TW201638296A - Curing composition containing quantum dots, color filter produced by utilizing the same, and image display device - Google Patents
Curing composition containing quantum dots, color filter produced by utilizing the same, and image display device Download PDFInfo
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Abstract
Description
本發明涉及包含量子點之固化性組合物、利用其製造之濾色器及影像顯示裝置。 The present invention relates to a curable composition comprising quantum dots, a color filter manufactured therewith, and an image display device.
濾色器為能夠自白色光中提取紅色、綠色、藍色3種顏色而形成微細之像素單元之薄膜膜型光學部件，一個像素之尺寸為數十至數百微米左右。此類濾色器具有：為了將各像素間之邊界部分遮光而在透明基板上由預定之圖案形成之黑矩陣層及為了形成各像素而將多個顏色(通常為紅色(R)、綠色(G)及藍色(B)3原色)以預定之順序組態之像素部依次層疊的結構。一般而言，濾色器能夠藉由染色法、電沈積法、印刷法、顏料分散法等將3種以上顏色塗覆於透明基板上而製造，近來，利用顏料分散型之感光性樹脂之顏料分散法成為主流。 The color filter is a thin film film type optical member capable of extracting three kinds of red, green, and blue colors from white light to form a fine pixel unit, and the size of one pixel is about several tens to several hundreds of micrometers. Such a color filter has a black matrix layer formed of a predetermined pattern on a transparent substrate in order to shield a boundary portion between pixels, and a plurality of colors (usually red (R), green (in order to form each pixel) G) and blue (B) 3 primary colors) A structure in which pixel portions configured in a predetermined order are sequentially stacked. In general, a color filter can be produced by applying three or more colors to a transparent substrate by a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, or the like. Recently, a pigment of a pigment-dispersed photosensitive resin is used. The decentralization method has become mainstream.
作為實現濾色器之方法中之一種的顏料分散法為藉由重複如下一系列過程而形成著色薄膜之方法：將包含著色劑且包含鹼溶性樹脂、光聚合單體、光聚合引發劑、環氧樹脂、溶劑、其他添加劑之感光性樹脂組合物塗覆在設有黑色矩陣之透明基板上，將所要形成之形態之圖案曝光後，用溶劑將非曝光部位移除且進行熱固化，其活躍地應用於製造手機、筆記本電腦、監視器、電視機等之LCD。近年來，實際情況為對於利用了具有各種優勢之顏料分散法之濾色器用感光性樹脂組合物，不僅要求優異之圖案特性，而且要求高顏色再現率以及 高亮度及高對比度等進一步提高了之效能。 The pigment dispersion method as one of the methods for realizing a color filter is a method of forming a colored film by repeating a series of processes: containing a coloring agent and containing an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a ring The photosensitive resin composition of an oxyresin, a solvent, and other additives is coated on a transparent substrate provided with a black matrix, and after exposing the pattern of the form to be formed, the non-exposed portion is removed by a solvent and thermally cured, which is active. It is used in the manufacture of LCDs for mobile phones, notebook computers, monitors, televisions, etc. In recent years, the photosensitive resin composition for color filters using the pigment dispersion method having various advantages not only requires excellent pattern characteristics, but also requires high color reproduction rate and High brightness and high contrast further enhance the performance.
然而，顏色再現為自光源照射之光透過濾色器而實現的，在該過程中，光之一部分經濾色器吸收，因此光效率降低，此外，由於作為濾色器之顏料特性，因而存在諸如不足以再現完美顏色之根本性限制。 However, the color reproduction is realized by the light illuminating the color filter from the light source, in which part of the light is absorbed by the color filter, so the light efficiency is lowered, and further, due to the pigment characteristics as the color filter, there is Such as a fundamental limitation that is not sufficient to reproduce a perfect color.
此外，韓國專利公開公報第10-2013-0000506號揭示了一種顯示裝置，其包括光源及自上述光源出射之光所入射之顯示面板，上述顯示面板包含多個顏色變換部，上述顏色變換部包含使上述光之波長變換之多個波長變換粒子及在上述光中吸收預定的波長帶之光之多個濾色器粒子。 In addition, Korean Patent Publication No. 10-2013-0000506 discloses a display device including a light source and a display panel on which light emitted from the light source is incident, the display panel including a plurality of color conversion sections, and the color conversion section includes a plurality of wavelength-converting particles that convert the wavelength of the light and a plurality of color filter particles that absorb light of a predetermined wavelength band in the light.
