JP2017173822A - Wavelength conversion material and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wavelength conversion material (up-conversion material) that has a high quantum yield, enables up-conversion even with excitation light of very low energy, and allows sufficient light emission to be secured, thereby realizing the use of up-conversion in various fields of application such as solar cells, photo-molding systems, and display devices.SOLUTION: A wavelength conversion material comprises (A) an organic photosensitizing compound, (B) an organic light emitting compound and (C) a compound having sulfur in a molecule.SELECTED DRAWING: None

Description

  The present invention relates to a wavelength conversion material that converts long wavelength light into short wavelength light with high efficiency, and an application thereof.

  While there is a strong need for alternative energy such as global warming countermeasures and clean energy, technology development to convert sunlight into secondary energy (electric power, hydrogen, etc.) with high efficiency is an urgent task. Expectations for light-secondary energy conversion elements (elements that convert light into secondary energy) such as solar cells with high light-secondary energy conversion efficiency (light-to-secondary energy conversion efficiency) and hydrogen-generating photocatalysts Is growing. Light-secondary energy conversion elements, such as general solar cells and hydrogen-generating photocatalysts, have a certain threshold wavelength that is unique to the light-secondary energy conversion element among light in a wide wavelength range included in sunlight. Only short wavelength components are used for conversion, and components longer than the threshold wavelength are unused. Therefore, as one of the technologies for effectively using light in a wide wavelength range included in sunlight, light up-conversion (that is, light by absorbing light of a long wavelength and emitting light of a shorter wavelength) Are being studied.

  As means for optical up-conversion, there are a method using harmonic generation and a method using a large multiphoton absorption characteristic by an organic dye. However, these methods require light from a laser having a pulse width of nanoseconds or femtoseconds, and the phenomenon does not occur with non-coherent light irradiation. Moreover, research on optical up-conversion using multi-photon absorption of rare earth elements in materials doped with rare earth elements in metal oxides has a history of more than 50 years. However, this method generally requires a very high incident light intensity, and it has been difficult to convert weak light such as sunlight as a conversion target.

In recent years, many compositions exhibiting optical up-conversion characteristics using a triplet triplet annihilation (TTA) process using both an organic photosensitizing compound and an organic light emitting compound have been reported. In this composition, generally, an organic photosensitizing compound having a small energy difference (ΔE _ST ) between an excited singlet state (S ₁ ) and an excited triplet state (T ₁ ), an organic light-emitting compound having a large ΔE _ST , and the like All combinations (compositions) and combinations of these with other additives are included.

Non-Patent Patent 1 describes a composition in which at least phthalocyanine, metal porphyrin, and metal phthalocyanine are dissolved as an organic photosensitizing compound, and diphenylanthracene as an organic light-emitting compound is dissolved in an organic solvent such as tetrahydrofuran (THF). ing. In these compositions, a quantum yield of optical up-conversion exceeding 20% is obtained at a light intensity of 5 mW / cm ² or less. However, when these compositions are put out into the atmosphere, oxygen penetrates into the solvent, and the optical up-conversion characteristics are significantly deteriorated.

Non-Patent Document 2 reports an example in which an ionic liquid is used as a medium in which an organic photosensitizing compound and an organic light emitting compound are dissolved. However, a light intensity of several hundred mW / cm ² or more is still necessary to obtain a large quantum yield in the atmosphere.

Non-Patent Document 3 reports an example using a material in which an organic photosensitizing compound is dissolved in a liquid organic light emitting compound. However, a light intensity of 50 mW / cm ² or more is still necessary to obtain a large quantum yield in the atmosphere.

  As described above, optical up-conversion is very useful as a wavelength conversion method and has been intensively studied, but has not yet been put into practical use. One cause of this is the problem that oxygen and moisture are present in the composition under conditions where oxygen and moisture are present in the atmosphere and the quantum yield is significantly reduced due to these.

For example, Non-Patent Document 4 reports an example of a material in which an organic photosensitizing compound and a supramolecular nanofiber of an organic light emitting compound are added to a solvent. With this material, an upconversion quantum yield of more than 20% at a light intensity of 20 mW / cm ² or less has been reported. However, such a specific supramolecular structure is limited in molecular structure and cannot be applied to all organic light-emitting compounds.

  Non-Patent Document 5 reports an example of a material in which an organic photosensitizing compound is chemically bonded to the surface of a crystal of an organic light emitting compound. This material has the problem that the quantum yield of up-conversion is low at low light intensity.

  Therefore, it is desired to develop an optical up-conversion material that shows an equivalent quantum yield in the atmosphere under deoxygenation by combining an organic sensitizing compound and an organic light-emitting compound.

A. Monguzzi, et al. , Physical Chemical Physics, vol. 14, p. 4322-4332, 2012. Y. Murakami, et al. , Chemical Physics Letters, vol. 516, p. 56-61, 2011. P. Duan, et al. , Journal of the American Chemical Science, vol. 135, p. 19056-19059, 2013. T.A. Ogawa, et al. , Scientific Reports, vol. 5, p. 10882-1 to 10882-9, 2015. P. Mahato, et al. , Nature Materials, vol. 14, p. 924-930, 2015.

  In view of the above circumstances, an object of the present application is to provide a wavelength conversion material (up-conversion material) having a high quantum yield by weak light irradiation in the atmosphere and its application (solar cell, display device, etc.).

  As a result of intensive studies, the present inventors have found that a wavelength conversion material containing (A) an organic photosensitizing compound, (B) an organic light emitting compound, and (C) a compound having sulfur in the molecule solves the above problems. The present invention was found out and reached the present invention.

４）上記（Ｃ）分子内に硫黄を有する化合物が、下記式（３）で表される化合物及び／又は下記式（４）で表される化合物である上記１）乃至３）のいずれか一項に記載の波長変換材料。

（上記式（３）において、Ｒ^１〜Ｒ^５はそれぞれ独立して、水素原子、置換基を有しても良いアルキル基又は置換基を有しても良いアルコキシ基を表す。なお、Ｒ^１〜Ｒ^５が置換基を有しても良いアルキル基又は置換基を有しても良いアルコキシ基である場合のいずれか一つの置換基は一つ以上の硫黄を有する。）

（上記式（４）において、Ｘ^１〜Ｘ^４はそれぞれ独立して、水素原子、ホルミル基、置換基を有しても良いアルキル基、置換基を有しても良いアルコキシ基、置換基を有しても良いアルキルカルボニル基、置換基を有しても良いアルコキシカルボニル基、置換基を有しても良いアシルオキシ基又は置換基を有しても良いアルキルチオ基を表す。また、Ｘ^１とＸ^２、Ｘ^３とＸ^４はそれぞれ互い結合して環構造を形成していても良い。）
５）前記（Ｃ）分子内に硫黄を有する化合物が、下記式（１６）で表されるアルキルチオエーテル化合物及び／又は下記式（１７）で表されるアルキルチオエーテル化合物である上記１）に記載の波長変換材料。

（前記式（１６）において、Ｒ^１６及びＲ^１８はそれぞれ独立して、置換基を有しても良いアルキル基又は置換基を有しても良いアリール基を表す。Ｒ^１７は、置換基を有しても良いアルケニル基又は置換基を有しても良いアリーレン基を表す。ｎは０から１２の整数を表す。）

（前記式（１７）において、Ｒ^１９及びＲ^２０はそれぞれ独立して、置換基を有しても良いアルケニル基又は置換基を有しても良いアリーレン基を表す。ｍは０から１２の整数を表す。）
６）上記（Ｃ）分子内に硫黄を有する化合物が、０．０１体積％以上９５体積％以下を占める上記１）乃至５）のいずれか一項に記載の波長変換材料。
７）上記（Ａ）有機光増感化合物が、５００〜８００ｎｍに吸収極大波長を有する化合物である上記１）乃至６）のいずれか一項に記載の波長変換材料。
８）上記（Ａ）有機光増感化合物が、ポルフィリン化合物である上記１）乃至７）のいずれか一項に記載の波長変換材料。
９）上記（Ｂ）有機発光化合物が、分子内にベンゼン環を３以上有する化合物である上記１）乃至８）のいずれか一項に記載の波長変換材料。
１０）上記（Ｂ）有機発光化合物が、アントラセン化合物である上記１）乃至９）のいずれか一項に記載の波長変換材料。
１１）更に、（Ｄ）有機溶剤を含有する上記１）乃至１０）のいずれか一項に記載の波長変換材料。
１２）上記（Ｃ）分子内に硫黄を有する化合物と（Ｄ）有機溶剤の体積比率（体積％：体積％）が２：８〜１：９である上記１１）に記載の波長変換材料。
１３）上記１）乃至１２）のいずれか一項に記載の波長変換材料を有する太陽電池。
１４）上記１）乃至１２）のいずれか一項に記載の波長変換材料を有する光造形システム。
１５）上記１）乃至１２）のいずれか一項に記載の波長変換材料を有する表示装置。
１６）上記１）乃至１２）のいずれか一項に記載の波長変換材料を有する立体映像表示装置。 That is, the present invention relates to the following 1) to 16).
1) A wavelength conversion material containing (A) an organic photosensitizing compound, (B) an organic light emitting compound, and (C) a compound having sulfur in the molecule.
2) The wavelength conversion material according to 1), wherein the compound (C) having sulfur in the molecule is a compound having at least one ring structure in the molecule.
3) The wavelength conversion material according to 1) or 2), wherein the compound (C) having sulfur in the molecule is a compound having a skeleton represented by the following formula (1) or the following formula (2).

4) Any one of the above 1) to 3), wherein the compound (C) having sulfur in the molecule is a compound represented by the following formula (3) and / or a compound represented by the following formula (4): The wavelength conversion material according to Item.

