WO2022264896A1 - 色変換シート、それを含む光源ユニット、ディスプレイおよび照明装置 - Google Patents
色変換シート、それを含む光源ユニット、ディスプレイおよび照明装置 Download PDFInfo
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Images
Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
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- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C08L33/04—Homopolymers or copolymers of esters
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
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- F21V9/00—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters
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- G—PHYSICS
- G02—OPTICS
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/1336—Illuminating devices
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
Definitions
- the present invention relates to a color conversion sheet, a light source unit including the same, a display and a lighting device.
- Color conversion refers to conversion of light emitted from a light-emitting body into light having a longer wavelength, and includes, for example, conversion of blue light emission into green or red light emission.
- a composition having this color conversion function (hereinafter referred to as a color conversion composition) is formed into a sheet and combined with, for example, a blue light source to obtain the three primary colors of blue, green, and red from the blue light source, i.e., obtain white light. becomes possible.
- a white light source that combines such a blue light source and a sheet having a color conversion function (hereinafter referred to as a color conversion sheet) is used as a light source unit such as a backlight unit. The combination allows the creation of full-color displays.
- a white light source obtained by combining a blue light source and a color conversion sheet can also be used as it is as a white light source such as LED lighting.
- Improvements in color reproducibility and durability can be cited as challenges for liquid crystal displays that use the color conversion method.
- it is effective to narrow the half width of each emission spectrum of blue, green, and red of the light source unit to increase the color purity of each of blue, green, and red.
- color conversion materials containing pyrromethene compounds have been proposed (see, for example, Patent Documents 1 and 2).
- Patent Document 3 a technique of adding a light stabilizer
- durability is still insufficient with this technique. Therefore, as a technique for improving color reproducibility and durability, a luminescent material having an electron-withdrawing group has been proposed (see, for example, Patent Document 4).
- the present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a color conversion sheet with excellent chromaticity durability.
- a second object of the present invention is to provide a light source unit, a display, and a lighting device including the color conversion sheet.
- a color conversion sheet according to the present invention is a color conversion sheet that converts incident light into light of a wavelength different from that of the incident light, and comprises at least delayed fluorescence and a binder resin, wherein the amount of solvent in the color conversion layer is 10 ppm by mass or more and 30000 ppm by mass or less.
- the binder resin has a partial structure represented by the general formula (3) and a partial structure represented by the general formula (4) in the molecular structure. and having.
- Z 1 and Z 2 may be the same or different, and are hydrogen atoms or organic groups having 1 to 20 carbon atoms.
- Y 1 to Y 4 which may be the same or different, each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and at least one of Y 1 to Y 4 is a group containing an aliphatic cyclic hydrocarbon structure; is.
- the color conversion sheet according to the present invention is characterized in that, in the above invention, at least one of Y 1 to Y 4 in the general formula (4) is a substituted or unsubstituted cyclohexyl group. .
- one of Y 1 to Y 4 in the general formula (4) is a substituted or unsubstituted cyclohexyl group and the other three are hydrogen atoms. It is characterized by
- the solvent in the color conversion layer has an SP value of 11.0 (cal/cm 3 ) 1/2 or more and 20.0 (cal/cm 3 ). It is characterized by having 1/2 or less functional groups.
- the color conversion sheet according to the present invention is characterized in that, in the above invention, the compound that emits delayed fluorescence is at least one of the following luminescent material (a) and luminescent material (b). .
- the color conversion sheet according to the present invention is characterized in that, in the above invention, the compound that emits delayed fluorescence contains a compound represented by the following general formula (1) or general formula (2).
- ring Za, ring Zb and ring Zc are each independently a substituted or unsubstituted aryl ring having 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl ring having 6 to 30 carbon atoms
- Z 1 and Z 2 are each independently an oxygen atom, NRa (a nitrogen atom having a substituent Ra) or a sulfur atom
- the substituent Ra may combine with the ring Za or the ring Zb to form a ring.
- the substituent Ra may combine with the ring Za or the ring Zc to form a ring
- the compound that emits delayed fluorescence is a compound represented by the general formula (1), and E in the general formula (1) is boron. and Z 1 and Z 2 are each independently NRa, or the compound that emits delayed fluorescence is a compound represented by the general formula (2), wherein E 1 and E 2 of are each independently BRa.
- a light source unit according to the present invention is characterized by including a light source and the color conversion sheet according to any one of the above inventions.
- the light source unit according to the present invention is characterized in that, in the above invention, the light source is a light emitting diode having maximum light emission in a wavelength range of 400 nm or more and 500 nm or less.
- a display according to the present invention is characterized by comprising the light source unit according to the above invention.
- a lighting device is characterized by comprising the light source unit according to the above invention.
- the present invention it is possible to provide a color conversion sheet with excellent chromaticity durability.
- the color conversion sheet of the present invention can improve durability against changes in chromaticity.
- the light source unit, the display, and the lighting device of the present invention can improve durability against changes in chromaticity by including the color conversion sheet.
- FIG. 1 is a schematic cross-sectional view showing a first example of a color conversion sheet according to an embodiment of the invention.
- FIG. 2 is a schematic cross-sectional view showing a second example of the color conversion sheet according to the embodiment of the invention.
- FIG. 3 is a schematic cross-sectional view showing a third example of the color conversion sheet according to the embodiment of the invention.
- FIG. 4 is a schematic cross-sectional view showing a fourth example of the color conversion sheet according to the embodiment of the invention.
- a color conversion sheet according to an embodiment of the present invention is a color conversion sheet that converts incident light from a light-emitting body such as a light source into light with a wavelength different from that of the incident light, and comprises at least a compound that emits delayed fluorescence. and a binder resin.
- the amount of solvent in the color conversion layer is 10 mass ppm or more and 30000 mass ppm or less.
- "converting into light with a wavelength different from that of the incident light” preferably means converting the incident light into light with a longer wavelength than the incident light.
- the color conversion sheet according to the embodiment of the present invention may be abbreviated as the color conversion sheet of the present invention.
- the color conversion sheet of the present invention includes a color conversion layer which is a layer made of a color conversion composition or a cured product thereof, which will be described later.
- the cured product of the color conversion composition is preferably included in the color conversion sheet as a layer obtained by curing the color conversion composition (a layer made of the cured product of the color conversion composition).
- As representative structural examples of the color conversion sheet of the present invention there are, for example, the following four structures.
- FIG. 1 is a schematic cross-sectional view showing a first example of a color conversion sheet according to an embodiment of the invention.
- the color conversion sheet 1A of this first example is a single-layer sheet composed of a color conversion layer 11.
- the color conversion layer 11 is a layer made of a cured product of the color conversion composition of the invention.
- FIG. 2 is a schematic cross-sectional view showing a second example of the color conversion sheet according to the embodiment of the invention.
- the color conversion sheet 1B of this second example is a laminate of a substrate layer 10 and a color conversion layer 11.
- 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 invention.
- the color conversion sheet 1C of this third example is a laminate of a plurality of base material layers 10 and a color conversion layer 11.
- a color conversion layer 11 is sandwiched between a plurality of base 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 invention.
- the color conversion sheet 1D of this fourth example is a laminate of a plurality of base layers 10, a color conversion layer 11, and a plurality of barrier films 12.
- a color conversion layer 11 is sandwiched between a plurality of barrier films 12, and a laminate of these color conversion layers 11 and a plurality of barrier films 12 is composed of a plurality of base layers 10. sandwiched by. That is, the color conversion sheet 1D may have a barrier film 12 as shown in FIG. 4 in order to prevent deterioration of the color conversion layer 11 due to oxygen, moisture and heat.
- the thickness of the color conversion sheet of the present invention is preferably 30 ⁇ m or more and 300 ⁇ m or less.
- the thickness of the color conversion sheet refers to the total thickness of all layers included in the color conversion sheet. It refers to the film thickness (average film thickness) measured based on the measurement method A method.
- the thickness of the color conversion sheet of the present invention By setting the thickness of the color conversion sheet of the present invention to 30 ⁇ m or more, the toughness of the color conversion sheet can be improved. Further, by setting the thickness of the color conversion sheet of the present invention to 300 ⁇ m or less, cracks in the color conversion sheet can be suppressed.
- the color conversion layer (for example, the color conversion layer 11 shown in FIGS. 1 to 4) includes a compound that emits delayed fluorescence (hereinafter sometimes abbreviated as “delayed fluorescence material”), a binder resin, and a minute Contains a small amount of solvent.
- the minute amount of solvent is defined as residual solvent in the color conversion layer.
- the thickness of the color conversion layer is not particularly limited, it is preferably 10 ⁇ m or more and 1000 ⁇ m or less.
- the lower limit of the thickness of the color conversion layer is more preferably 30 ⁇ m or more.
- the upper limit of the thickness of the color conversion layer is more preferably 200 ⁇ m or less, even more preferably 100 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
- the thickness of the color conversion layer in the present invention is a film thickness (average film thickness) measured based on Method A for measuring thickness by mechanical scanning in JIS K7130 (1999) Plastics - Films and sheets - Thickness measurement method. That's what I mean.
- the color conversion layer as described above can be formed by applying a color conversion composition prepared by a method described below onto a substrate such as a base material layer or a barrier film and drying it.
- the color conversion layer may be one layer or two or more layers.
- the color conversion layer contains light stabilizers, antioxidants, processing and heat stabilizers, light resistance stabilizers such as ultraviolet absorbers, scattering particles, and silicone fine particles. and other components (additives) such as a silane coupling agent.
- a compound that emits fluorescence by transitioning from a triplet excited state to a singlet excited state with high efficiency is referred to as a “compound that emits delayed fluorescence” or It is abbreviated as "delayed fluorescence material”.
- the delayed fluorescence material has the characteristic that it is difficult to generate singlet oxygen because its triplet excited state is quickly converted to a singlet excited state. It has been found that this feature prevents deterioration of the light-emitting material, suppresses changes in chromaticity over time, and improves durability against changes in chromaticity. This mechanism will be explained in order. Note that, hereinafter, the durability against changes in chromaticity may be abbreviated as “durability of chromaticity” or simply “durability”.
- the chromaticity change of the color conversion composition is caused by the deterioration of the luminescent material.
- This degradation of the luminescent material is caused by singlet oxygen.
- Singlet oxygen is a singlet state in which the two electrons in the ⁇ * orbital (antibonding ⁇ orbital) of the molecular orbital of the oxygen molecule have different spin directions, that is, the excitation in which the total spin quantum number is 0 is the oxygen molecule in the state
- Such excited states include the ⁇ 1 state in which each of the two ⁇ * orbitals is occupied by electrons with different spin directions, and the There are ⁇ 1 states occupied by two different electrons.