然而，雖然上述以往技術在包含量子點方面類似，但對於感光性樹脂組合物之含量沒有具體說明，僅揭示了具有高顏色再現率及亮度之顯示裝置，因此有必要對感光性樹脂組合物進行追加開發。 However, although the above-described prior art is similar in terms of containing quantum dots, the content of the photosensitive resin composition is not specifically described, and only a display device having high color reproduction ratio and brightness is disclosed. Therefore, it is necessary to carry out the photosensitive resin composition. Additional development.
專利文獻1：韓國專利公開案第10-2013-0000506號公報 Patent Document 1: Korean Patent Publication No. 10-2013-0000506
本發明之目的在於，提供一種包含量子點之固化性組合物，其使量子點粒子均勻地分散，且在濾色器製造工序中沒有光效率降低及感光特性不良等問題，從而能夠製造優異之濾色器。 An object of the present invention is to provide a curable composition containing quantum dots, which can uniformly disperse quantum dot particles, and which has no problems such as a decrease in light efficiency and a poor photosensitive property in a color filter manufacturing process, and can be manufactured excellently. Color filter.
此外，本發明之目的在於，提供由此類包含量子點之固化性組合物製造之濾色器及包含其之影像顯示裝置。 Further, it is an object of the present invention to provide a color filter made of such a curable composition containing quantum dots and an image display device comprising the same.
為了實現上述目的，本發明之實施例之包含量子點的固化性組合物包含黏合劑及量子點，上述黏合劑包含下述化學式1、化學式2及 其組合中之一者以上。 In order to achieve the above object, a curable composition comprising a quantum dot according to an embodiment of the present invention comprises a binder and a quantum dot, and the binder comprises the following chemical formula 1 and chemical formula 2; One of the combinations is more than one.
(上述化學式1中，R1表示氫或C1~C6烷基，R2表示氧、-NH-或基，R3表示C1~C30伸烷基、C1~C30伸烷基氧基或C1~C30乙基氧基羰基胺基乙基，R4表示含有不飽和雙鍵之基團。) (In the above Chemical Formula 1, R 1 represents hydrogen or a C1 to C6 alkyl group, and R 2 represents oxygen, -NH- or Further, R 3 represents a C1 to C30 alkyl group, a C1 to C30 alkyloxy group or a C1 to C30 ethyloxycarbonylaminoethyl group, and R 4 represents a group containing an unsaturated double bond. )
(上述化學式2中，R5~R6各自獨立地彼此相同或不同，且表示氫或C1~C6烷基，R7表示氧、-NH-或基，R8表示C1~C30伸烷基、C1~C30伸烷基氧基或C1~C30乙基氧基羰基胺基乙基，R9表示含有不飽和雙鍵之基團，X表示0<X<100之值。) (In the above Chemical Formula 2, R 5 to R 6 are each independently the same or different from each other, and represent hydrogen or a C1 to C6 alkyl group, and R 7 represents oxygen, -NH- or a group, R 8 represents a C1 to C30 alkyl group, a C1 to C30 alkyloxy group or a C1 to C30 ethyloxycarbonylaminoethyl group, and R 9 represents a group having an unsaturated double bond, and X represents 0< The value of X < 100. )
如上所述，本發明之包含量子點之固化性組合物包含特定化合物之黏合劑，從而具有能夠提供顏色再現性及亮度特性優異之高品質濾色器之效果。 As described above, the curable composition containing a quantum dot of the present invention contains a binder of a specific compound, and has an effect of providing a high-quality color filter excellent in color reproducibility and brightness characteristics.
此外，本發明具有能夠提供由上述包含量子點之固化性組合物 製造之濾色器及包含其之影像顯示裝置之效果。 Further, the present invention has a curable composition capable of providing the above-described quantum dot-containing composition The effect of the manufactured color filter and the image display device including the same.
本發明之包含量子點之固化性組合物包含黏合劑及量子點，上述黏合劑之特徵在於下述化學式1或化學式2。 The curable composition containing quantum dots of the present invention comprises a binder and a quantum dot, and the binder is characterized by the following Chemical Formula 1 or Chemical Formula 2.