(In the above formula (3), R ^{1 to} R ⁵ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent. R ¹ any one of the substituents in the case to R ⁵ is an alkoxy group which may have a alkyl group or a substituted group may have a substituent having one or more sulfur.)

(In the above formula (4), X ^{1 to} X ⁴ each independently represents a hydrogen atom, a formyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. which may have an alkyl group, an alkoxycarbonyl group, an optionally substituted alkoxycarbonyl group which may have a optionally substituted acyloxy group or an optionally substituted alkylthio group. Further, X ¹ and X ² , X ³ and X ⁴ may be bonded to each other to form a ring structure.)
5) The compound (C) having sulfur in the molecule is an alkyl thioether compound represented by the following formula (16) and / or an alkyl thioether compound represented by the following formula (17). Wavelength conversion material.

(In the formula (16), R ¹⁶ and R ¹⁸ each independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent. R ¹⁷ represents a substituent. An alkenyl group that may have or an arylene group that may have a substituent, and n represents an integer of 0 to 12.)

(In the formula (17), R ¹⁹ and R ²⁰ each independently represents an alkenyl group which may have a substituent or an arylene group which may have a substituent. M is an integer of 0 to 12 Represents.)
6) The wavelength conversion material according to any one of 1) to 5) above, wherein the compound (C) having sulfur in the molecule occupies 0.01% by volume to 95% by volume.
7) The wavelength conversion material according to any one of 1) to 6) above, wherein the organic photosensitizing compound (A) is a compound having an absorption maximum wavelength at 500 to 800 nm.
8) The wavelength conversion material according to any one of 1) to 7), wherein the organic photosensitizing compound (A) is a porphyrin compound.
9) The wavelength conversion material according to any one of 1) to 8), wherein the organic light-emitting compound (B) is a compound having 3 or more benzene rings in the molecule.
10) The wavelength conversion material according to any one of 1) to 9), wherein the organic light-emitting compound (B) is an anthracene compound.
11) The wavelength conversion material according to any one of 1) to 10), further comprising (D) an organic solvent.
12) The wavelength conversion material according to 11) above, wherein the volume ratio (volume%: volume%) of the compound (C) having sulfur in the molecule and (D) the organic solvent is 2: 8 to 1: 9.
13) A solar cell comprising the wavelength conversion material according to any one of 1) to 12) above.
14) An optical modeling system comprising the wavelength conversion material according to any one of 1) to 12) above.
15) A display device comprising the wavelength conversion material according to any one of 1) to 12) above.
16) A stereoscopic image display device comprising the wavelength conversion material according to any one of 1) to 12) above.

  Since the present invention is a wavelength conversion material having a high quantum yield, up-conversion is possible even with very low energy excitation light, and sufficient light emission can be extracted. Therefore, various applications such as solar cells and display devices can be developed.

  Hereinafter, the present invention will be described in more detail.

  The wavelength conversion material of the present invention contains (A) an organic photosensitizing compound and (B) an organic light emitting compound. Any combination of (A) and (B) can be used as long as the combination shows a TTA process (light emission based on the TTA process). The light absorption wavelength of the organic photosensitizer molecule (A) and the light emission wavelength of the organic light emitting molecule (B) can be selected without limitation from the wavelength range of sunlight. For example, in the light wavelength conversion element that up-converts light in the visible to near infrared region, a π-conjugated molecule having a light absorption band in the visible to near infrared region is used as the organic photosensitizer molecule (A). A π-conjugated molecule having an emission band in the visible to near-infrared region can be used as the organic light-emitting molecule (B). Examples of the organic photosensitizer molecule (A) and the organic light emitting molecule (B) include aromatic π-electron conjugated compounds, particularly polycyclic aromatic π-electron conjugated compounds, and, for example, described in Non-Patent Document 1. A wide range of low molecules and polymers can be used.

[(A) Organic photosensitizing compound]
The (A) organic photosensitizing compound used in the present invention can be used without limitation as long as it has an absorption maximum peak wavelength within the wavelength range of sunlight, but normally absorbs within the range of 200 to 1000 nm. Those having a maximum peak wavelength are used, preferably those having an absorption maximum peak wavelength in the range of 500 to 800 nm. As a result, light having a relatively long wavelength that is not used in a light-secondary energy conversion element such as a general solar cell or a hydrogen generation photocatalyst can be converted into a relatively short wavelength that is used in a general light-secondary energy conversion element Therefore, light in a wide wavelength range included in sunlight can be effectively used by the light-secondary energy conversion element.
Moreover, you may use what has an absorption maximum wavelength in the range of 250-499 nm as said organic photosensitizer molecule | numerator (A). This makes it possible to effectively use light having wavelengths in the blue region, purple region, and ultraviolet region.

  As the organic photosensitizing molecule (A), any molecular species that has not been called a dye can be used as long as it has light absorption in the range from the ultraviolet region to the infrared region. Examples of the organic photosensitizer molecule (A) include acenaphthene derivatives, acetophenone derivatives, anthracene derivatives, diphenylacetylene derivatives, acridan derivatives, acridine derivatives, acridone derivatives, thioacridone derivatives, angelicin derivatives, anthracene derivatives, anthraquinone derivatives, azafluorenes. Derivatives, azulene derivatives, benzyl derivatives, carbazole derivatives, coronene derivatives, sumanene derivatives, biphenylene derivatives, fluorene derivatives, perylene derivatives, phenanthrene derivatives, phenanthroline derivatives, phenazine derivatives, benzophenone derivatives, pyrene derivatives, benzoquinone derivatives, biacetyl derivatives, bianthranyl derivatives , Fullerene derivatives, graphene derivatives, carotene derivatives, chlorophyll derivatives, Derivatives, cinnoline derivatives, coumarin derivatives, curcumin derivatives, dansylamide derivatives, flavone derivatives, fluorenone derivatives, fluorescein derivatives, helicene derivatives, indene derivatives, lumichrome derivatives, lumiflavin derivatives, oxadiazole derivatives, oxazole derivatives, perifuranthene derivatives, perylene derivatives Phenanthrene derivatives, phenanthroline derivatives, phenazine derivatives, phenol derivatives, phenothiazine derivatives, phenoxazine derivatives, phthalazine derivatives, phthalocyanine derivatives, picene derivatives, porphyrin derivatives, porphycene derivatives, hemiporphycene derivatives, subphthalocyanine derivatives, psoralen derivatives, angelicin derivatives, purines Derivatives, pyrene derivatives, pyromethene derivatives, pyridyl ketone derivatives , Phenyl ketone derivatives, pyridyl ketone derivatives, thienyl ketone derivatives, furanyl ketone derivatives, quinazoline derivatives, quinoline derivatives, quinoxaline derivatives, retinal derivatives, retinol derivatives, rhodamine derivatives, riboflavin derivatives, rubrene derivatives, squalene derivatives, stilbene derivatives, tetracene derivatives, Pentacene derivative, anthraquinone derivative, tetracenequinone derivative, pentacenequinone derivative, thiophosgene derivative, indigo derivative, thioinzogo derivative, thioxanthene derivative, thymine derivative, triphenylene derivative, triphenylmethane derivative, triaryl derivative, tryptophan derivative, uracil derivative, xanthene derivative , Ferrocene derivatives, azulene derivatives, biacetyl derivatives, terphenyl derivatives, Examples include, but are not limited to, terfuran derivatives, terthiophene derivatives, oligoaryl derivatives, fullerene derivatives, conjugated polyene derivatives, 14-group element condensed polycyclic aromatic compound derivatives, and condensed polycyclic heteroaromatic compound derivatives. is not.

Specific examples of the organic photosensitizing molecule (A) include metal porphyrins (metal complexes of porphyrins); metal tetraazaporphyrins; metal phthalocyanines; and iodine derivatives of 3,5-dimethyl-boron dipyrromethene. Boron dipyrromethenes such as iodine derivatives of 3,5-dimethyl-8-phenylboron dipyrromethene; Schiff base metal complexes such as salen metal complexes; metals such as rubidium-bipyridine complexes and iridium-phenanthroline complexes; Bipyridine complexes; metal phenanthroline complexes; naphthalenediimides such as N-alkylnaphthalenediimide; and acridones such as N-methylacridone, but are not limited thereto. As a metal atom contained in the metal porphyrins and metal phthalocyanines, Pt, Pd, Ru, Rh, Ir, Zn, Cu and the like can be used. Examples of the metal tetraazaporphyrins include metal tetraazaporphyrins having a structure in which carbon atoms at positions 5, 10, 15, and 20 and R ⁷ bonded thereto in the general formula (2) described later are replaced with nitrogen atoms. .

（式中、Ｒ^６はそれぞれ、水素原子を含む任意の置換基を表し、Ｒ^６は同じでも異なっていてもよく、互いに隣接する２つのＲ^６が互いに連結して水素原子を含む任意の置換基を有する５員環または６員環を形成してもよく、Ｒ^７はそれぞれ、水素原子又は、水素原子を含む任意の置換基を有するアリール基を表し、Ｒ^７は同じでも異なっていてもよく、ＭはＨ_２又は金属原子を表す。またメソ位（Ｒ^７が置換している位置）やピロール環のβ位（Ｒ^６が置換している位置）を介して２以上のポルフィリンが結合していてもよい。） As an example of a compound preferable as said (A) organic photosensitizer molecule, as a compound which has an absorption maximum wavelength in the range of 500-800 nm, the compound represented by following General formula (5) is mentioned. Here, the “arbitrary substituent containing a hydrogen atom” means a hydrogen atom or an arbitrary substituent other than a hydrogen atom.

