JP6304228B2 - Wavelength conversion film, wavelength conversion substrate, wavelength conversion element and display element - Google Patents
Wavelength conversion film, wavelength conversion substrate, wavelength conversion element and display element Download PDFInfo
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- JP6304228B2 JP6304228B2 JP2015501290A JP2015501290A JP6304228B2 JP 6304228 B2 JP6304228 B2 JP 6304228B2 JP 2015501290 A JP2015501290 A JP 2015501290A JP 2015501290 A JP2015501290 A JP 2015501290A JP 6304228 B2 JP6304228 B2 JP 6304228B2
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- wavelength conversion
- resin
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- conversion film
- semiconductor quantum
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- 239000004332 silver Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical class Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
- C09K11/562—Chalcogenides
- C09K11/565—Chalcogenides with zinc cadmium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
- C09K11/582—Chalcogenides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
Description
本発明は、波長変換フィルム、波長変換基板、波長変換素子および表示素子に関する。 The present invention relates to a wavelength conversion film, a wavelength conversion substrate, a wavelength conversion element, and a display element.
電子を閉じ込めるために形成された極小さな粒（ドット）が、量子ドットと称され、近年注目を集めている。１粒の量子ドットの大きさは、直径数ナノメートルから数１０ナノメートルであり、約１万個の原子で構成されている。 Extremely small particles (dots) formed to confine electrons are called quantum dots and have recently attracted attention. The size of one quantum dot is several nanometers to several tens of nanometers in diameter, and is composed of about 10,000 atoms.
量子ドットは、太陽電池パネルの半導体の薄膜の中に分散させると、エネルギー変換効率を大幅に向上させることができることから太陽電池への適用が検討されている（例えば、特許文献１を参照のこと。）。また、量子ドットのサイズを変える（バンドギャップを変える）ことで、発光する蛍光の色（発光波長）を変えること（波長変換）ができるため、量子ドットは、バイオ研究における蛍光プローブ（非特許文献１を参照のこと。）や、波長変換材料として、波長変換素子への適用、例えば、照明装置や表示素子への適用（特許文献２および特許文献３を参照のこと。）が検討されている。 When quantum dots are dispersed in a semiconductor thin film of a solar cell panel, energy conversion efficiency can be greatly improved, so application to solar cells has been studied (for example, see Patent Document 1). .) In addition, by changing the size of the quantum dots (changing the band gap), it is possible to change the color (emission wavelength) of the emitted fluorescence (wavelength conversion). 1) and as a wavelength conversion material, application to a wavelength conversion element, for example, application to a lighting device or a display element (see Patent Document 2 and Patent Document 3) has been studied. .
非特許文献１や特許文献１の実施例に示されるように、代表的な量子ドットは、ＩＩ−Ｖ族の半導体のＣｄＳｅ（セレン化カドミウム）、ＣｄＴｅ（テルル化カドミウム）およびＰｂＳ等からなる半導体量子ドットである。 As shown in Examples of Non-Patent Document 1 and Patent Document 1, typical quantum dots are semiconductors made of II-V semiconductors such as CdSe (cadmium selenide), CdTe (cadmium telluride), and PbS. It is a quantum dot.
しかし、例えば、鉛（Ｐｂ）は、毒性への懸念が良く知られた材料である。また、カドミウム（Ｃｄ）とその化合物は、低濃度でも極めて強い毒性を示し、腎臓機能障害や発がん性が懸念される材料である。したがって、より安全な材料からなる半導体量子ドットの形成が求められている。 However, for example, lead (Pb) is a material well known for its toxicity concerns. Further, cadmium (Cd) and its compounds are extremely toxic even at low concentrations, and are materials for which renal dysfunction and carcinogenicity are a concern. Therefore, there is a demand for the formation of semiconductor quantum dots made of a safer material.
また、半導体量子ドットを太陽電池パネルや照明装置や表示素子のディスプレイ等に適用しようとする場合、その蛍光発光を利用するため、粒子形態の半導体量子ドットからなる膜の形成が求められる場合がある。すなわち、蛍光発光を示す、波長変換膜（波長変換フィルム）の形成が求められることがある。 In addition, when a semiconductor quantum dot is to be applied to a solar cell panel, a lighting device, a display of a display element, or the like, there is a case where formation of a film composed of semiconductor quantum dots in the form of particles is required in order to use the fluorescence emission . That is, the formation of a wavelength conversion film (wavelength conversion film) that exhibits fluorescence may be required.
粒子形態の半導体量子ドットを用いた膜の形成方法としては、例えば、特許文献１の実施例や特許文献２に示されるように、適当な基板上に直接、半導体量子ドットの膜を形成する方法が知られている。しかしながら、このような方法では、形成される半導体量子ドットの膜の安定性が乏しい。特に、形成された膜と基板との結着性に懸念がある。 As a method for forming a film using semiconductor quantum dots in the form of particles, for example, as shown in the Examples of Patent Document 1 and Patent Document 2, a method of directly forming a film of semiconductor quantum dots on an appropriate substrate It has been known. However, in such a method, the stability of the formed semiconductor quantum dot film is poor. In particular, there is concern about the binding property between the formed film and the substrate.
そこで、粒子形態の半導体量子ドットを樹脂材料中に混合または埋め込んでフィルム形成を行う方法が提案されている。しかしながら、半導体量子ドットを用い、樹脂とともにフィルム形成を行う方法は十分な検討がなされていない。そのため、例えば、半導体量子ドットとともに用いられ、半導体量子ドットの蛍光発光特性を低下させることなく、そのフィルム形成に好適な樹脂材料が求められている。 Therefore, a method for forming a film by mixing or embedding semiconductor quantum dots in a particle form in a resin material has been proposed. However, a method for forming a film with a resin using semiconductor quantum dots has not been sufficiently studied. Therefore, for example, there is a demand for a resin material that is used together with semiconductor quantum dots and that is suitable for film formation without reducing the fluorescence emission characteristics of the semiconductor quantum dots.
その場合、特に、安全な材料からなる半導体量子ドットとともに用いられ、フィルム形成に好適となる樹脂材料であることが望ましい。 In that case, it is particularly desirable that the resin material be used together with a semiconductor quantum dot made of a safe material and be suitable for film formation.
本発明は、以上のような問題に鑑みてなされたものである。すなわち、本発明の目的は、安全な材料からなる半導体量子ドットを含んで優れた蛍光（波長変換）特性を有し、安定性の高い波長変換フィルムを提供することにある。 The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a highly stable wavelength conversion film having excellent fluorescence (wavelength conversion) characteristics including semiconductor quantum dots made of a safe material.
また、本発明の目的は、安全な材料からなる半導体量子ドットを含んで優れた蛍光（波長変換）特性の波長変換フィルムを有し、安定性の高い波長変換基板を提供することにある。 Another object of the present invention is to provide a highly stable wavelength conversion substrate having a wavelength conversion film having excellent fluorescence (wavelength conversion) characteristics including semiconductor quantum dots made of a safe material.
また、本発明の目的は、安全な材料からなる半導体量子ドットを含んで優れた蛍光（波長変換）特性の波長変換フィルムを有し、安定性の高い波長変換素子を提供することにある。 Another object of the present invention is to provide a highly stable wavelength conversion element having a wavelength conversion film having excellent fluorescence (wavelength conversion) characteristics including semiconductor quantum dots made of a safe material.
また、本発明の目的は、安全な材料からなる半導体量子ドットを含んで構成されて安定性の高い波長変換フィルムを備えた表示素子を提供することにある。 Moreover, the objective of this invention is providing the display element provided with the highly stable wavelength conversion film comprised including the semiconductor quantum dot which consists of a safe material.
本発明の他の目的および利点は、以下の記載から明らかとなるであろう。 Other objects and advantages of the present invention will become apparent from the following description.
本発明の第１の態様は、半導体量子ドットおよび樹脂を含むことを特徴とする波長変換フィルムに関する。 1st aspect of this invention is related with the wavelength conversion film characterized by including a semiconductor quantum dot and resin.
本発明の第１の態様において、半導体量子ドットが、
コアシェル構造型半導体量子ドットであるＩｎＰ／ＺｎＳ、ＣｕＩｎＳ２／ＺｎＳおよび（ＺｎＳ／ＡｇＩｎＳ２）固溶体／ＺｎＳ、並びに、均質構造型半導体量子ドットであるＡｇＩｎＳ２およびＺｎドープＡｇＩｎＳ２よりなる群から選ばれる少なくとも１つであることが好ましい。In the first aspect of the present invention, the semiconductor quantum dot comprises:
It is selected from the group consisting of InP / ZnS, CuInS 2 / ZnS and (ZnS / AgInS 2 ) solid solution / ZnS that are core-shell structure semiconductor quantum dots, and AgInS 2 and Zn-doped AgInS 2 that are homogeneous structure type semiconductor quantum dots At least one is preferred.
本発明の第１の態様において、樹脂が、環状ポリオレフィン系樹脂、芳香族ポリエーテル系樹脂、ポリイミド系樹脂、フルオレンポリカーボネート系樹脂、フルオレンポリエステル系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリアリレート系樹脂、ポリサルホン系樹脂、ポリエーテルサルホン系樹脂、ポリパラフェニレン系樹脂、ポリアミドイミド系樹脂、ポリエチレンナフタレート系樹脂、フッ素化芳香族ポリマー系樹脂、（変性）アクリル系樹脂、エポキシ系樹脂、アリルエステル系硬化型樹脂およびシルセスキオキサン系紫外線硬化樹脂からなる群より選ばれる少なくとも１種であることが好ましい。 In the first aspect of the present invention, the resin is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, a polyamide resin, or a polyarylate resin. , Polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester It is preferably at least one selected from the group consisting of a system curable resin and a silsesquioxane ultraviolet curable resin.
本発明の第１の態様において、半導体量子ドットが、５００ｎｍ〜６００ｎｍの波長領域に蛍光極大を有する材料（Ａ）および／または６００ｎｍ〜７００ｎｍの波長領域に蛍光極大を有する材料（Ｂ）からなることが好ましい。 In the first aspect of the present invention, the semiconductor quantum dot is made of a material (A) having a fluorescence maximum in a wavelength region of 500 nm to 600 nm and / or a material (B) having a fluorescence maximum in a wavelength region of 600 nm to 700 nm. Is preferred.
本発明の第２の態様は、本発明の第１の態様の波長変換フィルムと基材とを備えることを特徴とする波長変換基板に関する。 A second aspect of the present invention relates to a wavelength conversion substrate comprising the wavelength conversion film of the first aspect of the present invention and a base material.
本発明の第３の態様は、本発明の第１の態様の波長変換フィルムを備えることを特徴とする波長変換素子に関する。 A 3rd aspect of this invention is related with the wavelength conversion element provided with the wavelength conversion film of the 1st aspect of this invention.
本発明の第４の態様は、本発明の第１の態様の波長変換フィルムを備えることを特徴とする表示素子に関する。 A 4th aspect of this invention is related with the display element characterized by including the wavelength conversion film of the 1st aspect of this invention.
本発明の第１の態様によれば、安全な材料からなる量子ドットを含んで優れた波長変換特性を有し、安定性の高い波長変換フィルムが提供される。 According to the first aspect of the present invention, a wavelength conversion film having excellent wavelength conversion characteristics including a quantum dot made of a safe material and having high stability is provided.
また、本発明の第２の態様によれば、安全な材料からなる半導体量子ドットを含んで優れた蛍光（波長変換）特性の波長変換フィルムを有し、安定性の高い波長変換基板が提供される。 Further, according to the second aspect of the present invention, there is provided a wavelength conversion substrate having a wavelength conversion film having excellent fluorescence (wavelength conversion) characteristics including a semiconductor quantum dot made of a safe material and having high stability. The
また、本発明の第３の態様によれば、安全な材料からなる量子ドットを含んで構成されて安定性の高い波長変換フィルムを備えた波長変換素子が提供される。 Moreover, according to the 3rd aspect of this invention, the wavelength conversion element provided with the highly stable wavelength conversion film comprised including the quantum dot which consists of a safe material is provided.
また、本発明の第３の態様によれば、安全な材料からなる量子ドットを含んで構成されて安定性の高い波長変換フィルムを備えた表示素子が提供される。 Moreover, according to the 3rd aspect of this invention, the display element provided with the highly stable wavelength conversion film comprised including the quantum dot which consists of a safe material is provided.
本発明の実施形態の波長変換フィルムは、半導体量子ドットおよび樹脂を含んで構成される。本発明の実施形態の波長変換フィルムに含有される半導体量子ドットは、ＣｄやＰｂを構成成分とせず、Ｉｎ（インジウム）を構成成分として構成された、安全な材料からなる半導体量子ドットである。また、本発明の実施形態の波長変換フィルムに含有される樹脂は、その半導体量子ドットを用いて、優れた蛍光特性、すなわち、優れた波長変換特性を示す波長変換フィルムを構成するのに好適な樹脂である。
以下、本発明の実施形態の波長変換フィルムに含有される半導体粒子ドットおよび樹脂について説明する。The wavelength conversion film of the embodiment of the present invention includes a semiconductor quantum dot and a resin. The semiconductor quantum dot contained in the wavelength conversion film of the embodiment of the present invention is a semiconductor quantum dot made of a safe material that does not contain Cd or Pb as a constituent component but contains In (indium) as a constituent component. The resin contained in the wavelength conversion film of the embodiment of the present invention is suitable for constituting a wavelength conversion film that exhibits excellent fluorescence characteristics, that is, excellent wavelength conversion characteristics, using the semiconductor quantum dots. Resin.
Hereinafter, the semiconductor particle dots and the resin contained in the wavelength conversion film of the embodiment of the present invention will be described.
＜半導体量子ドット＞
本発明の実施形態の波長変換フィルムに含有される半導体量子ドットは、２族元素、１１族元素、１２族元素、１３族元素、１４族元素、１５族元素および１６族元素で示される元素の群から選ばれる少なくとも２種以上の元素を含む化合物からなる、半導体量子ドットであることが好ましい。<Semiconductor quantum dots>
The semiconductor quantum dots contained in the wavelength conversion film according to the embodiment of the present invention are composed of elements represented by Group 2 element, Group 11 element, Group 12 element, Group 13 element, Group 14 element, Group 15 element and Group 16 element. A semiconductor quantum dot made of a compound containing at least two elements selected from the group is preferable.