此外，關於本發明之包含量子點之固化性組合物，除了上述黏合劑及量子點以外，在以正型構成之情況下，能夠進一步含有鄰萘醌二疊氮化合物，在以負型構成之情況下，能夠進一步含有具有1個以上乙烯性不飽和基團之單體或低聚物。根據需要，亦可進一步含有交聯劑等其他成分。此外，在以上述正型構成之情況下，能夠進一步含有上述單體、低聚物或光聚合引發劑。 Further, the curable composition containing a quantum dot according to the present invention may further contain an o-naphthoquinonediazide compound and a negative type in addition to the above-mentioned binder and quantum dots. In this case, a monomer or oligomer having one or more ethylenically unsaturated groups can be further contained. Further, other components such as a crosslinking agent may be further contained as needed. Further, in the case of the above-described positive type, the above monomer, oligomer or photopolymerization initiator can be further contained.
首先，本發明之包含量子點之固化性組合物能夠包含化學式1之黏合劑，玻璃化轉變溫度可為-20~250℃。此時，黏合劑為具有聚合性側鏈之共聚物。 First, the curable composition containing quantum dots of the present invention can contain the binder of Chemical Formula 1, and the glass transition temperature can be -20 to 250 °C. At this time, the binder is a copolymer having a polymerizable side chain.
上述化學式1中，R1表示氫或C1~C6烷基。更佳地，R1能夠考慮膜之強度、彈性模數、黏彈性、耐熱性、顯影性、聚合物之玻璃化轉變溫度(Tg)、溶解性、合成適合性等而自由選擇。 In the above Chemical Formula 1, R 1 represents hydrogen or a C1 to C6 alkyl group. More preferably, R 1 can be freely selected in consideration of the strength of the film, the modulus of elasticity, the viscoelasticity, the heat resistance, the developability, the glass transition temperature (Tg) of the polymer, the solubility, the suitability for synthesis, and the like.
R2表示氧、-NH-或基。更佳地，R2能夠考慮膜之強度、彈性模數、黏彈性、耐熱性、顯影性、合成適合性、聚合物之玻璃化轉變溫度(Tg)、溶解性等而自由選擇。 R 2 represents oxygen, -NH- or base. More preferably, R 2 can be freely selected in consideration of film strength, elastic modulus, viscoelasticity, heat resistance, developability, synthetic suitability, glass transition temperature (Tg) of the polymer, solubility, and the like.
R3表示C1~C30伸烷基、C1~C30伸烷基氧基或C1~C30乙基氧基羰基胺基乙基。R3較佳為C1~C25伸烷基、C1~C25伸烷基氧基或C1~C25乙基氧基羰基胺基乙基，進一步較佳為C1~C20伸烷基、C1~C20烷基氧基或C1~C20乙基氧基羰基胺基乙基，特別較佳為亞甲基、伸乙基、伸丙基、伸丁基、伸乙基氧基、二伸乙基氧基、三伸乙基氧基、乙基氧基羰基胺基乙基。此等基團可具有取代基。此時，作為上述R3之取代基，較佳為C1~C20烷基，其中，更佳為C1~C15烷基，進一步較佳為C1~C10烷基，特別較佳為C1~C7烷基。作為上述取代基，具體而言，考慮到原料及合成適合性等，最佳為甲基、乙基、分支鏈或直鏈之丙基、丁基、戊基、己基。其中，由於醇系羥基有時會使玻璃化轉變溫度(Tg)降低，因此自較佳之例子中排除。 R 3 represents a C1 to C30 alkylene group, a C1 to C30 alkyleneoxy group or a C1 to C30 ethyloxycarbonylaminoethyl group. R 3 is preferably C1 to C25 alkylene, C1 to C25 alkyloxy or C1 to C25 ethyloxycarbonylaminoethyl, further preferably C1 to C20 alkyl, C1 to C20 alkyl Oxyl or C1~C20 ethyloxycarbonylaminoethyl, particularly preferably methylene, ethyl, propyl, butyl, ethyloxy, diethyloxy, triple Ethyloxy, ethyloxycarbonylaminoethyl. These groups may have a substituent. In this case, the substituent of R 3 is preferably a C1 to C20 alkyl group, more preferably a C1 to C15 alkyl group, still more preferably a C1 to C10 alkyl group, and particularly preferably a C1 to C7 alkyl group. . Specifically, the substituent is preferably a methyl group, an ethyl group, a branched chain or a linear propyl group, a butyl group, a pentyl group or a hexyl group in consideration of a raw material, a synthetic suitability and the like. Among them, since the alcoholic hydroxyl group sometimes lowers the glass transition temperature (Tg), it is excluded from the preferred examples.
