TW201910484A - Uv curable acrylate compositions for nanocrystal mixture - Google Patents

Uv curable acrylate compositions for nanocrystal mixture Download PDF

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TW201910484A
TW201910484A TW107123735A TW107123735A TW201910484A TW 201910484 A TW201910484 A TW 201910484A TW 107123735 A TW107123735 A TW 107123735A TW 107123735 A TW107123735 A TW 107123735A TW 201910484 A TW201910484 A TW 201910484A
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methacrylate
nanocrystal composition
composition according
nanocrystal
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荔蓉 曹
提姆 姆 查潘金
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德商漢高智慧財產控股公司
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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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • C08K2003/3036—Sulfides of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds

Abstract

The present invention relates to a nanocrystal composition comprising a plurality of nanocrystals comprising a core comprising a metal or a semiconductive compound or a mixture thereof and at least one ligand, wherein said core is surrounded by at least one ligand, and a polymeric matrix, wherein said polymeric matrix is formed by polymerisation of one or more chemically functionalised methacrylate oligomer and one or more methacrylate monomer, wherein said nanocrystals are embedded into said polymeric matrix.

Description

用於奈米晶體混合物之UV可固化丙烯酸酯組成物  UV curable acrylate composition for nanocrystal mixture  

本發明係有關於一種奈米晶體組成物，其包括一些在聚合基材(polymeric matrix)中之奈米晶體。本發明之各種組成物對該等奈米晶體，提供許多良好之光學性質、良好之熱與光熱安定性，而且是具有良好儲存保存期限之隨時可用之組成物，能在薄膜塗佈機上塗佈。 The present invention is directed to a nanocrystalline composition comprising a plurality of nanocrystals in a polymeric matrix. The various compositions of the present invention provide a number of good optical properties, good thermal and photothermal stability to the nanocrystals, and are ready-to-use compositions with good shelf life and can be applied to film coaters. cloth.

許多半導體奈米晶體(NC)(或量子點(QD))能被用來當作光降轉換器(light down-converters)，即較短波長之光被轉換成較長波長之光。該等奈米晶體(NC)組成物被使用於廣泛範圍之應用，包括顯示器(displays)、照明(lighting)、保安油墨(security inks)、生物標示(bio-labelling)及太陽能集中器(solar concentrators)。在所有案例中，該等NC組成物係被暴露於某種光通量(light flux)與溫度下。由於許多奈米晶體具有狹窄之光發射波峰，所以其能顯著地提高色彩品質(colour quality)，以及擴大LCD顯示器之色域(colour gamut)。 Many semiconductor nanocrystals (NC) (or quantum dots (QD)) can be used as light down-converters, ie shorter wavelengths of light are converted to longer wavelengths of light. These nanocrystal (NC) compositions are used in a wide range of applications, including displays, lighting, security inks, bio-labelling, and solar concentrators. ). In all cases, the NC constituents were exposed to some light flux and temperature. Since many nanocrystals have narrow light emission peaks, they can significantly improve the color quality and expand the color gamut of LCD displays.

在LCD顯示器中，有關NC應用之較佳方法為，係將一NC薄膜用於顯示器之LED背光中。在此結構中，一些綠色與紅色NC被併入一聚合物材料中，並且被塗佈成一薄膜。此NC薄膜被用於一藍色LED背光。該等綠色與紅色NC將一部分藍光轉換成綠色與紅色光，並且該藍色、綠色與紅色之組合，產生該背光所需之白光。調整藍色、綠色與紅色光之比率， 以符合個別顯示器之設計準則(design criteria)係很重要。不同顯示器製造商對該NC背光之色點(colour point)、色域(colour gamut)及亮度(brightness)，會有不同需求。許多因素會影響該NC背光之該等光學性質，如NC薄膜之厚度、綠色與紅色NC發射波峰波長與波峰寬度、綠色與紅色NC裝載量(loading)、散射粒子之存在等。此外，在空氣與濕氣存在下，該NC組成物暴露於光子與溫度，會造成該組成物之該等光學性質之減低。 In LCD displays, a preferred method for NC applications is to use an NC film for the LED backlight of the display. In this configuration, some of the green and red NC are incorporated into a polymeric material and coated into a film. This NC film is used for a blue LED backlight. The green and red NCs convert a portion of the blue light into green and red light, and the combination of blue, green, and red produces the white light required for the backlight. It is important to adjust the ratio of blue, green and red light to meet the design criteria of individual displays. Different display manufacturers have different needs for the color point, color gamut and brightness of the NC backlight. Many factors affect the optical properties of the NC backlight, such as the thickness of the NC film, the green and red NC emission peak wavelength and peak width, the green and red NC loading, the presence of scattering particles, and the like. Furthermore, exposure of the NC composition to photons and temperatures in the presence of air and moisture can result in a reduction in the optical properties of the composition.

許多NC係於溶液中被合成，並且能被進一步嵌入一些聚合物基材中，其充當一載體(carrier)與第一保護層。許多NC溶液與一聚合物溶液或一交聯調配物(formulation)之物理性混合，係一通常使用於所屬技術領域之方法，用以獲得一些NC-聚合物組成物材料。 Many NC systems are synthesized in solution and can be further embedded in some polymeric substrates that act as a carrier and a first protective layer. The physical mixing of a plurality of NC solutions with a polymer solution or a cross-linking formulation is generally used in the art to obtain some NC-polymer composition materials.

對許多用於降轉換(down-conversion)之NC組成物而言，最常見之基材係以丙烯酸酯或環氧樹脂為基礎。對大尺寸薄膜製造而言，藉由UV輻射及/或提高溫度而引發之快速固化速率，使其易於加工。許多嵌入一些丙烯酸酯類或環氧類基材之NC，在一些操作條件下會有降解傾向。因此，需要一額外阻障薄膜，來防止氧氣與濕氣滲透至該黏著劑內部，這會增加最終產品之成本與厚度。 For many NC compositions for down-conversion, the most common substrates are based on acrylate or epoxy. For large-size film manufacturing, the rapid cure rate induced by UV radiation and/or increased temperature makes it easy to process. Many NCs embedded in some acrylate or epoxy substrates have a tendency to degrade under some operating conditions. Therefore, an additional barrier film is needed to prevent oxygen and moisture from penetrating into the interior of the adhesive, which increases the cost and thickness of the final product.

為了克服這些與該等NC之熱及光子劣化有關之問題，有兩種方法已經被使用及報導。在第一種方法中，一含有NC之環氧-胺類樹脂，被置於阻障層間。在第二種方法中，該等NC被嵌入一丙烯酸可聚合調配物中，隨後，該NC組成物被進一步封入一玻璃管中。該製程需要一在無氧氣及/或濕氣環境下之複雜生產線。此外，這些脆弱之產品需要修改產品結構 與生產程序。 In order to overcome these problems associated with the thermal and photon degradation of such NCs, two methods have been used and reported. In the first method, an epoxy-amine-based resin containing NC is placed between barrier layers. In the second method, the NCs are embedded in an acrylic polymerizable formulation, and then the NC composition is further enclosed in a glass tube. The process requires a complex production line in an oxygen-free and/or moisture-free environment. In addition, these fragile products require modifications to the product structure and production processes.

在另外一種方法中，使用一些硫醇(thiols)，當作用於量子點(奈米晶體)組成物之黏著劑基材之一部分。已經得知許多硫醇對其熱安定性係有益，這擴大具良好之NC分散之基材化學之範圍。然而，與所屬技術之聚合物基材之情況結合，由光子所造成之劣化不能被完全防止。 In another method, some thiols are used as part of an adhesive substrate for a quantum dot (nanocrystal) composition. It has been known that many mercaptans are beneficial to their thermal stability, which extends the range of substrate chemistry with good NC dispersion. However, in combination with the case of the polymer substrate of the prior art, the deterioration caused by photons cannot be completely prevented.

此外，在許多黏著劑組成物中，當分散時，該等NC通常不穩定。聚合基材與NC間之交互作用會造成NC之光學性質或分散狀態改變與惡化。結果為，常常需要在正要塗佈之前，將NC與黏著劑混合。因為許多NC基本上對周圍之氧氣與濕氣敏感，所以在正要開始塗佈之前，混合NC/聚合基材，需要複雜且昂貴之混合、儀表測量與惰性化設備，此非許多薄膜塗佈機所需要。 Moreover, in many adhesive compositions, such NCs are generally unstable when dispersed. The interaction between the polymeric substrate and the NC can cause changes or deterioration in the optical properties or dispersion state of the NC. As a result, it is often necessary to mix the NC with the adhesive before it is being coated. Because many NCs are essentially sensitive to the surrounding oxygen and moisture, mixing NC/polymeric substrates prior to the start of coating requires complex and expensive mixing, instrumentation and inertization equipment, many of which are not coated. The machine needs it.

因此，仍然需要一種隨時可用之NC組成物，其在長時間之期間內，係為NC與聚合基材可相容的，並且其提供良好之光學品質、改善該等奈米晶體之熱與光熱安定性，並且能在該薄膜塗佈機上塗佈。 Thus, there remains a need for a ready-to-use NC composition that is compatible with a polymeric substrate for a prolonged period of time and that provides good optical quality and improves the heat and light heat of the nanocrystals. It is stable and can be coated on the film coater.

本發明係有關於一種奈米晶體(nanocrystal)組成物，其包括(a)複數個奈米晶體，其包括一包括金屬或半導電化合物或其混合物之核，及至少一配位子(ligand)，其中，該核被至少一配位子所包圍，以及(b)一聚合基材，其中，該聚合基材係由一或更多個經化學官能基化之甲基丙烯酸酯寡聚體(oligomer)與一或更多個甲基丙烯酸酯單體聚合而成，而且其中，該等奈米晶體被嵌入該聚合基材。 The present invention relates to a nanocrystal composition comprising (a) a plurality of nanocrystals comprising a core comprising a metal or semiconductive compound or a mixture thereof, and at least one ligand. Wherein the core is surrounded by at least one ligand, and (b) a polymeric substrate, wherein the polymeric substrate is comprised of one or more chemically functionalized methacrylate oligomers ( The oligomer is polymerized with one or more methacrylate monomers, and wherein the nanocrystals are embedded in the polymeric substrate.

本發明亦有關於一種經固化之本發明之奈米晶體組成物。 The invention also relates to a cured nanocrystalline composition of the invention.

本發明包含一薄膜，其包括本發明之奈米晶體組成物，其中，該薄膜包括一第一阻障薄膜與一第二阻障薄膜，其中該奈米晶體組成物係在該第一與第二阻障薄膜之間。 The present invention comprises a film comprising the nanocrystal composition of the present invention, wherein the film comprises a first barrier film and a second barrier film, wherein the nanocrystal composition is in the first and the Between the two barrier films.

本發明亦包含一種產品，其包括本發明之奈米晶體組成物，其中該產品係選自於由顯示裝置(display device)、發光裝置(light emitting device)、光伏電池(photovoltaic cell)、光偵測器(photodetector)、能量轉換裝置(energy converter device)、雷射器(laser)、感測器(sensor)、熱電裝置(thermoelectric device)、保安油墨(security ink)、照明裝置(lighting device)及在催化或生物醫學之應用所組成之群組。 The present invention also encompasses a product comprising the nanocrystal composition of the present invention, wherein the product is selected from the group consisting of a display device, a light emitting device, a photovoltaic cell, and a light detector. Photodetector, energy converter device, laser, sensor, thermoelectric device, security ink, lighting device, and A group of applications in catalysis or biomedical applications.

本發明之奈米晶體組成物能被用來當作光致發光(photoluminescence)或電致發光(electroluminescence)源。 The nanocrystal composition of the present invention can be used as a source of photoluminescence or electroluminescence.

本發明之詳細描述 Detailed description of the invention

在下列段落中，更詳細描述本發明。所述之每一方面可與其他任一方面或各種方面組合，除非有與此相反之明確敘述。尤其，任何被敘述為較佳或有益之性質，可與其他任一被敘述為較佳或有益之性質或各種性質組合。 In the following paragraphs, the invention is described in more detail. Each of the aspects described may be combined with any other aspect or aspects unless explicitly stated to the contrary. In particular, any of the properties described as preferred or beneficial may be combined with any other property or property which is described as preferred or beneficial.

在本發明之上下文中，所使用之術語應依據下列之定義來解釋，除非上下文有不同之要求。 In the context of the present invention, the terms used should be interpreted in accordance with the following definitions unless the context requires different requirements.

在此處使用時，單數型「一(a)」、「一(an)」與「該(the)」，包含單數與複數兩者之指示對象，除非上下文有明確不同之要求。 As used herein, the singular "a", "an" and "the" are intended to include the singular and the plural, unless the context clearly requires.

此處所使用之術語「包括(comprising)」、「包括(comprises)」與「包括(comprised of)」係與「包含(including)」、「包含(includes)」或「含 (containing)」、「含(contains)」同義，並且係包含一切或開放式的，而且不排除額外、未引用之構件(members)、元素或方法步驟。 As used herein, the terms "comprising", "comprises" and "comprised of" and "including", "includes" or "containing", Contains are synonymous and contain everything or open, and do not exclude additional, unreferenced members, elements, or method steps.

一些數字端點之引用，包含在該各自範圍內，所有被包含之數字與分數，以及該些被引用之端點。 References to some numerical endpoints are included in the respective ranges, all included numbers and fractions, and the recited endpoints.

當數量、濃度或其他數值或參數，以範圍、較佳範圍或較佳上限值與較佳下限值之形式表示時，應被理解為藉由組合任一上限或較佳數值，與任一下限或較佳數值而得之任何範圍，已被明確揭露，不考慮該所得之範圍是否在上下文中被明確提及。 When a quantity, a concentration or other value or parameter is expressed in the form of a range, a preferred range or a preferred upper limit and a preferred lower limit, it should be understood that by combining any upper or preferred value, Any range of lower limit or preferred values is expressly disclosed, regardless of whether the range of the income is explicitly mentioned in the context.

