CN110832361B

CN110832361B - Color conversion composition, color conversion sheet, and light source module, display, and lighting device each comprising color conversion sheet

Info

Publication number: CN110832361B
Application number: CN201880043174.2A
Authority: CN
Inventors: 境野裕健
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2017-08-21
Filing date: 2018-07-19
Publication date: 2021-12-17
Anticipated expiration: 2038-07-19
Also published as: WO2019039142A1; JP7163773B2; TWI771462B; CN110832361A; KR20200034949A; TW201912762A; JPWO2019039142A1; KR102629175B1

Abstract

A color conversion composition that converts incident light into light having a longer wavelength than the incident light, characterized in that the color conversion composition comprises the following components (a), (B), and (C); (A) at least 1 organic light-emitting material (B), a binder resin (C), and at least one of a boron compound, an oligosaccharide compound, a cyclic siloxane compound, and an orthosilicic acid derivative, wherein the molar absorptivity ε of the component (C) is 100 or less over the entire wavelength range of 400nm to 800 nm.

Description

Color conversion composition, color conversion sheet, and light source module, display, and lighting device each comprising color conversion sheet

Technical Field

The invention relates to a color conversion composition, a color conversion sheet, and a light source module, a display and a lighting device comprising the color conversion sheet.

Background

Research is actively being conducted to apply a multicolor technology based on a color conversion method to a liquid crystal display, an organic EL display, an illumination device, and the like. Color conversion means converting light emitted from a light-emitting body into light having a longer wavelength, for example, converting blue light emission into green light emission or red light emission.

By forming a composition having such a color conversion function (hereinafter referred to as a "color conversion composition") into a sheet and combining it with, for example, a blue light source, it is possible to extract three primary colors of blue, green, and red, that is, white light, from the blue light source. A full-color display can be manufactured by using a white light source obtained by combining such a blue light source and a sheet having a color conversion function (hereinafter referred to as a "color conversion sheet") as a backlight unit, and combining the backlight unit with a liquid crystal driving section and a color filter. In addition, if there is no liquid crystal driving portion, it can be used as a white light source directly, for example, as a white light source for LED lighting or the like.

As a problem of the liquid crystal display using the color conversion method, there is an improvement in color reproducibility. In order to improve color reproducibility, it is effective to narrow the half-peak width of each emission spectrum of blue, green, and red of the backlight unit, and to improve the color purity of each color of blue, green, and red.

As a means for solving this problem, a technique of using quantum dots formed of inorganic semiconductor fine particles as a component of a color conversion composition has been proposed (for example, see patent document 1). In the technique using quantum dots, the half-peak widths of the emission spectra of green and red are actually narrowed, and the color reproducibility is improved. However, the quantum dots have poor resistance to heat, moisture in air, and oxygen, and thus have insufficient durability. In addition, there is a problem that cadmium and the like are contained.

In addition, a technique of using an organic light emitting material instead of quantum dots as a component of a color conversion composition has also been proposed. As examples of techniques for using an organic light emitting material as a component of a color conversion composition, a technique using a coumarin derivative (for example, see patent document 2), a technique using a rhodamine derivative (for example, see patent document 3), and a technique using a methylene pyrrole derivative (for example, see patent document 4) are disclosed.

In addition, in order to prevent deterioration of an organic light-emitting material and improve durability, a technique of adding a light stabilizer is also disclosed (for example, see patent document 5).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2012-22028

Patent document 2: japanese patent laid-open publication No. 2007-273440

Patent document 3: japanese patent laid-open No. 2001-164245

Patent document 4: japanese patent laid-open publication No. 2011-

Patent document 5: international publication No. 2017/014068

Disclosure of Invention

However, in recent years, along with the high contrast due to high definition, high dynamic light rendering (HDR), and local dimming such as 4K and 8K, the illuminance required for the backlight unit of the liquid crystal display has been increasing, and the temperature of the backlight unit has been increasing due to the driving heat. The conventional technique such as the light stabilizer described in patent document 5 has an effect of improving durability, but is not sufficient as a technique for improving durability at high temperature. In particular, a color conversion composition using an organic light emitting material has a problem that durability at high temperature is remarkably deteriorated, and the problem has not been sufficiently solved in the prior art.

The invention aims to improve color reproducibility and durability, especially to realize high color purity light emission and durability in a color conversion composition used for liquid crystal displays and LED illumination. In particular, it is an object to provide a color conversion composition and a color conversion sheet having improved durability at high temperatures.

In order to solve the above problems and achieve the object, the present invention is a color conversion composition for converting incident light into light having a longer wavelength than the incident light, the color conversion composition comprising the following components (a), (B) and (C);

(A) at least 1 organic light-emitting material

(B) Binder resin

(C) At least one of a boron compound, an oligosaccharide compound, a cyclic siloxane compound and an orthosilicic acid derivative,

the molar absorptivity epsilon of the component (C) in the whole wavelength region of 400 nm-800 nm is less than 100.

ADVANTAGEOUS EFFECTS OF INVENTION

The color conversion composition of the present invention and the color conversion sheet using the same can simultaneously achieve high color purity and durability, so that color reproducibility and durability can be simultaneously achieved.

Drawings

FIG. 1 is a schematic cross-sectional view showing an example of a color conversion sheet of the present invention.

FIG. 2 is a schematic cross-sectional view showing an example of a color conversion sheet of the present invention.

FIG. 3 is a schematic cross-sectional view showing an example of a color conversion sheet of the present invention.

FIG. 4 is a schematic cross-sectional view showing an example of a color conversion sheet of the present invention.

FIG. 5 is a schematic cross-sectional view showing an example of a color conversion sheet of the present invention.

FIG. 6 is a schematic cross-sectional view showing an example of a color conversion sheet of the present invention.

FIG. 7 is a schematic cross-sectional view showing an example of a color conversion sheet of the present invention.

FIG. 8 is a schematic cross-sectional view showing an example of a color conversion sheet of the present invention.

FIG. 9 shows an absorption spectrum of the compound of Synthesis example 1.

FIG. 10 shows the luminescence spectrum of the compound of Synthesis example 1.

FIG. 11 shows an absorption spectrum of the compound of Synthesis example 2.

FIG. 12 shows the luminescence spectrum of the compound of Synthesis example 2.

Detailed Description

The present invention is not limited to the following embodiments, and can be carried out by various modifications according to the purpose and use.

A color conversion composition of an embodiment of the present invention is a color conversion composition that converts incident light into light having a longer wavelength than the incident light, and includes the following components (a), (B), and (C);

(A) at least 1 organic light-emitting material

(B) Binder resin

< organic light-emitting Material >

The color conversion composition in an embodiment of the present invention comprises at least 1 organic light emitting material. Here, the light-emitting material in the present invention refers to a material which emits light having a wavelength different from that of a certain light when irradiated with the light. Organic light emitting materials are organic light emitting materials.

In order to realize high-efficiency color conversion, the light-emitting material is preferably a material exhibiting light-emitting characteristics with high emission quantum yield. In general, known light-emitting materials such as inorganic phosphors, fluorescent pigments, fluorescent dyes, and quantum dots can be used as the light-emitting material, but an organic light-emitting material is preferable from the viewpoint of uniformity of dispersion, reduction in the amount used, and reduction in environmental load.

Examples of the organic light-emitting material include those shown below. Preferred examples of the organic light-emitting material include naphthalene, anthracene, phenanthrene, pyrene, perylene, and the like,

And compounds having a condensed aromatic ring such as tetracene, triphenylene, perylene, fluoranthene, fluorene, and indene, and derivatives thereof. Further, preferable examples of the organic light-emitting material include a compound having a heteroaromatic ring such as furan, pyrrole, thiophene, silole (silole), 9-silafluorene (9-silafluorene), 9 '-spirodisilylheterofluorene (9, 9' -spirobiiilaflurene), benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyridine, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, and derivatives thereof, and borane derivatives.

Further, preferable examples of the organic light-emitting material include stilbene derivatives such as 1, 4-distyrylbenzene, 4 '-bis (2- (4-diphenylaminophenyl) vinyl) biphenyl, 4' -bis (N- (stilbene-4-yl) -N-phenylamino) stilbene, aromatic acetylene derivatives, tetraphenylbutadiene derivatives, aldazine (aldazine) derivatives, methylenepyrrole derivatives, diketopyrrolo [3, 4-c ] pyrrole derivatives, and the like. Preferred examples of the organic light-emitting material include coumarin derivatives such as coumarin 6, coumarin 7, and coumarin 153, azole derivatives such as imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, and triazole, metal complexes thereof, cyanine compounds such as indocyanine green, xanthene compounds such as fluorescein, eosin, and rhodamine, and thioxanthene compounds.

Further, preferable examples of the organic light-emitting material include 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, spiroene compounds, and aromatic amine derivatives such as N, N '-diphenyl-N, N' -bis (3-methylphenyl) -4, 4 '-diphenyl-1, 1' -diamine. Further, preferable organic light-emitting materials include organic metal complex compounds such as iridium (Ir), ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt), osmium (Os), and rhenium (Re). However, the organic light emitting material of the present invention is not limited to the above materials.

The organic light-emitting material may be a fluorescent light-emitting material or a phosphorescent light-emitting material, but in order to achieve high color purity, a fluorescent light-emitting material is preferable. Among the above materials, compounds having a condensed aromatic ring or derivatives thereof are preferable from the viewpoint of high thermal stability and light stability.

In addition, as the organic light-emitting material, a compound having a coordinate bond is preferable from the viewpoint of solubility and diversity of molecular structure. From the viewpoint of narrow half-width and high-efficiency light emission, a boron-containing compound such as a boron fluoride complex is also preferable.

Among the above compounds, a methylene pyrrole derivative can be preferably used from the viewpoint of imparting a high fluorescence quantum yield and good durability. More preferably a compound represented by the general formula (1).

[ chemical formula 1]

X is C-R⁷Or N. R¹～R⁹Each of which may be the same or different, is selected from the following groups: hydrogen, alkyl, cycloalkyl, heterocyclic group, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, alkoxy, alkylthio, aryl ether group, aryl thioether group, aryl group, heteroaryl, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxane group, borane group, sulfo group, phosphine oxide group, and a condensed ring and an aliphatic ring formed between adjacent substituents.

In all of the above groups, hydrogen may be deuterium. The same applies to the compounds described below or a partial structure thereof. In the following description, for example, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms is an aryl group having 6 to 40 carbon atoms in total including the carbon atoms contained in a substituent group substituted on the aryl group. The same applies to other substituents having a predetermined number of carbon atoms.

Among all the above groups, the substituent to be substituted is preferably an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, an alkoxy group, an alkylthio group, an aryl ether group, an aryl thioether group, an aryl group, a heteroaryl group, a halogen group, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxane group, a borane group, a sulfo group, or a phosphine oxide group, and more preferably a specific substituent is preferable in the description of each substituent. These substituents may be further substituted with the above-mentioned substituents.

The "unsubstituted" in the case of "substituted or unsubstituted" means being substituted with a hydrogen atom or a deuterium atom. In the compounds or their partial structures described below, the case of "substituted or unsubstituted" is also the same as described above.

In all the above groups, the alkyl group represents, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group, and may or may not have a substituent. The substituent to be added when substituted is not particularly limited, and examples thereof include an alkyl group, a halogen group, an aryl group, and a heteroaryl group, and these substituents are also common in the following description. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably in the range of 1 to 20, more preferably 1 to 8, from the viewpoint of ease of availability and cost.

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

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

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

The cycloalkenyl group represents an unsaturated alicyclic hydrocarbon group having a double bond, such as a cyclopentenyl group, a cyclopentadienyl group, or a cyclohexenyl group, and may or may not have a substituent.

The alkynyl group represents an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group, and 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 to 20.

The alkoxy group represents, 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, or a propoxy group, and the aliphatic hydrocarbon group may or may not have a substituent. The number of carbon atoms of the alkoxy group is not particularly limited, and is preferably in the range of 1 to 20.

The alkylthio group means a group obtained by substituting an oxygen atom of an ether bond of an alkoxy group with a sulfur atom. The hydrocarbyl group of the alkylthio group may or may not have a substituent. The number of carbon atoms of the alkylthio group is not particularly limited, and is preferably in the range of 1 to 20.