R4表示含有不飽和雙鍵之基團。具體而言，較佳為乙烯基氧基、烯丙基氧基、(甲基)丙烯醯基氧基、4-乙烯基苯基氧基、4-乙烯基苯基甲基氧基、乙烯基酯基等。其中，作為R4，更佳為乙烯基氧基、烯丙基氧基、(甲基)丙烯醯基氧基、4-乙烯基苯基甲基氧基、乙烯基酯基，特別較佳為烯丙基氧基、(甲基)丙烯醯基氧基、4-乙烯基苯基甲基氧基。 R 4 represents a group containing an unsaturated double bond. Specifically, a vinyloxy group, an allyloxy group, a (meth)acrylenyloxy group, a 4-vinylphenyloxy group, a 4-vinylphenylmethyloxy group, a vinyl group is preferred. Ester group and the like. Among them, R 4 is more preferably a vinyloxy group, an allyloxy group, a (meth)acrylenyloxy group, a 4-vinylphenylmethyloxy group or a vinyl ester group, and particularly preferably Allyloxy, (meth)acrylenyloxy, 4-vinylphenylmethyloxy.
含有化學式1所表示之結構單元之本發明的黏合劑之玻璃化轉變溫度(Tg)能夠利用黏合劑自身之分子量、分子結構、氫鍵性相互作用等來調整，可考慮併用之黏合劑之玻璃化轉變溫度(Tg)、與併用之黏合劑及其他成分之親和性、體系整體的黏彈性等決定。在黏合劑之玻璃化轉變溫度(Tg)過低之情況下，所形成之圖案之耐熱性降低，產生諸如熱流動之問題。此外，亦產生塗佈膜之黏接性增加，作業性降低等問題。因而，不較佳在黏合劑中含有醇系羥基。此外，由於醇系羥基之氫鍵性相互作用較弱，因此自該觀點出發，多數情況下無法發揮較大之效果。 The glass transition temperature (Tg) of the binder of the present invention containing the structural unit represented by Chemical Formula 1 can be adjusted by the molecular weight, molecular structure, hydrogen bonding interaction, and the like of the binder itself, and the glass of the binder can be considered in combination. The transformation temperature (Tg), the affinity of the binder and other components used in combination, and the viscoelasticity of the entire system are determined. In the case where the glass transition temperature (Tg) of the binder is too low, the heat resistance of the formed pattern is lowered to cause problems such as heat flow. In addition, problems such as an increase in the adhesion of the coating film and a decrease in workability are also caused. Therefore, it is not preferable to contain an alcoholic hydroxyl group in the binder. Further, since the hydrogen bond interaction of the alcohol-based hydroxyl group is weak, from this viewpoint, in many cases, a large effect cannot be exhibited.
本發明之黏合劑之玻璃化轉變溫度(Tg)較佳處於-20~250℃之範圍，進一步較佳處於-15~250℃之範圍，特別較佳處於-10~250℃之範圍。此外，本發明之黏合劑可與其他黏合劑併用。此外，對於上述以外之黏合劑進行後述。 The glass transition temperature (Tg) of the binder of the present invention is preferably in the range of -20 to 250 ° C, more preferably in the range of -15 to 250 ° C, and particularly preferably in the range of -10 to 250 ° C. Further, the adhesive of the present invention can be used in combination with other adhesives. In addition, the binder other than the above will be described later.
本發明之黏合劑之分子量為重量平均分子量，較佳為500~10,000,000Da(道爾頓(dalton)：分子量之單位)，進一步較佳為1,000~5,000,000Da，特別較佳為2,000~5,000,000Da。 The molecular weight of the binder of the present invention is a weight average molecular weight, preferably 500 to 10,000,000 Da (dalton: unit of molecular weight), further preferably 1,000 to 5,000,000 Da, particularly preferably 2,000 to 5,000,000 Da.
作為與化學式1所表示之結構單元一同構成本發明之黏合劑的成分(即，共聚成分)，只要能夠(2元以上之)共聚就沒有特別限制。 The component (that is, the copolymerization component) constituting the binder of the present invention together with the structural unit represented by Chemical Formula 1 is not particularly limited as long as it can be copolymerized (2 or more).