(In the formula, each R ⁶ represents an arbitrary substituent containing a hydrogen atom, and R ⁶ may be the same or different, and two adjacent R ^{6 s} connected to each other are connected to each other to include a hydrogen atom. A 5-membered ring or a 6-membered ring having a group may be formed, and R ⁷ represents a hydrogen atom or an aryl group having an optional substituent containing a hydrogen atom, and R ⁷ may be the same or different. Often, M represents H ₂ or a metal atom, and _two or more porphyrins are bonded via the meso position (position where R ⁷ is substituted) or the β position of the pyrrole ring (position where R ⁶ is substituted). You may do it.)

Examples of R ^{6 in} the general formula (5) include hydrogen atom, alkyl group (for example, alkyl group having 1 to 12 carbon atoms), alkenyl group, alkynyl group, halogen atom, hydroxy group (hydroxyl group), alkylcarbonyloxy. Group, arylcarbonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carboxylate, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aminocarbonyl group, alkylaminocarbonyl group, dialkylaminocarbonyl group, alkylthiocarbonyl Group, alkoxyl group, phosphate group, phosphonate group, phosphinate group, cyano group, amino group (including alkylamino group, dialkylamino group, arylamino group, diarylamino group, and alkylarylamino group), Silamino group (including alkylcarbonylamino group, arylcarbonylamino group, carbamoyl group, and ureido group), amidino group, imino group, sulfhydryl group, alkylthio group, arylthio group, thiocarboxylate group, sulfate group, alkylsulfinyl group, Examples include, but are not limited to, sulfonate groups, sulfamoyl groups, sulfonamido groups, nitro groups, trifluoromethyl groups, cyano groups, azide groups, heterocyclic rings, alkylaryl groups, or aryl groups, or heteroaryl groups. Examples of the substituent contained in the 5-membered ring or 6-membered ring formed by connecting two adjacent R ^{6 s} contained in the general formula (5) are the substituents exemplified as R ^6. However, it is not limited to these. The 5-membered ring or 6-membered ring may be linked to another porphyrin ring which may have a substituent. Examples of R ^{6 in} the general formula (5) include, but are not limited to, the substituents mentioned as examples of R ⁶ . When M in the general formula (5) is a metal atom, Pt, Pd, Ru, Rh, Ir, Zn, Cu and the like can be mentioned.

  Examples of the metal porphyrins represented by the general formula (5) include meso-tetraphenyl-tetrabenzoporphyrin metal complexes such as meso-tetraphenyl-tetrabenzoporphyrin palladium (CAS number: 119654-64-7), Octaethylporphyrin metal complexes such as octaethylporphyrin palladium (CAS number: 24804-00-0), and octane such as meso-tetraphenyl-octamethoxy-tetranaphtho [2,3] porphyrin palladium described in Non-Patent Document 2. An ethyl porphyrin metal complex etc. are mentioned.

（上記式（６）中、Ｒ^８〜Ｒ^１２はそれぞれ独立に水素原子を含む任意の置換基を表し、互いに隣接する置換基（Ｒ^８とＲ^９との対、Ｒ^９とＲ^１１との対、Ｒ^８とＲ^１０との対、Ｒ^１０とＲ^１１との対）はそれぞれ互いに連結して水素原子を含む任意の置換基を有する５員環または６員環を形成してもよく、Ｒ^１３はハロゲン原子、置換基を有してもよい炭素数１〜５のアルキル基、または置換基を有してもよい炭素数１〜５のアルコキシル基を表す。） The organic photosensitizing molecule (A) may be an organic photosensitizing molecule having a structure that does not contain a metal in its structure, and as an organic photosensitizing molecule having a structure that does not contain a metal in its structure, Specific examples include compounds represented by the following general formula (6) (boron dipyrromethenes), and the compounds represented by the following general formula (6) are either alone or R ^{8 to} R ¹² . A multimer such as a dimer or trimer having a binding site may be formed, and a multimer may be formed via a saturated hydrocarbon chain or an unsaturated hydrocarbon chain as a linking group.

(In the formula ^{(6), R} 8 ~R ¹² each independently represent any substituent containing a hydrogen atom, a pair of the adjacent substituents ^{(R 8} and ^{R 9} together with ^{R 9} and ^{R 11} A pair, a pair of R ⁸ and R ¹⁰ and a pair of R ¹⁰ and R ¹¹ ) may be connected to each other to form a 5-membered ring or a 6-membered ring having an optional substituent containing a hydrogen atom, R ¹³ represents a halogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, or an optionally substituted alkoxyl group having 1 to 5 carbon atoms.

Examples of R ^{8 to} R ^{12 in} the general formula (6) include a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a halogen atom, a hydroxy group (hydroxyl group), an alkylcarbonyloxy group, an arylcarbonyloxy group, and an alkoxy group. Carbonyloxy group, aryloxycarbonyloxy group, carboxylate, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aminocarbonyl group, alkylaminocarbonyl group, dialkylaminocarbonyl group, alkylthiocarbonyl group, alkoxyl group, phosphate group Phosphonate group, phosphinate group, cyano group, amino group (including alkylamino group, dialkylamino group, arylamino group, diarylamino group, and alkylarylamino group), acylamino group (alkylcarbon group) Nilamino group, arylcarbonylamino group, carbamoyl group, and ureido group), amidino group, imino group, sulfhydryl group, alkylthio group, arylthio group, thiocarboxylic acid group, sulfate group, alkylsulfinyl group, sulfonate group, sulfamoyl group Group, sulfonamido group, nitro group, trifluoromethyl group, cyano group, azide group, heterocycle, alkylaryl group, aryl group, heteroaryl group, silyl group which may have a substituent, substituent Examples thereof include, but are not limited to, a condensed polycyclic group such as a carbazolyl group which may have or a fluorenyl group which may have a substituent. In the general formula (6), adjacent substituents (a pair of R ⁸ and R ⁹ , a pair of R ⁹ and R ¹¹ , a pair of R ⁸ and R ¹⁰ , a pair of R ¹⁰ and R ¹¹ Examples of the substituent that the 5-membered ring or 6-membered ring formed by connecting the pair) to each other include the substituents exemplified as examples of R ^{8 to} R ¹² , but are not limited thereto.

R ^{8 to} R ¹² in the general formula (6) are a hydrogen atom, a halogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 4 carbon atoms, or a phenyl group optionally having a substituent. , A phenoxy group which may have a substituent, a thienyl group which may have a substituent, a thienoxy group which may have a substituent, a 2-carboxyl ethenyl group represented by the following formula (7), Or it is preferable that it is 2-carboxyl-2-cyanoethenyl group represented by following formula (8). Among them, R ⁸ and R ¹¹ are more preferably an alkyl group having 1 to 3 carbon atoms which may have a substituent, and more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms. Particularly preferred is a substituted methyl group. R ⁹ and R ¹⁰ are more preferably a hydrogen atom, a bromine atom, or an iodine atom, and even more preferably a hydrogen atom or an iodine atom. R ¹² is more preferably a phenyl group which may have a substituent, and even more preferably an unsubstituted or alkyl-substituted phenyl group.

R ¹³ in the general formula (6) is a halogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, or an optionally substituted alkoxyl group having 1 to 5 carbon atoms. However, it is preferably a fluorine atom.

  The organic photosensitizing molecule (A) may be an organic photosensitizing molecule having a structure containing no metal. A fullerene derivative is known as an organic photosensitizing molecule having a structure that does not contain a metal in the structure, and can be sensitized particularly by long-wavelength light. C60 derivatives, C70 derivatives, and carbon nanotubes are known as fullerene derivatives. Specifically, [6,6] -phenyl-C61-butylicacid methyl ester, [6,6] -phenyl-C71-butylicacid methyl ester. Bis-PCBM (60), Bis-PCBM (70), [6,6] -Phenyl-C61-butylicacid butyester, [6,6] -Phenyl-C61-butylicacid n-octylester, [6,6] -Phenyl-C61-butyricacid dodecyl ester, C60-fused N-methylpyrrolidine-m-C12-phenyl, etc. .

  The (A) organic photosensitizing molecule is preferably a metal porphyrin represented by the general formula (5) or a compound represented by the general formula (6), and when using a metal porphyrin, For example, the compounds described in Table 1 below are preferably used. However, the present invention is not limited to these. In the table, the central metal M represents palladium (Pd), iridium (Ir), platinum (Pt), zinc (Zn), cobalt (Co), iron (Fe), or the like.

When the compound represented by the general formula (6) is used, in the formula (6), R ^{8 to} R ¹² each independently have 1 to 4 carbon atoms which may have a hydrogen atom, a halogen atom or a substituent. An aliphatic hydrocarbon group, an optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted thienyl group, and an optionally substituted thienoxy group More preferably, the compound is a 2-carboxyl ethenyl group represented by the above formula (7) or a 2-carboxyl-2-cyanoethenyl group represented by the above formula (8). Further, as the compound represented by the general formula (6), specifically, compounds described in the following Table 2 are preferably used. However, the present invention is not limited to these.

In addition to (A) organic photosensitizing molecules, other than boron dipyrromethenes and porphyrins, for example, a compound having a fluorene skeleton (preferably a polyfluorene compound), a polyphenylene compound, a compound having a tetracene skeleton, a thermally activated type A compound exhibiting delayed fluorescence (TADF), a compound used for photodynamic therapy (PDT), a compound described in Table 3 below, and the like can be suitably used.

  (A) The organic photosensitizer molecules may be used alone or in combination of two or more. However, in the case of a video apparatus application to be described later, it is particularly preferable to use in combination of three or more.