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

The aryl thioether group is a group obtained by substituting an oxygen atom of an ether bond of an aryl ether group with a sulfur atom. The aromatic hydrocarbon group in the aryl sulfide group may or may not have a substituent. The number of carbon atoms of the aryl sulfide group is not particularly limited, and is preferably in the range of 6 to 40.

Aryl represents, for example, phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, anthracenyl, benzophenanthrenyl, benzanthracenyl,

Aromatic hydrocarbon groups such as pyrenyl, fluoranthenyl, triphenylenyl, benzofluoranthenyl, dibenzanthracene, perylenyl, and spiroalkenyl (helicenyl). Among them, preferred are phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthryl, anthracyl, pyrenyl, fluoranthenyl, triphenylenyl. The aryl group may have a substituent or may have no substituent. The number of carbon atoms of the aryl group is not particularly limited, but is preferably in the range of 6 to 40, more preferably 6 to 30.

R¹～R⁹In the case of 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 more preferably a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group. More preferred are phenyl, biphenyl, terphenyl, and especially preferred is phenyl.

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 more preferably a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group. Particularly preferred is phenyl.

Heteroaryl represents, for example, a cyclic aromatic group having an atom other than carbon in one or more rings, such as pyridyl, furyl, thienyl, quinolyl, isoquinolyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, naphthyridinyl, cinnolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, benzofuryl, benzothienyl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl, benzocarbazolyl, carbolinyl, indolocarbazolyl, benzofurocarbazolyl, benzothienocarbazolyl, dihydroindenocarbazolyl, benzoquinolyl, acridinyl, dibenzoacridinyl, benzimidazolyl, imidazopyridinyl, benzoxazolyl, benzothiazolyl, phenanthrolinyl and the like. Wherein the naphthyridinyl group represents any one of 1, 5-naphthyridinyl group, 1, 6-naphthyridinyl group, 1, 7-naphthyridinyl group, 1, 8-naphthyridinyl group, 2, 6-naphthyridinyl group, and 2, 7-naphthyridinyl group. The heteroaryl group may have a substituent or may have no substituent. The number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably 2 or more and 40 or less, and more preferably 2 or more and 30 or less.

R¹～R⁹In the case of a substituted or unsubstituted heteroaryl group, the heteroaryl group is preferably a pyridyl group, furyl group, thienyl group, quinolyl group, pyrimidinyl group, triazinyl group, benzofuryl group, benzothienyl group, indolyl group, dibenzofuryl group, dibenzothienyl group, carbazolyl group, benzimidazolyl group, imidazopyridinyl group, benzoxazolyl group, benzothiazolyl group, or phenanthrolinyl group, and more preferably a pyridyl group, furyl group, thienyl group, or quinolyl group. Especially preferred is pyridyl.

When each substituent is further substituted with a heteroaryl group, the heteroaryl group is preferably a pyridyl group, a furyl group, a thienyl group, a quinolyl group, a pyrimidyl group, a triazinyl group, a benzofuryl group, a benzothienyl group, an indolyl group, a dibenzofuryl group, a dibenzothienyl group, a carbazolyl group, a benzimidazolyl group, an imidazopyridinyl group, a benzoxazolyl group, a benzothiazolyl group, or a phenanthrolinyl group, and more preferably a pyridyl group, a furyl group, a thienyl group, or a quinolyl group. Especially preferred is pyridyl.

Halogen represents an atom selected from fluorine, chlorine, bromine and iodine. The carbonyl group, the carboxyl group, the ester group, and the carbamoyl group may or may not have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group, and these substituents may be further substituted.

The amino group is a substituted or unsubstituted amino group. Examples of the substituent in the case of substitution include aryl, heteroaryl, straight-chain alkyl, and branched-chain alkyl. As the aryl group and the heteroaryl group, a phenyl group, a naphthyl group, a pyridyl group and a quinolyl group are preferable. The above substituents may be further substituted. The number of carbon atoms 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 means, for example, an alkylsilyl group such as trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, propyldimethylsilyl or vinyldimethylsilyl, an arylsilyl group such as phenyldimethylsilyl, t-butyldiphenylsilyl, triphenylsilyl or trinaphthylsilyl. The substituents on silicon may be further substituted. The number of carbon atoms of the silyl group is not particularly limited, and is preferably in the range of 1 to 30.

The siloxane group represents a silicon compound group formed via an ether bond, such as a trimethylsiloxy group. The substituents on silicon may be further substituted. Further, the boryl group is a substituted or unsubstituted boryl group. Examples of the substituent in the case of substitution include aryl, heteroaryl, straight-chain alkyl, branched-chain alkyl, aryl ether, alkoxy, and hydroxyl. Among them, aryl group and aryl ether group are preferable. Further, 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 straight-chain alkyl group, a branched-chain alkyl group, an aryl ether group, and an alkoxy group. Among them, linear alkyl groups and aryl groups are preferable. The phosphine oxide group is-P (═ O) R¹⁰R¹¹The group shown. R¹⁰R¹¹Is selected from the group consisting of¹～R⁹Same group。

The condensed ring and aliphatic ring formed between adjacent substituents mean any of 2 adjacent substituents (for example, R in the general formula (1))¹And R²) Bonded to each other to form a conjugated or non-conjugated cyclic skeleton. The constituent elements of such a condensed ring and an aliphatic ring may include an element selected from nitrogen, oxygen, sulfur, phosphorus, and silicon in addition to carbon. These condensed rings and aliphatic rings may be further condensed with other rings.

The compound represented by the general formula (1) exhibits a high luminescence quantum yield and a small half-width of the luminescence spectrum, and therefore can realize both efficient color conversion and high color purity. Further, the compound represented by the general formula (1) can be adjusted in various properties and physical properties such as luminous efficiency, color purity, thermal stability, light stability, and dispersibility by introducing an appropriate substituent into an appropriate position. For example, with R¹、R³、R⁴And R⁶Compared with the case of all hydrogen, R¹、R³、R⁴And R⁶The case where at least one of them is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group shows better thermal stability and light stability.

At R¹、R³、R⁴And R⁶When at least one of the alkyl groups is a substituted or unsubstituted alkyl group, the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, or a hexyl group. In addition, from the viewpoint of excellent thermal stability, such an alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group. In addition, from the viewpoint of preventing concentration quenching and improving the luminescence quantum yield, tertiary butyl having a large steric bulk is more preferable as the alkyl group. In addition, from the viewpoint of ease of synthesis and availability of raw materials, it is also preferable to use a methyl group as the alkyl group.

At R¹、R³、R⁴And R⁶Is to takeIn the case of a substituted or unsubstituted aryl group, the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group, and more preferably a phenyl group or a biphenyl group. Particularly preferred is phenyl.

At R¹、R³、R⁴And R⁶In the case where at least one of them is a substituted or unsubstituted heteroaryl group, the heteroaryl group is preferably a pyridyl group, a quinolyl group or a thienyl group, and more preferably a pyridyl group or a quinolyl group. Especially preferred is pyridyl.

At R¹、R³、R⁴And R⁶When the alkyl groups are the same or different and are each substituted or unsubstituted, the solubility in the binder resin or the solvent is good, which is preferable. In this case, the alkyl group is preferably a methyl group from the viewpoint of ease of synthesis and ease of availability of raw materials.

At R¹、R³、R⁴And R⁶When each of the aryl groups may be the same or different and each is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, it is preferable because it exhibits more excellent thermal stability and light stability. In this case, R is more preferably¹、R³、R⁴And R⁶Each of which may be the same or different and is a substituted or unsubstituted aryl group.

Although substituents exist to enhance a variety of properties, there are limits to substituents that will allow all properties to exhibit adequate performance. In particular, it is difficult to achieve both high luminous efficiency and high color purity. Therefore, by introducing a plurality of substituents to the compound represented by the general formula (1), a compound having a balanced emission characteristic, color purity, and the like can be obtained.

Especially in R¹、R³、R⁴And R⁶When each of the aryl groups which may be the same or different and are each a substituted or unsubstituted aryl group, it is preferable to add, for example, R¹≠R⁴、R³≠R⁶、R¹≠R³Or R⁴≠R⁶And the like. Here, "≠" is expressed as distinctGroups of the structure. For example, R¹≠R⁴Represents R¹And R⁴Are groups of different structures. As described above, by introducing a plurality of substituents, an aryl group which affects color purity and an aryl group which affects luminous efficiency can be introduced at the same time, and thus fine adjustment can be achieved.

Among them, R is preferable from the viewpoint of improving the luminous efficiency and the color purity in a well-balanced manner¹≠R³Or R⁴≠R⁶. In this case, the compound represented by the general formula (1) can introduce 1 or more aryl groups that affect color purity into the pyrrole rings on both sides and can introduce aryl groups that affect luminous efficiency into the positions other than the pyrrole rings, thereby improving both properties to the maximum. At R¹≠R³Or R⁴≠R⁶In the case of (2), R is more preferably R from the viewpoint of improving both heat resistance and color purity¹＝R⁴And R³＝R⁶。

As the aryl group which mainly affects the color purity, an aryl group substituted with an electron donating group is preferable. The electron donating group is a group that donates electrons to a substituted group by utilizing an induction effect or a resonance effect in the organic electron theory. Examples of the electron donating group include groups having a negative substituent constant (. sigma. (para)) in Hammett's equation. The substituent constants (. sigma.) (para)) of the Hammett's equation can be introduced from the basic revision 5 th edition (pages II-380) of the handbook of chemistry (list K30990, 5 th edition (II-380 ).

Specific examples of the electron donating group include, for example, an alkyl group (. sigma.p: -0.17 in the case of a methyl group), an alkoxy group (. sigma.p: -0.27 in the case of a methoxy group), and an amino group (-NH-)₂σ p of (a): -0.66), etc. In particular, 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, or a methoxy group is more preferable. In particular, from the viewpoint of dispersibility, a tert-butyl group and a methoxy group are preferable, and when these groups are used as the electron-donating group, quenching due to aggregation of molecules can be prevented in the compound represented by the general formula (1). Substituent group derivationThe substitution position is not particularly limited, but since it is necessary to suppress the twist of the bond in order to improve the photostability of the compound represented by the general formula (1), it is preferable to bond a substituent at a position meta or para to the bonding position with the methylene pyrrole skeleton. On the other hand, as the aryl group which mainly affects the light emission efficiency, an aryl group having a substituent having a large volume such as a tert-butyl group, an adamantyl group, or a methoxy group is preferable.

At R¹、R³、R⁴And R⁶When each of the groups may be the same or different and is a substituted or unsubstituted aryl group, R¹、R³、R⁴And R⁶Phenyl groups, which may each be the same or different, and which are substituted or unsubstituted, are preferred. In this case, R is more preferably¹、R³、R⁴And R⁶Are respectively selected from the following Ar-1 to Ar-6. In this case, as R¹、R³、R⁴And R⁶Preferred combinations of (A) and (B) include those shown in tables 1-1 to 1-11, but are not limited to these combinations.

[ chemical formula 2]

[ tables 1-1]

[ tables 1-2]

[ tables 1 to 3]

[ tables 1 to 4]

[ tables 1 to 5]

[ tables 1 to 6]

[ tables 1 to 7]

[ tables 1 to 8]

[ tables 1 to 9]

[ tables 1 to 10]

[ tables 1 to 11]

R²And R⁵Any of hydrogen, alkyl, carbonyl, ester and aryl is preferable, and hydrogen or alkyl is preferable from the viewpoint of thermal stability, and a narrow half-width is easily obtained in the emission spectrumMore preferably hydrogen.

R⁸And R⁹Preferably alkyl, aryl, heteroaryl, fluoro, fluoroalkyl, fluoroheteroaryl or fluoroaryl. R is more preferably R from the viewpoint of stability to excitation light and obtaining a higher fluorescence quantum yield⁸And R⁹Is fluorine or fluorine-containing aryl. And, from the viewpoint of ease of synthesis, R⁸And R⁹More preferably fluorine.

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

In addition, in the general formula (1), X is preferably C-R from the viewpoint of photostability⁷. X is C-R⁷When the substituent R is⁷The durability of the compound represented by the general formula (1), that is, the deterioration of the emission intensity of the compound with time, is significantly affected. In particular, R⁷In the case of hydrogen, since the reactivity of the site is high, the site is likely to react with moisture and oxygen in the air. This causes decomposition of the compound represented by the general formula (1). In addition, in R⁷In the case of a substituent having a large degree of freedom of molecular chain movement, such as an alkyl group, although reactivity is certainly lowered, the compounds aggregate with time in the color conversion sheet, and as a result, the emission intensity is lowered due to concentration quenching. Thus, R⁷The group is preferably rigid, has a small freedom of movement, and is less likely to cause aggregation, and specifically, is preferably any of a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group.

