WO2020050144A1

WO2020050144A1 - Color conversion material, color conversion member, light source unit, display device, lighting device, color conversion substrate and ink

Info

Publication number: WO2020050144A1
Application number: PCT/JP2019/034006
Authority: WO
Inventors: 裕健境野; 泰宜市橋; 祐一辻
Original assignee: 東レ株式会社
Priority date: 2018-09-06
Filing date: 2019-08-29
Publication date: 2020-03-12
Also published as: JP7380216B2; KR20210055677A; TW202020107A; JPWO2020050144A1; TWI808253B; CN112639542B; CN112639542A

Abstract

The present invention addresses the problem of achieving a good balance between improvement of color reproducibility and durability, especially a good balance between light emission with high color purity and durability with respect to a color conversion composition that is used for liquid crystal display devices or LED lighting devices, and with respect to a color conversion material that is used for liquid crystal display devices or LED lighting devices. A particulate color conversion material which contains a matrix resin and at least one light emitting material, and which is configured such that the light emitting material contains a compound represented by general formula (1).

Description

Color conversion material, color conversion member, light source unit, display, lighting device, color conversion substrate and ink

The present invention relates to a color conversion material, a color conversion member, a light source unit, a display, a lighting device, a color conversion substrate, and ink.

The application of the multi-color conversion technology based on the color conversion method to liquid crystal displays, organic EL displays, lighting devices, and the like has been actively studied. The color conversion is to convert light emitted from a light emitter to light having a longer wavelength, for example, to convert blue light to green or red light.

The composition having the color conversion function (hereinafter, referred to as “color conversion composition”) is formed into a sheet and combined with, for example, a blue light source to extract three primary colors of blue, green, and red from the blue light source, ie, white light. Can be taken out. A white light source combining such a blue light source and a sheet having a color conversion function (hereinafter, referred to as a “color conversion sheet”) is used as a backlight unit, and this backlight unit, a liquid crystal driving portion, and a color filter are combined. Thus, a full-color display can be manufactured. In addition, if there is no liquid crystal driving portion, it can be used as it is as a white light source, and can be applied as a white light source such as LED lighting.

One of the problems with liquid crystal displays that use the color conversion method is to improve color reproducibility. To improve the color reproducibility, it is effective to narrow the half width of each of the blue, green, and red emission spectra of the backlight unit and increase the color purity of each of the blue, green, and red colors.

As a means for solving this problem, a technique using quantum dots made of inorganic semiconductor fine particles as a component of a color conversion composition has been proposed (for example, see Patent Document 1).
In addition, a technique has been proposed in which an organic light emitting material is used as a component of a color conversion composition instead of a quantum dot. Examples of techniques using an organic light emitting material as a component of a color conversion composition include those using a coumarin derivative (for example, see Patent Document 2), those using a rhodamine derivative (for example, see Patent Document 3), and pyromethene derivatives. (For example, see Patent Document 4).
Further, a technique of adding a light stabilizer to prevent deterioration of an organic light emitting material and improve durability has been disclosed (for example, see Patent Document 5).

JP 2012-22028 A JP 2007-273440 A JP 2001-164245 A JP 2011-241160 A International Publication No. 2011/149028

The technology using quantum dots described in Document 1 certainly has narrow half-widths of green and red emission spectra, and improves color reproducibility. On the other hand, the quantum dots were weak to heat, moisture and oxygen in the air, and had insufficient durability. In addition, there are also problems such as containing cadmium.
In recent years, with high definition such as 4K and 8K, high dynamic range (HDR), and high contrast by local dimming, the illuminance required for a backlight unit of a liquid crystal display is increasing, and the backlight unit by driving heat is used. Has become hot. However, existing techniques such as the light stabilizer described in Patent Document 5 have an effect of improving durability, but are insufficient as techniques for improving durability at high temperatures. In particular, a color conversion material using an organic light emitting material has a problem that durability is significantly deteriorated at a high temperature, and the existing technology has not been able to sufficiently solve this problem.
The problem to be solved by the present invention is to achieve both improved color reproducibility and durability in a color conversion material used for a liquid crystal display or LED lighting. It is to make them compatible. In particular, an object of the present invention is to provide a color conversion material and a color conversion member having improved durability at high temperatures.

In order to solve the above-described problems and achieve the object, the present invention is a particulate color conversion material having a matrix resin and at least one luminescent material, wherein the luminescent material is represented by a general formula (1). Is a particulate color conversion material containing

X is CR ⁷ or N. R ¹ to R ⁹ may be the same or different and each may be 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, or an aryl group. Ether group, arylthioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, It is selected from a phosphine oxide group, and the selected group may form a condensed ring or an aliphatic ring with an adjacent substituent.

The color conversion material and the color conversion member using the same according to the present invention have both high color purity and durability, so that both color reproducibility and durability can be achieved.

FIG. 2 is a schematic sectional view illustrating an example of the color conversion member of the present invention. FIG. 2 is a schematic sectional view illustrating an example of the color conversion member of the present invention. FIG. 2 is a schematic sectional view illustrating an example of the color conversion member of the present invention. 9 is an emission spectrum in Example 2 of the present invention.

Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments, and can be implemented with various changes depending on purposes and applications.

<Light-emitting material>
The particulate color conversion material according to the embodiment of the present invention contains at least one kind of luminescent material. Here, the light-emitting material in the present invention refers to a material that emits light having a different wavelength from the light when the light is irradiated. The organic light emitting material is an organic light emitting material.
In order to achieve high-efficiency color conversion, it is preferable that the light-emitting material is a material exhibiting high emission quantum yield and high emission characteristics. In general, known light-emitting materials such as inorganic phosphors, fluorescent pigments, fluorescent dyes, and quantum dots are used as the light-emitting materials. Among them, an organic luminescent material is preferable from the viewpoint of uniformity of dispersion, reduction of the amount of use, and reduction of environmental load.

Examples of the organic light emitting material include the following. For example, a compound having a condensed aryl ring such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, triphenylene, perylene, fluoranthene, fluorene, or indene, or a derivative thereof may be mentioned as a suitable organic light emitting material. Furan, pyrrole, thiophene, silole, 9-silafluorene, 9,9′-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyridine, pyrazine, naphthyridine, quinoxaline, Suitable organic light-emitting materials include compounds having a heteroaryl ring such as pyrrolopyridine, derivatives thereof, and borane derivatives.

Also, 1,4-distyrylbenzene, 4,4′-bis (2- (4-diphenylaminophenyl) ethenyl) biphenyl, 4,4′-bis (N- (stilben-4-yl) -N-phenyl Suitable organic light-emitting materials include stilbene derivatives such as amino) stilbene, aromatic acetylene derivatives, tetraphenylbutadiene derivatives, aldazine derivatives, pyromethene derivatives, and diketopyrrolo [3,4-c] pyrrole derivatives. In addition, coumarin derivatives such as coumarin 6, coumarin 7, coumarin 153, azole derivatives such as imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, and triazole and metal complexes thereof, cyanine compounds such as indocyanine green, fluorescein, Xanthene-based compounds such as eosin and rhodamine, thioxanthene-based compounds, and the like are mentioned as suitable organic light-emitting materials.

Also, polyphenylene compounds, naphthalimide derivatives, phthalocyanine derivatives and metal complexes thereof, porphyrin derivatives and metal complexes thereof, oxazine compounds such as Nile Red and Nile Blue, helicene compounds, N, N′-diphenyl-N, N ′ Suitable organic light emitting materials include aromatic amine derivatives such as -di (3-methylphenyl) -4,4'-diphenyl-1,1'-diamine. In addition, organic metal complex compounds such as iridium (Ir), ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt), osmium (Os), and rhenium (Re) are suitable for organic light emission. As a material. However, the organic light emitting material in the present invention is not limited to those described above.

The organic light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, but a fluorescent light emitting material is preferable in order to achieve high color purity. Among these, compounds having a condensed aryl ring and derivatives thereof are preferable because of high thermal stability and high light stability.

化合物 As the organic light emitting material, a compound having a coordination bond is preferable from the viewpoint of solubility and diversity of molecular structure. A boron-containing compound such as a boron fluoride complex is also preferable in that the half width is small and light emission with high efficiency is possible.

中でも Among these compounds, a pyrromethene derivative can be suitably used because it gives a high fluorescence quantum yield and has good durability. More preferably, it is a compound represented by the general formula (1). The particulate color conversion material according to the embodiment of the present invention preferably contains at least a compound represented by the general formula (1) as a light emitting material.

X is CR ⁷ or N. R ¹ to R ⁹ may be the same or different and each may be 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, or an aryl group. Ether, arylthioether, aryl, heteroaryl, halogen, cyano, aldehyde, carbonyl, carboxyl, ester, carbamoyl, amino, nitro, silyl, siloxanyl, boryl, sulfo Group, a phosphine oxide group, and a condensed ring and an aliphatic ring formed between adjacent groups.

水素 In all of the above groups, hydrogen may be deuterium. The same applies to the compounds described below and their partial structures. Further, in the following description, for example, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms has 6 to 40 carbon atoms including the number of carbon atoms contained in the substituent substituted with the aryl group. An aryl group. The same applies to other substituents defining the number of carbon atoms.