そして、より具体的には、人に対する安全性について懸念の大きい、例えば、ＰｂおよびＣｄ等の元素が除外され、Ｂｅ（ベリリウム）、Ｍｇ（マグネシウム），Ｃａ（カルシウム）、Ｓｒ（ストロンチウム）、Ｂａ（バリウム）、Ｃｕ（銅）、Ａｇ（銀）、金（Ａｕ）、亜鉛（Ｚｎ）、Ｂ（ホウ素）、Ａｌ（アルミニウム）、Ｇａ（ガリウム）、Ｉｎ（インジウム）、Ｔｌ（タリウム）、Ｃ（炭素）、Ｓｉ（珪素）、Ｇｅ（ゲルマニウム）、Ｓｎ（錫）、Ｎ（窒素）、Ｐ（リン）、Ａｓ（ヒ素）、Ｓｂ（アンチモン）、Ｂｉ（ビスマス）、Ｏ（酸素）、Ｓ（硫黄）、Ｓｅ（セレン）、Ｔｅ（テルル）およびＰｏ（ポロニウム）群から選ばれる少なくとも２種以上の元素を含む化合物からなる、半導体量子ドットであることが好ましい。 More specifically, elements such as Pb and Cd, which are of great concern for human safety, are excluded, and Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (Barium), Cu (copper), Ag (silver), gold (Au), zinc (Zn), B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), C (Carbon), Si (silicon), Ge (germanium), Sn (tin), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), O (oxygen), S (Sulfur), Se (selenium), Te (tellurium), and a semiconductor quantum dot which consists of a compound containing at least 2 or more types of elements chosen from Po (polonium) group are preferable.
このとき、半導体量子ドットが５００ｎｍ〜６００ｎｍの波長領域に蛍光極大を有する化合物（Ａ）および／または６００ｎｍ〜７００ｎｍの波長領域に蛍光極大を有する化合物（Ｂ）からなることが好ましい。 At this time, it is preferable that the semiconductor quantum dot is composed of a compound (A) having a fluorescence maximum in a wavelength region of 500 nm to 600 nm and / or a compound (B) having a fluorescence maximum in a wavelength region of 600 nm to 700 nm.
半導体量子ドットは、このような蛍光発光特性を有する化合物（Ａ）および／または化合物（Ｂ）からなることで、５００ｎｍ〜６００ｎｍの波長領域、および／または、６００ｎｍ〜７００ｎｍの波長領域に蛍光極大を有することができる。その結果、半導体量子ドットは、可視域の光を用いて画像の表示を行う表示素子の構成に好適な波長変換フィルムを構成することができる。 The semiconductor quantum dot is composed of the compound (A) and / or the compound (B) having such a fluorescence emission characteristic, and thereby has a fluorescence maximum in a wavelength region of 500 nm to 600 nm and / or a wavelength region of 600 nm to 700 nm. Can have. As a result, the semiconductor quantum dots can constitute a wavelength conversion film suitable for the structure of a display element that displays an image using light in the visible range.
そしてさらに、本発明の実施形態の波長変換フィルムに含有される半導体量子ドットが、Ｉｎを構成成分として含む化合物からなる半導体量子ドットであることがより好ましい。半導体量子ドットの成分構成をそのようにすることで、安全で、優れた波長変換特性を有する波長変換フィルムを提供することができる。 Furthermore, the semiconductor quantum dots contained in the wavelength conversion film of the embodiment of the present invention are more preferably semiconductor quantum dots made of a compound containing In as a constituent component. By making the component structure of the semiconductor quantum dot as such, a wavelength conversion film that is safe and has excellent wavelength conversion characteristics can be provided.
また、本発明の実施形態の波長変換フィルムに含有される半導体量子ドットは、１種の化合物からなる均質構造型、および、２種以上の化合物からなるコアシェル構造型から選ばれる少なくとも一方の構造型の半導体量子ドットであることが好ましい。 Moreover, the semiconductor quantum dot contained in the wavelength conversion film of the embodiment of the present invention is at least one structural type selected from a homogeneous structural type composed of one compound and a core-shell structural type composed of two or more compounds. The semiconductor quantum dot is preferably used.
コアシェル構造型の半導体量子ドットは、１つの種類の化合物でコア構造を形成し、別の化合物でコア構造の周囲を被覆して構成される。例えば、バンドギャップのより大きい半導体でコアの半導体を被覆することにより、光励起によって生成された励起子（電子−正孔対）はコア内に閉じ込められる。その結果、量子ドット表面での無輻射遷移の確率が減少し、発光の量子収率および半導体量子ドットの安定性が向上する。 A core-shell structure type semiconductor quantum dot is formed by forming a core structure with one kind of compound and coating the periphery of the core structure with another compound. For example, by covering the core semiconductor with a semiconductor having a larger band gap, excitons (electron-hole pairs) generated by photoexcitation are confined in the core. As a result, the probability of non-radiative transition on the surface of the quantum dot is reduced, and the quantum yield of light emission and the stability of the semiconductor quantum dot are improved.
本発明の実施形態の波長変換フィルムに含有される半導体量子ドットは、成分構成と構造を考慮した場合、コアシェル構造型半導体量子ドットであるＩｎＰ／ＺｎＳ、ＣｕＩｎＳ２／ＺｎＳおよび（ＺｎＳ／ＡｇＩｎＳ２）固溶体／ＺｎＳ、並びに、均質構造型半導体量子ドットであるＡｇＩｎＳ２およびＺｎドープＡｇＩｎＳ２よりなる群から選ばれる少なくとも１つであることが好ましい。
半導体量子ドットがそのような構成とすることで、安全で、より優れた波長変換特性を有する安定な波長変換フィルムを提供することができる。The semiconductor quantum dots contained in the wavelength conversion film of the embodiment of the present invention are InP / ZnS, CuInS 2 / ZnS, and (ZnS / AgInS 2 ), which are core-shell structure type semiconductor quantum dots, in consideration of the component configuration and structure. It is preferably at least one selected from the group consisting of solid solution / ZnS and homogeneous structure type semiconductor quantum dots AgInS 2 and Zn-doped AgInS 2 .
When the semiconductor quantum dot has such a configuration, it is possible to provide a stable wavelength conversion film that is safe and has more excellent wavelength conversion characteristics.
また、本発明の実施形態の波長変換フィルムに含有される半導体量子ドットは、平均粒径が約１．０ｎｍ〜１０ｎｍであることが望ましい。平均粒径が約１．０ｎｍ未満である場合には、半導体量子ドットを調製することが難しく、半導体量子ドットを調製できたとしても、半導体量子ドットが不安定な状態になる場合がある。平均粒径が１０ｎｍを超える場合には、半導体量子ドットの大きさによる量子閉じ込め効果が得られない場合があって、望ましくない。 Moreover, as for the semiconductor quantum dot contained in the wavelength conversion film of embodiment of this invention, it is desirable that an average particle diameter is about 1.0 nm-10 nm. When the average particle size is less than about 1.0 nm, it is difficult to prepare a semiconductor quantum dot, and even if the semiconductor quantum dot can be prepared, the semiconductor quantum dot may be in an unstable state. When the average particle diameter exceeds 10 nm, the quantum confinement effect due to the size of the semiconductor quantum dots may not be obtained, which is not desirable.
本発明の実施形態の波長変換フィルムに含有される半導体量子ドットを得る方法としては、配位性有機溶媒中で有機金属化合物を熱分解する公知の方法を利用することができる。また、コアシェル構造型の半導体量子ドットは、反応により均質なコア構造を形成した後、反応系内に、コア表面にシェルを形成するための前駆体を添加し、シェル形成の後、反応を停止し、溶媒から分離することで得ることができる。尚、市販されているものを利用することも可能である。 As a method for obtaining the semiconductor quantum dots contained in the wavelength conversion film of the embodiment of the present invention, a known method for thermally decomposing an organometallic compound in a coordinating organic solvent can be used. For core-shell structure type semiconductor quantum dots, after forming a homogeneous core structure by reaction, a precursor for forming a shell on the core surface is added to the reaction system, and the reaction is stopped after the shell formation. And can be obtained by separating from the solvent. A commercially available product can also be used.
＜樹脂＞
本発明の実施形態の波長変換フィルムは、上述の半導体量子ドットと樹脂とを含有していれば特に制限されないが、その樹脂としては透明樹脂が好ましい。このような樹脂としては、本発明の波長変換フィルムの効果を損なわないものである限り特に制限されないが、例えば、熱安定性およびフィルムへの成形性を確保し、また、表示素子等に適用されて１００℃以上の加熱製造工程に対して耐性を示すように、ガラス転移温度（Ｔｇ）が、好ましくは１１０℃〜３８０℃、より好ましくは１１０℃〜３７０℃、さらに好ましくは１２０℃〜３６０℃である樹脂が挙げられる。<Resin>
Although the wavelength conversion film of embodiment of this invention will not be restrict | limited especially if the above-mentioned semiconductor quantum dot and resin are contained, As that resin, transparent resin is preferable. Such a resin is not particularly limited as long as it does not impair the effect of the wavelength conversion film of the present invention. For example, it ensures thermal stability and moldability to a film, and is applied to display elements and the like. The glass transition temperature (Tg) is preferably 110 ° C. to 380 ° C., more preferably 110 ° C. to 370 ° C., and further preferably 120 ° C. to 360 ° C. The resin which is is mentioned.
また、上述の樹脂としては、厚さ０．１ｍｍでの全光線透過率（ＪＩＳ Ｋ７１０５）が、好ましくは７５％〜９５％であり、より好ましくは７８％〜９５％であり、さらに好ましくは８０％〜９５％である樹脂を用いることができる。全光線透過率がこのような範囲であれば、得られる波長変換フィルムは、光学フィルムとしても良好な透明性を示す。 Moreover, as said resin, the total light transmittance (JIS K7105) in thickness 0.1mm becomes like this. Preferably it is 75%-95%, More preferably, it is 78%-95%, More preferably, it is 80 % -95% resin can be used. When the total light transmittance is in such a range, the obtained wavelength conversion film exhibits good transparency as an optical film.
また、半導体量子ドットとともに用いられ、半導体量子ドットの蛍光発光特性を低下させることなく、そのフィルム形成に好適な樹脂が好ましい。 Also, a resin that is used together with semiconductor quantum dots and is suitable for film formation without reducing the fluorescence emission characteristics of the semiconductor quantum dots is preferable.
その場合、特に、安全な材料からなる半導体量子ドット、特に、コアシェル構造型半導体量子ドットであるＩｎＰ／ＺｎＳ、ＣｕＩｎＳ２／ＺｎＳおよび（ＺｎＳ／ＡｇＩｎＳ２）固溶体／ＺｎＳ、並びに、均質構造型半導体量子ドットであるＡｇＩｎＳ２およびＺｎドープＡｇＩｎＳ２よりなる群から選ばれる少なくとも１つとともに用いられ、その半導体量子ドットを含むフィルムの形成に好適となる樹脂材料であることが望ましい。In that case, in particular, semiconductor quantum dots made of a safe material, particularly InP / ZnS, CuInS 2 / ZnS and (ZnS / AgInS 2 ) solid solution / ZnS, which are core-shell structure type semiconductor quantum dots, and homogeneous structure type semiconductor quantum A resin material that is used together with at least one selected from the group consisting of dots of AgInS 2 and Zn-doped AgInS 2 and is suitable for forming a film including the semiconductor quantum dots is desirable.
上述のような樹脂としては、例えば、環状ポリオレフィン系樹脂、芳香族ポリエーテル系樹脂、ポリイミド系樹脂、フルオレンポリカーボネート系樹脂、フルオレンポリエステル系樹脂、ポリカーボネート系樹脂、ポリアミド（アラミド）系樹脂、ポリアリレート系樹脂、ポリサルホン系樹脂、ポリエーテルサルホン系樹脂、ポリパラフェニレン系樹脂、ポリアミドイミド系樹脂、ポリエチレンナフタレート（ＰＥＮ）系樹脂、フッ素化芳香族ポリマー系樹脂、（変性）アクリル系樹脂、エポキシ系樹脂、アリルエステル系硬化型樹脂およびシルセスキオキサン系紫外線硬化樹脂を挙げることができる。 Examples of the resin as described above include cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, and polyarylate resins. Resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate (PEN) resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins Examples thereof include resins, allyl ester curable resins, and silsesquioxane ultraviolet curable resins.
以下、本発明の実施形態の波長変換フィルムの形成に好ましいものとして挙げられた樹脂について、特に好ましいものをより詳しく説明する。 Hereinafter, particularly preferred resins will be described in more detail with respect to the resins listed as preferred for forming the wavelength conversion film of the embodiment of the present invention.
（１）環状オレフィン系樹脂
上述の環状オレフィン系樹脂としては、下記式（Ｘ０）で表される単量体および下記式（Ｙ０）で表される単量体からなる群より選ばれる少なくとも１つの単量体から得られる樹脂、または必要に応じてさらにその樹脂を水素添加することで得られる樹脂が好ましい。(1) Cyclic olefin resin The cyclic olefin resin described above is at least selected from the group consisting of a monomer represented by the following formula (X 0 ) and a monomer represented by the following formula (Y 0 ). A resin obtained from one monomer or a resin obtained by hydrogenating the resin as required is preferred.
