TW202336212A - Composition for forming wavelength conversion film for display - Google Patents

Abstract

Provided is a composition for forming a wavelength conversion film for a display which yields a wavelength conversion film having excellent wavelength conversion efficiency and has excellent storage stability. The composition for forming a wavelength conversion film for a display includes (A) a phosphor, (B) titanium oxide particles, and (C) a binder. The (B) titanium oxide particles may be coated on the surface thereof with an inorganic compound. The (B) titanium oxide particles have an average particle size greater than 50 nm and less than 200 nm and a viscosity of 10,000 mPa.s or less at 25 DEG C.

Description

顯示器用波長轉換膜形成用組成物Composition for forming wavelength conversion film for display

本發明關於一種顯示器用波長轉換膜形成用組成物，若進一步詳細敘述，則關於適合使用於液晶顯示器、有機EL顯示器、微LED顯示器等的各種顯示器之顯示器用波長轉換膜形成用組成物。The present invention relates to a composition for forming a wavelength conversion film for displays. If described in further detail, the present invention relates to a composition for forming a wavelength conversion film for displays that is suitable for use in various displays such as liquid crystal displays, organic EL displays, micro-LED displays, and the like.

微LED顯示器可達成高對比、高亮度，而且應用幅度也擴大到大畫面化或透明顯示器等，因此可期待成為液晶顯示器、有機EL顯示器之後的新一代顯示器。 微LED顯示器通常在各畫素配置了微小LED晶片。 該LED晶片的配置方式，已知有實裝三色LED的RGB-LED式，在此方式中，會有LED的發光控制複雜、紅色LED性能低的課題，能夠解決此課題的波長轉換方式正受到矚目。 波長轉換式僅使用了藍色LED晶片，並藉由波長轉換材料來取出紅色、綠色光線，因此有只使用藍色LED晶片即可作出三原色的優點。 Micro-LED displays can achieve high contrast and high brightness, and their application range has also expanded to large-screen or transparent displays, so they are expected to become a new generation of displays after liquid crystal displays and organic EL displays. Micro-LED displays usually have tiny LED chips placed in each pixel. The arrangement method of this LED chip is known as the RGB-LED type in which three-color LEDs are installed. In this method, there are problems such as complex LED light emission control and low performance of red LEDs. The wavelength conversion method that can solve this problem is the right one. Get noticed. The wavelength conversion type only uses blue LED chips, and uses wavelength conversion materials to extract red and green light. Therefore, it has the advantage of using only blue LED chips to produce the three primary colors.

關於波長轉換材料，過去有文獻提出使用有機物的發光材料的技術，揭示了例如使用吡啶-酞醯亞胺縮合體(專利文獻1等)、使用香豆素衍生物(專利文獻2等)、使用苝衍生物(專利文獻3等)、使用羅丹明衍生物(專利文獻4)、使用吡咯次甲基衍生物(專利文獻5、6等)。Regarding wavelength conversion materials, there have been documents in the past that have proposed technologies for using organic light-emitting materials. For example, the use of pyridine-phthalimide condensates (Patent Document 1, etc.), the use of coumarin derivatives (Patent Document 2, etc.), the use of Perylene derivatives (Patent Document 3, etc.), rhodamine derivatives (Patent Document 4), and pyrromethine derivatives (Patent Documents 5, 6, etc.) are used.

這些波長轉換材料，一般而言，需要有良好的波長轉換效率、色純度及耐光性等的特性。 關於這點，例如專利文獻7揭示了一種紅色轉換材料，其係包含由特定甲基丙烯酸系聚合物所形成的黏結劑樹脂，特定螢光色素及可光聚合的丙烯酸酯的組成物，高性能且耐光性良好。 另外還有文獻揭示為了防止有機發光材料劣化，提升耐久性而添加光安定化劑的技術(專利文獻8等)。 此外，還已知藉由在波長轉換材料中添加微粒子，因為色轉換層內的光散射，光路長增大，藍色光吸收率會提升，同時被界面反射的光再度散射，發光效率會提升(專利文獻9、10等)。 Generally speaking, these wavelength conversion materials need to have characteristics such as good wavelength conversion efficiency, color purity, and light resistance. In this regard, for example, Patent Document 7 discloses a red conversion material, which is a composition containing a binder resin formed from a specific methacrylic polymer, a specific fluorescent dye, and a photopolymerizable acrylate, and has high performance. And it has good light resistance. There are also documents disclosing the technology of adding a photostabilizer in order to prevent the degradation of organic light-emitting materials and improve durability (Patent Document 8, etc.). In addition, it is also known that by adding microparticles to the wavelength conversion material, the optical path length increases due to light scattering in the color conversion layer, and the blue light absorption rate increases. At the same time, the light reflected by the interface is scattered again, and the luminous efficiency increases ( Patent documents 9, 10, etc.).

但是，隨著近年來顯示器技術的發展，對於顯示器用波長轉換膜形成用組成物而言，從提升顯示器性能的觀點看來，波長轉換材料的波長轉換效率需要進一步改良，從生產性的觀點看來，組成物的保存安定性也需要進一步改良。 [先前技術文獻] [專利文獻] However, with the development of display technology in recent years, the wavelength conversion efficiency of the wavelength conversion material needs to be further improved from the perspective of improving display performance, and from the perspective of productivity, the composition for forming a wavelength conversion film for a display needs to be further improved. In the future, the storage stability of the composition will also need to be further improved. [Prior technical literature] [Patent Document]

[專利文獻1]日本特開2002-348568號公報 [專利文獻2]日本特開2007-273440號公報 [專利文獻3]日本特開2002-317175號公報 [專利文獻4]日本特開2001-164245號公報 [專利文獻5]日本特開2011-241160號公報 [專利文獻6]日本特開2014-136771號公報 [專利文獻7]日本特開2006-89724號公報 [專利文獻8]日本特開2011-149028號公報 [專利文獻9]國際公開第2020/189678號 [專利文獻10]國際公開第2019/181698號 [Patent Document 1] Japanese Patent Application Publication No. 2002-348568 [Patent Document 2] Japanese Patent Application Publication No. 2007-273440 [Patent Document 3] Japanese Patent Application Publication No. 2002-317175 [Patent Document 4] Japanese Patent Application Publication No. 2001-164245 [Patent Document 5] Japanese Patent Application Publication No. 2011-241160 [Patent Document 6] Japanese Patent Application Publication No. 2014-136771 [Patent Document 7] Japanese Patent Application Publication No. 2006-89724 [Patent Document 8] Japanese Patent Application Publication No. 2011-149028 [Patent Document 9] International Publication No. 2020/189678 [Patent Document 10] International Publication No. 2019/181698

[發明所欲解決的課題][Problem to be solved by the invention]

本發明是鑑於上述狀況而完成，目的為提供一種顯示器用波長轉換膜形成用組成物，可產生波長轉換效率優異的波長轉換膜，同時保存安定性也優異。 [用於解決課題的手段] The present invention was made in view of the above-mentioned situation, and its object is to provide a composition for forming a wavelength conversion film for a display, which can produce a wavelength conversion film with excellent wavelength conversion efficiency and also has excellent storage stability. [Means used to solve problems]

本發明人等為了解決上述課題反覆鑽研檢討，結果發現，包含具有特定範圍平均粒徑的氧化鈦粒子，將黏度調整成特定範圍之顯示器用波長轉換膜形成用組成物可解決上述課題，而完成了本發明。The inventors of the present invention have made repeated studies and examinations in order to solve the above-mentioned problems. As a result, they have found that a composition for forming a wavelength conversion film for a display containing titanium oxide particles having an average particle diameter in a specific range and adjusting the viscosity to a specific range can solve the above-mentioned problems and completed it. of the present invention.

亦即，本發明提供以下的顯示器用波長轉換膜形成用組成物。 1. 一種顯示器用波長轉換膜形成用組成物，其係含有(A)螢光體、(B)氧化鈦粒子與(C)黏結劑， 上述(B)氧化鈦粒子其表面可被無機化合物被覆，其平均粒徑超過50nm~未達200nm， 25℃的黏度為10,000mPa･s以下。 2. 如1之顯示器用波長轉換膜形成用組成物，其中上述(B)氧化鈦粒子的平均粒徑為60~190nm。 3. 如1或2之顯示器用波長轉換膜形成用組成物，其中上述(B)氧化鈦粒子為該氧化鈦粒子的表面並未被被覆的粒子。 4. 如1~3中任一項之顯示器用波長轉換膜形成用組成物，其中上述(B)氧化鈦粒子的含量為在固體成分中占3~10質量%。 5. 如1~4中任一項之顯示器用波長轉換膜形成用組成物，其中上述(A)螢光體為有機色素。 6. 如1~5中任一項之顯示器用波長轉換膜形成用組成物，其中由上述組成物所形成的膜的霧度值為18%以上。 [發明之效果] That is, the present invention provides the following composition for forming a wavelength conversion film for displays. 1. A composition for forming a wavelength conversion film for a display, which contains (A) phosphor, (B) titanium oxide particles and (C) binder, The surface of the above-mentioned (B) titanium oxide particles can be coated with an inorganic compound, and its average particle size exceeds 50nm to less than 200nm. The viscosity at 25℃ is 10,000mPa･s or less. 2. The composition for forming a wavelength conversion film for a display as in 1, wherein the average particle size of the titanium oxide particles (B) is 60 to 190 nm. 3. The composition for forming a wavelength conversion film for a display according to 1 or 2, wherein the titanium oxide particles (B) are particles whose surfaces are not covered. 4. The composition for forming a wavelength conversion film for a display according to any one of 1 to 3, wherein the content of the titanium oxide particles (B) is 3 to 10% by mass in the solid content. 5. The composition for forming a wavelength conversion film for a display according to any one of 1 to 4, wherein the phosphor (A) is an organic pigment. 6. The composition for forming a wavelength conversion film for displays according to any one of 1 to 5, wherein the haze value of the film formed from the above composition is 18% or more. [Effects of the invention]

依據本發明，可提供一種顯示器用波長轉換膜形成用組成物，可產生波長轉換效率優異的波長轉換膜，同時保存安定性也優異。According to the present invention, a composition for forming a wavelength conversion film for a display can be provided, which can produce a wavelength conversion film with excellent wavelength conversion efficiency and also has excellent storage stability.

以下針對本發明進一步詳細說明。 本發明之顯示器用波長轉換膜形成用組成物，其特徵為：含有(A)螢光體、(B)氧化鈦粒子與(C)黏結劑，上述(B)氧化鈦粒子其表面可被無機化合物被覆，其平均粒徑超過50nm~未達200nm，25℃的黏度為10,000mPa･s以下。在(B)氧化鈦粒子表面被無機化合物被覆的情況，其平均粒徑為被無機化合物被覆的氧化鈦粒子的平均粒徑。 此外，在以下的說明之中，固體成分意指構成顯示器用波長轉換膜形成用組成物的成分當中溶劑以外的成分。 The present invention will be described in further detail below. The composition for forming a wavelength conversion film for a display of the present invention is characterized by containing (A) phosphor, (B) titanium oxide particles and (C) binder, and the surface of the above-mentioned (B) titanium oxide particles can be inorganically Coated with a compound, its average particle size ranges from more than 50nm to less than 200nm, and its viscosity at 25°C is 10,000mPa･s or less. (B) When the surface of the titanium oxide particles is coated with an inorganic compound, the average particle diameter is the average particle diameter of the titanium oxide particles coated with the inorganic compound. In addition, in the following description, the solid content means components other than the solvent among the components constituting the wavelength conversion film forming composition for displays.

上述(A)螢光體，可由過去周知的無機螢光體、有機色素、半導體奈米粒子(量子點、量子棒等)等適當地選擇，從顯示器的高精細化及組成物的保存安定性的觀點看來，以有機色素為佳。此外，在本發明中，以不含半導體奈米粒子為佳。The above-mentioned (A) phosphor can be appropriately selected from conventionally known inorganic phosphors, organic pigments, semiconductor nanoparticles (quantum dots, quantum rods, etc.), in view of the high definition of the display and the storage stability of the composition. From this point of view, organic pigments are better. In addition, in the present invention, it is preferable that the semiconductor nanoparticles are not included.