所有在本說明書中所引用之參考文獻，係透過引用之方式而合併其全部內容。 All references cited in this specification are incorporated by reference in their entirety.

除非以另外之方式定義，否則使用於所揭露發明中之所有術語，包括技術與科學術語，具有本發明所屬技術領域中，通常知識者所通常理解之意義。藉由進一步之指導，包含各種術語之定義，使本發明之教示能有較好之領會。 All terms used in the disclosed invention, including technical and scientific terms, have the meaning as commonly understood by one of ordinary skill in the art to which the invention pertains, unless otherwise defined. The teachings of the present invention are well understood by further guidance, including the definition of various terms.

在此處使用時，術語「(甲基(meth))」之使用，其緊接著另一術語，例如丙烯酸酯(acrylate)，係指丙烯酸酯與甲基丙烯酸酯(methacrylates)兩者。例如：術語「(甲基)丙烯酸酯」，係指丙烯酸酯或甲基丙烯酸酯之任一者。 As used herein, the term "(meth)", which is used next to another term, such as acrylate, refers to both acrylate and methacrylates. For example, the term "(meth)acrylate" means either acrylate or methacrylate.

為了開發一種隨時可用之NC組成物，需要具有良好之NC相容性與可塗佈性之黏著劑組成物。一種成功之黏著劑組成物需要具有適合之流變與固化性質，才能用於高速捲對捲(roll to roll)薄膜塗佈製程。此外，該組成物需要與用於該NC塗佈之基質阻障薄膜(substrate barrier film)呈現 強黏著力。最重要地，組成物需要與所使用之該等NC相容，以提供最終NC薄膜之良好光學性質與良好之可靠性。 In order to develop a ready-to-use NC composition, an adhesive composition having good NC compatibility and coatability is required. A successful adhesive composition needs to have suitable rheology and cure properties for use in a high speed roll to roll film coating process. In addition, the composition needs to exhibit strong adhesion to a substrate barrier film for the NC coating. Most importantly, the composition needs to be compatible with the NCs used to provide good optical properties and good reliability of the final NC film.

本發明係提供一種奈米晶體組成物，其包括複數個奈米晶體，該等奈米晶體包括一包括金屬或半導電化合物或其混合物之核，及至少一配位子(ligand)，其中，該核被至少一配位子所包圍，以及一聚合基材，其中，該聚合基材係由一或更多個經化學官能基化之甲基丙烯酸酯寡聚體(oligomer)與一或更多個甲基丙烯酸酯單體聚合而成，而且其中，該等奈米晶體係被嵌入該聚合基材。 The present invention provides a nanocrystal composition comprising a plurality of nanocrystals, the nanocrystals comprising a core comprising a metal or semiconductive compound or a mixture thereof, and at least one ligand, wherein The core is surrounded by at least one ligand, and a polymeric substrate, wherein the polymeric substrate is comprised of one or more chemically functionalized methacrylate oligomers and one or more A plurality of methacrylate monomers are polymerized, and wherein the nanocrystalline systems are embedded in the polymeric substrate.

根據本發明，該奈米晶體組成物提升該等奈米晶體之光熱(photothermal)與熱安定性，使其能有長儲存時間及能為隨時可用之NC組成物。此外，本發明之奈米晶體組成物提供良好之起始光學性質與良好之可靠性(reliability)。 In accordance with the present invention, the nanocrystal composition enhances the photothermal and thermal stability of the nanocrystals to provide long storage times and ready-to-use NC compositions. Furthermore, the nanocrystal composition of the present invention provides good initial optical properties and good reliability.

所有本發明之性質將被詳細討論。 All properties of the invention will be discussed in detail.

根據本發明，NC組成物包括複數個NC，該等NC包括一包括金屬或半導電化合物或其混合物之核。 According to the invention, the NC composition comprises a plurality of NCs comprising a core comprising a metal or semiconductive compound or a mixture thereof.

根據本發明，該等NC之核具有一結構，該結構單獨包括該核或包括該核與一或更多個包圍該核之殼。每一殼可具有一結構，該結構包括一或更多之層，意指每一殼可具有單層或多層之結構。每一層可具有單一組成物或一摻雜物(alloy)或濃度梯度。 According to the invention, the cores of the NCs have a structure comprising the core alone or comprising the core and one or more shells surrounding the core. Each shell may have a structure comprising one or more layers, meaning that each shell may have a single or multiple layer structure. Each layer can have a single composition or an alloy or concentration gradient.

較佳地，依據本發明，該等NC之核之尺寸係小於100nm，較佳小於50，更佳小於10，然而，較佳地，該核係大於1nm。顆粒尺寸係使用穿透式電子顯微鏡(transmission electron microscopy，TEM)來測量。 Preferably, in accordance with the present invention, the cores of the NCs have a size of less than 100 nm, preferably less than 50, more preferably less than 10. However, preferably, the core is greater than 1 nm. Particle size was measured using a transmission electron microscopy (TEM).

該NC之形狀可選自多種幾何形狀。較佳地，依據本發明，該等NC之核之形狀係球形、矩形、棒狀或三角形。 The shape of the NC can be selected from a variety of geometric shapes. Preferably, in accordance with the present invention, the cores of the NCs are spherical, rectangular, rod-shaped or triangular in shape.

包括金屬或半導電化合物或其混合物之該等NC之核，係由各種元素所組成，該等元素係選自週期表之一或更多個不同族之組合。 The cores of such NCs comprising a metal or semiconducting compound or a mixture thereof are composed of various elements selected from one or a combination of different groups of the periodic table.

較佳地，該金屬或半導電化合物係一或更多個選自第IV族之元素；一或更多個選自第II與第VI族之元素；一或更多個選自第III與第V族之元素；一或更多個選自第IV與第VI族之元素；一或更多個選自第I與第III與第VI族之元素之組合或其組合。 Preferably, the metal or semiconductive compound is one or more elements selected from Group IV; one or more elements selected from Group II and Group VI; one or more selected from Group III and An element of Group V; one or more elements selected from Groups IV and VI; one or more combinations of elements selected from Groups I and III and Group VI, or a combination thereof.

更佳地，該金屬或半導電化合物係選自於由矽(Si)、鍺(Ge)、碳化矽(SiC)、與鍺化矽(SiGe)、硫化鎘(CdS)、硒化鎘(CdSe)、碲化鎘(CdTe)、硫化鋅(ZnS)、硒化鋅(ZnSe)、碲化鋅(ZnTe)、氧化鋅(ZnO)、硫化汞(HgS)、硒化汞(HgSe)、碲化汞(HgTe)、硫化鎂(MgS)、硒化鎂(MgSe)、氮化鎵(GaN)、磷化鎵(GaP)、銻化鎵(GaSb)、氮化鋁(AlN)、磷化鋁(AlP)、砷化鋁(AlAs)、三銻化鋁(AlSb3)、三氮化銦(InN3)、磷化銦(InP)、砷化銦(InAs)、硫化錫(SnS)、硒化錫(SnSe)、碲化錫(SnTe)、硫化鉛(PbS)、硒化鉛(PbSe)、碲化鉛(PbTe)、磷化銦錳(MnInP)、磷化銦銅(CuInP)、二硫化銦銅(CuInS2)、二硒化銦銅(CuInSe2)、二硫化鎵銅(CuGaS2)、二硒化鎵銅(CuGaSe2)、二硫化銦銀(AgInS2)、二硒化銦銀(AgInSe2)、二硫化鎵銀(AgGaS2)與二硒化鎵銀(AgGaSe2)及其混合物所組成之群組。甚至更佳地，該金屬或半導電化合物係選自由硒化鎘(CdSe)、磷化銦(InP)及其混合物所組成之群組。 More preferably, the metal or semiconductive compound is selected from the group consisting of bismuth (Si), germanium (Ge), tantalum carbide (SiC), tantalum telluride (SiGe), cadmium sulfide (CdS), and cadmium selenide (CdSe). ), cadmium telluride (CdTe), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), zinc oxide (ZnO), mercury sulfide (HgS), mercury selenide (HgSe), deuterated Mercury (HgTe), magnesium sulfide (MgS), magnesium selenide (MgSe), gallium nitride (GaN), gallium phosphide (GaP), gallium antimonide (GaSb), aluminum nitride (AlN), aluminum phosphide ( AlP), aluminum arsenide (AlAs), aluminum trioxide (AlSb 3 ), indium trinitride (InN 3 ), indium phosphide (InP), indium arsenide (InAs), tin sulfide (SnS), selenization Tin (SnSe), antimony telluride (SnTe), lead sulfide (PbS), lead selenide (PbSe), lead telluride (PbTe), indium phosphide (MnInP), indium phosphide (CuInP), disulfide Indium copper (CuInS 2 ), indium copper diselenide (CuInSe 2 ), copper gallium disulfide (CuGaS 2 ), copper selenide copper (CuGaSe 2 ), indium silver disulfide (AgInS 2 ), indium silver selenide (AgInSe 2), silver gallium sulfide (AgGaS 2) group and the silver gallium diselenide (AgGaSe 2), and the mixtures thereof. Even more preferably, the metal or semiconductive compound is selected from the group consisting of cadmium selenide (CdSe), indium phosphide (InP), and mixtures thereof.

上述較佳之金屬或半導電化合物提供許多更好之光學性質。 The preferred metal or semiconductive compounds described above provide a number of better optical properties.

較佳地，本發明之NC具有粒徑(particle diameter)(例如：最 大粒徑，包括核與殼)範圍從1nm至100nm，較佳為從1nm至50nm，而且更佳為從1nm至15nm。該顆粒尺寸係使用穿透式電子顯微鏡(TEM)來測量。 Preferably, the NC of the present invention has a particle diameter (e.g., the largest particle diameter, including the core and the shell) ranging from 1 nm to 100 nm, preferably from 1 nm to 50 nm, and more preferably from 1 nm to 15 nm. The particle size was measured using a transmission electron microscope (TEM).

在一實施例中，本發明之該等NC之核具有一結構，該結構包括一核及至少一單層或多層之殼。 In one embodiment, the cores of the NCs of the present invention have a structure comprising a core and at least one single or multiple layers of shells.

然而，在另一實施例中，本發明之該等NC之核具有一結構，該結構包括一核與至少二單層及/或多層之殼。 However, in another embodiment, the cores of the NCs of the present invention have a structure comprising a core and at least two monolayers and/or multiple layers of shells.

該殼亦包括金屬或半導體材料，並且因此，所有上面列出之適合用來當作核之材料，亦適合用來當作殼材料。在一較佳實施例中，該殼包括硫化鋅(ZnS)、硒化鋅(ZnSe)或硫化鎘(CdS)。 The shell also includes metal or semiconducting materials and, therefore, all of the materials listed above as suitable for use as core materials are also suitable for use as shell materials. In a preferred embodiment, the shell comprises zinc sulfide (ZnS), zinc selenide (ZnSe) or cadmium sulfide (CdS).

在本發明之一實施例中，該等NC可被進一步封裝入一些無機氧化物殼中，例如二氧化矽(silica)或氧化鋁(alumina)，來保護該等NC免於空氣與濕氣。 In one embodiment of the invention, the NCs may be further encapsulated into some inorganic oxide shells, such as silica or alumina, to protect the NC from air and moisture.

該等NC之核(包括該(等)殼層，如果存在的話)係被至少一配位子所包圍。較佳地，該等NC之全部表面被許多配位子所覆蓋。由理論可以相信，當該NC之全部表面被許多配位子所覆蓋時，該NC之光學表現會更好。 The cores of the NCs (including the shell, if present) are surrounded by at least one ligand. Preferably, all of the surfaces of the NCs are covered by a number of ligands. It is believed by theory that the optical performance of the NC will be better when the entire surface of the NC is covered by many ligands.

許多合適用於本發明之配位子為烷基膦(alkyl phosphines)、烷基氧化膦(alkyl phosphine oxides)、胺類(amines)、硫醇(thiols)、聚硫醇(polythiols)、羧酸(carboxylic acids)與類似化合物及其混合物。 Many suitable ligands for use in the present invention are alkyl phosphines, alkyl phosphine oxides, amines, thiols, polythiols, carboxylic acids. Carboxylic acids and similar compounds and mixtures thereof.

適合使用於本發明，當作配位子之烷基膦之實例為三正辛基膦(tri-n-octylphosphine)、三羥基丙基膦(trishydroxylpropylphosphine)、三丁基膦(tributylphosphine)、三(十二基)膦(tri(dodecyl)phosphine)、亞磷酸二 丁酯(dibutyl-phosphite)、亞磷酸三丁酯(tributyl phosphite)、亞磷酸三十八酯(trioctadecyl phosphite)、亞磷酸三月桂酯(trilauryl phosphite)、亞磷酸三(十三基)酯(tris(tridecyl)phosphite)、亞磷酸三異癸酯(triisodecyl phosphite)、磷酸雙(2-乙基己基)酯(bis(2-ethylhexyl)phosphate)、磷酸三(十三基)酯(tris(tridecyl)phosphate)及其混合物。 Suitable for use in the present invention, examples of alkylphosphines as ligands are tri-n-octylphosphine, trishydroxylpropylphosphine, tributylphosphine, tris( Tri(dodecyl)phosphine, dibutyl-phosphite, tributyl phosphite, trioctadecyl phosphite, trilauryl phosphite (trilauryl phosphite), tris (tridecyl) phosphite, triisodecyl phosphite, bis(2-ethylhexyl) phosphate (bis(2-ethylhexyl)) Phosphate), tris(tridecyl)phosphate, and mixtures thereof.