In all of the above groups, when substituted, the substituent includes 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, and an alkylthio group. , Aryl ether, aryl thioether, aryl, heteroaryl, halogen, cyano, aldehyde, carbonyl, carboxyl, ester, carbamoyl, amino, nitro, silyl, siloxanyl, boryl , A sulfo group, and a phosphine oxide group are preferable, and specific substituents which are preferable in the description of each substituent are preferable. Further, these substituents may be further substituted by the above-mentioned substituents.

「" Unsubstituted "in the case of" substituted or unsubstituted "means that a hydrogen atom or a deuterium atom has been substituted. The same applies to the case of “substituted or unsubstituted” in the compounds described below or their partial structures.

Among all the above groups, the alkyl group means, for example, a saturated aliphatic hydrocarbon such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. Represents a group, which may or may not have a substituent. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20 and more preferably 1 to 8 from the viewpoint of availability and cost.

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

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

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

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

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

The alkoxy group refers to, for example, a functional group in which an aliphatic hydrocarbon group is bonded via an ether bond such as a methoxy group, an ethoxy group, and a propoxy group.The aliphatic hydrocarbon group has a substituent. May not be included. The carbon number of the alkoxy group is not particularly limited, but is preferably in the range of 1 or more and 20 or less.

An alkylthio group is a group in which an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom. The hydrocarbon group of the alkylthio group may or may not have a substituent. The carbon number of the alkylthio group is not particularly limited, but is preferably in the range of 1 to 20.

An aryl ether group refers to, for example, a functional group in which an aromatic hydrocarbon group is bonded via an ether bond, such as a phenoxy group, and the aromatic hydrocarbon group may or may not have a substituent. Is also good. The carbon number of the aryl ether group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.

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

The aryl group includes, for example, phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, anthracenyl, benzophenanthryl, benzoanthracene And an aromatic hydrocarbon group such as a phenyl group, a chrysenyl group, a pyrenyl group, a fluoranthenyl group, a triphenylenyl group, a benzofluoranthenyl group, a dibenzoanthracenyl group, a perylenyl group, and a helicenyl 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 preferred. The aryl group may or may not have a substituent. The carbon number of the aryl group is not particularly limited, but is preferably in the range of 6 or more and 40 or less, and more preferably in the range of 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, and a phenyl group, a biphenyl group Groups, terphenyl groups and naphthyl groups are more preferred. More preferred are phenyl, biphenyl and terphenyl, with phenyl being particularly preferred.

When each substituent is further substituted with an 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, and a phenyl group, a biphenyl group, A phenyl group and a naphthyl group are more preferred. Particularly preferred is a phenyl group.

Heteroaryl group, for example, pyridyl group, furanyl group, thienyl group, quinolinyl group, isoquinolinyl group, pyrazinyl group, pyrimidyl group, pyridazinyl group, triazinyl group, naphthyridinyl group, cinnolinyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, Benzofuranyl, benzothienyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, benzocarbazolyl, carbolinyl, indolocarbazolyl, benzofurcarbazolyl, benzothienocarbazolyl Group, dihydroindenocarbazolyl group, benzoquinolinyl group, acridinyl group, dibenzoacridinyl group, benzimidazolyl group, imidazopyridyl group, benzoxazolyl group, benzothiazolyl group, phenanthrolinyl group, etc. Atoms other than carbon shows a cyclic aromatic group having a single or a plurality of rings. However, naphthyridinyl means any of 1,5-naphthyridinyl, 1,6-naphthyridinyl, 1,7-naphthyridinyl, 1,8-naphthyridinyl, 2,6-naphthyridinyl, and 2,7-naphthyridinyl. Indicates The heteroaryl group may or may not have a substituent. Although the carbon number of the heteroaryl group is not particularly limited, it is preferably in the range of 2 or more and 40 or less, more preferably 2 or more and 30 or less.

When R ¹ to R ⁹ are a substituted or unsubstituted heteroaryl group, examples of the heteroaryl group include pyridyl, furanyl, thienyl, quinolinyl, pyrimidyl, triazinyl, benzofuranyl, benzothienyl, and indolyl. Group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, benzimidazolyl group, imidazopyridyl group, benzoxazolyl group, benzothiazolyl group, phenanthrolinyl group is preferred, and pyridyl group, furanyl group, thienyl group, quinolinyl group is preferred. More preferred. Particularly preferred is a pyridyl group.

When each substituent is further substituted with a heteroaryl group, examples of the heteroaryl group include pyridyl, furanyl, thienyl, quinolinyl, pyrimidyl, triazinyl, benzofuranyl, benzothienyl, indolyl, and dibenzoyl. A furanyl group, a dibenzothienyl group, a carbazolyl group, a benzimidazolyl group, an imidazopyridyl group, a benzoxazolyl group, a benzothiazolyl group, and a phenanthrolinyl group are preferred, and a pyridyl group, a furanyl group, a thienyl group, and a quinolinyl group are more preferred. Particularly preferred is a pyridyl group.

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

The ester group is, for example, a functional group in which an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group and the like are bonded via an ester bond, and the substituent may be further substituted. The carbon number of the ester group is not particularly limited, but is preferably in the range of 1 or more and 20 or less. More specifically, a methyl ester group such as a methoxycarbonyl group, an ethyl ester group such as an ethoxycarbonyl group, a propyl ester group such as a propoxycarbonyl group, a butyl ester group such as a butoxycarbonyl group, and an isopropyl group such as an isopropoxymethoxycarbonyl group. Examples include an ester group, a hexyl ester group such as a hexyloxycarbonyl group, and a phenyl ester group such as a phenoxycarbonyl group. Further, the carbonyl group, carboxyl group, ester group, and carbamoyl group may or may not have a substituent.

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 linear 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 carbon number is not particularly limited, but is preferably in the range of 2 to 50, more preferably 6 to 40, and particularly preferably 6 to 30.

The silyl group includes, for example, an alkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a propyldimethylsilyl group, a vinyldimethylsilyl group, a phenyldimethylsilyl group, a tert-butyldiphenylsilyl group, And an arylsilyl group such as a phenylsilyl group and a trinaphthylsilyl group. Substituents on silicon may be further substituted. The carbon number of the silyl group is not particularly limited, but is preferably in the range of 1 to 30.

The siloxanyl group indicates, for example, a silicon compound group via an ether bond such as a trimethylsiloxanyl group. Substituents on silicon may be further substituted.
The boryl group is a substituted or unsubstituted boryl group. Examples of the substituent in the case of substitution include an aryl group, a heteroaryl group, a linear alkyl group, a branched alkyl group, an aryl ether group, an alkoxy group, and a hydroxyl group. Among them, an aryl group and an aryl ether group are preferable.

The sulfo group is a substituted or unsubstituted sulfo group. Examples of the substituent in the case of substitution include an aryl group, a heteroaryl group, a linear alkyl group, a branched alkyl group, an aryl ether group, and an alkoxy group. Especially, a linear alkyl group and an aryl group are preferable.
A phosphine oxide group is a group represented by —P (＝ O) R ¹⁰ R ¹¹ . R ¹⁰ R ¹¹ is selected from the same group as R ¹ to R ⁹ .

A condensed ring and an aliphatic ring formed between adjacent substituents are conjugated or non-conjugated when any two adjacent substituents (for example, R ¹ and R ^{2 in} the general formula (1)) are bonded to each other. To form a cyclic skeleton. Such a constitutive element of the condensed ring and the aliphatic ring may include an element selected from nitrogen, oxygen, sulfur, phosphorus, and silicon, in addition to carbon. Further, these condensed ring and aliphatic ring may be further condensed with another ring.

The compound represented by the general formula (1) exhibits a high emission quantum yield and has a small half width of the emission spectrum, so that both efficient color conversion and high color purity can be achieved. Furthermore, the compound represented by the general formula (1) has various characteristics such as luminous efficiency, color purity, thermal stability, light stability and dispersibility by introducing an appropriate substituent at an appropriate position. And physical properties can be adjusted. For example, compared to the case where all of R ¹ , R ³ , R ⁴ and R ⁶ are hydrogen, at least one of R ¹ , R ³ , R ⁴ and R ⁶ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkyl group. An aryl group or a substituted or unsubstituted heteroaryl group shows better thermal stability and light stability.

When at least one of R ¹ , R ³ , R ⁴ and R ⁶ is a substituted or unsubstituted alkyl group, the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, An alkyl group having 1 to 6 carbon atoms such as a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group is preferred. Further, as the alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group are preferable from the viewpoint of excellent thermal stability. From the viewpoint of preventing concentration quenching and improving the emission quantum yield, a sterically bulky tert-butyl group is more preferred as the alkyl group. From the viewpoint of ease of synthesis and availability of raw materials, a methyl group is also preferably used as the alkyl group.

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 and a biphenyl group. Particularly preferred is a phenyl group.

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 thienyl group, more preferably a pyridyl group. Quinolinyl group. Particularly preferred is a pyridyl group.

R ¹ , R ³ , R ⁴ and R ⁶ may all be the same or different, and are preferably a substituted or unsubstituted alkyl group because of good solubility in a matrix resin and a solvent. In this case, the alkyl group is preferably a methyl group from the viewpoint of ease of synthesis and availability of raw materials.

