CN116917300A - Polycyclic aromatic compound, color conversion composition, color conversion sheet, light source unit, display, and lighting device - Google Patents

Polycyclic aromatic compound, color conversion composition, color conversion sheet, light source unit, display, and lighting device Download PDF

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CN116917300A
CN116917300A CN202280019133.6A CN202280019133A CN116917300A CN 116917300 A CN116917300 A CN 116917300A CN 202280019133 A CN202280019133 A CN 202280019133A CN 116917300 A CN116917300 A CN 116917300A
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ring
polycyclic aromatic
group
aromatic compound
color conversion
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市桥泰宜
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Toray Industries Inc
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Toray Industries Inc
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Priority claimed from PCT/JP2022/017461 external-priority patent/WO2022230643A1/en
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Abstract

The polycyclic aromatic compound as an embodiment of the present invention is a compound which exhibits luminescence observed in a region having a peak wavelength of 500nm to 750nm by using excitation light, has a HOMO level of-5.7 eV or less, and emits delayed fluorescence.

Description

Polycyclic aromatic compound, color conversion composition, color conversion sheet, light source unit, display, and lighting device
Technical Field
The invention relates to a polycyclic aromatic compound, a color conversion composition, a color conversion sheet, a light source unit, a display and a lighting device.
Background
The application of color conversion-based multicolor technology to liquid crystal displays or organic Electroluminescence (EL) displays, lighting devices, and the like is actively studied. The color conversion means converting light emission 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 sheeting a composition having the color conversion function (hereinafter referred to as "color conversion composition") and combining it with, for example, a blue light source, it is possible to extract 3 primary colors of blue, green, and red, that is, white light from the blue light source. A full-color display (full colour display) can be manufactured by combining a white light source, which is formed by combining such a blue light source and a sheet having a color conversion function (hereinafter referred to as a "color conversion sheet"), with a liquid crystal driving portion and a color filter, as a light source unit. Further, without the liquid crystal driving portion, the liquid crystal display device can be directly used as a white light source, and for example, a white light source such as a light emitting diode (light emitting diode, LED) lighting can be applied.
As a problem of the liquid crystal display, improvement of color reproducibility is exemplified. In order to improve color reproducibility, it is effective to narrow the half-widths of the emission spectra of the blue, green, and red colors of the light source unit, thereby improving the color purity of each of the blue, green, and red colors. As a means for solving the above-mentioned problems, a technique has been proposed in which quantum dots of inorganic semiconductor fine particles are used as components of a color conversion composition (for example, refer to patent document 1). In the above-described technique using quantum dots, the half-value width of the emission spectrum of green and red is surely small and the color reproducibility is improved, but on the other hand, the quantum dots are weak in tolerance to heat, moisture in air, or oxygen, and insufficient in durability.
In addition, a technique of using a light-emitting material of an organic substance as a component of a color conversion composition instead of quantum dots has also been proposed. As an example of a technique using an organic light-emitting material as a component of a color conversion composition, a technique using a pyrrole methylene derivative is disclosed (for example, refer to patent documents 1 and 2).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2011-241160
Patent document 2: japanese patent laid-open publication No. 2014-136771
Disclosure of Invention
Problems to be solved by the invention
However, even when these organic light-emitting materials are used to produce a color conversion composition, the production is insufficient from the viewpoints of improvement in color reproducibility and durability. In particular, a technique for achieving both high-color purity green emission and high durability is insufficient.
The object of the present invention is to provide an organic light-emitting material which is preferable as a color conversion material for use in a display such as a liquid crystal display or an illumination device such as an LED illumination, and which has both improved color reproducibility and high durability.
Technical means for solving the problems
That is, in order to solve the above problems and achieve the object, the polycyclic aromatic compound according to the present invention is characterized in that: a compound which emits delayed fluorescence when excited light is used and exhibits luminescence observed in a region having a peak wavelength of 500nm to 750nm inclusive, and has a highest occupied molecular orbital (Highest Occupied Molecular Orbital, HOMO) energy level of-5.7 eV or less.
The polycyclic aromatic compound according to the present invention is characterized in that: in the above invention, the HOMO level of the polycyclic aromatic compound is-6.0 eV or less.
The polycyclic aromatic compound according to the present invention is characterized in that: in the above invention, the HOMO level of the polycyclic aromatic compound is-6.2 eV or less.
The polycyclic aromatic compound according to the present invention is characterized in that: in the above invention, the HOMO level of the polycyclic aromatic compound is-6.5 eV or less.
The polycyclic aromatic compound according to the present invention is characterized in that: in the above invention, the half-width of the emission spectrum of the polycyclic aromatic compound at the emission peak wavelength is 40nm or less.
The polycyclic aromatic compound according to the present invention is characterized in that: in the above invention, the polycyclic aromatic compound is a compound represented by the general formula (1) or the general formula (2).
[ chemical 1]
(Ring Za, ring Zb and ring Zc are each independently a substituted or unsubstituted aryl ring having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl ring having 6 to 30 carbon atoms; Z 1 Z is as follows 2 Each independently is an oxygen atom, NRa (nitrogen atom having substituent Ra), or a sulfur atom; at Z 1 In the case of NRa, the substituent Ra may bond to the ring Za or the ring Zb to form a ring; at Z 2 In the case of NRa, the substituent Ra may bond to the ring Za or the ring Zc to form a ring; e is a boron atom, a phosphorus atom, a SiRa (silicon atom having a substituent Ra), or p=o; e (E) 1 E and E 2 Each independently is BRa (boron atom having substituent Ra), PRa (phosphorus atom having substituent Ra), siRa 2 (silicon atom having two substituents Ra), P (=O) Ra 2 (phosphine oxide having two substituents Ra) or P (=S) Ra 2 (phosphine sulfide having two substituents Ra), S (=o) or S (=o) 2 The method comprises the steps of carrying out a first treatment on the surface of the At E 1 BRa, PRa, siRa of a shape of BRa, PRa, siRa 2 、P(＝O)Ra 2 Or P (=S) Ra 2 In the above, the substituent Ra may be bonded to the ring Za or the ring Zb to form a ring; at E 2 BRa, PRa, siRa of a shape of BRa, PRa, siRa 2 、P(＝O)Ra 2 Or P (=S) Ra 2 In the above, the substituent Ra may be bonded to the ring Za or the ring Zc to form a ring; the substituents Ra are each independently substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted alkyl
The polycyclic aromatic compound according to the present invention is characterized in that: in the invention, the compound represented by the general formula (1) or the general formula (2) has at least one electron withdrawing group.
The polycyclic aromatic compound according to the present invention is characterized in that: in the invention, the compound represented by the general formula (1) or the general formula (2) has two or more electron withdrawing groups.
The polycyclic aromatic compound according to the present invention is characterized in that: in the invention, the electron withdrawing group is a cyano group, an acyl group, an ester group, an amide group, a sulfonyl group, a sulfonate group, or a sulfonamide group.
The polycyclic aromatic compound according to the present invention is characterized in that: in the invention, the electron withdrawing group is an ester group.
The polycyclic aromatic compound according to the present invention is characterized in that: in the invention, the Z 1 The Z is 2 Is an oxygen atom or NRa.
The polycyclic aromatic compound according to the present invention is characterized in that: in the invention, the E is a boron atom, and 1 the E is 2 Is BRa.
The polycyclic aromatic compound according to the present invention is characterized in that: in the above invention, the ring Za, the ring Zb, and the ring Zc are benzene rings.
The polycyclic aromatic compound according to the present invention is characterized in that: in the invention, the polycyclic aromatic compound exhibits luminescence observed in a region having a peak wavelength of 500nm or more and less than 580nm by using excitation light.
The polycyclic aromatic compound according to the present invention is characterized in that: in the above invention, the polycyclic aromatic compound exhibits luminescence observed in a region having a peak wavelength of 580nm or more and 750nm or less by using excitation light.
The color conversion composition according to the present invention is a color conversion composition for converting incident light into light different from the incident light, and is characterized by comprising: comprising the polycyclic aromatic compound according to any one of the above, and a binder resin.
The color conversion sheet according to the present invention is a color conversion sheet for converting incident light into light different from the incident light, and is characterized by comprising: comprising the polycyclic aromatic compound according to any one of the above, and a binder resin.
The color conversion sheet according to the present invention is characterized in that: in the invention, a barrier film is further provided.
The light source unit according to the present invention is characterized by comprising: a light source, and a color conversion sheet as described in any one of the above.
The light source unit according to the present invention is characterized in that: in the invention, the light source is a light emitting diode having maximum light emission in a wavelength range of 430nm to 500 nm.
The display according to the present invention is characterized by comprising: the color conversion sheet described in any one of the above.
The lighting device according to the present invention is characterized by comprising: the color conversion sheet described in any one of the above.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, the following effects are exhibited: a polycyclic aromatic compound and a color conversion composition which are preferable as a color conversion material capable of improving color reproducibility and having high durability can be realized. The color conversion sheet according to the present invention uses such a polycyclic aromatic compound and the like, and therefore exhibits an effect of improving color reproducibility and achieving high durability. The light source unit, the display, and the lighting device according to the present invention use such a color conversion sheet, and therefore, can exhibit an effect of improving color reproducibility and achieving high durability.
Drawings
Fig. 1 is a schematic cross-sectional view showing a first example of a color conversion sheet according to an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view showing a second example of the color conversion sheet according to the embodiment of the present invention.
Fig. 3 is a schematic cross-sectional view showing a third example of the color conversion sheet according to the embodiment of the present invention.
Fig. 4 is a schematic cross-sectional view showing a fourth example of the color conversion sheet according to the embodiment of the present invention.
Detailed Description
Hereinafter, preferred embodiments of the polycyclic aromatic compound, the color conversion composition, the color conversion sheet, the light source unit, the display and the lighting device according to the present invention will be specifically described, but the present invention is not limited to the following embodiments, and may be variously modified according to purposes or applications.
