 was carried out except that the color conversion layer was made using the composition for color conversion layer production prepared in Comparative Example 2 to prepare a light emitting body. A sample for measuring the transmittance was prepared by the same procedure as in Example 3, and the transmittance was measured.

In Comparative Example 4, the same operation as in Example 9 was carried out except that the color conversion layer was prepared using the composition for color conversion layer production prepared in Comparative Example 2 to prepare a light emitting body. A sample for measuring the transmittance was prepared by the same procedure as in Example 9, and the transmittance was measured.

In Comparative Example 5, the same operation as in Comparative Example 4 was performed except that an aluminum substrate was used as the substrate, to prepare a light emitting body. A sample for measuring the transmittance was prepared by the same procedure as in Example 9, and the transmittance was measured.

In Comparative Example 6, the same operation as in Example 27 was carried out except that the color conversion layer was prepared using the composition for color conversion layer production prepared in Comparative Example 2 to prepare a light emitting body. A sample for measuring the transmittance was prepared by the same procedure as in Example 27, and the transmittance was measured.

In Comparative Example 7, the same operation as in Comparative Example 3 was carried out, except that the shape of the concave portion formed by the reflector was designed to be a rectangular parallelepiped having a bottom surface of 1 mm x 0.3 mm and a depth of 0.5 mm. However, since the phosphor particles are aggregated, the color conversion composition can not be injected into the concave portion formed by the reflector.

Table 12 shows the evaluation results of the phosphor prepared in Comparative Examples 2 to 6. In addition, the results of Comparative Example 1 are posted again.

It was found that the luminous bodies of Comparative Examples 2 to 6 using the inorganic phosphors had a resin layer between the LED and the color conversion layer, the surface temperature of the color conversion layer was lowered but the luminous flux maintenance rate was not affected. It was also found that the luminous bodies of Comparative Examples 2 to 6 using the inorganic phosphors had a lower total luminous flux when the resin layer had a heat insulating material.

[Table 12]

1 substrate
2 LEDs
3 wire
4 Reflector
5-color conversion layer
6 resin layer
7 Heat-radiating layer
8 Heat-dissipating substrate
9 lens
10 Length of recess
11 Width of recess
12 Length of bottom
13 Bottom width
14 opening of the recess

Claims (27)

A light emitting device having an LED and a color conversion layer, wherein the color conversion layer includes an organic light emitting material, and a resin layer is provided between the LED and the color conversion layer. The light emitting body according to claim 1, wherein the resin layer comprises a heat insulating material. The light emitting body according to claim 2, wherein the content of the heat insulating material in the resin layer is not less than 10% by volume and not more than 80% by volume. The light emitting body according to claim 2 or 3, wherein the heat insulating material is hollow particles or porous particles. The light emitting body according to claim 4, wherein the heat insulating material is hollow particles, and the hollow particles are hollow silica particles. The light emitting body according to claim 4, wherein the heat insulating material is porous particles, and the porous particles are porous silica particles. The light emitting body according to any one of claims 1 to 6, wherein the heat insulating material has an average particle diameter of not less than 0.01 탆 and not more than 50 탆. The light emitting body according to any one of claims 1 to 7, wherein the thickness of the resin layer is 50 占 퐉 or more and 500 占 퐉 or less. The light emitting body according to any one of claims 1 to 8, wherein the porosity of the resin layer is 30% or more and 90% or less. The light emitting body according to any one of claims 1 to 9, wherein the color conversion layer and the resin layer are not in direct contact with each other. 11. The light emitting body according to any one of claims 1 to 10, wherein the resin layer has a transmittance of at least 70% at a wavelength of 450 nm. The light emitting device according to any one of claims 1 to 11, wherein the LED is mounted on a heat dissipating substrate. The light emitting body according to any one of claims 1 to 12, further comprising a translucent heat radiation layer on top of the color conversion layer. The light emitting device according to any one of claims 1 to 13, further comprising a reflector, wherein the LED and the color conversion layer are disposed in a recess formed by the reflector. The light emitting body according to claim 14, wherein the opening of the recess formed by the reflector is substantially rectangular. The light emitting body according to claim 15, wherein a width of the concave portion formed by the reflector is 0.05 mm or more and 0.3 mm or less. 17. The organic electroluminescent device according to any one of claims 1 to 16, wherein the organic luminescent material comprises the following organic luminescent material (A) and organic luminescent material (B):
(A) an organic luminescent material exhibiting luminescence observed in a region having a peak wavelength of 500 nm or more and 580 nm or less by using excitation light having a wavelength of 400 nm or more and 500 nm or less;
(B) excited by either or both of excitation light in a wavelength range of 400 nm or more and 500 nm or less or light emission from the organic light emitting material (A), whereby an organic luminescence exhibiting luminescence observed in a region having a peak wavelength of 580 nm or more and 750 nm or less material. 18. The light emitting body according to any one of claims 1 to 17, wherein the organic luminescent material contains a compound represented by the general formula (1).

(X is CR ⁷ or N. Each of R ¹ to R ⁹ may be the same or different and is a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a thiol group, An aryl group, a heteroaryl group, a halogen, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxanyl group, A boron group, a phosphine oxide group, and condensed rings formed between adjacent substituents and an aliphatic ring. The light emitting body according to claim 18, wherein X in the general formula (1) is CR ⁷ , and R ⁷ is a group represented by the general formula (2).

(r ¹ represents hydrogen, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a thiol group, an alkoxy group, an alkylthio group, an arylether group, an arylthioether group, A halogen atom, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxanyl group, a boryl group and a phosphine oxide group. When k is 2 or more, r &lt; ¹ &gt; may be the same or different.) The light emitting body according to claim 18 or 19, wherein all of R ¹ , R ³ , R ⁴ and R ⁶ in the general formula (1) may be the same or different and are a substituted or unsubstituted phenyl group. The organic electroluminescent device according to any one of claims 18 to 20, wherein R ¹ , R ³ , R ⁴ and R ⁶ in the general formula (1) may be the same or different from each other, Gt;

(r ² are selected from alkyl group, a cycloalkyl group, an alkoxy group and a group consisting of an alkylthio. m is an integer from 1 to 3. When m is 2 or more, and may each r ² may be the same or different. However, R ¹ ≠ R ³ or R ⁴ ≠ R ^6, where ≠ represents a group of another structure, and R ⁷ represents an aryl group or a heteroaryl group. The light emitting body according to claim 21, wherein at least one of R ¹ , R ³ , R ⁴ and R ⁶ in the general formula (1) is a group represented by the general formula (3), and r ² is an alkoxy group. The light emitting body according to claim 18 or 19, wherein all of R ¹ , R ³ , R ⁴ and R ⁶ in the general formula (1) may be the same or different and are a substituted or unsubstituted alkyl group. 18. The organic electroluminescent device according to claim 17, wherein the color conversion layer comprises a layer which is a layer containing the organic luminescent material (A) and a b layer which is a layer including the organic luminescent material (B) And the b layer is formed. A light source unit comprising the light emitter according to any one of claims 1 to 24. 25. A display comprising the illuminant of any one of claims 1 to 24. A lighting device comprising the light emitter according to any one of claims 1 to 24.

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