上記式（Ｘ０）中、Ｒｘ１〜Ｒｘ４は、それぞれ独立に下記（ｉ’）〜（ｖｉｉｉ’）より選ばれる原子または基を表し、ｋｘ、ｍｘおよびｐｘは、それぞれ独立に０または正の整数を表す。
（ｉ’）水素原子
（ｉｉ’）ハロゲン原子
（ｉｉｉ’）トリアルキルシリル基
（ｉｖ’）酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有する、置換または非置換の炭素数１〜３０の炭化水素基
（ｖ’）置換または非置換の炭素数１〜３０の炭化水素基
（ｖｉ’）極性基（但し（ｉｖ’）を除く）
（ｖｉｉ’）Ｒｘ１とＲｘ２またはＲｘ３とＲｘ４とが、相互に結合して形成されたアルキリデン基を表し、該結合に関与しないＲｘ１〜Ｒｘ４は、それぞれ独立に上述の（ｉ’）〜（ｖｉ’）より選ばれる原子または基を表す。
（ｖｉｉｉ’）Ｒｘ１とＲｘ２またはＲｘ３とＲｘ４とが、相互に結合して形成された単環もしくは多環の炭化水素環または複素環を表し、その結合に関与しないＲｘ１〜Ｒｘ４は、それぞれ独立に上述の（ｉ’）〜（ｖｉ’）より選ばれる原子または基を表すか、Ｒｘ２とＲｘ３とが、相互に結合して形成された単環の炭化水素環または複素環を表し、その結合に関与しないＲｘ１〜Ｒｘ４は、それぞれ独立に上述の（ｉ’）〜（ｖｉ’）より選ばれる原子または基を表す。In the formula (X 0), R x1 ~R x4 each independently represent the following (i ') ~ (viii' ) than chosen atom or group, k x, m x and p x are each independently Represents 0 or a positive integer.
(I ′) a hydrogen atom (ii ′) a halogen atom (iii ′) a trialkylsilyl group (iv ′) a substituted or unsubstituted carbon atom having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom -30 hydrocarbon group (v ') substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (vi') polar group (excluding (iv '))
(Vii ′) R x1 and R x2 or R x3 and R x4 represent an alkylidene group formed by bonding to each other, and R x1 to R x4 not participating in the bonding are each independently the above (i Represents an atom or group selected from ') to (vi').
(Viii ′) R x1 and R x2 or R x3 and R x4 represent a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring formed by bonding to each other, and R x1 to R not participating in the bonding x4 each independently represents an atom or group selected from the above (i ′) to (vi ′), or a monocyclic hydrocarbon ring formed by bonding R x2 and R x3 to each other; R x1 to R x4 representing a heterocyclic ring and not involved in the bond each independently represent an atom or group selected from the above (i ′) to (vi ′).
上記式（Ｙ０）中、Ｒｙ１およびＲｙ２は、それぞれ独立に上述の（ｉ’）〜（ｖｉ’）より選ばれる原子または基を表すか、下記（ｉｘ’）を表し、ｋｙおよびｐｙは、それぞれ独立に０または正の整数を表す。
（ｉｘ’）Ｒｙ１とＲｙ２とが、相互に結合して形成された単環または多環の脂環式炭化水素、芳香族炭化水素または複素環を表す。In the above formula (Y 0 ), R y1 and R y2 each independently represent an atom or group selected from the above (i ′) to (vi ′), or the following (ix ′), and k y and p y independently represents 0 or a positive integer.
(Ix ′) R y1 and R y2 represent a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocyclic ring formed by bonding to each other.
（２）芳香族ポリエーテル系樹脂
上述の芳香族ポリエーテル系樹脂は、下記式（１）で表される構造単位および下記式（２）で表される構造単位からなる群より選ばれる少なくとも１つの構造単位を有することが好ましい。(2) Aromatic polyether-based resin The aromatic polyether-based resin described above is at least one selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). It preferably has one structural unit.
上記式（１）中、Ｒ１〜Ｒ４は、それぞれ独立に炭素数１〜１２の１価の有機基を示し、ａ〜ｄは、それぞれ独立に０〜４の整数を示す。The formula (1), R 1 to R 4 are each independently a monovalent organic group having 1 to 12 carbon atoms, to d represents an integer of 0 to 4 independently.
上記式（２）中、Ｒ１〜Ｒ４およびａ〜ｄは、それぞれ独立に上記式（１）中のＲ１〜Ｒ４およびａ〜ｄと同義であり、Ｙは単結合、−ＳＯ２−または＞Ｃ＝Ｏを示し、Ｒ７およびＲ８は、それぞれ独立にハロゲン原子、炭素数１〜１２の１価の有機基またはニトロ基を示し、ｇおよびｈは、それぞれ独立に０〜４の整数を示し、ｍは０または１を示す。
但し、ｍが０の時、Ｒ７はシアノ基ではない。In the above formula (2), R 1 to R 4 and a~d are the same as R 1 to R 4 and a~d each independently the above formula (1), Y represents a single bond, -SO 2 -Or> C = O, R 7 and R 8 each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h each independently represent 0 to 4 And m represents 0 or 1.
However, when m is 0, R 7 is not a cyano group.
また、上述の芳香族ポリエーテル系樹脂は、さらに下記式（３）で表される構造単位および下記式（４）で表される構造単位からなる群より選ばれる少なくとも１つの構造単位を有することが好ましい。 The aromatic polyether-based resin described above further has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). Is preferred.
上記式（３）中、Ｒ５およびＲ６は、それぞれ独立に炭素数１〜１２の１価の有機基を示し、Ｚは、単結合、−Ｏ−、−Ｓ−、−ＳＯ２−、＞Ｃ＝Ｏ、−ＣＯＮＨ−、−ＣＯＯ−または炭素数１〜１２の２価の有機基を示し、ｅおよびｆは、それぞれ独立に０〜４の整数を示し、ｎは０または１を示す。In the above formula (3), R 5 and R 6 each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z represents a single bond, —O—, —S—, —SO 2 —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1 .
上記式（４）中、Ｒ７、Ｒ８、Ｙ、ｍ、ｇおよびｈは、それぞれ独立に上記式（２）中のＲ７、Ｒ８、Ｙ、ｍ、ｇおよびｈと同義であり、Ｒ５、Ｒ６、Ｚ、ｎ、ｅおよびｆは、それぞれ独立に上記式（３）中のＲ５、Ｒ６、Ｚ、ｎ、ｅおよびｆと同義である。In the above formula (4), R 7 , R 8 , Y, m, g and h are each independently synonymous with R 7 , R 8 , Y, m, g and h in the above formula (2), R 5, R 6, Z, n, e and f have the same meanings as respectively R 5, R 6, Z independently in the above formula (3) in, n, e and f.
（３）ポリイミド系樹脂
上述のポリイミド系樹脂としては、特に制限されず、繰り返し単位にイミド結合を含む高分子化合物であればよく、例えば、特開２００６−１９９９４５号公報や特開２００８−１６３１０７号公報に記載されている方法で合成することができる。(3) Polyimide-based resin The polyimide-based resin described above is not particularly limited, and may be any polymer compound including an imide bond in a repeating unit. For example, JP-A-2006-199945 and JP-A-2008-163107. It can be synthesized by the method described in the publication.
（４）フルオレンポリカーボネート系樹脂
上述のフルオレンポリカーボネート系樹脂としては、特に制限されず、フルオレン部位を含むポリカーボネート樹脂であればよく、例えば、特開２００８−１６３１９４号公報に記載されている方法で合成することができる。(4) Fluorene polycarbonate-based resin The fluorene polycarbonate-based resin is not particularly limited, and may be any polycarbonate resin including a fluorene moiety. For example, the fluorene polycarbonate-based resin is synthesized by a method described in Japanese Patent Application Laid-Open No. 2008-163194. be able to.
（５）フルオレンポリエステル系樹脂
上述のフルオレンポリエステル系樹脂としては、特に制限されず、フルオレン部位を含むポリエステル樹脂であればよく、例えば、特開２０１０−２８５５０５号公報や特開２０１１−１９７４５０号公報に記載されている方法で合成することができる。(5) Fluorene polyester-based resin The fluorene polyester-based resin is not particularly limited as long as it is a polyester resin containing a fluorene moiety. For example, in JP 2010-285505 A and JP 2011-197450 A It can be synthesized by the method described.
（６）フッ素化芳香族ポリマー系樹脂
上述のフッ素化芳香族ポリマー系樹脂としては、特に制限されないが、少なくとも１つのフッ素を有する芳香族環と、エーテル結合、ケトン結合、スルホン結合、アミド結合、イミド結合およびエステル結合からなる群より選ばれる少なくとも１つの結合を含む繰り返し単位とを含有するポリマーであればよく、例えば、特開２００８−１８１１２１号公報に記載されている方法で合成することができる。(6) Fluorinated aromatic polymer-based resin The above-mentioned fluorinated aromatic polymer-based resin is not particularly limited, but includes an aromatic ring having at least one fluorine, an ether bond, a ketone bond, a sulfone bond, an amide bond, Any polymer containing a repeating unit containing at least one bond selected from the group consisting of an imide bond and an ester bond may be used. For example, the polymer can be synthesized by the method described in JP-A-2008-181121. .
（７）市販品
本発明の実施形態の波長変換フィルムの構成に好ましいとして挙げられた樹脂は購入により入手することも可能である。
本発明の実施形態の波長変換フィルムの構成に好ましい樹脂の市販品としては、以下の市販品等を挙げることができる。環状オレフィン系樹脂の市販品としては、例えば、ＪＳＲ株式会社製アートン（登録商標）、日本ゼオン株式会社製ゼオノア（登録商標）、三井化学株式会社製ＡＰＥＬ（登録商標）、ポリプラスチックス株式会社製ＴＯＰＡＳ（登録商標）等を挙げることができる。ポリエーテルサルホン系樹脂の市販品としては、例えば、住友化学株式会社製スミカエクセル（登録商標）ＰＥＳ等を挙げることができる。ポリイミド系樹脂の市販品としては、例えば、三菱ガス化学株式会社製ネオプリム（登録商標）Ｌ等を挙げることができる。ポリカーボネート系樹脂の市販品として、例えば、帝人株式会社製ピュアエース（登録商標）等を挙げることができる。フルオレンポリカーボネート系樹脂の市販品として、例えば、三菱ガス化学株式会社製ユピゼータ（登録商標）ＥＰ−５０００等を挙げることができる。フルオレンポリエステル系樹脂の市販品として、例えば、大阪ガスケミカル株式会社製ＯＫＰ４ＨＴ等を挙げることができる。アクリル系樹脂の市販品として、例えば、株式会社日本触媒製アクリビュア（登録商標）等を挙げることができる。シルセスキオキサン系ＵＶ硬化樹脂の市販品として、例えば、新日鐵化学株式会社製シルプラス（登録商標）等を挙げることができる。(7) Commercial product The resin mentioned as preferable for the configuration of the wavelength conversion film of the embodiment of the present invention can be obtained by purchase.
Examples of commercially available resins preferable for the configuration of the wavelength conversion film of the embodiment of the present invention include the following commercially available products. Examples of commercially available products of cyclic olefin resins include Arton (registered trademark) manufactured by JSR Corporation, ZEONOR (registered trademark) manufactured by ZEON CORPORATION, APEL (registered trademark) manufactured by Mitsui Chemicals, Inc., and manufactured by Polyplastics Corporation. And TOPAS (registered trademark). Examples of commercially available polyethersulfone resins include Sumika Excel (registered trademark) PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include Neoprim (registered trademark) L manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available polycarbonate resins include Pure Ace (registered trademark) manufactured by Teijin Limited. As a commercial item of a fluorene polycarbonate-type resin, Mitsubishi Gas Chemical Co., Ltd. Iupizeta (trademark) EP-5000 etc. can be mentioned, for example. Examples of commercially available fluorene polyester resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. As a commercial item of acrylic resin, for example, Nippon Catalyst Co., Ltd. AKRIVIEWER (registered trademark) can be cited. Examples of commercially available silsesquioxane-based UV curable resins include Silplus (registered trademark) manufactured by Nippon Steel Chemical Co., Ltd.
＜波長変換フィルムの製造方法＞
本発明の実施形態の波長変換フィルムは、半導体量子ドットおよび樹脂を含んで構成されるが、半導体量子ドットの含有量は、波長変換フィルム製造時に用いる樹脂１００重量部に対して、好ましくは０．０１重量部〜１００重量部、より好ましくは０．０２重量部〜５０重量部、特に好ましくは０．０３重量部〜３０重量部である。半導体量子ドットの含有量が上述の範囲内にあると、優れた波長変換特性を有する波長変換フィルムを提供することができる。<Method for producing wavelength conversion film>
The wavelength conversion film of the embodiment of the present invention includes a semiconductor quantum dot and a resin, and the content of the semiconductor quantum dot is preferably 0. The amount is from 01 to 100 parts by weight, more preferably from 0.02 to 50 parts by weight, particularly preferably from 0.03 to 30 parts by weight. When the content of the semiconductor quantum dots is within the above range, a wavelength conversion film having excellent wavelength conversion characteristics can be provided.
そして、本発明の実施形態の波長変換フィルムは、例えば、溶融成形またはキャスト成形により形成することができ、必要により、成形後に、反射防止剤、ハードコート剤および／または帯電防止剤等のコーティング剤をコーティングする方法により製造することができる。
以下で、波長変換フィルムの製造方法について説明する。The wavelength conversion film according to the embodiment of the present invention can be formed by, for example, melt molding or cast molding, and if necessary, a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent after molding. Can be produced by a coating method.
Below, the manufacturing method of a wavelength conversion film is demonstrated.
（１）溶融成形
本発明の実施形態の波長変換フィルムは、樹脂と半導体量子ドットとを溶融混練りして得られたペレットを溶融成形する方法、樹脂と半導体量子ドットとを含有する樹脂組成物を溶融成形する方法、または、半導体量子ドット、樹脂および溶剤を含む樹脂組成物から溶剤を除去して得られたペレットを溶融成形する方法等により製造することができる。溶融成形方法としては、例えば、射出成形、溶融押出成形またはブロー成形等を挙げることができる。(1) Melt molding A wavelength conversion film according to an embodiment of the present invention is a method for melt-molding pellets obtained by melt-kneading a resin and semiconductor quantum dots, and a resin composition containing the resin and semiconductor quantum dots. Can be produced by a melt molding method, a pellet obtained by removing a solvent from a resin composition containing semiconductor quantum dots, a resin and a solvent, or the like. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.