[(B) Organic light-emitting molecule]
The organic light emitting molecule (B) is not particularly limited as long as it is an organic compound that can emit light up-converted by the TTA process when used together with the organic photosensitizing molecule (A). Can be used. Examples of the organic luminescent molecule (B) include acenaphthene derivatives, acetophenone derivatives, anthracene derivatives, diphenylacetylene derivatives, acridan derivatives, acridine derivatives, acridone derivatives, thioacridone derivatives, angelicin derivatives, anthracene derivatives, anthraquinone derivatives, azafluorene derivatives, Azulene derivatives, benzyl derivatives, carbazole derivatives, coronene derivatives, sumanene derivatives, biphenylene derivatives, fluorene derivatives, perylene derivatives, phenanthrene derivatives, phenanthroline derivatives, phenazine derivatives, benzophenone derivatives, pyrene derivatives, benzoquinone derivatives, biacetyl derivatives, bianthranyl derivatives, fullerenes Derivatives, graphene derivatives, carotene derivatives, chlorophyll derivatives, chrysanthemum Derivatives, cinnoline derivatives, coumarin derivatives, curcumin derivatives, dansylamide derivatives, flavone derivatives, fluorenone derivatives, fluorescein derivatives, helicene derivatives, indene derivatives, lumichrome derivatives, lumiflavin derivatives, oxadiazole derivatives, oxazole derivatives, perifuranthene derivatives, perylene derivatives, Phenanthrene derivatives, phenanthroline derivatives, phenazine derivatives, phenol derivatives, phenothiazine derivatives, phenoxazine derivatives, phthalazine derivatives, phthalocyanine derivatives, picene derivatives, porphyrin derivatives, porphycene derivatives, hemiporphycene derivatives, subphthalocyanine derivatives, psoralen derivatives, angelicin derivatives, purine derivatives , Pyrene derivatives, pyromethene derivatives, pyridyl ketone derivatives , Phenyl ketone derivative, pyridyl ketone derivative, thienyl ketone derivative, furanyl ketone derivative, quinazoline derivative, quinoline derivative, quinoxaline derivative, retinal derivative, retinol derivative, rhodamine derivative, riboflavin derivative, rubrene derivative, squalene derivative, stilbene derivative, tetracene derivative, pentacene Derivatives, anthraquinone derivatives, tetracenequinone derivatives, pentacenequinone derivatives, thiophosgene derivatives, indigo derivatives, thioinzogo derivatives, thioxanthene derivatives, thymine derivatives, triphenylene derivatives, triphenylmethane derivatives, triaryl derivatives, tryptophan derivatives, uracil derivatives, xanthene derivatives, Ferrocene derivatives, azulene derivatives, biacetyl derivatives, terphenyl derivatives, -Furan derivatives, terthiophene derivatives, oligoaryl derivatives, fullerene derivatives, conjugated polyene derivatives, group 14 element condensed polycyclic aromatic compound derivatives, condensed polycyclic heteroaromatic compound derivatives, etc. is not.

  Specific examples of the organic light emitting molecule (B) include 9,10-diphenylanthracene (CAS number: 1499-10-1) and derivatives thereof, and 9,10-bis (phenylethynyl) anthracene (CAS number: 10075). -85-1) and derivatives thereof (eg 1-chloro-9,10-bis (phenylethynyl) anthracene), perylene (CAS number: 198-55-0) and derivatives thereof (eg perylene diimide), pyrene and derivatives thereof , Rubrene and its derivatives, naphthalene and its derivatives (eg naphthalene diimide, perfluoronaphthalene, 1-cyanonaphthalene, 1-methoxynaphthalene), 9,10-bis (phenylethynyl) naphthacene, 4,4′-bis (5- Tetraacenyl) -1,1'-biphenylene, indole, benzene Zofran, benzothiophene, biphenyl, bifuran, bithiophene, 4,4-difluoro-4-bora -3a, 4a-diaza -s- indacene (boron dipyrromethene) or the like include, but are not limited to. In addition, condensed polycyclic aromatic compounds such as perylene and pyrene are also preferably used. These organic light emitting molecules (B) may be used alone or in combination of two or more.

  As the (B) organic light emitting molecule, compounds shown in Tables 4 to 6 below can be preferably used. However, the (B) organic light emitting molecule used in the present invention is not limited to these.

[(C) Compound having sulfur in molecule]
The wavelength conversion material of the present invention contains (C) a compound having sulfur in the molecule.
(C) The compound having sulfur in the molecule is a compound having sulfur (S) in the molecule regardless of whether it is an aromatic compound or an aliphatic compound. A compound having a carbon-sulfur bond (CS) or a hydrogen-sulfur bond (HS) has an unshared electron pair in the outermost shell and interacts with the components (A) and (B). It is thought to give a high quantum yield.
Examples of the compound having sulfur in the molecule include a thiol compound (—SH), a sulfide compound (—S—), a thioester compound (—C (═S) —S—, —C (═O) —S—, — C (= S) -O-), thioxo compound (= S), epithio compound, thioaldehyde compound (-CHS), thiophene compound, thiazole compound, thiadiazole compound, phenothiazine compound, thioxanthone compound, tetrathiafulvalene compound, etc. be able to.

The compound (C) having sulfur in the molecule is preferably a compound having at least one ring structure in the molecule. The ring structure may be an aliphatic ring, an aromatic ring, or a heterocyclic ring. The ring structure is preferably a 5- to 10-membered ring, more preferably a 5- to 8-membered ring, and particularly preferably a 5- to 6-membered ring.
Moreover, what has the ring structure represented by the said Formula (1) or (2) as this ring structure is one of the more preferable aspects.

Examples of the compound having a skeleton represented by the above formula (1) include phenol compounds, catechol compounds, resorcinol compounds, hydroquinone compounds, and the like.
In addition, examples of the compound having a skeleton represented by the above formula (2) include a tetrathiafulvalene compound, specifically, tetrathiafulvalene, bis (carbonyldithio) tetrathiafulvalene, bis (methylene). Dithio) tetrathiafulvalene, bis (ethylenedithio) tetrathiafulvalene, bis (trimethylenedithio) tetrathiafulvalene, dimethyltetrathiafulvalene, formyltetrathiafulvalene, 2,3,6,7-tetrakis (2-cyanoethylthio) Examples thereof include tetrathiafulvalene, tetrakis (methylthio) tetrathiafulvalene, tetrakis (ethylthio) tetrathiafulvalene, tetrakis (pentylthio) tetrathiafulvalene and the like.

  The compound having sulfur in the molecule (C) is particularly preferably a compound represented by the above formula (3) or a compound represented by the above formula (4).

R ^{1 to} R ⁵ in the above formula (3) each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an alkoxy group that may have a substituent. In addition, any one substituent of the alkyl group which may have a substituent, and the alkoxy group which may have a substituent has one or more sulfur.
The alkyl group represents a C1-C10 linear, branched or cyclic alkyl group, preferably a C1-C5 alkyl group, more preferably a methyl group or an ethyl group. The alkoxy group represents a C1-C10 linear, branched or cyclic alkoxy group, preferably a C1-C5 alkoxy group, more preferably a methoxy group or an ethoxy group.

The alkyl group or the alkoxy group of R ^{1 to} R ⁵ in the above formula (3) may further have a substituent. Examples of this substituent are selected from the group consisting of a halogen atom, a cyano group, a hydroxy group, a sulfo group, a carboxy group, an amino group, a nitro group, a C1-C20 alkoxy group, a hydroxy group, a sulfo group, and a carboxy group. C1-C20 alkoxy group substituted with at least one group; C1-C20 alkylthio group; C1-C20 alkylthio substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group Group, preferably a C1-C20 alkoxy group; a C1-C20 alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group; a C1-C20 alkylthio group; A small number selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group; Both a one C1~C20 alkylthio group substituted with a group, more preferably a C1~C10 alkylthio group.

X ^{1 to} X ⁴ in the formula (4) are each independently a hydrogen atom, a formyl group (—CHO), an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. An alkylcarbonyl group that may have a group, an alkoxycarbonyl group that may have a substituent, an acyloxy group that may have a substituent, or an alkylthio group that may have a substituent. X ¹ and X ² , X ³ and X ⁴ may be bonded to each other to form a ring structure.

  The alkyl group which may have a substituent in the above formula (4) includes the same meaning as the alkyl group which may have a substituent in the above (3).

  The alkoxy group which may have a substituent in the above formula (4) includes the same meaning as the alkoxy group which may have a substituent in the above (3), including preferable ones.

  The alkyl in the alkylcarbonyl group which may have a substituent of the above formula (4) represents a C1-C10 linear, branched or cyclic alkyl group, preferably a C1-C5 alkyl group, more preferably methyl. Group or ethyl group. The alkyl may further have a substituent. Examples of the substituent include a halogen atom; a cyano group; a hydroxy group; a sulfo group; a carboxy group; an amino group; a nitro group; a C1-C20 alkoxy group; A C1-C20 alkoxy group substituted with at least one group selected from the group consisting of a group, a sulfo group and a carboxy group; a C1-C20 alkylthio group; a group consisting of a hydroxy group, a sulfo group and a carboxy group A C1-C20 alkylthio group substituted with at least one kind of group. A particularly preferred alkylcarbonyl group which may have a substituent is an acetyl group.

  The alkoxy in the alkoxycarbonyl group which may have a substituent of the above formula (4) represents that the alkyl part is a C1-C10 linear, branched or cyclic alkyl, preferably a C1-C5 alkyl. And more preferably methyl or ethyl. The alkyl may further have a substituent. Examples of the substituent include a halogen atom; a cyano group; a hydroxy group; a sulfo group; a carboxy group; an amino group; a nitro group; a C1-C20 alkoxy group; A C1-C20 alkoxy group substituted with at least one group selected from the group consisting of a group, a sulfo group and a carboxy group; a C1-C20 alkylthio group; a group consisting of a hydroxy group, a sulfo group and a carboxy group A C1-C20 alkylthio group substituted with at least one group selected from An acetoxycarbonyl group is particularly preferable as the alkoxycarbonyl group which may have a substituent.