From the viewpoint of imparting a higher fluorescence quantum yield, being less likely to cause thermal decomposition, and from the viewpoint of photostability, X is preferably C-R⁷And R is⁷Is a substituted or unsubstituted aryl group. As the aryl group, preferred are a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group and an anthracyl group from the viewpoint of not impairing the emission wavelength。

Furthermore, in order to improve the photostability of the compound represented by the general formula (1), it is necessary to appropriately suppress R⁷Twisting of the carbon-carbon bond to the methylene pyrrole backbone. The reason is that if the twist is too large, the light stability is lowered due to, for example, an increase in reactivity with the excitation light. From such a viewpoint, R is⁷Preferred are a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, and a substituted or unsubstituted naphthyl group, and more preferred are a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, and a substituted or unsubstituted terphenyl group. Particularly preferred is a substituted or unsubstituted phenyl group.

In addition, R⁷Substituents with a moderately large volume are preferred. By reacting R⁷Having a certain degree of bulk, the aggregation of molecules can be prevented, and as a result, the luminous efficiency and durability of the compound represented by the general formula (1) can be further improved.

As a more preferable example of such bulky substituent, R represented by the following general formula (2) may be mentioned⁷The structure of (1).

[ chemical formula 3]

In the general formula (2), r is selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclic group, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, alkoxy, alkylthio, aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxane group, borane group, sulfo group, phosphine oxide group. k is an integer of 1 to 3. When k is 2 or more, r may be the same or different.

From the viewpoint of imparting a higher emission quantum yield, r is preferably a substituted or unsubstituted aryl group. Among such aryl groups, preferred examples include phenyl and naphthyl. When r is an aryl group, k in the general formula (2) is preferably 1 or 2, and among them, k is more preferably 2 from the viewpoint of further preventing aggregation of molecules. When k is 2 or more, at least 1 of r is preferably substituted with an alkyl group. In this case, the alkyl group is particularly preferably a methyl group, an ethyl group or a tert-butyl group from the viewpoint of thermal stability.

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

In another embodiment of the compound represented by the general formula (1), R is preferably¹～R⁷At least one of which is an electron withdrawing group. Particularly preferred are: (1) r¹～R⁶At least one of which is an electron withdrawing group; (2) r⁷Is an electron withdrawing group; or (3) R¹～R⁶At least one of which is an electron withdrawing group and R⁷Are electron withdrawing groups. By introducing an electron-withdrawing group into the methylene pyrrole skeleton of the above compound as described above, the electron density of the methylene pyrrole skeleton can be greatly reduced. This further improves the stability of the compound against oxygen, 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 in the organic electron theory, is a group that withdraws electrons from a substituted group by an induction effect or a resonance effect. Examples of the electron-withdrawing group include groups having a positive value as a substituent constant (σ p (para)) of the Hammett's equation. The substituent constants (. sigma.) (para)) of the Hammett's equation can be introduced from the basic revision 5 th edition (pages II-380) of the handbook of chemistry (list K30990, 5 th edition (II-380 ). Although the phenyl group may take a positive value, the electron-withdrawing group of the present application does not include a phenyl group.

Examples of electron-withdrawing groups include: -F (σ p: +0.06), -Cl (σ p:+0.23)、-Br(σp：+0.23)、-I(σp：+0.18)、-CO₂R¹²(σp：R¹²ethyl being +0.45), -CONH₂(σp：+0.38)、-COR¹²(σp：R¹²Methyl is +0.49), -CF₃(σp：+0.50)、-SO₂R¹²(σp：R¹²Methyl is +0.69), -NO₂(σ p: +0.81), and the like. R¹²Each independently represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring-forming carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring-forming carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms. Specific examples of the above groups include the same ones as described above.

Preferred examples of the electron-withdrawing group include fluorine, a fluorine-containing aryl group, a fluorine-containing heteroaryl group, a fluorine-containing alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted amide group, a substituted or unsubstituted sulfonyl group, and a cyano group. Since these groups are not susceptible to chemical decomposition.

More preferred examples of the electron-withdrawing group include a fluoroalkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted ester group, and a cyano group. The reason is that these groups can bring about an effect of preventing concentration quenching and improving the luminescence quantum yield. Particularly preferred electron withdrawing groups are substituted or unsubstituted ester groups.

Wherein R is²And R⁵At least one of the above groups may be the same or different and is preferably a substituted or unsubstituted ester group because durability can be improved without lowering color purity. From the viewpoint of improving durability, R is particularly preferable²And R⁵Each of which may be the same or different and is a substituted or unsubstituted ester group.

As one of preferable examples of the compound represented by the general formula (1), the following can be mentioned: r¹、R³、R⁴And R⁶Each of which may be the same or different and is a substituted or unsubstituted alkyl group, and X is C-R⁷，R⁷Is a group represented by the general formula (2).At this time, R⁷Particularly preferred is a group represented by the general formula (2) wherein r is contained in the form of a substituted or unsubstituted phenyl group.

Further, as another preferable example of the compound represented by the general formula (1), the following can be mentioned: r¹、R³、R⁴And R⁶Each of which may be the same or different and is selected from the group consisting of Ar-1 to Ar-6, and X is C-R⁷，R⁷Is a group represented by the general formula (2). At this time, R⁷More preferably, r is a group represented by the general formula (2) which is contained in the form of a tert-butyl group or a methoxy group, and particularly preferably a group represented by the general formula (2) which is contained in the form of a methoxy group.

In addition, as another preferable example of the compound represented by the general formula (1), the following may be mentioned: r¹、R³、R⁴And R⁶Each of which may be the same or different and is a substituted or unsubstituted alkyl group, and R²And R⁵Each of which may be the same or different and is a substituted or unsubstituted ester group, and X is C-R⁷、R⁷Is a group represented by the general formula (2). At this time, R⁷Particularly preferred is a group represented by the general formula (2) wherein r is contained in the form of a substituted or unsubstituted phenyl group.

Further, as another preferable example of the compound represented by the general formula (1), the following can be mentioned: r¹、R³、R⁴And R⁶Each of which may be the same or different and is selected from the group consisting of Ar-1 to Ar-6 described above, and R²And R⁵Each of which may be the same or different, is a substituted or unsubstituted ester group, and X is C-R⁷，R⁷Is a group represented by the general formula (2). At this time, R⁷More preferably, r is a group represented by the general formula (2) which is contained in the form of a tert-butyl group or a methoxy group, and particularly preferably a group represented by the general formula (2) which is contained in the form of a methoxy group.

Examples of the compounds represented by the general formula (1) are given below, but the compounds are not limited to these compounds.

[ chemical formula 4]

[ chemical formula 5]

[ chemical formula 6]

[ chemical formula 7]

[ chemical formula 8]

[ chemical formula 9]

[ chemical formula 10]

[ chemical formula 11]

[ chemical formula 12]

[ chemical formula 13]

[ chemical formula 14]

[ chemical formula 15]

[ chemical formula 16]

[ chemical formula 17]

[ chemical formula 18]

[ chemical formula 19]

[ chemical formula 20]

[ chemical formula 21]

[ chemical formula 22]

[ chemical formula 23]

[ chemical formula 24]

[ chemical formula 25]

[ chemical formula 26]

[ chemical formula 27]

[ chemical formula 28]

The compound represented by the general formula (1) can be synthesized, for example, by the method described in Japanese patent application laid-open No. 8-509471 or Japanese patent application laid-open No. 2000-208262. That is, the intended methylene-pyrrole metal complex can be obtained by reacting a methylene-pyrrole compound with a metal salt in the presence of a base.

Further, as for the synthesis of the methylene pyrrole-boron fluoride complex, the compound represented by the general formula (1) can be synthesized by the method described in j.org.chem., vol.64, No.21, pp7813-7819(1999), angelw.chem., int.ed.engl., vol.36, pp1333-1335(1997), etc. For example, the following methods can be mentioned: the compound represented by the following general formula (3) and the compound represented by the following general formula (4) are heated in 1, 2-dichloroethane in the presence of phosphorus oxychloride, and then the compound represented by the following general formula (5) is reacted in 1, 2-dichloroethane in the presence of triethylamine, thereby obtaining the compound represented by the general formula (1). However, the present invention is not limited thereto. Here, R¹～R⁹The same as described above. J represents a halogen.

[ chemical formula 29]

Further, when an aryl group or a heteroaryl group is introduced, a method of generating a carbon-carbon bond by a coupling reaction of a halogenated derivative with a mono-substituted boronic acid or a mono-substituted boronic acid-esterified derivative may be mentioned, but the present invention is not limited thereto. Similarly, when the amino group or the carbazole group is introduced, for example, a method of generating a carbon-nitrogen bond by a coupling reaction of a halogenated derivative and an amine or carbazole derivative in the presence of a metal catalyst such as palladium may be mentioned, but the present invention is not limited thereto.

The color conversion composition according to the embodiment of the present invention may contain other compounds as needed in addition to the compound represented by the general formula (1). For example, in order to further improve the energy transfer efficiency from the excitation light to the compound represented by the general formula (1), an auxiliary dopant such as rubrene may be contained. When a light-emitting color other than the light-emitting color of the compound represented by the general formula (1) is to be doped, a desired organic light-emitting material, for example, an organic light-emitting material such as a coumarin-based dye or a rhodamine-based dye, may be added. In addition to these organic light-emitting materials, known light-emitting materials such as inorganic phosphors, fluorescent pigments, fluorescent dyes, and quantum dots may 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 to these.

[ chemical formula 30]

The color conversion composition according to the embodiment of the present invention preferably contains a light-emitting material (hereinafter referred to as "light-emitting material (a)") that exhibits light emission in which a peak wavelength is observed in a region of 500nm or more and 580nm or less by using excitation light having a wavelength in a range of 400nm or more and 500nm or less. Hereinafter, emission in which a peak wavelength is observed in a region of 500nm to 580nm is referred to as "green emission".

The color conversion composition according to the embodiment of the present invention preferably contains a light-emitting material (hereinafter referred to as "light-emitting material (b)") which exhibits light emission in which a peak wavelength is observed in a region having a wavelength of 580nm or more and 750nm by excitation with either or both of excitation light having a wavelength of 400nm or more and 500nm or less or light emitted from the light-emitting material (a). Hereinafter, light emission in which a peak wavelength is observed in a region of 580nm to 750nm is referred to as "red light emission".

In general, the greater the energy of the excitation light, the more likely the material is decomposed. However, the excitation light having a wavelength in the range of 400nm to 500nm is light having relatively small excitation energy. Therefore, the luminescent material in the color conversion composition is not decomposed, and the luminescence with good color purity can be obtained.

The color conversion composition according to the embodiment of the present invention may include only one of the light-emitting material (a) and the light-emitting material (b), or both of them. The light-emitting material (a) may be used alone in only 1 kind, or may be used in combination in plural kinds. Similarly, only 1 kind of the above-mentioned light-emitting material (b) may be used alone, or a plurality of kinds may be used in combination.

A part of the excitation light having a wavelength in the range of 400nm or more and 500nm or less will partially transmit through the color conversion composition of the embodiment of the present invention, and thus, itself can be used as light emission of blue. Therefore, when the color conversion composition according to the embodiment of the present invention includes the organic light emitting material (a) that emits green light and the organic light emitting material (b) that emits red light, and a blue LED having a sharp emission peak is used as blue light, a sharp emission spectrum is exhibited in each of blue, green, and red, and white light having good color purity can be obtained. As a result, particularly in a display, a more vivid and larger color gamut can be efficiently formed. In addition, in illumination applications, since the emission characteristics of the green region and the red region are improved in particular as compared with those of a white LED obtained by combining a blue LED and a yellow phosphor, which has been the mainstream at present, a satisfactory white light source having improved color reproduction characteristics (color rendering properties in japanese) can be obtained.