（２）キャスト成形
本発明の実施形態の波長変換フィルムは、半導体量子ドット、樹脂および溶剤を含む樹脂組成物を適当な基材の上にキャスティングして溶剤を除去する方法；反射防止剤、ハードコート剤および帯電防止剤等であるコーティング剤と、半導体量子ドットと、樹脂とを含む樹脂組成物を適当な基材の上にキャスティングする方法；または、反射防止剤、ハードコート剤および／または帯電防止剤等のコーティング剤と、半導体量子ドットと、樹脂とを含む硬化性組成物を適当な基材の上にキャスティングして硬化および乾燥させる方法等により製造することもできる。(2) Cast molding A wavelength conversion film according to an embodiment of the present invention is a method of removing a solvent by casting a resin composition containing semiconductor quantum dots, a resin and a solvent on a suitable base material; A method of casting a resin composition comprising a coating agent such as a coating agent and an antistatic agent, a semiconductor quantum dot, and a resin on an appropriate substrate; or an antireflection agent, a hard coating agent and / or a charge It can also be produced by a method in which a curable composition containing a coating agent such as an inhibitor, a semiconductor quantum dot, and a resin is cast on a suitable substrate and cured and dried.
上述の基材としては、例えば、ガラス板、スチールベルト、スチールドラムおよび透明樹脂（例えば、ポリエステルフィルム、環状オレフィン系樹脂フィルム）等が挙げられる。 Examples of the substrate include a glass plate, a steel belt, a steel drum, and a transparent resin (for example, a polyester film and a cyclic olefin resin film).
上述の本発明の実施形態の波長変換フィルムは、基材から剥離することにより得ることができ、また、本発明の効果を損なわない限り、基材から剥離せずに基材と塗膜との積層体を本発明の実施形態の波長変換フィルムを備えた波長変換基板としてもよい。 The wavelength conversion film of the above-described embodiment of the present invention can be obtained by peeling from the substrate, and unless the effect of the present invention is impaired, the substrate and the coating film are not peeled off from the substrate. It is good also as a wavelength conversion board | substrate provided with the wavelength conversion film of embodiment of this invention for a laminated body.
また、本発明の実施形態の波長変換フィルムは、例えば、液晶等を用いたフラットパネルディスプレイのカラーフィルタのように、パターニングされた層または膜として用いることもできる。その場合、半導体量子ドット、樹脂および溶剤を含む樹脂組成物を、適当な表示素子用の基板で、スクリーン印刷等の適当な印刷法により、所望のパターニングがなされた層または膜として形成する。その後、溶剤を除去して、パターニングされた波長変換フィルムとして、本発明の実施形態の波長変換フィルムを形成することが可能である。 Moreover, the wavelength conversion film of embodiment of this invention can also be used as a patterned layer or film | membrane like the color filter of the flat panel display using a liquid crystal etc., for example. In that case, a resin composition containing semiconductor quantum dots, a resin, and a solvent is formed as a layer or film that has been subjected to desired patterning by an appropriate printing method such as screen printing on an appropriate substrate for a display element. Thereafter, the solvent is removed, and the wavelength conversion film of the embodiment of the present invention can be formed as a patterned wavelength conversion film.
さらに、ガラス板、石英または透明プラスチック製等の光学部品に、上述の樹脂組成物をコーティングして溶剤を乾燥させる方法、または、上述の硬化性組成物をコーティングして硬化および乾燥させる方法などにより、光学部品上に、直接に、樹脂製基板を形成することもできる。 Further, by a method of coating the above resin composition on an optical component such as a glass plate, quartz or transparent plastic and drying the solvent, or a method of coating and curing and drying the above curable composition A resin substrate can also be formed directly on the optical component.
以上の方法で得られた波長変換フィルム中の残留溶剤量は可能な限り少ない方がよい。具体的には、その残留溶剤量は、フィルムの重さに対して、好ましくは３重量％以下、より好ましくは１重量％以下、さらに好ましくは０．５重量％以下である。残留溶剤量が上述の範囲にあると、変形や特性が変化しにくい、所望の機能を容易に発揮できる波長変換フィルムが得られる。 The amount of residual solvent in the wavelength conversion film obtained by the above method should be as small as possible. Specifically, the amount of the residual solvent is preferably 3% by weight or less, more preferably 1% by weight or less, and still more preferably 0.5% by weight or less based on the weight of the film. When the amount of residual solvent is in the above-mentioned range, a wavelength conversion film that can easily exhibit a desired function is obtained, in which deformation and characteristics hardly change.
＜波長変換フィルム、波長変換基板および表示素子＞
図１は、本発明の実施形態の波長変換基板の一例を模式的に示す断面図である。<Wavelength conversion film, wavelength conversion substrate and display element>
FIG. 1 is a cross-sectional view schematically showing an example of a wavelength conversion substrate according to an embodiment of the present invention.
図１に示すように、本発明の実施形態の一例となる波長変換基板１は、基材２と、基材２上に配置された波長変換フィルム３とからなる。 As shown in FIG. 1, a wavelength conversion substrate 1 that is an example of an embodiment of the present invention includes a base material 2 and a wavelength conversion film 3 disposed on the base material 2.
波長変換基板１の波長変換フィルム３は、上述した半導体量子ドットおよび樹脂を含んで構成されたものである。基材２は、ガラス、石英、または、透明樹脂（例えば、透明ポリイミド、ポリエチレンナフタレート、ポリエチレンテレフタレート、ポリエステルフィルム、環状オレフィン系樹脂フィルム等）等からなる。 The wavelength conversion film 3 of the wavelength conversion substrate 1 includes the semiconductor quantum dots and the resin described above. The substrate 2 is made of glass, quartz, or transparent resin (for example, transparent polyimide, polyethylene naphthalate, polyethylene terephthalate, polyester film, cyclic olefin resin film, etc.).
波長変換基板１は、波長変換フィルム３が、半導体量子ドットを用いて励起光源からの励起光を波長変換し、所望とする波長の光に変換する。したがって、波長変換基板１は、太陽電池用のエネルギー変換基板として好適なものとなる。また、適当な励起光源と組み合わされて波長変換素子を提供することができ、例えば、照明装置や表示素子の構成用として好適なものとなる。 In the wavelength conversion substrate 1, the wavelength conversion film 3 converts the wavelength of the excitation light from the excitation light source using semiconductor quantum dots and converts it into light having a desired wavelength. Therefore, the wavelength conversion board | substrate 1 becomes a suitable thing as an energy conversion board | substrate for solar cells. In addition, a wavelength conversion element can be provided in combination with an appropriate excitation light source, and is suitable for, for example, a configuration of a lighting device or a display element.
尚、波長変換基板１について、例えば、フルドット表示の可能な表示素子の全面に１つを設けてカラー表示の形成を行おうとする場合、ＲＧＢそれぞれの光を取り出すために波長変換基板の対向側にカラーフィルタを用いることが好ましい。そのカラーフィルタとしては公知の方法で製造されたものを好適に用いることができる。 For example, when a color display is to be formed by providing one on the entire surface of a display element capable of full dot display, the wavelength conversion substrate 1 is provided on the opposite side of the wavelength conversion substrate in order to extract RGB light. It is preferable to use a color filter. As the color filter, those produced by a known method can be suitably used.
そして、表示素子用として用いる場合、波長変換フィルムの膜厚は、１００ｎｍ〜１００μｍ程度が好ましく、１μｍ〜１００μｍがより好ましい。膜厚が１００ｎｍ未満であると、励起光を十分吸収することができず、光変換効率が低下するためにパネルの輝度が十分に確保できないといった問題が生じる。さらに、励起光の吸収を高め、パネルの輝度を十分に確保するためには、膜厚として、１μｍ以上とすることが好ましい。 When used for a display element, the film thickness of the wavelength conversion film is preferably about 100 nm to 100 μm, and more preferably 1 μm to 100 μm. When the film thickness is less than 100 nm, excitation light cannot be sufficiently absorbed, and the light conversion efficiency is lowered, so that there is a problem that sufficient brightness of the panel cannot be secured. Furthermore, the film thickness is preferably 1 μm or more in order to enhance absorption of excitation light and sufficiently ensure the brightness of the panel.
本発明の実施形態の波長変換基板を表示素子の構成に用いる場合、例えば、有機ＥＬ素子等の発光素子と組み合わせてそれを励起光源とし、発光型の表示素子を構成することができる。 When the wavelength conversion substrate of the embodiment of the present invention is used for the configuration of a display element, for example, a light-emitting display element can be configured by combining with a light-emitting element such as an organic EL element as an excitation light source.
その場合、本実施形態の波長変換フィルムを備えた本実施形態の波長変換基板は、従来の液晶表示素子等におけるカラーフィルタと同様に、例えば、赤色光、緑色光および青色光をそれぞれ独立に放出する機能を有することが好ましい。 In that case, the wavelength conversion substrate of the present embodiment provided with the wavelength conversion film of the present embodiment emits, for example, red light, green light, and blue light independently as in the case of a color filter in a conventional liquid crystal display element or the like. It is preferable to have the function of
すなわち、従来のカラーフィルタを用いたフルカラー表示の液晶表示素子等では、赤色表示を行うサブ画素と、緑色表示を行うサブ画素と、青色表示を行うサブ画素との３種のサブ画素により、画像を構成する最小単位となる１つの画素が構成される。そして、カラーフィルタは、赤色の着色層と緑色の着色層と青色の着色層とが、赤色表示を行うサブ画素と緑色表示を行うサブ画素と青色表示を行うサブ画素に対応するように、それぞれパターニングされて配置されている。３種の各サブ画素間には、例えば、混色等を防止するためのブラックマトリクスが設けられる。 That is, in a conventional full color liquid crystal display element using a color filter, an image is formed by three types of subpixels: a subpixel that performs red display, a subpixel that performs green display, and a subpixel that performs blue display. One pixel which is the minimum unit constituting the. Then, the color filter is configured so that the red coloring layer, the green coloring layer, and the blue coloring layer correspond to the sub pixel that performs red display, the sub pixel that performs green display, and the sub pixel that performs blue display, respectively. Patterned and arranged. For example, a black matrix for preventing color mixing or the like is provided between the three types of sub-pixels.
したがって、本実施形態の波長変換フィルムを用いた本実施形態の波長変換基板においても、表示素子におけるフルカラー表示を可能とするように構成されることが好ましい。すなわち、赤色、緑色および青色の各色の光を発光する波長変換フィルムを、赤色表示を行うサブ画素、緑色表示を行うサブ画素および青色表示を行うサブ画素のそれぞれに対応するように、パターニングして設けることが好ましい。 Therefore, it is preferable that the wavelength conversion substrate of the present embodiment using the wavelength conversion film of the present embodiment is also configured to enable full color display on the display element. That is, the wavelength conversion film that emits light of each color of red, green, and blue is patterned so as to correspond to the sub-pixel that displays red, the sub-pixel that displays green, and the sub-pixel that displays blue. It is preferable to provide it.
図２は、本発明の実施形態の波長変換フィルムの別の例を模式的に示す断面図である。 FIG. 2 is a cross-sectional view schematically showing another example of the wavelength conversion film of the embodiment of the present invention.
図２に示すように、本発明の実施形態の別の例の波長変換基板１１は、基材１２と、基材１２上に配置された波長変換フィルム１３ａ、１３ｂ、１３ｃとからなる。各波長変換フィルム１３ａ、１３ｂ、１３ｃ間には、ブラックマトリクス１４が配置されている。ブラックマトリクス１４は、公知の遮光性の材料を用い、公知の方法に従ってパターニングして形成することができる。尚、ブラックマトリクス１４は、波長変換基板１１において、必須の構成要素ではなく、波長変換基板１１は、ブラックマトリクス１４を設けない構成とすることも可能である。 As shown in FIG. 2, another example of the wavelength conversion substrate 11 according to the embodiment of the present invention includes a base material 12 and wavelength conversion films 13 a, 13 b, and 13 c disposed on the base material 12. A black matrix 14 is disposed between the wavelength conversion films 13a, 13b, and 13c. The black matrix 14 can be formed by using a known light-shielding material and patterning it according to a known method. Note that the black matrix 14 is not an essential component in the wavelength conversion substrate 11, and the wavelength conversion substrate 11 may be configured without the black matrix 14.
波長変換基板１１では、励起光を赤色の光に変換する波長変換フィルム１３ａと、励起光を緑色の光に変換する波長変換フィルム１３ｂと、励起光を青色の光に変換する波長変換フィルム１３ｃとが、それぞれパターニングされて配置されている。 In the wavelength conversion substrate 11, a wavelength conversion film 13a that converts excitation light into red light, a wavelength conversion film 13b that converts excitation light into green light, and a wavelength conversion film 13c that converts excitation light into blue light Are respectively patterned and arranged.
波長変換フィルム１３ａ、１３ｂ、１３ｃの膜厚は、１００ｎｍ〜１００μｍ程度が好ましく、１μｍ〜１００μｍがより好ましい。膜厚が１００ｎｍ未満であると、励起光を十分吸収することができず、光変換効率の低下による輝度の不足が生じる恐れがある。特に、青色光等の可視光を励起光とする場合には、光変換効率の低下の他、必要とされる色に励起光の透過光が混じることによる色純度の悪化といった問題が生じる。励起光の吸収を高め、色純度の悪影響を及ぼさない程度に励起光の透過光を低減するためには、膜厚として、１μｍ以上とすることが好ましい。 The film thickness of the wavelength conversion films 13a, 13b, and 13c is preferably about 100 nm to 100 μm, and more preferably 1 μm to 100 μm. When the film thickness is less than 100 nm, the excitation light cannot be sufficiently absorbed, and there is a risk that luminance is insufficient due to a decrease in light conversion efficiency. In particular, when visible light such as blue light is used as excitation light, there arises a problem of deterioration in color purity due to mixing of the transmitted light of excitation light with a required color in addition to a decrease in light conversion efficiency. In order to increase the absorption of the excitation light and reduce the transmitted light of the excitation light to such an extent that the color purity is not adversely affected, the film thickness is preferably 1 μm or more.
３種の波長変換フィルム１３ａ〜１３ｃの間に設けられたブラックマトリクス１４は、例えば、各波長変換フィルム１３ａ〜１３ｃから放射される着色光の混色を抑えるように設けられる。 The black matrix 14 provided between the three types of wavelength conversion films 13a to 13c is provided, for example, so as to suppress color mixing of colored light emitted from the wavelength conversion films 13a to 13c.