< polycyclic aromatic Compounds >)
The polycyclic aromatic compound according to the embodiment of the present invention is a color conversion material constituting a color conversion composition, a color conversion sheet, or the like. Specifically, the polycyclic aromatic compound emits light in a region having a peak wavelength of 500nm to 750nm, which is observed by using excitation light, has a HOMO level of-5.7 eV or less, and emits delayed fluorescence. Hereinafter, the polycyclic aromatic compound according to the embodiment of the present invention may be simply referred to as "the polycyclic aromatic compound of the present invention".
(luminescence wavelength)
The polycyclic aromatic compound of the present invention is a compound that exhibits luminescence observed in a region having a peak wavelength of 500nm to 750nm by using excitation light. For example, the polycyclic aromatic compound of the present invention preferably exhibits luminescence observed in a region having a peak wavelength of 500nm or more and less than 580nm by using excitation light. Hereinafter, the emission observed in a region having a peak wavelength of 500nm or more and less than 580nm is referred to as "green emission".
The polycyclic aromatic compound of the present invention preferably exhibits green luminescence by using excitation light having a wavelength in a range of 430nm to 500 nm. In general, the larger the energy of the excitation light is, the more easily the light-emitting material is decomposed. However, the excitation light having a wavelength of 430nm or more and 500nm or less has a relatively small excitation energy. Therefore, the decomposition of the light-emitting material in the color conversion composition is suppressed, and green light emission with good color purity can be obtained.
The polycyclic aromatic compound of the present invention preferably exhibits luminescence observed in a region having a peak wavelength of 580nm or more and 750nm or less by using excitation light. Hereinafter, the luminescence observed in a region having a peak wavelength of 580nm or more and 750nm or less is referred to as "red luminescence".
The polycyclic aromatic compound of the present invention preferably exhibits red luminescence by using excitation light having a wavelength in a range of 430nm to 500 nm. In general, the larger the energy of the excitation light is, the more easily the light-emitting material is decomposed. However, the excitation light having a wavelength of 430nm or more and 500nm or less has a relatively small excitation energy. Therefore, the decomposition of the light-emitting material in the color conversion composition is suppressed, and the light emission of red with good color purity can be obtained.
(delayed fluorescence)
Since a compound that emits delayed fluorescence is rapidly converted from its triplet excited state to its singlet excited state, it is characterized in that it is difficult to generate singlet oxygen. Further, it has been found that by the above feature, deterioration of the light emitting material is prevented, and temporal change in chromaticity is suppressed, thereby improving durability. The present mechanism is explained in turn.
First, a degradation mechanism of a light emitting material is explained. The chromaticity change of the color conversion composition is caused by the deterioration of the luminescent material. The degradation of such luminescent materials is caused by singlet oxygen. Singlet oxygen is an oxygen molecule in which the spins of two electrons in pi orbitals (anti-bonding pi orbitals) that enter the molecular orbital of the oxygen molecule are oriented in different singlet states, that is, in an excited state in which all spin quanta are 0. In such an excited state, there are a Σ1 state in which electrons having different spin orientations each occupy each of the orbitals of pi where two exist, and a Δ1 state in which two electrons having different spin orientations each occupy only one of the pi orbitals. Singlet oxygen has a strong electrophilicity with an empty electron orbit in the Δ1 state and a strong oxidizing power. Therefore, singlet oxygen is considered to cause deterioration due to oxidation of the light emitting material.
Next, the mechanism of singlet oxygen generation will be described. Singlet oxygen is considered to be difficult to directly generate triplet oxygen in a basic state by photoexcitation. The reason for this is that: the transition from triplet oxygen of the base state to singlet oxygen of the excited state is a spin-forbidden transition, and therefore the transition probability is very low.
Thus, it is believed that the generation of singlet oxygen in the color conversion composition is caused by the dye sensitization. That is, it is considered that singlet oxygen is generated by exchange of electrons and energy between triplet excited states of the light emitting material and triplet oxygen molecules in a basic state. The mechanism of its generation is considered as follows.
First, a light-emitting material is changed from a singlet basic state to a singlet excited state by light excitation, and further, a part of the light-emitting material is changed from a singlet excited state to a triplet excited state by intersystem crossing. The transition from the triplet excited state to the singlet basic state of the light emitting material produced is a spin-forbidden transition, and therefore the probability of transition is generally low and the lifetime of the triplet excited state is long. However, in the case where triplet oxygen in the basic state is present together, the spin inhibition is released by the excitation of singlet oxygen from the triplet oxygen in the basic state to the excited state, and thus the light-emitting material can be rapidly deactivated from the triplet excited state to the singlet basic state. This mechanism is called the Dexter mechanism (electron exchange mechanism).
In order to advance the texel mechanism, an overlapping electron exchange via the intermolecular wave function is required. Therefore, it is considered that the energy donor molecule (the light-emitting material in the triplet excited state in this case) and the energy acceptor molecule (the triplet oxygen in the basic state in this case) need to collide directly.
As described above, the compound that emits delayed fluorescence has a property that the triplet excited state is rapidly converted into the singlet excited state, that is, the triplet excited state has a short lifetime. Therefore, the probability of direct collision of the triplet excited state of the light emitting material with triplet oxygen in the basic state becomes small, and it is difficult to generate singlet oxygen.
As described above, the polycyclic aromatic compound of the present invention is a compound that emits delayed fluorescence, whereby the generation of singlet oxygen can be suppressed, and the durability of the color conversion composition can be improved.
(HOMO energy level)
The polycyclic aromatic compound of the present invention is a light-emitting material having a HOMO energy level of-5.7 eV or less. When the HOMO level of the light-emitting material is higher than-5.7 eV, the light-emitting material is oxidized and quenched by interaction with oxygen contained in the composition containing the light-emitting material when the cycle of excitation-light emission is repeated, and thus the durability is deteriorated. By the HOMO level of the light-emitting material being-5.7 eV or less, the electron density of the light-emitting material decreases. This improves the stability of the light-emitting material against oxygen and improves the durability.
According to the above, by using a compound which has a HOMO level of-5.7 eV or less and emits delayed fluorescence as a light-emitting material (the polycyclic aromatic compound of the present invention), the generation of singlet oxygen can be suppressed, and the reaction of part of the generated singlet oxygen with the light-emitting material can be suppressed. Accordingly, the durability of the polycyclic aromatic compound of the present invention can be improved, and further the durability of the color conversion composition including the polycyclic aromatic compound can be improved.
The HOMO level of the polycyclic aromatic compound of the present invention is preferably-6.0 eV or less. If the HOMO level of the compound is-6.0 eV or less, the electron density of the compound can be further reduced. Therefore, the stability to oxygen of the polycyclic aromatic compound of the present invention is improved, and the durability of the polycyclic aromatic compound can be improved. From the viewpoint of further improving the effect, the HOMO level of the polycyclic aromatic compound of the present invention is more preferably-6.2 eV or less, and still more preferably-6.5 eV or less.
The HOMO level of a compound can be calculated by calculation. In the present invention, the following values are set: the structure was optimized by using the general Quantum chemistry calculation program "Gaussian" 16 "package (Gaussian) manufactured by Gaussian), using the B3LYP density functional theory, and the values calculated by calculating the structure based on the optimized structure using the B3LYP density functional theory and the 6-311++ G (d, p) basis.
(half value width)
The half-width of the emission spectrum of the polycyclic aromatic compound of the present invention at the emission peak wavelength is preferably 40nm or less, more preferably 30nm or less, and even more preferably 25nm or less, from the viewpoint of obtaining high color purity emission and achieving a high color gamut of the display when used in a liquid crystal display.
(chemical structure)
The polycyclic aromatic compound of the present invention is not particularly limited, and is preferably a compound having a structure represented by the following general formula (1) or general formula (2).
[ chemical 2]
In the general formula (1) or the general formula (2), the ring Za, the ring Zb and the ring Zc are each independently a substituted or unsubstituted ring forming an aryl ring having 6 to 30 carbon atoms or a substituted or unsubstituted ring forming a heteroaryl ring having 6 to 30 carbon atoms.
In the general formula (1), Z 1 Z is as follows 2 Each independently is an oxygen atom, NRa (nitrogen atom having substituent Ra), or a sulfur atom. At Z 1 In the case of NRa, the substituent Ra may bond to the ring Za or the ring Zb to form a ring. At Z 2 In the case of NRa, the substituent Ra may bond to the ring Za or the ring Zc to form a ring. E is a boron atom, a phosphorus atom, a SiRa (silicon atom having a substituent Ra), or p=o.
In the general formula (2), E 1 E and E 2 Each independently is BRa (boron atom having substituent Ra), PRa (phosphorus atom having substituent Ra), siRa 2 (silicon atom having two substituents Ra), P (=O) Ra 2 (phosphine oxide having two substituents Ra) or P (=S) Ra 2 (phosphine sulfide having two substituents Ra), S (=o) or S (=o) 2 . At E 1 BRa, PRa, siRa of a shape of BRa, PRa, siRa 2 、P(＝O)Ra 2 Or P (=S) Ra 2 In the above case, the substituent Ra may be bonded to the ring Za or the ring Zb to form a ring. At E 2 BRa, PRa, siRa of a shape of BRa, PRa, siRa 2 、P(＝O)Ra 2 Or P (=S) Ra 2 In the above case, the substituent Ra may be bonded to the ring Za or the ring Zc to form a ring.
The substituents Ra are each independently a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, or a substituted or unsubstituted alkyl.
In all of the radicals, hydrogen may be deuterium. The same applies to the compounds described below or part of their structures. In addition, all of the groups may be substituted or unsubstituted groups. In the compounds or partial structures thereof described below, the compounds or partial structures thereof may be substituted or unsubstituted. In the following description, for example, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms refers to an aryl group having 6 to 40 carbon atoms including all carbon atoms contained in a substituent in which an aryl group is substituted. The same applies to other substituents having a predetermined carbon number.