When R ¹ , R ³ , R ⁴ and R ⁶ are all the same or different and are each a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, better thermal stability and It is preferable because it shows light stability. In this case, all of R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different, and are more preferably a substituted or unsubstituted aryl group.

置換 Some substituents improve multiple properties, but those 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 types of substituents into the compound represented by the general formula (1), it is possible to obtain a compound that is balanced in light emission characteristics, color purity, and the like.

In particular, all of R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different, and in the case of a substituted or unsubstituted aryl group, for example, R ¹ ≠ R ⁴ , R ³ ≠ R ⁶ , R It is preferable to introduce a plurality of types of substituents such as ¹ ≠ R ³ or R ⁴ ≠ R ⁶ . Here, “≠” indicates a group having a different structure. For example, R ¹ ≠ R ⁴ indicates that R ¹ and R ⁴ are groups having different structures. By introducing a plurality of types of substituents as described above, an aryl group that affects color purity and an aryl group that affects luminous efficiency can be simultaneously introduced, so that fine adjustment can be performed.

Among them, it is preferable that R ¹ ≠ R ³ or R ⁴ ≠ R ⁶ from the viewpoint of improving the luminous efficiency and the color purity in a well-balanced manner. In this case, for the compound represented by the general formula (1), one or more aryl groups that affect color purity are introduced into the pyrrole rings on both sides, and aryl groups that affect luminous efficiency at other positions. Since a group can be introduced, both properties can be maximized. When R ¹ ≠ R ³ or R ⁴ ≠ R ⁶ , it is more preferable that R ¹ ＲR ⁶ and R ³ ＲR ⁴ from the viewpoint of improving both heat resistance and color purity.

アリール As the aryl group that mainly affects color purity, an aryl group substituted with an electron donating group is preferable. The electron donating group is an atomic group that provides an electron to a substituted atomic group due to an induction effect or a resonance effect in organic electron theory. Examples of the electron donating group include those having a negative value as a substituent constant (σp (para)) according to the Hammett rule. The substituent constant (σp (para)) of the Hammett's rule can be quoted from Chemical Handbook Basic Edition, Revised 5th Edition (page II-380).

Specific examples of electron donating groups, for example, an alkyl group (.sigma.p methyl group: -0.17) and alkoxy groups (.sigma.p methoxy groups: -0.27), .sigma.p amino group (-NH _2: - 0.66). 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 preferred. When these are used as the above-mentioned electron donating group, quenching due to aggregation of molecules in the compound represented by the general formula (1) is prevented. be able to. Although the substitution position of the substituent is not particularly limited, it is necessary to suppress the twist of the bond in order to enhance the photostability of the compound represented by the general formula (1). It is preferred to attach to the position or para. On the other hand, as an aryl group that mainly affects luminous efficiency, an aryl group having a bulky substituent such as a tert-butyl group, an adamantyl group, and a methoxy group is preferable.

R ¹ , R ³ , R ⁴ and R ⁶ may be the same or different, and when each is a substituted or unsubstituted aryl group, R ¹ , R ³ , R ⁴ and R ⁶ are the same or different. And it is preferably a substituted or unsubstituted phenyl group. At this time, R ¹ , R ³ , R ⁴ and R ⁶ are more preferably selected from the following Ar-1 to Ar-6, respectively.

In the general formula (1), X, it is preferable from the viewpoint of light stability is ^{C-R 7.} When X is C—R ⁷ , the substituent R ⁷ has a great effect on the durability of the compound represented by the general formula (1), that is, the decrease over time in the emission intensity of the compound. Specifically, when R ⁷ is hydrogen, the reactivity of this site is high, and this site easily reacts with moisture or oxygen in the air. This causes decomposition of the compound represented by the general formula (1). Further, when R ⁷ is a substituent having a large degree of freedom of movement of a molecular chain such as an alkyl group, the reactivity certainly decreases, but the compounds aggregate over time in the color conversion material, As a result, the emission intensity is reduced due to concentration quenching. Therefore, R ⁷ is preferably a group that is rigid, has a small degree of freedom of movement, and hardly causes aggregation. Specifically, R ⁷ is preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. Preferably, it is either one.

It is preferable that X is CR ⁷ and R ⁷ is a substituted or unsubstituted aryl group from the viewpoints of giving a higher fluorescence quantum yield, harder thermal decomposition, and 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.

Furthermore, in order to enhance the photostability of the compound represented by the general formula (1), it is necessary to appropriately suppress the twist of the carbon-carbon bond between R ⁷ and the pyromethene skeleton. This is because if the twist is excessively large, the photostability decreases, for example, the reactivity to the excitation light increases. From such a viewpoint, R ⁷ is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, or a substituted or unsubstituted naphthyl group, and is preferably a substituted or unsubstituted naphthyl group. Is more preferably a phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group. Particularly preferred is a substituted or unsubstituted phenyl group.

Also, R ⁷ is preferably a suitably bulky substituent. R ⁷ is, it is possible to prevent aggregation of the molecules to have some bulkiness, as a result, emission efficiency and durability of the compound represented by the general formula (1) is further improved.

A more preferable example of such a bulky substituent includes a structure of R ⁷ represented by the following general formula (2).

In the general formula (2), r is 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, or an arylthioether. Group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, sulfo group, phosphine oxide group Selected from the group consisting of k is an integer of 1 to 3. When k is 2 or more, r may be the same or different.

R From the viewpoint that a higher emission quantum yield can be obtained, r is preferably a substituted or unsubstituted aryl group. Of these aryl groups, particularly preferred are a phenyl group and a naphthyl group. When r is an aryl group, k in the general formula (2) is preferably 1 or 2, and more preferably 2 from the viewpoint of further preventing aggregation of molecules. Further, when k is 2 or more, it is preferable that at least one of r 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.

Further, from the viewpoint of controlling the fluorescence wavelength or absorption wavelength or increasing the compatibility with the solvent, r is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a halogen. , A methyl group, an ethyl group, a tert-butyl group and a methoxy group are more preferred. From the viewpoint of dispersibility, a tert-butyl group and a methoxy group are particularly preferred. When r is a tert-butyl group or a methoxy group, it is more effective in preventing quenching due to aggregation of molecules.

In another embodiment 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. In particular, (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 It is preferred that one is an electron withdrawing group and that R ⁷ is an electron withdrawing group. As described above, by introducing an electron withdrawing group into the pyrromethene skeleton of the compound, the electron density of the pyrromethene skeleton can be significantly reduced. Thereby, the stability of the compound to oxygen is further improved, and as a result, the durability of the compound can be further improved.

An electron-withdrawing group is also called an electron-accepting group, and is an atomic group that attracts electrons from a substituted atomic group due to an induction effect or a resonance effect in organic electron theory. Examples of the electron withdrawing group include those having a positive value as a substituent constant (σp (para)) according to the Hammett rule. The substituent constant (σp (para)) of the Hammett's rule can be quoted from Chemical Handbook Basic Edition, Revised 5th Edition (page II-380). Although the phenyl group may have a positive value as described above, the electron-withdrawing group does not include the phenyl group in the present invention.

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

Preferred electron withdrawing groups include fluorine, a fluorinated aryl group, a fluorinated heteroaryl group, a fluorinated alkyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted amide group, Examples thereof include a substituted or unsubstituted sulfonyl group or a cyano group. This is because they are hardly chemically decomposed.

More preferred electron withdrawing groups include fluorinated alkyl groups, substituted or unsubstituted carbonyl groups, substituted or unsubstituted ester groups, and cyano groups. This is because these lead to the effect of preventing concentration quenching and improving the emission quantum yield. Particularly preferred electron withdrawing groups are substituted or unsubstituted ester groups.

R ² and R ⁵ are preferably hydrogen, an alkyl group, or an aryl group from the viewpoint of thermal stability, and more preferably hydrogen from the viewpoint that a narrow half-value width is easily obtained in an emission spectrum.

From the viewpoint of improving durability, at least one of R ² and R ⁵ may be the same or different, and is preferably an electron-withdrawing group. Among them, at least one of R ² and R ⁵ may be the same or different, and a substituted or unsubstituted ester group can improve durability without reducing color purity. preferable. In particular, both R ² and R ⁵ may be the same or different, and it is particularly preferable that they are substituted or unsubstituted ester groups from the viewpoint of improving durability.

R ⁸ and R ⁹ are preferably an alkyl group, an aryl group, a heteroaryl group, fluorine, a fluorine-containing alkyl group, a fluorine-containing heteroaryl group or a fluorine-containing aryl group, and a cyano group. In particular, R ⁸ and R ⁹ are more preferably fluorine, a fluorine-containing aryl group, or a cyano group because they are stable to excitation light and can obtain a higher fluorescence quantum yield.

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 fluorine-containing heteroaryl group, 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.

By lowering the electron density on the boron atom, the stability of the compound represented by the general formula (1) to oxygen is further improved, and as a result, the durability of the compound can be further improved. More preferably, it is a cyano group. In particular, it is preferable that at least one of R ⁸ and R ⁹ is a cyano group, because the electron density on the boron atom is further reduced. On the other hand, R ⁸ and R ⁹ are also preferably fluorine from the viewpoint of obtaining a high fluorescence quantum yield and the ease of synthesis.