  In the case of the acyloxy group which may have a substituent of the above formula (4), the alkyl moiety corresponding to acyl represents a C1-C10 linear, branched or cyclic alkyl, preferably C1-C5 alkyl. More preferably, it is methyl or ethyl. The alkyl may further have a substituent. Examples of the substituent include a halogen atom; a hydroxy group; a sulfo group; a carboxy group; an amino group; a nitro group; a C1-C20 alkoxy group; A C1-C20 alkoxy group substituted with at least one group selected from the group consisting of a group, a sulfo group and a carboxy group; a C1-C20 alkylthio group; a group consisting of a hydroxy group, a sulfo group and a carboxy group A C1-C20 alkylthio group substituted with at least one group selected from Particularly preferred as the acyloxy group which may have a substituent is an acetoxy group.

  The alkyl in the alkylthio group which may have a substituent of the above formula (4) represents a C1-C10 linear, branched or cyclic alkyl group, preferably a C1-C5 alkyl group, more preferably a methyl group or An ethyl group. The alkyl may further have a substituent. Examples of the substituent include a halogen atom; a cyano group; a hydroxy group; a sulfo group; a carboxy group; an amino group; a nitro group; a C1-C20 alkoxy group; A C1-C20 alkoxy group substituted with at least one group selected from the group consisting of a group, a sulfo group and a carboxy group; a C1-C20 alkylthio group; a group consisting of a hydroxy group, a sulfo group and a carboxy group A C1-C20 alkylthio group substituted with at least one group selected from As the alkylthio group which may have a substituent, a methylthio group, an ethylthio group, a cyanoethylthio group, and a pentylthio group are preferable.

In the above formula (4), X ¹ and X ² , X ³ and X ⁴ may be bonded to each other to form a ring structure. The ring structure is preferably a 5- to 8-membered ring or a 5- to 7-membered ring, and more preferably has a sulfur atom in the ring.

  Examples of the compound having sulfur in the molecule (C) include a wide range of thioether compounds such as linear alkyl thioether, branched alkyl thioether, cyclic alkyl thioether compound, alkylene polythioether, alkylaryl thioether, and alkylarylene polythioether. Can be mentioned. The alkyl group, aryl group, and arylene group of the thioether compound may have a substituent or may have no substituent. As a structure of the thioether compound, an alkylthioether compound represented by the formula (16) or the formula (17) is one of preferred embodiments.

R ¹⁶ and R ¹⁸ in the above formula (16) each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent. The alkyl group represents a C1-C10 linear, branched or cyclic alkyl group, preferably a C1-C5 alkyl group, more preferably a methyl group or an ethyl group. The aryl group represents a functional group derived from an aromatic hydrocarbon, and is preferably a phenyl group, a benzyl group, or a naphthyl group. Moreover, R <^17> , R <^19> , R < ²⁰ > in the said Formula (16) and Formula (17) represents the alkylene group which may have a substituent each independently, or the arylene group which may have a substituent. The arylene group represents a C1-C10 linear, branched or cyclic alkylene group, preferably a C1-C5 alkylene group, more preferably a methylene group, an ethylene group or a propylene group. The arylene group represents a linking group derived from an aromatic hydrocarbon, preferably a phenylene group, a naphthylene group, a biphenylene group, or a xylylene group.

R ^{16 to} R ²⁰ in the above formula (16) and formula (17) may have a substituent. Examples of such substituents include C1-C10 linear alkyl groups, C1-C10 branched alkyl groups, C1-C10 cyclic alkyl groups, C1-C10 alkoxy groups, C1-C10 alkylthio groups, aryls. Group, halogen atom, cyano group, hydroxy group, sulfo group, amino group, nitro group, carboxy group, oxo group and the like.

  Examples of the compound represented by the above formula (16) include methyl sulfide, amyl sulfide, 4,7-dithiadecane, 3,6-dithiadecane, 1- (ethylsulfanyl) -2-{[2- (ethylsulfanyl) Ethyl] sulfanyl} ethane, 2,5,8,11-tetrathiadecane, allyl methyl sulfide, amyl methyl sulfide, benzyl methyl sulfide, bis (benzoylmethyl) sulfide, bis (methylthio) methane, t-butylmethyl sulfide, butyl Examples include methyl sulfide, decyl methyl sulfide, dodecyl methyl sulfide, ethyl methyl sulfide, heptyl methyl sulfide, isopropyl methyl sulfide, methionol, methyl thioethanol, and 1,2-bis (phenylthio) ethane. .

  Examples of the compound represented by the above formula (17) include pentamethylene sulfide, tetrahydrothiophene, trimethylene sulfide, 1,4,7-trithiacyclononane, 1,4,8,11-tetrathiacyclo. Tetradecane, 1,3-dithiane, 2-methyltetramethylthiophene, 4-oxothiane, 4,5-dihydro-3 (2H) -thiophenone, 2-methyl-3-tetrahydrothiophenone, tetrahydro-2H-thiopyran-4- All, 2,5-dihydro-1,4-dithiane and the like.

The content ratio of the (A) organic photosensitizing molecule and the (B) organic light emitting molecule in the light wavelength conversion element of the present invention is 0.1: 99.9 to 10 in A: B on the basis of the substance amount (mol). : 90 is preferable, and 0.5: 99.5 to 5:95 is more preferable.
In addition, the content of the organic photosensitizer molecule (A) in the light wavelength conversion element of the present invention is preferably 1.0 × 10 ^{−6 to} 1.0 × 10 ⁻³ mol / L, and 1.0 × 10 ^{6. −5 to} 5.0 × 10 ⁻⁴ mol / L is more preferable, and 3.0 × 10 ^{−5 to} 3.0 × 10 ⁻⁴ mol / L is particularly preferable.
The content of the organic photosensitizing molecule (B) in the light wavelength conversion element of the present invention is preferably 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻¹ mol / L, and 1.0 × 10 ^−3. ˜5.0 × 10 ⁻¹ mol / L is more preferable, and 3.0 × 10 ^{−3 to} 3.0 × 10 ⁻² mol / L is particularly preferable.

  100% by volume of the total of the light wavelength conversion element of the present invention ((A) organic photosensitizer molecule, (B) organic light emitting molecule, (C) compound having sulfur in the molecule, and (D) organic solvent described below) And (C) the compound having sulfur in the molecule occupies 0.01 vol% or more and 95 vol% or less, more preferably 0.1 vol% or more and 90 vol% or less.

[(D) Organic solvent]
The wavelength conversion material of the present invention may further contain (D) an organic solvent.
The organic solvent is preferably (A) an organic photosensitizing compound, (B) an organic light emitting compound, and (C) a compound that dissolves a compound having sulfur in the molecule. Therefore, it may be a water-soluble organic solvent or a water-insoluble organic solvent.
Examples of the water-soluble organic solvent include C1-C4 alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol; N, N-dimethylformamide, N, N Amides such as dimethylacetamide; 2-pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2 Heterocyclic ketones such as -one; ketones or keto alcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1, 2- or 1, 3-propylene glycol, 1,2- or , 4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol and the like mono, oligo, Or polyalkylene glycol or thioglycol; polyol (preferably triol) such as trimethylolpropane, glycerin, hexane-1,2,6-triol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol Monomethyl ether, C1 -C4 mono-alkyl ethers of polyhydric alcohol such as triethylene glycol monoethyl ether; .gamma.-butyrolactone; dimethyl sulfoxide, and the like.

  The water-soluble organic solvent includes a substance that is solid at room temperature, such as trimethylolpropane. However, even if the substance or the like is solid, it shows water solubility, and an aqueous solution containing the substance or the like shows the same properties as the water-soluble organic solvent and can be used with the expectation of the same effect. Therefore, in this specification, for the sake of convenience, such a solid substance is included in the category of a water-soluble organic solvent as long as it can be used in expectation of the same effect as described above.

  Examples of water-insoluble organic solvents include n-hexane, benzene, toluene, chloroform, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,2,3-trichloropropane, 2-heptanone, 3,5,5-trimethyl-2 -Cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene , M-dichlorobenzene, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, t- Butylbenzene, γ- Tyrolactone, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate , Ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether Ter, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol mono Butyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, 2-ethyl-1,3-hexanediol, 2,4-diethyl-1,5-pentanediol, monoacetin, diacetin, triacetin, tripropionine Tributyrin 2-methylpentane-2,4-diol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl Ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl Ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl Cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. Further, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-methyl-1,3-propanediol, 3-methyl-1 , 3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, N, N-dimethylacetamide, N, N-dimethylformamide, n-butanol and the like.

  When the component (D) contains an organic solvent, the volume ratio (volume%: volume%) of the compound (C) having sulfur in the molecule and the organic solvent (D) may be 2: 8 to 9: 1. The case of 3: 7 to 8: 2 is more preferable, and 4: 6 to 7.5: 2.5 is particularly preferable.

[(E) Others]
The wavelength conversion material of the present invention is one obtained by dissolving and / or dispersing (A) to (C) in the organic solvent, and may be one obtained by dissolving and / or dispersing in a polymer. This is obtained by dissolving and / or dispersing the above (A) to (C) in a polymerizable compound and polymerizing them with light and / or heat.

  The polymerizable compound is preferably a compound capable of forming a transparent polymer. For example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta) ) Acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol Lysidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, Tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylic ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylates, (meth) acrylic acid, styrene, Vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydro Shimechiru (meth) acrylamide, N- vinylformamide, although acrylonitrile is not necessarily limited thereto. A photopolymerizable compound can be used individually or in mixture of 2 or more types.