Among these groups, the substituent at the time of substitution is preferably an alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, arylene sulfide group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, acyl group, ester group, amide group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxane group, oxyboronyl group, or phosphine oxide group, and further, a specific substituent is preferable in the description of each substituent. In addition, these substituents may be further substituted with the substituents.
By "unsubstituted" in the case of reference to "substituted or unsubstituted" is meant that a hydrogen atom or deuterium atom is substituted. In the compounds described below or part of the structures thereof, the case where "substituted or unsubstituted" is mentioned is also the same as described.
The alkyl group in all the above groups represents, for example, a saturated aliphatic hydrocarbon group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl, and may or may not have a substituent. The additional substituent in the case of substitution is not particularly limited, and examples thereof include: alkyl, halogen, aryl, heteroaryl, and the like are also described below. The carbon number of the alkyl group is not particularly limited, but is preferably in the range of 1 to 20, more preferably in the range of 1 to 8, in terms of ease of acquisition and cost.
The alkylene group means a divalent or more group derived from a saturated aliphatic hydrocarbon group such as a methyl group or an ethyl group, and these may or may not have a substituent. As the preferable alkylene group, there may be mentioned: methylene, ethylene, n-propylene, isopropylene, n-butylene, pentylene, and hexylene. The carbon number of the alkylene moiety is not particularly limited, and is preferably in the range of 1 to 20, more preferably in the range of 1 to 6.
The cycloalkyl group means a saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group, and may or may not have a substituent. The carbon number of the alkyl moiety is not particularly limited, and is preferably in the range of 3 to 20.
The cycloalkyl group means a divalent or more group derived from a saturated alicyclic hydrocarbon group such as a cyclopropyl group or a cyclohexyl group, and may have a substituent or may have no substituent. As a preferred cycloalkylene group, there may be mentioned: saturated alicyclic hydrocarbon groups such as cyclopropyl group, cyclohexyl group, norbornylene group and adamantylene group. The number of carbons of the cycloalkylene moiety is not particularly limited, and is preferably in the range of 3 to 20.
The heterocyclic group means, for example, an aliphatic ring having an atom other than carbon in the ring, such as a pyran ring, a piperidine ring, and 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 means 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 carbon number of the alkenyl group is not particularly limited, and is preferably in the range of 2 to 20.
The cycloalkenyl group means an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, or a cyclohexenyl group, and may or may not have a substituent. The carbon number of the cycloalkenyl group is not particularly limited, and is preferably in the range of 3 to 20.
The alkynyl group means 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 carbons of the alkynyl group is not particularly limited, and is preferably in the range of 2 to 20.
The alkoxy group means a functional group in which an aliphatic hydrocarbon group, which may or may not have a substituent, is bonded to the methoxy group, ethoxy group, propoxy group, or the like via an ether bond. The carbon number of the alkoxy group is not particularly limited, and is preferably in the range of 1 to 20.
Alkylthio refers to an alkylthio group in which an oxygen atom of an ether bond of an alkoxy group is replaced with a sulfur atom. The hydrocarbyl group of the alkylthio group may or may not have a substituent. The carbon number of the alkylthio group is not particularly limited, and is preferably in the range of 1 to 20.
The aryl ether group means a functional group such as a phenoxy group to which an aromatic hydrocarbon group is bonded via an ether bond, and the aromatic hydrocarbon group may or may not have a substituent. The carbon number of the aryl ether group is not particularly limited, and is preferably in the range of 6 to 40.
The term "arylene sulfide" refers to an arylene sulfide in which an oxygen atom of an ether bond of an arylene ether group is replaced with a sulfur atom. The aromatic hydrocarbon group in the arylene sulfide group may have a substituent or may not have a substituent. The carbon number of the arylene sulfide group is not particularly limited, and is preferably in the range of 6 to 40.
The aryl group means an aromatic hydrocarbon group such as a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenanthryl group, an anthryl group, a benzophenanthryl group, a 1, 2-benzophenanthryl group, a pyrenyl group, a propylene [ di ] alkenylfluorenyl group (fluoranthenyl group), a triphenylene group (triphenylenyl group), a benzo [ di ] alkenylfluorenyl group, a dibenzoanthracenyl group, a perylenyl group, a helical hydrocarbon group (helicenyl group), or the like. Among them, phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthryl, anthracenyl, pyrenyl, prop [ di ] alkenylfluorenyl, triphenylenyl are preferable. Aryl groups may or may not have substituents. In the case where an aryl group has a substituent, the substituents may form a cyclic structure with each other. Examples of the aryl group having a cyclic structure as a substituent include a spirofluorene group. The carbon number of the aryl group is not particularly limited, but is preferably in the range of 6 to 100, more preferably in the range of 6 to 50, and even more preferably in the range of 6 to 30.
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 anthracyl group, and more preferably a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group. Phenyl is particularly preferred.
The heteroaryl group means, for example, a cyclic aromatic group having an atom other than carbon in one or more rings such as pyridyl, furyl, thienyl, quinolinyl, isoquinolinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, naphthyridinyl, cinnolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, benzofuryl, benzothienyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, carbolinyl (carbolinyl group), indolocarbazolyl, benzofurocarbazolyl, benzothiocarbazolyl, indanocarbazolyl, benzoquinolinyl, acridinyl, dibenzoacridinyl, benzimidazolyl, imidazopyridyl, benzoxazolyl, benzothiazolyl, phenanthroline, and the like. Wherein naphthyridinyl refers to any one of 1, 5-naphthyridinyl, 1, 6-naphthyridinyl, 1, 7-naphthyridinyl, 1, 8-naphthyridinyl, 2, 6-naphthyridinyl and 2, 7-naphthyridinyl. Heteroaryl groups may or may not have substituents. The carbon number of the heteroaryl group is not particularly limited, but is preferably in the range of 2 to 40, more preferably in the range of 2 to 30.
In the case where 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 pyrimidinyl group, a triazinyl group, a benzofuryl group, a benzothienyl group, an indolyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, a benzimidazolyl group, an imidazopyridyl group, a benzoxazolyl group, a benzothiazolyl group, a phenanthroline group, and more preferably a pyridyl group, a furyl group, a thienyl group, or a quinolyl group. Particularly preferred is a pyridyl group.
Halogen means an atom selected from fluorine, chlorine, bromine and iodine. The carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group may have a substituent or may not have a substituent. Examples of the substituent include: alkyl, cycloalkyl, aryl, heteroaryl, etc., which substituents may also be further substituted. The carbon number of the carbonyl group is not particularly limited, and is preferably in the range of 6 to 40.
The ester group means, for example, a functional group in which an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, or the like is bonded via an ester bond, and the substituent may be further substituted. The carbon number of the ester group is not particularly limited, but is preferably in the range of 1 to 200, more preferably 1 to 100. More specifically, examples of the ester group include: methyl ester groups such as methoxycarbonyl groups, ethyl ester groups such as ethoxycarbonyl groups, propyl ester groups such as propoxycarbonyl groups, butyl ester groups such as butoxycarbonyl groups, isopropyl ester groups such as isopropoxymethoxycarbonyl groups, hexyl ester groups such as hexyloxycarbonyl groups, phenyl ester groups such as phenoxycarbonyl groups.
The amide group means a functional group in which a substituent such as an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group is bonded via an amide bond, and the substituent may be further substituted. The carbon number of the amide group is not particularly limited, and is preferably in the range of 1 to 20. More specifically, as the amide group, there may be mentioned: methylamido, ethylamido, propylamido, butylamido, isopropylamido, hexylamido, phenylamido, and the like.
Amino refers to a substituted or unsubstituted amino group. The amino group may have a substituent or may not have a substituent, and examples of the substituent when substituted include: aryl, heteroaryl, straight chain alkyl, branched alkyl. The aryl group and heteroaryl group are preferably phenyl, naphthyl, pyridyl, or quinolyl. These substituents may be further substituted. The carbon number is not particularly limited, but is preferably in the range of 2 to 50, more preferably in the range of 6 to 40, and particularly preferably in the range of 6 to 30.
The silane group means, for example, an alkylsilane group such as trimethylsilyl group, triethylsilane group, t-butyldimethylsilyl group, propyldimethylsilyl group, or vinyldimethylsilyl group, or an arylsilane group such as phenyldimethylsilyl group, t-butyldiphenylsilane group, triphenylsilane group, or trinaphthylsilane group. The substituents on the silicon may also be further substituted. The number of carbons of the silane group is not particularly limited, and is preferably in the range of 1 to 30.
The siloxane group means, for example, a silicon compound group such as a trimethylsiloxane group via an ether bond. The substituents on the silicon may also be further substituted. The number of carbons of the siloxane group is not particularly limited, and is preferably in the range of 1 to 30. The oxyboronyl group means a substituted or unsubstituted oxyboronyl group. The oxyboronyl group may have a substituent or may not have a substituent, and examples of the substituent at the time of substitution include: aryl, heteroaryl, straight chain alkyl, branched alkyl, aryl ether, alkoxy, hydroxy. Among them, aryl groups and aryl ether groups are preferable. The carbon number of the oxyboronyl group is not particularly limited, and is preferably in the range of 1 to 30.
The acyl group means a functional group in which a substituent such as an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group is bonded via a carbonyl group, and the substituent may be further substituted. The carbon number of the acyl group is not particularly limited, and is preferably in the range of 1 to 20. More specifically, examples of the acyl group include an acetyl group, a propionyl group, a benzoyl group, an acryl group, and the like.
Sulfonyl represents, for example, alkyl, cycloalkyl, aryl, heteroaryl, etc., substituents via-S (=o) 2 -a bonded functional group, said substituent may also be further substituted. Carbon number of sulfonyl groupThe range is not particularly limited, and is preferably 1 to 30.