As one of preferred examples of 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 each is a substituted or unsubstituted alkyl group. Further, there is a case where X is C—R ⁷ and R ⁷ is a group represented by the general formula (2). In this case, R ⁷ is particularly preferably a group represented by the general formula (2) in which r is contained as a substituted or unsubstituted phenyl group.

As another preferable example of 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 the above-mentioned Ar-1 To Ar-6, wherein X is CR ⁷ and R ⁷ is a group represented by the general formula (2). In this case, R ⁷ is more preferably a group represented by the general formula (2) in which r is contained as a tert-butyl group or a methoxy group, and represented by a general formula (2) in which r is contained as a methoxy group. It is particularly preferred that the group is

Further, as another preferable example of 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 may be substituted or unsubstituted. An alkyl group, and R ² and R ⁵ may be the same or different, each being a substituted or unsubstituted ester group, X is C—R ⁷ , and R ⁷ is a general formula The case represented by (2) is exemplified. In this case, R ⁷ is particularly preferably a group represented by the general formula (2) in which r is contained as a substituted or unsubstituted phenyl group.

As another preferable example of 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 the above-mentioned Ar-1 To R-6, and R ² and R ⁵ may be the same or different, each being a substituted or unsubstituted ester group, X is CR ⁷ , and R ⁷ is Examples thereof include a group represented by the general formula (2). In this case, R ⁷ is more preferably a group represented by the general formula (2) in which r is contained as a tert-butyl group or a methoxy group, and represented by a general formula (2) in which r is contained as a methoxy group. It is particularly preferred that the group is

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

化合物 The compound represented by the general formula (1) can be synthesized, for example, by the method described in Japanese Patent Application Laid-Open No. Hei 8-509471 or JP-A-2000-208262. That is, by reacting a pyromethene compound with a metal salt in the presence of a base, the intended pyrromethene-based metal complex can be obtained.

The synthesis of a pyrromethene-boron fluoride complex is described in J. Am. Org. Chem. , Vol. 64, no. 21 pp. 7813-7819 (1999), Angew. Chem. , Int. Ed. Engl. , Vol. 36, pp. The compound represented by the general formula (1) can be synthesized with reference to the method described in 1333-1335 (1997) and the like. For example, after heating a compound represented by the following general formula (3) and a compound represented by the general formula (4) in 1,2-dichloroethane in the presence of phosphorus oxychloride, A method of reacting the compound represented by 1,2-dichloroethane in the presence of triethylamine to obtain a compound represented by the general formula (1) is mentioned. However, the present invention is not limited to this. Here, R ¹ to R ⁹ are the same as described above. J represents a halogen.

Furthermore, when an aryl group or a heteroaryl group is introduced, a method of generating a carbon-carbon bond by using a coupling reaction between a halogenated derivative and a boronic acid or a boronic esterified derivative may be mentioned. However, the present invention is not limited to this. Similarly, when an amino group or a carbazolyl group is introduced, for example, a method of generating a carbon-nitrogen bond by using a coupling reaction between a halogenated derivative and an amine or a carbazole derivative under a metal catalyst such as palladium. However, the present invention is not limited to this.

粒子 The particulate color conversion material according to the embodiment of the present invention can appropriately 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 excitation 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 dye or a rhodamine dye may be added. it can. In addition to these organic light-emitting materials, known light-emitting materials such as inorganic phosphors, fluorescent pigments, fluorescent dyes, and quantum dots can be added in combination.

Examples of organic light-emitting materials other than the compound represented by the general formula (1) are shown below, but the present invention is not particularly limited thereto.

粒子 It is preferable that the particulate color conversion material according to the embodiment of the present invention includes a light-emitting material exhibiting light emission observed in a region having a peak wavelength of 500 nm or more and less than 580 nm (hereinafter, referred to as “first light-emitting material”). Hereinafter, light emission observed in a region having a peak wavelength of 500 nm or more and less than 580 nm is referred to as “green light emission”.

Further, the particulate color conversion material according to the embodiment of the present invention may include a light-emitting material which emits light whose peak wavelength is observed in a range of 580 nm to 750 nm (hereinafter, referred to as “second light-emitting material”). preferable. Hereinafter, the emission observed in the region where the peak wavelength is 580 nm or more and 750 nm or less is referred to as “red emission”.

Generally, the greater the energy of the excitation light, the more easily the material is decomposed. However, excitation light having a wavelength of 400 nm or more and 500 nm or less is preferable because the excitation energy is relatively small. By using the excitation light having a wavelength of 400 nm or more and 500 nm or less, light emission with good color purity can be obtained without causing decomposition of the light emitting material in the color conversion material.

粒子 In the particulate color conversion material according to the embodiment of the present invention, either the first light emitting material and / or the second light emitting material may be included, or both may be included. Further, only one kind of the first light emitting material may be used alone, or a plurality of kinds of the first light emitting materials may be used in combination. Similarly, only one kind of the second light emitting material may be used alone, or a plurality of kinds of second light emitting materials may be used in combination.

(4) Part of the excitation light having a wavelength of 400 nm or more and 500 nm or less partially passes through the particulate color conversion material according to the embodiment of the present invention, and thus can itself be used as blue light emission. Therefore, the particulate color conversion material according to the embodiment of the present invention includes a first light emitting material emitting green light and a second light emitting material emitting red light, and uses a blue LED having a sharp emission peak as blue light. In this case, a sharp emission spectrum is shown in each of the blue, green, and red colors, and white light with good color purity can be obtained. As a result, particularly in a display, colors can be more vivid and a larger color gamut can be efficiently created. Further, in lighting applications, compared to a white LED combining a mainstream blue LED and a yellow phosphor, the emission characteristics, particularly in the green and red regions, are improved. A light source can be obtained.

Examples of the first light emitting material include coumarin derivatives such as coumarin 6, coumarin 7, and coumarin 153, cyanine derivatives such as indocyanine green, fluorescein derivatives such as fluorescein, fluorescein isothiocyanate, carboxyfluorescein diacetate, and phthalocyanine derivatives such as phthalocyanine green. Perylene derivatives such as diisobutyl-4,10-dicyanoperylene-3,9-dicarboxylate, as well as pyromethene derivatives, stilbene derivatives, oxazine derivatives, naphthalimide derivatives, pyrazine derivatives, benzimidazole derivatives, benzoxazole derivatives, benzothiazole derivatives , Imidazopyridine derivatives, azole derivatives, compounds having fused aryl rings such as anthracene and derivatives thereof, aromatic amine derivatives, organic Metal complex compounds, and the like as preferred. However, the first light emitting material is not particularly limited to these.

中でも Among these compounds, the pyrromethene derivative is a particularly suitable compound because it gives a high emission quantum yield and has good durability. As the pyrromethene derivative, for example, a compound represented by the general formula (1) is preferable because it emits light with high color purity.

Examples of the second light emitting material include cyanine derivatives such as 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran, and rhodamine derivatives such as rhodamine B, rhodamine 6G, rhodamine 101, and sulfolhodamine 101. Pyridine derivatives such as N, N-N'-bis (2,6-diisopropylphenyl) -1, 1-ethyl-2- (4- (p-dimethylaminophenyl) -1,3-butadienyl) -pyridinium-perchlorate Derivatives such as, 6,7,12-tetraphenoxyperylene-3,4,9,10-bisdicarboximide, porphyrin derivatives, pyromethene derivatives, oxazine derivatives, pyrazine derivatives, naphthacene and dibenzodiindenoperylene, etc. Having a condensed aryl ring, derivatives thereof, and organometallic complexes Compounds and the like as preferred. However, the second light emitting material is not particularly limited to these.

The content of the luminescent material in the particulate color conversion material according to the embodiment of the present invention is the molar extinction coefficient of the compound, the emission quantum yield and the absorption intensity at the excitation wavelength, and the size of the color conversion material or color conversion member to be produced Usually, the amount is 1.0 × 10 ⁻⁴ parts by mass to 30 parts by mass with respect to 100 parts by mass of the matrix resin, though it depends on the thickness, transmittance and the like. Among them, the amount is more preferably 1.0 × 10 ⁻³ parts by mass to 10 parts by mass, and particularly preferably 5.0 × 10 ⁻³ parts by mass to 5 parts by mass.

When the color conversion material contains both a first light emitting material that emits green light and a second light emitting material that emits red light, a part of the green light is converted to red light. the content of _{w 1} of the first light-emitting material, the content _{w 2} of the second light-emitting material is preferably a relationship of _{w 1} ≧ _{w 2.} The ratio between the content w ₁ and the content w ₂ is w ₁ : w ₂ = 1000: 1 to 1: 1, preferably 500: 1 to 2: 1, and more preferably 200: 1 to 2: 1. A ratio of 3: 1 is particularly preferred. However, the content of w ₁ and the content w ₂ is the weight percent of the mass of the matrix resin.