波長変換基板１１は、励起光源となる発光素子（図示されない）とともに用いられて発光型の表示素子を構成することができる。その場合、各波長変換フィルム１３ａ〜１３ｃが、赤色表示を行うサブ画素、緑色表示を行うサブ画素および青色表示を行うサブ画素にそれぞれ対応して設けられており、表示素子におけるフルカラーの表示を可能とする。 The wavelength conversion substrate 11 can be used together with a light emitting element (not shown) serving as an excitation light source to constitute a light emitting display element. In this case, the wavelength conversion films 13a to 13c are provided corresponding to the sub-pixel that performs red display, the sub-pixel that performs green display, and the sub-pixel that performs blue display, respectively, and can display full color on the display element. And
図３は、本発明の実施形態の表示素子を模式的に示す断面図である。 FIG. 3 is a cross-sectional view schematically showing the display element of the embodiment of the present invention.
本実施形態の表示素子１００は、上述の本実施形態の波長変換基板１１を用いて構成される。したがって、図２の波長変換基板１１と共通する構成要素については、同一の符号を付し、重複する説明は省略する。 The display element 100 of this embodiment is configured using the wavelength conversion substrate 11 of this embodiment described above. Therefore, the same components as those of the wavelength conversion substrate 11 in FIG. 2 are denoted by the same reference numerals, and redundant description is omitted.
本実施形態の表示素子１００は、基材１２上に波長変換フィルム１３ａ、１３ｂ、１３ｃとブラックマトリクス１４とを設けて構成された波長変換基板１１と、波長変換基板１１上に接着剤層１５を介して貼り合わされた光源基板１８とを有する。接着剤層１５は、後述する波長の紫外光または青色光を透過する公知の接着剤を用いて形成される。尚、接着剤層１５は、図３に示すように、基材１２上に波長変換フィルム１３ａ、１３ｂ、１３ｃの全面を被覆するように設ける必要はなく、波長変換基板１１の周囲のみに設けることも可能である。 The display element 100 of this embodiment includes a wavelength conversion substrate 11 configured by providing wavelength conversion films 13 a, 13 b, 13 c and a black matrix 14 on a base material 12, and an adhesive layer 15 on the wavelength conversion substrate 11. And a light source substrate 18 bonded to each other. The adhesive layer 15 is formed using a known adhesive that transmits ultraviolet light or blue light having a wavelength described later. As shown in FIG. 3, the adhesive layer 15 does not need to be provided on the base 12 so as to cover the entire surface of the wavelength conversion films 13 a, 13 b, and 13 c, and is provided only around the wavelength conversion substrate 11. Is also possible.
光源基板１８は、基材１６と、基材１６の波長変換基板１１の側に配置された光源１７ａ、１７ｂ、１７ｃとを備えている。光源１７ａ、１７ｂ、１７ｃからはそれぞれ、励起光として紫外光または青色光が出射される。 The light source substrate 18 includes a base material 16 and light sources 17a, 17b, and 17c disposed on the wavelength conversion substrate 11 side of the base material 16. Each of the light sources 17a, 17b, and 17c emits ultraviolet light or blue light as excitation light.
光源１７ａ、１７ｂ、１７ｃとしては、公知の構造の紫外発光有機ＥＬ素子および青色発光有機ＥＬ素子等の使用が可能であり、特に限定されるものではなく、公知の材料、公知の製造方法で作製することが可能である。ここで、紫外光としては、主発光ピークが３６０ｎｍ〜４３５ｎｍの発光が好ましく、青色光としては、主発光ピークが４３５ｎｍ〜４８０ｎｍの発光が好ましい。光源１７ａ、１７ｂ、１７ｃは、それぞれの出射光が対向する波長変換フィルム１３ａ、１３ｂ、１３ｃを照射するように、指向性を有していることが望ましい。 As the light sources 17a, 17b, and 17c, ultraviolet light emitting organic EL elements and blue light emitting organic EL elements having a known structure can be used, and are not particularly limited, and are manufactured using known materials and known manufacturing methods. Is possible. Here, as the ultraviolet light, light emission having a main emission peak of 360 nm to 435 nm is preferable, and as the blue light, light emission having a main emission peak of 435 nm to 480 nm is preferable. It is desirable that the light sources 17a, 17b, and 17c have directivity so as to irradiate the wavelength conversion films 13a, 13b, and 13c opposed to the respective emitted lights.
本実施形態の表示素子１００は、光源１７ａ、１７ｂ、１７ｃからの励起光を、波長変換基板１１の波長変換フィルム１３ａ、１３ｂ、１３ｃの半導体量子ドットにより波長変換し、所望とする波長の可視光に変換して表示に用いる。 The display element 100 of the present embodiment converts the wavelength of the excitation light from the light sources 17a, 17b, and 17c by the semiconductor quantum dots of the wavelength conversion films 13a, 13b, and 13c of the wavelength conversion substrate 11, and displays visible light having a desired wavelength. Used for display.
表示素子１００の波長変換基板１１は、上述したように、半導体量子ドットと樹脂とを用いてなる波長変換フィルム１３ａ、１３ｂ、１３ｃを基材１２の上にパターニングして配置するものである。 As described above, the wavelength conversion substrate 11 of the display element 100 is formed by patterning the wavelength conversion films 13 a, 13 b, and 13 c using semiconductor quantum dots and resin on the base material 12.
尚、波長変換基板１１においては、後述するように、波長変換フィルム１３ｃにおいて励起光を青色光に変換する。このとき、波長変換基板１１は、波長変換フィルム１３ｃに代えて、波長変換フィルム１３ｃが用いたのと同様の樹脂中に光酸散乱粒子を分散して構成された光散乱フィルムを用いることも可能である。こうすることで、励起光が青色光である場合、その励起光を波長変換することなく、そのままの波長特性で使用することができる。 In addition, in the wavelength conversion board | substrate 11, excitation light is converted into blue light in the wavelength conversion film 13c so that it may mention later. At this time, instead of the wavelength conversion film 13c, the wavelength conversion substrate 11 can use a light scattering film configured by dispersing photoacid scattering particles in the same resin as that used by the wavelength conversion film 13c. It is. By doing so, when the excitation light is blue light, the excitation light can be used as it is without converting the wavelength.
表示素子１００においては、波長変換フィルム１３ａの設けられた部分が、赤色表示を行うサブ画素を構成する。すなわち、波長変換基板１１の波長変換フィルム１３ａは、光源基板１８の対向する光源１７ａからの励起光を赤色に変換する。また、波長変換フィルム１３ｂの設けられた部分が、緑色表示を行うサブ画素を構成する。すなわち、波長変換フィルム１３ｂは、光源基板１８の対向する光源１７ｂからの励起光を緑色に変換する。また、波長変換フィルム１３ｃの設けられた部分が、青色表示を行うサブ画素を構成する。すなわち、波長変換フィルム１３ｃは、光源基板１８の対向する光源１７ｃからの励起光を青色に変換する。 In the display element 100, the portion provided with the wavelength conversion film 13a constitutes a sub-pixel that performs red display. That is, the wavelength conversion film 13a of the wavelength conversion substrate 11 converts the excitation light from the light source 17a facing the light source substrate 18 into red. In addition, the portion where the wavelength conversion film 13b is provided constitutes a sub-pixel that performs green display. That is, the wavelength conversion film 13b converts the excitation light from the light source 17b facing the light source substrate 18 into green. Further, the portion provided with the wavelength conversion film 13c constitutes a sub-pixel that performs blue display. That is, the wavelength conversion film 13c converts the excitation light from the light source 17c facing the light source substrate 18 into blue.
そして、表示素子１００は、波長変換フィルム１３ａ、１３ｂ、１３ｃを備えた３種のサブ画素により、画像を構成する最小単位である１つの画素を構成する。 And the display element 100 comprises one pixel which is the minimum unit which comprises an image by three types of subpixels provided with wavelength conversion film 13a, 13b, 13c.
以上の構成を有する本実施形態の表示素子１００は、波長変換フィルム１３ａ、１３ｂ、１３ｃを備えた３種のサブ画素毎に、赤色、緑色および青色の３種の色の光の出射が制御され、フルカラーの表示が行われる。 In the display element 100 of the present embodiment having the above-described configuration, the emission of light of three types of red, green, and blue is controlled for each of the three types of subpixels including the wavelength conversion films 13a, 13b, and 13c. Full color display is performed.
尚、本発明の実施形態の表示素子においては、波長変換フィルム１３ａ、１３ｂ、１３ｃと基材１２との間に、カラーフィルタを設けることが可能である。すなわち、波長変換フィルム１３ａと基材１２との間に赤色のカラーフィルタを設け、波長変換フィルム１３ｂと基材１２との間に緑色のカラーフィルタを設け、波長変換フィルム１３ｃと基材１２との間に赤色のカラーフィルタを設けることができる。 In the display element according to the embodiment of the present invention, a color filter can be provided between the wavelength conversion films 13 a, 13 b, 13 c and the substrate 12. That is, a red color filter is provided between the wavelength conversion film 13a and the substrate 12, a green color filter is provided between the wavelength conversion film 13b and the substrate 12, and the wavelength conversion film 13c and the substrate 12 A red color filter can be provided therebetween.
カラーフィルタを設けることで、本発明の実施形態の表示素子は、表示の色の純度を高めることができる。ここで、カラーフィルタとしては、液晶表示素子用等として公知のものを公知の方法で形成して用いることができる。 By providing the color filter, the display element of the embodiment of the present invention can increase the purity of the display color. Here, as a color filter, what is known for liquid crystal display elements etc. can be formed and used by a well-known method.
＜照明装置＞
本発明の実施形態の波長変換フィルムは、波長変換素子の構成に用いることができ、例えば、上述したように、表示素子を提供することができる。そして、その他の波長変換素子として、例えば、適当な励起用の光源と組み合わせて、照明装置を提供することができる。<Lighting device>
The wavelength conversion film of embodiment of this invention can be used for the structure of a wavelength conversion element, for example, as mentioned above, can provide a display element. As another wavelength conversion element, for example, an illumination device can be provided in combination with an appropriate excitation light source.
図４は、本発明の実施形態の照明装置の構成を模式的に示す断面図である。 FIG. 4 is a cross-sectional view schematically showing the configuration of the illumination device according to the embodiment of the present invention.
図４に示すように、本発明の実施形態の照明装置２００は、光源１０１と、波長変換フィルム１０２とを有して構成される。そして、それらを保持して光源１０１からの光を波長変換フィルム１０２に効率的に導くための保持体１０３を有することができる。また、必要な場合に、波長変換フィルム１０２から射出された光を多様な方向に拡散させるための拡散板１０４を有することができる。 As shown in FIG. 4, the illumination device 200 according to the embodiment of the present invention includes a light source 101 and a wavelength conversion film 102. And it can have the holding body 103 for hold | maintaining them and guide | inducing the light from the light source 101 to the wavelength conversion film 102 efficiently. In addition, when necessary, it can have a diffusion plate 104 for diffusing light emitted from the wavelength conversion film 102 in various directions.
尚、図４に示す例において、波長変換フィルム１０２は、図示されない基材上に設けられて、基材とともに保持体１０３に保持されるようにすることができる。
また図４で、波長変換フィルム１０２は、光源１０１と離間するように配置されているが、光源１０１上に直接に、または、光源１０１上に適当な基材を介して配置することも可能である。In the example shown in FIG. 4, the wavelength conversion film 102 can be provided on a base material (not shown) and held by the holding body 103 together with the base material.
In FIG. 4, the wavelength conversion film 102 is disposed so as to be separated from the light source 101, but can be disposed directly on the light source 101 or on the light source 101 via an appropriate base material. is there.
光源１０１としては、例えば、青色発光する青色ＬＥＤ（Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇ Ｄｉｏｄｅ）、および、紫外線を発光する紫外発光ＬＥＤ等を用いることができる。 As the light source 101, for example, a blue LED (Light Emitting Diode) that emits blue light, an ultraviolet light-emitting LED that emits ultraviolet light, or the like can be used.
照明装置２００において、波長変換フィルム１０２は、上述した半導体量子ドットおよび樹脂を含んで構成されたものである。波長変換フィルム１０２が、半導体量子ドットを用いて光源１０１からの励起光を波長変換し、所望とする波長の光に変換したうえで、拡散板１０４側に射出する。 In the illumination device 200, the wavelength conversion film 102 includes the semiconductor quantum dots and the resin described above. The wavelength conversion film 102 converts the wavelength of excitation light from the light source 101 using semiconductor quantum dots, converts the light into light having a desired wavelength, and then emits the light to the diffusion plate 104 side.
例えば、光源１０１が、青色ＬＥＤである場合、波長変換フィルム１０２は、光源１０１からの青色光を黄色の光に変換する半導体量子ドットを含んで構成されたものであることが好ましい。その場合、波長変換フィルム１０２は、光源１０１からの青色光の一部を、その補色に当たる黄色の光に変換し、それらを足し合わせた白色光として射出させることができる。そして、照明装置２００は、拡散板１０４によって、波長変換フィルム１０２から射出された白色光を拡散させ、照明光として利用することができる。 For example, when the light source 101 is a blue LED, the wavelength conversion film 102 is preferably configured to include semiconductor quantum dots that convert blue light from the light source 101 into yellow light. In that case, the wavelength conversion film 102 can convert a part of the blue light from the light source 101 into yellow light corresponding to the complementary color, and emit it as white light added together. And the illuminating device 200 can diffuse the white light inject | emitted from the wavelength conversion film 102 with the diffuser plate 104, and can utilize it as illumination light.
その結果、照明装置２００は、光源１０１からの光を、波長変換フィルム１０２を用いて、白色光として取り出すことができ、白色発光用の照明装置として用いることができる。 As a result, the lighting device 200 can extract light from the light source 101 as white light using the wavelength conversion film 102, and can be used as a lighting device for white light emission.
尚、上述の例において、波長変換フィルム１０２に含有させる半導体量子ドットとしては、青色光を黄色の光に変換するもののほか、赤色の光や青緑色の光に変換するものも用いることができる。そのような複数種類の半導体量子ドットを用いることにより、波長変換フィルム１０２を用いて取り出される白色光の演色性を向上させることができる。 In addition, in the above-mentioned example, as a semiconductor quantum dot contained in the wavelength conversion film 102, what converts blue light into yellow light, and what converts red light and blue-green light can also be used. By using such a plurality of types of semiconductor quantum dots, the color rendering property of white light extracted using the wavelength conversion film 102 can be improved.