The sulfoxide group means a functional group in which a substituent such as an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group is bonded via an-S (=o) -bond, and the substituent may be further substituted. The carbon number of the sulfoxide group is not particularly limited, and is preferably in the range of 1 to 30.
The term "phosphino" means a group represented by-P (=O) R 10 R 11 A group represented. R of phosphine oxide group 10 R is R 11 Can be selected in the same manner as the substituent Ra. The number of carbon atoms of the phosphine oxide group is not particularly limited, and is preferably in the range of 1 to 30.
Examples of the ring-forming aryl ring having 6 to 30 carbon atoms include: benzene ring, naphthalene ring, fluorene ring, benzofluorene ring, dibenzofluorene ring, phenanthrene ring, anthracene ring, benzophenanthrene ring, benzanthracene ring, 1, 2-benzophenanthrene ring, pyrene ring, prop [ di ] enefluorene ring, triphenylene ring, benzo [ di ] enefluorene ring, dibenzoanthracene ring, perylene ring, spiral hydrocarbon ring, and the like.
Examples of the heteroaryl ring having 6 to 30 carbon atoms are: pyridine ring, furyl, thiophene ring, quinoline ring, isoquinoline ring, pyrazine ring, pyrimidine ring, pyridazine ring, naphthyridine ring, cinnoline ring, phthalazine ring, quinoxaline ring, quinazoline ring, benzofuran ring, benzothiophene ring, indole ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring, benzocarbazole ring, carboline ring, indolocarbazole ring, benzofurocarbazole ring, benzothiocarbazole ring, indanocarbazole ring, benzoquinoline ring, acridine ring, dibenzoacridine ring, imidazole ring, oxazole ring, thiazole ring, benzimidazole ring, imidazopyridine ring, benzoxazole ring, benzothiazole ring, phenanthroline ring, and the like.
The compound represented by the general formula (1) or the general formula (2) has a strong skeleton with high planarity. Therefore, the compound represented by the general formula (1) or the general formula (2) exhibits a high luminescence quantum yield, and the peak half-width of the luminescence spectrum of the compound represented by the general formula (1) or the general formula (2) is small. Therefore, the compound represented by the general formula (1) or the general formula (2) can achieve high efficiency of color conversion and high color purity.
In addition, the compound represented by the general formula (1) or the general formula (2) is a compound which emits delayed fluorescence by using an electron donating substituent and an electron accepting substituent to localize HOMO and the lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbital, LUMO) in the molecule, thereby efficiently causing an intersystem crossing from a triplet excited state to a singlet excited state. Therefore, the durability of the compound represented by the general formula (1) or the general formula (2) can be improved.
In addition, in the case where the compound represented by the general formula (1) or the general formula (2) has at least one electron withdrawing group, the electron density of the compound represented by the general formula (1) or the general formula (2) is lowered as compared with the case where the compound does not have an electron withdrawing group. Thus, the stability of the compound represented by the general formula (1) or the general formula (2) to singlet oxygen is improved, and as a result, the durability of the compound is further improved. Therefore, the compound represented by the general formula (1) or the general formula (2) preferably has at least one electron withdrawing group.
The compound represented by the general formula (1) or the general formula (2) preferably has at least one electron withdrawing group as a substituent of the ring Za, the ring Zb or the ring Zc, or at least one electron withdrawing group as a substituent in the ring when these rings form a ring with an adjacent group. Examples of the latter include those having an electron withdrawing group as Z 1 Substituents in the ring when NRa and substituent Ra bonds to ring Zb to form a ring.
The compound represented by the general formula (1) or the general formula (2) preferably has two or more electron withdrawing groups. Thus, the stability of the compound represented by the general formula (1) or the general formula (2) to singlet oxygen is further improved, and as a result, the durability of the compound is further improved.
The electron withdrawing group is also called an electron accepting group, and in the organic electronics theory, an electron is attracted from a substituted radical by an induction effect or a resonance effect. Examples of the electron withdrawing group include electron withdrawing groups having a positive value as a substituent constant (σp (para)) in Hammett's rule. The substituent constant (σp (para)) of the Hammett's law can be referenced from the chemical review base revision 5 (pages II-380). Further, the electron withdrawing group of the present invention does not include a phenyl group, although a phenyl group may take a positive value.
Preferable examples of the electron withdrawing group include: cyano, acyl, ester, amide, sulfonyl, sulfonate or sulfonamide groups. These groups can effectively reduce the electron density of the basic skeleton. Further, these groups are preferable because they have a proper polarity, and therefore, the solubility of the compound represented by the general formula (1) or the general formula (2) in a solvent, a resin, or the like is improved in the production of the color conversion composition. Thus, the stability of the compound represented by the general formula (1) or the general formula (2) to singlet oxygen is further improved, and as a result, the durability of the compound is further improved.
Particularly preferred examples of electron withdrawing groups are ester groups. When the electron withdrawing group is an ester group, the electron density of the basic skeleton can be appropriately reduced without expanding the conjugation of the basic skeleton. Therefore, the compound represented by the general formula (1) or the general formula (2) can further improve the durability without impairing the luminous efficiency and the color purity.
Among the ester groups, a fluorine-containing ester group (an ester group containing a fluorine atom) is particularly preferable. For example, the alkyl ester group such as methyl ester group or the aryl ester group such as phenyl ester group is preferably substituted with a fluorine atom or a group containing a fluorine atom. Examples of the methyl ester group substituted with a fluorine atom include a trifluoromethyl ester group and the like. Examples of the phenyl ester group substituted with a group containing a fluorine atom include a trifluoromethylphenyl group, a (3, 5-bistrifluoromethylphenyl) phenyl ester group, and the like.
In addition, the electron withdrawing group is preferably sterically bulky. If the electron-withdrawing matrix is large, the degree of freedom in molecular movement of the compound represented by the general formula (1) or the general formula (2) is reduced due to the structure, and the molecular movement in the resin is suppressed. In addition, the electron withdrawing group functions as a steric hindrance group, and thus the compounds represented by the general formula (1) or the general formula (2) do not interact with each other, thereby further improving the stability. Thus, the electron withdrawing group is sterically bulky, whereby aggregation of molecules can be suppressed, and durability of the compound represented by the general formula (1) or the general formula (2) can be improved.
The number of carbons constituting the electron withdrawing group is not particularly limited, but is preferably in the range of 2 to 200, more preferably in the range of 6 to 200, and particularly preferably in the range of 20 to 200.
In the general formula (1), Z 1 Z is as follows 2 Preferably an oxygen atom or NRa. The reason for this is that: the pi-conjugated system of the compound represented by the general formula (1) expands efficiently and further efficiently causes a transition from a triplet excited state to a singlet excited state, and thus the durability of the compound can be further improved.
In the general formula (1) or the general formula (2), E is preferably a boron atom, E 1 E and E 2 BRa is preferred. The reason for this is that: the pi conjugated system of the compound represented by the general formula (1) or the general formula (2) efficiently expands and further efficiently causes the inversion system to cross from the triplet excited state to the singlet excited state, and thus the durability of the compound can be further improved.
In the general formula (1) or the general formula (2), the ring Za, the ring Zb, and the ring Zc are preferably benzene rings. The reason for this is that: the pi conjugated system of the compound represented by the general formula (1) or the general formula (2) efficiently expands and further efficiently causes the inversion system to cross from the triplet excited state to the singlet excited state, and thus the durability of the compound can be further improved.
The following shows an example of the polycyclic aromatic compound of the present invention, but the polycyclic aromatic compound of the present invention is not limited to these.
[ chemical 3]
[ chemical 4]
The polycyclic aromatic compound of the present invention can be produced by referring to, for example, the method described in Japanese patent application laid-open No. 2020-097561, international publication No. 2015/102118, or International publication No. 2019/164340. That is, the target polycyclic aromatic compound can be obtained by reacting the halogen compound with the boron raw material in the coexistence of butyllithium. However, the present invention is not limited thereto.
Further, in the case of introducing an aryl group or a heteroaryl group, a method of forming a carbon-carbon bond by a coupling reaction between a halogenated derivative and boric acid or a boric acid esterified derivative is exemplified, but the present invention is not limited thereto. Similarly, when the electron withdrawing group is introduced, for example, a halogenated derivative in which the electron withdrawing group is substituted is used as a raw material or introduced by various reactions after the skeleton is formed, but the present invention is not limited thereto.
(polycyclic aromatic Compounds according to other aspects of the invention)
The polycyclic aromatic compound according to another aspect of the present invention is a compound represented by general formula (11) or general formula (12), and has at least one electron withdrawing group.
[ chemical 5]
In the general formula (11) or the general formula (12), the ring Za, the ring Zb and the ring Zc are each independently a substituted or unsubstituted ring forming an aryl ring having 6 to 30 carbon atoms or a substituted or unsubstituted ring forming a heteroaryl ring having 6 to 30 carbon atoms.
In the general formula (11), Z 1 Z is as follows 2 Each independently is an oxygen atom, NRa (nitrogen atom having substituent Ra), or a sulfur atom. At Z 1 In the case of NRa, the substituent Ra may bond to the ring Za or the ring Zb to form a ring. At Z 2 In the case of NRa, the substituent Ra may bond to the ring Za or the ring Zc to form a ring. E is a boron atom, a phosphorus atom, a SiRa (silicon atom having a substituent Ra), or p=o.
In the general formula (12), E 1 E and E 2 Each independently is BRa (boron atom having substituent Ra), PRa (phosphorus atom having substituent Ra), siRa 2 (withSilicon atom of two substituents Ra), P (=o) Ra 2 (phosphine oxide having two substituents Ra) or P (=S) Ra 2 (phosphine sulfide having two substituents Ra), S (=o) or S (=o) 2 . At E 1 BRa, PRa, siRa of a shape of BRa, PRa, siRa 2 、P(＝O)Ra 2 Or P (=S) Ra 2 In the above case, the substituent Ra may be bonded to the ring Za or the ring Zb to form a ring. At E 2 BRa, PRa, siRa of a shape of BRa, PRa, siRa 2 、P(＝O)Ra 2 Or P (=S) Ra 2 In the above case, the substituent Ra may be bonded to the ring Za or the ring Zc to form a ring.