有機色素，可列舉例如萘、蒽、菲、芘、䓛、并四苯、聯伸三苯、苝、熒蒽、芴、茚等的具有縮合芳香基環的化合物或其衍生物；呋喃、吡咯、噻吩、矽咯、9-矽芴、9,9'-螺雙矽芴、苯并噻吩、苯并呋喃、吲哚、二苯并噻吩、二苯并呋喃、咪唑并吡啶、啡啉、吡啶、吡嗪、萘啶、喹惡啉、吡咯并吡啶等的具有雜芳香基環的化合物或其衍生物；1,4-二苯乙烯基苯、4,4'-雙(2-(4-二苯基胺基苯基)乙烯基)聯苯、4,4'-雙(N-(茋-4-基)-N-苯基胺基)茋等的茋衍生物；芳香族乙炔衍生物；四苯基丁二烯衍生物；醛連氮衍生物；吡咯次甲基衍生物；二酮吡咯并[3,4-c]吡咯衍生物；香豆素6、香豆素7、香豆素153、專利文獻7所揭示的化合物等的香豆素衍生物；萘并磷唑氧化物衍生物；咪唑、噻唑、噻二唑、咔唑、噁唑、噁二唑、***等的唑衍生物及其金屬錯合物；靛氰綠等的花青苷系化合物；螢光素、伊紅、羅丹明等的呫噸系化合物或噻噸系化合物；聚苯系化合物、萘二甲醯亞胺衍生物、酞菁衍生物及其金屬錯合物、卟啉衍生物及其金屬錯合物；尼羅紅或尼羅藍等的噁嗪系化合物；螺烯系化合物；N,N'-二苯基-N,N'-二(3-甲基苯基)-4,4'-二苯基-1,1'-二胺等的芳香族胺衍生物；銥(Ir)、釕(Ru)、銠(Rh)、鈀(Pd)、鉑(Pt)、鋨(Os)、錸(Re)等的有機金屬錯合物化合物等，但並不受這些化合物限定。 此外，在本發明中，有機色素不包括日本特開2021-128338號公報所揭示的具有由一般式[1]所表示的部分構造的色素(B1)。 Examples of organic dyes include compounds having condensed aromatic rings such as naphthalene, anthracene, phenanthrene, pyrene, pyrene, tetracene, diphenyl, perylene, fluoranthene, fluorene, indene, and the like; furan, pyrrole, Thiophene, silroles, 9-silicofluorene, 9,9'-spirobissilicofluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyridine, Compounds with heteroaryl rings such as pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, or their derivatives; 1,4-distyrylbenzene, 4,4'-bis(2-(4-di Stilbene derivatives such as phenylaminophenyl)vinyl)biphenyl, 4,4'-bis(N-(stilbene-4-yl)-N-phenylamino)stilbene; aromatic acetylene derivatives; Tetraphenylbutadiene derivatives; aldazine derivatives; pyrrolemethine derivatives; diketopyrro[3,4-c]pyrrole derivatives; coumarin 6, coumarin 7, coumarin 153. Coumarin derivatives of the compounds disclosed in Patent Document 7; naphthophosphorus azole oxide derivatives; azole derivatives of imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, triazole, etc. substances and their metal complexes; anthocyanin-based compounds such as indocyanine green; xanthene-based compounds or thioxanthene-based compounds such as fluorescein, eosin, rhodamine, etc.; polyphenylene-based compounds, naphthalene dimethyl Amine derivatives, phthalocyanine derivatives and their metal complexes, porphyrin derivatives and their metal complexes; oxazine compounds such as Nile red or Nile blue; helicene compounds; N,N'- Aromatic amine derivatives such as diphenyl-N,N'-bis(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine; iridium (Ir), ruthenium ( Organic metal complex compounds such as Ru), rhodium (Rh), palladium (Pd), platinum (Pt), osmium (Os), rhenium (Re), etc. are not limited to these compounds. In addition, in the present invention, the organic dye does not include the dye (B1) having a partial structure represented by general formula [1] disclosed in Japanese Patent Application Laid-Open No. 2021-128338.

在本發明中，上述有機色素之中，香豆素衍生物、萘并磷唑氧化物衍生物、吡咯次甲基衍生物及苝衍生物為佳。In the present invention, among the above-mentioned organic pigments, coumarin derivatives, naphthophosphorazole oxide derivatives, pyrromethine derivatives and perylene derivatives are preferred.

上述香豆素衍生物，以由下述式(1)所表示的香豆素衍生物為佳。The above-mentioned coumarin derivative is preferably a coumarin derivative represented by the following formula (1).

式(1)之中，R ¹及R ²各自獨立地表示碳數2~10之烷基，R ³及R ⁴各自獨立地表示碳數2~8之烷基，R ³及R ⁴亦可互相結合，與氮原子一起形成環。 上述碳數2~10之烷基可為直鏈、分支、環狀之任一者，其具體例子，可列舉乙基、正丙基、異丙基、正丁基、正己基、正辛基、2-乙基己基、環己基甲基、新戊基。 上述碳數2~8之烷基可為直鏈、分支、環狀之任一者，其具體例子，可列舉上述碳數2~10之烷基當中碳數2~8之烷基。 In formula (1), R ¹ and R ² each independently represent an alkyl group having 2 to 10 carbon atoms, and R ³ and R ⁴ each independently represent an alkyl group having 2 to 8 carbon atoms. R ³ and R ⁴ may also be Combine with each other and form a ring with nitrogen atoms. The above-mentioned alkyl group having 2 to 10 carbon atoms may be linear, branched, or cyclic. Specific examples thereof include ethyl, n-propyl, isopropyl, n-butyl, n-hexyl, and n-octyl. , 2-ethylhexyl, cyclohexylmethyl, neopentyl. The alkyl group having 2 to 8 carbon atoms may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 2 to 8 carbon atoms among the alkyl groups having 2 to 10 carbon atoms.

其中，R ¹及R ²以一者為直鏈狀烷基，另一者為分支狀或環狀烷基為佳，正己基與環己基甲基的組合為較佳。 R ³及R ⁴以乙基、正丙基、正丁基、正己基、正辛基、2-乙基己基為佳，正丁基、正己基為較佳。 由式(1)所表示的香豆素衍生物的適合例子，可列舉由下述式(1A)所表示的化合物，但是並不受其限定。 Among them, one of R ¹ and R ² is preferably a linear alkyl group, and the other is a branched or cyclic alkyl group, and the combination of n-hexyl and cyclohexylmethyl is preferred. R ³ and R ⁴ are preferably ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, and 2-ethylhexyl, and n-butyl or n-hexyl is preferred. Suitable examples of the coumarin derivative represented by formula (1) include, but are not limited to, compounds represented by the following formula (1A).

由上述式(1A)所表示的香豆素衍生物，例如可使用如以下路徑圖所示般的周知反應來合成。The coumarin derivative represented by the above formula (1A) can be synthesized, for example, using a well-known reaction as shown in the following pathway.

亦即，在第1階段中，依據中國專利公開公報105001666A的段落[0037]等所記載的反應，使間胺基酚、溴環己基甲烷等的鹵化環己基甲烷及1-溴己烷等的1-鹵化己烷在鹼的存在下在溶劑中反應，合成出化合物A-1。 在此反應之中，鹵化環己基甲烷及1-鹵化己烷的使用量，相對於間胺基酚1mol，分別以0.5mol左右為佳。 鹼可使用碳酸鈉、碳酸鉀等，其使用量，相對於間胺基酚1mol，以1~2mol為佳，1~1.5mol左右為較佳。 溶劑可使用水；甲醇、乙醇、異丙醇等的醇溶劑；水與醇溶劑的混合溶劑(例如異丙醇/水(v/v)=1：1)等。 反應溫度可採用從室溫到溶劑沸點的任意溫度，以50~100℃為佳，60~90℃為較佳。 反應時間通常為1~48小時左右，如果在上述溫度範圍，則以12~36小時左右為佳，18~24小時左右為較佳。 反應氣體環境並未受到特別限定，以氮氣等的惰性氣體環境為佳。 反應結束後，依據慣用方法進行後處理，因應必要純化，而得到化合物A-1。 That is, in the first stage, according to the reaction described in paragraph [0037] of Chinese Patent Publication No. 105001666A, halogenated cyclohexylmethane such as meta-aminophenol, bromocyclohexylmethane and 1-bromohexane are made. 1-Hexane halide is reacted in a solvent in the presence of a base to synthesize compound A-1. In this reaction, the usage amounts of halogenated cyclohexylmethane and 1-halogenated hexane are preferably about 0.5 mol each relative to 1 mol of meta-aminophenol. As the base, sodium carbonate, potassium carbonate, etc. can be used. The usage amount is preferably 1 to 2 mol relative to 1 mol of meta-aminophenol, and preferably about 1 to 1.5 mol. As the solvent, water; alcohol solvents such as methanol, ethanol, isopropyl alcohol, etc.; mixed solvents of water and alcohol solvents (for example, isopropyl alcohol/water (v/v) = 1:1), etc. can be used. The reaction temperature can be any temperature from room temperature to the boiling point of the solvent, preferably 50 to 100°C, and 60 to 90°C. The reaction time is usually about 1 to 48 hours. If it is within the above temperature range, it is preferably about 12 to 36 hours, and preferably about 18 to 24 hours. The reaction gas environment is not particularly limited, but an inert gas environment such as nitrogen is preferred. After the reaction is completed, post-treatment is carried out according to common methods, and purification is performed if necessary, to obtain compound A-1.

在第2階段中，使化合物A-1的苯環甲醯化，合成出化合物A-2。 甲醯化的手段為任意，以使用***或亞硫醯氯等的脫水氯化劑與N,N-二甲基甲醯胺(DMF)，所謂的維爾斯邁爾-哈克反應為適合。 具體而言，在DMF中加入脫水氯化劑，在所調製出的溶液中加入化合物A-1的DMF溶液，加熱攪拌之後，加水使其水解，往化合物A-2反應。 反應溫度以50~100℃左右為佳，60~80℃為較佳。 反應時間通常為1~24小時左右，以1~12小時為佳，1~6小時為較佳。 反應氣體環境並未受到特別限定，可在大氣環境或氮氣等的惰性氣體環境。 反應結束後，依據慣用方法進行後處理，因應必要純化，得到化合物A-2。 In the second step, the benzene ring of compound A-1 is carboxylated to synthesize compound A-2. The method of formadomylation is arbitrary, and the so-called Welsmeier-Hacker reaction using a dehydrating chlorinating agent such as phosphorus oxychloride or thionyl chloride and N,N-dimethylformamide (DMF) is used. for fit. Specifically, a dehydrating chlorinating agent is added to DMF, a DMF solution of compound A-1 is added to the prepared solution, and after heating and stirring, water is added to hydrolyze the mixture, and the mixture is reacted with compound A-2. The reaction temperature is preferably about 50 to 100°C, and preferably 60 to 80°C. The reaction time is usually about 1 to 24 hours, preferably 1 to 12 hours, and preferably 1 to 6 hours. The reaction gas environment is not particularly limited, and may be an atmospheric environment or an inert gas environment such as nitrogen. After the reaction is completed, post-processing is carried out according to common methods, and purification is performed if necessary to obtain compound A-2.