- Singlet oxygen has a strong electrophilicity due to its vacant electron orbit in the ⁇ 1 state, and has a strong oxidizing power. Therefore, it is considered that singlet oxygen causes deterioration due to oxidation of the light-emitting material.
- Singlet oxygen is thought to be unlikely to be generated by direct photoexcitation of ground-state triplet oxygen. This is because the transition from triplet oxygen in the ground state to singlet oxygen in the excited state is a spin-forbidden transition, and the transition probability is very low.
- the generation of singlet oxygen in the color conversion composition is due to dye sensitization.
- singlet oxygen is generated by the exchange of electrons and energy between the light-emitting material in the triplet excited state and the triplet oxygen molecule in the ground state.
- the generation mechanism is considered as follows.
- the light-emitting material changes from the singlet ground state to the singlet excited state by photoexcitation, and further, part of the light-emitting material changes from the singlet excited state to the triplet excited state due to intersystem crossing. Since the transition from the triplet excited state of the generated luminescent material to the singlet ground state is a spin-forbidden transition, the transition probability is usually low and the triplet excited state has a long lifetime. However, when triplet oxygen in the ground state coexists, the spin inhibition is lifted by the excitation of the triplet oxygen in the ground state to the singlet oxygen in the excited state. It can be rapidly deactivated to the ground state. This mechanism is called the Dexter mechanism (electronic exchange mechanism).
- the Dexter mechanism In order for the Dexter mechanism to proceed, it is necessary to exchange electrons through wave function overlap between molecules. Therefore, it is considered necessary to directly collide the energy donor molecule (in this case, the triplet excited light-emitting material) and the energy acceptor molecule (in this case, ground state triplet oxygen).
- the energy donor molecule in this case, the triplet excited light-emitting material
- the energy acceptor molecule in this case, ground state triplet oxygen
- the delayed fluorescence material has the property that the triplet excited state quickly converts to the singlet excited state, that is, the triplet excited state has a short lifetime. Therefore, the probability of direct collision between the light-emitting material in the triplet excited state and the triplet oxygen in the ground state is reduced, and singlet oxygen is less likely to occur.
- the electron donor skeleton and electron acceptor skeleton may be directly bonded or may be bonded via a linking group.
- the linking group in this case is preferably a skeleton containing an aromatic hydrocarbon.
- Examples of electron-donating skeletons include skeletons having an amine nitrogen atom.
- a skeleton containing diarylamine or triarylamine a skeleton containing carbazole, a skeleton containing benzocarbazole, a skeleton containing indolocarbazole, a skeleton containing phenoxazine, and a skeleton containing phenothiazine are preferable.
- a carbazole-containing skeleton, a benzocarbazole-containing skeleton, an indolocarbazole-containing skeleton, and a phenoxazine-containing skeleton are more preferred, and a carbazole-containing skeleton and a phenoxazine-containing skeleton are even more preferred.
- electron-accepting skeletons generally include skeletons containing electron-withdrawing substituents (that is, electron-withdrawing groups).
- An electron-withdrawing group also called an electron-accepting group, is an atomic group that attracts electrons from a substituted atomic group by an inductive effect or a resonance effect in organic electronic theory.
- Examples of the electron-withdrawing group include those having a positive value as the substituent constant ( ⁇ p (para)) of Hammett's rule.
- Hammett's rule substituent constant ( ⁇ p (para)) can be quoted from Kagaku Handan Basic Edition 5th Revised Edition (page II-380).
- electron withdrawing groups examples include -F ( ⁇ p: +0.20), -Cl ( ⁇ p: +0.28), -Br ( ⁇ p: +0.30), -I ( ⁇ p: +0.30), -CO 2 R 12 ( ⁇ p: +0.45 when R 12 is an ethyl group), -CONH 2 ( ⁇ p: +0.38), -COR 12 ( ⁇ p: +0.49 when R 12 is a methyl group), - CF 3 ( ⁇ p: +0.51), —SO 2 R 12 ( ⁇ p: +0.69 when R 12 is a methyl group), —NO 2 ( ⁇ p: +0.81), and the like.
- Each R 12 is independently a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring-forming carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring-forming atoms, a substituted or unsubstituted It represents a substituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms. Specific examples of each of these groups include the same examples as the substituents in the compounds represented by general formula (1) or general formula (2) described below.
- a skeleton containing an electron-withdrawing group a skeleton containing a heteroaryl group having a partial structure in which a carbon atom and a nitrogen atom are bonded by a double bond, a skeleton containing a fluorinated substituent, a skeleton containing a cyano group, A skeleton containing a carbonyl group, a skeleton containing a sulfoxide or disulfoxide, a skeleton containing a phosphine oxide group, and the like are preferred.
- a skeleton containing a heteroaryl group having a partial structure in which a carbon atom and a nitrogen atom are bonded by a double bond, a skeleton containing a fluorinated substituent, and a skeleton containing a cyano group are the delayed fluorescence materials. From the viewpoint of stability, it is more preferable.
- skeletons containing a heteroaryl group having a partial structure in which a carbon atom and a nitrogen atom are bonded by a double bond specific examples include pyridine, pyrimidine, pyrazine, triazine, quinoline, quinoxaline, quinazoline, or phenanthroline.
- a skeleton is preferred.
- skeletons containing pyrimidines, triazines, quinoxalines, or quinazolines are more preferred, and skeletons containing triazines are even more preferred.
- skeletons containing fluorinated substituents skeletons containing a fluorinated aryl group or a fluoroalkyl group are more preferred.
- the skeleton containing a fluorinated aryl group is preferably a fluorinated benzene ring, and more specifically, a skeleton containing fluorobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene or pentafluorobenzene is more preferable.
- a skeleton containing a fluoroalkyl group a skeleton containing a benzene ring substituted with a trifluoromethyl group is preferable, and among these, a skeleton containing mono(trifluoromethyl)benzene or bis(trifluoromethyl)benzene is more preferable.
- skeletons having a cyano group skeletons containing cyanobenzene, dicyanobenzene, and tricyanobenzene are more preferable.
- Examples of compounds in which the above-described electron-donating skeleton and electron-accepting skeleton are combined are shown below, but the compound is not particularly limited to these. It should be noted that the compounds shown here are known from past literature to emit delayed fluorescence.
- a compound represented by the following general formula (1) or general formula (2) is preferable in addition to the above-described compound in which the electron donor skeleton and the electron acceptor skeleton are combined.
- ring Za, ring Zb and ring Zc are each independently a substituted or unsubstituted aryl ring having 6 to 30 ring carbon atoms, or a substituted or unsubstituted ring It is a heteroaryl ring having 6 to 30 carbon atoms.
- Z 1 and Z 2 are each independently an oxygen atom, NRa (a nitrogen atom having a substituent Ra) or a sulfur atom.
- substituent Ra may combine with ring Za or ring Zb to form a ring.
- substituent Ra may combine with ring Za or ring Zc to form a ring.
- E 1 is BRa
- substituent Ra may combine with ring Za or ring Zb to form a ring.
- E 2 is BRa
- substituent Ra may combine with ring Za or ring Zc to form a ring.
- the above substituents Ra are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted alkyl group.
- hydrogen may be deuterium.
- a substituted or unsubstituted aryl group having 6 to 40 carbon atoms is an aryl group having 6 to 40 carbon atoms including the carbon atoms contained in the substituents substituted on the aryl group. The same applies to other substituents defining the number of carbon atoms.
- substituents when substituted include alkyl groups, cycloalkyl groups, heterocyclic groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, hydroxyl groups, and thiol groups.
- the alkyl group is, for example, a saturated aliphatic hydrocarbon group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, etc., which are substituted It may or may not have a group. Additional substituents when substituted are not particularly limited, and include, for example, alkyl groups, halogens, aryl groups, heteroaryl groups, etc. This point is also common to the following description.
- the number of carbon atoms in the alkyl group is not particularly limited, but is preferably in the range of 1 to 20, more preferably 1 to 8, from the viewpoint of availability and cost.
- a cycloalkyl group is, for example, a saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group, which may or may not have a substituent.
- the number of carbon atoms in the alkyl group portion is not particularly limited, but is preferably in the range of 3 or more and 20 or less.
- the heterocyclic group is, for example, a pyran ring, a piperidine ring, an aliphatic ring having a non-carbon atom in the ring such as a cyclic amide, which may or may not have a substituent. good.
- the number of carbon atoms in the heterocyclic group is not particularly limited, it is preferably in the range of 2 or more and 20 or less.
- the alkenyl group is, for example, a vinyl group, an allyl group, an unsaturated aliphatic hydrocarbon group containing a double bond such as a butadienyl group, which may or may not have a substituent.
- the number of carbon atoms in the alkenyl group is not particularly limited, it is preferably in the range of 2 or more and 20 or less.
- a cycloalkenyl group is, for example, an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, a cyclohexenyl group, and the like, even if it has a substituent. It does not have to be.
- the number of carbon atoms in the cycloalkenyl group is not particularly limited, but is preferably in the range of 3 or more and 20 or less.
- An alkynyl group is, for example, an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group, which may or may not have a substituent.
- the number of carbon atoms in the alkynyl group is not particularly limited, it is preferably in the range of 2 or more and 20 or less.
- An alkoxy group is, for example, a functional group in which an aliphatic hydrocarbon group is bonded via an ether bond such as a methoxy group, an ethoxy group, a propoxy group, and the aliphatic hydrocarbon group has a substituent. does not have to be
- the number of carbon atoms in the alkoxy group is not particularly limited, but is preferably in the range of 1 to 20.
- An alkylthio group is an alkoxy group in which the oxygen atom of the ether bond is substituted with a sulfur atom.
- the hydrocarbon group of the alkylthio group may or may not have a substituent.
- the number of carbon atoms in the alkylthio group is not particularly limited, but is preferably in the range of 1 to 20.
- An aryl ether group is a functional group in which an aromatic hydrocarbon group is bonded via an ether bond, such as a phenoxy group, and the aromatic hydrocarbon group may or may not have a substituent. good too.
- the number of carbon atoms in the aryl ether group is not particularly limited, it is preferably in the range of 6 or more and 40 or less.
- An arylthioether group is an arylether group in which the oxygen atom of the ether bond is substituted with a sulfur atom.
- the aromatic hydrocarbon group in the arylthioether group may or may not have a substituent.