The substituents Ra are each independently a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, or a substituted or unsubstituted alkyl. The compound represented by the general formula (11) or the general formula (12) has at least one electron withdrawing group.
The compound represented by the general formula (11) is a compound having at least one electron withdrawing group among the compounds represented by the general formula (1). The compound represented by the general formula (12) is a compound having at least one electron withdrawing group among the compounds represented by the general formula (2). The description of each group in the compound represented by the general formula (11) or the general formula (12) is the same as that in the compound represented by the general formula (1) or the general formula (2).
The compound represented by the general formula (11) or the general formula (12) has at least one electron withdrawing group, and thus the electron density of the compound represented by the general formula (11) or the general formula (12) is reduced as compared with the case where the compound does not have an electron withdrawing group. Thus, the stability of the compound represented by the general formula (11) or the general formula (12) to singlet oxygen is improved, and as a result, the durability of the compound is particularly improved. Therefore, in the case of the compound represented by the general formula (11) or the general formula (12), the following effects are exhibited regardless of whether the HOMO level is-5.7 eV or less: a polycyclic aromatic compound and a color conversion composition which are preferable as a color conversion material capable of improving color reproducibility and having high durability can be realized.
< color conversion composition >)
The color conversion composition according to the embodiment of the present invention is a composition that converts incident light from a light-emitting body such as a light source into light having a wavelength different from that of the incident light, and preferably includes the polycyclic aromatic compound according to the present invention and a binder resin. Here, "converted into light having a wavelength different from that of the incident light" is preferably converted into light having a wavelength longer than that of the incident light.
The color conversion composition according to the embodiment of the present invention may contain other compounds as necessary in addition to the polycyclic aromatic compound of the present invention. For example, in order to further improve the energy transfer efficiency from the excitation light to the polycyclic aromatic compound of the present invention, an auxiliary dopant such as rubrene (rubrene) may be contained. In addition, when a luminescent color other than the luminescent color of the polycyclic aromatic compound of the present invention is to be incorporated, a desired organic luminescent material, for example, an organic luminescent material such as a coumarin derivative or a rose bengal (rhodomine) derivative, may be added. In addition to the organic light-emitting material, conventional light-emitting materials such as inorganic fluorescent materials, fluorescent pigments, fluorescent dyes, and quantum dots may be added in combination.
The following shows an example of the organic light-emitting material other than the polycyclic aromatic compound of the present invention, but the present invention is not particularly limited to these.
[ chemical 6]
/>
In the present invention, the color conversion composition preferably exhibits green luminescence by using excitation light. In addition, the color conversion composition preferably exhibits red luminescence by using excitation light.
(adhesive resin)
The binder resin is a binder resin forming a continuous phase, and may be any material having excellent molding processability, transparency, heat resistance, and the like. Examples of the binder resin include: conventional resins such as epoxy resins, silicone resins (including cured organopolysiloxane (crosslinked product) 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, cellulose resins, aliphatic ester resins, aromatic ester resins, aliphatic polyolefin resins and aromatic polyolefin resins, and the like, which have reactive vinyl groups, such as acrylic, methacrylic, polyvinyl cinnamate and cyclic rubber. In addition, these copolymer resins can also be used as binder resins. By properly designing these resins, a binder resin useful in the color conversion composition and the color conversion sheet according to the embodiment of the present invention can be obtained. Among these resins, thermoplastic resins are more preferable in terms of easiness of the process of flaking. Among thermoplastic resins, epoxy resins, silicone resins, acrylic resins, ester resins, olefin resins, or mixtures of these can be preferably used from the viewpoints of transparency, heat resistance, and the like. In addition, particularly preferred thermoplastic resins from the viewpoint of durability are acrylic resins, ester resins, cycloolefin resins.
Preferable specific examples of the binder resin include those described in, for example, international publication No. 2016/190283, international publication No. 2017/61337, international publication No. 2018/43237, international publication No. 2019/21813, and International publication No. 2019/188019.
In addition, a dispersant, leveling agent, or the like for stabilizing the coating film may be added as an additive to the binder resin, and a bonding aid, or the like, such as a silane coupling agent, may be added as a modifier for the sheet surface. In addition, inorganic particles such as silica particles or silicone microparticles may be added to the binder resin as a sedimentation inhibitor for the color conversion material.
In the color conversion composition for producing a color conversion sheet according to the embodiment of the present invention, it is preferable that a hydrosilylation reaction retarder such as ethinyl alcohol is blended as another component into the binder resin in order to suppress hardening at normal temperature and to extend pot life. Further, as far as the effect of the present invention is not impaired, fine particles such as fumed silica, glass powder, quartz powder, etc., inorganic fillers or pigments such as titanium oxide, zirconium oxide, barium titanate, zinc oxide, etc., flame retardants, heat-resistant agents, antioxidants, dispersants, solvents, silane coupling agents, titanium coupling agents, etc., adhesion imparting agents, etc., may be blended to the binder resin as necessary.
(solvent)
The color conversion composition according to the embodiment of the present invention may also contain a solvent. The solvent is not particularly limited as long as the viscosity of the resin in a flowing state can be adjusted and the light emission and durability of the light emitting substance are not excessively affected. Examples of such solvents include: toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (texanol), methyl cellosolve, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and the like. Two or more of these solvents may be used in combination. Among these solvents, toluene is preferably used in view of not affecting the deterioration of the polycyclic aromatic compound of the present invention and less residual solvent after drying.
(other Components)
The color conversion composition according to the embodiment of the present invention may contain other components (additives) such as a light stabilizer, an antioxidant, a processing and heat stabilizer, a light stabilizer such as an ultraviolet absorber, scattering particles, silicone microparticles, and a silane coupling agent, in addition to the polycyclic aromatic compound and the binder resin according to the present invention.
Examples of the light stabilizer include tertiary amines, catechol derivatives, nickel compounds, complexes containing at least one transition metal selected from the group consisting of Sc, V, mn, fe, co, cu, Y, zr, mo, ag and lanthanoids (lanthanoids), and salts with organic acids, and the like, and are not particularly limited. In addition, these light stabilizers may be used alone or in combination.
Examples of the antioxidant include phenol antioxidants such as 2, 6-di-t-butyl-p-cresol and 2, 6-di-t-butyl-4-ethylphenol, but are not particularly limited thereto. In addition, 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. In addition, these stabilizers may be used alone or in combination.
Examples of the light-resistant stabilizer include benzotriazole compounds such as 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- [ 2-hydroxy-3, 5-bis (α, α -dimethylbenzyl) phenyl ] -2H-benzotriazole, but are not particularly limited thereto. In addition, these light resistance stabilizers may be used alone or in combination.
The scattering particles are preferably inorganic particles having a refractive index of 1.7 to 2.8, for example. Examples of the inorganic particles include: titanium dioxide, zirconium oxide, aluminum oxide, cerium oxide, tin oxide, indium oxide, iron oxide, zinc oxide, aluminum nitride, aluminum, tin, titanium or zirconium sulfide, titanium or zirconium hydroxide, and the like.
In the color conversion composition according to the embodiment of the present invention, the content of these additives is also determined by the molar absorptivity of the compound, the luminescence quantum yield, the absorption intensity at the excitation wavelength, and the thickness or transmittance of the color conversion sheet to be produced, but is usually preferably 1.0X10 to 100 parts by weight based on 100 parts by weight of the binder resin -3 More than 30 parts by weight and less than 30 parts by weight. Further, the content of these additives is more preferably 1.0X10 with respect to 100 parts by weight of the binder resin -2 More preferably not less than 15 parts by weight, particularly preferably 1.0X10 -1 More than 10 parts by weight.
Process for producing color-converting composition
An example of a method for producing the color conversion composition according to the embodiment of the present invention will be described below. In the above-described production method, a predetermined amount of the polycyclic aromatic compound of the present invention, a binder resin, a solvent, and the like are mixed. The above-mentioned components are mixed so as to have a predetermined composition, and then, the mixture is homogeneously mixed and dispersed by a stirring/kneading machine such as a homogenizer, a rotation/revolution type stirrer, a three-roll, ball mill, a planetary ball mill, or a bead mill, thereby obtaining a color conversion composition. After or during the mixing and dispersing, the defoaming may be performed under vacuum or reduced pressure. Alternatively, a specific component may be mixed in advance, or a treatment such as aging may be performed. The solvent may be removed by an evaporator to adjust the concentration of the solid content to a desired concentration.
< color conversion sheet >)
The color conversion sheet according to the embodiment of the present invention is a sheet for converting incident light from a light-emitting body such as a light source into light having a wavelength different from that of the incident light, and preferably includes the polycyclic aromatic compound according to the present invention and a binder resin. Here, "converted into light having a wavelength different from that of the incident light" is preferably converted into light having a wavelength longer than that of the incident light.
In the present invention, the color conversion sheet preferably includes a color conversion layer which is a layer containing the color conversion composition or a cured product obtained by curing the color conversion composition. The cured product of the color conversion composition is preferably contained in the color conversion sheet as a layer (layer containing the cured product of the color conversion composition) obtained by curing the color conversion composition. As typical examples of the structure of the color conversion sheet, the following four examples are given.
Fig. 1 is a schematic cross-sectional view showing a first example of a color conversion sheet according to an embodiment of the present invention. As shown in fig. 1, the color conversion sheet 1A of the first example is a single-layer film composed of a color conversion layer 11. The color conversion layer 11 is a layer containing a cured product of the color conversion composition.