As the organic light-emitting material (a), the following compounds are preferably mentioned: coumarin derivatives such as coumarin 6, coumarin 7 and coumarin 153; cyanine derivatives such as indocyanine green; fluorescein derivatives such as fluorescein, fluorescein isothiocyanate, and carboxyfluorescein diacetate; phthalocyanine derivatives such as phthalocyanine green; perylene derivatives such as diisobutyl-4, 10-dicyanoperylenyl-3, 9-dicarboxylate; and a methylene pyrrole derivative; stilbene (stilbene) derivatives; an oxazine derivative; naphthalimide derivatives; pyrazine derivatives; compounds having a condensed aromatic ring such as benzimidazole derivatives, benzoxazole derivatives, benzothiazole derivatives, imidazopyridine derivatives, oxazole derivatives, and anthracene, or derivatives thereof; an aromatic amine derivative; organometallic complex compounds, and the like. However, the organic light-emitting material (a) is not particularly limited to these compounds.

Among these compounds, a methylene pyrrole derivative is particularly preferable because it can provide a high emission quantum yield and has good durability. Among them, the methylene pyrrole derivative is preferably a compound represented by the following general formula (1), for example, because it emits light with high color purity.

As the organic light-emitting material (b), the following compounds are preferably mentioned: cyanine derivatives such as 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran; rhodamine derivatives such as rhodamine B, rhodamine 6G, rhodamine 101, sulforhodamine 101 and the like; pyridine derivatives such as 1-ethyl-2- (4- (p-dimethylaminophenyl) -1, 3-butadienyl) -pyridinium perchlorate; n, N' -bis (2, 6-diisopropylphenyl) -1, 6, 7, 12-tetraphenoxyperylenyl-3, 4: perylene derivatives such as 9, 10-biscarbodiimide, and porphyrin derivatives; a methylene pyrrole derivative; an oxazine derivative; pyrazine derivatives; compounds having a condensed aromatic ring such as tetracene or dibenzodiindenoperylene, or derivatives thereof; organometallic complex compounds, and the like. However, the organic light-emitting material (b) is not particularly limited thereto.

Among these compounds, a methylene pyrrole derivative is particularly preferable because it can provide a high emission quantum yield and has good durability. As the methylene pyrrole derivative, for example, a compound represented by the following general formula (1) exhibits luminescence with high color purity, and is therefore preferable.

The content of the component (a) in the color conversion composition according to the embodiment of the present invention is generally 1.0 × 10 based on 100 parts by weight of the component (B), although it depends on the molar absorption coefficient, the luminescence quantum yield, the absorption intensity at the excitation wavelength, and the thickness and transmittance of the color conversion sheet to be produced^-4And (3) 30 parts by weight. Among them, 1.0 × 10 is more preferable^-3From 10 to 5 parts by weight, particularly preferably 5.0X 10^-3And (5) parts by weight.

In addition, when both the light-emitting material (a) emitting green light and the light-emitting material (b) emitting red light are contained in the color conversion composition, since a part of the green light is converted into red light, the content w of the light-emitting material (a) is increased_aWith the content w of the luminescent material (b)_bPreferably satisfies w_a≥w_bThe relationship (2) of (c). In addition, the content w_aWith the content w_bHas a ratio of w_a∶w_b1000: 1-1: 1, preferably 500: 1-2: 1, especiallyThe preferred ratio is 200: 1-3: 1. Wherein, the content w_aAnd content w_bIn weight percent relative to the weight of component (B).

< adhesive resin (B) >

In the color conversion composition according to the embodiment of the present invention, a material excellent in moldability, transparency, heat resistance, and the like is preferably used as the binder resin. Examples of the binder resin include the following known resins: photocurable resist materials having a reactive vinyl group such as acrylic, methacrylic, polyvinyl cinnamate, and cyclized rubber (ring rubber), epoxy resins, silicone resins (including cured products (crosslinked products) of organopolysiloxanes such as silicone rubber and silicone gel), urea resins, fluorine resins, polycarbonate resins, acrylic resins, urethane resins, melamine resins, polyvinyl resins, polyamide resins, phenol resins, polyvinyl alcohol resins, polyvinyl butyral resins, cellulose resins, aliphatic ester resins, aromatic ester resins, aliphatic polyolefin resins, and aromatic polyolefin resins. Further, as the binder resin, a mixture or a copolymer of these resins may be used. By appropriately designing these resins, a binder resin useful for the color conversion composition of the embodiment of the present invention can be obtained.

Among these resins, from the viewpoint of transparency, heat resistance, and the like, an epoxy resin, a silicone resin, an acrylic resin, a polyester resin, or a mixture thereof can be preferably used. In addition, a thermosetting resin or a photocurable resin can be preferably used from the viewpoint of ease of a film forming process.

The glass transition temperature (Tg) of the binder resin is not particularly limited, but is preferably 30 ℃ or higher and 180 ℃ or lower. When Tg is lower than 30 ℃, the molecular motion of the binder resin increases by heat caused by incident light from a light source or driving heat of a machine, and the dispersion state of the light-emitting material changes, thereby deteriorating durability. When Tg is higher than 180 ℃, the resin becomes brittle and the flexibility in molding into a sheet or the like is reduced. The Tg of the binder resin is more preferably 50 ℃ to 160 ℃, more preferably 70 ℃ to 150 ℃, and particularly preferably 90 ℃ to 140 ℃.

The molecular weight of the binder resin is not particularly limited, and varies depending on the kind of the resin, but is preferably 3000 or more and 1500000 or less. When the molecular weight is less than 3000, the resin becomes brittle, and the flexibility when molded into a sheet or the like is reduced. Further, when the molecular weight is larger than 1500000, there is a problem that the viscosity during molding becomes too large and the chemical stability of the resin itself is lowered. The molecular weight of the binder resin is more preferably 5000 or more and 1200000 or less, more preferably 7000 or more and 1000000 or less, and particularly preferably 10000 or more and 800000 or less.

Boron compound, oligosaccharide compound, cyclic siloxane compound, and orthosilicic acid derivative >

In order to prevent deterioration of the light-emitting material and improve durability, that is, to suppress deterioration of emission intensity over time, it is effective to include at least one of a specific boron compound, an oligosaccharide compound, a cyclic siloxane compound, and an orthosilicic acid derivative in the color conversion composition.

The above compound plays a role in improving the dispersibility of the light-emitting material in the color conversion composition and the color conversion sheet produced by curing the composition.

A color conversion composition obtained using an organic light emitting material and a color conversion sheet produced by curing the same have a problem of remarkably deteriorated durability at high temperatures. The inventors of the present application have conducted extensive studies and, as a result, have found that the cause of the decrease in durability at high temperatures is a change in the dispersion state of the organic light-emitting material and activation of energy transfer and charge transfer between molecules.

The molecular motion of the binder resin is activated at high temperature, thereby causing the movement of the organic light emitting material in the composition to be also activated. When the organic light emitting materials are close to each other, intermolecular charge transfer activation is caused by excitation energy transfer by a Dexter mechanism or a Foerster mechanism, a super-conjugation mechanism, or the like, and as a result, quenching or deterioration of the organic light emitting materials occurs. In particular, the compound represented by the general formula (1) is a compound which is easily subjected to concentration quenching, and has a large influence on durability due to a change in the dispersion state.

Therefore, the inventors of the present application have found that by adding a compound that assists dispersion of the organic light emitting material at a molecular level as a component of the color conversion composition in addition to the binder resin (B), the organic light emitting material can be stably dispersed even at high temperatures, and durability can be improved. As a result of the research, it was found that specific boron compounds, oligosaccharide compounds, cyclic siloxane compounds and orthosilicic acid derivatives are particularly effective, and are effective for improving the durability of the compound represented by the general formula (1) in an organic light emitting material.

The boron compound is a compound containing a boron atom, and examples thereof include usually an organoboron compound such as boric acid or a salt thereof, and an inorganic boron compound such as boron nitride. Among them, from the viewpoint of solubility and dispersibility in the composition, organoboron compounds are preferable.

The organoboron compound is not particularly limited, but examples thereof include boric acid (boric acid) derivatives, mono-substituted boric acid (boric acid) derivatives, diboronic acid (diboronic acid) derivatives, boroxine derivatives, borinic acid (borinic acid) derivatives, borane derivatives, diborane derivatives, borate derivatives, and salts of these compounds.

In the color conversion composition according to the embodiment of the present invention, the boron compound is not particularly limited, and is preferably at least one of a borate (boronate) derivative, a monobasic borate (boronate) derivative, a diboronate (diboronic acid ester) derivative, and a boroxine derivative.

Examples of the substituent on the boron atom or on the oxygen atom of these derivatives include substituted or unsubstituted alkyl groups, cycloalkyl groups, heterocyclic groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, hydroxyl groups, mercapto groups, alkoxy groups, alkylthio groups, aryl ether groups, aryl thioether groups, aryl groups, heteroaryl groups, halogens, cyano groups, aldehyde groups, carbonyl groups, carboxyl groups, ester groups, carbamoyl groups, amino groups, nitro groups, silyl groups, siloxane groups, borane groups, sulfo groups, and phosphine oxide groups. Among them, preferred are alkyl, cycloalkyl, heterocyclic, aryl, heteroaryl, halogen, cyano and silyl groups, and more preferred are alkyl, cycloalkyl, heterocyclic, aryl, heteroaryl and silyl groups. More preferred are alkyl groups, cycloalkyl groups, aryl groups and silyl groups, and particularly preferred are alkyl groups and cycloalkyl groups.

An example of a preferable boron compound will be described below, but the present invention is not limited thereto.

[ chemical formula 31]

The oligosaccharide compound is an oligosaccharide compound of a saccharide in which a plurality of monosaccharides are bonded via glycosidic bonds. Here, the number of monosaccharides constituting the oligosaccharide compound in the present invention is 2 or more and 20 or less.

In the color conversion composition according to the embodiment of the present invention, the oligosaccharide compound is not particularly limited, and an oligosaccharide containing a pentose derivative or a hexose derivative as a component can be preferably used. Among these oligosaccharides, preferred are oligosaccharides comprising at least one of substituted or unsubstituted glucose, substituted or unsubstituted galactose, substituted or unsubstituted fructose, and substituted or unsubstituted rhamnose, more preferred are oligosaccharides comprising at least one of substituted or unsubstituted glucose, substituted or unsubstituted galactose, and substituted or unsubstituted fructose, and particularly preferred are oligosaccharides comprising substituted or unsubstituted glucose.

Further, from the viewpoint of not having a highly active terminal, a substituted or unsubstituted cyclic oligosaccharide is preferable. The cyclic oligosaccharide is not particularly limited, but a substituted or unsubstituted α -cyclodextrin, a substituted or unsubstituted β -cyclodextrin, and a substituted or unsubstituted γ -cyclodextrin can be preferably used.

Examples of the substituent in the case where the oligosaccharide compound or the monosaccharide constituting the compound is substituted include substituted or unsubstituted alkyl groups, cycloalkyl groups, heterocyclic groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, hydroxyl groups, mercapto groups, alkoxy groups, alkylthio groups, aryl ether groups, aryl thioether groups, aryl groups, heteroaryl groups, halogens, cyano groups, aldehyde groups, carbonyl groups, carboxyl groups, ester groups, carbamoyl groups, amino groups, nitro groups, silyl groups, siloxane groups, borane groups, sulfo groups, and phosphine oxide groups. Among them, alkyl, cycloalkyl, heterocyclic, aryl, heteroaryl and silyl are more preferable, alkyl and silyl are more preferable, and alkyl is particularly preferable.

The cyclic siloxane compound is a cyclic compound formed by siloxane bonds, and may have a monocyclic structure or a polycyclic structure.

In the color conversion composition according to the embodiment of the present invention, the cyclic siloxane compound is not particularly limited, and a cyclic siloxane compound such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, octaphenylcyclotetrasiloxane, etc., or a silsesquioxane compound such as octaphenyloctasilsesquioxane, etc., can be preferably used. The above compounds may be substituted with functional groups. Among them, a silsesquioxane compound is preferable because of high thermal stability.

The functional group of the cyclosiloxane compound or the silsesquioxane compound is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, an alkoxy group, an alkylthio group, an aryl ether group, an aryl thioether group, an aryl group, a heteroaryl group, a halogen group, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxane group, a borane group, a sulfone group, and a phosphine oxide group. Among them, alkyl, cycloalkyl, heterocyclic, aryl, heteroaryl and silyl are more preferable, and alkyl, silyl and aryl are more preferable.