また、光源１０１が、紫外発光ＬＥＤである場合、波長変換フィルム１０２は、光源１０１からの紫外線を赤色の光に変換する半導体量子ドットと緑色の光に変換する半導体量子ドットと青色の光に変換する半導体量子ドットとを含んで構成されたものであることが好ましい。 When the light source 101 is an ultraviolet light emitting LED, the wavelength conversion film 102 converts the semiconductor quantum dot that converts ultraviolet light from the light source 101 into red light, the semiconductor quantum dot that converts green light, and blue light. It is preferable that it is comprised including the semiconductor quantum dot to perform.
その結果、照明装置２００は、光源１０１からの光を、波長変換フィルム１０２を用いて、優れた演色性の白色光として取り出すことができ、高演色性の白色発光用照明装置として用いることができる。 As a result, the lighting device 200 can extract light from the light source 101 as white light with excellent color rendering properties using the wavelength conversion film 102, and can be used as a lighting device for white light emission with high color rendering properties. .
以下、実施例に基づいて本発明をより具体的に説明するが、本発明はこれら実施例に何ら限定されるものではない。尚、記載中の「部」は、特に断りのない限り「重量部」を意味する。また、各物性値の測定方法は以下の通りである。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all. In the description, “parts” means “parts by weight” unless otherwise specified. Moreover, the measuring method of each physical property value is as follows.
＜分子量＞
樹脂の分子量は、各樹脂の溶剤への溶解性等を考慮し、下記の（ａ）または（ｂ）の方法にて測定を行った。
（ａ）ウオターズ（ＷＡＴＥＲＳ）社製のゲルパーミエ−ションクロマトグラフィー（ＧＰＣ）装置（１５０Ｃ型、カラム：東ソー社製Ｈタイプカラム、展開溶剤：ｏ−ジクロロベンゼン）を用い、標準ポリスチレン換算の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）を測定した。
（ｂ）東ソー社製ＧＰＣ装置（ＨＬＣ−８２２０型、カラム：ＴＳＫｇｅｌα−Ｍ、展開溶剤：ＴＨＦ）を用い、標準ポリスチレン換算の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）を測定した。<Molecular weight>
The molecular weight of the resin was measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent.
(A) Weight average molecular weight in terms of standard polystyrene using a gel permeation chromatography (GPC) apparatus (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by WATERS (Mw) and number average molecular weight (Mn) were measured.
(B) The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured using a GPC apparatus (HLC-8220 type, column: TSKgel α-M, developing solvent: THF) manufactured by Tosoh Corporation.
尚、後述する樹脂合成例３で合成した樹脂については、上記方法による分子量の測定ではなく、下記方法（ｃ）による対数粘度の測定を行った。
（ｃ）ポリイミド樹脂溶液の一部を無水メタノールに投入してポリイミド樹脂を析出させ、ろ過して未反応単量体から分離した。８０℃で１２時間真空乾燥して得られたポリイミド０．１ｇをＮ−メチル−２−ピロリドン２０ｍＬに溶解し、キャノン−フェンスケ粘度計を使用して３０℃における対数粘度（μ）を下記式により求めた。In addition, about the resin synthesize | combined in the resin synthesis example 3 mentioned later, the logarithmic viscosity was measured by the following method (c) instead of the molecular weight measurement by the said method.
(C) A part of the polyimide resin solution was added to anhydrous methanol to precipitate the polyimide resin, and filtered to separate from the unreacted monomer. 0.1 g of polyimide obtained by vacuum drying at 80 ° C. for 12 hours is dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity (μ) at 30 ° C. is obtained by the following formula using a Canon-Fenske viscometer. Asked.
ｔ０：溶媒の流下時間
ｔｓ：希薄高分子溶液の流下時間
Ｃ：０．５ｇ／ｄＬ t 0 : Flowing time of solvent t s : Flowing time of dilute polymer solution C: 0.5 g / dL
＜ガラス転移温度（Ｔｇ）＞
エスアイアイ・ナノテクノロジーズ株式会社製の示差走査熱量計（ＤＳＣ６２００）を用いて、昇温速度：毎分２０℃、窒素気流下で測定した。<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (DSC6200) manufactured by SII Nano Technologies, Inc., the rate of temperature increase was measured at 20 ° C. per minute under a nitrogen stream.
＜半導体量子ドット＞
本実施例で用いた半導体量子ドットとその蛍光極大波長を次に示す。
半導体量子ドットＡ：ＩｎＰ／ＺｎＳコアシェル型量子ドット（蛍光極大波長：６３０ｎｍ）
半導体量子ドットＢ：ＩｎＣｕＳ２／ＺｎＳコアシェル型量子ドット（蛍光極大波長：６４０ｎｍ）
半導体量子ドットＣ：ＡｇＩｎＳ２量子ドット（蛍光極大波長：６５０ｎｍ）
半導体量子ドットＤ：ＺｎＳ−ＡｇＩｎＳ２固溶体／ＺｎＳコアシェル型量子ドット（蛍光極大波長：６４０ｎｍ）
半導体量子ドットＥ：ＺｎドープＡｇＩｎＳ２量子ドット（蛍光極大波長：６３０ｎｍ）<Semiconductor quantum dots>
The semiconductor quantum dots used in this example and their fluorescence maximum wavelengths are shown below.
Semiconductor quantum dot A: InP / ZnS core-shell quantum dot (fluorescence maximum wavelength: 630 nm)
Semiconductor quantum dot B: InCuS 2 / ZnS core-shell type quantum dot (fluorescence maximum wavelength: 640 nm)
Semiconductor quantum dot C: AgInS 2 quantum dot (fluorescence maximum wavelength: 650 nm)
Semiconductor quantum dot D: ZnS-AgInS 2 solid solution / ZnS core-shell quantum dot (fluorescence maximum wavelength: 640 nm)
Semiconductor quantum dot E: Zn-doped AgInS 2 quantum dot (fluorescence maximum wavelength: 630 nm)
そして、下記実施例で用いた半導体量子ドットＡ：ＩｎＰ／ＺｎＳコアシェル型量子ドット、半導体量子ドットＢ：ＩｎＣｕＳ２／ＺｎＳコアシェル型量子ドット、半導体量子ドットＣ：ＡｇＩｎＳ２量子ドット、半導体量子ドットＤ：ＺｎＳ−ＡｇＩｎＳ２固溶体／ＺｎＳコアシェル型量子ドット、および、半導体量子ドットＥ：ＺｎドープＡｇＩｎＳ２量子ドットは一般的に知られている方法で合成することができる。Then, semiconductor quantum dots A: InP / ZnS core-shell quantum dots, semiconductor quantum dots B: InCuS 2 / ZnS core-shell quantum dots, semiconductor quantum dots C: AgInS 2 quantum dots, semiconductor quantum dots D: ZnS-AgInS 2 solid solution / ZnS core-shell quantum dots and semiconductor quantum dots E: Zn-doped AgInS 2 quantum dots can be synthesized by a generally known method.
例えば、半導体量子ドットＡ：ＩｎＰ／ＺｎＳコアシェル型量子ドットに関しては技術文献「Ｊｏｕｒｎａｌ ｏｆ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ． ２００７， １２９， １５４３２−１５４３３」に、半導体量子ドットＢ：ＩｎＣｕＳ２／ＺｎＳコアシェル型量子ドットに関しては技術文献「Ｊｏｕｒｎａｌ ｏｆ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ． ２００９， １３１， ５６９１−５６９７」および技術文献「Ｃｈｅｍｉｓｔｒｙ ｏｆ Ｍａｔｅｒｉａｌｓ． ２００９， ２１， ２４２２−２４２９」に、半導体量子ドットＣ：ＡｇＩｎＳ２量子ドットに関しては技術文献「Ｊｏｕｒｎａｌ ｏｆ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ． ２００９， １３１， ５６９１−５６９７」に、半導体量子ドットＤ：ＺｎＳ−ＡｇＩｎＳ２固溶体／ＺｎＳコアシェル型量子ドットに関しては技術文献「Ｃｈｅｍｉｃａｌ Ｃｏｍｍｕｎｉｃａｔｉｏｎｓ． ２０１０， ４６， ２０８２−２０８４」に、半導体量子ドットＥ：ＺｎドープＡｇＩｎＳ２量子ドットに関しては技術文献「Ｊｏｕｒｎａｌ ｏｆ Ｐｈｙｓｉｃａｌ Ｃｈｅｍｉｓｔｒｙ Ｃ． ２０１２， １１６， ９７６９−９７７３」に記載されている方法を参照して合成することができる。For example, regarding the semiconductor quantum dot A: InP / ZnS core-shell type quantum dot, the technical literature “Journal of American Chemical Society. 2007, 129, 15432-15433” and the semiconductor quantum dot B: InCuS 2 / ZnS core-shell type quantum dot In the technical document “Journal of American Chemical Society. 2009, 131, 5691-5697” and the technical document “Chemistry of Materials. 2009, 21, 2422-2429”, the semiconductor quantum dot C: AgInS 2 quantum ur of American Chemical Society. 2009, 131, 5691-5697 " , Semiconductor quantum dots D: technical literature with respect to ZnS-AgInS 2 solid solution / ZnS core-shell quantum dots "Chemical Communications 2010, 46, 2082-2084.", The semiconductor quantum dot E: technical literature with respect to Zn-doped AgInS 2 quantum dots It can be synthesized with reference to the method described in “Journal of Physical Chemistry C. 2012, 116, 9769-9773”.
＜樹脂合成例１＞
下記式（ａ）で表される８−メチル−８−メトキシカルボニルテトラシクロ［４．４．０．１２，５．１７，１０］ドデカ−３−エン（以下「ＤＮＭ」ともいう。）１００部、１−ヘキセン（分子量調節剤）１８部およびトルエン（開環重合反応用溶媒）３００部を、窒素置換した反応容器に仕込み、この溶液を８０℃に加熱した。次いで、反応容器内の溶液に、重合触媒として、トリエチルアルミニウムのトルエン溶液（０．６ｍｏｌ／リットル）０．２部と、メタノール変性の六塩化タングステンのトルエン溶液（濃度０．０２５ｍｏｌ／リットル）０．９部とを添加し、この溶液を８０℃で３時間加熱攪拌することにより開環重合反応させて開環重合体溶液を得た。この重合反応における重合転化率は９７％であった。<Resin synthesis example 1>
8-methyl-8-methoxycarbonyltetracyclo represented by the following formula (a) [4.4.0.1 2,5 . 1 7,10 ] Dodeca-3-ene (hereinafter also referred to as “DNM”) 100 parts, 1-hexene (molecular weight regulator) 18 parts and toluene (ring-opening polymerization solvent) 300 parts nitrogen-substituted reaction The vessel was charged and the solution was heated to 80 ° C. Next, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol / liter) as a polymerization catalyst and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) were added to the solution in the reaction vessel. 9 parts was added and this solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.
このようにして得られた開環重合体溶液１０００部をオートクレーブに仕込み、この開環重合体溶液に、ＲｕＨＣｌ（ＣＯ）［Ｐ（Ｃ６Ｈ５）３］３を０．１２部添加し、水素ガス圧１００ｋｇ／ｃｍ２、反応温度１６５℃の条件下で、３時間加熱撹拌して水素添加反応を行った。1000 parts of the ring-opening polymer solution thus obtained was charged into an autoclave, and 0.12 part of RuHCl (CO) [P (C 6 H 5 ) 3 ] 3 was added to the ring-opening polymer solution. Under the conditions of a hydrogen gas pressure of 100 kg / cm 2 and a reaction temperature of 165 ° C., the hydrogenation reaction was performed by heating and stirring for 3 hours.
得られた反応溶液（水素添加重合体溶液）を冷却した後、水素ガスを放圧した。この反応溶液を大量のメタノール中に注いで凝固物を分離回収し、これを乾燥して、水素添加重合体（以下、「樹脂Ａ」ともいう。）を得た。得られた樹脂Ａは、数平均分子量（Ｍｎ）が３２０００、重量平均分子量（Ｍｗ）が１３７０００であり、ガラス転移温度（Ｔｇ）が１６５℃であった。 After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover a coagulated product, which was dried to obtain a hydrogenated polymer (hereinafter also referred to as “resin A”). The obtained resin A had a number average molecular weight (Mn) of 32000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 ° C.
＜樹脂合成例２＞
３Ｌの４つ口フラスコに２，６−ジフルオロベンゾニトリル３５．１２ｇ（０．２５３モル）、９，９−ビス（４−ヒドロキシフェニル）フルオレン８７．６０ｇ（０．２５０モル）、炭酸カリウム４１．４６ｇ（０．３００モル）、Ｎ，Ｎ−ジメチルアセトアミド（以下、「ＤＭＡｃ」ともいう。）４４３ｇおよびトルエン１１１ｇを添加した。続いて、４つ口フラスコに温度計、撹拌機、窒素導入管付き三方コック、ディーンスターク管および冷却管を取り付けた。<Resin synthesis example 2>
In a 3 L four-necked flask, 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 41. 46 g (0.300 mol), 443 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask.
次いで、フラスコ内を窒素置換した後、得られた溶液を１４０℃で３時間反応させ、生成する水をディーンスターク管から随時取り除いた。水の生成が認められなくなったところで、徐々に温度を１６０℃まで上昇させ、そのままの温度で６時間反応させた。 Next, after the atmosphere in the flask was replaced with nitrogen, the resulting solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 6 hours.
室温（２５℃）まで冷却後、生成した塩をろ紙で除去し、ろ液をメタノールに投じて再沈殿させ、ろ別によりろ物（残渣）を単離した。得られたろ物を６０℃で一晩真空乾燥し、白色粉末（以下、「樹脂Ｂ」ともいう。）を得た（収率９５％）。得られた樹脂Ｂは、数平均分子量（Ｍｎ）が７５０００、重量平均分子量（Ｍｗ）が１８８０００であり、ガラス転移温度（Ｔｇ）が２８５℃であった。 After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder (hereinafter also referred to as “resin B”) (yield 95%). The obtained resin B had a number average molecular weight (Mn) of 75000, a weight average molecular weight (Mw) of 188000, and a glass transition temperature (Tg) of 285 ° C.