Fig. 2 is a schematic cross-sectional view showing a second example of the color conversion sheet according to the embodiment of the present invention. As shown in fig. 2, the color conversion sheet 1B of the second example is a laminate of a base material layer 10 and a color conversion layer 11. In the structural example of the color conversion sheet 1B, the color conversion layer 11 is laminated on the base material layer 10.
Fig. 3 is a schematic cross-sectional view showing a third example of the color conversion sheet according to the embodiment of the present invention. As shown in fig. 3, the color conversion sheet 1C of the third example is a laminate of a plurality of base material layers 10 and a color conversion layer 11. In the structural example of the color conversion sheet 1C, the color conversion layer 11 is sandwiched by a plurality of base material layers 10.
Fig. 4 is a schematic cross-sectional view showing a fourth example of the color conversion sheet according to the embodiment of the present invention. As shown in fig. 4, the color conversion sheet 1D of the fourth example is a laminate of a plurality of base material layers 10, a color conversion layer 11, and a plurality of barrier films 12. In the above-described configuration example of the color conversion sheet 1D, the color conversion layer 11 is sandwiched between the plurality of barrier films 12, and further, the laminate of the color conversion layer 11 and the plurality of barrier films 12 is sandwiched between the plurality of base material layers 10. That is, in the color conversion sheet 1D, in order to prevent degradation of the color conversion layer 11 due to oxygen, moisture, or heat, a barrier film 12 may be provided as shown in fig. 4.
(substrate layer)
As the base material layer (for example, the base material layer 10 shown in fig. 2 to 4), conventional metals, films, glass, ceramics, paper, and the like can be used without particular limitation. Among them, glass or a resin film can be preferably used in terms of ease of manufacturing the color conversion sheet or ease of forming the color conversion sheet. In addition, a film having high strength is preferable so that there is no fear of breakage or the like when the film-like base material layer is treated. From the viewpoint of these required characteristics and economical efficiency, a resin film is preferable, and from the viewpoint of economical efficiency and handling, in particular, a plastic film selected from the group consisting of polyethylene terephthalate (polyethylene terephthalate, PET), polyphenylene sulfide, polycarbonate and polypropylene is preferable. In addition, in the case of drying the color conversion sheet or in the case of press-molding the color conversion sheet at a high temperature of 200 ℃ or higher by an extruder, a polyimide film is preferable in terms of heat resistance. The surface of the base material layer may be subjected to a mold release treatment in advance in terms of the ease of peeling the film.
The thickness of the base material layer is not particularly limited, but is preferably 25 μm or more, more preferably 38 μm or more, as a lower limit. The upper limit is preferably 5000 μm or less, more preferably 3000 μm or less.
(color conversion layer)
The color conversion layer (e.g., the color conversion layer 11 shown in fig. 1 to 4) may be formed by: the color conversion composition produced by the method is coated on a substrate such as a base layer or a barrier film and dried.
The thickness of the color conversion layer is not particularly limited, and is preferably 10 μm to 1000 μm. The lower limit of the thickness of the color conversion layer is more preferably 30 μm or more. The upper limit of the thickness of the color conversion layer is more preferably 200 μm or less, still more preferably 100 μm or less, and particularly preferably 50 μm or less. The film thickness of the color conversion sheet in the present invention refers to the film thickness (average film thickness) measured by the method a of measuring the thickness by mechanical scanning in the plastic-film and sheet-thickness measuring method based on japanese industrial standards (Japanese Industrial Standard, JIS) K7130 (1999).
In the color conversion sheet of the present invention, the color conversion layer may be one layer or two or more layers. In the case where the color conversion layer is two or more layers, it is preferable that the polycyclic aromatic compound of the present invention is contained in at least one of these layers.
The color conversion layer may contain, in addition to the polycyclic aromatic compound and the binder resin of the present invention, other components (additives) such as light stabilizers, antioxidants, processing and heat stabilizers, light stabilizers such as ultraviolet absorbers, scattering particles, silicone microparticles, and silane coupling agents.
(Barrier film)
A barrier film (e.g., the barrier film 12 shown in fig. 4) can be suitably used in the case of improving the gas barrier property to the color conversion layer, or the like. Examples of the barrier film 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, or a mixture of these, a metal oxide film or a metal nitride film obtained by adding other elements thereto, or films containing various resins such as polyvinylidene chloride, an acrylic resin, a silicon resin, a melamine resin, a urethane resin, a fluorine resin, and a polyvinyl alcohol resin such as saponified products of vinyl acetate. Examples of the barrier film having a barrier function against moisture include: films comprising various resins such as polyethylene, polypropylene, nylon, polyvinylidene chloride, a copolymer of vinylidene chloride and vinyl chloride, a copolymer of vinylidene chloride and acrylonitrile, a polyvinyl alcohol resin such as a fluororesin or a saponified product of vinyl acetate.
The barrier film may be provided on both sides of the color conversion layer 11 as the barrier film 12 illustrated in fig. 4, or may be provided only on one side of the color conversion layer 11. In addition, an auxiliary layer having an antireflection function, an antiglare function, an antireflection antiglare function, a hard coat function (an antifriction function), an antistatic function, an antifouling function, an electromagnetic wave shielding function, an infrared ray cut-off function, an ultraviolet ray cut-off function, a polarizing function, and a color matching function may be further provided according to the functions required for the color conversion sheet.
(other films)
The color conversion sheet according to the embodiment of the present invention may further include a dual brightness enhancement film (dual brightness enhancement film, DBEF), a diffusion sheet, a prism sheet, a wavelength selective reflection film, and the like. Preferable specific examples of the wavelength selective reflection film include those described in, for example, international publication No. 2017/164155 and Japanese patent application laid-open No. 2018-81250.
< light source unit >)
The light source unit according to the embodiment of the present invention includes at least a light source and the color conversion sheet. The light source included in the light source unit according to the embodiment of the present invention serves as a source of the excitation light. The method of disposing the light source and the color conversion sheet is not particularly limited, and may be a structure in which the light source and the color conversion sheet are closely adhered to each other, or may be a remote phosphor (remote phosphor) form in which the light source and the color conversion sheet are separated from each other. In addition, the light source unit may also have a structure further including a color filter for the purpose of improving color purity.
(light source)
The type of excitation light from the light source may be any excitation light that exhibits luminescence in a wavelength region where the luminescent material mixed with the polycyclic aromatic compound or the like of the present invention can absorb. For example, any of excitation light such as a fluorescent light source such as a hot cathode tube, a cold cathode tube, or an inorganic Electroluminescence (EL), an organic EL element light source, an LED light source, a white heat light source, and sunlight can be used in principle. In particular, light from an LED light source is the preferred excitation light.
The excitation light may be excitation light having one emission peak or excitation light having two or more emission peaks, but in order to improve color purity, excitation light having one emission peak is preferable. In addition, a plurality of excitation light sources having different types of emission peaks may be used in combination as desired.
In the display or illumination application, the light source of the excitation light is preferably a light emitting diode having maximum light emission in a range of from 430nm to 500nm in terms of improving color purity of blue light. Further, the light source preferably has maximum light emission in a wavelength range of 440nm to 470 nm. The excitation light in the wavelength range of 430nm to 500nm has relatively small excitation energy, and can prevent the decomposition of the luminescent material such as the polycyclic aromatic compound of the present invention.
The light source unit in the present invention can be used for display, lighting, interior, sign, signboard, etc., and is particularly preferably used for display or lighting purposes.
< display, lighting device >)
A display according to an embodiment of the present invention includes at least the color conversion sheet. For example, in a display such as a liquid crystal display, the light source unit having the light source, the color conversion sheet, and the like is used as a backlight unit. Further, the lighting device according to the embodiment of the present invention includes at least the color conversion sheet. For example, the lighting device is configured in the following manner: a blue LED light source as a light source unit is combined with a color conversion sheet that converts blue light from the blue LED light source into light having a longer wavelength than the blue light, thereby emitting white light.
< light-emitting element >)
In an embodiment of the present invention, a light-emitting element includes an anode and a cathode, and an organic layer interposed between the anode and the cathode. The organic layer of the light emitting element emits light by electric energy. The polycyclic aromatic compound of the present invention can be used in any of the layers in the light-emitting element, and is preferably used in the light-emitting layer of the light-emitting element because of high fluorescence quantum yield. In particular, the polycyclic aromatic compound is preferable as a dopant material for the light emitting layer because of its excellent fluorescence quantum yield.
Examples
The present invention will be described below by way of examples, but the present invention is not limited to the examples. In the following examples and comparative examples, the compounds G-1, G-2, and G-101 to G-103 are the following compounds.
[ chemical 7]
The evaluation methods related to the structural analysis in examples and comparative examples are as follows.
< determination of fluorescence Spectrum >
In the measurement of the fluorescence spectrum of the compound, an F-2500 type spectrofluorometer (manufactured by Hitachi Ltd.) was used to measure the compound at 1X 10 -5 The concentration of mol/L was dissolved in toluene and fluorescence spectrum at excitation was carried out at a wavelength of 460 nm.
< determination of luminescence Quantum yield >)
In the measurement of the luminescence quantum yield of the compound, the compound was measured at 1×10 using an absolute Photoluminescence (PL) quantum yield measuring device (manufactured by kuntaaus) -QY, bingo photon (Hamamatsu Photonics) corporation) -5 The concentration of mol/L was dissolved in toluene and the luminescence quantum yield upon excitation was carried out at a wavelength of 460 nm.
(HOMO energy level)
In the calculation of HOMO levels of the compounds, the compounds of each of the examples and comparative examples were subjected to the structure optimization by the 6-31G (d) base system using the B3LYP density functional theory using the general Quantum chemical computing program "Gaussian" 16 "package (manufactured by Gaussian). The HOMO energy level was calculated using the B3LYP density functional theory based on the most preferred structure, with a 6-311++ G (d, p) basis.
Synthesis example 1
The method for synthesizing the compound G-1 of Synthesis example 1 in the present invention will be described below.