In order to polymerize the polymerizable compound, a photo radical polymerization initiator and / or a thermal radical polymerization initiator is used.
Examples of the radical photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, -Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- Acetophenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Or benzoin compounds such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ' Benzophenone compounds such as 1,4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethyl Thioxanthone compounds such as thioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-me Xylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxy) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6- Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole A imidazole compound; a titanocene compound, or the like. A photoinitiator can be used 1 type or in mixture of 2 or more types.

The thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating and initiates a chain polymerization reaction, but there are organic peroxides, azo compounds, benzoin compounds, benzoin ether compounds, acetophenone compounds, benzopinacols and the like. And benzopinacol is preferably used. For example, examples of the organic peroxide include Kayamek ^RTM A, M, R, L, LH, SP-30C, Parkadox CH-50L, BC-FF, Kadox B-40ES, Parkadox 14, Trigonox ^RTM 22-70E, 23-C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kaya Ester ^RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl ^RTM B, Parkardox 16 , Kayacaron ^RTM BIC-75, AIC-75 (manufactured by Kayaku Akzo Co., Ltd.), Permec ^RTM N, H, S, F, D, G, Perhexa ^RTM H, HC, Pat TMH, C, V, 22, MC, Percure ^RTM AH, AL, HB, Perbutyl ^RTM H, C, ND, L, Parkmill ^{RT M} H, D, Peroyl ^RTM IB, IPP, Perocta ^RTM ND, is available as such is a commercially available product (manufactured by NOF Co., Ltd.).

  Moreover, as an azo compound, VA-044, V-070, VPE-0201, VSP-1001 (made by Wako Pure Chemical Industries Ltd.), etc. are available as a commercial item. Particularly suitable as the thermal radical polymerization initiator is a thermal radical polymerization initiator having no oxygen-oxygen bond (—O—O—) or nitrogen-nitrogen bond (—N═N—) in the molecule. A thermal radical polymerization initiator having an oxygen-oxygen bond (—O—O—) or a nitrogen-nitrogen bond (—N═N—) in the molecule emits a large amount of oxygen or nitrogen when a radical is generated. There is a risk of polymerizing in a state where air bubbles remain in the wavelength conversion material, thereby reducing the characteristics. Particularly preferred are benzopinacol-based thermal radical polymerization initiators (including those obtained by chemically modifying benzopinacol). Specifically, benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy- 1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra (4-methylphenyl) ethane, 1,2-diphenoxy-1,1,2,2-tetra (4-methoxyphenyl) ethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, 1,2-bis (triethylsiloxy) -1,1,2,2-tetraphenyl Ethane, 1,2-bis (t-butyldimethylsiloxy) -1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1- Hydroxy-2-trie Lucyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-t-butyldimethylsiloxy-1,1,2,2-tetraphenylethane and the like can be mentioned, and preferably 1-hydroxy-2 -Trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-t-butyldimethylsiloxy-1 1,2,2-tetraphenylethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, more preferably 1-hydroxy-2-trimethylsiloxy-1,1. 2,2-tetraphenylethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, particularly preferably 1,2-biphenyl. It is (trimethylsiloxy) 1,1,2,2-phenylethane.

  The wavelength conversion material of the present invention may further contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinones Derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives , Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives , Tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spiro Oxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes or Michlerketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) ben Examples include zophenone and 4,4'-diethylaminobenzophenone. A sensitizer can be used 1 type or in mixture of 2 or more types.

  The light wavelength conversion element of the present invention preferably has a moisture content of 1% by mass or less, more preferably 0.1% by mass or less, and further preferably 0.01% by mass or less. Most preferably, it is 0.001 mass% or less. Thereby, the optical wavelength conversion element which has higher optical wavelength conversion efficiency is realizable.

  The light wavelength conversion element of the present invention preferably has an oxygen concentration of 100 ppm by mass or less, more preferably 10 ppm by mass or less, still more preferably 1 ppm by mass or less. Most preferably, it is 1 mass ppm or less. Thereby, the optical wavelength conversion element which has higher optical wavelength conversion efficiency is realizable.

  The light wavelength conversion material of the present invention can be used for display devices, optical modeling systems, solar cells, photocatalysts, photocatalytic hydrogen / oxygen generators, optical up-conversion filters, and the like.

For example, in the case of a display device, (I) a region that holds the above (A), (B), and (C), and (II) a light source that emits light that scans the holding region.
[(I) Region holding (A), (B) and (C) above]
This region may be liquid or solid.
When this region is liquid, for example, water, alcohol, tetrahydrofuran (hereinafter abbreviated as THF), other organic solvents, resins, and the like are used as the medium. In this case, by the method of dissolving and / or dispersing the above-mentioned (A) organic photosensitizer molecule, (B) organic light emitting molecule and (C) sulfur-containing compound in the medium to obtain a solution or dispersion. Can be manufactured. If necessary, use a known disperser such as an ultrasonic disperser, a bead mill, a homogenizer, a wet jet mill, a ball mill, an attritor, a sand mill, a roll mill, or a microwave disperser, either alone or in combination. (A) and the organic light emitting molecule (B) may be finely pulverized and finely dispersed to obtain a solution or dispersion.
When this region is solid, a cured curable resin or the like is preferable. In this case, the above (A) organic photosensitizer molecule, (B) organic light emitting molecule, and (C) a compound having sulfur in the molecule are dissolved or dispersed in the curable resin, and then by heat or light. Manufactured by curing a curable resin. Examples of the curable resin include an epoxy resin composition, an acrylic resin composition, a methacrylic resin composition, and a mixture thereof.
Of the above, (I) is more preferably a liquid.

[(II) Light source emitting light for scanning the holding area]
The video apparatus of the present invention includes (II) a light source that emits light for scanning the holding area. As the light source, the following two methods are possible. Note that it is preferable to use a laser as the light source because of its high spatial coherence.
[1.1 Light emitting from a single light source]
By condensing the light emitted from the light source with the condenser lens, the energy can be concentrated in an arbitrary space. In this method, one point is emitted by light emitted from one light source, and tens of thousands to tens of millions of pixels can be formed by scanning.
[2.2 Method of emitting one point with light from two light sources]
A light emitting point can be formed in an arbitrary space by intersecting two kinds of light emitted from two light sources at one point.
In the present invention, the above 1. Alternatively, any of the two methods may be used, but a case where a point is emitted by light from one light source is preferable.
In order to use the video apparatus of the present invention as a full-color stereoscopic video apparatus, a system using at least three types of light sources is preferable.

  The video apparatus of the present invention can easily obtain a stereoscopic image. In particular, a natural three-dimensional effect can be reproduced as compared with a method of presenting separate planar images in consideration of parallax between the left and right eyes. Further, by using a plurality of two-photon absorption materials and light sources, full color can be achieved. Therefore, it is useful not only for 3D television with a sense of reality, but also for videophones that can be used as a place for doctors' interviews and conversations between family members who live far away. It is also very useful as a monitor for a personal computer such as a monitor used for Internet shopping and a monitor used for designing a three-dimensional structure. It can also be used as a projector that does not require a screen.

また、上記の化合物９の１ｍｌとＴＨＦの９ｍｌからなる溶液を溶液Ｂとして用意した。溶液Ｂを厚み１ｍｍの石英セルに入れ、絶対発光量子収率測定装置（浜松ホトニクス社製、Ｃ９９２０-０２Ｇ）中に置いた。次に直径２．０ｍｍの５３２ｎｍの固体レーザーからの光を２．０Ｗ／ｃｍ^２の強度で溶液Ｂが満たされた厚み１．０ｍｍの石英セルに照射し、その際に検出される放射スペクトル及び強度を測定した。次に石英セルの中身を溶液Ｂから溶液Ａに入れ替え、その石英セルを絶対発光量子収率測定装置（浜松ホトニクス社製、Ｃ９９２０-０２Ｇ）中に置いた。次に５３２ ｎｍの固体レーザーからの２ｍｍの直径を有する光を１．０Ｗ／ｃｍ^２の強度で石英セルに照射し、その際に検出される放射スペクトルと強度を測定した。溶液Ｂを用いた際に放射されるスペクトル及び溶液Ａを用いた際に放射されるスペクトルを用いて、５３２ｎｍ以上の波長域に放射されるアップコンバージョンの発光量子収率(Φ)を算出したところ３．２%であった。同様にして５３２ｎｍのパワーをさまざまに変化させた際のΦを同様に測定した。５３２ｎｍの光強度Ｉが小さい領域でΦのＩに関する傾きが１．０となる接線と、Ｉが無限大に近づく際のΦの値の交点におけるパワーをアップコンバージョンの閾値（Ｉ_ｔｈ）と定義すると、Ｉ_ｔｈの値は１３ｍＷ／ｃｍ^２であった。 Example 1
0.727 mg of Pt (II) Octaethylporphine (hereinafter abbreviated as PtOEP: manufactured by Tokyo Chemical Industry Co., Ltd.) as an organic photosensitizing compound and 9,10-diphenylanthracene (hereinafter abbreviated as DPA) as an organic light emitting compound: Tokyo 33.0 mg of Chemical Industries, Ltd.), a mixed solvent comprising 1 ml of a compound having sulfur in the molecule represented by the following formula (9) (hereinafter abbreviated as compound 9: IRGANOX1520L made by BASF) and 9 ml of THF Solution A was dissolved in

A solution consisting of 1 ml of the above compound 9 and 9 ml of THF was prepared as solution B. Solution B was put in a quartz cell having a thickness of 1 mm and placed in an absolute light emission quantum yield measurement apparatus (C9920-02G, manufactured by Hamamatsu Photonics). Next, a 1.0-mm-thick quartz cell filled with solution B with an intensity of 2.0 W / cm ² is irradiated with light from a 532-nm solid laser having a diameter of 2.0 mm, and a radiation spectrum detected at that time and The strength was measured. Next, the contents of the quartz cell were changed from solution B to solution A, and the quartz cell was placed in an absolute light emission quantum yield measurement device (C9920-02G, manufactured by Hamamatsu Photonics). Next, a quartz cell was irradiated with light having a diameter of 2 mm from a solid laser of 532 nm at an intensity of 1.0 W / cm ² , and the radiation spectrum and intensity detected at that time were measured. Using the spectrum emitted when using solution B and the spectrum emitted when using solution A, the emission quantum yield (Φ) of up-conversion emitted in the wavelength region of 532 nm or more was calculated. 3.2%. Similarly, Φ was similarly measured when the power at 532 nm was changed in various ways. When the power at the intersection of the tangent line where the slope of Φ with respect to I is 1.0 and the value of Φ when I approaches infinity in the region where the light intensity I at 532 nm is small, is defined as the up-conversion threshold (I _th ). , I _th was 13 mW / cm ² .