＜樹脂合成例３＞
温度計、撹拌器、窒素導入管、側管付き滴下ロート、ディーンスターク管および冷却管を備えた５００ｍＬの５つ口フラスコに、窒素気流下、１，４−ビス（４−アミノ−α，α−ジメチルベンジル）ベンゼン２７．６６ｇ（０．０８モル）および４，４’−ビス（４−アミノフェノキシ）ビフェニル７．３８ｇ（０．０２モル）を入れて、γ―ブチロラクトン６８．６５ｇおよびＮ，Ｎ−ジメチルアセトアミド１７．１６ｇに溶解させた。得られた溶液を、氷水バスを用いて５℃に冷却し、同温に保ちながら１，２，４，５−シクロヘキサンテトラカルボン酸二無水物２２．６２ｇ（０．１モル）およびイミド化触媒としてトリエチルアミン０．５０ｇ（０．００５モル）を一括添加した。添加終了後、１８０℃に昇温し、随時留出液を留去させながら、６時間還流させた。反応終了後、内温が１００℃になるまで空冷した後、Ｎ，Ｎ−ジメチルアセトアミド１４３．６ｇを加えて希釈し、攪拌しながら冷却し、固形分濃度２０重量％のポリイミド樹脂溶液２６４．１６ｇを得た。このポリイミド樹脂溶液の一部を１Ｌのメタノール中に注ぎ入れてポリイミドを沈殿させた。濾別したポリイミドをメタノールで洗浄した後、１００℃の真空乾燥機中で２４時間乾燥させて白色粉末（以下、「樹脂Ｃ」ともいう。）を得た。得られた樹脂ＣのＩＲスペクトルを測定したところ、イミド基に特有の１７０４ｃｍ−１、１７７０ｃｍ−１の吸収が見られた。樹脂Ｃはガラス転移温度（Ｔｇ）が３１０℃であり、対数粘度を測定したところ、０．８７であった。<Resin synthesis example 3>
In a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, a dropping funnel with a side tube, a Dean-Stark tube and a cooling tube, 1,4-bis (4-amino-α, α -Dimethylbenzyl) benzene (27.66 g, 0.08 mol) and 4,4'-bis (4-aminophenoxy) biphenyl (7.38 g, 0.02 mol) were added, and γ-butyrolactone (68.65 g) and N, It was dissolved in 17.16 g of N-dimethylacetamide. The resulting solution was cooled to 5 ° C. using an ice-water bath, and while maintaining the same temperature, 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and an imidization catalyst As a result, 0.50 g (0.005 mol) of triethylamine was added all at once. After completion of the addition, the temperature was raised to 180 ° C. and refluxed for 6 hours while distilling off the distillate as needed. After completion of the reaction, the reaction mixture was air-cooled until the internal temperature reached 100 ° C., diluted by adding 143.6 g of N, N-dimethylacetamide, cooled with stirring, and 264.16 g of a polyimide resin solution having a solid content concentration of 20% by weight. Got. A part of this polyimide resin solution was poured into 1 L of methanol to precipitate the polyimide. The polyimide separated by filtration was washed with methanol and then dried in a vacuum dryer at 100 ° C. for 24 hours to obtain a white powder (hereinafter also referred to as “resin C”). The IR spectrum of the obtained resin C was measured, 1704 cm -1 characteristic of imido group, absorption of 1770 cm -1 were observed. Resin C had a glass transition temperature (Tg) of 310 ° C. and a logarithmic viscosity of 0.87.
＜樹脂合成例４＞
９，９−ビス｛４−（２−ヒドロキシエトキシ）フェニル｝フルオレン９．１６７ｋｇ（２０．９０モル）、ビスフェノールＡ ４．５８５ｋｇ（２０．０８４モル）、ジフェニルカーボネート９．０００ｋｇ（４２．０１モル）、および炭酸水素ナトリウム０．０２０６６ｋｇ（２．４５９×１０−４モル）を、攪拌機および留出装置を備えた５０Ｌ反応器に入れ、窒素雰囲気で７６０Ｔｏｒｒの下、１時間かけて２１５℃に加熱・攪拌した。その後、１５分かけて減圧度を１５０Ｔｏｒｒに調整し、２１５℃、１５０Ｔｏｒｒの条件下で２０分間保持し、エステル交換反応を行った。さらに３７．５℃／Ｈｒの速度で２４０℃まで昇温し、２４０℃、１５０Ｔｏｒｒで１０分間保持した。その後、１０分かけて１００Ｔｏｒｒに調整し、２４０℃、１２０Ｔｏｒｒで７０分間保持した。その後、１０分かけて１００Ｔｏｒｒに調整し、２４０℃、１００Ｔｏｒｒで１０分間保持した。さらに４０分かけて１Ｔｏｒｒ以下とし、２４０℃、１Ｔｏｒｒ以下の条件下で１０分間攪拌して重合反応を行った。反応終了後、反応器内に窒素を導入し加圧にし、生成したポリカーボネート樹脂（以下、「樹脂Ｄ」ともいう。）をペレット化しながら抜き出した。得られた樹脂Ｄは、重量平均分子量が４１０００であり、ガラス転移温度（Ｔｇ）が１５２℃であった。<Resin synthesis example 4>
9.167 kg (20.90 mol) of 9,9-bis {4- (2-hydroxyethoxy) phenyl} fluorene, 4.585 kg (20.08 mol) of bisphenol A, 9.000 kg (42.01 mol) of diphenyl carbonate , And 0.02066 kg (2.459 × 10 −4 mol) of sodium bicarbonate were placed in a 50 L reactor equipped with a stirrer and a distillation apparatus, and heated to 215 ° C. over 1 hour under a nitrogen atmosphere at 760 Torr. Stir. Thereafter, the degree of vacuum was adjusted to 150 Torr over 15 minutes, and the mixture was held at 215 ° C. and 150 Torr for 20 minutes to conduct a transesterification reaction. Further, the temperature was raised to 240 ° C. at a rate of 37.5 ° C./Hr, and held at 240 ° C. and 150 Torr for 10 minutes. Thereafter, the pressure was adjusted to 100 Torr over 10 minutes and maintained at 240 ° C. and 120 Torr for 70 minutes. Thereafter, the pressure was adjusted to 100 Torr over 10 minutes and held at 240 ° C. and 100 Torr for 10 minutes. The polymerization reaction was further carried out by stirring for 10 minutes under the conditions of 240 ° C. and 1 Torr or less, at 40 ° C. for 1 Torr or less. After completion of the reaction, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin (hereinafter also referred to as “resin D”) was extracted while being pelletized. The obtained resin D had a weight average molecular weight of 41,000 and a glass transition temperature (Tg) of 152 ° C.
＜樹脂合成例５＞
反応器に、９，９−ビス｛４−（２−ヒドロキシエトキシ）−３，５−ジメチルフェニル｝フルオレン０．８モル、エチレングリコール２．２モルおよびイソフタル酸ジメチル１．０モルを加え、攪拌しながら徐々に加熱溶融してエステル交換反応を行った後、酸化ゲルマニウム２０×１０−４モルを加え、２９０℃、１Ｔｏｒｒ以下に到達するまで徐々に昇温および減圧を行いながらエチレングリコールを除去した。この後、内容物を反応器から取り出し、ポリエステル樹脂（以下、「樹脂Ｅ」ともいう。）のペレットを得た。得られた樹脂Ｅは、数平均分子量が４００００であり、ガラス転移温度が１４５℃であった。<Resin synthesis example 5>
To the reactor, 0.8 mol of 9,9-bis {4- (2-hydroxyethoxy) -3,5-dimethylphenyl} fluorene, 2.2 mol of ethylene glycol and 1.0 mol of dimethyl isophthalate were added and stirred. The mixture was gradually heated and melted to carry out a transesterification reaction, and then 20 × 10 −4 moles of germanium oxide was added, and ethylene glycol was removed while gradually increasing the temperature and reducing the pressure until reaching 290 ° C. and 1 Torr or less. . Thereafter, the contents were taken out of the reactor to obtain pellets of polyester resin (hereinafter also referred to as “resin E”). The obtained resin E had a number average molecular weight of 40000 and a glass transition temperature of 145 ° C.
＜樹脂合成例６＞
温度計、冷却管、ガス導入管および攪拌機を備えた反応器に、４，４’−ビス（２，３，４，５，６−ペンタフルオロベンゾイル）ジフェニルエーテル（ＢＰＤＥ）１６．７４部、９，９−ビス（４−ヒドロキシフェニル）フルオレン（ＨＦ）１０．５部、炭酸カリウム４．３４部およびＤＭＡｃ９０部を仕込んだ。この混合物を８０℃に加温し、８時間反応させた。反応終了後、反応溶液をブレンダーで激しく攪拌しながら、１％酢酸水溶液中に添加した。析出した反応物を濾別し、蒸留水およびメタノールで洗浄した後、減圧乾燥して、フッ素化ポリエーテルケトン（以下、「樹脂Ｆ」ともいう。）を得た。得られた樹脂Ｆは、数平均分子量が７１０００であり、ガラス転移温度（Ｔｇ）が２４２℃であった。<Resin synthesis example 6>
To a reactor equipped with a thermometer, a cooling pipe, a gas introduction pipe and a stirrer, 4,74′-bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether (BPDE) 16.74 parts, 10.5 parts of 9-bis (4-hydroxyphenyl) fluorene (HF), 4.34 parts of potassium carbonate and 90 parts of DMAc were charged. The mixture was warmed to 80 ° C. and reacted for 8 hours. After completion of the reaction, the reaction solution was added into a 1% aqueous acetic acid solution with vigorous stirring with a blender. The precipitated reaction product was separated by filtration, washed with distilled water and methanol, and then dried under reduced pressure to obtain a fluorinated polyether ketone (hereinafter also referred to as “resin F”). The obtained resin F had a number average molecular weight of 71,000 and a glass transition temperature (Tg) of 242 ° C.
［実施例１］
容器に、合成例１で得られた樹脂Ａ１００重量部、半導体量子ドットＡ（蛍光極大波長：６３０ｎｍ） １０重量部、さらに塩化メチレンを加えることで、樹脂濃度が２０重量％の樹脂溶液を得た。次いで、得られた半導体量子ドットＡ含有の樹脂溶液を平滑なガラス板上にキャストし、２０℃で８時間乾燥した後、ガラス板から剥離した。剥離した塗膜をさらに減圧下１００℃で８時間乾燥して、厚さ０．１ｍｍ、縦６０ｍｍ、横６０ｍｍの波長変換フィルムを得た。[Example 1]
By adding 100 parts by weight of the resin A obtained in Synthesis Example 1, 10 parts by weight of semiconductor quantum dots A (fluorescence maximum wavelength: 630 nm), and further adding methylene chloride to the container, a resin solution having a resin concentration of 20% by weight was obtained. . Next, the obtained semiconductor quantum dot A-containing resin solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a wavelength conversion film having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
青色ＬＥＤを用い、得られた波長変換フィルムに、励起光として、ピーク波長４５０ｎｍの青色光を照射したところ、波長変換フィルムにおいて励起光の波長の変換がなされ、波長変換フィルムから赤色光が放出されることを確認した。 When blue light having a peak wavelength of 450 nm was irradiated as excitation light to the obtained wavelength conversion film using a blue LED, the wavelength of the excitation light was converted in the wavelength conversion film, and red light was emitted from the wavelength conversion film. I was sure that.
［実施例２］〜［実施例１１］
表１に示す樹脂、溶媒およびフィルム乾燥条件を採用したこと以外は、実施例１と同様にして、厚さ０．１０５ｍｍの波長変換フィルムを製造した。波長変換フィルムの製造条件を表１に示す。尚、表１において、樹脂の添加部数はいずれも１００重量部であり、樹脂溶液の濃度はいずれも２０重量％である。また、実施例１〜実施例５５で使用した樹脂Ａ〜Ｆ以外の樹脂と、溶媒と、フィルム乾燥条件は下記に示した通りである。[Example 2] to [Example 11]
A wavelength conversion film having a thickness of 0.105 mm was produced in the same manner as in Example 1 except that the resin, solvent, and film drying conditions shown in Table 1 were employed. The production conditions of the wavelength conversion film are shown in Table 1. In Table 1, the number of added parts of the resin is 100 parts by weight, and the concentration of the resin solution is 20% by weight. Moreover, resin other than resin AF used in Example 1-Example 55, a solvent, and film drying conditions are as having shown below.
［実施例１２］〜［実施例２２］
半導体量子ドットに半導体量子ドットＢ（蛍光極大波長：６４０ｎｍ）を用い、表１に示す樹脂、溶媒およびフィルム乾燥条件を採用したこと以外は、実施例１と同様にして、厚さ０．１０５ｍｍの波長変換フィルムを製造した。波長変換フィルムの製造条件を表１に示す。[Example 12] to [Example 22]
A semiconductor quantum dot B (fluorescence maximum wavelength: 640 nm) was used as the semiconductor quantum dot, and the thickness of 0.105 mm was the same as in Example 1 except that the resin, solvent, and film drying conditions shown in Table 1 were employed. A wavelength conversion film was produced. The production conditions of the wavelength conversion film are shown in Table 1.
［実施例２３］〜［実施例３３］
半導体量子ドットに半導体量子ドットＣ（蛍光極大波長：６５０ｎｍ）を用い、表１に示す樹脂、溶媒およびフィルム乾燥条件を採用したこと以外は、実施例１と同様にして、厚さ０．１０５ｍｍの波長変換フィルムを製造した。波長変換フィルムの製造条件を表１に示す。[Example 23] to [Example 33]
A semiconductor quantum dot C (fluorescence maximum wavelength: 650 nm) was used as the semiconductor quantum dot, and the thickness of 0.105 mm was the same as in Example 1 except that the resin, solvent, and film drying conditions shown in Table 1 were employed. A wavelength conversion film was produced. The production conditions of the wavelength conversion film are shown in Table 1.