合適用於本發明，當作配位子之烷基氧化膦(alkyl phosphine oxides)實例為三正辛基氧化膦(tri-n-octylphosphine oxide)。 An example of an alkyl phosphine oxides suitable as a ligand for use in the present invention is tri-n-octylphosphine oxide.

合適用於本發明，當作配位子之胺類實例為油胺(oleylamine)、十六基胺(hexadecylamine)、十八基胺(octadecylamine)、雙(2-乙基己基)胺(bis(2-ethylhexyl)amine)、二辛基胺(dioctylamine)、三辛基胺(trioctylamine)、辛基胺(octylamine)、十二基胺(dodecylamine)/月桂基胺(laurylamine)、二十二基胺(didodecylamine)、三十二基胺(tridodecylamine)、二十八基胺(dioctadecylamine)、三十八基胺(trioctadecylamine)、聚(丙二醇)雙(2-氨基丙基醚)(poly(propylene glycol)bis(2-amino propyl ether))及其混合物。 Examples of amines suitable for use as ligands in the present invention are oleylamine, hexadecylamine, octadecylamine, bis(2-ethylhexyl)amine (bis) 2-ethylhexyl)amine), dioctylamine, trioctylamine, octylamine, dodecylamine/laurylamine, behenylamine (didodecylamine), tridodecylamine, dioctadecylamine, trioctadecylamine, poly(propylene glycol) bis(2-aminopropyl ether) (poly(propylene glycol) Bis(2-amino propyl ether)) and mixtures thereof.

合適用於本發明，當作配位子之硫醇實例為1-十二烷硫醇(1-dodecanethiol)。 An example of a thiol which is suitable for use as a ligand in the present invention is 1-dodecanethiol.

合適用於本發明，當作配位子之聚硫醇實例為季戊四醇四(3-巰基丁酸酯)(pentaerythritol tetrakis(3-mercaptobutylate))、季戊四醇四(3-巰基丙酸酯)(pentaerythritol tetrakis(3-mercaptopropionate))、三羥甲基丙烷三(3-巰基丙酸酯)(trimethylolpropane tri(3-mercaptopropionate))、三[2-(3-巰基丙醯氧基)乙基]異氰脲酸酯(tris[2-(3-mercaptopropionyloxy) ethyl]isocyanurate)、二季戊四醇六(3-巰基丙酸酯)(dipenta-erythritol hexakis(3-mercaptopropionate))、乙氧基化三羥甲基丙烷三-3-巰基丙酸酯(ethoxilatedtri-methylolpropan tri-3-mercapto-propionate)及其混合物。 An example of a polythiol suitable for use as a ligand in the present invention is pentaerythritol tetrakis (3-mercaptobutylate), pentaerythritol tetrakis(3-mercaptopropionate) (pentaerythritol tetrakis) (3-mercaptopropionate)), trimethylolpropane tri(3-mercaptopropionate), tris[2-(3-mercaptopropoxy)ethyl]isocyanurate Tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate), dipenta-erythritol hexakis (3-mercaptopropionate), ethoxylated trimethylolpropane Ethoxilated tri-methylolpropan tri-3-mercapto-propionate and mixtures thereof.

硫醇亦可以其去質子形態使用於本發明中。 Mercaptans can also be used in the present invention in their deprotonated form.

合適用於本發明，當作配位子之羧酸與膦酸之實例為油酸(oleic acid)、苯基膦酸(phenylphosphonic acid)、己基膦酸(hexylphosphonic acid)、十四基膦酸(tetradecylphosphonic acid)、辛基膦酸(octylphosphonic acid)、十八基膦酸(octadecylphosphonic acid)、丙烯二膦酸(propylenediphosphonic acid)、苯基膦酸(phenylphosphonic acid)、氨基己基膦酸(aminohexylphosphonic acid)及其混合物。 Examples of carboxylic acid and phosphonic acid suitable for use as a ligand in the present invention are oleic acid, phenylphosphonic acid, hexylphosphonic acid, tetradecylphosphonic acid ( Tetradecylphosphonic acid), octylphosphonic acid, octadecylphosphonic acid, propylenediphosphonic acid, phenylphosphonic acid, aminohexylphosphonic acid, and Its mixture.

羧酸與膦酸亦可以其去質子之形態被使用於本發明。 Carboxylic acids and phosphonic acids can also be used in the present invention in the form of their protons.

其他合適用於本發明之配位子之實例為二辛基醚(dioctyl ether)、二苯基醚(diphenyl ether)、肉荳蔻酸甲酯(methyl myristate)、辛酸辛酯(octyl octanoate)、辛酸己酯(hexyl octanoate)、吡啶(pyridine)及其混合物。 Other examples of suitable ligands for use in the present invention are dioctyl ether, diphenyl ether, methyl myristate, octyl octanoate, octanoic acid. Hexyl octanoate, pyridine, and mixtures thereof.

在溶液中，合適且經挑選之配位子能穩定該等NC。 Suitable and selected ligands in the solution stabilize the NC in solution.

合適用於本發明之該等NC，係使用文獻之各種習知製程來製備或商業所購得。合適之該等NC能以將所有反應物混合在一起之數種方式來製備。本發明之NC能由各種核材料單獨或與各種殼材料及各種不同種類之配位子結合來生產。 Such NCs suitable for use in the present invention are prepared or commercially available using various conventional processes of the literature. Suitable such NCs can be prepared in a number of ways in which all of the reactants are mixed together. The NC of the present invention can be produced from a variety of core materials either alone or in combination with various shell materials and various types of ligands.

適合使用於本發明之可商業取得之NC包括，但不限於，來自西格瑪奧德里奇(Sigma Aldrich)之硫硒化鎘(CdSeS)/硫化鋅(ZnS)。 Commercially available NCs suitable for use in the present invention include, but are not limited to, cadmium sulfide selenide (CdSeS) / zinc sulfide (ZnS) from Sigma Aldrich.

本發明之NC組成物包括該NC組成物總重之0.01至10重量% 之該等NC，較佳為0.05至7.5%，更佳為0.1至5%。 The NC composition of the present invention comprises from 0.01 to 10% by weight, based on the total weight of the NC composition, of such NC, preferably from 0.05 to 7.5%, more preferably from 0.1 to 5%.

依據本發明，許多NC組成物亦能以較高之NC數量製備，然而，如果該數量係>10%，該等NC之光學性質將會因其之間之交互作用，而受到負面之影響。另一方面，如果該數量係<0.01%，所形成之薄膜將展現非常低之亮度(brightness)。 Many NC compositions can also be prepared in higher NC quantities in accordance with the present invention, however, if the amount is >10%, the optical properties of the NCs will be negatively affected by the interaction between them. On the other hand, if the amount is <0.01%, the formed film will exhibit very low brightness.

依據本發明，許多NC係被嵌入該聚合基材中。 In accordance with the present invention, a number of NC systems are embedded in the polymeric substrate.

本發明之聚合基材係由一或更多個經化學官能基化之甲基丙烯酸酯寡聚體與一或更多個甲基丙烯酸酯單體聚合而成。 The polymeric substrate of the present invention is formed by polymerizing one or more chemically functionalized methacrylate oligomers with one or more methacrylate monomers.

依據本發明，在某些實施例中，該聚合基材係由一或更多個經化學官能基化之甲基丙烯酸酯寡聚體、一或更多個甲基丙烯酸酯單體與一或更多個具有一丙烯酸酯基團之丙烯酸酯單體聚合而成。 According to the invention, in certain embodiments, the polymeric substrate is comprised of one or more chemically functionalized methacrylate oligomers, one or more methacrylate monomers, and More acrylate monomers having an acrylate group are polymerized.

依據本發明，在某些實施例中，該聚合基材係由一或更多個經化學官能基化之甲基丙烯酸酯寡聚體、一或更多個甲基丙烯酸酯單體與一或更多個具有二或更多個丙烯酸酯基團之丙烯酸酯單體聚合而成，其中，以該聚合基材之總重為基準，該具有二或更多個丙烯酸酯基團之丙烯酸酯單體之數量係小於15重量%。 According to the invention, in certain embodiments, the polymeric substrate is comprised of one or more chemically functionalized methacrylate oligomers, one or more methacrylate monomers, and More polymerized acrylate monomers having two or more acrylate groups, wherein the acrylate monomer having two or more acrylate groups is based on the total weight of the polymeric substrate The number of bodies is less than 15% by weight.

依據本發明，在某些實施例中，該聚合基材係由一或更多個經化學官能基化之甲基丙烯酸酯寡聚體、一或更多個甲基丙烯酸酯單體、一或更多個具有一丙烯酸酯基團之丙烯酸酯單體與一或更多個具有二或更多個丙烯酸酯基團之丙烯酸酯單體聚合而成，其中，以該聚合基材之總重為基準，該具有二或更多個丙烯酸酯基團之丙烯酸酯單體之數量係小於15重量%。 According to the invention, in certain embodiments, the polymeric substrate is comprised of one or more chemically functionalized methacrylate oligomers, one or more methacrylate monomers, or More acrylate monomers having an acrylate group are polymerized with one or more acrylate monomers having two or more acrylate groups, wherein the total weight of the polymeric substrate is The amount of the acrylate monomer having two or more acrylate groups is less than 15% by weight.

依據本發明，該經化學官能基化之甲基丙烯酸酯寡聚體會改善該組成物之機械性質。 According to the present invention, the chemically functionalized methacrylate oligomer improves the mechanical properties of the composition.

此處憑藉術語「經化學官能基化(chemically functionalised)」，意指連接至甲基丙烯酸酯寡聚體之各種官能基，如環氧與氨基甲酸乙酯基團。 By the term "chemically functionalised" herein is meant the various functional groups attached to the methacrylate oligomer, such as epoxy and urethane groups.

合適之經化學官能基化之甲基丙烯酸酯寡聚體係選自於由乙氧基化(2-200)雙酚甲基丙烯酸酯(ethoxylated(2-200)bisphenol methacrylate)、雙酚A環氧基甲基丙烯酸酯寡聚體(bisphenol A epoxy methacrylate oligomer)、脂肪族聚酯類氨基甲酸乙酯(urethane)二甲基丙烯酸酯(dimethacrylate)寡聚體、芳香族聚酯類氨基甲酸乙酯二甲基丙烯酸酯寡聚體、脂肪族聚醚(polyether)氨基甲酸乙酯甲基丙烯酸酯寡聚體、芳香族聚醚氨基甲酸乙酯甲基丙烯酸酯寡聚體及其混合物所組成之群組。 A suitable chemically functionalized methacrylate oligomerization system is selected from the group consisting of ethoxylated (2-200) bisphenol methacrylate, bisphenol A epoxy Bisphenol A epoxy methacrylate oligomer, aliphatic polyester urethane dimethacrylate oligomer, aromatic polyester urethane II a group consisting of a methacrylate oligomer, an aliphatic polyether urethane methacrylate oligomer, an aromatic polyether urethane methacrylate oligomer, and a mixture thereof .

較佳地，經化學官能基化之甲基丙烯酸酯寡聚體係選自於由雙酚A環氧基甲基丙烯酸酯寡聚體、脂肪族聚酯類氨基甲酸乙酯二甲基丙烯酸酯寡聚體、乙氧基化(2-200)雙酚甲基丙烯酸酯及其混合物所組成之群組。 Preferably, the chemically functionalized methacrylate oligomerization system is selected from the group consisting of bisphenol A epoxy methacrylate oligomers, aliphatic polyester urethane dimethacrylate oligomers A group of polymers, ethoxylated (2-200) bisphenol methacrylates, and mixtures thereof.

使用上述所列之各種經化學官能基化之甲基丙烯酸酯寡聚體，係因其對本發明之組成物，提供良好之黏著力及可靠性表現。 The use of the various chemically functionalized methacrylate oligomers listed above provides good adhesion and reliability to the compositions of the present invention.

適合使用於本發明之商業可取得之經化學官能基化之甲基丙烯酸酯寡聚體包括，但不限於來自阿科瑪(Arkema)之CN154、CN159 NS，來自阿科瑪之CN1963，來自阿科瑪之SR480，來自銳昂美國(Rahn USA)之環氧甲基丙烯酸酯97-053(epoxy methacrylate 97-053)及來自化藥化工 (Kayaku Chemical)之KEMA-100與KEMA-104。 Commercially available chemically functionalized methacrylate oligomers suitable for use in the present invention include, but are not limited to, CN154, CN159 NS from Arkema, CN1963 from Arkema, from Azerbaijan Kema's SR480, from Ethan USA's epoxy methacrylate 97-053 (epoxy methacrylate 97-053) and from Kayaku Chemical's KEMA-100 and KEMA-104.

本發明之該聚合基材，包括經化學官能基化之甲基丙烯酸酯寡聚體之聚合基材總重之從25至80重量%，較佳為30至75%，並且更佳為35至75%。 The polymeric substrate of the present invention comprises a chemically functionalized methacrylate oligomer having a polymeric substrate having a total weight of from 25 to 80% by weight, preferably from 30 to 75%, and more preferably from 35 to 75%.

本發明之聚合基材係由一或更多個甲基丙烯酸酯單體聚合而成。該甲基丙烯酸酯單體當作稀釋劑(diluent)，並且因此控制該組成物之黏度。 The polymeric substrate of the present invention is formed by polymerizing one or more methacrylate monomers. The methacrylate monomer acts as a diluent and thus controls the viscosity of the composition.