<Matrix resin>
In the particulate color conversion material according to the embodiment of the present invention, a material having excellent moldability, transparency, heat resistance, and the like is suitably used as the matrix resin. Examples of the matrix resin include, for example, a photocurable resist material having a reactive vinyl group such as an acrylic acid type, a methacrylic acid type, a polyvinyl cinnamate type, a ring rubber type, an epoxy resin, a silicone resin (silicone rubber, silicone Organopolysiloxane cured products such as gels (including crosslinked products), urea resins, fluorine resins, polycarbonate resins, acrylic resins, urethane resins, melamine resins, polyvinyl resins, polyamide resins, phenol resins, polyvinyl alcohol resins, polyvinyl butyral resins And polyester resins such as cellulose resins, aliphatic ester resins and aromatic ester resins, aliphatic polyolefin resins such as cycloolefin resins, and aromatic polyolefin resins. As the matrix resin, a mixture or a copolymer of these resins may be used. By appropriately designing these resins, a matrix resin useful for the particulate color conversion material according to the embodiment of the present invention can be obtained.

Among these resins, from the viewpoint of transparency and dispersibility of the organic light-emitting material, an acrylic resin, a copolymer resin containing an acrylate or methacrylate portion, a polyester resin, a cycloolefin resin, or an epoxy resin is used. Is preferred.

ガラス The glass transition temperature (Tg) of the matrix resin is not particularly limited, but is preferably from 30 ° C to 180 ° C. When Tg is 30 ° C. or higher, the molecular motion of the matrix resin due to the heat due to the incident light from the light source or the driving heat of the device is suppressed, and the change in the dispersion state of the light emitting material is suppressed, thereby preventing the deterioration of the durability. Can be. When Tg is 180 ° C. or lower, flexibility when formed into a sheet or the like can be ensured. The Tg of the matrix resin is more preferably from 50 ° C to 170 ° C, further preferably from 70 ° C to 160 ° C, and particularly preferably from 90 ° C to 150 ° C.

分子 The molecular weight of the matrix resin is not particularly limited depending on the type of the resin, but is preferably 3,000 to 1500,000. When the molecular weight is smaller than 3000, the resin becomes brittle, and the flexibility when molded becomes low. Further, when the molecular weight is larger than 1500000, there are problems that the viscosity at the time of molding becomes excessively large and the chemical stability of the resin itself is reduced. The molecular weight of the matrix resin is more preferably 5,000 to 1,200,000, still more preferably 7,000 to 1,000,000, and particularly preferably 10,000 to 800,000.

粒子 The particulate color conversion material according to the embodiment of the present invention is a particulate color conversion material having a light emitting material containing a matrix resin and a compound represented by the general formula (1). Specifically, it is a particulate color conversion material in which at least one kind of luminescent material is contained in a matrix resin.

<Additives>
The particulate color conversion material according to the embodiment of the present invention is, besides the light emitting material and the matrix resin, an antioxidant, a processing and heat stabilizer, a light resistance stabilizer such as an ultraviolet absorber, a plasticizer, and an epoxy compound. And the like. Curing agents such as amine, acid anhydride and imidazole, inorganic particles such as silica particles and silicone fine particles, and additives such as silane coupling agents can be contained.

Examples of the antioxidant include, but are not particularly limited to, phenolic antioxidants. The antioxidants may be used alone or in combination of two or more.
Examples of the processing and heat stabilizers include, but are not particularly limited to, phosphorus-based stabilizers. The stabilizers may be used alone or in combination.
Examples of the light resistance stabilizer include, for example, benzotriazoles, but are not particularly limited thereto. Further, the light resistance stabilizer may be used alone or in combination of two or more.

From the viewpoint that these additives do not inhibit light from a light source or light emission of a light-emitting material, it is preferable that these additives have a small absorption coefficient in the visible region. Specifically, the molar extinction coefficient ε of these additives is preferably 200 or less, more preferably 100 or less, over the entire wavelength range of 400 nm to 800 nm. It is more preferably at most 80, particularly preferably at most 50.

Further, as the light fastness stabilizer, a compound having a role as a singlet oxygen quencher can also be suitably used. The singlet oxygen quencher is a material that traps and inactivates singlet oxygen generated by activation of oxygen molecules by light energy. The coexistence of the singlet oxygen quencher in the color conversion material can prevent the light-emitting material from being deteriorated by singlet oxygen.
Examples of the compound serving as a singlet oxygen quencher include, but are not limited to, specific tertiary amines and metal salts. Further, these compounds (lightfastness stabilizer) may be used alone or in combination of two or more.
Further, as the light fastness stabilizer, a compound having a role as a radical quencher can also be suitably used. Especially, a hindered amine compound is mentioned as a suitable example.
In the particulate color conversion material according to the embodiment of the present invention, the content of these additives depends on the molar extinction coefficient of the compound, the emission quantum yield and the absorption intensity at the excitation wavelength, and the color conversion material or color conversion to be produced. Although it depends on the size, thickness and transmittance of the member, it is preferably at least 1.0 × 10 ⁻³ parts by mass, more preferably at least 1.0 × 10 ⁻² parts by mass, per 100 parts by mass of the matrix resin. More preferably, the content is more preferably 1.0 × 10 ^-1 part by mass or more. Further, the content of these additives is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, and more preferably 10 parts by mass or less, based on 100 parts by mass of the matrix resin. More preferred.

<Particulate color conversion material>
Since the particulate color conversion material according to the embodiment of the present invention contains the compound represented by the general formula (1), it emits light with extremely high color purity.
In addition, since it can be handled as a powder, it is easy to mix and use a plurality of types of particulate color conversion materials and finely adjust the wavelength conversion characteristics. For example, when white light is obtained by performing color conversion on a part of blue light, a green conversion material containing a light emitting material emitting green light and a red conversion material containing a light emitting material emitting red light are prepared. The white balance and color temperature of white light can be easily adjusted by adjusting the amount of mixing.
Further, by controlling the particle diameter and shape of the color conversion material, the refractive index of the matrix resin, and the like, the color conversion characteristics can be adjusted, and functions other than the color conversion function can be provided. For example, a light scattering function can be exhibited.

In the particulate color conversion material according to the embodiment of the present invention, since each particle is individually independent, when highly active species such as radical species are generated by light irradiation at a high temperature condition, the high active species is entirely And the accelerated deterioration of the entire color conversion member can be suppressed.

The particulate color conversion material according to the embodiment of the present invention preferably has an average particle size of 0.010 μm or more and 100 μm or less, more preferably 0.010 μm or more and 30 μm or less, and 0.010 μm or more and 10 μm or less. Is more preferable. The average particle size is obtained by observing the particle size distribution by microscopic observation or laser diffraction scattering method, but it is basically measured by microscopic observation. However, when the measurement result by the laser diffraction scattering method has a particle size of 1 μm or less, the particle size by the laser diffraction scattering method is adopted. In the case of microscopic observation, although not particularly limited, it can be obtained by measuring the particle size of about 100 isolated particles and calculating the average value.

<Method for producing particulate color conversion material>
The method for producing the particulate color conversion material according to the embodiment of the present invention is not particularly limited as long as the particulate color conversion material can be formed into particles containing a light emitting material and a matrix resin. For example, an interfacial polymerization method, a W / O-based in-liquid drying method, a Stover method, and a spray drying method, an in situ polymerization method, a phase separation method from an aqueous solution, a phase separation method from an organic solvent, a melting dispersion cooling method, and an airborne method It can be produced by a suspension coating method.
Above all, as a simple method, a method in which a composition prepared by mixing predetermined amounts of the above-described materials such as the light-emitting material, the matrix resin, and the solvent, and then dried by a spray-drying method to form particles is used.

As the solvent to be used, for example, water, 2-propanol, ethanol, toluene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, hexane, cyclohexane, tetrahydrofuran, acetone, terpineol, texanol, 1,2-dimethoxyethane, methylcellosolve, ethylcellosolve, butyl carbitol, butyl carbitol acetate, 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate, etc., and a mixture of two or more of these solvents It is also possible to use it. Among these solvents, toluene, methyl ethyl ketone, methyl acetate, ethyl acetate, and tetrahydrofuran are preferably used because the residual solvent after drying is small.

<Support>
The particulate color conversion material according to the embodiment of the present invention may be used by itself. Further, from the viewpoint of further improving the applicability to the optical member, it is preferable to use a support containing a particulate color conversion material. The support containing the particulate color conversion material according to the embodiment of the present invention can be used as a color conversion member.

材質 The material of the support is not particularly limited, and known metals, resins, glass, ceramics, papers, and the like can be used. From the viewpoint of transparency and workability, the support is preferably made of resin. When the support is made of a resin, it is more preferable that the particulate color conversion material is dispersed in the support. In the present invention, the term “dispersion” means that other substances are scattered in one phase, and the distribution may be uneven or uniform. However, when it is described that the particulate color conversion material is dispersed, a mode in which the particulate color conversion material is completely dissolved in the dispersion medium to form one uniform phase is excluded. In order to confirm whether or not the particulate color conversion material according to the present invention is dispersed in the support, methods such as visual observation, microscopic observation, emission spectroscopy measurement, and refractive index measurement can be used as appropriate. . As the preferable resin, the resin exemplified as the matrix resin described above can be suitably used as the support.