作為上述共聚成分，可舉出例如日本特開昭59-44615號、日本特公昭54-34327號、日本特公昭58-12577號、日本特公昭54-25957號、日本特開昭59-53836號、日本特開昭59-71048號公報之說明書中所記載之彼等甲基丙烯酸共聚物、丙烯酸共聚物、衣康酸共聚物、巴豆酸共聚物、順丁烯二酸(酐)共聚物、部分酯化順丁烯二酸共聚物、部分醯胺化順丁烯二酸共聚物中使用之單體、(甲基)丙烯酸酯類、(甲基)丙烯醯胺類、具有乙烯基之芳族烴環類、具有乙烯基之雜芳族環類、順丁烯二酸酐、衣康酸酯類、巴豆酸酯類、(甲基)丙烯腈、(甲基)巴豆腈、各種苯乙烯類、各種苯甲酸乙烯酯類、各種乙酸乙烯酯類、乙烯基咔唑類、乙烯基吡咯啶酮等。 Examples of the copolymerization component include, for example, JP-A-59-44615, JP-A-54-34327, JP-A-58-12577, JP-A-54-25957, and JP-A-59-53836 And the methacrylic acid copolymer, the acrylic copolymer, the itaconic acid copolymer, the crotonic acid copolymer, the maleic acid (anhydride) copolymer, and the copolymer described in the specification of JP-A-59-71048, Partially esterified maleic acid copolymer, partially used in the amidated maleic acid copolymer, (meth) acrylate, (meth) acrylamide, vinyl Hydrocarbon ring, heteroaromatic ring with vinyl, maleic anhydride, itaconate, crotonate, (meth)acrylonitrile, (methyl)crotononitrile, various styrenes And various vinyl benzoates, various vinyl acetates, vinyl carbazoles, vinyl pyrrolidone, and the like.
其中，作為上述共聚成分，較佳為(甲基)丙烯酸、C1~C25(環)烷基(甲基)丙烯酸酯、C1~C25具有雙環之(甲基)丙烯酸酯、C1~C25芳烷基(甲基)丙烯酸酯、C1~C25芳基(甲基)丙烯酸酯、(甲基)丙烯醯胺、C1~C25第二或第三(環)烷基(甲基)丙烯醯胺、C1~C25具有第二或第三雙環之(甲基)丙烯醯胺、C1~C25第二或第三芳烷基(甲基)丙烯醯胺、C1~C25第二或第三芳基(甲基)丙烯醯胺、C1~C25(甲基)丙烯醯基嗎啉、具有乙烯基之經取代或未經取代之C1~C25芳族烴環、具有 乙烯基之經取代或未經取代之碳C1~C25雜芳族環、順丁烯二酸酐、經取代或未經取代之C1~C25(α-甲基-)苯乙烯、乙烯基咪唑、乙烯基***、順丁烯二酸酐、經取代或未經取代之C1~C25部分酯化順丁烯二酸共聚物、經取代或未經取代之C1~C25部分醯胺化順丁烯二酸、茉莉酸甲酯(Methyl Jasmonate)、衣康酸、C1~C25衣康酸(環)烷基酯、C1~C25具有雙環之衣康酸酯、C1~C25衣康酸芳烷基酯、C1~C25衣康酸芳基酯、巴豆酸、C1~C25巴豆酸(環)烷基酯、C1~C25具有雙環之巴豆酸酯、C1~C25巴豆酸芳烷基酯、C1~C25巴豆酸芳基酯、C1~C25苯甲酸乙烯酯類、C1~C25乙酸乙烯酯類、(甲基)丙烯腈、(甲基)巴豆腈、C1~C25乙烯基咔唑、乙烯基吡咯啶酮。 Among them, as the copolymerization component, (meth)acrylic acid, C1 to C25 (cyclo)alkyl (meth) acrylate, C1 to C25 having a bicyclo (meth) acrylate, and a C1 to C25 aralkyl group are preferable. (Meth) acrylate, C1~C25 aryl (meth) acrylate, (meth) acrylamide, C1~C25 second or third (cyclo)alkyl (meth) acrylamide, C1~ C25 has a second or third bicyclic (meth) acrylamide, a C1 to C25 second or third aralkyl (meth) acrylamide, a C1 to C25 second or a third aryl (methyl) Acrylamide, C1~C25(meth)acrylinylmorpholine, substituted or unsubstituted C1~C25 aromatic hydrocarbon ring having a vinyl group, Substituted or unsubstituted carbon C1~C25 heteroaromatic ring of vinyl, maleic anhydride, substituted or unsubstituted C1~C25(α-methyl-)styrene, vinylimidazole, ethylene Triazole, maleic anhydride, substituted or unsubstituted C1~C25 partially esterified maleic acid copolymer, substituted or unsubstituted C1~C25 partially amided maleic acid Methyl Jasmonate, itaconic acid, C1~C25 itaconic acid (cyclo)alkyl ester, C1~C25 with bicyclic itaconate, C1~C25 itaconic acid aralkyl ester, C1 ~C25 itaconic acid aryl ester, crotonic acid, C1~C25 crotonic acid (cyclo)alkyl ester, C1~C25 with bicyclic crotonate, C1~C25 aryl crotonate, C1~C25 crotonic acid Base ester, C1~C25 vinyl benzoate, C1~C25 vinyl acetate, (meth)acrylonitrile, (methyl)crotononitrile, C1~C25 vinylcarbazole, vinyl pyrrolidone.