適合用於本發明之甲基丙烯酸酯單體係選自於由 其中，o係0~18，較佳o係2~18； 其中，n係2~18，較佳n係6~17； 其中，X係CH2，或伸苯基(phenylene，C6H4)； 其中，R1係選自於由以下所組成之群組：-CH3,-CH2CH3,-C(CH3)3,-OH；三羥甲基丙烷三甲基丙烯酸酯(trimethylolpropane trimethacrylate，TMPTMA)；甲基丙烯酸異莰酯(isobornyl methacrylate，IBOMA)；甲基丙烯酸四氫糠酯(tetrahydrofurfuryl methacrylate，THFMA)；甲基丙烯酸羥丙酯(hydroxypropyl methacrylate，HPMA)；三甘醇二甲基丙烯酸酯(triethylene glycol dimethacrylate，TEGDMA)；二甘醇二甲基丙烯酸酯(diethylene glycol dimethacrylate，DEGDMA)；酸性官能之甲基丙烯酸酯(acid functional methacrylate)；酸性官能之金剛烷基甲基丙烯酸酯(acid functional adamantyl methacrylate)；甲基丙烯酸三級丁酯(tert-butyl methacrylate，TBMA)；甲基丙烯酸環己酯(cyclohexyl methacrylate，CHMA)；甘油二甲基丙烯酸酯(glycerol dimethacrylate)；雙酚A二甲基丙烯酸酯(bisphenol A dimethacrylate)；雙酚F二甲基丙烯酸酯(bisphenol F dimethacrylate)；甲基丙烯酸2-苯氧乙酯(2-phenoxyethyl methacrylate)及其混合物。 A monomethacrylate monoester suitable for use in the present invention is selected from Wherein, o is 0~18, preferably o is 2~18; Wherein n is 2 to 18, preferably n is 6 to 17; Wherein, X is CH 2 or phenylene (C 6 H 4 ); Wherein R 1 is selected from the group consisting of: -CH 3 , -CH 2 CH 3 , -C(CH 3 ) 3 , -OH; trimethylolpropane trimethacrylate (trimethylolpropane trimethacrylate) , TMPTMA); isobornyl methacrylate (IBOMA); tetrahydrofurfuryl methacrylate (THFMA); hydroxypropyl methacrylate (HPMA); triethylene glycol dimethyl Triethylene glycol dimethacrylate (TEGDMA); diethylene glycol dimethacrylate (DEGDMA); acid functional methacrylate; acid functional adamantyl methacrylate Acid functional adamantyl methacrylate); tert-butyl methacrylate (TBMA); cyclohexyl methacrylate (CHMA); glycerol dimethacrylate; bisphenol A Bisphenol A dimethacrylate; bisphenol F dimethacrylate; 2-phenoxyethyl methacrylate (2-phenoxyethyl methacrylate), and mixtures thereof.

較佳地，一或更多個甲基丙烯酸酯單體，其係選自於由甲基丙烯酸異莰酯(isobornyl methacrylate，IBOMA)、甲基丙烯酸月桂酯 (laurylmethacrylate)、三羥甲基丙烷三甲基丙烯酸酯(TMPTMA)、三環癸烷二甲醇二甲基丙烯酸酯及其混合物所組成之群組。 Preferably, one or more methacrylate monomers are selected from the group consisting of isobornyl methacrylate (IBOMA), laurylmethacrylate methacrylate, trimethylolpropane tris A group consisting of methacrylate (TMPTMA), tricyclodecane dimethanol dimethacrylate, and mixtures thereof.

合適使用於本發明之商業可取得之甲基丙烯酸酯單體包括，但不限於來自阿科瑪(Arkema)之SR423A，來自阿科瑪之SR248，來自阿科瑪之SR313A及來自阿科瑪之SR262，來自山依斯特股份有限公司(San Esters Corporation)之LMA、TDMA、CHMA與IBXMA，來自日本化藥之NK Ester NPG、NK Ester IB、NK Ester DCP等。 Commercially available methacrylate monomers suitable for use in the present invention include, but are not limited to, SR423A from Arkema, SR248 from Arkema, SR313A from Arkema, and from Arkema. SR262, LMA, TDMA, CHMA and IBXMA from San Esters Corporation, NK Ester NPG, NK Ester IB, NK Ester DCP from Nippon Kayaku.

本發明之該聚合基材，包括甲基丙烯酸酯單體之該聚合基材總重之從20至75重量%，較佳為25至70%，更佳為25至65%。 The polymeric substrate of the present invention, comprising the methacrylate monomer, has a total weight of the polymeric substrate of from 20 to 75% by weight, preferably from 25 to 70%, more preferably from 25 to 65%.

本發明之奈米晶體組成物可進一步包括具有一丙烯酸酯基團之丙烯酸酯單體及/或具有二或更多個丙烯酸酯基團之丙烯酸酯單體。 The nanocrystal composition of the present invention may further comprise an acrylate monomer having an acrylate group and/or an acrylate monomer having two or more acrylate groups.

合適使用於本發明之具有一或更多個丙烯酸酯基團之丙烯酸酯單體係選自於由 其中，o係2~10，較佳o係4~6； 其中，p係0~10，q係0~10，R2與R3係相同或不同，並且係獨立選自H、-CH3； 其中，r係0~10，s係0~10，t係0~10； 丙烯酸異莰酯(isobornyl acrylate)，丙烯酸月桂酯(lauryl acrylate)，丙烯酸十三酯(tridecyl acrylate)，丙烯酸十八酯(stearyl acrylate)及其混合物所組成之群組。 An acrylate monosystem having one or more acrylate groups suitable for use in the present invention is selected from Wherein, o is 2 to 10, preferably o is 4 to 6; Wherein, based P 0 ~ 10, q lines 0 ~ 10, R 2 and R 3 are the same or different system, and the system is independently selected from H, -CH 3; Where r is 0~10, s is 0~10, t is 0~10; A group consisting of isobornyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, and mixtures thereof.

較佳地，該丙烯酸酯單體係選自於由具有三個乙氧基基團(ethoxy groups)之乙氧基化雙酚A二丙烯酸酯(ethoxylated bisphenol A diacrylate)，具有二個乙氧基基團之乙氧基化雙酚A二丙烯酸酯，1,6-己二醇 二丙烯酸酯(1,6-hexanediol diacrylate)，三羥甲基丙烷三甲基丙烯酸酯(trimethylolpropane trimethacrylate)，具有三個乙氧基基團之乙氧基化三羥甲基丙烷三丙烯酸酯(ethoxylated trimethylolpropane triacrylate)，雙酚A類寡聚體，丙烯酸異莰酯(isobornyl acrylate)，丙烯酸月桂酯(lauryl acrylate)，丙烯酸十三酯(tridecyl acrylate)及其混合物所組成之群組。 Preferably, the acrylate monosystem is selected from the group consisting of ethoxylated bisphenol A diacrylate having three ethoxy groups, having two ethoxy groups. a group of ethoxylated bisphenol A diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane trimethacrylate, having three Ethoxylated ethoxylated trimethylolpropane triacrylate, bisphenol A oligomer, isobornyl acrylate, lauryl acrylate, A group consisting of tridecyl acrylate and mixtures thereof.

上面所述較佳具有二或更多個丙烯酸酯基團之丙烯酸酯單體為較佳，因其提供理想固化速率、透明性(transparency)及良好之光學性質。此外，其對QDs提供安定性，尤其是該具有二個乙氧基基團之乙氧基化雙酚A二丙烯酸酯。另一方面，1,6-己二醇二丙烯酸酯具有低黏度，而且能被用來當作反應稀釋劑。 The acrylate monomers preferably having two or more acrylate groups as described above are preferred because they provide desirable cure rates, transparency, and good optical properties. In addition, it provides stability to the QDs, especially the ethoxylated bisphenol A diacrylate having two ethoxy groups. On the other hand, 1,6-hexanediol diacrylate has a low viscosity and can be used as a reactive diluent.

適合用於本發明之商業上可取得，具有二或更多個丙烯酸酯基團之丙烯酸酯單體，為來自沙多瑪(Sartomer)之SR 349、SR 348與SR 238及來自湛新(Allnex)之HDDA。 Commercially available acrylate monomers having two or more acrylate groups suitable for use in the present invention are SR 349, SR 348 and SR 238 from Sartomer and from Allnex ) HDDA.

根據本發明之奈米晶體組成物包括具有二或更多個丙烯酸酯基團之丙烯酸酯單體時，以該聚合基材之總重為基準，其數量係小於15重量%(但大於0.1%)，較佳為小於10%。 When the nanocrystal composition according to the present invention comprises an acrylate monomer having two or more acrylate groups, the amount is less than 15% by weight (but more than 0.1%) based on the total weight of the polymeric substrate. ), preferably less than 10%.

根據本發明之奈米晶體組成物包括具有一個丙烯酸酯基團之丙烯酸酯單體時，以該聚合基材之總重為基準，其數量能從0.1至25重量%。 When the nanocrystal composition according to the present invention comprises an acrylate monomer having one acrylate group, the amount thereof can be from 0.1 to 25% by weight based on the total weight of the polymer substrate.

根據本發明之奈米晶體組成物包括該組成物總重之90至99.99重量%之一聚合物基材，較佳為92.5至99.95%，更佳為95至99.9%。如果該聚合基材之數量係低於90%，且該NC之數量係大於10%，該等奈米晶 體之光學性質將因其之間之交互作用而受到負面之影響。 The nanocrystal composition according to the present invention comprises a polymer substrate of 90 to 99.99% by weight based on the total weight of the composition, preferably 92.5 to 99.95%, more preferably 95 to 99.9%. If the amount of the polymeric substrate is less than 90% and the number of the NC is greater than 10%, the optical properties of the nanocrystals will be adversely affected by the interaction therebetween.

根據本發明之奈米晶體組成物可進一步包括光起始劑。適合用於本發明之光起始劑係選自於由1,5,7-三氮雜雙環[4.4.0]癸-5-烯氫四苯基硼酸鹽(1,5,7-triazabicyclo[4.4.0]dec-5-enehydrogen tetraphenyl borate，TBD．HBPh4)，2-甲基-4-(甲硫基)-2-嗎啉基乙基苯基酮(2-methyl-4-(methylthio)-2-morpholinopropiophenone)，2-(9-氧代苯芴酮-2-基)丙酸-1,5,7-三氮雜雙環[4.4.0]癸-5-烯(2-(9-oxoxanthen-2-yl)propionic acid-1,5,7 triazabicyclo[4.4.0]dec-5-ene)，2-羥基-2-甲基-1-苯基丙酮(2-hydroxy-2-methyl-1-phenylpropanone)，1-羥基環己基-苯基酮(1-hydroxycyclohexyl-phenyl ketone)，2,4,6-三甲基苯甲醯基-二苯基氧化膦(2,4,6-trimethylbenzoyl-diphenyl phosphine oxide，TPO)，(2,4,6-三甲基苯甲醯基)-苯基膦酸乙酯(ethyl(2,4,6-trimethylbenzoyl)-phenyl phosphinate，TPO-L)，雙(2,4,6-三甲基苯甲醯基)苯基氧化膦(bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide)及其混合物所組成之群組。 The nanocrystal composition according to the present invention may further comprise a photoinitiator. A photoinitiator suitable for use in the present invention is selected from the group consisting of 1,5,7-triazabicyclo[4.4.0]non-5-enehydrotetraphenylborate (1,5,7-triazabicyclo[ 4.4.0] dec-5-enehydrogen tetraphenyl borate, TBD.HBPh 4 ), 2-methyl-4-(methylthio)-2-morpholinylethyl phenyl ketone (2-methyl-4-(methylthio) )-2-morpholinopropiophenone), 2-(9-oxobenzophenone-2-yl)propionic acid-1,5,7-triazabicyclo[4.4.0]non-5-ene (2-(9) -oxoxanthen-2-yl)propionic acid-1,5,7 triazabicyclo[4.4.0]dec-5-ene), 2-hydroxy-2-methyl-1-phenylacetone (2-hydroxy-2-methyl) 1-phenylpropanone), 1-hydroxycyclohexyl-phenyl ketone, 2,4,6-trimethylbenzylidene-diphenylphosphine oxide (2,4,6- Trimethylbenzoyl-diphenyl phosphine oxide (TPO), (2,4,6-trimethylbenzoyl)-phenyl phosphinate (TPO-L) a group consisting of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and mixtures thereof.

較佳地，光起始劑係選自於由2,4,6-三甲基苯甲醯基-二苯基氧化膦(2,4,6-trimethylbenzoyl-diphenyl phosphine oxide)、2-羥基-2-甲基乙基苯基酮(2-hydroxy-2-methylpropiophenone)、1-羥基環己基-1-苯基甲酮(1-hydroxycyclohexyl-1-phenyl methanone)及其混合物所組成之群組。 Preferably, the photoinitiator is selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, 2-hydroxy- A group consisting of 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl-1-phenyl methanone, and mixtures thereof.

合適使用於本發明之可商業取得之光起始劑包括，但不限於來自IGM之Omnirad TPO(2,4,6-三甲基苯甲醯基-二苯基氧化膦(2,4,6-trimethylbenzoyl-diphenyl phosphine oxide))、來自IGM之Omnirad 1173 (2-羥基-2-甲基乙基苯基酮(2-hydroxy-2-methylpropiophenone)及來自IGM之Omnirad 184(1-羥基環己基-1-苯基甲酮(1-hydroxycyclohexyl-1-phenyl methanone)。 Commercially available photoinitiators suitable for use in the present invention include, but are not limited to, Omnirad TPO (2,4,6-trimethylbenzimidyl-diphenylphosphine oxide (2,4,6) from IGM. -trimethylbenzoyl-diphenyl phosphine oxide)), Omnirad 1173 from IGM (2-hydroxy-2-methylpropiophenone) and Omnirad 184 from IGM (1-hydroxycyclohexyl- 1-hydroxycyclohexyl-1-phenyl methanone.

根據本發明之奈米晶體組成物包括一光起始劑，當存在時，從該組成物總重之0.01至6重量%，較佳為0.01至3%，更佳為0.01至2%。 The nanocrystal composition according to the present invention comprises a photoinitiator, when present, from 0.01 to 6% by weight, preferably from 0.01 to 3%, more preferably from 0.01 to 2%, based on the total weight of the composition.