在第3階段中，根據例如Analytical Chemistry, Vol. 89, Issue 20, Pages 11098-11106,2017, DOI: 10.1021/ acs.analchem.7b03229等所記載的反應，使化合物A-2及2-氰基甲基苯并噻唑溶於甲醇等的溶劑之後，在攪拌下加入濃鹽酸等的強酸，加熱使其反應，然後加入醋酸鈉等的弱鹼，進一步進行加熱回流，而得到化合物A-3。 在此反應之中，2-氰基甲基苯并噻唑的使用量，相對於化合物A-2 1mol，以1~2mol為佳，1~1.5mol為較佳，1.1~1.3mol為更佳。 反應溫度以所使用的溶劑回流的溫度為佳。 反應時間通常為1~12小時左右，以1~6小時左右為佳。 反應氣體環境並未受到特別限定，可在大氣環境，或氮氣等的惰性氣體環境。 反應結束後，依據慣用方法進行後處理，因應必要純化，而得到化合物A-3。 In the third stage, compound A-2 and 2-cyano are reacted according to the reaction described in Analytical Chemistry, Vol. 89, Issue 20, Pages 11098-11106, 2017, DOI: 10.1021/acs.analchem.7b03229, etc. After methylbenzothiazole is dissolved in a solvent such as methanol, a strong acid such as concentrated hydrochloric acid is added with stirring, and the mixture is heated to react. Then a weak base such as sodium acetate is added, and the mixture is further heated and refluxed to obtain compound A-3. In this reaction, the amount of 2-cyanomethylbenzothiazole used is preferably 1 to 2 mol, preferably 1 to 1.5 mol, and even more preferably 1.1 to 1.3 mol relative to 1 mol of compound A-2. The reaction temperature is preferably the reflux temperature of the solvent used. The reaction time is usually about 1 to 12 hours, preferably about 1 to 6 hours. The reaction gas environment is not particularly limited, and may be an atmospheric environment or an inert gas environment such as nitrogen. After the reaction is completed, post-treatment is carried out according to common methods, and purification is performed if necessary, to obtain compound A-3.

在第4階段中，依據例如Dyes and Pigments, Vol. 51, Issues2-3, Pages153-159, 2001等所記載的反應，將化合物A-3與氯磺酸加熱，使其反應，將所產生的生成物以水洗淨，然後加入水與二丁胺，進一步使其反應，而得到由式(1A)所表示的香豆素衍生物。 在此反應之中，氯磺酸的使用量，相對於化合物A-3 1mol，以1.5~3mol為佳，2~2.5mol為較佳。 另外，二丁胺的使用量，相對於化合物A-3 1mol，以1~3mol為佳，1.5~2mol為較佳。 氯磺酸在反應中的反應溫度以50~180℃為佳，80~150℃為較佳，100~140℃為更佳，反應時間通常為1~12小時左右，以2~6小時左右為佳。 二丁胺在反應中的反應溫度以10~50℃為佳，15~40℃為較佳，20~30℃為更佳，反應時間通常為0.5~12小時左右，以1~4小時左右為佳。 反應氣體環境並未受到特別限定，可在大氣環境或氮氣等的惰性氣體環境。 反應結束後，依據慣用方法進行後處理，純化，得到由式(1A)所表示的香豆素衍生物。 In the fourth stage, compound A-3 and chlorosulfonic acid are heated and reacted according to the reaction described in, for example, Dyes and Pigments, Vol. 51, Issues2-3, Pages153-159, 2001, and the resulting The product is washed with water, and then water and dibutylamine are added and further reacted to obtain a coumarin derivative represented by formula (1A). In this reaction, the amount of chlorosulfonic acid used is preferably 1.5 to 3 mol, and 2 to 2.5 mol is preferred relative to 1 mol of compound A-3. In addition, the usage amount of dibutylamine is preferably 1 to 3 mol, and more preferably 1.5 to 2 mol relative to 1 mol of compound A-3. The reaction temperature of chlorosulfonic acid in the reaction is preferably 50~180℃, 80~150℃ is better, and 100~140℃ is even better. The reaction time is usually about 1~12 hours, preferably about 2~6 hours. good. The reaction temperature of dibutylamine in the reaction is preferably 10~50℃, 15~40℃ is better, and 20~30℃ is even better. The reaction time is usually about 0.5~12 hours, preferably about 1~4 hours. good. The reaction gas environment is not particularly limited, and may be an atmospheric environment or an inert gas environment such as nitrogen. After the reaction is completed, post-treatment and purification are performed according to conventional methods to obtain the coumarin derivative represented by formula (1A).

上述萘并磷唑氧化物衍生物的具體例子，可列舉由下述式(1B)所表示的萘并磷唑氧化物衍生物。Specific examples of the naphthophosphorus azole oxide derivative include a naphthophosphorus azole oxide derivative represented by the following formula (1B).

上述吡咯次甲基衍生物的具體例子，可列舉由下述式(1C)所表示的吡咯次甲基衍生物。Specific examples of the pyrromethine derivative include a pyrromethine derivative represented by the following formula (1C).

上述苝衍生物的具體例子，可列舉由下述式(1D)所表示的苝衍生物。Specific examples of the perylene derivative include a perylene derivative represented by the following formula (1D).

上述(A)螢光體的含量，若考慮所得到的波長轉換膜的波長轉換效率，則以在固體成分中占0.1~10質量%為佳，0.2~7質量%為較佳，0.3~5質量%為更佳。The content of the above (A) phosphor, considering the wavelength conversion efficiency of the obtained wavelength conversion film, is preferably 0.1 to 10 mass % in the solid content, more preferably 0.2 to 7 mass %, and 0.3 to 5 mass %. Quality % is better.

上述(B)氧化鈦粒子是作為光散射粒子來摻合。氧化鈦粒子並不受特別限制，例如只要由過去被使用在波長轉換材料的氧化鈦粒子適當地選擇即可。 一般而言，已知藉由在顯示器用波長轉換膜形成用組成物中摻合光散射粒子，進入波長轉換膜的光線在膜中的光路長會增加，在波長轉換膜內部波長被轉換的機會增加，結果波長轉換效率會提升，另外，藉由在波長轉換膜界面的反射，回到膜內部的光線會再度散射，結果光取出效率會提升。 The titanium oxide particles (B) mentioned above are blended as light scattering particles. The titanium oxide particles are not particularly limited, and may be appropriately selected from titanium oxide particles that have been used in wavelength conversion materials in the past. Generally speaking, it is known that by blending light scattering particles into a composition for forming a wavelength conversion film for a display, the optical path length of the light entering the wavelength conversion film will be increased in the film, and the chance of the wavelength being converted inside the wavelength conversion film will be increased. As a result, the wavelength conversion efficiency will be improved. In addition, through reflection at the wavelength conversion film interface, the light returned to the inside of the film will be scattered again, resulting in an increase in light extraction efficiency.

氧化鈦粒子可使用銳鈦礦型、金紅石型之任一者，若考慮365nm的紫外光穿透率，則金紅石型氧化鈦的穿透率較高，故較為適合。As titanium oxide particles, either anatase type or rutile type can be used. Considering the ultraviolet light transmittance at 365 nm, rutile type titanium oxide has a higher transmittance and is therefore more suitable.

氧化鈦粒子亦可使用實施表面處理的粒子，在本發明中，若考慮組成物的保存安定性，則以不實施表面處理為佳。 在進行表面處理的情況，表面處理的具體的材料，可列舉氧化矽或氧化鋯等的異種無機氧化物、氫氧化鋁等的金屬氫氧化物、有機矽氧烷、硬脂酸等的有機酸等。這些表面處理材可單獨使用一種，或將多種組合使用。 The titanium oxide particles may be surface-treated. In the present invention, in consideration of the storage stability of the composition, it is preferable not to undergo surface treatment. When surface treatment is performed, specific materials for surface treatment include dissimilar inorganic oxides such as silicon oxide or zirconium oxide, metal hydroxides such as aluminum hydroxide, organic acids such as organosiloxane, and stearic acid. wait. These surface treatment materials can be used individually by 1 type, or in combination of multiple types.

氧化鈦粒子的平均粒徑為超過50nm~未達200nm。平均粒徑的下限，從波長轉換效率的觀點看來，以60nm以上為佳，70nm以上為較佳。從波長轉換效率的觀點加上若考慮圖型化特性，則i射線(365nm)的總光線反射率低的觀點看來，以超過100nm的平均粒徑為較佳。平均粒徑的上限，從保存安定性的觀點看來，以190nm以下為佳，180nm以下為較佳。此外，在本說明書之中，平均粒徑是藉由穿透式電子顯微鏡觀察所測得的粒徑，動態光散射粒徑是利用動態光散射法進行的體積基準粒度分佈測定中累積頻率分佈為50%時的粒徑(中位粒徑D ₅₀)。 The average particle size of titanium oxide particles ranges from more than 50 nm to less than 200 nm. From the viewpoint of wavelength conversion efficiency, the lower limit of the average particle diameter is preferably 60 nm or more, and more preferably 70 nm or more. From the viewpoint of wavelength conversion efficiency and the low total light reflectance of i-rays (365 nm) when patterning properties are taken into consideration, an average particle diameter exceeding 100 nm is preferred. From the viewpoint of storage stability, the upper limit of the average particle size is preferably 190 nm or less, and more preferably 180 nm or less. In addition, in this specification, the average particle size is the particle size measured by transmission electron microscopy observation, and the dynamic light scattering particle size is the cumulative frequency distribution in the volume-based particle size distribution measurement using the dynamic light scattering method. Particle size at 50% (median particle size D ₅₀ ).

氧化鈦粒子可使用市售品，其具體例子，可列舉PT-401M(金紅石型、平均粒徑70nm)、PT-401L(金紅石型、平均粒徑130nm)、PT-501R(金紅石型、平均粒徑180nm)等，但是並不受這些例子限定。此外，所例示的氧化鈦粒子的平均粒徑可能會有±10nm的變動。Commercially available titanium oxide particles can be used. Specific examples thereof include PT-401M (rutile type, average particle diameter: 70 nm), PT-401L (rutile type, average particle diameter: 130 nm), and PT-501R (rutile type). , average particle diameter 180 nm), etc., but are not limited to these examples. In addition, the average particle diameter of the titanium oxide particles illustrated may vary by ±10 nm.

上述(B)氧化鈦粒子的含量，若考慮波長轉換效率與保存安定性，則以在固體成分中占0.1~20質量%為佳，0.2~15質量%為較佳，0.3~10質量%為更佳，3~10質量%為更佳。The content of the titanium oxide particles (B) mentioned above, considering wavelength conversion efficiency and storage stability, is preferably 0.1 to 20 mass % in the solid content, more preferably 0.2 to 15 mass %, and 0.3 to 10 mass %. More preferably, 3 to 10% by mass is more preferably.

上述(C)黏結劑，只要由顯示器用波長轉換膜形成用組成物當中作為黏結劑使用的周知樹脂等選擇即可。The above-mentioned (C) binder may be selected from well-known resins used as binders in the composition for forming a wavelength conversion film for displays.

樹脂可由被利用作為顯示器用波長轉換膜形成用組成物的基底樹脂的樹脂適當地選擇使用，可列舉例如聚苯乙烯(PS)、聚乙烯(PE)、聚丙烯(PP)、聚甲基戊烯等的聚烯烴樹脂；聚甲基甲基丙烯酸酯(PMMA)、甲基丙烯酸甲酯-甲基丙烯酸共聚物、甲基丙烯酸苄基-甲基丙烯酸共聚物等的丙烯酸系樹脂、乙烯-醋酸乙烯酯共聚物(EVA)；聚乙烯基丁酸酯(PVB)；三乙醯基纖維素(TAC)、硝基纖維素等的纖維素酯樹脂等。 這些之中以丙烯酸系樹脂為佳，甲基丙烯酸甲酯-甲基丙烯酸共聚物為較佳。 上述各樹脂可使用市售品，或可使用依據使用聚合起始劑的自由基聚合等的慣用方法所合成出的樹脂。 The resin can be appropriately selected and used from a resin used as a base resin of a composition for forming a wavelength conversion film for a display, and examples thereof include polystyrene (PS), polyethylene (PE), polypropylene (PP), and polymethylpentane. Polyolefin resins such as polyethylene; acrylic resins such as polymethyl methacrylate (PMMA), methyl methacrylate-methacrylic acid copolymer, benzyl methacrylate-methacrylic acid copolymer, ethylene-acetic acid Vinyl ester copolymer (EVA); polyvinyl butyrate (PVB); cellulose ester resins such as triacetyl cellulose (TAC), nitrocellulose, etc. Among these, acrylic resin is preferred, and methyl methacrylate-methacrylic acid copolymer is preferred. As each of the above-mentioned resins, a commercially available product may be used, or a resin synthesized by a conventional method such as radical polymerization using a polymerization initiator may be used.

上述樹脂的平均分子量並不受特別限制，其重量平均分子量(Mw)通常為5,000~100,000，宜為10,000~ 50,000。 此外，平均分子量是由凝膠滲透層析所得到的聚苯乙烯換算值。 The average molecular weight of the above-mentioned resin is not particularly limited, and its weight average molecular weight (Mw) is usually 5,000 to 100,000, preferably 10,000 to 50,000. In addition, the average molecular weight is a polystyrene-converted value obtained by gel permeation chromatography.