其中，更佳為(甲基)丙烯酸、C1~C20(環)烷基(甲基)丙烯酸酯、C1~C20具有雙環之(甲基)丙烯酸酯、C1~C20芳烷基(甲基)丙烯酸酯、C1~C20芳基(甲基)丙烯酸酯、(甲基)丙烯醯胺、C1~C20第二或第三(環)烷基(甲基)丙烯醯胺、C1~C20具有第二或第三雙環之(甲基)丙烯醯胺、C1~C20第二或第三芳烷基(甲基)丙烯醯胺、C1~C20第二或第三芳基(甲基)丙烯醯胺；C1~C20(甲基)丙烯醯基嗎啉、具有乙烯基之經取代或未經取代之C1~C20芳族烴環、具有乙烯基之經取代或未經取代之C1~C20雜芳族環、順丁烯二酸酐、經取代或未經取代之C1~C20部分酯化順丁烯二酸共聚物、經取代或未經取代之C1~C20部分醯胺化順丁烯二酸、經取代或未經取代之C1~C20(α-甲基-)苯乙烯類、茉莉酸甲酯、衣康酸、C1~C20衣康酸(環)烷基酯、C1~C20具有雙環之衣康酸酯、C1~C20衣康酸芳烷基酯、C1~C20衣康酸芳基酯、巴豆酸、C1~C20巴豆酸(環)烷基酯、C1~C20具有雙環之巴豆酸酯、C1~C20巴豆酸芳烷基酯、C1~C20巴豆酸芳基酯、C1~C20苯甲酸乙烯酯類、C1~C20乙酸乙烯酯類、C1~C20乙烯基咔唑、乙烯基吡咯啶酮；(甲基)丙烯腈、(甲基)巴豆腈。 More preferably, it is (meth)acrylic acid, C1~C20 (cyclo)alkyl (meth) acrylate, C1~C20 has a bicyclo (meth) acrylate, C1~C20 aralkyl (meth) acrylate Ester, C1~C20 aryl (meth) acrylate, (meth) acrylamide, C1~C20 second or third (cyclo)alkyl (meth) acrylamide, C1~C20 have the second or a third bicyclic (meth) acrylamide, a C1 to C20 second or third aralkyl (meth) acrylamide, a C1 to C20 second or a third aryl (meth) acrylamide; C1 ~C20 (meth) propylene decylmorpholine, a substituted or unsubstituted C1 to C20 aromatic hydrocarbon ring having a vinyl group, a substituted or unsubstituted C1 to C20 heteroaromatic ring having a vinyl group, Maleic anhydride, substituted or unsubstituted C1 to C20 partially esterified maleic acid copolymer, substituted or unsubstituted C1 to C20 partially amided maleic acid, substituted or Unsubstituted C1~C20(α-methyl-)styrene, methyl jasmonate, itaconic acid, C1~C20 itaconic acid (cyclo)alkyl ester, C1~C20 with bicyclic itaconate , C1~C20 arylalkyl itaconate, C1~C20 itaconic acid aryl ester, crotonic acid, C1~C20 Croton Acid (cyclo)alkyl ester, C1~C20 with bicyclic crotonate, C1~C20 aryl crotonate, C1~C20 aryl crotonate, C1~C20 vinyl benzoate, C1~C20 acetic acid Vinyl esters, C1 to C20 vinyl carbazole, vinyl pyrrolidone; (meth)acrylonitrile, (methyl) crotononitrile.