根據本發明，在一實施例中，該奈米晶體組成物包括至少二光起始劑，其中，第一光起始劑係用短波長UV光照射，及第二光起始劑係用長波長UV光照射。在此實施例中，2-羥基-2-甲基-1-苯基丙酮(2-hydroxy-2-methyl-1-phenylpropanone)單體或寡聚體，1-羥基環己基-苯基酮(1-hydroxycyclohexyl-phenyl ketone)，2-羥基-1-(4-(4-(2-羥基-2-甲基丙醯基)芐基)苯基)-2-甲基丙-1-酮(2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one)，1-[4-(2-羥基乙氧基)-苯基]-2-羥基-甲基丙酮(1-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone)，2,2-二甲氧基-2-苯基苯乙酮(2,2-dimethoxy-2-phenylacetophenone)及其混合物，及第二光起始劑係選自於由2,4,6-三甲基苯甲醯基-二苯基氧化膦(2,4,6-trimethylbenzoyl-diphenyl phosphine oxide)，(2,4,6-三甲基苯甲醯基)-苯基膦酸乙酯(ethyl(2,4,6-trimethylbenzoyl)-phenyl phosphinate)，雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦(bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide)及其混合物所組成之群組。 According to the present invention, in one embodiment, the nanocrystal composition comprises at least two photoinitiators, wherein the first photoinitiator is irradiated with short-wavelength UV light, and the second photoinitiator is long. Wavelength UV light illumination. In this embodiment, 2-hydroxy-2-methyl-1-phenylpropanone monomer or oligomer, 1-hydroxycyclohexyl-phenyl ketone ( 1-hydroxycyclohexyl-phenyl ketone), 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropenyl)benzyl)phenyl)-2-methylpropan-1-one ( 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one), 1-[4-(2-hydroxyethoxy)-benzene 2-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone), 2,2-dimethoxy-2-phenylacetophenone (2 , 2-dimethoxy-2-phenylacetophenone) and mixtures thereof, and a second photoinitiator selected from the group consisting of 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide (2,4,6 -trimethylbenzoyl-diphenyl phosphine oxide), (2,4,6-trimethylbenzoyl)-phenyl phosphinate, double (2, a group consisting of 4,6-trimethylbenzoylphosphine oxide (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) and mixtures thereof.

許多具有二或更多個光起始劑之組成物，在兩步驟塗佈(two-step coating)與積層製程(lamination process)中很有用。已經在實例5 中，舉例說明這些組成物與兩步驟塗佈及積層製程。 Many compositions having two or more photoinitiators are useful in two-step coating and lamination processes. These compositions and two-step coating and lamination processes have been illustrated in Example 5.

根據本發明之奈米晶體組成物可進一步包括一些散射粒子。該等散射粒子係被物理性混入該組成物，以散射光線。該等散射粒子不與該聚合基材之樹脂反應。在NC薄膜中，散射粒子會增加有效光路徑，這會提供NC被藍光活化之機會。此有助於減少達到某一白點(white point)所需之NC裝載量(NC loading)。 The nanocrystal composition according to the present invention may further comprise some scattering particles. The scattering particles are physically mixed into the composition to scatter light. The scattering particles do not react with the resin of the polymeric substrate. In NC films, scattering particles increase the effective light path, which provides the opportunity for NC to be activated by blue light. This helps to reduce the NC loading required to reach a certain white point.

合適之散射粒子係選自於由二氧化鈦(TiO2)、硫化鋅(ZnS)、二氧化鋯(ZrO2)、氧化鋁(Al2O3)、氧化鎂(MgO)、氧化鈣(CaO)、五氧化二鉭(Ta2O5)、二氧化矽(silica)、矽氧樹脂(silicone)及其混合物所組成之群組。 Suitable scattering particles are selected from the group consisting of titanium dioxide (TiO 2 ), zinc sulfide (ZnS), zirconium dioxide (ZrO 2 ), aluminum oxide (Al 2 O 3 ), magnesium oxide (MgO), calcium oxide (CaO), A group consisting of tantalum pentoxide (Ta 2 O 5 ), silica, silicone, and mixtures thereof.

合適使用於本發明之可商業取得之散射粒子包括，但不限於來自莎哈利本(Sachtleben)之Sachtolith HDS硫化鋅(ZnS)粉末。 Commercially available scattering particles suitable for use in the present invention include, but are not limited to, Sachtolith HDS zinc sulfide (ZnS) powder from Sachtleben.

根據本發明之奈米晶體組成物包括該組成物總重之0.01至3重量%之散射粒子，較佳為0.05至2.5%，更佳為0.01至2%。 The nanocrystal composition according to the present invention comprises from 0.01 to 3% by weight of the scattering particles of the total weight of the composition, preferably from 0.05 to 2.5%, more preferably from 0.01 to 2%.

根據本發明之奈米晶體組成物可進一步包括流變改質劑(rheology modifier)。合適之流變改質劑不會與該聚合基材之樹脂反應，但是會改變流變性。 The nanocrystal composition according to the present invention may further comprise a rheology modifier. A suitable rheology modifier will not react with the resin of the polymeric substrate, but will alter the rheology.

合適之流變改質劑係選自於由經改質之尿素(urea)、聚氨基甲酸乙酯(polyurethane)、聚胺(polyamine)、聚丙烯酸酯(polyacrylates)及其混合物所組成之群組。 Suitable rheology modifiers are selected from the group consisting of modified urea (urea), polyurethane, polyamine, polyacrylates, and mixtures thereof. .

合適使用於本發明之商業可取得之流變改質劑包括，但不限於來自阿爾塔納(Altana)之BYK-410與BYK-7410ET。 Commercially available rheology modifiers suitable for use in the present invention include, but are not limited to, BYK-410 and BYK-7410ET from Altana.

根據本發明之奈米晶體組成物包括流變改質劑，當存在時， 從該組成物總重之0.01至2重量%，較佳為0.1至1.5%，更佳為0.2至1%。 The nanocrystal composition according to the present invention comprises a rheology modifier, when present, from 0.01 to 2% by weight, preferably from 0.1 to 1.5%, more preferably from 0.2 to 1%, based on the total weight of the composition.

根據本發明之奈米晶體組成物可進一步包括分散劑(dispersant)。合適之分散劑不會與該聚合基材之樹脂反應，但是會改變該等散射粒子之沉澱行為(settling behavior)。 The nanocrystal composition according to the present invention may further comprise a dispersant. A suitable dispersant will not react with the resin of the polymeric substrate, but will alter the settling behavior of the scattering particles.

合適之分散劑係選自於由酸酯類(acid esters)與聚氨基甲酸乙酯及其混合物所組成之群組。 Suitable dispersing agents are selected from the group consisting of acid esters and polyurethanes and mixtures thereof.

合適使用於本發明之商業可取得之分散劑包括，但不限於來自阿爾塔納(Altana)之BYK-110與BYK-180。 Commercially available dispersing agents suitable for use in the present invention include, but are not limited to, BYK-110 and BYK-180 from Altana.

根據本發明之奈米晶體組成物包括一分散劑，當存在時，從該組成物總重之0.01至2重量%，較佳為0.1至1.5%，更佳為0.2至1%。 The nanocrystal composition according to the present invention comprises a dispersing agent, when present, from 0.01 to 2% by weight, preferably from 0.1 to 1.5%, more preferably from 0.2 to 1%, based on the total mass of the composition.

根據本發明之奈米晶體組成物，其較佳具有從100cps至5500cps之黏度，其中，黏度係在25℃，以博勒飛(Brookfield)DVII+Pro黏度計(Viscometer)，使用錐與板轉軸(cone and plate spindles)CP51與CP52，或低黏度杯轉軸SP18與SP21，於恆定剪切速率測量。 The nanocrystal composition according to the present invention preferably has a viscosity of from 100 cps to 5500 cps, wherein the viscosity is at 25 ° C, using a Brookfield DVII+Pro viscometer (Viscometer), using a cone and a plate shaft (cone and plate spindles) CP51 and CP52, or low viscosity cup spindles SP18 and SP21, measured at constant shear rate.

根據本發明之該等NC組成物能以一起混合所有成分之數種方式被製備。 The NC compositions according to the present invention can be prepared in a number of ways in which all ingredients are mixed together.

在一較佳實施例中，除NC與散射粒子外，如果有的話，所有原物料係被一起混合，並且混合物係被混合直到該光起始劑溶於該樹脂中為止。接著，該等NC與散射粒子，如果有的話，被混合至該組成物中。在某些實施例中，該所有原物料之混合係在氮氣下完成。 In a preferred embodiment, all of the raw materials, if any, are mixed together, with the exception of NC and scattering particles, and the mixture is mixed until the photoinitiator is dissolved in the resin. The NC and scattering particles, if any, are then mixed into the composition. In certain embodiments, the mixing of all of the raw materials is accomplished under nitrogen.

本發明亦有關於一種經固化之奈米晶體組成物。在室溫下固化後，本發明之NC組成物為固體。根據本發明之該NC組成物係UC可固化， 而且能使用一些普通之UV燈來固化。 The invention also relates to a cured nanocrystalline composition. After curing at room temperature, the NC composition of the present invention is a solid. The NC composition UC according to the present invention is curable and can be cured using some conventional UV lamps.

在某些實施例中，根據本發明之NC組成物之UV固化強度係從0.1至3J/cm2，較佳為0.5至1J/cm2。 In certain embodiments, the NC composition according to the present invention has a UV cure strength of from 0.1 to 3 J/cm 2 , preferably from 0.5 to 1 J/cm 2 .

依據本發明，該奈米晶體組成物之UV固化時間，係從0.5秒至500秒，較佳為1秒至120秒，更佳為1秒至60秒。 According to the present invention, the UV curing time of the nanocrystal composition is from 0.5 second to 500 seconds, preferably from 1 second to 120 seconds, more preferably from 1 second to 60 seconds.

本發明亦有關於一種薄膜，其包括根據本發明之奈米晶體組成物，其中該薄膜包括一第一阻障薄膜與一第二阻障薄膜，其中該奈米晶體組成物在該第一與第二阻障薄膜之間。 The present invention also relates to a film comprising the nanocrystal composition according to the present invention, wherein the film comprises a first barrier film and a second barrier film, wherein the nanocrystal composition is in the first Between the second barrier films.

第一與第二阻障薄膜能以任何有用之薄膜材料形成，該等材料能保護該等NC，免於許多環境條件，如氧氣與濕氣。許多合適之阻障薄膜，舉例來說，包括一些聚合物、玻璃或介電材料。合適用於本發明之阻障層材料包括，但不限於聚合物，例如聚對苯二甲酸乙二酯(polyethylene terephthalate，PET)；氧化物，例如矽氧化物(SiO2,Si2O3)，鈦氧化物(TiO2)或鋁氧化物(Al2O3)；及其混合物。 The first and second barrier films can be formed from any useful film material that protects the NC from many environmental conditions such as oxygen and moisture. Many suitable barrier films include, by way of example, some polymers, glasses or dielectric materials. Barrier layer materials suitable for use in the present invention include, but are not limited to, polymers such as polyethylene terephthalate (PET); oxides such as cerium oxide (SiO 2 , Si 2 O 3 ) , titanium oxide (TiO 2 ) or aluminum oxide (Al 2 O 3 ); and mixtures thereof.

在各種不同之實施例中，該NC薄膜之每一阻障層包括至少二層不同材料或組成物，使該多層障礙物清除或減少針孔缺陷(pinhole defect)排列於該阻障層中，對氧氣與濕氣之穿透到該NC材料中，提供有效之障礙。該NC薄膜能包括任何合適之材料或材料之組合，以及在該NC組成物材料之任一側或兩側上，任何合適之數目之阻障層。該等阻障層之材料、厚度與數目會依特別之應用而定，而且會選擇讓NC之障礙保護與亮度最大化，同時將該NC薄膜之厚度最小化。 In various embodiments, each of the barrier layers of the NC film includes at least two layers of different materials or compositions that cause the multilayer barrier to clear or reduce pinhole defects in the barrier layer. The penetration of oxygen and moisture into the NC material provides an effective barrier. The NC film can comprise any suitable material or combination of materials, as well as any suitable number of barrier layers on either or both sides of the NC composition material. The material, thickness and number of such barrier layers will depend on the particular application and will be chosen to maximize the barrier protection and brightness of the NC while minimizing the thickness of the NC film.

在各種不同之實施例中，第一與第二阻障層係一積層薄膜 (laminate film)，例如雙積層薄膜，其中該第一與第二阻障層之厚度係夠厚，足以除去在捲對捲(roll-to-roll)或積層製造製程中之皺紋。在一較佳實施例中，該第一與第二阻障薄膜係一些具有一氧化物層之聚酯薄膜(例如，PET)。 In various embodiments, the first and second barrier layers are a laminate film, such as a double-layer film, wherein the first and second barrier layers are thick enough to remove the roll. Wrinkles in a roll-to-roll or laminate manufacturing process. In a preferred embodiment, the first and second barrier films are polyester films (e.g., PET) having an oxide layer.

本發明亦有關於一種包括根據本發明奈米晶體組成物之產品，其中該產品係選自於由顯示裝置(display device)、發光裝置(light emitting device)、光伏電池(photovoltaic cell)、光偵測器(photodetector)、能量轉換裝置(energy converter device)、雷射器(laser)、感測器(sensor)、熱電裝置(thermoelectric device)、保安油墨(security ink)、照明裝置(lighting device)及在催化或生物醫學之應用所組成之群組。 The invention also relates to a product comprising a nanocrystal composition according to the invention, wherein the product is selected from the group consisting of a display device, a light emitting device, a photovoltaic cell, a light detector Photodetector, energy converter device, laser, sensor, thermoelectric device, security ink, lighting device, and A group of applications in catalysis or biomedical applications.