(Example 2)
The formulation of Compound 9 in Example 1 3 ml, except that the formulation of THF and 7ml was measured Φ and I _th perform the same experiment as in Example 1. Φ is 4.8% when the light intensity of 1.0 W / cm ² of 532 _{nm, I th} was 6.8 mW / cm ^2.

(Example 3)
The formulation of Compound 9 in Example 1 5ml, except that the formulation of THF and 5ml was measured Φ and I _th perform the same experiment as in Example 1. Was measured. Φ is 5.8% when the light intensity of 1.0 W / cm ² of 532 _{nm, I th} was 6.6mW / cm ^2.

Example 4
The formulation of Compound 9 in Example 1 7 ml, except that the formulation of THF and 3ml were measured Φ and I _th perform the same experiment as in Example 1. Φ is 7.1% when the light intensity of 1.0 W / cm ² of 532 _{nm, I th} was 5.8 mW / cm ^2.

(Example 5)
The formulation of Compound 9 in Example 1 9 ml, except that the formulation of THF and 1ml was measured Φ and I _th perform the same experiment as in Example 1. Φ is 7.0% when the light intensity of 1.0 W / cm ² of 532 _{nm, I th} was 6.0 mW / cm ^2.

(Example 6)
In Example 1, a quartz cell having a thickness of 1.0 mm containing the solution B was placed on an integrating sphere, and light having a diameter of 2.0 mm from a 532 nm solid-state laser was applied at an intensity of 1.0 W / cm ^{2 to} the solution B. The quartz cell filled with was irradiated, and the radiation spectrum and intensity detected at that time were measured. Next, the solution A was put into a quartz cell having a thickness of 1.0 mm with a Tunberg tube, and oxygen was removed from the solution A by repeating freeze degassing five times using liquid nitrogen and a vacuum pump. Thereafter, the quartz cell with the Tunberg tube was placed in an absolute light emission quantum yield measuring apparatus (C9920-02G, manufactured by Hamamatsu Photonics). Next, the quartz cell was irradiated with light having a diameter of 2.0 mm from a 532 nm solid-state laser at an intensity of 1.0 W / cm ² , and the radiation spectrum and intensity detected at that time were measured. The Φ was calculated using the radiation spectrum when using the solution B and the radiation spectrum when using the solution A, and it was 3.5%. Similarly, as a result of measuring Φ when the power at 532 nm was variously changed, the value of I _th was 10 mW / cm ² .

(Example 7)
The formulation of Compound 9 were measured 3 ml, the Φ and I _th perform the same experiment as in Example 6 except that the formulation of THF and 7ml in Example 6. Φ is 5.2% when the light intensity of 1.0 W / cm ² of 532 _{nm, I th} was 6.5 mW / cm ^2.

(Example 8)
The formulation of Compound 9 were measured 5ml, the Φ and I _th perform the same experiment as in Example 6 except that the formulation of THF and 5ml in Example 6. Φ is 6.7% when the light intensity of 1.0 W / cm ² of 532 _{nm, I th} was 5.8 mW / cm ^2.

(Comparative Example 1)
0ml The formulation of Compound 9 in Example 1, except that the formulation of THF and 10ml was measured Φ and _{I th} perform the same experiment as in Example 1. Φ is 3.4% when the light intensity of 1.0 W / cm ² of 532 _{nm, I th} was 1000 mW / cm ^2.

(Comparative Example 2)
The formulation of Compound 9 in Example 6 0 ml, except that the 10ml The formulation of THF were measured Φ and _{I th} perform the same experiment as in Example 6. At a light intensity of 532 nm of 1.0 W / cm ² , Φ was 6.7% and I _th was 32 mW / cm ² .

Here, when Examples 1 to 5 and Comparative Example 1 are compared, it is understood that the addition of Compound 9, which is a compound having sulfur in the molecule, improves Φ and significantly reduces I _th even in the atmosphere. Let's be done.

Moreover, when Example 1-Example 5 and Comparative Example 2 are compared, the compound 9 which is a compound having sulfur in the molecule is added, which is much larger than the case where the conventional solvent is deoxygenated. decrease of I _th it will be confirmed. Here, the conditions of the material of Comparative Example 2 correspond to those of Non-Patent Document 1. Non-Patent Document 1, 0.4 mW / cm ² of _{I th} and 1.0 W / cm when light irradiation ² of 532nm or more 26% [Phi is obtained. In this measurement system, the value of Φ at 532 nm light irradiation with I _th of 32 mW / cm ² and 1.0 W / cm ² is 6.7%, but the compound 1 is a compound having sulfur in the molecule. reduction significant I _th against the material by the addition of it will be verified.

Moreover, when Example 1 and Example 6, Example 2 and Example 7, Example 3 and Example 8 are compared, it can be understood that performance equivalent to that under deoxygenation conditions can be obtained even in the atmosphere. As a comparison generally Comparative Example 1 and Comparative Example 2, the performance in oxygen conditions is reduced growth and I _th of Φ than conditions of atmospheric is observed, with a sulfur in the molecule It will be understood that by adding the compound 9 which is a compound, performance equivalent to that under deoxygenation can be obtained in the atmosphere.

Example 9
In the air, 0.0639 mg of Pd (II) Octaethylporphine (PdOEP: manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 1 mL of toluene to prepare a PdOEP stock solution (1 × 10 ⁻⁴ M). 3.48 mL of this PdOEP stock solution was weighed into a glass vial. Subsequently, 4.95 mg of DPA powder was added to the glass vial. Furthermore, 3.47 mg of powder of tetrathiafulvalene (hereinafter abbreviated as TTF: manufactured by Tokyo Chemical Industry Co., Ltd.) was added to this solution, and an orange liquid was obtained as Example 9.

(Comparative Example 3)
A pale red liquid of Comparative Example 3 was obtained in the same manner as in Example 9 except that TTF was not added.

When Example 9 and Comparative Example 3 were irradiated with green laser light (wavelength: 532 nm, intensity: about 20 mW), Comparative Example 3 showed only green scattered light, and no upconversion was confirmed. On the other hand, in the case of Example 9, up-conversion was confirmed, and blue light emission with a wavelength of about 410 nm to 460 nm was confirmed.
From the comparison of Example 9 and Comparative Example 3, it will be confirmed that it is possible to cause upconversion by adding a compound having sulfur in the molecule even under conditions in which upconversion does not occur.

(Example 10)
0.99 mg of Pd (II) tetraphenyl-tetrabenzopophyrin (PdPh4TBP: manufactured by Frontier Scientific) as an organic photosensitizing compound, 25.2 mg of Perylene (manufactured by Tokyo Chemical Industry Co., Ltd.) as an organic light emitting compound, and compound 9 Was dissolved in a mixed solvent consisting of 5 ml and 5 ml of THF to obtain a solution C.
In addition, a solution in which 5 ml of Compound 9 and 5 ml of THF were mixed was prepared as Solution D. Solution B was put in a quartz cell having a thickness of 1 mm and placed in an absolute light emission quantum yield measurement apparatus (C9920-02G, manufactured by Hamamatsu Photonics). Next, light from a 638 nm solid-state laser having a diameter of 2.0 mm is irradiated onto a quartz cell with a thickness of 1 mm filled with solution B with an intensity of 1.0 W / cm ² , and the radiation spectrum and intensity detected at that time are measured. It was measured. Next, the contents of the quartz cell were changed from solution D to solution C, and the quartz cell was placed in an absolute light emission quantum yield measurement apparatus (C9920-02G, manufactured by Hamamatsu Photonics). Next, the quartz cell was irradiated with light having a diameter of 2 mm from a solid laser of 638 nm at an intensity of 1.0 W / cm ² , and the radiation spectrum and intensity detected at that time were measured. Using the spectrum emitted when using Solution B and the spectrum emitted when using Solution A, the emission quantum yield (Φ) of up-conversion emitted in the wavelength region of 638 nm or less was calculated. 3.1%. Similarly, Φ was similarly measured when the power at 638 nm was changed in various ways. If the power at the intersection of the tangent line where the slope of Φ with respect to I is 1.0 in the region where the light intensity I at 638 nm is small and the value of Φ when I approaches infinity is defined as the up-conversion threshold (I _th ). , I _th was 23 mW / cm ² .