作為上述(C)黏結劑，亦可將聚合性單體與光聚合起始劑摻合，在製膜後使其聚合。這些可與上述樹脂併用。 上述聚合性單體可與光聚合起始劑一起使用，只要是藉由光線的照射而聚合的單體，則不受特別限定，以乙烯性不飽和單體為佳。在本發明中，上述乙烯性不飽和單體，可使用單官能單體、二官能單體及三官能以上的單體之任一者。 As the above-mentioned (C) binder, a polymerizable monomer and a photopolymerization initiator may be blended and polymerized after film formation. These can be used together with the above-mentioned resin. The above-mentioned polymerizable monomer can be used together with a photopolymerization initiator, and is not particularly limited as long as it is a monomer that polymerizes by irradiation with light, but an ethylenically unsaturated monomer is preferred. In the present invention, any of a monofunctional monomer, a difunctional monomer, and a trifunctional or higher monomer can be used as the ethylenically unsaturated monomer.

單官能單體，可列舉例如由下述式(M1)所表示的單(甲基)丙烯酸酯。Examples of the monofunctional monomer include mono(meth)acrylate represented by the following formula (M1).

式(M1)之中，R ^m1表示氫原子或甲基，R ^m2表示一價烴基(但是，包含乙烯性不飽和基者除外)。烴基可為直鏈狀、分支狀或環狀之任一者。從噴墨法的吐出安定性優異的觀點及外部量子效率的提升效果更優異的觀點看來，烴基的碳數宜為7以下。換言之，單官能單體以並非上述式(M1)中的R ^m2為碳數8以上的烴基的單體為佳。烴基亦可經取代，例如，可具有醚鍵。 In the formula (M1), R ^m1 represents a hydrogen atom or a methyl group, and R ^m2 represents a monovalent hydrocarbon group (except those containing an ethylenically unsaturated group). The hydrocarbon group may be linear, branched or cyclic. From the viewpoint of excellent discharge stability in the inkjet method and a more excellent improvement effect of external quantum efficiency, the carbon number of the hydrocarbon group is preferably 7 or less. In other words, the monofunctional monomer is preferably a monomer in which R ^m2 in the above formula (M1) is not a hydrocarbon group having 8 or more carbon atoms. The hydrocarbyl group may also be substituted, for example, may have an ether bond.

單官能單體的具體例子，可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸壬基苯氧基乙酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸二甲基胺乙酯、(甲基)丙烯酸二乙基胺乙酯、(甲基)丙烯酸乙氧基乙氧基乙酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊烷基酯、(甲基)丙烯酸二環戊烯基酯、(甲基)丙烯酸二環戊烯基氧乙酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯基苄酯、琥珀酸單(2-丙烯醯氧基乙基)、N-[2-(丙烯醯氧基)乙基]酞醯亞胺、N-[2-(丙烯醯氧基)乙基]四氫酞醯亞胺等。這些之中，適合使用(甲基)丙烯酸乙氧基乙氧基乙酯。Specific examples of the monofunctional monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and amyl (meth)acrylate. 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, cetyl (meth)acrylate, Octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxy (meth)acrylate Ethyl ester, nonylphenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, dimethylamineethyl (meth)acrylate, diethylamineethyl (meth)acrylate, ( Ethoxyethoxyethyl methacrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (methyl) Dicyclopentenyloxyethyl acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, tetrahydrofuran methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylate )Benzyl acrylate, phenylbenzyl (meth)acrylate, mono(2-propenyloxyethyl) succinate, N-[2-(acrylyloxy)ethyl]phthalimide, N- [2-(propenyloxy)ethyl]tetrahydrophthaloimide, etc. Among these, ethoxyethoxyethyl (meth)acrylate is suitably used.

單官能單體，從容易提升噴墨法的吐出安定性的觀點看來，以黏度為10,000mPa･s以下，8,000mPa･s以下，5,000mPa･s以下或1,000mPa･s以下的單體為佳。此外，本說明書中，單官能單體等的具有乙烯性不飽和基的單體的黏度，是藉由例如EMS黏度計測得的25℃的黏度。From the viewpoint of easily improving the discharge stability of the inkjet method, the monofunctional monomer has a viscosity of 10,000mPa･s or less, 8,000mPa･s or less, 5,000mPa･s or less, or 1,000mPa･s or less. good. In addition, in this specification, the viscosity of a monomer having an ethylenically unsaturated group such as a monofunctional monomer is the viscosity at 25° C. measured with, for example, an EMS viscometer.

二官能單體，可列舉例如由下述式(M2)所表示的二(甲基)丙烯酸酯。Examples of the difunctional monomer include di(meth)acrylate represented by the following formula (M2).

式(M2)之中，多個R ^m3各自獨立地表示氫原子或甲基，R ^m4表示二價烴基(但是，包含乙烯性不飽和基者除外)。烴基可為直鏈狀、分支狀或環狀之任一者。從吐出安定性優異的觀點及外部量子效率的提升效果較優異的觀點看來，烴基的碳數宜為7以下。烴基亦可經取代，例如，可具有醚鍵。 In the formula (M2), a plurality of R ^m3 each independently represents a hydrogen atom or a methyl group, and R ^m4 represents a divalent hydrocarbon group (except those containing an ethylenically unsaturated group). The hydrocarbon group may be linear, branched or cyclic. From the viewpoint of excellent discharge stability and the excellent improvement effect of external quantum efficiency, the carbon number of the hydrocarbon group is preferably 7 or less. The hydrocarbyl group may also be substituted, for example, may have an ether bond.

二官能單體的具體例子，可列舉1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,5-戊二醇二(甲基)丙烯酸酯、3-甲基-1,5-戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,8-辛二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、羥基特戊酸新戊二醇酯二丙烯酸酯、參(2-羥乙基)異氰尿酸酯的兩個羥基被(甲基)丙烯醯氧基取代而成的二(甲基)丙烯酸酯、1莫耳新戊二醇加成4莫耳以上的環氧乙烷或環氧丙烷所得到的二醇的兩個羥基被(甲基)丙烯醯氧基經取代而成的二(甲基)丙烯酸酯、1莫耳雙酚A加成2莫耳的環氧乙烷或環氧丙烷所得到的二醇的兩個羥基被(甲基)丙烯醯氧基取代而成的二(甲基)丙烯酸酯、1莫耳三羥甲基丙烷加成3莫耳以上的環氧乙烷或環氧丙烷所得到的三醇的兩個羥基被(甲基)丙烯醯氧基經取代而成的二(甲基)丙烯酸酯、1莫耳雙酚A加成4莫耳以上的環氧乙烷或環氧丙烷所得到的二醇的兩個羥基被(甲基)丙烯醯氧基經取代而成的二(甲基)丙烯酸酯等。這些之中，適合使用二丙二醇二(甲基)丙烯酸酯。Specific examples of the difunctional monomer include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,5-pentanediol di(meth)acrylate. acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate Ester, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate (meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol The two hydroxyl groups of di(meth)acrylate, hydroxypivalate neopentyl glycol diacrylate, and ginseng (2-hydroxyethyl) isocyanurate are replaced by (meth)acryloxy groups. The two hydroxyl groups of the diol obtained by adding more than 4 moles of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol and di(meth)acrylate are replaced by (meth)acryloxy groups. Substituted di(meth)acrylate, 1 mole of bisphenol A is added to 2 moles of ethylene oxide or propylene oxide, and the two hydroxyl groups of the diol are replaced by (meth)acryloxy groups. The two hydroxyl groups of the triol obtained by adding 1 mole of substituted di(meth)acrylate and 1 mole of trimethylolpropane to more than 3 moles of ethylene oxide or propylene oxide are replaced by (meth)propylene. The two hydroxyl groups of the diol obtained by adding more than 4 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A are di(meth)acrylates with substituted acyloxy groups. ) Di(meth)acrylate with substituted acryloxy group, etc. Among these, dipropylene glycol di(meth)acrylate is suitably used.

二官能單體，從容易提升噴墨法的吐出安定性的觀點看來，以黏度為10,000mPa･s以下，5,000mPa･s以下或1,000mPa･s以下的單體為佳。上述黏度是25℃的黏度。From the viewpoint of easily improving the discharge stability of the inkjet method, the bifunctional monomer is preferably a monomer with a viscosity of 10,000mPa･s or less, 5,000mPa･s or less, or 1,000mPa･s or less. The above viscosity is the viscosity at 25°C.

三官能單體，可列舉例如由下述式(M3)所表示的三(甲基)丙烯酸酯。Examples of the trifunctional monomer include tri(meth)acrylate represented by the following formula (M3).

式(M3)之中，多個R ^m5各自獨立地表示氫原子或甲基，R ^m6表示三價烴基(但是，包含乙烯性不飽和基者除外)。烴基可為直鏈狀、分支狀或環狀之任一者。從吐出安定性優異的觀點及外部量子效率的提升效果更優異的觀點看來，烴基的碳數宜為4以下。烴基亦可經取代，例如，可具有醚鍵。 In the formula (M3), a plurality of R ^m5 each independently represents a hydrogen atom or a methyl group, and R ^m6 represents a trivalent hydrocarbon group (except those containing an ethylenically unsaturated group). The hydrocarbon group may be linear, branched or cyclic. From the viewpoint of excellent discharge stability and a more excellent improvement effect on external quantum efficiency, the number of carbon atoms in the hydrocarbon group is preferably 4 or less. The hydrocarbyl group may also be substituted, for example, may have an ether bond.

三官能單體的具體例子，可列舉甘油三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯等。這些之中，適合使用甘油三(甲基)丙烯酸酯。Specific examples of the trifunctional monomer include glycerol tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and the like. Among these, glyceryl tri(meth)acrylate is suitably used.

三官能單體，從容易提升噴墨法的吐出安定性的觀點看來，以黏度為10,000mPa･s以下，5,000mPa･s以下或1,000mPa･s以下的單體為佳。上述黏度是25℃的黏度。From the viewpoint of easily improving the discharge stability of the inkjet method, the trifunctional monomer is preferably a monomer with a viscosity of 10,000mPa･s or less, 5,000mPa･s or less, or 1,000mPa･s or less. The above viscosity is the viscosity at 25°C.

光聚合起始劑可使用光自由基聚合起始劑、光陽離子聚合起始劑等。若考慮波長轉換構件在一般製造方法的適合性，則以使用光自由基聚合性化合物為佳，從硬化程序中不會接受到氧阻礙，可形成畫素部(墨水組成物的硬化物)的觀點看來，以使用光陽離子聚合性化合物為佳。As the photopolymerization initiator, a photoradical polymerization initiator, a photocationic polymerization initiator, etc. can be used. Considering the suitability of the wavelength conversion member for general manufacturing methods, it is better to use a photoradically polymerizable compound, which does not receive oxygen hindrance from the curing process and can form the pixel portion (cured product of the ink composition). From this viewpoint, it is preferable to use a photocationically polymerizable compound.

光自由基聚合起始劑適合使用分子裂解型或奪氫型的光自由基聚合起始劑。As the photoradical polymerization initiator, a molecular cleavage type or hydrogen abstraction type photoradical polymerization initiator is suitably used.

分子裂解型光自由基聚合起始劑，可列舉例如安息香異丁醚、2,4-二乙基噻噸酮、2-異丙基噻噸酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、苯基(2,4,6-三甲基苯甲醯基)膦酸乙酯、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁-1-酮、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、(2,4,6-三甲基苯甲醯基)乙氧基苯基氧化膦。這些之外的分子裂解型光自由基聚合起始劑，亦可併用例如1-羥基環己基苯酮、安息香乙基醚、苄基二甲基縮酮、2-羥基-2-甲基-1-苯基丙-1-酮、2,2-二甲氧基-1,2-二苯基乙-1-酮、2,2-二甲氧基-2-苯基苯乙酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙-1-酮、2-甲基-1-(4-甲硫基苯基)-2-嗎啉基丙-1-酮。Examples of molecular cleavage type photoradical polymerization initiators include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2,4,6-trimethylbenzyl Ethyl diphenylphosphine oxide, phenyl(2,4,6-trimethylbenzoyl)phosphonate, 2-benzyl-2-dimethylamino-1-(4-morpholine phenyl)-butan-1-one, bis(2,6-dimethoxybenzyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-tri Toluyl)phenylphosphine oxide, (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide. Other than these molecular cleavage type photoradical polymerization initiators, for example, 1-hydroxycyclohexylbenzophenone, benzoin ethyl ether, benzyldimethyl ketal, 2-hydroxy-2-methyl-1 can also be used in combination. -Phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 1- (4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1- ketone.