此外，其中，特別較佳為(甲基)丙烯酸、甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、直鏈或分支鏈之丙基(甲基)丙烯酸酯、直鏈或分支鏈之丁基(甲基)丙烯酸酯、直鏈或分支鏈之戊基(甲基)丙烯酸酯、正己基(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、正庚基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、正辛基(甲基)丙烯酸酯、正癸基(甲基)丙烯酸酯、正十二烷基(甲基)丙烯酸酯、金剛烷基(甲基)丙烯酸酯、異冰片基(甲基)丙烯酸酯、異冰片烷甲基(甲基)丙烯酸酯、降冰片烯甲基(甲基)丙烯酸酯；苄基(甲基)丙烯酸酯、萘基甲基(甲基)丙烯酸酯、蒽甲基(甲基)丙烯酸酯、苯基乙基(甲基)丙烯酸酯；苯基(甲基)丙烯酸酯、萘基(甲基)丙烯酸酯、(甲基)丙烯醯胺、(二)甲基(甲基)丙烯醯胺、(二)乙基(甲基)丙烯醯胺、直鏈或分支鏈之(二)丙基(甲基)丙烯醯胺、直鏈或分支鏈之(二)丁基(甲基)丙烯醯胺、直鏈或分支鏈之(二)戊基(甲基)丙烯醯胺、(二)正己基(甲基)丙烯醯胺、(二)環己基(甲基)丙烯醯胺、(二-)2-乙基己基(甲基)丙烯醯胺；金剛烷基(甲基)丙烯醯胺、正金剛烷基(甲基)丙烯醯胺；苄基(甲基)丙烯醯胺、萘基乙基(甲基)丙烯醯胺、苯基乙基(甲基)丙烯醯胺；(二)苯基(甲基)丙烯醯胺、萘基(甲基)丙烯醯胺、(甲基)丙烯醯基嗎啉、哌啶基丙烯醯胺、吡咯啶基丙烯醯胺、(α-甲基)苯乙烯、乙烯基吡啶、乙烯基咪唑、乙烯基***、順丁烯二酸酐、茉莉酸甲酯；衣康酸；巴豆酸、甲基巴豆酸酯、乙基巴豆酸酯、直鏈或分支鏈之丙基巴豆酸酯、直鏈或分支鏈之丁基巴豆酸酯、直鏈或分支鏈之戊基巴豆酸酯、正己基巴豆酸酯、環己基巴豆酸酯、正庚基巴豆酸酯、2-乙基己基巴豆酸酯、正辛基巴豆酸酯、正癸基巴豆酸酯、正十二烷基巴豆酸酯；金剛烷基巴豆酸酯、異冰片基巴豆酸酯、異冰片烷甲基巴豆酸酯、降冰片烯甲基巴豆酸酯；苄基巴豆酸酯、萘基甲基巴豆酸酯、蒽甲基巴豆酸酯、苯基乙基巴豆酸酯；苯基巴豆酸酯、萘基巴豆酸酯、 苯甲酸乙烯酯、乙酸乙烯酯、乙烯基咔唑、乙烯基吡咯啶酮等。 Further, among them, (meth)acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, linear or branched propyl (meth) acrylate, linear or Branched chain butyl (meth) acrylate, linear or branched pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (a Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, Donkey Kong Alkyl (meth) acrylate, isobornyl (meth) acrylate, isobornyl methyl (meth) acrylate, norbornene methyl (meth) acrylate; benzyl (meth) acrylate Ester, naphthylmethyl (meth) acrylate, fluorenyl methyl (meth) acrylate, phenyl ethyl (meth) acrylate; phenyl (meth) acrylate, naphthyl (meth) acrylate Ester, (meth) acrylamide, (di)methyl (meth) acrylamide, (di) ethyl (meth) acrylamide, linear or branched (di) propyl (methyl) Acetylene amide, linear or branched (B) butyl (meth) acrylamide, linear or branched (di)pentyl (meth) acrylamide, (di) n-hexyl (meth) acrylamide, (b) ring Hexyl (meth) acrylamide, (di-) 2-ethylhexyl (meth) acrylamide; adamantyl (meth) acrylamide, n-adamantyl (meth) acrylamide; benzyl (meth) acrylamide, naphthylethyl (meth) acrylamide, phenylethyl (meth) acrylamide; (b) phenyl (meth) acrylamide, naphthyl (A Base acrylamide, (meth) propylene decyl morpholine, piperidinyl acrylamide, pyrrolidinyl acrylamide, (α-methyl) styrene, vinyl pyridine, vinyl imidazole, vinyl three Azole, maleic anhydride, methyl jasmonate; itaconic acid; crotonic acid, methyl crotonate, ethyl crotonate, linear or branched crotonate, linear or branched Butyl crotonate, linear or branched pentyl crotonate, n-hexyl crotonate, cyclohexyl crotonate, n-heptyl crotonate, 2-ethylhexyl crotonate, n-octyl croton Acid ester, n-decyl crotonate, n-dodecyl Oxalate; adamantyl crotonate, isobornyl crotonate, isobornyl methyl crotonate, norbornene methyl crotonate; benzyl crotonate, naphthyl methyl crotonate,蒽Methyl crotonate, phenylethyl crotonate; phenyl crotonate, naphthyl crotonate, Vinyl benzoate, vinyl acetate, vinyl carbazole, vinyl pyrrolidone, and the like.