Orthosilicic acid derivatives are a group of compounds in which the hydrogen of the silanol group of orthosilicic acid is substituted by a functional group.

Examples of the functional group include a substituted or unsubstituted alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, and a heteroaryl group. In the color conversion composition according to the embodiment of the present invention, an alkyl group, a cycloalkyl group, and an aryl group are more preferable, and an alkyl group and a cycloalkyl group are more preferable.

That is, in the color conversion composition according to the embodiment of the present invention, the orthosilicic acid derivative is not particularly limited, and a tetraalkoxysilane compound in which hydrogen of a silanol group of orthosilicic acid is substituted with an alkyl group or a cycloalkyl group can be preferably used.

In the color conversion composition according to the embodiment of the present invention, the compound of component (C) preferably does not contain both a nitrogen atom and a phosphorus atom. When the compound of component (C) contains a nitrogen atom or a phosphorus atom, charge is transferred to and from the organic light-emitting material at high temperature, and quenching and deterioration of the organic light-emitting material are likely to occur.

The compound of component (C) preferably does not contain an aromatic hydrocarbon group having 11 or more carbon atoms forming a ring, or an aromatic heterocyclic group having 11 or more carbon atoms forming a ring. These groups have a broad pi-conjugated system, and therefore have high charge affinity, activate charge transfer, and easily cause quenching and deterioration of the organic light-emitting material.

In order to suppress light from a light source or light emission of a light-emitting material, the compound of component (C) preferably has a small absorption coefficient in a visible light region. Specifically, the molar absorption coefficient ε is 100 or less in the whole wavelength region of 400nm to 800 nm. The smaller the ε, the more preferable it is 80 or less. ε is more preferably 50 or less, and particularly preferably 30 or less. By using a component that absorbs little in the visible light region, the durability of the color conversion composition can be improved without lowering the luminous efficiency.

The compounds listed as the component (C) may be used alone or in combination of two or more.

In order to stably disperse the organic light-emitting material even at high temperatures, the molar numbers of the component (A) and the component (C) are each defined as n_A、n_CWhen n is more preferable_A、n_CSatisfies (formula-1).

0.1≤n_C/n_ALess than or equal to 200 (formula-1)

n_C/n_AWhen the amount is 0.1 or more, the dispersion of the organic light-emitting material can be sufficiently assisted, and therefore, the organic light-emitting material is preferable. n is_C/n_AMore preferably 1.0 or more, still more preferably 2.0 or more, and particularly preferably 5.0 or more. In addition, n_C/n_AWhen the amount of the component (C) is 200 or less, the component (C) is added to the component (A)It is preferable because the strength, thermal stability, and the like are sufficient when the composition is formed into a sheet or the like. n is_C/n_AMore preferably 100 or less, still more preferably 50 or less, and particularly preferably 30 or less.

< other additives >

The color conversion composition according to the embodiment of the present invention may contain, in addition to the above-described components (a), (B) and (C), other additives such as a light resistance stabilizer such as an antioxidant, a processing and heat stabilizer, and an ultraviolet absorber, a dispersant or a leveling agent for stabilizing a coating film, a plasticizer, a crosslinking agent such as an epoxy compound, a curing agent such as an amine, an acid anhydride, and imidazole, a bonding assistant such as a silane coupling agent as a modifier for a sheet surface, silica particles as a color conversion material sedimentation inhibitor, inorganic particles such as fine silicone particles, and a silane coupling agent.

Examples of the antioxidant include, but are not particularly limited to, phenol-based antioxidants such as 2, 6-di-tert-butyl-p-cresol and 2, 6-di-tert-butyl-4-ethylphenol. These antioxidants may be used alone or in combination.

Examples of the processing and heat stabilizer include phosphorus stabilizers such as tributyl phosphite, tricyclohexyl phosphite, triethylphosphine, and diphenylbutylphosphine, but are not particularly limited thereto. These stabilizers may be used alone or in combination.

Examples of the light resistance stabilizer include, but are not particularly limited to, benzotriazoles such as 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- [ 2-hydroxy-3, 5-bis (. alpha.,. alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole. These light-resistance stabilizers may be used alone or in combination.

In view of not inhibiting light from a light source or light emission of a light-emitting material, these additives preferably have a small absorption coefficient in the visible region. Specifically, the molar absorption coefficient ε of the additive is preferably 200 or less, more preferably 100 or less, over the entire wavelength region of 400nm to 800 nm. More preferably 80 or less, and particularly preferably 50 or less.

Further, as the light resistance stabilizer, a compound having an action as a singlet oxygen quencher can also be preferably used. The singlet oxygen quencher is a material that inactivates by capturing singlet oxygen generated by activation of oxygen molecules with light energy. By allowing a singlet oxygen quencher to coexist in the color conversion sheet, the light-emitting material can be prevented from being deteriorated by singlet oxygen.

Singlet oxygen is known to be generated by electron-energy conversion between triplet excited state of pigment such as rose bengal or methylene blue and oxygen molecule in ground state.

With the color conversion composition of the embodiment of the present invention, the organic light emitting material contained is excited by the excitation light to emit light having a wavelength different from that of the excitation light, thereby performing color conversion of light. Since this cycle of excitation-emission is repeated, the probability of singlet oxygen generation is increased by the interaction between the generated excited species and oxygen contained in the color conversion plate. Therefore, the probability of collision between the organic light emitting material and singlet oxygen is also increased, and thus deterioration of the organic light emitting material is easily progressed.

Organic light emitting materials are susceptible to singlet oxygen compared to inorganic light emitting materials. In particular, the compound represented by the general formula (1) has higher reactivity with singlet oxygen than a compound having a condensed aromatic ring such as perylene or a derivative thereof, and has a large influence on durability by singlet oxygen. Therefore, by rapidly deactivating the generated singlet oxygen with a singlet oxygen quencher, the durability of the compound represented by the general formula (1) excellent in the emission quantum yield and color purity can be further improved.

Examples of the compound having the function as a singlet oxygen quencher include specific tertiary amines and metal salts, but the compound is not particularly limited to these compounds. These compounds (light-resistant stabilizers) may be used alone or in combination.

The tertiary amine is a compound having a structure in which all of the N-H bonds of ammonia are replaced with N-C bonds. As the substituent on the nitrogen atom, one selected from the following groups: alkyl, cycloalkyl, heterocyclyl, alkenyl, cycloalkenyl, alkynyl, aryl, heteroaryl, aldehyde, carbonyl, carboxyl, oxycarbonyl, carbamoyl, and fused and aliphatic rings formed between adjacent substituents. In addition, these substituents may be further substituted with the above-mentioned substituents.

Preferred tertiary amines include triethylamine, 1, 4-diazabicyclo [2.2.2] octane, tri-N-butylamine, N-diethylaniline, and 2, 2, 6, 6-tetramethylpiperidine, but are not particularly limited to these tertiary amines.

Examples of the metal salt include inorganic salts such as chlorides and organic acid salts such as sulfates. Among them, metal salts of organic acids are preferable from the viewpoint of uniform dispersion in the color conversion composition.

The metal salt of an organic acid is a salt formed from an organic acid and a metal element. The organic acid represents an organic compound having a carboxyl group, a sulfonyl group, a phenolic hydroxyl group, and a mercapto group. As the metal element, a transition element can be cited, and among them, nickel is preferably used. Namely, nickel salts of organic acids are preferred.

Examples of the nickel salt of an organic acid which can be preferably used as a singlet oxygen quencher include, but are not particularly limited to, acetylacetone-based nickel complexes, bisdithio- α -diketone-based nickel complexes, dithiolate (dithiolate) -based nickel complexes, aminothiolate-based nickel complexes, thiocatechol-based nickel complexes, salicylaldoxime-based nickel complexes, thiobisphenolate-based nickel complexes, indoaniline-based nickel compounds, carboxylic acid-based nickel salts, sulfonic acid-based nickel salts, phenolic nickel salts, carbamic acid-based nickel salts, and dithiocarbamic acid-based nickel salts.

Among the above compounds, sulfonic acid-based nickel salts are preferable from the viewpoint that the molar absorption coefficient in the visible region is small and the light emission from the light source or the light-emitting material is not absorbed. Furthermore, from the viewpoint of exhibiting a better singlet oxygen quenching effect, a nickel salt of an arylsulfonic acid is more preferable, and from the viewpoint of solubility in various solvents, a nickel salt of an alkylsulfonic acid is preferable. As the aryl group of the arylsulfonic acid, a substituted or unsubstituted phenyl group is preferable, and a phenyl group substituted with an alkyl group is more preferable from the viewpoint of solubility in a solvent and dispersibility.

In addition, both of the acetylacetone nickel complex and the thiobisphenolate nickel complex are preferable from the viewpoint of solubility in an organic solvent and a small molar absorption coefficient in a visible region. The ligand on nickel in the above-mentioned compounds may be substituted with a substituent such as an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a mercapto group, an alkoxy group, an alkylthio group, an aryl ether group, an aryl thioether group, an aryl group, a heteroaryl group, a halogen group, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxane group, a borane group, a phosphine oxide group or the like. In addition, these substituents may be further substituted with the above-mentioned substituents.

Among them, from the viewpoint of light stability, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and halogen are preferable, and substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, and halogen are more preferable. In addition, from the viewpoint of less discoloration after the reaction with the singlet oxygen quencher, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a halogen are more preferable. Particularly preferred is a substituted or unsubstituted alkyl group.

Examples of the nickel salt of an organic acid having a molar absorption coefficient epsilon of 200 or less in the entire wavelength region of 400nm or more and 800nm or less include a nickel salt of p-tolylsulfonic acid, a nickel (II) acetylacetonate complex, a nickel (II) hexafluoroacetylacetonate complex, a 2, 2 '-thiobisphenoxide-n-butylamino nickel (II) complex, and a [2, 2' -thiobis (4-tert-octylphenolate) ] -2-ethylhexylamino nickel (II) complex. However, the organic acid nickel salt is not limited to these compounds, and among the various organic acid nickel salts described above, a compound having a small molar absorption coefficient ε in the entire wavelength region of 400nm to 800nm is preferably used, and a compound having ε of 200 or less is particularly preferably used.

Further, as the light resistance stabilizer, a compound having an action as a radical quencher can also be preferably used. Among them, hindered amine compounds are preferable. Examples of the hindered amine-based compound include 2, 2, 6, 6-tetramethylpiperidine, 4-hydroxy-1, 2, 2, 6, 6-pentamethylpiperidine, 4-methoxy-2, 2, 6, 6-tetramethylpiperidine, 4-methoxy-1, 2, 2, 6, 6-pentamethylpiperidine, piperidine derivatives and oxides thereof such as bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate, 2, 2, 6, 6-tetramethyl-4-piperidyl) methacrylate and 1, 2, 2, 6, 6-pentamethyl-4-piperidyl methacrylate.

In the color conversion composition and the color conversion sheet according to the embodiment of the present invention, the content of the additive is preferably 1.0 × 10 parts by weight based on 100 parts by weight of the binder resin, although it depends on the molar absorption coefficient of the compound, the luminescence quantum yield, the absorption intensity of the excitation wavelength, and the thickness or transmittance of the color conversion sheet to be produced^-3More than the weight part, preferably 1.0X 10^-2More preferably 1.0X 10 parts by weight or more^-1And (3) parts by weight. The content of the additive is preferably 30 parts by weight or less, more preferably 15 parts by weight or less, and still more preferably 10 parts by weight or less, based on 100 parts by weight of the binder resin.

< solvent >

The color-converting composition of embodiments of the present invention may comprise a solvent. The solvent is not particularly limited as long as the viscosity of the resin in a fluid state can be adjusted without excessively affecting the light emission and durability of the light-emitting substance. The solvent may be removed by drying. Examples of such a solvent include water, 1-propanol, 2-propanol, 1-butanol, ethanol, toluene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, hexane, cyclohexane, tetrahydrofuran, acetone, terpineol, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (Texanol), 1, 2-dimethoxyethane, methyl cellosolve, ethyl cellosolve, butyl carbitol acetate, 1-methoxy-2-propanol, and propylene glycol monomethyl ether acetate, and these solvents may be mixed with 2 or more kinds. Among the solvents, toluene is particularly preferably used from the viewpoint of not affecting the deterioration of the compound represented by the general formula (1). In addition, methyl ethyl ketone, methyl acetate, and ethyl acetate can be preferably used from the viewpoint of reducing the residual solvent after drying.