［実施例３４］〜［実施例４４］
半導体量子ドットに半導体量子ドットＤ（蛍光極大波長：６４０ｎｍ）を用い、表２に示す樹脂、溶媒およびフィルム乾燥条件を採用したこと以外は、実施例１と同様にして、厚さ０．１０５ｍｍの波長変換フィルムを製造した。波長変換フィルムの製造条件を表２に示す。[Example 34] to [Example 44]
A semiconductor quantum dot D (fluorescence maximum wavelength: 640 nm) was used as the semiconductor quantum dot, and the thickness of 0.105 mm was the same as in Example 1 except that the resin, solvent, and film drying conditions shown in Table 2 were employed. A wavelength conversion film was produced. Table 2 shows the production conditions of the wavelength conversion film.
［実施例４５］〜［実施例５５］
半導体量子ドットに半導体量子ドットＥ（蛍光極大波長：６３０ｎｍ）を用い、表２に示す樹脂、溶媒およびフィルム乾燥条件を採用したこと以外は、実施例１と同様にして、厚さ０．１０５ｍｍの波長変換フィルムを製造した。波長変換フィルムの製造条件を表２に示す。[Example 45] to [Example 55]
A semiconductor quantum dot E (fluorescence maximum wavelength: 630 nm) was used as the semiconductor quantum dot, and the thickness of 0.105 mm was the same as in Example 1 except that the resin, solvent, and film drying conditions shown in Table 2 were employed. A wavelength conversion film was produced. Table 2 shows the production conditions of the wavelength conversion film.
樹脂Ｇ：環状オレフィン系樹脂「ゼオノア（登録商標） １４２０Ｒ」（日本ゼオン（株）製）
樹脂Ｈ：環状オレフィン系樹脂「ＡＰＥＬ（登録商標） ＃６０１５」（三井化学（株）製）
樹脂Ｉ：ポリカーボネート系樹脂「ピュアエース（登録商標）」（帝人（株）製）
樹脂Ｊ：ポリエーテルサルホン系樹脂「スミライト（登録商標） ＦＳ−１３００」（住友ベークライト（株）製）
樹脂Ｋ：耐熱アクリル系樹脂「アクリビュア（登録商標）」（（株）日本触媒製）
溶媒（１）：塩化メチレン
溶媒（２）：Ｎ，Ｎ−ジメチルアセトアミド
溶媒（３）：酢酸エチル／トルエン（重量比：５／５）
溶媒（４）：シクロヘキサン／キシレン（重量比：７／３）
溶媒（５）：シクロヘキサン／塩化メチレン（重量比：９９／１）
溶媒（６）：Ｎ−メチル−２−ピロリドンResin G: Cyclic Olefin Resin “Zeonor (registered trademark) 1420R” (manufactured by Nippon Zeon Co., Ltd.)
Resin H: Cyclic olefin-based resin “APEL (registered trademark) # 6015” (manufactured by Mitsui Chemicals, Inc.)
Resin I: Polycarbonate resin “Pure Ace (registered trademark)” (manufactured by Teijin Limited)
Resin J: Polyethersulfone resin “Sumilite (registered trademark) FS-1300” (manufactured by Sumitomo Bakelite Co., Ltd.)
Resin K: Heat-resistant acrylic resin “Acryview (registered trademark)” (manufactured by Nippon Shokubai Co., Ltd.)
Solvent (1): Methylene chloride Solvent (2): N, N-dimethylacetamide Solvent (3): Ethyl acetate / toluene (weight ratio: 5/5)
Solvent (4): cyclohexane / xylene (weight ratio: 7/3)
Solvent (5): cyclohexane / methylene chloride (weight ratio: 99/1)
Solvent (6): N-methyl-2-pyrrolidone
また、表１および表２における、実施例１〜実施例５５のフィルム乾燥条件は以下の通りである。 Moreover, the film drying conditions of Example 1-Example 55 in Table 1 and Table 2 are as follows.
条件（１）：２０℃／８ｈｒ→減圧下 １００℃／８ｈｒ
条件（２）：６０℃／８ｈｒ→８０℃／８ｈｒ→減圧下 １４０℃／８ｈｒ
条件（３）：６０℃／８ｈｒ→８０℃／８ｈｒ→減圧下 １００℃／２４ｈｒ
条件（４）：４０℃／４ｈｒ→６０℃／４ｈｒ→減圧下 １００℃／８ｈｒCondition (1): 20 ° C./8 hr → under reduced pressure 100 ° C./8 hr
Condition (2): 60 ° C./8 hr → 80 ° C./8 hr → under reduced pressure 140 ° C./8 hr
Condition (3): 60 ° C./8 hr → 80 ° C./8 hr → under reduced pressure 100 ° C./24 hr
Condition (4): 40 ° C./4 hr → 60 ° C./4 hr → under reduced pressure 100 ° C./8 hr
実施例２〜実施例１１で得られた波長変換フィルムをそれぞれ用い、青色ＬＥＤを用いて、ピーク波長４５０ｎｍの青色光を照射した。その結果、それぞれの波長変換フィルムにおいて励起光の一部の波長変換がなされ、赤色光が放出されることを確認した。 Each of the wavelength conversion films obtained in Examples 2 to 11 was used, and blue light having a peak wavelength of 450 nm was irradiated using a blue LED. As a result, it was confirmed that some wavelength conversion of excitation light was performed in each wavelength conversion film, and red light was emitted.
実施例１２〜実施例２２で得られた波長変換フィルムをそれぞれ用い、青色ＬＥＤを用いて、ピーク波長４５０ｎｍの青色光を照射した。その結果、それぞれの波長変換フィルムにおいて励起光の一部の波長変換がなされ、赤色光が放出されることを確認した。 Each of the wavelength conversion films obtained in Examples 12 to 22 was used, and blue light having a peak wavelength of 450 nm was irradiated using a blue LED. As a result, it was confirmed that some wavelength conversion of excitation light was performed in each wavelength conversion film, and red light was emitted.
実施例２３〜実施例３３で得られた波長変換フィルムをそれぞれ用い、青色ＬＥＤを用いて、ピーク波長４５０ｎｍの青色光を照射した。その結果、それぞれの波長変換フィルムにおいて励起光の一部の波長変換がなされ、赤色光が放出されることを確認した。 Each of the wavelength conversion films obtained in Examples 23 to 33 was used, and blue light having a peak wavelength of 450 nm was irradiated using a blue LED. As a result, it was confirmed that some wavelength conversion of excitation light was performed in each wavelength conversion film, and red light was emitted.
実施例３４〜実施例４４で得られた波長変換フィルムをそれぞれ用い、青色ＬＥＤを用いて、ピーク波長４５０ｎｍの青色光を照射した。その結果、それぞれの波長変換フィルムにおいて励起光の一部の波長変換がなされ、赤色光が放出されることを確認した。 Each of the wavelength conversion films obtained in Examples 34 to 44 was used, and blue light having a peak wavelength of 450 nm was irradiated using a blue LED. As a result, it was confirmed that some wavelength conversion of excitation light was performed in each wavelength conversion film, and red light was emitted.
実施例４５〜実施例５５で得られた波長変換フィルムをそれぞれ用い、青色ＬＥＤを用いて、ピーク波長４５０ｎｍの青色光を照射した。その結果、それぞれの波長変換フィルムにおいて励起光の一部の波長変換がなされ、赤色光が放出されることを確認した。 Each of the wavelength conversion films obtained in Example 45 to Example 55 was used, and blue light having a peak wavelength of 450 nm was irradiated using a blue LED. As a result, it was confirmed that some wavelength conversion of excitation light was performed in each wavelength conversion film, and red light was emitted.
本発明の波長変換フィルムは安定性に優れ、表示素子やそれを用いた電子機器のほか、ＬＥＤおよび太陽電池の分野でも利用することができる。 The wavelength conversion film of the present invention is excellent in stability, and can be used in the fields of LEDs and solar cells in addition to display elements and electronic devices using the display elements.
１、１１ 波長変換基板
２、１２、１６ 基材
３、１３ａ、１３ｂ、１３ｃ、１０２ 波長変換フィルム
１４ ブラックマトリクス
１５ 接着剤層
１７ａ、１７ｂ、１７ｃ、１０１ 光源
１８ 光源基板
１００ 表示素子
１０３ 保持体
１０４ 拡散板
２００ 照明装置1, 11 Wavelength conversion substrate 2, 12, 16 Base material 3, 13a, 13b, 13c, 102 Wavelength conversion film 14 Black matrix 15 Adhesive layer 17a, 17b, 17c, 101 Light source 18 Light source substrate 100 Display element 103 Holding body 104 Diffuser 200 Lighting device
Claims (7)
該樹脂が、環状ポリオレフィン系樹脂、芳香族ポリエーテル系樹脂、フルオレンポリカーボネート系樹脂、フルオレンポリエステル系樹脂、ポリエーテルサルホン系樹脂、からなる群より選ばれる少なくとも１種であることを特徴とする波長変換フィルム。 Including semiconductor quantum dots and resins,
The resin, cyclic polyolefin resin, aromatic polyether-based resins, full Oren polycarbonate resin, fluorene polyester resins, at least one selected from Po Li polyethersulfone-based resins, or Ranaru group A wavelength conversion film characterized by being.
コアシェル構造型半導体量子ドットであるＩｎＰ／ＺｎＳ、ＣｕＩｎＳ２／ＺｎＳおよび（ＺｎＳ／ＡｇＩｎＳ２）固溶体／ＺｎＳ、並びに、均質構造型半導体量子ドットであるＡｇＩｎＳ２およびＺｎドープＡｇＩｎＳ２よりなる群から選ばれる少なくとも１つであることを特徴とする請求項１に記載の波長変換フィルム。 The semiconductor quantum dot is
At least one selected from the group consisting of InP / ZnS, CuInS2 / ZnS, and (ZnS / AgInS2) solid solution / ZnS that are core-shell structured semiconductor quantum dots, and AgInS2 and Zn-doped AgInS2 that are homogeneous structured semiconductor quantum dots The wavelength conversion film according to claim 1, wherein the wavelength conversion film is provided.
（ｉ’）水素原子 (I ′) hydrogen atom
（ｉｉ’）ハロゲン原子 (Ii ') a halogen atom
（ｉｉｉ’）トリアルキルシリル基 (Iii ') a trialkylsilyl group
（ｉｖ’）酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有する、置換または非置換の炭素数１〜３０の炭化水素基 (Iv ') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom
（ｖ’）置換または非置換の炭素数１〜３０の炭化水素基 (V ′) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms
（ｖｉ’）極性基（但し（ｉｖ’）を除く） (Vi ') polar group (excluding (iv'))
（ｖｉｉ’）Ｒｘ１とＲｘ２またはＲｘ３とＲｘ４とが、相互に結合して形成されたアルキリデン基を表し、該結合に関与しないＲｘ１〜Ｒｘ４は、それぞれ独立に上述の（ｉ’）〜（ｖｉ’）より選ばれる原子または基を表す。 (Vii ′) Rx1 and Rx2 or Rx3 and Rx4 represent an alkylidene group formed by bonding to each other, and Rx1 to Rx4 not involved in the bonding are independently the above (i ′) to (vi ′ ) Represents an atom or group selected from
（ｖｉｉｉ’）Ｒｘ１とＲｘ２またはＲｘ３とＲｘ４とが、相互に結合して形成された単環もしくは多環の炭化水素環または複素環を表し、その結合に関与しないＲｘ１〜Ｒｘ４は、それぞれ独立に上述の（ｉ’）〜（ｖｉ’）より選ばれる原子または基を表すか、Ｒｘ２とＲｘ３とが、相互に結合して形成された単環の炭化水素環または複素環を表し、その結合に関与しないＲｘ１〜Ｒｘ４は、それぞれ独立に上述の（ｉ’）〜（ｖｉ’）より選ばれる原子または基を表す。(Viii ′) Rx1 and Rx2 or Rx3 and Rx4 each represent a monocyclic or polycyclic hydrocarbon ring or heterocycle formed by bonding to each other, and Rx1 to Rx4 not participating in the bonding are each independently Represents an atom or group selected from the above (i ′) to (vi ′), or Rx2 and Rx3 represent a monocyclic hydrocarbon ring or heterocyclic ring formed by bonding to each other, and Rx1 to Rx4 that are not involved each independently represent an atom or group selected from the above (i ′) to (vi ′).
（ｉｘ’）Ｒｙ１とＲｙ２とが、相互に結合して形成された単環または多環の脂環式炭化水素、芳香族炭化水素または複素環を表す。(Ix ') Ry1 and Ry2 each represent a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocyclic ring formed by bonding to each other.
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| KR102651856B1 (en) * | 2018-09-11 | 2024-03-28 | 삼성디스플레이 주식회사 | Color conversion element and display device comprising the same |
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| JPWO2020162622A1 (en) | 2019-02-08 | 2021-12-16 | 国立大学法人東海国立大学機構 | Semiconductor nanoparticles and their manufacturing methods |
| JP2020193249A (en) * | 2019-05-27 | 2020-12-03 | 信越化学工業株式会社 | Quantum dot, quantum dot composition, wavelength conversion material, wavelength conversion film, backlight unit and image display device |
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| JP2006114909A (en) * | 2004-10-14 | 2006-04-27 | Agilent Technol Inc | Flash module |
| JP2008052950A (en) * | 2006-08-23 | 2008-03-06 | Sony Corp | Display device |
| DE102007009530A1 (en) * | 2007-02-27 | 2008-08-28 | Osram Opto Semiconductors Gmbh | Organic light-emitting diode for lighting purposes predominantly emitting white light mixed with colors and composite video signal conversation, comprises substrate layer structure, anode, cathode and intermediate arranged functional layer |
| WO2009011922A1 (en) * | 2007-07-18 | 2009-01-22 | Qd Vision, Inc. | Quantum dot-based light sheets useful for solid-state lighting |
| JP5572968B2 (en) * | 2009-03-06 | 2014-08-20 | 大日本印刷株式会社 | Quantum dot light emitting material and light emitting device |
| JP2012009443A (en) * | 2010-03-03 | 2012-01-12 | Sharp Corp | Wavelength conversion member, light emitting device, image display device and method of manufacturing wavelength conversion member |
| CN103650181A (en) * | 2011-06-29 | 2014-03-19 | 松下电器产业株式会社 | Light-emitting device |
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