- the number of carbon atoms in the arylthioether group is not particularly limited, it is preferably in the range of 6 or more and 40 or less.
- An aryl group includes, for example, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a benzofluorenyl group, a dibenzofluorenyl group, a phenanthryl group, anthracenyl group, a benzophenanthryl group, and a benzoanthracene.
- phenyl group, biphenyl group, terphenyl group, naphthyl group, fluorenyl group, phenanthryl group, anthracenyl group, pyrenyl group, fluoranthenyl group and triphenylenyl group are preferable.
- the aryl group may or may not have a substituent.
- the number of carbon atoms in the aryl group is not particularly limited, but is preferably 6 or more and 40 or less, more preferably 6 or more and 30 or less.
- the heteroaryl group includes, for example, pyridyl group, furanyl group, thienyl group, quinolinyl group, isoquinolinyl group, pyrazinyl group, pyrimidyl group, pyridazinyl group, triazinyl group, napthyridinyl group, cinnolinyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, benzofuranyl group, benzothienyl group, indolyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, benzocarbazolyl group, carbolinyl group, indolocarbazolyl group, benzofurocarbazolyl group, benzothienocarbazolyl non-carbon atoms such as dihydroindenocarbazolyl, benzoquinolinyl, acridinyl, dibenzoacridinyl
- the naphthyridinyl group is any of a 1,5-naphthyridinyl group, a 1,6-naphthyridinyl group, a 1,7-naphthyridinyl group, a 1,8-naphthyridinyl group, a 2,6-naphthyridinyl group and a 2,7-naphthyridinyl group.
- a heteroaryl group may or may not have a substituent.
- the number of carbon atoms in 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.
- Halogen means an atom selected from fluorine, chlorine, bromine and iodine.
- a carbonyl group, a carboxyl group, an oxycarbonyl group, and a carbamoyl group may or may not have a substituent. Examples of substituents include alkyl groups, cycloalkyl groups, aryl groups, and heteroaryl groups, and these substituents may be further substituted.
- An amino group is a substituted or unsubstituted amino group.
- Substituents for substitution include, for example, aryl groups, heteroaryl groups, linear alkyl groups, and branched alkyl groups.
- aryl group and the heteroaryl group a phenyl group, a naphthyl group, a pyridyl group and a quinolinyl group are preferable. These substituents may be further substituted.
- the number of carbon atoms is not particularly limited, but is preferably 2 or more and 50 or less, more preferably 6 or more and 40 or less, and particularly preferably 6 or more and 30 or less.
- the silyl group is, for example, a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a propyldimethylsilyl group, an alkylsilyl group such as a vinyldimethylsilyl group, a phenyldimethylsilyl group, a tert-butyldiphenylsilyl group, a tri It represents an arylsilyl group such as a phenylsilyl group and a trinaphthylsilyl group. Substituents on silicon may be further substituted.
- the number of carbon atoms in the silyl group is not particularly limited, it is preferably in the range of 1 or more and 30 or less.
- a siloxanyl group is, for example, a silicon compound group through an ether bond such as a trimethylsiloxanyl group. Substituents on silicon may be further substituted.
- a boryl group is a substituted or unsubstituted boryl group. Substituents for substitution include, for example, aryl groups, heteroaryl groups, linear alkyl groups, branched alkyl groups, aryl ether groups, alkoxy groups, and hydroxyl groups. Among them, an aryl group and an aryl ether group are preferable.
- R 10 R 11 of the phosphine oxide group is selected from the group shown below.
- R 10 and R 11 which may be the same or different, are a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a thiol group, and an alkoxy group.
- alkylthio group alkylthio group, arylether group, arylthioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, acyl group, ester group, amide group, carbamoyl group, amino group, nitro silyl groups, siloxanyl groups, boryl groups, sulfo groups, sulfonyl groups, phosphine oxide groups, and condensed rings and aliphatic rings formed between adjacent substituents.
- the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, an anthracenyl group, and a phenyl group or a biphenyl group.
- group, terphenyl group and naphthyl group are more preferred.
- Phenyl group, biphenyl group and terphenyl group are more preferable, and phenyl group is particularly preferable.
- the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, an anthracenyl group, a phenyl group, a biphenyl group, A terphenyl group and a naphthyl group are more preferable.
- a phenyl group is particularly preferred.
- the heteroaryl group includes pyridyl, furanyl, thienyl, quinolinyl, pyrimidyl, triazinyl, benzofuranyl, benzothienyl, and indolyl. group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, benzimidazolyl group, imidazopyridyl group, benzoxazolyl group, benzothiazolyl group and phenanthrolinyl group are preferred, and pyridyl group, furanyl group, thienyl group and quinolinyl group are preferred. more preferred. A pyridyl group is particularly preferred.
- the heteroaryl group includes a pyridyl group, a furanyl group, a thienyl group, a quinolinyl group, a pyrimidyl group, a triazinyl group, a benzofuranyl 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 and a phenanthrolinyl group are preferred, and a pyridyl group, a furanyl group, a thienyl group and a quinolinyl group are more preferred. .
- a pyridyl group is particularly preferred.
- any two adjacent substituents may be bonded to each other to form a conjugated or non-conjugated condensed ring.
- Constituent elements of the condensed ring may contain, in addition to carbon, an element selected from nitrogen, oxygen, sulfur, phosphorus and silicon.
- the condensed ring may be condensed with another ring.
- the substituted or unsubstituted aryl ring having 6 to 30 ring-forming carbon atoms in ring Za, ring Zb and ring Zc includes aromatic hydrocarbon rings such as benzene ring, naphthalene ring, phenanthrene ring, chrysene ring, anthracene ring and pyrene ring. is mentioned. Among these, a benzene ring is preferable from the viewpoint of ensuring solubility.
- the heteroaryl ring having 6 to 30 ring carbon atoms includes aromatic heteroaryl ring structures such as pyridine ring, quinoline ring and phenanthroline ring. Among these, a pyridine ring is preferable from the viewpoint of availability of raw materials and difficulty of synthesis.
- the substituent Ra is preferably a group having 6 to 40 carbon atoms including the substituent.
- Substituent Ra is more preferably a substituted or unsubstituted aryl group.
- the substituted or unsubstituted aryl group includes a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, and the like. is mentioned. Among these, a substituted or unsubstituted phenyl group is more preferred.
- substituent Ra is preferably a group having 6 to 40 carbon atoms including the substituent.
- Substituent Ra is more preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group.
- Z 1 and Z 2 in general formula (1) are preferably oxygen atoms or NRa. This is because the ⁇ -conjugated system of the compound represented by the general formula (1) expands efficiently, and reverse intersystem crossing occurs more efficiently from the triplet excited state to the singlet excited state, further improving the durability. This is because it is possible to
- E in general formula (1) is preferably a boron atom
- E 1 and E 2 in general formula (2) are preferably BRa. This is because the ⁇ -conjugated system of the compound represented by general formula (1) or general formula (2) is efficiently expanded, and reverse intersystem crossing occurs more efficiently from the triplet excited state to the singlet excited state. , the durability can be further improved.
- the above delayed fluorescence material is a compound represented by the general formula (1), wherein E in the general formula (1) is a boron atom, and Z 1 and Z 2 are each independently an oxygen atom or NRa is preferred.
- the delayed fluorescence material is preferably a compound represented by general formula (2), and E 1 and E 2 in general formula (2) are each independently BRa.
- ring Za, ring Zb and ring Zc are preferably benzene rings. This is because the ⁇ -conjugated system of the compound represented by general formula (1) or general formula (2) is efficiently expanded, and reverse intersystem crossing occurs more efficiently from the triplet excited state to the singlet excited state. , the durability can be further improved.
- E is an electron acceptor It is preferably a boron atom with a strong electron-donating property, and both Z 1 and Z 2 are NRa groups with a strong electron-donating property. That is, when the delayed fluorescence material is a compound represented by general formula (1), it is preferred that E is a boron atom and Z 1 and Z 2 are NRa.
- the emission spectrum of the compound represented by general formula (1) or general formula (2) is sharper than that of a compound in which an electron-donating skeleton and an electron-accepting skeleton are combined due to the multiple resonance effect of the compound. Become. Therefore, when the delayed fluorescence material is a compound represented by general formula (1) or (2), light emission with high color purity can be obtained. That is, the compound represented by general formula (1) or general formula (2) is advantageous for improving the color gamut of the display, and is therefore preferable as a delayed fluorescence material.
- the compound represented by the general formula (1) or general formula (2) has a ring Za, a ring Due to the presence of Zb, ring Zc, the LUMO orbitals can be delocalized from the E atom across each ring. By delocalizing the LUMO orbitals, the multiple resonance effect works efficiently, so that light emission with higher color purity can be obtained.
- the E atom is the E atom in the general formula (1), and the E 1 and E 2 atoms in the general formula (2).
- the substituent Ra in general formula (1) or general formula (2) more preferably forms a ring structure bonded to at least one of ring Za, ring Zb and ring Zc. This is because the substituent Ra binds to at least one ring of ring Za, ring Zb, and ring Zc, and the steric This is because it can be expected that the protective effect will be enhanced and the effect of suppressing the decrease in fluorescence quantum yield will be further enhanced. From the viewpoint of the steric protection effect of E, E 1 and E 2 , it is more preferable if the compound represented by general formula (1) is a compound represented by general formula (2).
- the delayed fluorescence material is preferably at least one of the following luminescent material (a) and luminescent material (b). That is, at least one of the luminescent material (a) and the luminescent material (b) is preferably a compound that emits delayed fluorescence.
- the luminescent material (a) is a luminescent material that emits light with a peak wavelength of 500 nm or more and less than 580 nm by using excitation light with a wavelength of 430 nm or more and 500 nm or less.
- the light-emitting material (b) is excited by either or both of excitation light having a wavelength of 430 nm or more and 500 nm or less, or light emitted from the light-emitting material (a), so that the peak wavelength is observed in the region of 580 nm or more and 750 nm or less. It is a light-emitting material that emits light that emits light.
- green light emission light emission observed in a region with a peak wavelength of 500 nm or more and less than 580 nm
- red light emission light emission observed in a region with a peak wavelength of 580 nm or more and 750 nm or less
- the color conversion layer contains a very small amount of residual solvent as described above.
- the lower limit of the amount of residual solvent in the color conversion layer is 10 mass ppm or more, preferably 100 mass ppm or more, and 500 mass ppm or more. is more preferred.
- the reason why the durability of the color conversion sheet is improved when the residual solvent amount is at least the above lower limit is considered as follows.