[ chemical 8]
In the method for synthesizing Compound G-1, a flask containing 2-bromo-1, 3-difluorobenzene (2.0G), bipyridylcarbazole (10.0G), potassium carbonate (5.0G) and N-methyl-2-pyrrolidone (25 mL) was heated and stirred at 170℃for 10 hours under nitrogen. Hereinafter, N-methyl-2-pyrrolidone is abbreviated as NMP. After the reaction of the solution in the flask was stopped, the reaction solution in the flask was cooled to room temperature, and water and toluene were added thereto to separate the reaction solution into an organic solvent layer and an aqueous layer. The solvent was distilled off from the organic solvent layer under reduced pressure, and then purified by silica gel column chromatography to obtain intermediate 1A.
A flask containing intermediate 1A (10.0 g) and xylene (30 mL) was cooled to-40℃and a 2.6M solution of n-butyllithium in hexane (4.0 mL) was added dropwise. After the completion of the dropwise addition, the solution in the flask was warmed to room temperature, cooled again to-40℃and boron tribromide (1.1 mL) was added to the solution. Then, the solution in the flask was warmed to room temperature and stirred for 13 hours, then cooled to 0 ℃, and thereafter, N-diisopropylethylamine (3.1 mL) was added to the solution in the flask, and heated and stirred at 130℃for 5 hours. The reaction solution after the reaction in the flask was cooled to room temperature, and an aqueous sodium acetate solution cooled by an ice bath was added thereto and stirred, and a solid precipitated by suction filtration of the stirred reaction solution was collected. The obtained solid was washed with water, methanol and then heptane in this order, and further recrystallized from chlorobenzene, whereby compound G-1 (0.8G) was obtained as a target.
The compounds G-2, G-101 to G-103 other than the above can be synthesized by changing various raw materials.
In the following examples and comparative examples, a backlight unit including each color conversion sheet, a blue LED element (emission peak wavelength: 445 nm), and a light guide plate was laminated on one surface of the light guide plate, a prism sheet was laminated on the color conversion sheet, and then a current was applied thereto, and the blue LED element was turned on, and the initial emission characteristics were measured using a spectroradiometer (CS-1000, manufactured by KONICA MINOLTA). Further, in the measurement of the initial light emission characteristic, the brightness of the light from the blue LED element was 800cd/m without inserting the color conversion sheet 2 The initial value is set by way of (a). Thereafter, light from the blue LED element was continuously irradiated at room temperature, and the time until the decrease in luminance was 5% was observed, thereby evaluating the light durability.
Example 1-1
Example 1-1 of the present invention is an example in which the polycyclic aromatic compound according to the embodiment is used as a light-emitting material (color conversion material). In example 1-1, an acrylic resin was used as a binder resin, and 0.25 parts by weight of compound G-1 as a light emitting material and 400 parts by weight of toluene as a solvent were mixed with respect to 100 parts by weight of the acrylic resin. Thereafter, the mixture was stirred and defoamed at 300rpm for 20 minutes using a planetary stirring and defoamation apparatus "Ma Zelu Stark (MAZERUSTAR) KK-400" (manufactured by Kurabo Co., ltd.) to obtain a color conversion composition.
Similarly, a polyester resin was used as the binder resin, and 300 parts by weight of toluene as a solvent was mixed with respect to 100 parts by weight of the polyester resin. Thereafter, the solution was stirred and defoamed at 300rpm for 20 minutes using a planetary stirring and defoamation apparatus "Ma Zelu Stark (MAZERUSTAR) KK-400" (manufactured by Kurabo Co., ltd.) to obtain an adhesive composition.
Next, the color conversion composition obtained as described above was applied onto "lumiphor" U48 (manufactured by eastern co., ltd., thickness 50 μm) as a first base material layer using a slot die coater, and heated and dried at 100 ℃ for 20 minutes to form a layer (a) having an average film thickness of 16 μm.
Similarly, the adhesive composition obtained as described above was applied to the PET substrate layer side of a light diffusion film "Chemical mat" 125PW (manufactured by woody (Kimoto)) as a second substrate layer, with a thickness of 138 μm, using a slot die coater, and heated and dried at 100 ℃ for 20 minutes to form a (B) layer with an average film thickness of 48 μm.
Next, the two (a) layers and (B) layer were heat laminated so as to directly laminate the color conversion layer of the (a) layer and the adhesive layer of the (B) layer, thereby producing a color conversion sheet having a laminated structure of "first base layer/color conversion layer/adhesive layer/second base layer/light diffusion layer".
The color conversion sheet was continuously irradiated with light from the blue LED element at room temperature, and as a result, the brightness was reduced by 5% for 1010 hours. The luminescent materials and evaluation results of example 1-1 are shown in Table 1 below.
(examples 1-2 and comparative examples 1-1 to 1-3)
A color conversion sheet was produced and evaluated in the same manner as in example 1-1, except that the compounds (compound G-2, compound G-101 to compound G-103) described in table 1 below were used as light-emitting materials in example 1-2 of the present invention and comparative examples 1-1 to 1-3 of the present invention. The luminescent materials and evaluation results of examples 1-2 and comparative examples 1-1 to 1-3 are shown in Table 1. The longer the light durability is, the more preferable, and specifically, 500 hours or more is preferable.
TABLE 1
(Table 1)
The present invention will be described below by way of examples, but the present invention is not limited to the examples. In the following examples and comparative examples, the compounds G-3 to G-8 and the compounds G-104 to G-107 are the following compounds.
[ chemical 9]
[ chemical 10]
The evaluation methods related to the structural analysis in examples and comparative examples are as follows.
< determination of fluorescence Spectrum >
In the measurement of the fluorescence spectrum of the compound, an F-2500 type spectrofluorometer (manufactured by Hitachi Ltd.) was used to measure the compound at 1X 10 -5 The concentration of mol/L was dissolved in toluene and fluorescence spectrum at excitation was carried out at a wavelength of 460 nm.
< determination of luminescence Quantum yield >)
In the measurement of the luminescence quantum yield of the compound, the compound was measured at 1×10 using an absolute PL quantum yield measuring device (made by quanta) -QY, bingo photon (Hamamatsu Photonics) company) - 5 The concentration of mol/L was dissolved in toluene and the luminescence quantum yield upon excitation was carried out at a wavelength of 460 nm.
Synthesis example 2
The method for synthesizing the compound G-3 of Synthesis example 2 in the present invention will be described below.
[ chemical 11]
/>
In the method for synthesizing Compound G-3, a flask containing 2-bromo-1, 3-difluorobenzene (20.0G), carbazole (50.0G), potassium carbonate (50.0G) and NMP (250 mL) was heated and stirred at 170℃for 10 hours under nitrogen atmosphere. After the reaction of the solution in the flask was stopped, the reaction solution in the flask was cooled to room temperature, and water and toluene were added thereto to separate the reaction solution into an organic solvent layer and an aqueous layer. The solvent was distilled off from the organic solvent layer under reduced pressure, and then purified by silica gel column chromatography to obtain intermediate 3A.
A flask containing intermediate 3A (44.2 g) and xylene (300 mL) was cooled to-40℃and a 2.6M solution of n-butyllithium in hexane (40.4 mL) was added dropwise. After the completion of the dropwise addition, the solution in the flask was warmed to room temperature, cooled again to-40℃and boron tribromide (10.2 mL) was added to the solution. Then, the solution in the flask was warmed to room temperature and stirred for 13 hours, then cooled to 0 ℃, and thereafter, N-diisopropylethylamine (30.8 mL) was added to the solution in the flask, and heated and stirred at 130℃for 5 hours. The reaction solution after the reaction in the flask was cooled to room temperature, and an aqueous sodium acetate solution cooled by an ice bath was added thereto and stirred, and a solid precipitated by suction filtration of the stirred reaction solution was collected. The obtained solid was washed with water, methanol and then heptane in this order, and further recrystallized from chlorobenzene, thereby obtaining intermediate 3B.
After dimethylformamide (10 mL) was mixed with dichloroethane (200 mL) in the flask, the mixtures were cooled to 0 ℃. Slowly dropwise adding POCl into the cooled mixture under nitrogen environment 3 After (10 mL), the solution in the flask was stirred at room temperature for 30 minutes. After adding intermediate 3B (10 g) to the stirred reaction solution, the temperature was raised to 60 ℃ and stirred for 1 hour. The solution of intermediate 3B was cooled to room temperature and then added to a mixture of ice and a saturated aqueous sodium hydroxide solution. After stirring the mixed solution at normal temperature for 2 hours, the organic solvent layer was extracted from the mixed solution with chloroform. The obtained organic solvent layer was dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to remove the solvent from the organic solvent layer. Thereafter, the process is carried out,intermediate 3C was obtained by a silica gel column.
Intermediate 3C (6.0 g) was reacted with NH 2 SO 3 H (1.2 g) was dissolved in tetrahydrofuran, and NaClO dissolved in water was slowly added dropwise to the solution at 0 ℃ 2 (1.1 g). Stirring the obtained solution at normal temperature for 1 hour, and then adding saturated Na into the solution 2 S 2 O 3 After that, the organic solvent layer was extracted from the mixed solution with chloroform. The obtained organic solvent layer was dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to remove the solvent from the organic solvent layer. Thereafter, intermediate 3D was obtained by a silica gel column.
Intermediate 3E (5.0 g), phenol (1.0 g) and 4-Dimethylaminopyridine (DMAP) (0.1 g) were dissolved in methylene chloride, and Dicyclohexylcarbodiimide (DCC) (2.2 g) dissolved in methylene chloride was slowly added dropwise to the solution at 0 ℃. After the obtained solution was stirred at normal temperature for 12 hours, a saturated sodium hydroxide solution was added to the solution, and thereafter, an organic solvent layer was extracted from the mixed solution with chloroform. The obtained organic solvent layer was dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to remove the solvent from the organic solvent layer. Thereafter, compound G-3 (4.3G) was obtained as a target substance through a silica gel column.