奪氫型的光自由基聚合起始劑，可列舉例如二苯酮、4-苯基二苯酮、間二(苯甲醯基)苯、4-苯甲醯基-4'-甲基-二苯基硫醚。亦可併用分子裂解型光自由基聚合起始劑與奪氫型光自由基聚合起始劑。Examples of the hydrogen abstraction type photoradical polymerization initiator include benzophenone, 4-phenylbenzophenone, m-bis(benzoyl)benzene, and 4-benzoyl-4'-methyl- Diphenyl sulfide. A molecular cleavage type photoradical polymerization initiator and a hydrogen abstraction type photoradical polymerization initiator may be used in combination.

光自由基聚合起始劑也能夠以市售品的形式取得。這樣的市售品，可列舉IGM resin公司製的Omnirad (註冊商標，以下同樣)TPO-H、Omnirad TPO-L、Omnirad 819等的醯基氧化膦化合物；Omnirad 651、Omnirad 184、Omnirad 1173、Omnirad 2959、Omnirad 127、Omnirad 907、Omnirad 369、Omnirad 369E、Omnirad 379EG等的烷基苯酮系化合物；Omnirad MBF、「Omnirad 754」等的分子內奪氫型化合物；BASF Japan公司製的Irgacure(註冊商標，以下同樣)OXE01、Irgacure OXE02、Irgacure OXE03、Irgacure OXE04、常州強力電子新材料公司製的TR-PBG-304、TR-PBG-305、ADEKA股份有限公司製的NCI-831、NCI-930等的肟酯系化合物。Photoradical polymerization initiators are also available as commercial products. Examples of such commercially available products include acylphosphine oxide compounds such as Omnirad (registered trademark, the same applies below) manufactured by IGM Resin Co., Ltd., Omnirad TPO-L, and Omnirad 819; Omnirad 651, Omnirad 184, Omnirad 1173, and Omnirad Alkylphenone compounds such as 2959, Omnirad 127, Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG; intramolecular hydrogen abstraction type compounds such as Omnirad MBF and "Omnirad 754"; Irgacure (registered trademark) manufactured by BASF Japan , the same below) OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04, TR-PBG-304, TR-PBG-305 made by Changzhou Qianli Electronic New Materials Co., Ltd., NCI-831, NCI-930 made by ADEKA Co., Ltd., etc. Oxime ester compounds.

肟酯系化合物除了這些之外，還可列舉例如日本特表2004-534797號公報所記載的化合物、日本特開2000-80068號公報所記載的化合物、國際公開第2012/ 45736號所記載的化合物、國際公開第2015/36910號所記載的化合物、日本特開2006-36750號公報所記載的化合物、日本特開2008-179611號公報所記載的化合物、國際公開第2009/131189號所記載的化合物、日本特表2012-526185號公報所記載的化合物、日本特表2012-519191號公報所記載的化合物、國際公開第2006/18973號所記載的化合物、國際公開第2008/78678號所記載的化合物、日本特開2011-132215號公報所記載的化合物等的肟酯化合物。In addition to these, examples of the oxime ester compound include compounds described in Japanese Patent Application Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2000-80068, and compounds described in International Publication No. 2012/45736. , compounds described in International Publication No. 2015/36910, compounds described in Japanese Patent Application Publication No. 2006-36750, compounds described in Japanese Patent Application Publication No. 2008-179611, compounds described in International Publication No. 2009/131189 , Compounds described in Japanese Patent Application Publication No. 2012-526185, Compounds described in Japanese Patent Application Publication No. 2012-519191, Compounds described in International Publication No. 2006/18973, Compounds described in International Publication No. 2008/78678 , oxime ester compounds such as the compounds described in Japanese Patent Application Laid-Open No. 2011-132215.

光陽離子聚合起始劑，可列舉三苯基鋶六氟銻酸鹽、三苯基鋶六氟磷酸鹽等的多芳香基鋶鹽；二苯基錪鎓六氟銻酸鹽、對壬基苯基錪鎓六氟銻酸鹽等的多芳香基錪鎓鹽等。Photocationic polymerization initiators include polyaromatic sulfonium salts such as triphenylsulfonium hexafluoroantimonate and triphenylsulfonium hexafluorophosphate; diphenyllonium hexafluoroantimonate and p-nonylbenzene Polyaromatic iodonium salts such as iodonium hexafluoroantimonate and the like.

光陽離子聚合起始劑也能夠以市售品的形式取得。這樣的市售品，可列舉San Apro股份有限公司製的CPI-100P、IGM resin公司製的Omnicat(註冊商標。以下同樣。) 270、BASF Japan公司製的Irgacure 290等的鋶鹽系光陽離子聚合起始劑；IGM resin公司製的Omnicat 250等的錪鎓鹽系光陽離子聚合起始劑等。Photocationic polymerization initiators are also available as commercial products. Examples of such commercially available products include sulfonium salt-based photocationic polymerization products such as CPI-100P manufactured by San Apro Co., Ltd., Omnicat (registered trademark. The same applies below) 270 manufactured by IGM Resin Co., Ltd., and Irgacure 290 manufactured by BASF Japan. Initiator: IGM resin company's Omnicat 250 and other photocationic polymerization initiators such as ionium salts.

上述光聚合起始劑的含量，從組成物的硬化性的觀點看來，相對於聚合性單體100質量%，以0.1質量%以上為佳，0.5質量%以上為較佳，1質量%為更佳。另外，其含量的上限，從組成物的保存安定性的觀點看來，以40質量%以下為佳，30質量%以下為較佳，20質量%以下為更佳。From the viewpoint of the curability of the composition, the content of the photopolymerization initiator is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and 1 mass% based on 100 mass% of the polymerizable monomer. Better. In addition, from the viewpoint of the storage stability of the composition, the upper limit of the content is preferably 40 mass% or less, more preferably 30 mass% or less, and more preferably 20 mass% or less.

上述(C)黏結劑的含量，以在固體成分中占70~99.8質量%為佳，85~99.8質量%為較佳，90~99質量%為更佳。The content of the above-mentioned (C) binder is preferably 70 to 99.8 mass% in the solid content, more preferably 85 to 99.8 mass%, and more preferably 90 to 99 mass%.

另外，本發明之顯示器用波長轉換膜形成用組成物，除了上述(A)~(C)成分之外，還可因應必要包含光安定劑、抗氧化劑、界面活性劑、阻燃劑、透明化劑、紫外線吸收劑、交聯劑、填充劑等周知的各種添加劑。 界面活性劑以氟系界面活性劑為佳，非離子性氟系界面活性劑為較佳。 其具體例子，可列舉Neos股份有限公司製的FTERGENT系列、212M、215M、250、222F、FTX-218、DFX-18等，但並不受這些例子限定。 在使用界面活性劑的情況，其摻合量並無特別限制，以在顯示器用波長轉換膜形成用組成物的固體成分中占0.01~1質量%為佳，0.01~0.5質量%為較佳。 In addition, the composition for forming a wavelength conversion film for a display of the present invention may, in addition to the above-mentioned components (A) to (C), also contain a light stabilizer, an antioxidant, a surfactant, a flame retardant, and a translucent agent as necessary. Agents, UV absorbers, cross-linking agents, fillers and other well-known additives. As the surfactant, a fluorine-based surfactant is preferred, and a nonionic fluorine-based surfactant is preferred. Specific examples include FTERGENT series manufactured by Neos Co., Ltd., 212M, 215M, 250, 222F, FTX-218, DFX-18, etc., but are not limited to these examples. When a surfactant is used, its blending amount is not particularly limited, but it is preferably 0.01 to 1 mass %, and more preferably 0.01 to 0.5 mass % of the solid content of the wavelength conversion film forming composition for displays.

此外，本發明之顯示器用波長轉換膜形成用組成物亦可因應必要包含溶劑。其具體例子，可列舉苯、甲苯、二甲苯、乙苯、氯苯等的芳香族或鹵化芳香族烴溶劑；正庚烷、正己烷、環己烷等的脂肪族烴類；二***、四氫呋喃、二噁烷、1,2-二甲氧基乙烷等的醚系溶劑；丙酮、甲基乙基酮、甲基異丁基酮、環己酮、環戊酮等的酮系溶劑；醋酸乙酯、醋酸正己酯、乳酸乙酯、γ-丁內酯、碳酸伸丙酯、丙二酸二異丙酯等的酯系溶劑；二氯甲烷、二氯甲烷、1,2-二氯乙烷、氯仿等的鹵化烴溶劑；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、1,3-二甲基-2-咪唑啉酮等的醯胺系溶劑；甲醇、乙醇、異丙醇、正丙醇、環己醇、二丙酮醇、2-苄氧基乙醇等的醇系溶劑；乙二醇單***、乙二醇單丁醚、乙二醇二縮水甘油醚、丙二醇單甲醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇二***、二乙二醇二甲醚、三乙二醇二甲醚、三乙二醇單丁醚、二乙二醇單***醋酸酯、二乙二醇單丁醚醋酸酯、二丙二醇單甲醚、丙二醇單甲醚醋酸酯等的二醇醚系溶劑；乙二醇、丙二醇、己二醇、3-辛二醇、二乙二醇、二丙二醇、三乙二醇、三丙二醇、1,3-丁二醇、2,3-丁二醇、1,4-丁二醇等的二醇系溶劑等的有機溶劑，這些可單獨使用一種，或將兩種以上組合使用。In addition, the composition for forming a wavelength conversion film for a display of the present invention may also contain a solvent if necessary. Specific examples thereof include aromatic or halogenated aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and chlorobenzene; aliphatic hydrocarbons such as n-heptane, n-hexane and cyclohexane; diethyl ether and tetrahydrofuran. , dioxane, 1,2-dimethoxyethane and other ether solvents; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone and other ketone solvents; acetic acid Ester solvents such as ethyl ester, n-hexyl acetate, ethyl lactate, γ-butyrolactone, propyl carbonate, diisopropyl malonate, etc.; dichloromethane, dichloromethane, 1,2-dichloroethyl Halogenated hydrocarbon solvents such as alkane and chloroform; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2- Amide solvents such as imidazolinone; alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-propanol, cyclohexanol, diacetone alcohol, 2-benzyloxyethanol, etc.; ethylene glycol monoethyl ether, ethylene glycol Alcohol monobutyl ether, ethylene glycol diglycidyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethyl Glycol ethers such as glycol dimethyl ether, triethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc. Solvents; ethylene glycol, propylene glycol, hexylene glycol, 3-octanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol , organic solvents such as glycol solvents such as 1,4-butanediol, etc. These may be used singly or in combination of two or more.

在顯示器用波長轉換膜形成用組成物包含溶劑的情況，顯示器用波長轉換膜形成用組成物的固體成分濃度會隨著目標的波長轉換膜的厚度或塗佈方法等而變動，因此無法一概而定，通常為10~70質量%，宜為20~60質量%。When the composition for forming a wavelength conversion film for a display contains a solvent, the solid content concentration of the composition for forming a wavelength conversion film for a display changes depending on the thickness of the target wavelength conversion film or the coating method, etc., so it cannot be determined uniformly. It is determined, usually 10~70% by mass, preferably 20~60% by mass.

上述顯示器用波長轉換膜形成用組成物的25℃的黏度的上限為10,000mPa･s以下，以1,000mPa･s以下為佳。若考慮保存安定性，則下限以5mPa･s以上為佳，10mPa･s以上為較佳。 此外，在本發明中，黏度意指利用EMS黏度計得到的測定值。 The upper limit of the viscosity at 25°C of the wavelength conversion film-forming composition for a display is 10,000 mPa･s or less, preferably 1,000 mPa･s or less. If storage stability is taken into consideration, the lower limit is preferably 5mPa･s or more, and 10mPa･s or more is preferably the lower limit. In addition, in the present invention, viscosity means a measured value obtained by an EMS viscometer.