When the support is made of a resin, it is preferable to use a resin different from the matrix resin, and the difference between the matrix resin of the particulate color conversion material and the resin forming the support has an SP value of 0.5 (cal / cm ³ ). It is preferably ^0.5 or more. When the difference in SP value is 0.5 (cal / cm ³ ) ^0.5 or more, the particulate color conversion material can be dispersed in the support without being dissolved. When the particulate color conversion material is dissolved in the resin constituting the support, the luminescent material is eluted also into the support, and the half width is reduced. The difference between the SP values is more preferably 1.0 (cal / cm ³ ) ^0.5 or more, still more preferably 1.5 (cal / cm ³ ) ^0.5 or more, and 2.0 (cal / cm ³ ) ^0.5 or more. (Cal / cm ³ ) is particularly preferably ^0.5 or more. If the difference in SP value is too large, the particles aggregate and cause quenching. Therefore, the upper limit is more preferably 4.0 (cal / cm ³ ) ^0.5 or less, and more preferably 3.0 (cal / cm ³ ). cm ³ ) ^0.5 or less, more preferably 2.5 (cal / cm ³ ) ^0.5 or less.
When the support is made of a resin, the SP value of the matrix resin of the particulate color conversion material is preferably larger than the SP value of the resin forming the support.

The shape of the support is not particularly limited, and examples thereof include a granular shape, a massive shape, and a sheet shape. In addition, a form filled in a mold is also included. Above all, from the viewpoint of further improving the applicability to a light source unit described later, the sheet is preferably used.
On the other hand, from the viewpoint of integration with the LED light source and integration with the patterned member, a method of filling the mold is also preferable.
The particulate color conversion material contained in the support may be one type or a plurality of types.

As one mode of the color conversion member according to the embodiment of the present invention, a particulate color conversion material containing a luminescent material emitting green light and a particulate color conversion material containing a luminescent material emitting red light are provided. It is preferable to include at least two types in the same support. Thus, white light can be obtained by converting a part of the blue light.

ともに Both the light emitting material emitting green light and the light emitting material emitting red light are preferably compounds represented by the general formula (1), since white light with high color reproducibility can be obtained. That is, as a preferred embodiment of the present invention, a first particulate color conversion material comprising a compound represented by the general formula (1) exhibiting light emission observed in a region having a peak wavelength of 500 nm or more and less than 580 nm and a first matrix resin is provided. A second particulate color conversion material comprising a compound represented by the general formula (1) exhibiting light emission having a peak wavelength of 580 nm or more and 750 nm or less, a second matrix resin, and a support containing them. Color conversion member.

として As another mode of the color conversion member according to the embodiment of the present invention, it is also preferable that a plurality of types of supports containing a particulate color conversion material are combined. For example, a support containing a particulate color conversion material emitting green light and a support containing a particulate color conversion material emitting red light can be used. Above all, it is preferable to combine the first support having the first particulate color conversion material with the second support having the second particulate color conversion material. The method of combining a plurality of supports depends on the shape of the supports, and examples thereof include a method of arranging them on the same plane and a method of stacking.

By optimizing the combination of the organic light emitting material and the matrix resin in each of the first particulate color converting material and the second particulate color converting material, the emission peak wavelength of the organic light emitting material is shifted to a desired wavelength, and the color gamut is changed. Can be expanded. Therefore, it is preferable that the first matrix resin is different from the second matrix resin. The difference between the two matrix resins means that the types and / or compositions of the resins are different.

Further, there is a strong relationship between the SP value, which is a solubility parameter of the matrix resin, and the emission peak wavelength of the organic light emitting material. In a matrix resin having a large SP value, the excited state of the organic light emitting material is stabilized by the interaction between the matrix resin and the organic light emitting material. Therefore, the emission peak wavelength of this organic light emitting material shifts to a longer wavelength side as compared with the matrix resin having a small SP value. Therefore, by dispersing the organic light emitting material in the matrix resin having the optimum SP value, it is possible to optimize the emission peak wavelength of the organic light emitting material.

When the SP value of the first matrix resin is SP ₁ (cal / cm ³ ) ^0.5 and the SP value of the second matrix resin is SP ₂ (cal / cm ³ ) ^0.5 , SP ₁ ≦ SP ₂ Preferably, there is. In this case, the difference between the emission peak wavelengths of the green light and the red light in the first particulate color conversion material and the second particulate color conversion material is smaller than the case where the organic light emitting material is dispersed in the same matrix resin. As a result, the color gamut is expanded.

Especially, it is preferable that SP ₂ ≧ 10.0. In this case, the emission peak wavelength of red light in the second particulate color conversion material is further increased, and as a result, deep red light can be emitted from the second particulate color conversion material. From the viewpoint of increasing the effect, SP ₂ ≧ 10.2 is more preferable, SP ₂ ≧ 10.4 is more preferable, and SP ₂ ≧ 10.6 is particularly preferable.

The upper limit of the SP ₂ is not particularly limited, the matrix resin is a SP ₂ ≦ 15.0, since good dispersibility of the organic light emitting material can be preferably used. From the viewpoint of increasing the effect, SP ₂ ≦ 14.0 is more preferable, SP ₂ ≦ 13.0 is more preferable, and SP ₂ ≦ 12.0 is particularly preferable.

Further, when SP ₁ ≦ 10.0, the emission peak wavelength of green light in the first particulate color conversion material is prevented from becoming longer, and as a result, the first particulate color conversion material and the second particulate color are converted. This is preferable because the difference in emission peak wavelength between green light and red light in the conversion material increases. From the viewpoint of increasing the effect, SP ₁ ≦ 9.8 is more preferable, SP ₁ ≦ 9.7 is more preferable, and SP ₁ ≦ 9.6 is particularly preferable.

Although the lower limit of SP ₁ is not particularly limited, a matrix resin satisfying SP ₁ ≧ 7.0 can be suitably used because the organic light emitting material has good dispersibility. From the viewpoint of increasing the effect, SP ₁ ≧ 7.4 is more preferable, SP ₁ ≧ 7.8 is more preferable, and SP ₁ ≧ 8.0 is particularly preferable.

Here, the dissolution parameter (SP value) is generally used, Poly. Eng. Sci. , Vol. 14, No. 2, pp. 147-154 (1974) and the like, and are values calculated from the types and ratios of the monomers constituting the resin using the Fedors estimation method. The same method can be used to calculate a mixture of a plurality of types of resins. For example, the SP value of polymethyl methacrylate is 9.9 (cal / cm ³ ) ^0.5 , the SP value of polyethylene terephthalate (PET) is 11.6 (cal / cm ³ ) ^0.5 , and a bisphenol A epoxy resin Can be calculated as 10.9 (cal / cm ³ ) ^0.5 .
Table 1 shows typical SP values of the resins. The first matrix resin and the second matrix resin can be used in any combination, for example, from the resins shown in Table 1.

As another aspect of the color conversion member according to the embodiment of the present invention, it is preferable that the support of the present invention contains at least one luminescent material in addition to the particulate color conversion material according to the present invention. Among them, from the viewpoint of color purity, it is more preferable that the support contains at least one kind of organic light emitting material, and it is more preferable that the support contains at least the compound represented by the general formula (1).

The support that can be used in the present invention includes, in addition to the particulate color conversion material and the light-emitting material, a light-resistant dye such as a light-absorbing dye, a light-absorbing pigment, an antioxidant, a processing and heat stabilizer, and an ultraviolet absorber. Agents, dispersants and leveling agents, plasticizers, crosslinking agents such as epoxy compounds, curing agents such as amines, acid anhydrides, imidazoles, adhesion aids, inorganic particles such as titanium oxide particles, zirconia particles, silica particles, and silane. An additive such as a coupling agent can be contained.

代表 A typical example of the structure of the color conversion member according to the embodiment of the present invention includes those shown in FIGS. 1 to 3 are schematic cross-sectional views illustrating an example of a color conversion member according to an embodiment of the present invention. As shown in FIG. 1, a color conversion member 1 according to an example of the present embodiment has a structure in which a particulate color conversion material 2 is dispersed inside a support 3. Further, as shown in FIG. 2, the color conversion member 1A as an example of the present embodiment has a structure in which a particulate color conversion material 2a and a particulate color conversion material 2b are dispersed inside a support 3. Further, as shown in FIG. 3, the color conversion member 1B as an example of the present embodiment has a support 3a in which the particulate color conversion material 2a is dispersed, and a particulate color conversion material 2b dispersed therein. This is a structure in which the supports 3b are stacked. Further, the color conversion member according to the embodiment of the present invention may have a structure in which another light emitting material is included in the inside of the

support

3, 3a, or 3b in FIGS. Preferably, the luminescent material is dispersed in the

support

3, 3a or 3b. The luminescent material added to the

color conversion members

1, 1A, 1B is preferably a compound represented by the general formula (1).

<Method for producing color conversion member>
The method for producing the color conversion member according to the embodiment of the present invention is not particularly limited as long as the support containing the particulate color conversion material of the present invention can be formed into a desired shape. For example, a method of mixing a particulate color conversion material according to the present invention, a resin used as a support, and a solvent, preparing a composition, applying the composition on a substrate, and drying the composition to form a sheet. Is mentioned. Further, there is also a method of kneading while heating the particulate color conversion material according to the present invention and a resin as a support, and molding the mixture using an extruder.