< method for producing color conversion composition >

An example of a method for producing a color conversion composition according to an embodiment of the present invention will be described below. The organic light-emitting material, the binder resin, and the solvent described below are mixed in predetermined amounts. The above materials are mixed so as to attain a predetermined combination, and then homogeneously mixed and dispersed by a stirring and kneading machine such as a homogenizer, a revolution and rotation type stirrer, a three-roll mill, a ball mill, a planetary ball mill, or a bead mill, thereby preparing a composition for producing a color conversion layer, that is, a color conversion composition. After or during the mixing and dispersing, it is also preferable to perform deaeration under vacuum or reduced pressure. Further, some specific components may be mixed in advance and/or subjected to a treatment such as aging. The solvent may be removed by an evaporator to obtain a desired solid content concentration.

< method for producing color conversion sheet >

The color conversion sheet according to the embodiment of the present invention is not limited in its configuration as long as it includes a color conversion layer which is a layer obtained by curing a color conversion composition. As a representative configuration example of the color conversion sheet, there can be mentioned: a laminate of a base material layer 10 and a color conversion layer 11 obtained by curing a color conversion composition as shown in fig. 1; alternatively, as shown in fig. 2, the color conversion layer 11 is sandwiched between a plurality of base material layers 10. In order to prevent the color conversion layer from being deteriorated by oxygen, moisture, or heat, a barrier layer 12 may be further provided on the color conversion sheet 1 as shown in fig. 3.

In addition, the color conversion sheet according to the embodiment of the present invention may include 2 or more color conversion layers. Examples thereof include: a laminate of the base material layer 10, the color conversion layer 11A, and the color conversion layer 11B as shown in fig. 4; alternatively, as shown in fig. 5, a laminate in which the color conversion layer 11A and the color conversion layer 11B are sandwiched between a plurality of base material layers 10; as shown in fig. 6, a laminate is formed by providing the transparent intermediate layer 13 between the color conversion layer 11A and the color conversion layer 11B. Further, a configuration may be adopted in which the same color conversion layers are continuous, such as the color conversion layers 11A/11B, the color conversion layers 11A/11B, and the color conversion layers 11A/11B.

The above example is an example, and the specific configuration of the color conversion sheet according to the embodiment of the present invention is not limited to this, and configurations appropriately modified from the matters described below are also included in the scope of the present invention.

(color conversion layer)

Next, an example of a method for manufacturing a color conversion layer of a color conversion sheet according to an embodiment of the present invention will be described. The color conversion composition produced by the above method is coated on a substrate such as a substrate layer or a barrier layer, and dried. Coating can be carried out by Reverse roll coaters, knife coaters, slot die coaters, direct slot roll coaters, offset slot roll coaters, kiss coaters, natural roll coaters, air knife coaters, roll knife coaters, Reverse roll blade coaters, double-flow coaters, bar coaters, wire bar coaters, dip coaters, curtain coaters, spin coaters, knife coaters, and the like. In order to obtain the film thickness uniformity of the color conversion layer, the coating is preferably performed by a slot die coater.

The color conversion layer can be dried by using a general heating device such as a hot air dryer or an infrared dryer. For heating the color conversion sheet, a general heating device such as a hot air dryer or an infrared dryer can be used. In this case, the heating condition is usually 1 minute to 5 hours at 40 to 250 ℃ and preferably 2 minutes to 4 hours at 60 to 200 ℃. Alternatively, stepwise heat curing (step cure) or the like may be employed.

After the color conversion layer is manufactured, the base material layer can be replaced according to the requirement. In this case, as a simple method, for example, a method of re-attaching using a hot plate, a method of using a vacuum laminator or a dry film laminator, and the like can be given, but the method is not limited to these methods.

When the color conversion sheet according to the embodiment of the present invention includes 2 or more color conversion layers, known methods such as coating and dry lamination can be used for laminating the respective layers. In the present invention, the method for laminating the layers is not particularly limited, and examples thereof include the following methods: a method of forming (color conversion layer B) on (color conversion layer a) by coating and drying when (color conversion layer a) and (color conversion layer B) are laminated; a method of forming (color conversion layer a) on (color conversion layer B) by coating and drying; a method of laminating a separately molded self-supporting film for the color conversion layer B on the color conversion layer a; a method of laminating a separately molded self-supporting film for the (color conversion layer a) on the (color conversion layer B); a method of bonding the laminated modules respectively prepared, such as bonding a laminated module having a laminated structure of "base layer/(color conversion layer a)" and a laminated module having a laminated structure of "(color conversion layer B)/base layer". In order to improve the stability of the color conversion sheet, it is also preferable to further perform a heat curing step, a photocuring step, a curing step, and the like after stacking the respective layers.

The thickness of the color conversion layer is not particularly limited, but is preferably 1 μm to 1000 μm, and more preferably 10 μm to 1000 μm. When the thickness of the color conversion layer is smaller than 1 μm, there is a problem that the toughness of the color conversion sheet is reduced. When the thickness of the color conversion layer exceeds 1000 μm, cracks are likely to occur, and molding of the color conversion sheet is difficult. The thickness of the color conversion layer is preferably 5 μm to 100 μm, more preferably 10 μm to 100 μm, and particularly preferably 15 μm to 100 μm.

The film thickness (layer thickness) in the present invention is a film thickness (average film thickness) measured by a method a of measuring a thickness by mechanical scanning in a method of measuring a plastic film and sheet thickness according to JIS K7130 (1999).

(substrate layer)

As the substrate layer, known metals, films, glasses, ceramics, papers, and the like can be used without particular limitation. Specifically, examples of the base material layer include: metal plates and foils of aluminum (including aluminum alloys), zinc, copper, iron, and the like; films of plastics such as cellulose acetate, PET, polyethylene, polyester, polyamide, polyimide, polyphenylene sulfide, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, aromatic polyamide, silicone, polyolefin, thermoplastic fluororesin, and copolymer of tetrafluoroethylene and ethylene (ETFE); a film of plastic formed of an α -polyolefin resin, a polycaprolactone resin, an acrylic resin, a silicone resin, and a copolymer resin thereof with ethylene; paper laminated with the plastic or coated with the plastic; paper on which the above metal is laminated or vapor-deposited; a plastic film on which the metal is laminated or vapor-deposited. When the substrate is a metal plate, the surface thereof may be subjected to plating treatment with chromium, nickel, or the like, or ceramic treatment.

Among the above materials, glass and resin films are preferably used in view of ease of manufacturing the color conversion sheet and ease of molding the color conversion sheet. In addition, a film having high strength is preferable in order to eliminate the risk of occurrence of breakage or the like when handling the film-like base material layer. Among the above materials, plastic films selected from the group consisting of PET, polyphenylene sulfide, polycarbonate and polypropylene are preferable from the viewpoints of the required characteristics and economy. Further, when the color conversion sheet is dried or when the color conversion sheet is pressure-bonded at a high temperature of 200 ℃ or higher by an extruder, a polyimide film is preferable from the viewpoint of heat resistance. The surface of the base material layer may be subjected to a release treatment in advance in view of easiness of film peeling. Similarly, in order to improve the interlayer adhesiveness, the surface of the base material layer may be subjected to an easy-adhesion treatment in advance.

The thickness of the base material layer is not particularly limited, and the lower limit is preferably 12 μm or more, and more preferably 38 μm or more. The upper limit is preferably 5000 μm or less, more preferably 3000 μm or less.

(Barrier layer)

The color conversion sheet according to the embodiment of the present invention may further include a barrier layer. The barrier layer is suitably used in order to prevent the color conversion layer from being deteriorated by oxygen, moisture, or heat. Examples of such a barrier layer include inorganic oxides such as silicon oxide, aluminum oxide, titanium oxide, tantalum oxide, zinc oxide, tin oxide, indium oxide, yttrium oxide, and magnesium oxide, inorganic nitrides such as silicon nitride, aluminum nitride, titanium nitride, and silicon carbonitride, mixtures thereof, and metal oxide thin films and metal nitride thin films obtained by adding other elements thereto; or films formed from various resins such as polyvinyl chloride resins, acrylic resins, silicone resins, melamine resins, urethane resins, fluorine resins, and polyvinyl alcohol resins such as saponified products of vinyl acetate.

Examples of the barrier resin preferably used for the barrier layer in the present invention include resins such as polyester, polyvinyl chloride, nylon, polyvinyl fluoride, polyvinylidene chloride, polyacrylonitrile, polyvinyl alcohol, and ethylene-vinyl alcohol copolymer, and mixtures of these resins. Among them, polyvinylidene chloride, polyacrylonitrile, ethylene-vinyl alcohol copolymer, and polyvinyl alcohol have a very small oxygen permeability coefficient, and therefore the barrier resin preferably contains the above-mentioned resins. Further, the barrier resin is preferably composed of polyvinylidene chloride, polyvinyl alcohol, and an ethylene-vinyl alcohol copolymer from the viewpoint of difficulty in discoloration, and is particularly preferably composed of polyvinyl alcohol or an ethylene-vinyl alcohol copolymer from the viewpoint of reducing the burden on the environment. These resins may be used alone or in combination with different resins, and a film formed from a single resin is more preferable from the viewpoint of film uniformity and cost.

As the polyvinyl alcohol, for example, a saponified product of polyvinyl acetate obtained by saponifying acetyl groups at 98 mol% or more can be used. The ethylene-vinyl alcohol copolymer may be, for example, a saponified ethylene-vinyl acetate copolymer having an ethylene content of 20% to 50% and obtained by saponifying an acetyl group at 98 mol% or more.

Further, commercially available resins and films may be used as the barrier layer. Specific examples thereof include KURARAAY CO., LTD polyvinyl alcohol resin PVA117 or KURARAAY CO., LTD ethylene-vinyl alcohol copolymer ("EVAL" (registered trademark)) resin L171B, F171B, and film EF-XL.

An antioxidant, a curing agent, a crosslinking agent, a processing and heat stabilizer, a light resistance stabilizer such as an ultraviolet absorber, and the like may be added to the barrier layer as necessary within a range not to excessively affect the light emission and durability of the color conversion layer.

The thickness of the barrier layer is not particularly limited, and is preferably 100 μm or less from the viewpoint of flexibility and cost of the entire color conversion sheet. More preferably 50 μm or less, and still more preferably 20 μm or less. Particularly preferably 10 μm or less, and may be 1 μm or less. However, the thickness of the barrier layer is preferably 0.01 μm or more from the viewpoint of ease of forming the layer.

In the present invention, the barrier layer may be provided on each end surface of the color conversion layer 11 on both sides in the stacking direction, as in the barrier layer 12 illustrated in fig. 3, or may be provided on one end surface of both sides in the stacking direction. When 2 or more color conversion layers are included, the color conversion layers may be provided on both surfaces of the color conversion layer 11A and the color conversion layer 11B, as in the barrier layer 12 illustrated in fig. 7, or may be provided on only one surface. Further, the color conversion layer 11A and the color conversion layer 11B may be provided on both surfaces thereof as in the barrier layer 12 illustrated in fig. 8.

(other functional layer)

The color conversion sheet according to the embodiment of the present invention may further include a light diffusion layer, and an auxiliary layer having an antireflection function, an antiglare function, an antireflection and antiglare function, a hard coat function (friction resistance function), an antistatic function, an antifouling function, an electromagnetic wave shielding function, an infrared ray blocking function, an ultraviolet ray blocking function, a polarization function, and a color toning function, depending on the required functions.

(adhesive layer)

In the color conversion sheet according to the embodiment of the present invention, an adhesive layer may be provided between the respective layers as needed. The adhesive layer is not particularly limited as long as it does not excessively affect the light emission and durability of the color conversion sheet, and known materials can be used. For example, when strong adhesion is required, a photocurable material, a thermosetting material, an anaerobic curable material, or a thermoplastic material can be preferably used as the adhesive layer. Among them, thermosetting materials are more preferable, and thermosetting materials curable at 0 to 150 ℃ are particularly preferable.

The thickness of the adhesive layer is not particularly limited, but is preferably 0.01 to 100. mu.m, more preferably 0.01 to 25 μm. More preferably 0.1 to 15 μm, and particularly preferably 1.0 to 15 μm.