本發明之顯示器用波長轉換膜形成用組成物，可將上述(A)~(C)成分、因應必要使用的界面活性劑等的其他添加劑及溶劑以任意順序混合來調製。The composition for forming a wavelength conversion film for a display of the present invention can be prepared by mixing the above components (A) to (C), other additives such as surfactants and solvents used as necessary, and solvents in any order.

將上述本發明之顯示器用波長轉換膜形成用組成物塗佈於例如基材上，因應必要藉由加熱等使溶劑蒸發，進一步因應必要進行活性能量射線(例如紫外光)的照射，可得到波長轉換膜。 塗佈方法，可列舉例如利用逆輥式塗佈機、刮刀式塗佈機、狹縫模具塗佈機、直接凹版塗佈機、平凹版塗佈機、吻合塗佈機、自然輥塗佈機、氣刀式塗佈機、輥刮刀塗佈機、可調刮棒輥刮刀塗佈機、雙流塗佈機、桿式塗佈機、線棒式塗佈機、施膠機、浸漬塗佈機、簾幕式塗佈機、旋轉塗佈機、刀式塗佈機、噴墨等的方法。 The above-mentioned composition for forming a wavelength conversion film for a display of the present invention is coated on, for example, a substrate, the solvent is evaporated by heating or the like as necessary, and further irradiation with active energy rays (such as ultraviolet light) is performed as necessary to obtain the wavelength. conversion film. Examples of coating methods include reverse roll coaters, blade coaters, slot die coaters, direct gravure coaters, flat gravure coaters, kiss coaters, and natural roll coaters. , air knife coater, roller blade coater, adjustable rod roller blade coater, two-flow coater, rod coater, wire rod coater, sizing machine, dip coater , curtain coater, spin coater, knife coater, inkjet and other methods.

加熱可使用例如烘箱或熱板等一般的加熱裝置來進行。 加熱條件，只要能夠形成膜，則並無特別限制，以在60~200℃下加熱5分鐘~2小時為佳，在80~200℃下加熱15分鐘~1小時為較佳。此外還可階段性加熱硬化。 Heating can be performed using a general heating device such as an oven or a hot plate. The heating conditions are not particularly limited as long as a film can be formed, but heating at 60 to 200°C for 5 minutes to 2 hours is preferred, and heating at 80 to 200°C for 15 minutes to 1 hour is preferred. In addition, it can be heated and hardened in stages.

紫外光的照射，只要能夠形成膜，則並無特別限制，使用水銀燈、金屬鹵素燈、氙燈、LED等的光源，並且因應必要組合帶通濾光片，即可照射出將目標曝光波長以外的光除去後的光線。所照射的光線的波長以200~440nm為佳，含波長300~400nm的光線為特佳。曝光量以10~4,000mJ/cm ²為佳。 There are no particular restrictions on the irradiation of ultraviolet light as long as it can form a film. Use light sources such as mercury lamps, metal halide lamps, xenon lamps, LEDs, etc., and combine band-pass filters as necessary to irradiate light beyond the target exposure wavelength. Light after light removal. The wavelength of the irradiated light is preferably 200~440nm, and light with a wavelength of 300~400nm is particularly suitable. The optimal exposure level is 10~4,000mJ/ ^cm2 .

前述加熱步驟與紫外光的曝光步驟能夠以任意順序組合進行。例如可在進行加熱之後進行紫外光的照射，或在進行紫外光的照射之後進行加熱，或在進行加熱之後進行紫外光的照射，然後進一步進行加熱。The aforementioned heating step and ultraviolet light exposure step can be combined in any order. For example, heating may be followed by irradiation with ultraviolet light, or irradiation with ultraviolet light may be followed by heating, or heating may be followed by irradiation with ultraviolet light and then further heating.

波長轉換膜的厚度並無特別限制，通常為1~1,000μm，宜為3~500μm，較佳為5~100μm。 波長轉換膜的霧度值並不受特別限制，從藉由使入射光在膜內散射來增加螢光體可吸收的光量的觀點看來，宜為18%以上，較佳為30%以上，較佳為40%以上。霧度值的上限並未受到特別限定，通常為95%左右。此外，在本發明中，霧度值是依據ASTM D1003-61所測得的值。另外，在本發明中，上述霧度值的測定條件，可列舉例如對於由氧化鈦粒子含量定為3.16~4.74質量%的組成物所形成的膜厚6μm的膜進行測定的條件。 The thickness of the wavelength conversion film is not particularly limited, but is usually 1 to 1,000 μm, preferably 3 to 500 μm, and more preferably 5 to 100 μm. The haze value of the wavelength conversion film is not particularly limited, but from the viewpoint of increasing the amount of light that can be absorbed by the phosphor by scattering incident light in the film, it is preferably 18% or more, and more preferably 30% or more. Preferably it is more than 40%. The upper limit of the haze value is not particularly limited, but is usually around 95%. In addition, in the present invention, the haze value is a value measured according to ASTM D1003-61. In the present invention, the haze value measurement conditions include, for example, conditions for measuring a film with a film thickness of 6 μm formed from a composition having a titanium oxide particle content of 3.16 to 4.74% by mass.

上述基材，只要由作為用來形成這種膜的基底基材使用的基材適當地選擇使用即可，以400~800nm的可見光區光線的穿透率為50%以上的玻璃基板或聚合物板為佳。 玻璃的具體例子，可列舉鈉鈣玻璃、含鋇･鍶的玻璃、鉛玻璃、鋁矽酸玻璃、硼矽酸玻璃、鋇硼矽酸玻璃、石英等。 聚合物的具體例子，可列舉聚碳酸酯、丙烯酸、聚對苯二甲酸乙二酯、聚醚硫醚、聚碸等。 The above-mentioned base material can be appropriately selected from those used as the base material for forming such a film, such as a glass substrate or a polymer with a transmittance of 50% or more in the visible light range of 400 to 800 nm. Board is better. Specific examples of glass include soda-lime glass, barium-strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, and the like. Specific examples of the polymer include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polyethylene, and the like.

藉由本發明的組成物所得到的波長轉換膜，波長轉換效率優異，因此適合作為微LED顯示器、有機EL顯示器、液晶顯示器等的顯示器或照明等的波長轉換膜(色轉換膜)來使用。 [實施例] The wavelength conversion film obtained by the composition of the present invention has excellent wavelength conversion efficiency and is therefore suitable for use as a wavelength conversion film (color conversion film) for displays such as micro-LED displays, organic EL displays, liquid crystal displays, or lighting. [Example]

以下列舉合成例、實施例及比較例更具體地說明本發明，然而本發明並不受下述實施例限定。The present invention will be explained more specifically below with reference to synthesis examples, working examples and comparative examples. However, the present invention is not limited to the following examples.

[分子量測定] 在本實施例之中，聚合物的分子量的測定，裝置是使用日本分光股份有限公司製GPC系統，管柱是使用Shodex (註冊商標)KF-804L及803L，依照下述條件來實施。 管柱烘箱：40℃ 流量：1ml/分鐘 溶離液：四氫呋喃 [Molecular weight determination] In this example, the molecular weight of the polymer was measured using a GPC system manufactured by JASCO Corporation and Shodex (registered trademark) KF-804L and 803L as columns, and was carried out under the following conditions. Column oven: 40℃ Flow rate: 1ml/minute Eluate: Tetrahydrofuran

本實施例所使用的簡寫記號的意思如以下所述。此外，Dye A的 ¹H-NMR的光譜的化學位移如以下所述。測定裝置使用了AVANCE III HD 500MHz(Bruker公司製)。 ¹H NMR(in CDCl ₃):δ/ppm 8.93(1H,s), 8.41(1H,d,J=1.6Hz), 8.05(1H,d,J=8.5Hz), 7.87(1H,dd,J=1.6,8.5Hz), 7.48(1H,d,J= 9.0Hz), 6.67(1H,dd,J=2.3,9.0Hz), 6.54(1H,d,J=2.3Hz), 3.40 (2H,t,J=7.8Hz), 3.24(2H,d,J=7.0Hz), 3.17 (4H,t,J=7.6Hz), 1.76-1.62 (9H,m), 1.52(4H,qui,J=7.8Hz), 1.34-1.16(12H,m), 1.00(2H,q,J=11.1Hz), 0.92(3H,t,J=6.9Hz), 0.92(6H,t,J=7.4 Hz) MMA：甲基丙烯酸甲酯 MAA：甲基丙烯酸 AIBN：α,α'-偶氮雙異丁腈 V#230：VISCOAT #230(1,6-己二醇二丙烯酸酯、大阪有機化學工業股份有限公司製) OXE-02：Irgacure OXE02(BASF公司製) PGME：丙二醇單甲醚 CPN：環戊酮 TTO-55(A)：氧化鈦粒子(金紅石型、平均粒徑50nm、AlOH ₃被覆、石原產業股份有限公司製) PT-401M：氧化鈦粒子(金紅石型、平均粒徑70nm、石原產業股份有限公司製) PT-401L：氧化鈦粒子(金紅石型、平均粒徑130nm、石原產業股份有限公司製) PT-501R：氧化鈦粒子(金紅石型、平均粒徑180nm、石原產業股份有限公司製) CR-EL：氧化鈦粒子(金紅石型、平均粒徑250nm、石原產業股份有限公司製) 光散射性粒子1：氧化鈦粒子(銳鈦礦型、平均粒徑100nm、SiO ₂-SnO ₂被覆) DFX-18：FTERGENT DFX-18(Neos股份有限公司製) The meanings of abbreviations used in this embodiment are as follows. In addition, the chemical shift of the ¹ H-NMR spectrum of Dye A is as follows. The measurement device used was AVANCE III HD 500MHz (manufactured by Bruker Corporation). ¹ H NMR (in CDCl ₃ ): δ/ppm 8.93(1H,s), 8.41(1H,d,J=1.6Hz), 8.05(1H,d,J=8.5Hz), 7.87(1H,dd,J =1.6,8.5Hz), 7.48(1H,d,J= 9.0Hz), 6.67(1H,dd,J=2.3,9.0Hz), 6.54(1H,d,J=2.3Hz), 3.40 (2H,t ,J=7.8Hz), 3.24(2H,d,J=7.0Hz), 3.17 (4H,t,J=7.6Hz), 1.76-1.62 (9H,m), 1.52(4H,qui,J=7.8Hz ), 1.34-1.16(12H,m), 1.00(2H,q,J=11.1Hz), 0.92(3H,t,J=6.9Hz), 0.92(6H,t,J=7.4 Hz) MMA: Methyl Methyl acrylate MAA: Methacrylic acid AIBN: α,α'-azobisisobutyronitrile V#230: VISCOAT #230 (1,6-hexanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) OXE -02: Irgacure OXE02 (manufactured by BASF) PGME: Propylene glycol monomethyl ether CPN: Cyclopentanone TTO-55 (A): Titanium oxide particles (rutile type, average particle diameter 50 nm, AlOH ₃ coating, Ishihara Industrial Co., Ltd. (manufactured by Ishihara Sangyo Co., Ltd.) PT-401M: Titanium oxide particles (rutile type, average particle size: 70 nm, manufactured by Ishihara Sangyo Co., Ltd.) PT-401L: Titanium oxide particles (rutile type, average particle size: 130 nm, manufactured by Ishihara Sangyo Co., Ltd.) PT-501R: Titanium oxide particles (rutile type, average particle diameter: 180 nm, manufactured by Ishihara Sangyo Co., Ltd.) CR-EL: Titanium oxide particles (rutile type, average particle diameter: 250 nm, manufactured by Ishihara Sangyo Co., Ltd.) Light scattering Sexual particles 1: Titanium oxide particles (anatase type, average particle diameter 100 nm, SiO ₂ -SnO ₂ coating) DFX-18: FTERGENT DFX-18 (manufactured by Neos Co., Ltd.)

Dye A：由下述式(1A)所表示的化合物 Dye A: compound represented by the following formula (1A)

Dye B：由下述式(1B)所表示的化合物、C-Naphox-TEG、東京化成工業股份有限公司製 Dye B: compound represented by the following formula (1B), C-Naphox-TEG, manufactured by Tokyo Chemical Industry Co., Ltd.