- the triplet-excited delayed fluorescent material contained in the color conversion layer contains charge delocalized excited species in which positively charged holes can move freely within the molecule, and charge sites in which holes cannot move freely within the molecule. There are extrinsic excited species and neutral excited species.
- the reverse conversion from the triplet excited state to the singlet excited state of the delayed fluorescence material occurs when the energy levels of the neutral excited species, which is a kind of triplet excited state, and the excited species in the singlet excited state are close.
- the energy level of the neutral excited species in the triplet excited state is preferably high.
- the solvent effect is to stabilize the energy state of a luminescent material by containing a solvent.
- the higher the polarity of the molecule the greater the effect of stabilizing the energy state due to the solvent effect.
- Stabilization of the excitation energy of the light-emitting material occurs due to the solvent effect. Less susceptible to energy stabilization. Therefore, the difference between the energy level of the excited species in the singlet excited state and the energy level of the neutral excited species in the triplet excited state is reduced, thereby improving the durability of the color conversion sheet. .
- the upper limit of the residual solvent amount in the color conversion layer is 30000 mass ppm or less, preferably 10000 mass ppm or less, and 5000 mass ppm or less. It is more preferable to have If the residual solvent amount is equal to or less than the above upper limit, the fluidity of the resin in the color conversion layer is low, so the probability of contact between the luminescent material in the color conversion layer and singlet oxygen is low. It is possible to reduce the reaction rate of the light-emitting material that is oxidatively deteriorated due to contact with oxygen.
- the amount of residual solvent in the color conversion layer can be measured by gas chromatography.
- the content of the solvent in the color conversion layer is adjusted to a very small amount by drying the color conversion layer. Drying of the color conversion layer can be performed using a general heating device such as a hot air dryer or an infrared dryer.
- the heating temperature is preferably 60 to 200° C.
- the heating time is preferably 2 minutes to 4 hours.
- the heating temperature is more preferably 100 to 200° C., and the heating time is 2 minutes to 2 hours. is more preferred.
- the residual solvent in the color conversion layer preferably has a functional group with an SP value of 11.0 or more and 20.0 or less.
- the residual solvent has a functional group in such an SP value range, the above-described solvent effect is increased, thereby promoting reverse conversion from the triplet excited state to the singlet excited state of the delayed fluorescence material. Therefore, the durability of the color conversion sheet can be further improved.
- E represents the molar heat of vaporization (cal/mol) and V represents the molar volume (cm 3 /mol). That is, the unit of the SP value of the functional group of the residual solvent in the color conversion layer is (cal/cm 3 ) 1/2 .
- E and V in the above SP value formula are molar evaporation of atomic groups described in "POLYMER ENGINEERING AND SCIENCE, 1974, Vol. 14, No. 2, ROBERT F. FEDORS, (pages 151-153)" Heat (E) and molar volume (V) can be used.
- solvents contained in the color conversion sheet of the present invention include cyclohexane, hexane, toluene, 1-methoxy-2-propanol, 2-propanol, ethyl acetate, ethanol, methyl ethyl ketone and acetone.
- the color conversion sheet of the present invention may contain two or more of these as solvents.
- Tables 1-1 and 1-2 show lists of functional groups and SP values possessed by the solvents.
- solvents highly polar solvents are preferred from the viewpoint of improving the durability of the color conversion sheet. preferable.
- a solvent having a functional group with an SP value of 11.0 or more and 20.0 or less is more preferable.
- 1-methoxy-2-propanol, ethyl acetate, methyl ethyl ketone, acetone and the like are more preferable.
- ethyl acetate is more preferable because it does not affect the deterioration of the delayed fluorescent material, and it is easy to adjust the amount of residual solvent after drying the color conversion layer to 10 ppm by mass or more and 30000 ppm by mass or less.
- binder resin forms a continuous phase and may be any material as long as it is excellent in moldability, transparency, heat resistance, and the like.
- binder resins include photocurable resist materials having reactive vinyl groups such as acrylic acid, methacrylic acid, polyvinyl cinnamate, ring rubber, epoxy resins, silicone resins (silicone rubber, silicone Organopolysiloxane cured products (crosslinked products such as gels), urea resins, fluororesins, polycarbonate resins, acrylic resins, urethane resins, melamine resins, polyvinyl resins, polyamide resins, phenol resins, polyvinyl alcohol resins, cellulose resins, Known resins such as aliphatic ester resins, aromatic ester resins, aliphatic polyolefin resins and aromatic polyolefin resins can be used.
- these copolymer resins may be used as the binder resin.
- binder resins useful for the color conversion sheet of the present invention and the color conversion composition used therein (hereinafter sometimes referred to as the color conversion composition of the present invention) can be obtained.
- thermoplastic resins are more preferable because the process of forming a sheet is easy.
- thermoplastic resins epoxy resins, silicone resins, acrylic resins, ester resins, olefin resins, or mixtures thereof can be preferably used from the viewpoint of transparency, heat resistance, and the like. From the standpoint of durability, particularly preferred thermoplastic resins are acrylic resins, ester resins, and cycloolefin resins.
- binder resin examples include those described in WO2016/190283, WO2017/61337, WO2018/43237 and WO2019/188019. mentioned.
- the binder resin is preferably a resin containing a partial structure represented by general formula (3) and a partial structure represented by general formula (4) in its molecular structure.
- the binder resin in the color conversion layer contains a partial structure represented by general formula (3) and a partial structure represented by general formula (4) in its molecular structure.
- the residual solvent in the color conversion layer preferably has a functional group with an SP value of 11.0 (cal/cm 3 ) 1/2 or more and 20.0 (cal/cm 3 ) 1/2 or less. .
- Z 1 and Z 2 which may be the same or different, are hydrogen atoms or organic groups having 1 to 20 carbon atoms.
- Y 1 to Y 4 which may be the same or different, are hydrogen atoms or organic groups having 1 to 20 carbon atoms. At least one of Y 1 to Y 4 is a group containing an aliphatic cyclic hydrocarbon structure.
- the delayed fluorescent material contained in the color conversion sheet of the present invention is excited by light. Since the delayed fluorescent material in the excited state has high reactivity, when the delayed fluorescent materials in the excited state are close to each other, the delayed fluorescent material accelerated deterioration. Therefore, in order to improve the durability of the delayed fluorescent material contained in the color conversion sheet, it is preferable that the delayed fluorescent material is well dispersed in the binder resin without aggregating.
- the binder resin in the color conversion layer should have a partial structure with high compatibility with the delayed fluorescence material and a partial structure with low compatibility with the delayed fluorescence material. It is preferable to have both.
- a more preferred form of such a binder resin is a copolymer randomly containing a partial structure having high compatibility with the delayed fluorescence material and a partial structure having low compatibility with the delayed fluorescence material.
- the delayed fluorescence material contained in the color conversion sheet of the present invention has good compatibility with the partial structure represented by general formula (3) in the molecular structure of the binder resin. It is characterized by poor compatibility with the partial structure. Therefore, when the binder resin has both the partial structure represented by the general formula (3) and the partial structure represented by the general formula (4), the light-emitting material such as the delayed fluorescent material can be used in the color conversion layer. It can be well dispersed in the binder resin. As a result, it is possible to realize high durability of the color conversion sheet. This effect is even greater when the delayed fluorescence material is an organic light-emitting material.
- the binder resin in the color conversion layer is preferably a resin with excellent heat resistance.
- Z 1 is preferably a hydrogen atom or a methyl group, more preferably a methyl group. preferable.
- Z 2 is a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group, or an alkenyl group. , a cycloalkenyl group, an alkynyl group, a hydroxyl group, a thiol group, an alkoxy group, an alkylthio group, an arylether group, an arylthioether group, an aryl group or a heteroaryl group.
- these groups may be further substituted with the substituents described above.
- Z 2 in the partial structure represented by general formula (3) is more preferably a methyl group from the viewpoint of availability and cost.
- Y 1 to Y 4 are hydrogen, an alkyl group, a cycloalkyl group, a heterocyclic group, Alkenyl groups, cycloalkenyl groups, alkynyl groups, hydroxyl groups, thiol groups, alkoxy groups, alkylthio groups, arylether groups, arylthioether groups, aryl groups or heteroaryl groups are preferred. In addition, these groups may be further substituted with the substituents described above.
- At least one of Y 1 to Y 4 in general formula (4) is a group containing an aliphatic cyclic hydrocarbon structure.
- aliphatic cyclic hydrocarbon structures include substituted or unsubstituted saturated cyclic hydrocarbon (cycloalkyl) structures and unsaturated cyclic hydrocarbon (cycloalkenyl) structures.
- a saturated cyclic hydrocarbon (cycloalkyl) structure is preferable from the viewpoint of durability.
- the number of carbon atoms constituting such an aliphatic cyclic hydrocarbon structure is not particularly limited, but is usually preferably 4 to 30, more preferably 5 to 20, and 5 to 15. is even more preferable. When the number of carbon atoms constituting the aliphatic cyclic hydrocarbon structure is within the above range, compatibility between the partial structure represented by the general formula (4) in the binder resin and the light emitting material is ensured, and high Durability can be obtained.
- saturated cyclic hydrocarbon (cycloalkyl) structures include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-hydroxystyrene, p-methylstyrene, p-ethylstyrene, p-isopropylstyrene, p- - hydrogenated the aromatic ring portion of polymers of aromatic vinyl monomers such as divinylbenzene, alkoxystyrene, chlorostyrene, stilbene, 1-vinylnaphthalene, diphenylethylene, triphenylethylene, tetraphenylethylene, and 4-vinylbiphenyl; structure and the like.
- a vinyl monomer having a saturated cyclic hydrocarbon structure such as vinylcyclohexane can also be used as a starting material.
- At least one of Y 1 to Y 4 in general formula (4) is an aliphatic cyclic hydrocarbon structure
- the combination of Y 1 to Y 4 is not particularly limited as long as it is a group containing
- at least one of Y 1 to Y 4 in general formula (4) is preferably a substituted or unsubstituted cyclohexyl group. More preferably, one of Y 1 to Y 4 in general formula (4) is a substituted or unsubstituted cyclohexyl group and the other three are hydrogen atoms.
- the content of the repeating unit of the partial structure represented by general formula (3) in the binder resin contained in the color conversion sheet of the present invention is not particularly limited, but is 30% by weight or more of the total amount of the binder resin. is preferably 50% by weight or more, more preferably 60% by weight or more, and particularly preferably 70% by weight or more.