本發明亦有關於根據本發明奈米晶體組成物之用途，當作光致發光(photoluminescence)或電致發光(electroluminescence)源。 The invention also relates to the use of a nanocrystal composition according to the invention as a source of photoluminescence or electroluminescence.

各種實例 Various examples

實例1： Example 1:

光起始劑之影響 Effect of photoinitiator

所有原物料用高速攪拌機(Speedmixer)混合，直到該光起始劑溶於該樹脂調配物(formulation)為止。得到低黏度透明UV可固化液體黏著劑。接著將該液體黏著劑除氣，然後移至氮氣手套箱(glovebox)中。在該手套箱中，將來自奈諾西斯股份有限公司(Nanosys Inc.)，在IBOA(1.23g)中3.8重量%之Green Gen 2.5 NC與在IBOA(0.88g)中2.7重量%之Red Gen 2.5 NC，與1重量%之Sachtolith HDS硫化鋅粉末(0.1g)一起分散到該上述之黏著劑中。此奈米晶體黏著劑調配物被積層於來自艾康柏能(iComponent)之兩個 阻障薄膜之間，並且在該手套箱中，使用365nm UV LED燈，以0.5J/cm2 UVA之用量(dosage)被固化。最終薄膜之該NC黏著劑層之厚度係約100微米(microns)。實例1之組成物舉例說明於表1中。 All raw materials were mixed using a speed mixer until the photoinitiator was dissolved in the resin formulation. A low viscosity, transparent UV curable liquid adhesive is obtained. The liquid adhesive was then degassed and then transferred to a nitrogen glove box. In the glove box, Green Gen 2.5 NC from Sinosys Inc., 3.8 wt% in IBOA (1.23 g) and 2.7 wt% Red Gen 2.5 in IBOA (0.88 g). NC was dispersed in the above-mentioned adhesive together with 1% by weight of Sachtolith HDS zinc sulfide powder (0.1 g). The nanocrystal adhesive formulation was laminated between two barrier films from iComponent, and in the glove box, a 365 nm UV LED lamp was used at a dose of 0.5 J/cm 2 UVA ( Dosage) is cured. The thickness of the NC adhesive layer of the final film is about 100 microns. The composition of Example 1 is illustrated in Table 1.

接著，將所得之NC薄膜切割成2.5”X3.5”之矩形或3.2”之正方形，並且其光學性質係以光研(Photo Research)之PR655分光輻射計(spectroradiometer)或海洋光學(Ocean Optics)之Torus Toroidal光柵光譜儀(Grating Spectrometer)來測量。該量子點薄膜係以藍色LED背光照射，並且從該奈米晶體薄膜所發出之光，係以PR655或Torus來測量。以此方式來獲得亮度(Luminance)與顏色座標(color coordinates)。 Next, the obtained NC film was cut into a 2.5" X 3.5" rectangle or a 3.2" square, and its optical properties were based on Photo Research's PR655 spectroradiometer or Ocean Optics. It is measured by a Torus Toroidal Grating Spectrometer. The quantum dot film is illuminated with a blue LED backlight, and the light emitted from the nanocrystalline film is measured by PR655 or Torus. (Luminance) and color coordinates.

該NC薄膜亦被沖壓成直徑19mm之圓盤，並且以濱松(Hamamatsu)之C9920量子產率系統來測量。該綠色及紅色NC之絕對量子產率(QY)與發射波長(emission wavelength)與相對強度能以C9920測量。 The NC film was also stamped into a 19 mm diameter disk and measured by Hamamatsu's C9920 quantum yield system. The absolute quantum yield (QY) and emission wavelength and relative intensity of the green and red NC can be measured as C9920.

為了研究黏著劑中，NC分散之安定性，將該等NC-黏著劑混合物儲存於一些密閉容器中，置於0~5℃之冰箱中。將該等NC混合物週期性地從該冰箱移出，再混合，然後再塗佈成NC薄膜。將該等在不同儲存時間之後所製備之NC薄膜之性質，與新鮮製成薄膜之性質比較，來確定在不同黏著劑中，該NC之儲存安定性。結果舉例說明於表2中。 In order to study the stability of NC dispersion in the adhesive, the NC-adhesive mixture was stored in some closed containers and placed in a refrigerator at 0 to 5 °C. The NC mixtures were periodically removed from the refrigerator, mixed, and then coated into an NC film. The properties of the NC film prepared after the different storage times were compared with the properties of the freshly formed film to determine the storage stability of the NC in different adhesives. The results are illustrated in Table 2.

在表2中，白點與亮度之結果清楚顯示，比較實例1.1具有較低得多之白點與Y亮度，這係該奈米晶體之淬熄(guenching)跡象。使用濱松所量測之量子產率亦顯示，與其他實例相比，比較實例1.1具有較低得多之QY。比較實例1.1之調配物係明顯與奈諾西斯之Gen 2.5 NC不相容，並且不 適合NC混合物之應用。 In Table 2, the results of white point and brightness clearly show that Comparative Example 1.1 has a much lower white point and Y brightness, which is an indication of the guenching of the nanocrystal. The quantum yield measured using Hamamatsu also showed that Comparative Example 1.1 had a much lower QY than the other examples. The formulation of Comparative Example 1.1 was clearly incompatible with the Gen 2.5 NC of Nanorcis and was not suitable for the application of the NC mixture.

相較之下，當改變比較實例1.1中之光起始劑，來製備實例1.1至1.3時，以新鮮NC混合物製成之各種NC薄膜，呈現出高白點、Y亮度及QY，這表示奈諾西斯之Gen 2.5 NC有良好之起始相容性。 In contrast, when the photoinitiators in Comparative Example 1.1 were changed to prepare Examples 1.1 to 1.3, various NC films made with a fresh NC mixture exhibited high white spots, Y brightness, and QY, which means Nai. Nosius's Gen 2.5 NC has good initial compatibility.

這些實例清楚地表示，在黏著劑設計中，光起始劑類型有強烈影響。該白點與亮度亦顯示，對該光起始劑之%裝載量(loading)之強烈相依性。在下列表3所提供之實例中，光起始劑類型固定使用氧化膦(phosphine oxide)，並且該裝載量係遞增地增加，從0.5%增至2%。 These examples clearly show that the type of photoinitiator has a strong influence in the adhesive design. The white point and brightness also show a strong dependence on the % loading of the photoinitiator. In the examples provided in Table 3 below, the photoinitiator type is fixedly using phosphine oxide, and the loading is incrementally increased from 0.5% to 2%.

從表4中之資料，亮度(Y)、白點(CIEx與CIEy)及量子產率(QY)，全部隨著該光起始劑裝載量之增加而下降。雖然機制未知，但是較高光起始劑濃度，將預期會在該黏著劑中，在UV/LED暴露時，增加自由基(free-radical)濃度，這亦會不利地淬熄該量子點。 From the data in Table 4, the brightness (Y), the white point (CIE x and CIE y ), and the quantum yield (QY) all decreased as the loading amount of the photoinitiator increased. Although the mechanism is unknown, higher photoinitiator concentrations will be expected to increase the free-radical concentration in the adhesive upon UV/LED exposure, which can also adversely quench the quantum dots.

實例2 Example 2

樹脂組成物之影響 Effect of resin composition

在下表5中，舉例說明一些黏著劑調配物，其係以秤重來製備，然後以高速攪拌機混合所有原物料，直到該光起始劑溶於該樹脂調配物中為止。獲得低黏度透明UV可固化液體黏著劑。接著添加NC。在NC調配物製備後，一些NC薄膜被塗佈與被測量。 In Table 5 below, some of the adhesive formulations are exemplified by weighing, and then all of the raw materials are mixed in a high speed mixer until the photoinitiator is dissolved in the resin formulation. A low viscosity, transparent UV curable liquid adhesive is obtained. Then add NC. After the NC formulation was prepared, some of the NC film was coated and measured.

為研究黏著劑中該NC分散之安定性，亦將該等NC-黏著劑混合物儲存於一些密閉容器中，置於0~5℃冰箱中。將等些NC混合物週期性地從該冰箱移出，再混合，然後再塗佈成NC薄膜。將該等在不同儲存時間之後所製備之NC薄膜之性質，與新鮮製成之薄膜之性質比較，來確定在不同黏著劑中，該NC之儲存安定性。 In order to study the stability of the NC dispersion in the adhesive, the NC-adhesive mixture was also stored in some closed containers and placed in a refrigerator at 0 to 5 °C. The NC mixture was periodically removed from the refrigerator, mixed, and then coated into an NC film. The properties of the NC film prepared after the different storage times were compared with the properties of the freshly formed film to determine the storage stability of the NC in different adhesives.

以PR655量測白點之結果，被列於表6中。 The results of measuring white spots with PR655 are listed in Table 6.

有關比較實例2.1與2.2之許多以新鮮NC混合物所製備之NC薄膜，呈現出高白點與Y亮度，這表示奈諾西斯之Gen 2.5 NC有良好之起始相容性。然而，當儲存該NC混合物時，該白點及Y亮度與該新鮮NC混合物 之那些性質相比，改變很大。結果，因在NC混合物儲存期間，該等光學性質不穩定，這些調配物亦不適於隨時可用之NC混合物應用。 A number of NC films prepared in a mixture of fresh NCs for Comparative Examples 2.1 and 2.2 exhibited high white and Y brightness, indicating that Genos NC of Nanorsum has good initial compatibility. However, when the NC mixture is stored, the white point and Y brightness vary greatly compared to those of the fresh NC mixture. As a result, these formulations are also unsuitable for ready-to-use NC mixture applications due to the unstable optical properties during storage of the NC mixture.

表7舉例說明各種本發明之組成物。以高速攪拌機(Speedmixer)混合所有原物料，直到該光起始劑溶於該樹脂調配物中為止。獲得一些低黏度透明UV可固化液體黏著劑。 Table 7 illustrates various compositions of the present invention. All raw materials were mixed with a speed mixer until the photoinitiator was dissolved in the resin formulation. Get some low viscosity transparent UV curable liquid adhesive.

上述黏著劑調配物之NC混合物，係以與該等比較實例之同樣方式，以來自奈諾西斯股份有限公司，在IBOA(1.23g)中3.8重量%之Green Gen 2.5 NC與在IBOA(0.88g)中2.7重量%之Red Gen 2.5 NC，和1%wt之Sachtolith HDS硫化鋅粉末(0.32g)一起來製備。 The NC mixture of the above adhesive formulations was in the same manner as the comparative examples, from Nanorsis Co., Ltd., in IBOA (1.23 g), 3.8 wt% of Green Gen 2.5 NC and at IBOA (0.88 g). 2.7% by weight of Red Gen 2.5 NC, prepared with 1% by weight of Sachtolith HDS zinc sulfide powder (0.32 g).

在不同儲存時間之後，以該NC混合物塗佈一些NC薄膜，並且使用PR655量測之結果列於表8中。 After varying storage times, some NC films were coated with the NC mixture and the results using PR655 measurements are listed in Table 8.

在新鮮製備時，在表8與9中，所有實例顯示高白點與Y亮度，指明與奈諾西斯之Gen 2.5 NC有良好之相容性。此外，在延長之儲存時間之後，能維持該亮度與白點。這顯示，當被分散於這些黏著劑調配物時，該些NC係隨時間安定。因此，這些黏著劑調配物係隨時可塗佈NC混合物之良好之候選物。 In the fresh preparation, in Tables 8 and 9, all examples showed high white point and Y brightness, indicating good compatibility with Genos NC of Genos. In addition, the brightness and white point can be maintained after an extended storage time. This shows that the NC systems settled over time when dispersed in these adhesive formulations. Therefore, these adhesive formulations are ready to coat good candidates for the NC mixture.

將實例2.3至2.6與比較實例2.1和2.2比較，很顯然，在延長之儲存時間之期間，在該黏著劑基材中，該黏著劑樹脂組成物對NC安定性有很強之影響。為達成良好之起始光學性質與良好之儲存安定性，許多多官能基丙烯酸酯樹脂，僅能以非常低濃度(10%或較低)被併入。 Comparing Examples 2.3 to 2.6 with Comparative Examples 2.1 and 2.2, it is apparent that the adhesive resin composition has a strong influence on NC stability in the adhesive substrate during the extended storage time. To achieve good initial optical properties and good storage stability, many polyfunctional acrylate resins can only be incorporated at very low concentrations (10% or less).

實例3 Example 3

可選擇之流變改質劑 Optional rheology modifier

許多典型NC黏著劑混合物調配物，在塗佈製程時需要低黏度。然而，較低黏度會造成無機粒子在調配物中快速沉澱，造成在最終薄膜產品中，白點與亮度不均勻(non-uniformity)。用來增強白點與薄膜亮度之該等NC與散射粒子，大部分係無機粒子，其會在低黏度基材中沉澱。一旦沉澱至容器底部，在塗佈製程之前，該混合物需要被再攪拌與混合。在儲存期間，非常需要在該調配物中，能夠懸浮(suspend)該等無機粒子。為達成如此之效果，可添加合適之流變改質劑至該黏著劑調配物，以增加搖變性(thixotropy)，並且有助於無機粒子之懸浮儲存。 Many typical NC adhesive blend formulations require low viscosity during the coating process. However, lower viscosity causes rapid precipitation of inorganic particles in the formulation, resulting in white spots and non-uniformity in the final film product. These NC and scattering particles, which are used to enhance the brightness of white spots and films, are mostly inorganic particles that precipitate in low viscosity substrates. Once precipitated to the bottom of the vessel, the mixture needs to be re-stirred and mixed prior to the coating process. During storage, it is highly desirable to be able to suspend the inorganic particles in the formulation. To achieve such an effect, a suitable rheology modifier can be added to the adhesive formulation to increase thixotropy and aid in the suspension storage of the inorganic particles.