Dye C：由下述式(1C)所表示的化合物、BDP FL、東京化成工業股份有限公司製 Dye C: compound represented by the following formula (1C), BDP FL, manufactured by Tokyo Chemical Industry Co., Ltd.

Dye D：由下述式(1D)所表示的化合物、FL 305、BASF公司製 Dye D: Compound represented by the following formula (1D), FL 305, manufactured by BASF Corporation

[合成例1]聚合物溶液的調製 將MMA 80.0g、MAA 20.0g、AIBN 2.5g溶解於CPN 190.0g，使其在90℃下反應20小時，而得到丙烯酸聚合物溶液P1(固體成分濃度30質量%)。所得到的丙烯酸聚合物的Mn為9,900、Mw為17,078。 [Synthesis Example 1] Preparation of polymer solution 80.0g of MMA, 20.0g of MAA, and 2.5g of AIBN were dissolved in 190.0g of CPN and reacted at 90° C. for 20 hours to obtain an acrylic polymer solution P1 (solid content concentration: 30% by mass). The obtained acrylic polymer had Mn of 9,900 and Mw of 17,078.

[合成例2]光散射性粒子1的調製 在5升容器中裝入純水1,429.1g，在攪拌下添加35質量%氫氧化四乙基銨水溶液315.6g、甘胺酸39.4g、四異丙氧基鈦213.2g(以TiO ₂換算含有59.9g)。所得到的混合溶液，氫氧化四乙基銨/鈦原子的莫耳比為1.00，甘胺酸/鈦原子的莫耳比為0.70。將該混合溶液在90℃下保持2小時，然後在95℃下保持5小時，而調製出鈦混合溶液。調製出來的鈦混合溶液的pH為11.2，TiO ₂為濃度3.0質量%。在3升的SUS製高壓滅菌釜容器中裝入上述鈦混合溶液1,500g，在150℃下進行水熱處理5小時。冷卻至室溫後，取出的水熱處理後之溶液為乳白色的氧化鈦膠體粒子的水分散液。所得到的分散液，pH為12.2、TiO ₂濃度為3.0質量%、動態光散射粒徑為141nm、在利用穿透式電子顯微鏡(JEM-F200、日本電子股份有限公司製)進行的觀察中，觀察到平均一次粒徑94nm的枕狀粒子。此外，動態光散射法的測定裝置使用了Malvern Instruments Ltd製的Zetasizer。 接下來，將所得到的氧化鈦膠體粒子的水分散液以超過濾裝置進行注水洗淨，將過剩的電解質除去，得到TiO ₂濃度3.0質量%的分散液。以所得到的氧化鈦膠體粒子作為成為核的氧化鈦粒子。 [Synthesis Example 2] Preparation of Light Scattering Particles 1: 1,429.1 g of pure water was put into a 5-liter container, and 315.6 g of a 35 mass% tetraethylammonium hydroxide aqueous solution, 39.4 g of glycine, and tetraisopropyl was added with stirring. 213.2 g of titanium oxide (containing 59.9 g in terms of TiO ₂ ). The obtained mixed solution had a molar ratio of tetraethylammonium hydroxide/titanium atom of 1.00 and a molar ratio of glycine/titanium atom of 0.70. This mixed solution was maintained at 90°C for 2 hours and then at 95°C for 5 hours to prepare a titanium mixed solution. The prepared titanium mixed solution had a pH of 11.2 and a TiO ₂ concentration of 3.0% by mass. 1,500 g of the above titanium mixed solution was put into a 3-liter SUS autoclave container, and hydrothermal treatment was performed at 150° C. for 5 hours. After cooling to room temperature, the solution taken out after hydrothermal treatment is a milky white aqueous dispersion of titanium oxide colloidal particles. The obtained dispersion had a pH of 12.2, a TiO ₂ concentration of 3.0 mass %, and a dynamic light scattering particle diameter of 141 nm. When observed with a transmission electron microscope (JEM-F200, manufactured by JEOL Ltd.), Pillow-shaped particles with an average primary particle size of 94 nm were observed. In addition, a Zetasizer manufactured by Malvern Instruments Ltd. was used as a measuring device for the dynamic light scattering method. Next, the obtained aqueous dispersion of titanium oxide colloidal particles was washed with water using an ultrafiltration device to remove excess electrolyte, thereby obtaining a dispersion with a TiO ₂ concentration of 3.0% by mass. The obtained titanium oxide colloidal particles serve as titanium oxide particles serving as nuclei.

另一方面，將矽酸鈉水溶液(JIS 3號矽酸鈉、以SiO ₂計含有34質量%、富士化學股份有限公司製)27.9g以純水27.9g稀釋之後，添加錫酸鈉三水合物(以SnO ₂計含有55質量%、昭和化工股份有限公司製)8.6g，在攪拌下使其溶解，而得到矽酸-錫酸鈉水溶液。將所得到的矽酸-錫酸鈉水溶液64.4g以純水411g稀釋，讓溶液通過填充了氫型陽離子交換樹脂(AMBERLITE(註冊商標)IR-120B)的管柱，而得到二氧化矽-氧化錫(IV)複合氧化物膠體粒子的水分散液570g。所得到的水分散液pH為2.7、金屬氧化物總濃度為2.5質量%。接下來，在所得到的二氧化矽-氧化錫(IV)複合氧化物膠體粒子的水分散液中添加二異丙基胺2.9g。所得到的分散液為鹼性的二氧化矽-氧化錫(IV)複合氧化物膠體粒子的水分散液，pH為8.2，膠體粒子一次粒徑為5nm以下。將所得到的二氧化矽-氧化錫(IV)複合氧化物膠體粒子定為被覆粒子。 On the other hand, after diluting 27.9 g of sodium silicate aqueous solution (JIS No. 3 sodium silicate, containing 34% by mass as _SiO2 , manufactured by Fuji Chemical Co., Ltd.) with 27.9 g of pure water, sodium stannate trihydrate was added (Containing 55% by mass as SnO ₂ , manufactured by Showa Chemical Co., Ltd.) 8.6 g was dissolved with stirring to obtain a silicic acid-sodium stannate aqueous solution. 64.4 g of the obtained silicic acid-sodium stannate aqueous solution was diluted with 411 g of pure water, and the solution was passed through a column filled with hydrogen-type cation exchange resin (AMBERLITE (registered trademark) IR-120B) to obtain silica-oxidized 570g of aqueous dispersion of tin(IV) complex oxide colloidal particles. The obtained aqueous dispersion had a pH of 2.7 and a total metal oxide concentration of 2.5% by mass. Next, 2.9 g of diisopropylamine was added to the obtained aqueous dispersion of silicon dioxide-tin(IV) oxide composite oxide colloidal particles. The obtained dispersion was an aqueous dispersion of alkaline silicon dioxide-tin(IV) oxide composite oxide colloidal particles, with a pH of 8.2 and a primary particle size of the colloidal particles of 5 nm or less. The obtained silicon dioxide-tin(IV) oxide composite oxide colloidal particles were defined as coated particles.

在前述成為核的氧化鈦粒子的水分散液1,200g中添加所調製出的由二氧化矽-氧化錫(IV)複合氧化物形成的被覆粒子144.0g，然後在溫度95℃下保持2小時，得到變性氧化鈦膠體粒子的水分散液。然後，讓所得到的變性氧化鈦膠體粒子的水分散液通過填充了氫型陽離子交換樹脂(AMBERLITE(註冊商標)IR-120B)的管柱，而得到酸性的變性氧化鈦膠體粒子的水分散液。接下來，將所得到的水分散液裝入附茄型燒瓶的蒸發器，進行濃縮，添加甲醇，同時在590Torr下將水餾除，而得到變性氧化鈦膠體粒子的甲醇分散液129.8g。所得到的甲醇分散液，黏度為1.2mPa･s，pH為6.4(以與分散液同質量的水來稀釋)，固體成分濃度為30.5質量%，水分為0.8質量%，動態光散射粒徑為140nm，在穿透式電子顯微鏡的觀察中，觀察到平均一次粒徑為101nm的枕狀粒子。144.0 g of the prepared coated particles composed of the silicon dioxide-tin(IV) oxide composite oxide were added to 1,200 g of the aqueous dispersion of the titanium oxide particles serving as the nuclei, and then maintained at a temperature of 95° C. for 2 hours. An aqueous dispersion of modified titanium oxide colloidal particles was obtained. Then, the obtained aqueous dispersion of modified titanium oxide colloidal particles was passed through a column filled with hydrogen-type cation exchange resin (AMBERLITE (registered trademark) IR-120B) to obtain an acidic aqueous dispersion of modified titanium oxide colloidal particles. . Next, the obtained aqueous dispersion was placed in an evaporator with an eggplant-shaped flask, and concentrated. Methanol was added and water was distilled off at 590 Torr to obtain 129.8 g of a methanol dispersion of modified titanium oxide colloidal particles. The obtained methanol dispersion had a viscosity of 1.2 mPa･s, a pH of 6.4 (diluted with water of the same mass as the dispersion), a solid content concentration of 30.5 mass%, a water content of 0.8 mass%, and a dynamic light scattering particle size of 140nm, and in transmission electron microscope observation, pillow-shaped particles with an average primary particle size of 101nm were observed.

[實施例1~10、比較例1~9]波長轉換膜形成用組成物的調製及其評估 (1)波長轉換膜形成用組成物的調製 依照表1所示的組成將各成分混合，使用孔徑5.0μm的聚四氟乙烯(PTFE)過濾器，將所得到的混合物過濾，而調製出波長轉換膜形成用組成物。此外，表1及表2中的組成比表示在固體成分中的質量比。 [Examples 1 to 10, Comparative Examples 1 to 9] Preparation of wavelength conversion film forming composition and evaluation thereof (1) Modulation of wavelength conversion film forming composition Each component was mixed according to the composition shown in Table 1, and the resulting mixture was filtered using a polytetrafluoroethylene (PTFE) filter with a pore size of 5.0 μm, to prepare a wavelength conversion film forming composition. In addition, the composition ratio in Table 1 and Table 2 shows the mass ratio in solid content.

(2)評估1：黏度的評估 對於實施例1~10及比較例1~9的波長轉換膜形成用組成物，依照以下所揭示的條件實施測定，將其定為各波長轉換膜形成用組成物的黏度。 裝置：EMS-1000 京都電子工業股份有限公司製 測定溫度：25℃ 探針尺寸：2.0mmΦ 轉速：500rpm 測定時間：5秒鐘 (2) Evaluation 1: Evaluation of viscosity The wavelength conversion film-forming compositions of Examples 1 to 10 and Comparative Examples 1 to 9 were measured according to the conditions disclosed below, and the viscosity of each wavelength conversion film-forming composition was determined. Device: EMS-1000 Made by Kyoto Electronics Industry Co., Ltd. Measuring temperature: 25℃ Probe size: 2.0mmΦ Speed: 500rpm Measurement time: 5 seconds

(3)評估2：膜特性的評估 將實施例1~7、9及10和比較例1、2及4~8的波長轉換膜形成用組成物使用旋轉塗佈機塗佈於石英基板上之後，在110℃熱板上進行預烘120秒鐘，得到膜厚6μm的塗膜試樣。然後，對於實施例1~6、9及比較例1、2、4~6、9的塗膜試樣，在160℃進行後烘60分鐘。對於實施例7、比較例7的塗膜試樣，在120℃進行後烘60分鐘。 將實施例8和比較例3及9之波長轉換膜形成用組成物使用棒式塗佈機塗佈於無鹼玻璃基板上之後，藉由批次式UV照射裝置(高壓水銀燈2kW×1燈)(EyeGraphics股份有限公司製)，以曝光量1000mJ/cm ²將365nm紫外線照射至前述樹脂膜的整個表面，在前述無鹼玻璃基板上形成硬化膜。 對於所得到的塗膜試樣，使用日本電色工業股份有限公司製濁度計NDH5000，以符合ASTM D1003-61的測定方法來測定霧度值。 (3) Evaluation 2: Evaluation of film characteristics After the wavelength conversion film forming compositions of Examples 1 to 7, 9 and 10 and Comparative Examples 1, 2 and 4 to 8 were coated on a quartz substrate using a spin coater , pre-baked on a 110°C hot plate for 120 seconds to obtain a coating sample with a film thickness of 6 μm. Then, the coating film samples of Examples 1 to 6 and 9 and Comparative Examples 1, 2, 4 to 6, and 9 were post-baked at 160° C. for 60 minutes. The coating film samples of Example 7 and Comparative Example 7 were post-baked at 120° C. for 60 minutes. After the wavelength conversion film forming compositions of Example 8 and Comparative Examples 3 and 9 were coated on an alkali-free glass substrate using a rod coater, a batch-type UV irradiation device (high-pressure mercury lamp 2kW × 1 lamp) was used. (Eye Graphics Co., Ltd.), 365 nm ultraviolet rays are irradiated to the entire surface of the resin film at an exposure dose of 1000 mJ/cm ² to form a cured film on the alkali-free glass substrate. The haze value of the obtained coating film sample was measured using a turbidity meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with the measurement method conforming to ASTM D1003-61.