- the content of the repeating unit of the partial structure represented by the general formula (3) is in the range of the above lower limit or more, the compatibility between the partial structure represented by the general formula (3) and the delayed fluorescence material is improved. can be ensured, and as a result, higher durability can be obtained.
- the content of the repeating unit of the partial structure represented by the general formula (3) in the binder resin contained in the color conversion sheet of the present invention should be 95% by weight or less of the total amount of the binder resin. is preferred, 90% by weight or less is more preferred, and 85% by weight or less is even more preferred.
- the content of the repeating unit of the partial structure represented by formula (3) is in the range of the above upper limit or less, a color conversion sheet having excellent crack resistance can be obtained.
- the content of the repeating unit of the partial structure represented by the general formula (4) in the binder resin contained in the color conversion sheet of the present invention is not particularly limited, but is 5% by weight or more of the total amount of the binder resin. is preferably 10% by weight or more, and particularly preferably 15% by weight or more.
- the content of the repeating unit of the partial structure represented by the general formula (4) is in the range of the above lower limit or more, it is possible to ensure the dispersibility of the delayed fluorescence material in the binder resin, as a result, higher Durability can be obtained.
- the content of the repeating unit of the partial structure represented by the general formula (4) in the binder resin contained in the color conversion sheet of the present invention should be 70% by weight or less of the total amount of the binder resin. is preferred, 50% by weight or less is more preferred, and 30% by weight or less is particularly preferred.
- the content of the repeating unit of the partial structure represented by the general formula (4) is in the range of the above upper limit or less, the compatibility between the partial structure represented by the general formula (4) and the delayed fluorescence material is improved. As a result, a color conversion sheet having excellent emission intensity can be obtained.
- the weight average molecular weight (Mw) of the binder resin contained in the color conversion sheet of the present invention is preferably 5,000 or more, more preferably 15,000 or more, and particularly preferably 20,000 or more. preferable. Moreover, the weight average molecular weight of the binder resin is preferably 500,000 or less, more preferably 100,000 or less, and particularly preferably 50,000 or less. If the weight-average molecular weight is within the above upper and lower limits, the compatibility between the binder resin and the luminescent material is good, and a color conversion sheet with higher durability can be obtained.
- the weight average molecular weight in the present invention is a value measured by gel permeation chromatography (GPC method). Specifically, after filtering the sample through a membrane filter with a pore size of 0.45 ⁇ m, a GPC device (manufactured by Tosoh Corporation HLC-82A) (developing solvent: toluene, developing speed: 1.0 ml/min, column: manufactured by Tosoh Corporation TSKgelG2000HXL) It is a value obtained by polystyrene conversion using .
- GPC method gel permeation chromatography
- the glass transition temperature (Tg) of the binder resin contained in the color conversion sheet of the present invention is preferably 50-200°C, more preferably 100-160°C. If the glass transition temperature of the binder resin is within the above range, the color conversion sheet formed from the color conversion composition of the present invention can have higher durability.
- the glass transition temperature of the binder resin can be measured with a commercially available measuring instrument, for example, a differential scanning calorimeter manufactured by Seiko Electronics Industries (trade name: DSC6220, temperature increase rate: 0.5°C/min).
- a commercially available measuring instrument for example, a differential scanning calorimeter manufactured by Seiko Electronics Industries (trade name: DSC6220, temperature increase rate: 0.5°C/min).
- the method for synthesizing the binder resin is not particularly limited, and a known method such as copolymerizing each raw material monomer in the presence of a polymerization initiator can be used as appropriate. Moreover, a commercial item can also be used as said binder resin. Commercially available products corresponding to the binder resin include, but are not limited to, Optimas7500 and Optimas6000 manufactured by Mitsubishi Gas Chemical Co., Ltd., for example.
- additives such as a dispersing agent and a leveling agent may be added to the binder resin to stabilize the coating film. can also be added. Inorganic particles such as silica particles and silicone fine particles can also be added to the binder resin as a color conversion material sedimentation inhibitor.
- the binder resin contains, as other components, a hydrosilylation reaction delaying agent such as acetylene alcohol in order to suppress hardening at room temperature and prolong the pot life. It is preferable to mix agents.
- the binder resin may contain fine particles such as fumed silica, glass powder, quartz powder, etc., titanium oxide, zirconia oxide, barium titanate, zinc oxide, etc., if necessary, as long as the effects of the present invention are not impaired.
- Inorganic fillers, pigments, flame retardants, heat-resistant agents, antioxidants, dispersants, solvents, adhesion-imparting agents such as silane coupling agents and titanium coupling agents, and the like may be blended.
- the color conversion sheet of the present invention contains a light stabilizer, an antioxidant, a processing and heat stabilizer, a light resistance stabilizer such as an ultraviolet absorber, and a scattering agent.
- a light stabilizer such as an antioxidant, a processing and heat stabilizer, a light resistance stabilizer such as an ultraviolet absorber, and a scattering agent.
- Other components such as particles, silicone fine particles and silane coupling agents may be contained.
- Examples of light stabilizers include tertiary amines, catechol derivatives, nickel compounds, and at least one selected from the group consisting of Sc, V, Mn, Fe, Co, Cu, Y, Zr, Mo, Ag, and lanthanoids. Examples include, but are not limited to, complexes containing transition metals, salts with organic acids, and the like. Moreover, these light stabilizers may be used alone or in combination.
- antioxidants examples include phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4-ethylphenol. It is not particularly limited to these. Moreover, these antioxidants may be used alone or in combination.
- processing and heat stabilizers include phosphorus-based stabilizers such as tributylphosphite, tricyclohexylphosphite, triethylphosphine, and diphenylbutylphosphine, but are not particularly limited thereto. Moreover, these stabilizers may be used alone or in combination.
- light stabilizers examples include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis( ⁇ , ⁇ -dimethylbenzyl)phenyl]-2H- Benzotriazoles such as benzotriazole can be mentioned, but are not particularly limited to these. Moreover, these light resistance stabilizers may be used alone or in combination.
- inorganic particles having a refractive index of 1.7 to 2.8 are preferable.
- the inorganic particles include titania, zirconia, alumina, ceria, tin oxide, indium oxide, iron oxide, zinc oxide, aluminum nitride, aluminum, tin, sulfides of titanium or zirconium, and hydroxides of titanium or zirconium. is mentioned.
- the content of these additives depends on the molar absorption coefficient of the compound, the emission quantum yield, the absorption intensity at the excitation wavelength, and the thickness and transmittance of the color conversion sheet to be produced. Normally, it is preferably 1.0 ⁇ 10 ⁇ 3 to 30 parts by weight with respect to 100 parts by weight of the binder resin. Further, the content of these additives is more preferably 1.0 ⁇ 10 -2 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the binder resin. Part or more and 10 parts by weight or less is particularly preferable.
- Method for producing color conversion composition An example of the method for producing the color conversion composition for producing the color conversion layer included in the color conversion sheet of the present invention is described below.
- a predetermined amount of the above-described delayed fluorescence material, binder resin, solvent, and, if necessary, additives and the like are mixed.
- a color conversion composition can be obtained by mixing or kneading these components homogeneously using a stirrer/kneader after mixing each of these components to obtain a predetermined composition.
- the stirring/kneading machine includes, for example, a homogenizer, a rotation-revolution stirrer, a three-roller, a ball mill, a planetary ball mill, and a bead mill.
- defoaming under vacuum or reduced pressure conditions is also preferably performed.
- Examples of the substrate layer (for example, the substrate layer 10 shown in FIGS. 2 to 4) in the color conversion sheet of the present invention include glass and resin films.
- the resin film plastic films such as polyethylene terephthalate (PET), polyphenylene sulfide, polycarbonate, polypropylene, and polyimide are preferable.
- PET polyethylene terephthalate
- the surface of the base material layer may be subjected to a release treatment in advance in order to facilitate the peeling of the film.
- the thickness of the substrate layer is not particularly limited, but the lower limit is preferably 25 ⁇ m or more, more preferably 38 ⁇ m or more.
- 5000 micrometers or less are preferable and 3000 micrometers or less are more preferable.
- the barrier film (for example, the barrier film 12 shown in FIG. 4) in the color conversion sheet of the present invention is appropriately used to improve the gas barrier properties of the color conversion layer.
- this barrier film also referred to as a barrier layer
- a film that suppresses penetration of oxygen, moisture, heat, etc. into the color conversion layer is preferable.
- the color conversion sheet of the present invention may have two or more layers of such barrier films.
- the color conversion sheet of the present invention may have barrier films on both sides of the color conversion layer like the barrier film 12 illustrated in FIG. 4, or may have a barrier film on only one side of the color conversion layer. good too.
- Barrier films having gas barrier properties include, for example, inorganic oxides such as silicon oxide, aluminum oxide, titanium oxide, tantalum oxide, zinc oxide, tin oxide, indium oxide, yttrium oxide and magnesium oxide, silicon nitride, aluminum nitride, Inorganic nitrides such as titanium nitride and silicon carbide nitride, metal oxide thin films and metal nitride thin films with other elements added to these, polyvinylidene chloride, acrylic resins, silicone resins, melamine resins, urethane resins , fluorine-based resins, and films containing various resins such as polyvinyl alcohol-based resins such as saponified products of vinyl acetate.
- inorganic oxides such as silicon oxide, aluminum oxide, titanium oxide, tantalum oxide, zinc oxide, tin oxide, indium oxide, yttrium oxide and magnesium oxide
- silicon nitride aluminum nitride
- Inorganic nitrides such as titanium
- the barrier film may contain two or more of these.
- Barrier films having a barrier function against moisture include, for example, polyethylene, polypropylene, nylon, polyvinylidene chloride, copolymers of vinylidene chloride and vinyl chloride, copolymers of vinylidene chloride and acrylonitrile, and fluorine-based resins.
- films containing various resins such as polyvinyl alcohol-based resins such as saponified products of vinyl acetate, and the like.
- the color conversion sheet of the present invention has a light diffusion layer, an adhesive layer, an antireflection function, an antiglare function, an antireflection antiglare function, a hard coat function (friction resistance function), an antistatic function, an antistatic function, and an antiglare function.
- An auxiliary layer having an antifouling function, an electromagnetic shielding function, an infrared ray cutting function, an ultraviolet ray cutting function, a polarizing function, and a toning function may be further provided.
- the color conversion sheet of the present invention may further include a polarizing reflective film, a diffusion sheet, a prism sheet, a wavelength selective reflective film, and the like.