As a method for laminating the layers, known methods such as coating and dry lamination can be used. In the present invention, the method of laminating the layers is not particularly limited, and examples thereof include a method of laminating the (L1) layer and the (L2) layer, a method of forming the (L2) layer by coating the (L1) layer and drying the layer, a method of forming the (L1) layer by coating the (L2) layer and drying the layer, a method of bonding a self-supporting film for the (L2) layer formed separately to the (L1) layer, a method of bonding a self-supporting film for the (L1) layer formed separately to the (L2) layer, and a method of bonding laminated modules prepared separately, such as bonding a laminated module having a laminated structure of "base layer/(L1) layer" and a laminated module having a laminated structure of "(L2) layer/base layer". In order to improve the stability of the color conversion sheet, it is preferable to further perform a thermosetting step, a photocuring step, a curing step, and the like after laminating the respective layers.

< excitation light >

As for the kind of the excitation light, any excitation light may be used as long as light emission is displayed in a wavelength region that the organic light emitting material used in the present invention can absorb. For example, excitation light from a fluorescent light source such as a hot cathode tube, a cold cathode tube, or an inorganic Electroluminescence (EL) device, an organic EL device light source, an LED light source, a white heat light source, or an arbitrary light source such as sunlight can be used. Among them, excitation light from an LED light source is preferable. In the display and illumination applications, excitation light from a blue LED light source having excitation light in a wavelength range of 400nm to 500nm is more preferable in terms of improving the color purity of blue light.

When the maximum emission wavelength of the excitation light is 430nm or more and 500nm or less, the excitation energy is preferably smaller and the degradation of the organic light-emitting material can be suppressed, and more preferably 440nm or more and 500nm or less. Particularly preferably 450nm or more and 500nm or less. Further, the maximum emission wavelength of the excitation light is preferably 480nm or less, more preferably 470nm or less, because the overlap of the emission spectra of the excitation light and the green light can be reduced and the color reproducibility can be improved.

The excitation light may have 1 kind of emission peak or 2 or more kinds of emission peaks, and 1 kind of emission peak is preferable for improving color purity. In addition, a plurality of excitation light sources having different kinds of emission peaks may be arbitrarily combined and used.

< light source Module >

The light source module according to the embodiment of the present invention is configured to include at least the light source and the color conversion composition or the color conversion sheet. When the light source module includes the color conversion composition, the light source and the method of disposing the color conversion composition are not particularly limited, and the color conversion composition may be directly applied to the light source or may be applied to a film or glass that is separated from the light source. When the light source module includes the color conversion sheet, the method of disposing the light source and the color conversion sheet is not particularly limited, and the light source and the color conversion sheet may be configured to be closely attached to each other, or may be in the form of Remote Phosphor (Remote Phosphor) for separating the light source and the color conversion sheet from each other. In addition, for the purpose of improving color purity, the light source module can also adopt a structure further provided with a color filter.

As described above, since excitation light having a wavelength in the range of 400nm to 500nm is low in excitation energy and can prevent decomposition of a light-emitting substance such as a compound represented by general formula (1), a light source provided in a light source module is preferably a light-emitting diode having maximum light emission in the wavelength range of 400nm to 500 nm. The light source preferably has a maximum light emission in a wavelength range of 430nm to 480nm, and more preferably in a wavelength range of 450nm to 470 nm. The light source module of the present invention can be used for applications such as displays, lighting, decorations, signs, and billboards, but is particularly preferably used for applications such as displays and lighting.

< display device, illumination device >

The display according to the embodiment of the present invention includes at least the light source module including the light source and the color conversion sheet as described above. For example, the light source module can be used as a backlight module in a display such as a liquid crystal display.

The lighting device according to the embodiment of the present invention includes at least the light source module including the light source and the color conversion sheet as described above. For example, the lighting device may be configured as follows: the blue LED light source as the light source module is combined with a color conversion sheet or a color conversion composition that converts blue light from the blue LED light source into light having a longer wavelength than the blue light, thereby emitting white light.

Examples

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

In the following examples and comparative examples, the compounds G-1 to G-3, R-1, R-2, S-1 to S-10 and Q-1 are the following compounds.

[ chemical formula 32]

[ chemical formula 33]

[ chemical formula 34]

The evaluation method for structural analysis is as follows.

<¹Measurement of H-NMR>

Process for preparing compounds¹The H-NMR was measured using a deuterated chloroform solution using a superconducting FTNMR EX-270 (manufactured by Nippon electronics Co., Ltd.).

< measurement of absorption Spectrum >

For the absorption spectrum of the compound, a 1X 10-type U-3200 spectrophotometer (manufactured by Hitachi, Ltd.) was used^-6The concentration of mol/L was measured by dissolving in toluene.

< measurement of fluorescence Spectroscopy >

For the fluorescence spectrum of the compound, a spectrofluorometer F-2500 (manufactured by Hitachi, Ltd.) was used to convert the compound to 1X 10^-6The concentration of mol/L was dissolved in toluene, and the fluorescence spectrum was measured when the solution was excited at a wavelength of 460 nm.

< measurement of color conversion characteristics >

In the measurement of the color conversion characteristics, a current of 30mA was passed through a planar light-emitting device having blue LED elements each having an emission peak wavelength of 447nm, with each color conversion sheet and a prism sheet mounted thereon, to light the blue LED elements, and the emission spectrum, chromaticity, and luminance were measured using a spectral radiance meter (CS-1000, manufactured by konica minolta).

< test for light durability >

In the light durability test, in a state where a planar light-emitting device having blue LED elements each having an emission peak wavelength of 447nm was mounted with each color conversion sheet and prism sheet, a current of 100mA was passed through the planar light-emitting device to light the blue LED elements, and the initial luminance was measured using a spectral radiance photometer (CS-1000, manufactured by konica minolta). Then, the light from the blue LED element was continuously irradiated in an environment of 50 ℃ and 27% RH, and the time until the luminance was reduced by a certain amount was observed, thereby evaluating the light durability. Wherein the brightness is measured as follows: the color conversion sheet and the planar light-emitting device were taken out of the oven and measured in a state where the temperature was lowered to room temperature.

< measurement of molar absorptivity >

The compound was measured at 1X 10 in the same manner as in the above-mentioned method for measuring absorption spectrum^-5mol/L、5×10^-5mol/L、1×10^-4mol/L、5×10^-4mol/L、1×10^-3The respective concentrations of mol/L were dissolved in toluene or ethanol, and the respective absorption spectra were measured. The absorbance at each wavelength was calculated from the obtained absorption spectrum, and a calibration curve was prepared from a graph having the absorbance as the vertical axis and the molar concentration (mol/L) as the horizontal axis, thereby obtaining the molar absorption coefficient at each wavelength.

The molar absorption coefficients obtained for compounds G-1, S-1 to S-10, and Q-1 are shown in Table 2. Wherein ε max in the table is the maximum value of molar absorption coefficient ε in the whole wavelength region of 400nm to 800 nm.

[ Table 2]

[ TABLE 2]

Synthesis example 1

Synthesis method of compound G-1

3, 5-dibromobenzaldehyde (3.0g), 4-tert-butylphenyl monosubstituted boronic acid (5.3g), tetrakis (triphenylphosphine) palladium (0) (0.4g) and potassium carbonate (2.0g) were added to the flask, and nitrogen substitution was performed. Degassed toluene (30mL) and degassed water (10mL) were added thereto and refluxed for 4 hours. The reaction solution was cooled to room temperature, and the organic layer was separated and washed with saturated brine. The organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off. The obtained reaction product was purified by silica gel chromatography to obtain 3, 5-bis (4-tert-butylphenyl) benzaldehyde (3.5g) as a white solid.

3, 5-bis (4-tert-butylphenyl) benzaldehyde (1.5g) and 2, 4-dimethylpyrrole (0.7g) were added to the reaction solution, dehydrated dichloromethane (200mL) and trifluoroacetic acid (1 drop) were added, and the mixture was stirred under a nitrogen atmosphere for 4 hours. A solution of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (0.85g) in dehydrated dichloromethane was added thereto, followed by stirring for 1 hour. After completion of the reaction, boron trifluoride-diethyl etherate (7.0mL) and diisopropylethylamine (7.0mL) were added thereto, and the mixture was stirred for 4 hours, followed by addition of water (100mL) and stirring to separate the organic layer. The organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off. The obtained reaction product was purified by silica gel chromatography to obtain 0.4G of Compound G-1 (yield: 18%) shown below.

¹H-NMR(CDCl₃，ppm)：7.95(s，1H)、7.63-7.48(m，10H)、6.00(s，2H)、2.58(s，6H)、1.50(s，6H)、1.37(s，18H)。

The absorption spectrum of this compound is shown in fig. 9, and a blue excitation light source (460nm) shows the absorption characteristics of light. The fluorescence spectrum is shown in FIG. 10, and the green region shows a sharp luminescence peak. The fluorescence quantum yield was 83%, and the compound was capable of color conversion with good efficiency.

Synthesis example 2

Synthesis method of compound R-1

A mixed solution of 300mg of 4- (4-tert-butylphenyl) -2- (4-methoxyphenyl) pyrrole, 201mg of 2-methoxybenzoyl chloride and 10ml of toluene was heated under a nitrogen stream at 120 ℃ for 6 hours. After cooling to room temperature, evaporation was carried out. After washing with 20ml of ethanol and vacuum drying, 260mg of 2- (2-methoxybenzoyl) -3- (4-tert-butylphenyl) -5- (4-methoxyphenyl) pyrrole was obtained.

Then, a mixed solution of 260mg of 2- (2-methoxybenzoyl) -3- (4-tert-butylphenyl) -5- (4-methoxyphenyl) pyrrole, 180mg of 4- (4-tert-butylphenyl) -2- (4-methoxyphenyl) pyrrole, 206mg of methanesulfonic anhydride and 10ml of degassed toluene was heated under a nitrogen stream at 125 ℃ for 7 hours. After cooling to room temperature, 20ml of water was poured and extracted with 30ml of dichloromethane. The organic layer was washed 2 times with 20ml of water, evaporated and dried in vacuo.

Then, to a mixed solution of the obtained methylene-pyrrole and 10ml of toluene, 305mg of diisopropylethylamine and 670mg of boron trifluoride diethyl etherate were added under a nitrogen stream, and the mixture was stirred at room temperature for 3 hours. 20ml of water was poured in and extracted with 30ml of dichloromethane. The organic layer was washed 2 times with 20ml of water, dried over magnesium sulfate and evaporated. Purification by silica gel column chromatography and vacuum drying gave 0.27g of a purple powder. Of the resulting powder¹As a result of H-NMR analysis, it was confirmed that the purple powder obtained above was R-1.

¹H-NMR(CDCl₃，ppm)：1.19(s，18H)、3.42(s，3H)、3.85(s，6H)、5.72(d，1H)、6.20(t，1H)、6.42-6.97(m，16H)，7.89(d，4H)。

The absorption spectrum of this compound is shown in fig. 11, and the blue and green excitation light sources exhibit light absorption characteristics. The fluorescence spectrum is shown in FIG. 12, and the red region shows a sharp luminescence peak. The fluorescence quantum yield was 90%, and the compound was capable of color conversion with good efficiency.

Example 1

In example 1 of the present invention, an acrylic resin "Oricox KC-7000" (manufactured by Kyoto chemical Co., Ltd.) was used as a binder resin, and 0.25 part by weight of Compound G-1 as component (A), 1.0 part by weight of Compound S-1 as component (C), 150 parts by weight of toluene as a solvent, and 150 parts by weight of 1-methoxy-2-propanol were mixed with 100 parts by weight of the binder resin. The mixture was stirred and defoamed at 300rpm for 30 minutes by a planetary stirring and defoaming device "MAZERUSTAR KK-400" (manufactured by Bin Pak Co., Ltd.) to obtain a color conversion composition. In this case, the molar ratio n of the component (A) to the component (C)_C/n_AIs 10.

Then, the color conversion composition was coated on "lumiror" U34 (manufactured by tokyo corporation, thickness 75 μm) as a base material layer using a slot coater. The resultant was heated at 120 ℃ and dried for 20 minutes to form a color conversion layer having an average film thickness of 18 μm.