在表10中，舉例說明之實例中，將BYK 410或BYK 7410 ET添加劑添加到該黏著劑調配物，以增加搖變性，並且防止散射粒子沉澱。在實例2.4中，沒有任何流變改質劑，大部分散射粒子在1至2天內沉澱至容器底部。相較之下，在實例3.1與3.2中，8週時間沒有觀察到任何顯而易見之粒子沉澱。此強烈顯示，在我們之黏著劑調配物中，許多流變改質劑，例如BYK 410與BYK 7410 ET，在懸浮散射粒子方面係有效用。 In Table 10, in the illustrated example, BYK 410 or BYK 7410 ET additive was added to the adhesive formulation to increase the shake densification and prevent the scattering particles from precipitating. In Example 2.4, there was no rheology modifier and most of the scattering particles settled to the bottom of the vessel within 1 to 2 days. In contrast, in Examples 3.1 and 3.2, no obvious particle precipitation was observed for 8 weeks. This strongly suggests that many rheology modifiers, such as BYK 410 and BYK 7410 ET, are effective in suspending scattering particles in our adhesive formulations.

亦藉由添加NC到上述該等調配物中，來研究流變改質劑對許多NC光學性質之影響，並且依照前面相同之程序，來製備一些NC薄膜。 The effect of the rheology modifier on the optical properties of many NCs was also investigated by adding NC to the above formulations, and some NC films were prepared according to the same procedure as before.

上表11呈現使用與不使用流變改質劑製備之NC薄膜之許多光學性質。實例3.1與3.2呈現出高Y亮度、白點與量子產率。這指明所使用之該流變改質劑與該NC係相容，並且不會與NC造成不利之交互作用。 Table 11 above shows a number of optical properties of NC films prepared with and without the use of rheology modifiers. Examples 3.1 and 3.2 exhibited high Y brightness, white point and quantum yield. This indicates that the rheology modifier used is compatible with the NC system and does not adversely interact with the NC.

實例4 Example 4

可選擇之分散劑 Optional dispersant

許多典型之NC黏著劑混合物調配物具有相對低之黏度，以高速率來塗佈薄膜。該低黏度基材會造成懸浮之無機粒子在溶液中凝聚(flocculate)，導致軟及/或硬沉澱或漂浮，這取決於該等粒子之密度。在一典型之NC黏著劑調配物中，該等量子點本身及散射劑，在塗佈前必須被均勻地分散，或在使用前必須再攪拌均勻。較佳地，在儲存期間，該等無機粒子保持懸浮於該調配物中，在塗佈前不需攪拌，以避免該等NC之偶然暴露。為達成如此之效應，可添加合適之分散(濕潤)劑到該黏著劑調配物中，以促進良好之懸浮液壽命(suspension lifetime)。 Many typical NC adhesive mixture formulations have a relatively low viscosity to coat the film at a high rate. The low viscosity substrate causes the suspended inorganic particles to flocculate in the solution, resulting in soft and/or hard precipitation or floating, depending on the density of the particles. In a typical NC adhesive formulation, the quantum dots themselves and the scattering agent must be uniformly dispersed prior to coating or must be stirred evenly before use. Preferably, the inorganic particles remain suspended in the formulation during storage without the need for agitation prior to coating to avoid accidental exposure of the NC. To achieve such an effect, a suitable dispersing (wetting) agent can be added to the adhesive formulation to promote a good suspension life.

在表12舉例說明之一些實例中，將Disperbyk 110或Disperbyk 180添加劑添加到該黏著劑調配物中，以防止NC或散射粒子沉澱。 In some examples exemplified in Table 12, Disperbyk 110 or Disperbyk 180 additives were added to the adhesive formulation to prevent precipitation of NC or scattering particles.

表13 Table 13

在表13中之結果表明，各新鮮樣品之亮度與白點很相似，這說明該分散劑沒有不利之影響。在比較實例4.1中，沒有任何沉澱劑，大部分散射粒子，在室溫下、一週內沉澱至容器之底部。相較之下，在實例4.1與4.2中，經過一週之後，沒有觀察到任何顯而易見之粒子沉澱。這強烈表示，許多分散劑，例如BYK 110及180，與一些NC相容，並且在所選擇之黏著劑調配物中，對懸浮無機粒子係有效。 The results in Table 13 show that the brightness of each fresh sample is very similar to the white point, indicating that the dispersant has no adverse effects. In Comparative Example 4.1, there was no precipitant, and most of the scattering particles settled to the bottom of the vessel at room temperature for one week. In contrast, in Examples 4.1 and 4.2, after one week, no obvious precipitation of particles was observed. This strongly indicates that many dispersants, such as BYK 110 and 180, are compatible with some NCs and are effective in suspending inorganic particle systems in selected adhesive formulations.

實例5 Example 5

用於兩步驟塗佈製程之雙PI(Dual PI) Dual PI (Dual PI) for two-step coating process

NC薄膜需要被積層(claminated)於兩阻障薄膜間，以防止NC受氧氣與濕氣作用而劣化，這在高速塗佈之與積層NC薄膜時非常需要。典型地，在用於NC薄膜之濕式積層製程中，未經固化之NC/黏著劑混合物係被積層於兩阻障薄膜之間，並且然後該黏著劑被UV固化。因為該黏著劑在積層階段未經固化，需要準確之間隙控制(gap control)，並且限制塗佈與積層速率。希望將該NC/黏著劑塗佈並固化在該第一阻障層上，然後積層該第二阻障層。在此製程流程中，能使用一些高速方法，例如狹縫式塗佈(slot die coating)、簾塗佈(curtain coating)、刮刀塗佈(knife coating)等，輕易地控制該黏著劑層之厚度。然而，在該NC/黏著劑固化後，將難以積層第二阻障薄膜並且仍然獲得良好之黏著力。 The NC film needs to be laminated between the two barrier films to prevent the NC from deteriorating by the action of oxygen and moisture, which is highly desirable when coating NC films at high speed. Typically, in a wet laminate process for NC films, an uncured NC/adhesive mixture is laminated between two barrier films and the adhesive is then UV cured. Since the adhesive is not cured during the lamination stage, accurate gap control is required and the coating and lamination rates are limited. It is desirable to coat and cure the NC/adhesive on the first barrier layer and then laminate the second barrier layer. In this process flow, the thickness of the adhesive layer can be easily controlled using some high speed methods such as slot die coating, curtain coating, knife coating, and the like. . However, after the NC/adhesive is cured, it will be difficult to laminate the second barrier film and still obtain good adhesion.

為實現此兩步驟塗佈與積層製程，開發雙固化製程之黏著劑調配物。在表14中，舉例說明一些調配物，實例5.3及5.4係依據本發明，並且與比較實例5.1及5.2做比較。 To achieve this two-step coating and lamination process, an adhesive formulation for the dual cure process was developed. In Table 14, some formulations are illustrated, examples 5.3 and 5.4 are in accordance with the present invention, and compared to Comparative Examples 5.1 and 5.2.

在上述表13中舉例說明之該等調配物，用8mil間隙之洩降棒(drawdown bar)，以自動薄膜塗佈機，被塗佈於阻障薄膜上，並且接著以395nm UV LED燈固化。在固化後，用壓力積層機(pressure laminator)，以3~5psi之壓力，將該第二阻障薄膜積層於該黏著劑上。然後再將該經積層之薄膜，以365nm LED燈或汞蒸汽UV燈固化。隨後，評估該薄膜之品質與黏著力。在不同固化條件下之結果，概述於表15中。 The formulations exemplified in Table 13 above were coated on a barrier film using an 8 mm gap drawdown bar, as an automatic film coater, and then cured with a 395 nm UV LED lamp. After curing, the second barrier film was laminated to the adhesive at a pressure of 3 to 5 psi using a pressure laminator. The laminated film is then cured with a 365 nm LED lamp or a mercury vapor UV lamp. Subsequently, the quality and adhesion of the film were evaluated. The results under different curing conditions are summarized in Table 15.

藉由修改實例5.3與實例5.4中該光起始劑之組合，使用該兩步驟固化製程，可達成極好之薄膜品質與黏著力。使用較長波長之UV光源，來執行該第一步驟之固化，並且在積層之後，以較短波長之UV光源，來執行第二固化，係很重要。 By modifying the combination of the photoinitiator in Example 5.3 and Example 5.4, excellent two-step curing process is used to achieve excellent film quality and adhesion. It is important to perform the curing of this first step using a longer wavelength UV light source and to perform a second curing with a shorter wavelength UV light source after lamination.

Claims (17)