The compounds G-4 to G-8 and the compounds G-104 to G-107 other than the above can be synthesized by changing various raw materials.
In the following examples and comparative examples, a backlight unit including each color conversion sheet, a blue LED element (emission peak wavelength: 445 nm), and a light guide plate was laminated on one surface of the light guide plate, a prism sheet was laminated on the color conversion sheet, and then a current was applied thereto, and the blue LED element was turned on, and the initial emission characteristics were measured using a spectroradiometer (CS-1000, manufactured by KONICA MINOLTA). Further, in the measurement of the initial light emission characteristic, the color conversion sheet was not inserted, and the brightness of the light from the blue LED element was used Becomes 800cd/m 2 The initial value is set by way of (a). Thereafter, light from the blue LED element was continuously irradiated at room temperature, and the time until the decrease in luminance was 5% was observed, thereby evaluating the light durability.
Example 2-1
Example 2-1 of the present invention is an example in which the polycyclic aromatic compound according to the embodiment is used as a light-emitting material (color conversion material). In example 2-1, an acrylic resin was used as a binder resin, and 0.25 parts by weight of compound G-3 as a light-emitting material and 400 parts by weight of toluene as a solvent were mixed with respect to 100 parts by weight of the acrylic resin. Thereafter, the mixture was stirred and defoamed at 300rpm for 20 minutes using a planetary stirring and defoamation apparatus "Ma Zelu Stark (MAZERUSTAR) KK-400" (manufactured by Kurabo Co., ltd.) to obtain a color conversion composition.
Similarly, a polyester resin was used as the binder resin, and 300 parts by weight of toluene as a solvent was mixed with respect to 100 parts by weight of the polyester resin. Thereafter, the solution was stirred and defoamed at 300rpm for 20 minutes using a planetary stirring and defoamation apparatus "Ma Zelu Stark (MAZERUSTAR) KK-400" (manufactured by Kurabo Co., ltd.) to obtain an adhesive composition.
Next, the color conversion composition obtained as described above was applied onto "lumiphor" U48 (manufactured by eastern co., ltd., thickness 50 μm) as a first base material layer using a slot die coater, and heated and dried at 100 ℃ for 20 minutes to form a layer (a) having an average film thickness of 16 μm.
Similarly, the adhesive composition obtained as described above was applied to the PET substrate layer side of a light diffusion film "Chemical mat" 125PW (manufactured by woody (Kimoto)) as a second substrate layer, with a thickness of 138 μm, using a slot die coater, and heated and dried at 100 ℃ for 20 minutes to form a (B) layer with an average film thickness of 48 μm.
Next, the two (a) layers and (B) layer were heat laminated so as to directly laminate the color conversion layer of the (a) layer and the adhesive layer of the (B) layer, thereby producing a color conversion sheet having a laminated structure of "first base layer/color conversion layer/adhesive layer/second base layer/light diffusion layer".
As a result of performing color conversion of light (blue light) from the blue LED element using the color conversion sheet, when only a light emitting region of green light is selected, high-color purity green light emission having a peak wavelength of 527nm and a half-width of an emission spectrum in the peak wavelength of 28nm can be obtained. In addition, the luminescence quantum yield was 0.95. In addition, light from the blue LED element was continuously irradiated at room temperature, and as a result, the time for 5% reduction in brightness was 810 hours. The luminescent materials and evaluation results of example 2-1 are shown in Table 2 below.
(examples 2-2 to 2-6 and comparative examples 2-1 to 2-4)
A color conversion sheet was produced and evaluated in the same manner as in example 2-1, except that the compounds (compound G-4 to compound G-8, compound G-104 to compound G-107) described in table 2 below were used as light-emitting materials in examples 2-2 to 2-6 of the present invention and comparative examples 2-1 to 2-4 of the present invention. The luminescent materials and evaluation results of examples 2-2 to 2-6 and comparative examples 2-1 to 2-4 are shown in Table 2. The longer the light durability is, the more preferable, and specifically, 800 hours or more is preferable.
TABLE 2
(Table 2)
Industrial applicability
As described above, the polycyclic aromatic compound, the color conversion composition, the color conversion sheet, the light source unit, the display, and the lighting device according to the present invention are suitable for improving color reproducibility and achieving high durability.
Description of symbols
1A, 1B, 1C, 1D: color conversion sheet
10: substrate layer
11: color conversion layer
12: barrier film

Claims (22)

1. A polycyclic aromatic compound characterized in that,
a compound which exhibits luminescence observed in a region having a peak wavelength of 500nm to 750nm by using excitation light, has a highest occupied molecular orbital level of-5.7 eV or less, and emits delayed fluorescence.
2. The polycyclic aromatic compound according to claim 1, wherein,
the highest occupied molecular orbital level of the polycyclic aromatic compound is-6.0 eV or less.
3. The polycyclic aromatic compound according to claim 1, wherein,
the highest occupied molecular orbital level of the polycyclic aromatic compound is-6.2 eV or less.
4. The polycyclic aromatic compound according to claim 1, wherein,
the highest occupied molecular orbital level of the polycyclic aromatic compound is-6.5 eV or less.
5. The polycyclic aromatic compound according to any one of claim 1 to 4,
the half-width of the emission spectrum of the polycyclic aromatic compound at the emission peak wavelength is 40nm or less.
6. The polycyclic aromatic compound according to any one of claim 1 to 5,
the polycyclic aromatic compound is a compound represented by the general formula (1) or the general formula (2).
[ chemical 1]
(Ring Za, ring Zb and ring Zc are each independently a substituted or unsubstituted aryl ring having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl ring having 6 to 30 carbon atoms; Z 1 Z is as follows 2 Each independently is an oxygen atom, NRa (nitrogen atom having substituent Ra), or a sulfur atom; at Z 1 In the case of NRa, the substituent Ra may bond to the ring Za or the ring Zb to form a ring; at Z 2 In the case of NRa, the substituent Ra may bond to the ring Za or the ring Zc to form a ring; e is a boron atom, a phosphorus atom, a SiRa (silicon atom having a substituent Ra), or p=o; e (E) 1 E and E 2 Each independently is BRa (boron atom having substituent Ra), PRa (phosphorus atom having substituent Ra), siRa 2 (silicon atom having two substituents Ra), P (=O) Ra 2 (phosphine oxide having two substituents Ra) or P (=S) Ra 2 (phosphine sulfide having two substituents Ra), S (=o) or S (=o) 2 The method comprises the steps of carrying out a first treatment on the surface of the At E 1 BRa, PRa, siRa of a shape of BRa, PRa, siRa 2 、P(＝O)Ra 2 Or P (=S) Ra 2 In the above, the substituent Ra may be bonded to the ring Za or the ring Zb to form a ring; at E 2 BRa, PRa, siRa of a shape of BRa, PRa, siRa 2 、P(＝O)Ra 2 Or P (=S) Ra 2 In the above, the substituent Ra may be bonded to the ring Za or the ring Zc to form a ring; the substituents Ra are each independently a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, or a substituted or unsubstituted alkyl. )
7. The polycyclic aromatic compound according to claim 6, wherein,
the compound represented by the general formula (1) or the general formula (2) has at least one electron withdrawing group.
8. The polycyclic aromatic compound according to claim 7, wherein,
The compound represented by the general formula (1) or the general formula (2) has two or more electron withdrawing groups.
9. The polycyclic aromatic compound according to claim 7 or 8, characterized in that,
the electron withdrawing group is cyano, acyl, ester, amido, sulfonyl, sulfonate or sulfonamide.
10. The polycyclic aromatic compound according to any one of claim 7 to 9,
the electron withdrawing group is an ester group.
11. The polycyclic aromatic compound according to any one of claim 6 to 10,
the Z is 1 The Z is 2 Is an oxygen atom or NRa.
12. The polycyclic aromatic compound according to any one of claim 6 to 11,
the E is a boron atom and the R is a boron atom,
the E is 1 The E is 2 Is BRa.
13. The polycyclic aromatic compound according to any one of claim 6 to 12,
the ring Za, the ring Zb, and the ring Zc are benzene rings.
14. The polycyclic aromatic compound according to any one of claim 1 to 13,
the polycyclic aromatic compound exhibits luminescence observed in a region having a peak wavelength of 500nm or more and less than 580nm by using excitation light.
15. The polycyclic aromatic compound according to any one of claim 1 to 13,
the polycyclic aromatic compound exhibits luminescence observed in a region having a peak wavelength of 580nm or more and 750nm or less by using excitation light.
16. A color conversion composition for converting incident light into light different from the incident light, comprising:
the polycyclic aromatic compound of any one of claims 1 to 15; and
and (3) a binder resin.
17. A color conversion sheet for converting incident light into light different from the incident light, comprising:
the polycyclic aromatic compound of any one of claims 1 to 15; and
and (3) a binder resin.
18. The color conversion sheet according to claim 17, wherein,
and further has a barrier film.
19. A light source unit characterized by comprising:
a light source; and
the color conversion sheet according to claim 17 or 18.
20. The light source unit according to claim 19, wherein,
the light source is a light emitting diode having maximum light emission in a wavelength range of 430nm to 500 nm.
21. A display, comprising:
the color conversion sheet according to claim 17 or 18.
22. A lighting device, comprising:
the color conversion sheet according to claim 17 or 18.
CN202280019133.6A 2021-04-28 2022-04-11 Polycyclic aromatic compound, color conversion composition, color conversion sheet, light source unit, display, and lighting device Pending CN116917300A (en)

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JP2021-075673 2021-04-28
JP2021082082 2021-05-14
JP2021-082082 2021-05-14
PCT/JP2022/017461 WO2022230643A1 (en) 2021-04-28 2022-04-11 Polycyclic aromatic compound, color conversion composition, color conversion sheet, light source unit, display and lighting device

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