- a polarizing reflective film e.g., a polarizing reflective film
- a diffusion sheet e.g., a diffusion sheet
- a prism sheet e.g., a wavelength selective reflective film
- a wavelength selective reflective film e.g., a polarizing reflective film, a diffusion sheet, a prism sheet, a wavelength selective reflective film, and the like.
- Preferred specific examples of the wavelength-selective reflective film include those described in International Publication No. 2017/164155 and Japanese Patent Application Laid-Open No. 2018-81250.
- the color conversion composition prepared by the method described above is applied onto a substrate such as a substrate layer or a barrier layer, and then dried. This forms a color conversion layer.
- the binder resin contained in the color conversion composition is a thermosetting resin
- the color conversion layer may be formed by coating the color conversion composition on an underlayer such as a substrate layer and then heat-curing it.
- the binder resin contained in the color conversion composition is a photocurable resin
- the color conversion layer may be formed by coating the color conversion composition on an underlayer such as a substrate layer and then photocuring it.
- Reverse roll coater, blade coater, comma coater, slit die coater, direct gravure coater, offset gravure coater, kiss coater, natural roll coater, air knife coater, roll blade coater, two stream coater, and rod coater are used to apply the color conversion composition.
- wire bar coater, applicator, dip coater, curtain coater, spin coater, knife coater and the like are used to apply the color conversion composition.
- the color conversion layer can be dried using a general heating device such as a hot air dryer or an infrared dryer.
- the heating temperature is preferably 60 to 200° C.
- the heating time is preferably 2 minutes to 4 hours. It is also possible to heat and harden the color conversion layer in stages by a method such as step curing.
- the heating device When the color conversion layer is formed by heat curing, the heating device includes a hot air oven.
- the heating conditions for heat-curing the color conversion layer can be selected according to the binder resin.
- the heating temperature is preferably 100° C. to 300° C.
- the heating time is preferably 1 minute to 2 hours.
- the color conversion layer When forming the color conversion layer by photocuring, it is preferable to irradiate the color conversion layer with high-energy light such as ultraviolet rays.
- the light irradiation conditions for photocuring the color conversion layer can be selected according to the binder resin.
- the wavelength of light to be irradiated is preferably 200 nm to 500 nm, and the irradiation amount of light is preferably 10 mJ/cm 2 to 10 J/cm 2 .
- a light source unit according to an embodiment of the present invention includes at least a light source and the color conversion composition or color conversion sheet described above.
- the light source included in the light source unit of the present invention is the source of the excitation light described above.
- the method of arranging the light source and the color conversion sheet is not particularly limited, and a configuration in which the light source and the color conversion sheet are in close contact with each other may be adopted, or a remote phosphor type in which the light source and the color conversion sheet are separated from each other may be adopted. good too.
- the light source unit of the present invention may further include a color filter for the purpose of increasing color purity.
- any light source can be used as the type of light source provided in the light source unit of the present invention as long as it emits light in a wavelength region that can be absorbed by the delayed fluorescence material.
- any excitation light source can be used, for example, hot cathode tubes, cold cathode tubes, fluorescent light sources such as inorganic electroluminescence (EL), organic EL element light sources, LED light sources, incandescent light sources, or sunlight. It is possible.
- an LED light source is a suitable light source.
- a blue LED light source that emits maximum light in a wavelength range of 430 nm or more and 500 nm or less is a more suitable light source because it can improve the color purity of blue light.
- the light source may have one type of emission peak, or may have two or more types of emission peaks, but preferably has one type of emission peak in order to increase color purity. It is also possible to arbitrarily combine and use a plurality of light sources having different types of emission peaks.
- the light source unit of the present invention is useful for various light sources such as space illumination and backlight.
- the light source unit of the present invention can be used for applications such as displays, lighting devices, interior decorations, signs, and signboards, and is particularly suitable for displays and lighting devices.
- a display according to an embodiment of the invention comprises at least the light source unit described above.
- a display such as a liquid crystal display
- a light source unit having the above-described light source, color conversion sheet, and the like is used as a backlight unit.
- a lighting device according to an embodiment of the present invention includes at least the light source unit described above.
- this illumination device combines a blue LED light source as a light source unit and a color conversion sheet that converts the blue light from the blue LED light source into light with a longer wavelength to emit white light. Configured.
- ⁇ Durability evaluation> In the durability evaluation, in each example and each comparative example, a current of 30 mA was applied to a light emitting device equipped with the prepared color conversion sheet and a blue LED element (manufactured by USHIO EPITEX; model number SMBB450H-1100, emission peak wavelength: 450 nm). was flowed to light the blue LED element, and the initial emission peak intensity of green light and the emission peak intensity of red light were measured using a spectral radiance meter (CS-1000, manufactured by Konica Minolta). The distance between the color conversion sheet and the blue LED element in each light emitting device was set to 3 cm.
- CS-1000 spectral radiance meter
- Emission peak intensity maintenance rate Z (%) Y/X x 100
- X is the initial emission peak intensity.
- Y is the emission peak intensity after continuous irradiation for 1000 hours.
- the residual solvent amount in the color conversion layer was measured by the following procedure. Specifically, first, a color conversion layer was formed on a polyester film “Lumirror” (registered trademark) U48 (manufactured by Toray Industries, Inc., thickness 50 ⁇ m). Subsequently, the formed color conversion layer was peeled off from the polyester film, and 20 mg of the obtained color conversion layer alone was weighed. Next, 20 mg of this color conversion layer was dissolved in 2 mL of NMP to prepare a sample for measuring the amount of residual solvent in the color conversion layer. Using a gas chromatograph (GC-2010) manufactured by Shimadzu Corporation as a measuring instrument, the amount of residual solvent in the sample was measured under the following conditions.
- GC-2010 gas chromatograph manufactured by Shimadzu Corporation
- Resin A Resin F described in International Publication No. 2019/021813 was used as Resin A in this specification.
- Resin A is a binder resin containing 95.0% by weight of the partial structure represented by general formula (3) and 5.0% by weight of the partial structure represented by general formula (4).
- one of Y 1 to Y 4 of the partial structure represented by general formula (4) is an unsubstituted cyclohexyl group, and the other three are hydrogen atoms.
- Resin B As resin B in this specification, resin G (Optimas 6000 (PMMA-hydrogenated styrene copolymer manufactured by Mitsubishi Gas Chemical Co., Ltd.)) described in International Publication No. 2019/021813 was used. Resin B is a binder resin containing 61.0% by weight of the partial structure represented by general formula (3) and 39.0% by weight of the partial structure represented by general formula (4). In this resin B, one of Y 1 to Y 4 of the partial structure represented by general formula (4) is an unsubstituted cyclohexyl group, and the other three are hydrogen atoms.
- resin G Optimas 6000 (PMMA-hydrogenated styrene copolymer manufactured by Mitsubishi Gas Chemical Co., Ltd.)
- Resin B is a binder resin containing 61.0% by weight of the partial structure represented by general formula (3) and 39.0% by weight of the partial structure represented by general formula (4).
- Resin C As Resin C in this specification, Resin H (Optimas 7500 (PMMA-hydrogenated styrene copolymer manufactured by Mitsubishi Gas Chemical Co., Ltd.)) described in International Publication No. 2019/021813 was used.
- Resin C is a binder resin containing 77.0% by weight of the partial structure represented by general formula (3) and 23.0% by weight of the partial structure represented by general formula (4).
- one of Y 1 to Y 4 of the partial structure represented by general formula (4) is an unsubstituted cyclohexyl group, and the other three are hydrogen atoms.
- Resin D Resin I described in International Publication No. 2019/021813 was used as Resin D in this specification.
- Resin D is a binder resin containing 75.7% by weight of the partial structure represented by general formula (3) and 24.3% by weight of the partial structure represented by general formula (4).
- this resin D one of Y 1 to Y 4 of the partial structure represented by general formula (4) is an unsubstituted cyclohexyl group, and the other three are hydrogen atoms.
- Example 1 to 4 In Examples 1 to 4, 0.40 of the compound G-1 as the luminescent material (a) was added to 100 parts by weight of the binder resin (resin A, resin B, resin C, or resin D) shown in Table 2 below. 0.01 parts by weight of compound R-1 as a light-emitting material (b) and 300 parts by weight of ethyl acetate as a solvent were mixed. After that, the mixture was stirred and defoamed at 1000 rpm for 20 minutes using a planetary stirring and defoaming device "Mazerustar KK-400" (manufactured by Kurabo Industries, Ltd.). was obtained.
- a polyester resin "Vylon 630" (manufactured by Toyobo Co., Ltd.) was used as the adhesive layer resin, and 300 parts by weight of ethyl acetate was mixed as a solvent with 100 parts by weight of this polyester resin. After that, the mixture is stirred and defoamed at 300 rpm for 20 minutes using a planetary stirring and defoaming device "Mazerustar KK-400" (manufactured by Kurabo Industries, Ltd.), thereby obtaining a resin composition as an adhesive composition. got
- the color conversion composition obtained as described above is coated on a polyester film “Lumirror” (registered trademark) U48 (manufactured by Toray Industries, Inc., thickness 50 ⁇ m) using a slit die coater, and heated at 130° C. for 20 minutes. Heated for 1 minute and dried. As a result, a color conversion layer having an average film thickness of 20 ⁇ m was formed, and a unit in which the color conversion layer and the polyester film (base material layer) were laminated was obtained.
- a polyester film “Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc., thickness 50 ⁇ m
- the resin composition obtained as an adhesive composition as described above is applied to the PET base layer side of the light diffusion film "Chemical Mat” 125PW (manufactured by Kimoto Co., Ltd., thickness 138 ⁇ m) using a slit die coater. It was applied, heated at 130° C. for 20 minutes, and dried. As a result, an adhesive layer having an average thickness of 15 ⁇ m was formed, and a unit in which the adhesive layer, the PET base layer, and the light diffusion film (light diffusion layer) were laminated was obtained.
- Example 5 In Example 5, a color conversion sheet was produced and various evaluations of the color conversion sheet were carried out in the same manner as in Example 1, except that compound R-2 was used as the luminescent material (b). Table 2 shows the configuration and evaluation results of the color conversion sheet in Example 5.
- Example 6 a color conversion sheet was produced and various evaluations of the color conversion sheet were carried out in the same manner as in Example 1, except that compound G-2 was used as the luminescent material (a). Table 2 shows the configuration and evaluation results of the color conversion sheet in Example 6.