(Example 11)
In Example 10, [6,6] -Phenyl-C61-butylicacid methyl ester (PCBM (60): manufactured by American Dye Source) 0.910 mg as an organic photosensitizing compound, and Rubene (Tokyo Kasei Co., Ltd.) as an organic light emitting compound (Company) 53.2 mg of compound 9 dissolved in a mixed solvent consisting of 5 mL and THF 5 ml was used in place of solution C, and compound 9 was mixed in 5 ml and THF 5 ml instead of solution B. Otherwise, perform the same experiment as in example 10, it was measured Φ and I _th. Φ at a light intensity of 638 nm of 1.0 W / cm ² was 0.094%.

Example 12
In Example 10, [6,6] -Phenyl-C71-butylicacid methyl ester (PCBM (70): manufactured by American Dye Source) 1.03 mg as an organic photosensitizing compound and Rubrene (Tokyo Kasei Co., Ltd.) as an organic light emitting compound (Company) 53.2 mg of compound 9 dissolved in a mixed solvent of 5 mL and THF 5 ml was used instead of solution C, and compound 9 was mixed with 5 ml of THF 5 ml instead of solution D. Otherwise, perform the same experiment as in example 1, it was measured Φ and I _th. Φ at a light intensity of 638 nm of 1.0 W / cm ² was 0.032%.

(Example 13)
In Example 10, 0.727 mg of PtOEP as an organic photosensitizing compound, 33.0 mg of DPA as an organic light emitting compound, and amyl sulfide which is a compound having sulfur in the molecule (hereinafter abbreviated as Compound 10): (Aldrich) dissolved in a mixed solvent consisting of 9 mL and 1 ml of THF was used instead of solution C, compound 9 was mixed with 9 ml of THF and 1 ml of THF, and instead of solution D, a 532 nm laser was used instead of the 638 nm laser. except for using the laser, the same experiment as in example 10, were measured Φ and I _th. Φ is 4.5% when the light intensity of 1.0 W / cm ² of 532 _{nm, I th} was 64 mW / cm ^2.

(Example 14)
In Example 10, 0.77 mg of PtOEP as an organic photosensitizing compound, 33.0 mg of DPA as an organic light emitting compound, and 4,7-Dithiadecane (hereinafter abbreviated as Compound 11), which is a compound having sulfur in the molecule. The product dissolved in a mixed solvent consisting of 9 mL and 1 ml of THF was used instead of the solution C, the compound 11 mixed with 9 ml and 1 ml of THF was used instead of the solution D, and a 532 nm laser was used instead of the 638 nm laser. except for using performs the same experiment as in example 10, it was measured Φ and I _th. At a light intensity of 532 nm of 1.0 W / cm ² , Φ was 4.8% and I _th was 30 mW / cm ² .

(Example 15)
In Example 10, 0.727 mg of PtOEP as an organic photosensitizing compound, 33.0 mg of DPA as an organic light emitting compound, 3,6-Dithiadecane (hereinafter referred to as Compound 12), which is a compound having sulfur in the molecule Abbreviation: Aldrich) Dissolved in a mixed solvent consisting of 9 mL and 1 ml of THF was used instead of solution C, compound 12 was mixed with 9 ml of THF and 1 ml of THF, and instead of solution D, instead of 638 nm laser except for using a laser of 532nm in performs the same experiment as in example 10, were measured Φ and _{I th.} Φ is 4.4% when the light intensity of 1.0 W / cm ² of 532 _{nm, I th} was 170 mW / cm ^2.

(Example 16)
In Example 10, 0.727 mg of PtOEP and 33.0 mg of DPA were used as organic photosensitizing compounds, and 1- (Ethylsulfanyl) -2-{[2- (ethylsulfanyl) ethyl which is a compound having sulfur in the molecule. ] Sulfanyl} ethan (hereinafter abbreviated as Compound 13: UkrOrg Syntez) dissolved in a mixed solvent of 9 mL and 1 mL of THF was used instead of Solution C, and a mixture of 9 mL of Compound 13 and 1 mL of THF was used as Solution D used in place of, except for using a laser of 532nm instead of laser 638nm performs the same experiment as in example 10, it was measured Φ and _{I th.} Φ at a light intensity of 532 nm of 1.0 W / cm ² was 4.3%, and I _th was 30 mW / cm ² .

(Example 17)
In Example 10, 0.727 mg of PtOEP as an organic photosensitizing compound, 33.0 mg of DPA as an organic light emitting compound, and 2,5,8,11-tetrathiadecane (hereinafter, a compound having sulfur in the molecule) Is abbreviated as compound 14. (manufactured by UkrOrgSyntez) 1 mL and 9 ml of THF dissolved in a mixed solvent were used instead of solution C, compound 14 was mixed with 1 ml and 9 ml of THF, and instead of solution D, 638 nm except for using a laser of 532nm instead of a laser, the same experiment as in example 10, were measured Φ and I _th. Φ is 7.7% when the light intensity of 1.0 W / cm ² of 532 _{nm, I th} was 58mW / cm ^2.

(Comparative Example 2)
In Example 10, 0.727 mg of PtOEP as an organic photosensitizing compound, 33.0 mg of DPA as an organic light emitting compound, and Diethylene Glycol Diethyl Ether (hereinafter abbreviated as Compound 15; manufactured by Tokyo Chemical Industry Co., Ltd.) 9 mL And a solution of 1 ml of THF dissolved in a mixed solvent was used instead of solution C, 9 ml of compound 15 and 1 ml of THF were used instead of solution D, and a 532 nm laser was used instead of a 638 nm laser. performs the same experiment as in example 10, it was measured Φ and I _th. Φ is 3.4% when the light intensity of 1.0 W / cm ² of 532 _{nm, I th} was 2000 mW / cm ^2.

  Here, as seen in Examples 10 to 12, even when an organic photosensitizing compound, an organic light emitting compound, or a laser beam different from that in Example 1 is used, a compound having sulfur in the molecule is added. The up-conversion emission characteristics can be confirmed.

  In addition, when Example 13 to Example 17 and Comparative Example 1 are compared, addition of Compound 10 to Compound 14, which is a compound having sulfur in the molecule, improves Φ and significantly reduces Ith even in the atmosphere. Will be understood.

The wavelength conversion material of the present invention exhibits a very high upconversion quantum yield. Therefore, excitation is possible even with light of weak energy, which has been considered difficult in the past, and sufficient light emission can be obtained.
In addition, since the viewing direction of the video apparatus using the wavelength conversion material, in particular, the stereoscopic video apparatus is not limited, a stereoscopic video apparatus that allows a large number of people to view from various angles at the same time is provided. This is considered to contribute to further development of 3D modeling technology including 3D printers.

Claims (16)

A wavelength conversion material containing (A) an organic photosensitizing compound, (B) an organic light emitting compound, and (C) a compound having sulfur in the molecule. The wavelength conversion material according to claim 1, wherein the compound (C) having sulfur in the molecule is a compound having at least one ring structure in the molecule. The wavelength conversion material according to claim 1 or 2, wherein the compound (C) having sulfur in the molecule is a compound having a skeleton represented by the following formula (1) or the following formula (2).

4. The compound according to claim 1, wherein the compound having sulfur in the molecule (C) is a compound represented by the following formula (3) and / or a compound represented by the following formula (4). Wavelength conversion material.

(In the formula (3), R ^{1 to} R ⁵ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an alkoxy group that may have a substituent. R ¹ any one of the substituents in the case to R ⁵ is an alkoxy group which may have a alkyl group or a substituted group may have a substituent having one or more sulfur.)

(In Formula (4), X ^{1 to} X ⁴ each independently represents a hydrogen atom, a formyl group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. which may have an alkyl group, an alkoxycarbonyl group, an optionally substituted alkoxycarbonyl group which may have a optionally substituted acyloxy group or an optionally substituted alkylthio group. Further, X ¹ and X ² , X ³ and X ⁴ may be bonded to each other to form a ring structure.) The wavelength conversion according to claim 1, wherein the compound (C) having sulfur in the molecule is an alkyl thioether compound represented by the following formula (16) and / or an alkyl thioether compound represented by the following formula (17). material.

(In the formula (16), R ¹⁶ and R ¹⁸ each independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent. R ¹⁷ represents a substituent. An alkenyl group that may have or an arylene group that may have a substituent, and n represents an integer of 0 to 12.)

(In the formula (17), R ¹⁹ and R ²⁰ each independently represents an alkenyl group which may have a substituent or an arylene group which may have a substituent. M is an integer of 0 to 12 Represents.) The wavelength conversion material according to claim 1, wherein the compound (C) having sulfur in the molecule occupies 0.01 volume% or more and 95 volume% or less. The wavelength conversion material according to any one of claims 1 to 6, wherein the (A) organic photosensitizing compound is a compound having an absorption maximum wavelength at 500 to 800 nm. The wavelength conversion material according to claim 1, wherein the organic photosensitizing compound (A) is a porphyrin compound. The wavelength conversion material according to any one of claims 1 to 8, wherein the organic light-emitting compound (B) is a compound having 3 or more benzene rings in the molecule. The wavelength conversion material according to claim 1, wherein the organic light emitting compound (B) is an anthracene compound. Furthermore, the wavelength conversion material as described in any one of Claims 1 thru | or 10 containing the organic solvent (D). The wavelength conversion material according to claim 11, wherein the volume ratio (volume%: volume%) of the compound (C) having sulfur in the molecule and the organic solvent (D) is 2: 8 to 1: 9. The solar cell which has the wavelength conversion material as described in any one of Claims 1 thru | or 12. The optical modeling system which has the wavelength conversion material as described in any one of Claims 1 thru | or 12. The display apparatus which has a wavelength conversion material as described in any one of Claims 1 thru | or 12. A stereoscopic image display apparatus comprising the wavelength conversion material according to any one of claims 1 to 12.