一種奈米晶體組成物，其包括(a)複數個奈米晶體，其包括一包括一金屬或一半導電化合物或其混合物之核，及至少一配位子，其中，該核被至少一配位子所包圍，以及(b)一聚合基材，其中，該聚合基材係由一或更多個經化學官能基化之甲基丙烯酸酯寡聚體與一或更多個甲基丙烯酸酯單體聚合而成，而且其中，該等奈米晶體被嵌入該聚合基材。  A nanocrystal composition comprising (a) a plurality of nanocrystals comprising a core comprising a metal or a semiconductive compound or a mixture thereof, and at least one ligand, wherein the core is at least one coordinated Surrounded by sub-, and (b) a polymeric substrate, wherein the polymeric substrate is comprised of one or more chemically functionalized methacrylate oligomers with one or more methacrylate esters The body is polymerized, and wherein the nanocrystals are embedded in the polymeric substrate.   如申請專利範圍第1項所述之奈米晶體組成物，其中，該包括一金屬或半導電化合物或其混合物之核，係由數個元素所組成，該等元素選自週期表之一或更多個不同族之組合，較佳地，該金屬或半導電化合物係一或更多個選自第IV族之元素；一或更多個選自第II與第VI族之元素；一或更多個選自第III與第V族之元素；一或更多個選自第IV與第VI族之元素；一或更多個選自第I與第III與第VI族之元素之組合或其組合，更佳地，該金屬或半導電化合物係選自於由矽(Si)、鍺(Ge)、碳化矽(SiC)、與鍺化矽(SiGe)、硫化鎘(CdS)、硒化鎘(CdSe)、碲化鎘(CdTe)、硫化鋅(ZnS)、硒化鋅(ZnSe)、碲化鋅(ZnTe)、氧化鋅(ZnO)、硫化汞(HgS)、硒化汞(HgSe)、碲化汞(HgTe)、硫化鎂(MgS)、硒化鎂(MgSe)、氮化鎵(GaN)、磷化鎵(GaP)、銻化鎵(GaSb)、氮化鋁(AlN)、磷化鋁(AlP)、砷化鋁(AlAs)、三銻化鋁(AlSb 3)、三氮化銦(InN 3)、磷化銦(InP)、砷化銦(InAs)、硫化錫(SnS)、硒化錫(SnSe)、碲化錫(SnTe)、硫化鉛(PbS)、硒化鉛(PbSe)、碲化鉛(PbTe)、磷化銦錳(MnInP)、磷化銦銅(CuInP)、二硫化銦銅(CuInS 2)、二硒化銦銅(CuInSe 2)、二硫化鎵銅(CuGaS 2)、二硒化鎵銅 (CuGaSe 2)、二硫化銦銀(AgInS 2)、二硒化銦銀(AgInSe 2)、二硫化鎵銀(AgGaS 2)與二硒化鎵銀(AgGaSe 2)所組成之群組，並且甚至更佳地，該金屬或半導電化合物係選自於由硒化鎘(CdSe)、磷化銦(InP)及其混合物所組成之群組。 The nanocrystal composition according to claim 1, wherein the core comprising a metal or semiconductive compound or a mixture thereof is composed of a plurality of elements selected from one of the periodic tables or a combination of more different families, preferably, the metal or semiconductive compound is one or more elements selected from Group IV; one or more elements selected from Group II and Group VI; More elements selected from Groups III and V; one or more elements selected from Groups IV and VI; one or more combinations selected from elements of Groups I and III and VI Or a combination thereof, more preferably, the metal or semiconductive compound is selected from the group consisting of bismuth (Si), germanium (Ge), tantalum carbide (SiC), tantalum telluride (SiGe), cadmium sulfide (CdS), selenium. Cadmium (CdSe), cadmium telluride (CdTe), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), zinc oxide (ZnO), mercury sulfide (HgS), mercury selenide (HgSe) ), mercury telluride (HgTe), magnesium sulfide (MgS), magnesium selenide (MgSe), gallium nitride (GaN), gallium phosphide (GaP), gallium antimonide (GaSb), aluminum nitride (AlN), Aluminum phosphide (AlP), aluminum arsenide (AlAs), aluminum trioxide (AlSb 3 ), trinitrogen Indium (InN 3 ), Indium Phosphide (InP), Indium Arsenide (InAs), Tin Sulfide (SnS), Tin Selenide (SnSe), Tin Tellurium (SnTe), Lead Sulfide (PbS), Lead Selenide (PbSe), lead telluride (PbTe), indium manganese phosphide (MnInP), indium phosphide (CuInP), indium copper disulfide (CuInS 2 ), indium copper diselenide (CuInSe 2 ), gallium disulfide copper (CuGaS 2), diselenide, gallium copper (CuGaSe 2), disulfide indium silver (AgInS 2), diselenide indium silver (AgInSe 2), disulfide silver gallium (AgGaS 2) with diselenide silver gallium (AgGaSe2 2 ) The group formed, and even more preferably, the metal or semiconductive compound is selected from the group consisting of cadmium selenide (CdSe), indium phosphide (InP), and mixtures thereof. 如申請專利範圍第1項或第2項所述之奈米晶體組成物，其中，該核包括一核與至少一單層或多層殼，或其中，該核包括一核與至少二單層及/或多層殼。  The nanocrystal composition of claim 1 or 2, wherein the core comprises a core and at least one single or multiple layer shell, or wherein the core comprises a core and at least two monolayers and / or multilayer shell.   如申請專利範圍第1項或第2項所述之奈米晶體組成物，其中，該一或更多個經化學官能基化之甲基丙烯酸酯寡聚體，係選自乙氧基化(2-200)雙酚甲基丙烯酸酯(bisphenol methacrylate)、雙酚A環氧基甲基丙烯酸酯(bisphenol A epoxy methacrylate)寡聚體、脂肪族聚酯類(aliphatic polyester based)氨基甲酸乙酯二甲基丙烯酸酯(urethane dimethacrylate)寡聚體、芳香族聚酯類氨基甲酸乙酯二甲基丙烯酸酯寡聚體、脂肪族聚醚(aliphatic polyether)氨基甲酸乙酯甲基丙烯酸酯寡聚體、芳香族聚醚氨基甲酸乙酯甲基丙烯酸酯寡聚體及其混合物。  The nanocrystal composition of claim 1 or 2, wherein the one or more chemically functionalized methacrylate oligomers are selected from the group consisting of ethoxylation ( 2-200) bisphenol methacrylate, bisphenol A epoxy methacrylate oligomer, aliphatic polyester based urethane II Urethane dimethacrylate oligomer, aromatic polyester urethane dimethacrylate oligomer, aliphatic polyether urethane methacrylate oligomer, Aromatic polyether urethane methacrylate oligomers and mixtures thereof.   如申請專利範圍第1項至第4項中任一項所述之奈米晶體組成物，其中，該甲基丙烯酸酯單體係選自由 其中，o係0~12，較佳地，o係2~12； 其中，n係2~12，較佳地，n係6~11； 其中，X係CH 2，或伸苯基(phenylene，C 6H 4)； 其中，R 1係選自由-CH 3，-CH 2CH 3，-C(CH 3) 3，-OH所組成之群組；三羥甲基丙烷三甲基丙烯酸酯(trimethylolpropane trimethacrylate，TMPTMA)；甲基丙烯酸異莰酯(isobornyl methacrylate，IBOMA)；甲基丙烯酸四氫糠酯(tetrahydrofurfuryl methacrylate，THFMA)；甲基丙烯酸羥丙酯(hydroxypropyl methacrylate，HPMA)；三甘醇二甲基丙烯酸酯(triethylene glycol dimethacrylate，TEGDMA)；二甘醇二甲基丙烯酸酯(diethylene glycol dimethacrylate，DEGDMA)；酸性官能之甲基丙烯酸酯 (acid functional methacrylate)；酸性官能之金剛烷基甲基丙烯酸酯(acid functional adamantyl methacrylate)；甲基丙烯酸三級丁酯(tert-butyl methacrylate，TBMA)；甲基丙烯酸環己酯(cyclohexyl methacrylate，CHMA)；甘油二甲基丙烯酸酯(glycerol dimethacrylate)；雙酚A二甲基丙烯酸酯(bisphenol A dimethacrylate)；雙酚F二甲基丙烯酸酯(bisphenol F dimethacrylate)；甲基丙烯酸2-苯氧乙酯(2-phenoxyethyl methacrylate)及其混合物所組成之群組。 The nanocrystal composition according to any one of claims 1 to 4, wherein the methacrylate monosystem is selected from the group consisting of Wherein, o is 0 to 12, preferably, o is 2 to 12; Wherein n is 2 to 12, preferably n is 6 to 11; Wherein, X is CH 2 or phenylene (C 6 H 4 ); Wherein R 1 is selected from the group consisting of -CH 3 , -CH 2 CH 3 , -C(CH 3 ) 3 , -OH; trimethylolpropane trimethacrylate (TMPTMA); Isobornyl methacrylate (IBOMA); tetrahydrofurfuryl methacrylate (THFMA); hydroxypropyl methacrylate (HPMA); triethylene glycol dimethacrylate (triethylene) Glycol dimethacrylate, TEGDMA); diethylene glycol dimethacrylate (DEGDMA); acid functional methacrylate; acid functional adamantyl methacrylate ); tert-butyl methacrylate (TBMA); cyclohexyl methacrylate (CHMA); glycerol dimethacrylate; bisphenol A dimethacrylate (bisphenol A dimethacrylate); bisphenol F dimethacrylate; 2-phenoxyethyl methacrylate (2-ph Group of enoxyethyl methacrylate) and mixtures thereof. 如申請專利範圍第1項至第5項中任一項所述之奈米晶體組成物，其包括該組成物總重之0.01至10重量%之數個奈米晶體，較佳為0.05至7.5%，更佳為0.1至5%。  The nanocrystal composition according to any one of claims 1 to 5, which comprises a plurality of nanocrystals of 0.01 to 10% by weight, preferably 0.05 to 7.5, of the total weight of the composition. %, more preferably 0.1 to 5%.   如申請專利範圍第1項至第6項中任一項所述之奈米晶體組成物，其包括該組成物總重之90至99.99重量%之一聚合物基材，較佳為92.5至99.95%，更佳為95至99.9%。  The nanocrystal composition according to any one of claims 1 to 6, which comprises a polymer substrate of 90 to 99.99% by weight, preferably 92.5 to 99.95, of the total weight of the composition. %, more preferably 95 to 99.9%.   如申請專利範圍第1項至第7項中任一項所述之奈米晶體組成物，其進一步包括一或更多個具有一丙烯酸酯基團之丙烯酸酯單體，及/或一或更多個具有二或更多個丙烯酸酯基團之丙烯酸酯單體，其中，以該聚合基材之總重為基準，該具有二或更多個丙烯酸酯基團之丙烯酸酯單體之數量小於15重量%。  The nanocrystal composition according to any one of claims 1 to 7, further comprising one or more acrylate monomers having an acrylate group, and/or one or more a plurality of acrylate monomers having two or more acrylate groups, wherein the number of acrylate monomers having two or more acrylate groups is less than the total weight of the polymeric substrate 15% by weight.   如申請專利範圍第1項至第8項中任一項所述之奈米晶體組成物，其進一步包括一光起始劑，選自於由1,5,7-三氮雜雙環[4.4.0]癸-5-烯‧氫四苯基硼酸鹽(1,5,7-triazabicyclo[4.4.0]dec-5-ene．hydrogen tetraphenyl borate，TBD．HBPh 4)、2-甲基-4-(甲硫基)-2-嗎啉基乙基苯基酮 (2-methyl-4-(methylthio)-2-morpholinopropiophenone)、2-(9-氧代苯芴酮-2-基)丙酸-1,5,7-三氮雜雙環[4.4.0]癸-5-烯(2-(9-oxoxanthen-2-yl)propionic acid-1,5,7 triazabicyclo[4.4.0]dec-5-ene)、2-羥基-2-甲基-1-苯基丙酮(2-hydroxy-2-methyl-1-phenylpropanone)、1-羥基環己基-苯基酮(1-hydroxycyclohexyl-phenyl ketone)、2,4,6-三甲基苯甲醯基-二苯基氧化膦(2,4,6-trimethylbenzoyl-diphenyl phosphine oxide，TPO)、(2,4,6-三甲基苯甲醯基)-苯基膦酸乙酯(ethyl(2,4,6-trimethylbenzoyl)-phenyl phosphinate，TPO-L)、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦(Bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide)及其混合物所組成之群組。 The nanocrystal composition according to any one of claims 1 to 8, further comprising a photoinitiator selected from the group consisting of 1,5,7-triazabicyclo[4.4. 0] 癸-5-ene ‧ hydrogen tetraphenyl borate (1,5,7-triazabicyclo[4.4.0]dec-5-ene.hydrogen tetraphenyl borate, TBD.HBPh 4 ), 2-methyl-4- (2-methyl-4-(methylthio)-2-morpholinopropiophenone), 2-(9-oxobenzophenone-2-yl)propionic acid- 1,5,7-triazabicyclo[4.4.0]non-5-ene (2-(9-oxoxanthen-2-yl)propionic acid-1,5,7 triazabicyclo[4.4.0]dec-5- Ene), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl-phenyl ketone, 2 , 4,6-trimethylbenzoyl-diphenyl phosphine oxide (TPO), (2,4,6-trimethylbenzylidene)- Ethyl phenylphosphonate (ethyl(2,4,6-trimethylbenzoyl)-phenyl phosphinate, TPO-L), bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide (Bis(2) , 4,6-trimethylbenzoyl)phenyl phosphine oxide) Of the group. 如申請專利範圍第9項所述之奈米晶體組成物，其中，該組成物包括至少二光起始劑，其中第一光起始劑係選自於由2-羥基-2-甲基-1-苯基丙酮(2-hydroxy-2-methyl-1-phenylpropanone)單體或寡聚體、1-羥基環己基-苯基酮(1-hydroxycyclohexyl-phenyl ketone)、2-羥基-1-(4-(4-(2-羥基-2-甲基丙醯基)芐基)苯基)-2-甲基丙-1-酮(2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one)、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-甲基丙酮(1-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone)、2,2-二甲氧基-2-苯基苯乙酮(2,2-dimethoxy-2-phenylacetophenone)及其混合物所組成之群組，而且第二光起始劑係選自於由2,4,6-三甲基苯甲醯基-二苯基氧化膦(2,4,6-trimethylbenzoyl-diphenyl phosphine oxide)、(2,4,6-三甲基苯甲醯基)-苯基膦酸乙酯 (ethyl(2,4,6-trimethylbenzoyl)-phenyl phosphinate)、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦(bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide)及其混合物所組成之群組。  The nanocrystal composition of claim 9, wherein the composition comprises at least two photoinitiators, wherein the first photoinitiator is selected from the group consisting of 2-hydroxy-2-methyl- 1-hydroxy-2-methyl-1-phenylpropanone monomer or oligomer, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-1-( 4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one (2-hydroxy-1-(4-(4-(2-) Hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylacetone (1-[4 -(2-hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone), 2,2-dimethoxy-2-phenylacetophenone and mixtures thereof a group, and the second photoinitiator is selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide (2,4,6-trimethylbenzoyl-diphenyl phosphine oxide), (2 ,4,6-trimethylbenzoyl-phenylphosphinate, bis(2,4,6-trimethylbenzamide) Phenylphosphine oxide (bis(2,4,6-trimethyl) Group of benzoyl)-phenyl phosphine oxides and mixtures thereof.   如申請專利範圍第1項至第10項中任一項所述之奈米晶體組成物，其包括該組成物總重之0.01至6重量%之一光起始劑，較佳為0.01至3%，更佳為0.01至2%。  The nanocrystal composition according to any one of claims 1 to 10, which comprises from 0.01 to 6% by weight, based on the total weight of the composition, of a photoinitiator, preferably from 0.01 to 3 %, more preferably 0.01 to 2%.   如申請專利範圍第1項至第11項中任一項所述之奈米晶體組成物，其進一步包括散射粒子，係選自於由二氧化鈦(TiO 2)、硫化鋅(ZnS)、二氧化鋯(ZrO 2)、氧化鋁(Al 2O 3)、氧化鎂(MgO)、氧化鈣(CaO)、五氧化二鉭(Ta 2O 5)、二氧化矽(silica)、矽氧樹脂(silicone)及其混合物所組成之群組。 The nanocrystal composition according to any one of claims 1 to 11, further comprising scattering particles selected from the group consisting of titanium dioxide (TiO 2 ), zinc sulfide (ZnS), and zirconium dioxide. (ZrO 2 ), aluminum oxide (Al 2 O 3 ), magnesium oxide (MgO), calcium oxide (CaO), tantalum pentoxide (Ta 2 O 5 ), silica, silicon oxide And a group of its mixtures. 如申請專利範圍第1項至第12項中任一項所述之奈米晶體組成物，其包括該組成物總重之0.01至3重量%之一散射粒子，較佳為0.05至2.5%，更佳為0.01至2%。  The nanocrystal composition according to any one of claims 1 to 12, which comprises from 0.01 to 3% by weight, based on the total weight of the composition, of scattering particles, preferably from 0.05 to 2.5%, More preferably, it is 0.01 to 2%.   一種經固化之如申請專利範圍第1項至第13項中任一項所述之奈米晶體組成物。  A nanocrystal composition as described in any one of claims 1 to 13 of the invention.   一種薄膜，其包括如申請專利範圍第1項至第14項中任一項所述之一奈米晶體組成物，其中，該薄膜包括一第一阻障薄膜(barrier film)與一第二阻障薄膜，其中該奈米晶體組成物係在該第一與第二阻障薄膜之間。  A film comprising a nanocrystal composition according to any one of claims 1 to 14, wherein the film comprises a first barrier film and a second resistance a barrier film, wherein the nanocrystalline composition is between the first and second barrier films.   一種產品，其包括如申請專利範圍第1項至第14項中任一項所述之一奈米晶體組成物，或如申請專利範圍第15項所述之一薄膜，其中，該產品係選自於由一顯示裝置(display device)、一發光裝置(light emitting device)、一光伏電池(photovoltaic cell)、一光偵測器(photodetector)、一能量轉換裝置(energy converter device)、一雷射器(laser)、一感測器(sensor)、一熱電裝置(thermoelectric device)、一保安油墨(security ink)、照明裝置(lighting device)及在催化或生物醫學之應用所組成之群組。  A product comprising a nanocrystal composition according to any one of claims 1 to 14, or a film according to claim 15 wherein the product is selected From a display device, a light emitting device, a photovoltaic cell, a photodetector, an energy converter device, a laser A group of lasers, a sensor, a thermoelectric device, a security ink, a lighting device, and a catalytic or biomedical application.   一種如申請專利範圍第1項至第13項中任一項所述之奈米晶體組成物之用途，其係作為一光致發光(photoluminescence)或電致發光(electroluminescence)源。  A use of the nanocrystal composition according to any one of claims 1 to 13 as a source of photoluminescence or electroluminescence.  
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