- Example 7-13 In Examples 7 to 13, color conversion sheets were produced and various evaluations of the color conversion sheets were performed in the same manner as in Example 1, except that the drying temperature and drying time were changed as shown in Table 3 below. . Table 3 shows the structure and evaluation results of the color conversion sheets in each of Examples 7 to 13.
- Example 14 In Example 14, a color conversion sheet was prepared and printed in the same manner as in Example 1 except that toluene was used as the solvent and the drying temperature and drying time were changed as shown in Table 3. Various evaluations were performed. Table 3 shows the configuration and evaluation results of the color conversion sheet in Example 14.
- Comparative example 1 In Comparative Example 1, the same procedure as in Example 1 was repeated except that compound G-2 was used as the luminescent material (a) and compound R-2 was used as the luminescent material (b). Various evaluations of the conversion sheet were carried out. Table 4 shows the configuration and evaluation results of the color conversion sheet in Comparative Example 1.
- Comparative example 2 In Comparative Example 2, a color conversion sheet was produced and various evaluations of the color conversion sheet were performed in the same manner as in Example 1, except that the drying temperature and drying time were changed as shown in Table 4. The configuration and evaluation results of the color conversion sheet in Comparative Example 2 are as shown in Table 4.
- Comparative Example 3 (Comparative Example 3)
- a color conversion sheet was produced and various evaluations of the color conversion sheet were performed in the same manner as in Comparative Example 1 except that the drying temperature and drying time were changed as shown in Table 4.
- Table 4 shows the configuration and evaluation results of the color conversion sheet in Comparative Example 3.
- green light emission peak intensity maintenance rate means the evaluation result of chromaticity durability of the luminescent material (a) contained in the color conversion sheet.
- Red light emission peak intensity maintenance ratio means the evaluation result of chromaticity durability of the light-emitting material (b) contained in the color conversion sheet.
- the color conversion sheet according to the present invention is suitable for realizing excellent chromaticity durability.
- Color Conversion Sheet 10 Base Layer 11 Color Conversion Layer 12 Barrier Film
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Abstract
Description
発光材料(a):波長430nm以上500nm以下の範囲の励起光を用いることにより、ピーク波長が500nm以上580nm未満の領域に観測される発光を呈する発光材料
発光材料(b):波長430nm以上500nm以下の範囲の励起光または前記発光材料(a)からの発光のいずれかまたは両方によって励起されることにより、ピーク波長が580nm以上750nm以下の領域に観測される発光を呈する発光材料
本発明の実施形態に係る色変換シートは、光源等の発光体からの入射光を、その入射光とは異なる波長の光に変換する色変換シートであって、少なくとも、遅延蛍光を放出する化合物とバインダー樹脂とを含有する色変換層を含む。当該色変換シートにおいて、色変換層中の溶媒量は、10質量ppm以上30000質量ppm以下である。ここで、「入射光とは異なる波長の光に変換する」とは、入射光を当該入射光よりも長波長の光に変換することが好ましい。以下、本発明の実施形態に係る色変換シートは、本発明の色変換シートと略記される場合がある。
本発明において、色変換層(例えば図1~4に示す色変換層11)は、遅延蛍光を放出する化合物(以下、「遅延蛍光材料」と略記する場合がある)と、バインダー樹脂と、微少量の溶媒とを含有する。当該微小量の溶媒は、色変換層中の残存溶媒と定義される。
遅延蛍光を放出する化合物(遅延蛍光材料)については、「最先端の有機EL」(安達千波矢、藤本弘編、シーエムシー出版発行)の87~103ページで解説されている。その文献の中で、発光材料の一重項励起状態と三重項励起状態のエネルギー準位を近接させることにより、通常は遷移確率が低い三重項励起状態から一重項励起状態への逆エネルギー移動が高効率で生じ、熱活性化遅延蛍光(Thermally Activated delayed Fluorescence,TADF)が発現すると説明されている。さらに、当該文献中の図5で、遅延蛍光の発生メカニズムが説明されている。遅延蛍光の発光は、過渡PL(Photo Luminescence)測定によって確認できる。
本発明の色変換シートにおいて、色変換層は、上述したように、微少量の溶媒である残存溶媒を含有している。色変換層中の残存溶媒量の下限値は、色変換シートの耐久性を向上させるという観点から、10質量ppm以上であり、100質量ppm以上であることが好ましく、500質量ppm以上であることがより好ましい。残存溶媒量が上記の下限値以上であるときに色変換シートの耐久性が向上するのは、以下の理由によると考えられる。
SP値(δ)=(E/V)1/2
バインダー樹脂は、連続相を形成するものであり、成型加工性、透明性、耐熱性等に優れる材料であればよい。バインダー樹脂の例としては、例えば、アクリル酸系、メタクリル酸系、ポリケイ皮酸ビニル系、環ゴム系等の反応性ビニル基を有する光硬化型レジスト材料、エポキシ樹脂、シリコーン樹脂(シリコーンゴム、シリコーンゲル等のオルガノポリシロキサン硬化物(架橋物)を含む)、ウレア樹脂、フッ素樹脂、ポリカーボネート樹脂、アクリル樹脂、ウレタン樹脂、メラミン樹脂、ポリビニル樹脂、ポリアミド樹脂、フェノール樹脂、ポリビニルアルコール樹脂、セルロース樹脂、脂肪族エステル樹脂、芳香族エステル樹脂、脂肪族ポリオレフィン樹脂、芳香族ポリオレフィン樹脂等の公知のものが挙げられる。また、バインダー樹脂としては、これらの共重合樹脂を用いても構わない。これらの樹脂を適宜設計することで、本発明の色変換シートおよびこれに用いられる色変換組成物(以下、本発明の色変換組成物という場合がある)に有用なバインダー樹脂が得られる。これらの樹脂の中でも、シート化のプロセスが容易であることから、熱可塑性樹脂がさらに好ましい。熱可塑性樹脂の中でも、透明性、耐熱性等の観点から、エポキシ樹脂、シリコーン樹脂、アクリル樹脂、エステル樹脂、オレフィン樹脂またはこれらの混合物を好適に用いることができる。また、耐久性の観点から特に好ましい熱可塑性樹脂は、アクリル樹脂、エステル樹脂、シクロオレフィン樹脂である。
本発明の色変換シートは、上述した遅延蛍光材料、バインダー樹脂および残存溶媒以外に、光安定化剤、酸化防止剤、加工および熱安定化剤、紫外線吸収剤等の耐光性安定化剤、散乱粒子、シリコーン微粒子およびシランカップリング剤等、その他の成分(添加剤)を含有してもよい。
以下に、本発明の色変換シートに含まれる色変換層を作製するための色変換組成物の製造方法の一例を説明する。この製造方法では、前述した遅延蛍光材料、バインダー樹脂、溶媒、必要に応じて添加剤等を所定量混合する。これらの各成分を所定の組成になるよう混合した後、撹拌・混練機を用いて均質に混合または混練することにより、色変換組成物を得ることができる。撹拌・混練機としては、例えば、ホモジナイザー、自公転型撹拌機、3本ローラー、ボールミル、遊星式ボールミル、ビーズミル等が挙げられる。混合または分散後、もしくは混合または分散の過程において、真空もしくは減圧条件下で脱泡することも好ましく行われる。また、ある特定の成分を事前に混合することや、エージング等の処理をしても構わない。エバポレーターによって溶媒を除去して所望の固形分濃度にすることも可能である。
本発明の色変換シートにおける基材層(例えば図2~4に示す基材層10)としては、例えば、ガラスや樹脂フィルム等が挙げられる。樹脂フィルムとしては、ポリエチレンテレフタレート(PET)、ポリフェニレンサルファイド、ポリカーボネート、ポリプロピレン、ポリイミド等のプラスチックのフィルムが好ましい。フィルムの剥離のし易さから、基材層は、あらかじめ表面が離型処理されていてもよい。基材層の厚さは、特に制限はないが、下限としては25μm以上が好ましく、38μm以上がより好ましい。また、上限としては5000μm以下が好ましく、3000μm以下がより好ましい。
本発明の色変換シートにおけるバリアフィルム(例えば図4に示すバリアフィルム12)は、色変換層に対してガスバリア性を向上させる場合等において適宜用いられる。このバリアフィルム(バリア層ともいう)としては、色変換層への酸素、水分、熱等の侵入を抑制するものが好ましい。本発明の色変換シートは、このようなバリアフィルムを2層以上有してもよい。例えば、本発明の色変換シートは、図4に例示したバリアフィルム12のように色変換層の両面にバリアフィルムを有してもよいし、色変換層の片面のみにバリアフィルムを有してもよい。
本発明の色変換シートは、偏光反射フィルム、拡散シート、プリズムシート、波長選択反射フィルム等をさらに備えていてもよい。波長選択反射フィルムの好適な具体例としては、例えば、国際公開第2017/164155号、特開2018-81250号公報に記載されているものが挙げられる。