<Color conversion board>
The color conversion substrate according to the embodiment of the present invention has a configuration including at least the particulate color conversion material or the color conversion member of the present invention. The color conversion substrate has a plurality of color conversion layers on a transparent substrate. In the present invention, the color conversion layer preferably includes a red conversion layer and a green conversion layer. The red conversion layer is formed of a phosphor material that absorbs at least blue light and emits red light. The green color conversion layer is formed of a phosphor material that absorbs at least blue light and emits green light. Further, a partition may be formed, and the color conversion layer is preferably disposed between the partition (recess). Excitation light may be made incident from the transparent substrate side and viewed from the side opposite to the transparent substrate, or excitation light may be made incident from the color conversion layer side and viewed from the transparent substrate side. When the color conversion substrate is irradiated with blue light having a peak wavelength of 440 to 460 nm, the quantum yield of the color conversion layer is usually 0.5 or more, preferably 0.7 or more, more preferably 0.8 or more. Preferably it is 0.9 or more.

<Ink>
The ink according to the embodiment of the present invention is a liquid, gel, or solid containing at least the particulate color conversion material or color conversion member of the present invention, which is used for writing characters and coloring the surface. It is. The ink according to the embodiment of the present invention can achieve both high-color purity light emission and durability by using the particulate color conversion material or the color conversion member of the present invention. Can be preferably used as a fluorescent ink.

<Excitation light>
Any kind of excitation light can be used as long as it emits light in a wavelength region that can be absorbed by the organic light-emitting material used in the present invention. For example, excitation light from any light source such as a fluorescent light source such as a hot cathode tube, a cold cathode tube, an inorganic electroluminescence (EL) device, an organic EL device light source, an LED light source, an incandescent light source, or sunlight can be used. is there. Above all, excitation light from an LED light source is preferable. In displays and lighting applications, excitation light from a blue LED light source having excitation light in a wavelength range of 400 nm or more and 500 nm or less is more preferable because the color purity of blue light can be increased.

The maximum emission wavelength of the excitation light is more preferably 430 nm or more and 500 nm or less, because the excitation energy is further reduced and deterioration of the organic light emitting material can be suppressed, and further preferably 440 nm or more and 500 nm or less. Particularly preferably, it is 450 nm or more and 500 nm or less. Further, the maximum emission wavelength of the excitation light is more preferably 480 nm or less, because the overlap of the emission spectra of the excitation light and the green light can be reduced and color reproducibility can be improved. Is more preferable.
The excitation light may have one type of emission peak or two or more types of emission peaks, but preferably has one type of emission peak in order to increase color purity. Further, a plurality of excitation light sources having different types of emission peaks can be arbitrarily combined and used.

<Light source unit>
The light source unit according to the embodiment of the present invention is configured to include at least the light source and the particulate color conversion material or the color conversion member of the present invention. The method of arranging the light source and the particulate color conversion material or the color conversion member is not particularly limited, and a configuration in which the light source and the particulate color conversion material or the color conversion member are in close contact with each other, or the light source and the particulate A remote phosphor type in which a color conversion material or a color conversion member is separated may be used. Further, the light source unit may be configured to further include a color filter in order to increase color purity.

As described above, the excitation light having a wavelength of 400 nm or more and 500 nm or less has relatively small excitation energy, and can prevent the decomposition of a luminescent material such as the compound represented by the general formula (1). Therefore, it is preferable that the light source included in the light source unit is a light emitting diode that emits maximum light in a wavelength range of 400 nm to 500 nm. Further, this light source preferably has a maximum emission in a wavelength range of 430 nm to 480 nm, and more preferably has a maximum emission in a wavelength range of 450 nm to 470 nm. The light source unit according to the present invention can be used for applications such as displays, lighting, interiors, signs, and signboards, but is particularly suitably used for displays and lighting.

<Display, lighting device>
A display according to an embodiment of the present invention includes at least a light source unit including a light source and a particulate color conversion material or a color conversion member. For example, in a display such as a liquid crystal display, the above-described light source unit is used as a backlight unit.
Further, the lighting device according to the embodiment of the present invention includes at least a light source unit including a light source and a particulate color conversion material or a color conversion member. For example, this lighting device combines a blue LED light source as a light source, and a particulate color conversion material or a color conversion member that converts blue light from the blue LED light source into light having a longer wavelength than the light source. Is configured to emit light.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
In the following Examples and Comparative Examples, Compounds G-1 and R-1 are the compounds shown below. Compounds G-1 and R-1 were synthesized and used by a known method.

The method for evaluating the color conversion characteristics and light durability of the color conversion member and the like of the present invention will be described below.
<Measurement of color conversion characteristics>
In the measurement of the color conversion characteristics, a current of 30 mA was passed through the surface light emitting device in a state where each color conversion member and the prism sheet were mounted on the surface light emitting device equipped with a blue LED element having an emission peak wavelength of 457 nm. The LED element was turned on, and the emission spectrum, chromaticity, and luminance were measured using a spectral radiance meter (CS-1000, manufactured by Konica Minolta).

<Calculation of color gamut>
The color gamut in the (u ′, v ′) color space when the color purity is improved by the color filter is calculated from the emission spectrum obtained by the measurement of the color conversion characteristics and the spectral data of the transmittance of the color filter. did. The area of the calculated color gamut in the (u ′, v ′) color space is BT. The evaluation was made based on the following criteria based on the ratio when the color gamut area of the 2020 standard was 100%. As the evaluation result of the area of the color gamut in the (u ′, v ′) color space, “A” indicates that the above ratio is 91% or more. “B” indicates that the ratio is 86% or more and 90% or less. "C" indicates that the ratio is 81% or more and 85% or less. "D" indicates that the above ratio is 80% or less. In this evaluation result, the higher the above ratio, the wider the color gamut and the better the color reproducibility of the color conversion member.

<Light durability test>
In the light durability test, a current of 100 mA was passed through the surface light emitting device with the respective color conversion members and the prism sheet mounted on the surface light emitting device equipped with a blue LED element having an emission peak wavelength of 447 nm. The LED element was turned on, and the initial luminance was measured using a spectroradiometer (CS-1000, manufactured by Konica Minolta). Thereafter, the light durability was evaluated by continuously irradiating light from the blue LED element under an environment of 50 ° C. and 27% RH using an oven, and observing a time until the luminance decreased by a certain amount. However, the luminance was measured with the color conversion member and the planar light emitting device taken out of the above-mentioned oven and cooled to room temperature.

Example 1
First, an acrylic resin T1 (SP value = 9.8 (cal / cm ³ ) ^0.5 ) was used as a matrix resin, and 0.3 part by mass of a compound G-1 was added to 100 parts by mass of the matrix resin. 400 parts by mass of toluene was mixed as a solvent. The mixture was stirred and defoamed at 300 rpm for 30 minutes using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries) to obtain a color conversion composition. The color conversion composition was dried by a spray drying method to prepare a particulate color conversion material. The particle size of 100 isolated particles was measured using ECLIPSE L200N (manufactured by Nikon Corporation), and the average value was calculated. The average particle size was 14 μm. The particle size was measured by selecting a portion having the largest diameter.
Next, using hydrogenated SEBS copolymer resin T2 (SP value = 8.5 (cal / cm ³ ) ^0.5 ), 300 parts by mass of cyclohexane as a solvent was mixed with 100 parts by mass of this resin. did. The mixture was stirred and defoamed at 300 rpm for 30 minutes using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries) to obtain a resin solution for a support.

Finally, the particulate color conversion material and the resin solution for a support were mixed and stirred to prepare a color conversion material dispersion. This color conversion material dispersion was applied onto a slide glass plate using a bar coater, heated at 100 ° C. for 20 minutes, and dried to prepare a color conversion member.
When the blue LED light was color-converted using the produced color conversion member, when only the emission region of the green light was extracted, high-purity green light emission having a peak wavelength of 528 nm and a half-value width of the emission spectrum at the peak wavelength of 33 nm was obtained. Was. Further, according to the above method, when the light from the blue LED element was continuously irradiated in an environment of 50 ° C. and 27% RH, the time required for the luminance to decrease by 10% was 120 hours. Table 2 shows the results.

Examples 2 and 3
A color conversion member was prepared and evaluated in the same manner as in Example 1 except that the matrix resin and the support resin shown in Table 2 were used. Table 2 shows the results.

Comparative Example 1
A color conversion member was prepared and evaluated in the same manner as in Example 1, except that Coumarine 6 (manufactured by Sigma-Aldrich) was used as the light emitting material. However, the mixing amount of the light emitting material was adjusted so as to have the same substance amount as G-1 in Example 1. Table 2 shows the results.

Comparative Example 2
The color conversion composition prepared in Example 1 was applied on a slide glass plate using a bar coater, heated at 100 ° C. for 20 minutes, and dried to prepare a color conversion member.

Example 4
First, an acrylic resin T1 (SP value = 9.8 (cal / cm ³ ) ^0.5 ) was used as a matrix resin, and 0.3 part by mass of a compound G-1 was added to 100 parts by mass of the matrix resin. 400 parts by mass of toluene was mixed as a solvent. The mixture was stirred and defoamed at 300 rpm for 30 minutes using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries) to obtain a color conversion composition. The color conversion composition was dried by a spray drying method to prepare a first particulate color conversion material.
Similarly, a polyester resin T11 (SP value = 10.7 (cal / cm ³ ) ^0.5 ) was used as the matrix resin, and 0.1 part by mass of the compound R-1 was added to 100 parts by mass of the matrix resin. 400 parts by mass of toluene was mixed as a solvent. The mixture was stirred and defoamed at 300 rpm for 30 minutes using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries) to obtain a color conversion composition. The color conversion composition was dried by a spray drying method to prepare a second particulate color conversion material.