Finally, a diffusion film ("Texcell" (registered trademark) TDF127 manufactured by tokyo shoji, ltd.) was laminated and then cured at 60 ℃ for 1 hour to obtain a color conversion sheet.

The color conversion sheet is used for converting the color of blue LED light, and when only a green light emitting region is selected, high-color-purity green light emission with a peak wavelength of 527nm and a half-peak width of the light emission spectrum at the peak wavelength of 33nm is obtained. When the intensity in the following comparative example 1 was taken as a relative value of 1.0, the light emission intensity at the peak wavelength was 1.0, and no light emission inhibition by the component (C) was observed. Further, according to the above method, the light from the blue LED element was continuously irradiated in an environment of 50 ℃ and 27% RH, and as a result, the time until the luminance was reduced by 10% was 80 hours. The results are shown in Table 3.

Comparative example 1

A color conversion sheet was produced and evaluated in the same manner as in example 1, except that the component (C) was not mixed. The results are shown in Table 3. The emission intensity (relative value) in the table is a relative value when the intensity in comparative example 1 is 1.0.

Examples 2 to 5 and comparative example 2

Except that the compounds shown in Table 3 were used as the component (C) and the molar ratio n of the component (A) to the component (C) was set to_C/n_AA color conversion sheet was produced and evaluated in the same manner as in example 1, except that the blending amount of component (C) was adjusted to 10. The results are shown in Table 3. The emission intensity (relative value) in the table is a relative value when the intensity in comparative example 1 is 1.0.

Examples 6 to 8

Except that the compound S-6 is used as the component (C) and the molar ratio n of the component (A) to the component (C) is set_C/n_AColor conversion sheets were produced and evaluated in the same manner as in example 1, except that the blending amount of component (C) was adjusted to the values shown in table 3. The results are shown in Table 3. The emission intensity (relative value) in the table is a relative value when the intensity in comparative example 1 is 1.0.

Example 9

A color conversion sheet was produced and evaluated in the same manner as in example 1, except that 0.15 parts by weight of compound G-3 as component (a) and 1.0 part by weight of compound S-1 as component (C) were mixed with 100 parts by weight of the binder resin. In this case, the molar ratio n of the component (A) to the component (C)_C/n_AIs 10. The results are shown in Table 3. The emission intensity (relative value) in the table is a relative value when the intensity in comparative example 1 is 1.0.

Comparative example 3

A color conversion sheet was produced and evaluated in the same manner as in example 9, except that the component (C) was not mixed. The results are shown in Table 3. The emission intensity (relative value) in the table is a relative value when the intensity in comparative example 1 is 1.0.

Examples 10 and 11

Except that the molar ratio n of the component (A) to the component (C) is_C/n_AColor conversion sheets were produced and evaluated in the same manner as in example 3, except that the blending amount of component (C) was adjusted to the values shown in table 3. The results are shown in Table 3. The emission intensity (relative value) in the table is a relative value when the intensity in comparative example 1 is 1.0. In example 11, the coating film was clouded at the time of forming the color conversion layer, and the visible light emission intensity and the light durability were reduced as compared with example 3.

Examples 12 to 14

Except that the compounds shown in Table 3 were used as the component (C) and the molar ratio n of the component (A) to the component (C) was set to_C/n_AColor conversion sheets were produced and evaluated in the same manner as in example 1, except that the blending amount of component (C) was adjusted to the values shown in table 3. The results are shown in Table 3. The emission intensity (relative value) in the table is a relative value when the intensity in comparative example 1 is 1.0.

Example 15

A color conversion sheet was produced in the same manner as in example 1, except that 0.10 parts by weight of the compound R-1 as the component (a) and 0.82 parts by weight of the compound S-2 as the component (C) were mixed with 100 parts by weight of the binder resin. In this case, the molar ratio n of the component (A) to the component (C)_C/n_AIs 25.

When the color conversion sheet is used to convert the color of blue LED light, a high-color-purity green emission having a peak wavelength of 635nm and a half-peak width of the emission spectrum at the peak wavelength of 50nm is obtained when only the emission region of red light is selected. When the intensity in the following comparative example 4 was regarded as a relative value of 1.0, the light emission intensity at the peak wavelength was 1.0, and no light emission inhibition by the component (C) was observed. Further, according to the above method, the light from the blue LED element was continuously irradiated in an environment of 50 ℃ and 27% RH, and as a result, the time until the luminance was decreased by 10% was 350 hours. The results are shown in Table 4.

Comparative example 4

A color conversion sheet was produced and evaluated in the same manner as in example 15, except that the component (C) was not mixed. The results are shown in Table 4. The emission intensity (relative value) in the table is a relative value when the intensity in comparative example 4 is 1.0.

Example 16 and comparative example 5

Except that the compounds shown in Table 4 were used as the component (C) and the molar ratio n of the component (A) to the component (C) was set to_C/n_AA color conversion sheet was produced and evaluated in the same manner as in example 15, except that the blending amount of component (C) was adjusted to 25. The results are shown in Table 4. The emission intensity (relative value) in the table is a relative value when the intensity in comparative example 4 is 1.0.

Example 17

A color conversion sheet was produced and evaluated in the same manner as in example 15, except that 0.1 part by weight of the compound R-2 as the component (A) and 0.53 part by weight of the compound S-4 as the component (C) were mixed with 100 parts by weight of the binder resin. In this case, the molar ratio n of the component (A) to the component (C)_C/n_AIs 25. The results are shown in Table 4. The emission intensity (relative value) in the table is a relative value when the intensity in comparative example 4 is 1.0.

[ Table 3]

[ TABLE 3]

[ Table 4]

[ TABLE 4]

Example 18

In example 18 of the present invention, an acrylic resin "Oricox KC-7000" (manufactured by Kyoeisha Co., Ltd.) was used as a binder resin, and the binder resin was used in an amount of 100 parts by weightThe resin mixture was mixed with 0.3 part by weight of Compound G-2 as component (A), 0.013 part by weight of R-1, 2.0 parts by weight of Compound S-4 as component (C), 150 parts by weight of toluene as a solvent, and 150 parts by weight of 1-methoxy-2-propanol. The mixture was stirred and defoamed at 300rpm for 30 minutes by a planetary stirring and defoaming device "MAZERUSTAR KK-400" (manufactured by Bin Pak Co., Ltd.) to obtain a color conversion composition. In this case, the molar ratio n of the component (A) to the component (C)_C/n_AIs 27.

Then, the color conversion composition was applied to "lumiror" U34 (made by Toray corporation, thickness: 75 μm) as a base material layer using a slot die coater, and heated and dried at 120 ℃ for 20 minutes to form a color conversion layer having an average film thickness of 14 μm.

The color conversion film was used to convert the color of blue LED light, and as a result, when only a light emitting region of green light was selected, high color purity green light with a peak wavelength of 527nm and a half-peak width of the emission spectrum at the peak wavelength of 32nm was obtained, and when only a light emitting region of red light was selected, high color purity green light with a peak wavelength of 625nm and a half-peak width of the emission spectrum at the peak wavelength of 50nm was obtained. The emission intensity at the peak wavelength of the green light emitting region was 1.0, and no light emission inhibition by the component (C) was observed, assuming that the intensity in comparative example 6 described later was 1.0. Similarly, the emission intensity at the peak wavelength of the emission region of red light was 1.0, and no light emission inhibition by the component (C) was observed, assuming that the intensity in comparative example 6 described later was 1.0. Further, according to the above method, the light from the blue LED element was continuously irradiated in an environment of 50 ℃ and 27% RH, and as a result, the time until the luminance was decreased by 10% was 300 hours. The results are shown in Table 5.

Comparative example 6

A color conversion sheet was produced and evaluated in the same manner as in example 18, except that the component (C) was not mixed. The results are shown in Table 5. The emission intensity (relative value) in the table is a relative value when the intensity in comparative example 6 is 1.0.

Example 19

A color conversion sheet was produced and evaluated in the same manner as in example 18, except that 0.50 parts by weight of the compound Q-1 was further mixed with 100 parts by weight of the binder resin. The results are shown in Table 5. The emission intensity (relative value) in the table is a relative value when the intensity in comparative example 6 is 1.0.

Comparative example 7

A color conversion sheet was produced and evaluated in the same manner as in example 19, except that the component (C) was not mixed. The results are shown in Table 5. The emission intensity (relative value) in the table is a relative value when the intensity in comparative example 6 is 1.0.

[ Table 5]

[ TABLE 5]

Description of the symbols

1 color conversion sheet

10 base material layer

11 colour conversion layer

11A color conversion layer

11B color conversion layer

12 Barrier layer

13 transparent intermediate layer

Claims

1. A color conversion composition that converts incident light into light having a longer wavelength than the incident light, characterized in that the color conversion composition comprises the following a-component, B-component, and C-component:

component A: at least 1 organic light emitting material;

and B component: a binder resin;

and C, component C: at least one of a boron compound, an oligosaccharide compound, a cyclic siloxane compound and an orthosilicic acid derivative,

the molar absorptivity epsilon of the component C in the whole wavelength region of 400 nm-800 nm is less than 100,

the component C at least contains a boron compound, and the boron compound is at least one of borate derivatives, mono-substituted borate derivatives, diboronate derivatives and boroxine derivatives.

2. The color conversion composition according to claim 1, wherein the molar numbers of the component A and the component C are respectively defined as n_A、n_CWhen n is greater than n_A、n_CSatisfies the following formula (1),

0.1≤n_C/n_Aless than or equal to 200 (formula-1).

3. The color conversion composition according to claim 1 or 2, wherein component C comprises at least an oligosaccharide compound that is a substituted or unsubstituted cyclic oligosaccharide.

4. The color conversion composition according to claim 1 or 2, wherein the C-component contains at least a cyclic siloxane compound, and the cyclic siloxane compound is a silsesquioxane compound.

5. The color conversion composition according to claim 1 or 2, wherein the component C contains at least an orthosilicic acid derivative, and the orthosilicic acid derivative is a tetraalkoxysilane compound.

6. The color conversion composition according to claim 1 or 2, wherein the C component is a compound that does not contain both a nitrogen atom and a phosphorus atom.

7. The color conversion composition according to claim 1 or 2, wherein the component A contains a compound represented by the general formula (1),

x is C-R⁷Or N; r¹～R⁷Each of which may be the same or different, is selected from the following groups: hydrogen, alkyl groups, cycloalkyl groups, heterocyclic groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, hydroxyl groups, mercapto groups, alkoxy groups, alkylthio groups, aryl ether groups, aryl thioether groups, aryl groups, heteroaryl groups, halogens, cyano groups, aldehyde groups, carbonyl groups, carboxyl groups, ester groups, carbamoyl groups, amino groups, nitro groups, silyl groups, siloxane groups, borane groups, sulfo groups, phosphine oxide groups, and condensed rings and aliphatic rings formed between adjacent substituents; r⁸And R⁹Each independently selected from alkyl, aryl, heteroaryl, halogen, fluoroalkyl, fluoroheteroaryl, or fluoroaryl.

8. The color conversion composition according to claim 7, wherein in the general formula (1), X is C-R⁷，R⁷Is a group represented by the general formula (2),

r is selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, alkoxy, alkylthio, aryl ether, aryl thioether, aryl, heteroaryl, halogen, cyano, aldehyde, carbonyl, carboxyl, ester, carbamoyl, amino, nitro, silyl, siloxane, borane, sulfo, phosphine oxide; k is an integer of 1 to 3; when k is 2 or more, r may be the same or different.

9. The color conversion composition according to claim 7, wherein in the general formula (1), R¹、R³、R⁴And R⁶Each of which may be the same or different, is a substituted or unsubstituted phenyl group.

10. The color conversion composition according to claim 7, wherein in the general formula (1)，R¹、R³、R⁴And R⁶Each of which may be the same or different, is a substituted or unsubstituted alkyl group.

11. The color conversion composition according to claim 7, wherein in the general formula (1), R²And R⁵At least one of the above groups may be the same or different and is a substituted or unsubstituted ester group.

12. A color conversion sheet comprising a color conversion layer obtained by curing the color conversion composition according to any one of claims 1 to 11.

13. A light source module comprising a light source and the color conversion sheet according to claim 12.

14. The light source module according to claim 13, wherein the light source is a light emitting diode having maximum light emission in a wavelength range of 400nm or more and 500nm or less.

15. A display or a lighting device comprising the light source module according to claim 13 or 14.