接下來，將塗膜試樣疊在CCS股份有限公司製藍色LED燈(發光峰波長450nm)上，將LED燈點亮，使用Ushio電機股份有限公司製分光放射照度計USR-45測定透過塗膜試樣發出的光，定為結果(1)。 同樣地，測定除去塗膜試樣僅由LED燈發出的光，定為結果(2)。由所得到的分光放射照度光譜，將結果(2)之波長480nm以下的光的光子數定為「激發光光子數」。同樣地，將結果(1)之波長480nm以下的光的光子數定為「透射光光子數」。同樣地，將結果(1)之波長超過480nm的光的光子數定為「發光光子數」。 依照以下的算式，計算出「藍色光吸收率」及「轉換效率」。 藍色光吸收率=(激發光光子數－透射光光子數)÷激發光光子數 轉換效率=發光光子數÷激發光光子數 Next, the coating film sample was stacked on a blue LED lamp (luminescence peak wavelength 450 nm) manufactured by CCS Co., Ltd., the LED lamp was lit, and the transmitted coating was measured using a spectroscopic radiation meter USR-45 manufactured by Ushio Electric Co., Ltd. The light emitted by the film sample is determined as the result (1). Similarly, the light emitted by the LED lamp alone was measured with the coating film removed from the sample, and was determined as the result (2). From the obtained spectral radiation illuminance spectrum, the number of photons of light with a wavelength of 480 nm or less in the result (2) was determined as the "excitation light photon number". Similarly, the number of photons of light with a wavelength of 480 nm or less in the result (1) is defined as the "number of photons of transmitted light". Similarly, the number of photons of light with a wavelength exceeding 480 nm in the result (1) is defined as the "number of luminous photons". Calculate the "blue light absorption rate" and "conversion efficiency" according to the following formulas. Blue light absorption rate = (number of excitation light photons - number of transmitted light photons) ÷ number of excitation light photons Conversion efficiency = number of luminous photons ÷ number of excitation photons

此外，將實施例1~3、9及10和比較例4的塗膜試樣的「轉換效率」除以比較例4的塗膜試樣的「轉換效率」所得到的數值、將實施例4、比較例5的塗膜試樣的「轉換效率」除以比較例5的塗膜試樣的「轉換效率」所得到的數值、將實施例5、比較例6的塗膜試樣的「轉換效率」除以比較例6的塗膜試樣的「轉換效率」所得到的數值、將實施例6、比較例7的塗膜試樣的「轉換效率」除以比較例7的塗膜試樣的「轉換效率」所得到的數值、將實施例7、比較例8的塗膜試樣的「轉換效率」除以比較例8的塗膜試樣的「轉換效率」所得到的數值、將實施例8、比較例9的塗膜試樣的「轉換效率」除以比較例9的塗膜試樣的「轉換效率」所得到的數值定為「轉換效率增強度」。根據所得到的轉換效率增強度，評估塗膜試樣的膜特性。判定基準如以下所述。將所得到的結果揭示於表3及表4。 ＜判定基準＞ A：轉換效率增強度大於2.5 B：轉換效率增強度大於2.1且在2.5以下 C：轉換效率增強度在2.1以下 In addition, the numerical value obtained by dividing the "conversion efficiency" of the coating film samples of Examples 1 to 3, 9 and 10 and Comparative Example 4 by the "conversion efficiency" of the coating film sample of Comparative Example 4, , the numerical value obtained by dividing the "conversion efficiency" of the coating film sample of Comparative Example 5 by the "conversion efficiency" of the coating film sample of Comparative Example 5, and dividing the "conversion efficiency" of the coating film sample of Example 5 and Comparative Example 6 The value obtained by dividing the "conversion efficiency" of the coating film sample of Comparative Example 6 by dividing the "conversion efficiency" of the coating film sample of Example 6 and Comparative Example 7 by the coating film sample of Comparative Example 7 The numerical value obtained by dividing the "conversion efficiency" of the coating film sample of Example 7 and Comparative Example 8 by the "conversion efficiency" of the coating film sample of Comparative Example 8 will be calculated The value obtained by dividing the "conversion efficiency" of the coating film sample of Example 8 and Comparative Example 9 by the "conversion efficiency" of the coating film sample of Comparative Example 9 was determined as the "conversion efficiency enhancement degree". Based on the obtained conversion efficiency enhancement, the film characteristics of the coating film sample were evaluated. The judgment criteria are as follows. The obtained results are shown in Table 3 and Table 4. ＜Judgment Criteria＞ A: Conversion efficiency enhancement is greater than 2.5 B: Conversion efficiency enhancement is greater than 2.1 and less than 2.5 C: Conversion efficiency enhancement is below 2.1

(4)評估3：製膜性的評估 在評估2中，將實施例1~10及比較例1~9的波長轉換膜形成用組成物塗佈於基板上時，以目視確認塗膜的狀態，評估製膜性。判定基準如以下所述。將所得到的結果揭示於表3及表4。 ＜判定基準＞ A：可得到均勻的塗膜、製膜性良好 B：塗佈不均勻發生，製膜性差 此外，比較例3的塗膜試樣，在膜表面以目視可確認的程度顯著出現放射線狀塗佈不均勻，製膜性極差。所以，比較例3無法測定評估2的「轉換效率」。 (4) Evaluation 3: Evaluation of film-forming properties In Evaluation 2, when the wavelength conversion film-forming compositions of Examples 1 to 10 and Comparative Examples 1 to 9 were applied on a substrate, the state of the coating film was visually confirmed to evaluate the film forming properties. The judgment criteria are as follows. The obtained results are shown in Table 3 and Table 4. ＜Judgment Criteria＞ A: A uniform coating film can be obtained and film-forming properties are good. B: Uneven coating occurs and film forming properties are poor. In addition, in the coating film sample of Comparative Example 3, radial coating unevenness was significantly visible on the film surface to an extent that could be visually confirmed, and the film forming properties were extremely poor. Therefore, the "conversion efficiency" of Evaluation 2 cannot be measured in Comparative Example 3.

(5)評估4：保存安定性的評估 將實施例1~10及比較例1~3的波長轉換膜形成用組成物在25℃下保存1週，以目視確認保存中的組成物狀態(氧化鈦粒子有無沉降)。判定基準如以下所述。將所得到的結果揭示於表3及表4。 ＜判定基準＞ A：到經過1週的時間點為止都沒有觀察到沉降 B：經過1天後沒有觀察到沉降，經過2天後觀察到沉降 C：經過1天後觀察到沉降 (5) Assessment 4: Assessment of preservation stability The wavelength conversion film forming compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were stored at 25° C. for one week to visually confirm the state of the composition during storage (whether titanium oxide particles had settled or not). The judgment criteria are as follows. The obtained results are shown in Table 3 and Table 4. ＜Judgment Criteria＞ A: No settlement was observed until one week passed. B: No settlement was observed after 1 day, and settlement was observed after 2 days. C: Sedimentation is observed after 1 day

(6)評估5：總光線反射率的評估 對於與評估2同樣的方法所得到的塗膜試樣，使用紫外線可見分光光度計(島津製作所股份有限公司製UV-2600)，測定波長365nm的總光線反射率。根據所得到的總光線反射率，評估塗膜試樣的膜特性。判定基準如以下所述。將所得到的結果揭示於表3及表4。 ＜判定基準＞ A：總光線反射率在15%以下 B：總光線反射率大於15% (6) Evaluation 5: Evaluation of total light reflectance For the coating film sample obtained by the same method as Evaluation 2, the total light reflectance at a wavelength of 365 nm was measured using an ultraviolet-visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation). Based on the obtained total light reflectance, the film properties of the coating sample were evaluated. The judgment criteria are as follows. The obtained results are shown in Table 3 and Table 4. ＜Judgment Criteria＞ A: The total light reflectance is below 15% B: The total light reflectance is greater than 15%

如表3及表4所示般，滿足本發明要件的實施例1~10，任一者在評估2中轉換效率增強度皆高，在評估4中保存安定性皆良好，可看出轉換效率與保存安定性的兼顧性。相對於此，不滿足本發明要件的比較例1~9，任一者在評估2中轉換效率增強度皆低，或在評估4中保存安定性皆不佳，看不出來轉換效率與保存安定性的兼顧性。此外，比較例3的黏度為10,143mPa･s，不滿足本發明要件，因此製膜性極差、塗膜物性評估難以進行。As shown in Table 3 and Table 4, for Examples 1 to 10 that meet the requirements of the present invention, the conversion efficiency enhancement degree is high in Evaluation 2, and the storage stability is good in Evaluation 4. It can be seen that the conversion efficiency Compatibility with storage stability. In contrast, Comparative Examples 1 to 9, which do not meet the requirements of the present invention, have low conversion efficiency enhancement in Evaluation 2, or poor storage stability in Evaluation 4, and the conversion efficiency and storage stability cannot be seen. Sexual balance. In addition, the viscosity of Comparative Example 3 was 10,143 mPa･s, which did not meet the requirements of the present invention. Therefore, the film forming properties were extremely poor, and it was difficult to evaluate the physical properties of the coating film.

Claims (6)

一種顯示器用波長轉換膜形成用組成物，其係含有(A)螢光體、(B)氧化鈦粒子與(C)黏結劑， 上述(B)氧化鈦粒子其表面可被無機化合物被覆，其平均粒徑超過50nm~未達200nm， 25℃的黏度為10,000mPa･s以下。 A composition for forming a wavelength conversion film for a display, which contains (A) phosphor, (B) titanium oxide particles and (C) binder, The surface of the above-mentioned (B) titanium oxide particles can be coated with an inorganic compound, and its average particle size exceeds 50nm to less than 200nm. The viscosity at 25℃ is 10,000mPa･s or less. 如請求項1之顯示器用波長轉換膜形成用組成物，其中上述(B)氧化鈦粒子的平均粒徑為60~190 nm。The composition for forming a wavelength conversion film for a display according to claim 1, wherein the average particle diameter of the titanium oxide particles (B) is 60 to 190 nm. 如請求項1或2之顯示器用波長轉換膜形成用組成物，其中上述(B)氧化鈦粒子為該氧化鈦粒子的表面並未被被覆的粒子。The composition for forming a wavelength conversion film for a display according to claim 1 or 2, wherein the titanium oxide particles (B) are particles whose surfaces are not covered. 如請求項1~3中任一項之顯示器用波長轉換膜形成用組成物，其中上述(B)氧化鈦粒子的含量為在固體成分中占3~10質量%。The composition for forming a wavelength conversion film for a display according to any one of claims 1 to 3, wherein the content of the titanium oxide particles (B) is 3 to 10% by mass in the solid content. 如請求項1~4中任一項之顯示器用波長轉換膜形成用組成物，其中上述(A)螢光體為有機色素。The composition for forming a wavelength conversion film for a display according to any one of claims 1 to 4, wherein the phosphor (A) is an organic pigment. 如請求項1~5中任一項之顯示器用波長轉換膜形成用組成物，其中由上述組成物所形成的膜的霧度值為18%以上。The composition for forming a wavelength conversion film for a display according to any one of claims 1 to 5, wherein the haze value of the film formed from the above composition is 18% or more.