Next, using hydrogenated SEBS copolymer resin T2 (SP value = 8.5 (cal / cm ³ ) ^0.5 ), 300 parts by mass of cyclohexane as a solvent was mixed with 100 parts by mass of this resin. did. The mixture was stirred and defoamed at 300 rpm for 30 minutes using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries) to obtain a resin solution for a support.
Finally, the first particulate color conversion material, the second particulate color conversion material, and the resin liquid for a support were mixed and stirred to prepare a color conversion dispersion. This color conversion dispersion was applied on a slide glass plate using a bar coater, heated at 100 ° C. for 20 minutes, and dried to prepare a color conversion member.
When the blue LED light was color-converted using the prepared color conversion member, the emission spectrum was as shown in FIG. 4, and white light was obtained. When only the green light emission region was extracted, high-purity green light emission having a peak wavelength of 527 nm and a half-value width of the emission spectrum at the peak wavelength of 27 nm was obtained. When only the emission region of red light was extracted, high-purity red emission having a peak wavelength of 641 nm and a half width of the emission spectrum at the peak wavelength of 49 nm was obtained. The area of the color gamut in the (u ′, v ′) color space is BT. It was 96% of the color gamut area of the 2020 standard. Table 3 shows the results. In Table 3, “color gamut area” is the area of the color gamut in the (u ′, v ′) color space. “A” to “D” in the “color gamut area” column show evaluation results of the area of the color gamut.

Example 5
A color conversion member was produced in the same manner as in Example 2, except that an acrylic resin T1 (SP value = 9.8 (cal / cm ³ ) ^0.5 ) was used as the matrix resin of the second particulate color conversion material. Was evaluated. Table 3 shows the results.

Example 6
A polyester resin T11 (SP value = 10.7 (cal / cm ³ ) ^0.5 ) was used as a matrix resin of the first particulate color conversion material, and an acrylic resin T1 was used as a matrix resin of the second particulate color conversion material. A color conversion member was prepared and evaluated in the same manner as in Example 4, except that (SP value = 9.8 (cal / cm ³ ) ^0.5 ) was used. Table 3 shows the results.

Comparative Example 3
Coumaline 6 (manufactured by Sigma-Aldrich) was used as the light emitting material of the first particulate color conversion material, and was adjusted so as to have the same substance amount as G-1 in Example 3 and mixed. A color conversion member was produced in the same manner as in Example 5, except that Lumogen F Red 305 (manufactured by BASF) was used as a light emitting material, and the mixture was adjusted so as to have the same substance amount as R-1 in Example 3. Was evaluated. Table 3 shows the results.

Example 7
Acrylic resin T1 (SP value = 9.8 (cal / cm ³ ) ^0.5 ) was used as a matrix resin, and 0.3 parts by weight of compound G-1 and 0.3 parts by weight of compound R were added to 100 parts by weight of this matrix resin. 0.011 parts by mass of -1 and 400 parts by mass of toluene as a solvent were mixed. The mixture was stirred and defoamed at 300 rpm for 30 minutes using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries) to obtain a color conversion composition. The color conversion composition was dried by a spray drying method to prepare a particulate color conversion material.
Next, using hydrogenated SEBS copolymer resin T2 (SP value = 8.5 (cal / cm ³ ) ^0.5 ), 300 parts by mass of cyclohexane as a solvent was mixed with 100 parts by mass of this resin. did. The mixture was stirred and defoamed at 300 rpm for 30 minutes using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries) to obtain a resin solution for a support.
Finally, the particulate color conversion material and the resin solution for a support were mixed and stirred to prepare a color conversion material dispersion. This color conversion material dispersion was applied onto a slide glass plate using a bar coater, heated at 100 ° C. for 20 minutes, and dried to prepare a color conversion member. Table 3 shows the results of the evaluation performed in the same manner as in Example 4.

Example 8
First, a polyester resin T12 (SP value = 10.9 (cal / cm ³ ) ^0.5 ) was used as the matrix resin, and 0.1 part by mass of the compound R-1 was added to 100 parts by mass of the matrix resin. 400 parts by mass of methyl ethyl ketone was mixed as a solvent. The mixture was stirred and defoamed at 300 rpm for 30 minutes using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries) to obtain a color conversion composition. The color conversion composition was dried by a spray drying method to prepare a particulate color conversion material.
Next, using an acrylic resin T2 (SP value = 9.9 (cal / cm ³ ) ^0.5 ), 0.3 parts by mass of the compound G-1 was used with respect to 100 parts by mass of the resin, and acetic acid was used as a solvent. 200 parts by mass of ethyl and 200 parts by mass of 1-methoxy-2-propanol were mixed. The mixture was stirred and defoamed at 300 rpm for 30 minutes using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries) to obtain a resin solution for a support.

Finally, the particulate color conversion material and the resin solution for a support were mixed and stirred to prepare a color conversion material dispersion. This color conversion material dispersion was applied onto a slide glass plate using a bar coater, heated at 100 ° C. for 20 minutes, and dried to prepare a color conversion member.
When the blue LED light was color-converted using the prepared color conversion member, when only the emission region of green light was extracted, high-purity green light emission with a peak wavelength of 529 nm and a half-width of the emission spectrum at the peak wavelength of 29 nm was obtained. Was. When only the emission region of red light was extracted, high-purity red emission having a peak wavelength of 641 nm and a half width of the emission spectrum at the peak wavelength of 48 nm was obtained. The area of the color gamut in the (u ′, v ′) color space is BT. It was 94% of the gamut area of the 2020 standard. Table 4 shows the results. In Table 4, “color gamut area” is the area of the color gamut in the (u ′, v ′) color space. “A” to “D” in the “color gamut area” column show evaluation results of the area of the color gamut.

1, 1A, 1B

Color conversion member

2, 2a, 2b Particulate

color conversion material

3, 3a, 3b Support

Claims

A particulate color conversion material having a matrix resin and at least one kind of luminescent material, wherein the luminescent material contains a compound represented by the general formula (1).

(X is C—R 7 or N. R 1 to R 9 may be the same or different and each is hydrogen, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, Hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, arylthioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, It is selected from a nitro group, a silyl group, a siloxanyl group, a boryl group, and a phosphine oxide group, and the selected group may form a condensed ring or an aliphatic ring with an adjacent substituent.)
It contains at least one of a first light emitting material exhibiting light emission observed in a region having a peak wavelength of 500 nm or more and less than 580 nm and / or a second light emitting material exhibiting light emission observed in a region having a peak wavelength of 580 nm or more and 750 nm or less. The particulate color conversion material according to claim 1.
The particulate color conversion material according to claim 1 or 2, wherein the average particle size is 0.010 µm or more and 100 µm or less.
4. The particulate color according to claim 1, wherein the matrix resin is an acrylic resin, a copolymer resin containing an acrylate or methacrylate ester site, a polyester resin, a cycloolefin resin, or an epoxy resin. Conversion material.
(5) A color conversion member comprising a support containing the particulate color conversion material according to any one of (1) to (4).
The color conversion member according to claim 5, wherein the support has a sheet shape.
7. The color conversion member according to claim 5, wherein the support is made of a resin.
The difference between the SP value of the resin forming the matrix resin and the support is that 0.5 (cal / cm 3) 0.5 or more, the color conversion member according to claim 7.
The particulate color conversion material,
A first particulate color conversion material comprising a compound represented by the general formula (1) exhibiting light emission having a peak wavelength of 500 nm or more and less than 580 nm, and a first matrix resin;
9. The composition according to claim 5, comprising a compound represented by the general formula (1) exhibiting light emission having a peak wavelength of 580 nm or more and 750 nm or less, and a second particulate color conversion material comprising a second matrix resin. The color conversion member according to any one of the above.
The color conversion member according to claim 9, wherein the first matrix resin and the second matrix resin are different.
When the SP values of the first matrix resin and the second matrix resin are respectively SP 1 (cal / cm 3 ) 0.5 and SP 2 (cal / cm 3 ) 0.5 , SP 1 ≦ SP 2 The color conversion member according to claim 9.
色 The color conversion member according to any one of claims 5 to 11, wherein the support comprises the particulate color conversion material according to any one of claims 1 to 4 and at least one luminescent material.
The color conversion member according to claim 12, wherein the light emitting material contains at least a compound represented by the general formula (1).
光源 A light source unit comprising a light source and the particulate color conversion material according to any one of claims 1 to 4 or the color conversion member according to any one of claims 5 to 11.
The light source unit according to claim 14, wherein the light source is a light emitting diode having a maximum light emission in a wavelength range of 400 nm or more and 500 nm or less.
A display comprising the light source unit according to claim 14.
An illumination device comprising the light source unit according to claim 14.
(4) A color conversion substrate comprising the particulate color conversion material according to any one of (1) to (4) or the color conversion member according to any one of (5) to (13).
インク An ink containing the particulate color conversion material according to any one of claims 1 to 4 or the color conversion member according to any one of claims 5 to 13.