次に、本発明の色変換シートの製造方法の一例を説明する。この色変換シートの製造方法では、上述した方法で作製した色変換組成物を、基材層やバリア層等の下地上に塗布し、乾燥させる。これにより、色変換層を形成する。色変換組成物に含まれるバインダー樹脂が熱硬化性樹脂である場合、色変換組成物を基材層等の下地上に塗布した後、加熱硬化して色変換層を形成してもよい。色変換組成物に含まれるバインダー樹脂が光硬化性樹脂である場合、色変換組成物を基材層等の下地上に塗布した後、光硬化して色変換層を形成してもよい。
本発明の実施形態に係る光源ユニット(以下、本発明の光源ユニットと略記する場合がある)は、少なくとも、光源と、上述の色変換組成物または色変換シートとを含むものである。本発明の光源ユニットに含まれる光源は、上述の励起光の発生源となるものである。光源と色変換シートとの配置方法については特に限定されず、光源と色変換シートとを密着させた構成を取ってもよいし、光源と色変換シートとを離したリモートフォスファー形式を取ってもよい。また、本発明の光源ユニットは、色純度を高める目的で、さらにカラーフィルターを備える構成を取ってもよい。
本発明の光源ユニットが備える光源の種類は、遅延蛍光材料が吸収可能な波長領域に発光を示すものであれば、いずれの光源でも用いることができる。例えば、熱陰極管や冷陰極管、無機エレクトロルミネッセンス(EL)などの蛍光性光源、有機EL素子光源、LED光源、白熱光源、あるいは太陽光など、いずれの励起光の光源でも原理的には利用可能である。これらの中でも、LED光源が好適な光源である。ディスプレイや照明用途では、青色光の色純度を高められる点で、波長430nm以上500nm以下の範囲に極大発光を有する青色LED光源が、さらに好適な光源である。
本発明の実施形態に係るディスプレイは、少なくとも、上述した光源ユニットを備える。例えば、液晶ディスプレイ等のディスプレイには、バックライトユニットとして、上述した光源および色変換シート等を有する光源ユニットが用いられる。また、本発明の実施形態に係る照明装置は、少なくとも、上述した光源ユニットを備える。例えば、この照明装置は、光源ユニットとしての青色LED光源と、この青色LED光源からの青色光をこれよりも長波長の光に変換する色変換シートとを組み合わせて、白色光を発光するように構成される。
耐久性評価では、各実施例および各比較例において、作製した色変換シートおよび青色LED素子(USHIO EPITEX社製;型番SMBB450H-1100、発光ピーク波長:450nm)を搭載した発光装置に、30mAの電流を流して青色LED素子を点灯させ、分光放射輝度計(CS-1000、コニカミノルタ社製)を用いて、初期の緑色光の発光ピーク強度と赤色光の発光ピーク強度とを測定した。なお、各発光装置における色変換シートと青色LED素子との距離は3cmとした。その後、50℃の環境下で青色LED素子からの光を1000時間連続照射したのち、同様にして緑色光の発光ピーク強度と赤色光の発光ピーク強度とを測定した。これら得られた緑色光および赤色光の各発光ピーク強度と上記初期の緑色光および赤色光の各発光ピーク強度とを比較し、緑色光および赤色光の各々について発光ピーク強度の維持率を算出することにより、色変換シートの色度の耐久性を評価した。発光ピーク強度の維持率は、以下の数式から求めることができる。
発光ピーク強度維持率Z(%)=Y/X×100
上式において、Xは、初期の発光ピーク強度である。Yは、1000時間連続照射したのちの発光ピーク強度である。
各実施例および各比較例において、作製した色変換シートを8mm角に断裁してサンプルを準備し、絶対蛍光量子収率測定装置(浜松ホトニクス社製 Quantaurus-QY)を用いて、波長450nmの励起光によって上記サンプルを励起させた際の蛍光量子収率を測定した。
色変換層中の残存溶媒量は、以下の手順によって測定した。詳細には、まず、ポリエステルフィルム“ルミラー”(登録商標)U48(東レ社製、厚さ50μm)上に色変換層を形成した。続いて、この形成した色変換層を当該ポリエステルフィルムから剥離し、得られた色変換層のみを20mg秤量した。次に、この20mgの色変換層を2mLのNMPに溶解させ、これにより、当該色変換層中の残存溶媒量を測定するためのサンプルを調製した。測定機として、島津製作所社製のガスクロマトグラフ(GC-2010)を用い、以下の条件において、上記サンプルの残存溶媒量を測定した。
(条件)
検出器:FID
使用カラム:CP-Select 624 CB
検出器温度:280℃
キャリアガス:He
キャリアガス流量:6mL/min
昇温条件:40℃で4分間保持した後、8℃/分の昇温速度によって260℃まで昇温し、その後、16分間保持する。
下記の実施例および比較例においては、発光材料(a)および発光材料(b)として、化合物G-1、G-2、R-1、R-2を用いた。化合物G-1、G-2、R-1、R-2は、以下に示す化合物である。これらのうち、化合物G-1および化合物R-1は、遅延蛍光を放出する化合物である。
各実施例および各比較例においては、バインダー樹脂として、以下に示す樹脂A、B、C、Dを用いた。
本明細書における樹脂Aとしては、国際公開第2019/021813号に記載の樹脂Fを用いた。樹脂Aは、一般式(3)で表される部分構造を95.0重量%含み、かつ、一般式(4)表される部分構造を5.0重量%含むバインダー樹脂である。この樹脂Aにおいて、一般式(4)で表される部分構造のY1~Y4のうち、一つは無置換のシクロヘキシル基であり、その他三つは水素原子である。
本明細書における樹脂Bとしては、国際公開第2019/021813号に記載の樹脂G(Optimas6000(三菱瓦斯化学社製 PMMA-水添スチレン共重合体))を用いた。樹脂Bは、一般式(3)で表される部分構造を61.0重量%含み、かつ、一般式(4)表される部分構造を39.0重量%含むバインダー樹脂である。この樹脂Bにおいて、一般式(4)で表される部分構造のY1~Y4のうち、一つは無置換のシクロヘキシル基であり、その他三つは水素原子である。
本明細書における樹脂Cとしては、国際公開第2019/021813号に記載の樹脂H(Optimas7500(三菱瓦斯化学社製 PMMA-水添スチレン共重合体))を用いた。樹脂Cは、一般式(3)で表される部分構造を77.0重量%含み、かつ、一般式(4)表される部分構造を23.0重量%含むバインダー樹脂である。この樹脂Cにおいて、一般式(4)で表される部分構造のY1~Y4のうち、一つは無置換のシクロヘキシル基であり、その他三つは水素原子である。
本明細書における樹脂Dとしては、国際公開第2019/021813号に記載の樹脂Iを用いた。樹脂Dは、一般式(3)で表される部分構造を75.7重量%含み、かつ、一般式(4)表される部分構造を24.3重量%含むバインダー樹脂である。この樹脂Dにおいて、一般式(4)で表される部分構造のY1~Y4のうち、一つは無置換のシクロヘキシル基であり、その他三つは水素原子である。
下記の実施例および比較例においては、散乱材として、二酸化チタン粒子“JR-301”(テイカ社製)を用いた。
実施例1~4では、後述の表2に示すバインダー樹脂(樹脂A、樹脂B、樹脂Cまたは樹脂D)の100重量部に対して、発光材料(a)として化合物G-1を0.40重量部、発光材料(b)として化合物R-1を0.01重量部、溶媒として酢酸エチルを300重量部、混合した。その後、これらの混合物を、遊星式撹拌・脱泡装置“マゼルスターKK-400”(クラボウ社製)を用いて1000rpmで20分間撹拌・脱泡し、これにより、色変換層作製用の樹脂液としての色変換組成物を得た。
実施例5では、発光材料(b)として化合物R-2を用いたこと以外は実施例1と同様の手法により、色変換シートの作製および色変換シートの各種評価を実施した。実施例5における色変換シートの構成および評価結果は、表2に示す通りである。
実施例6では、発光材料(a)として化合物G-2を用いたこと以外は実施例1と同様の手法により、色変換シートの作製および色変換シートの各種評価を実施した。実施例6における色変換シートの構成および評価結果は、表2に示す通りである。
実施例7~13では、乾燥温度および乾燥時間を後述の表3に示す通りに変更したこと以外は実施例1と同様の手法により、色変換シートの作製および色変換シートの各種評価を実施した。実施例7~13の各々における色変換シートの構成および評価結果は、表3に示す通りである。
実施例14では、溶媒としてトルエンを用いたことと、乾燥温度および乾燥時間を表3に示す通りに変更したこと以外は実施例1と同様の手法により、色変換シートの作製および色変換シートの各種評価を実施した。実施例14における色変換シートの構成および評価結果は、表3に示す通りである。
比較例1では、発光材料(a)として化合物G-2を用い、発光材料(b)として化合物R-2を用いたこと以外は実施例1と同様の手法により、色変換シートの作製および色変換シートの各種評価を実施した。比較例1における色変換シートの構成および評価結果は、表4に示す通りである。
比較例2では、乾燥温度および乾燥時間を表4に示す通りに変更したこと以外は実施例1と同様の手法により、色変換シートの作製および色変換シートの各種評価を実施した。比較例2における色変換シートの構成および評価結果は、表4に示す通りである。
比較例3では、乾燥温度および乾燥時間を表4に示す通りに変更したこと以外は比較例1と同様の手法により、色変換シートの作製および色変換シートの各種評価を実施した。比較例3における色変換シートの構成および評価結果は、表4に示す通りである。
10 基材層
11 色変換層
12 バリアフィルム
Claims (12)
- 入射光を、その入射光とは異なる波長の光に変換する色変換シートであって、
少なくとも、遅延蛍光を放出する化合物とバインダー樹脂とを含有する色変換層を含み、
前記色変換層中の溶媒量が、10質量ppm以上30000質量ppm以下である、
ことを特徴とする色変換シート。 - 前記一般式(4)中のY1~Y4のうち少なくとも一つが、置換もしくは無置換のシクロヘキシル基である、
ことを特徴とする請求項2に記載の色変換シート。 - 前記一般式(4)中のY1~Y4のうち、一つが置換もしくは無置換のシクロヘキシル基であり、その他三つが水素原子である、
ことを特徴とする請求項2または3に記載の色変換シート。 - 前記色変換層中の溶媒は、SP値が11.0(cal/cm3)1/2以上20.0(cal/cm3)1/2以下の官能基を有する、
ことを特徴とする請求項1~4のいずれか一つに記載の色変換シート。 - 前記遅延蛍光を放出する化合物は、下記の発光材料(a)および発光材料(b)のうち少なくとも一方である、
ことを特徴とする請求項1~5のいずれか一つに記載の色変換シート。
発光材料(a):波長430nm以上500nm以下の範囲の励起光を用いることにより、ピーク波長が500nm以上580nm未満の領域に観測される発光を呈する発光材料
発光材料(b):波長430nm以上500nm以下の範囲の励起光または前記発光材料(a)からの発光のいずれかまたは両方によって励起されることにより、ピーク波長が580nm以上750nm以下の領域に観測される発光を呈する発光材料 - 前記遅延蛍光を放出する化合物が、下記の一般式(1)または一般式(2)で表される化合物を含有する、
ことを特徴とする請求項1~6のいずれか一つに記載の色変換シート。
- 前記遅延蛍光を放出する化合物が前記一般式(1)で表される化合物であって、前記一般式(1)中のEがホウ素原子であり、かつZ1およびZ2はそれぞれ独立にNRaである、または、前記遅延蛍光を放出する化合物が前記一般式(2)で表される化合物であって、前記一般式(2)中のE1およびE2がそれぞれ独立にBRaである、
ことを特徴とする請求項7に記載の色変換シート。 - 光源と、
請求項1~8のいずれか一つに記載の色変換シートと、
を含むことを特徴とする光源ユニット。 - 前記光源が、波長400nm以上500nm以下の範囲に極大発光を有する発光ダイオードである、
ことを特徴とする請求項9に記載の光源ユニット。 - 請求項9または10に記載の光源ユニットを備える、
ことを特徴とするディスプレイ。 - 請求項9または10に記載の光源ユニットを備える、
ことを特徴とする照明装置。
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