此外，上述羧基可來自金屬鹽。 Further, the above carboxyl group may be derived from a metal salt.
作為上述取代基，較佳為C1~C20烷基、C1~C20烷氧基、C1~C20芳烷基、C1~C20芳基、C1~C20醯基氧基、C1~C20醯基、C1~C20烷氧基羰基、C1~C20芳基羰基、C1~C20二烷基胺基、C1~C20烷基胺基、鹵素原子、氰基、呋喃基、糠基、四氫呋喃基、四氫糠基、烷硫基、三甲基甲矽烷基、三氟甲基、羧基、噻吩基、嗎啉代基、嗎啉代基羰基等。 The substituent is preferably a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C1 to C20 aralkyl group, a C1 to C20 aryl group, a C1 to C20 decyloxy group, a C1 to C20 fluorenyl group, and a C1~ group. C20 alkoxycarbonyl, C1 to C20 arylcarbonyl, C1 to C20 dialkylamino, C1 to C20 alkylamino, halogen atom, cyano, furyl, fluorenyl, tetrahydrofuranyl, tetrahydroindenyl, An alkylthio group, a trimethylcarbinyl group, a trifluoromethyl group, a carboxyl group, a thienyl group, a morpholino group, a morpholinocarbonyl group, and the like.
其中，作為上述取代基，更佳為C1~C15烷基、C1~C15烷氧基、C1~C15芳烷基、C1~C15芳基、C1~C15醯基氧基、C1~C15醯基、C1~C15烷氧基羰基、C1~C15芳基羰基、C1~C15二烷基胺基、C1~C15烷基胺基、鹵素原子、氰基、呋喃基、糠基、四氫呋喃基、四氫糠基、烷硫基、三甲基甲矽烷基、三氟甲基、羧基、噻吩基、嗎啉代基、嗎啉代基羰基等。 In the above, the substituent is more preferably a C1 to C15 alkyl group, a C1 to C15 alkoxy group, a C1 to C15 aralkyl group, a C1 to C15 aryl group, a C1 to C15 fluorenyloxy group, or a C1 to C15 fluorenyl group. C1~C15 alkoxycarbonyl, C1~C15 arylcarbonyl, C1~C15 dialkylamino, C1~C15 alkylamino, halogen atom, cyano group, furyl group, decyl group, tetrahydrofuranyl group, tetrahydroanthracene Alkylthiol, trimethylcarbinyl, trifluoromethyl, carboxyl, thienyl, morpholino, morpholinocarbonyl, and the like.
此外，作為上述取代基，特別較佳為甲基、乙基、直鏈或分支鏈之丙基、直鏈或分支鏈之丁基、直鏈或分支鏈之戊基、正己基、環己基、正庚基、2-乙基己基、正辛基、正癸基、正十二烷基、甲基氧基、乙基氧基、直鏈或分支鏈之丙基氧基、直鏈或分支鏈之丁基氧基、直鏈或分支鏈之戊基氧基、正己基氧基、環己基氧基、正庚基氧基、2-乙基己基氧基、正辛基氧基、正癸基氧基、正十二烷基氧基、苄基、苯乙基、萘基甲基、萘基乙基、苯基、萘基、甲基羰基氧基、乙基羰基氧基、直鏈或分支鏈之丙基羰基氧基、直鏈或分支鏈之丁基羰基氧基、直鏈或分支鏈之戊基羰基氧基、正己基羰基氧基、環己基羰基氧基、正庚基羰基氧基、2-乙基己基羰基氧基、正辛基羰基氧基、正癸基羰基氧基、正十二烷基羰基氧基、甲基羰基(乙醯基)、乙基羰基、直鏈或分支鏈之丙基羰基、直鏈或分支鏈之丁基羰基、直鏈 或分支鏈之戊基羰基、正己基羰基、環己基羰基、正庚基羰基、2-乙基己基羰基、正辛基羰基、正癸基羰基、正十二烷基羰基、甲基氧基羰基、乙基氧基羰基、直鏈或分支鏈之丙基氧基羰基、直鏈或分支鏈之丁基氧基羰基、直鏈或分支鏈之戊基氧基羰基、正己基氧基羰基、環己基氧基羰基、正庚基氧基羰基、2-乙基己基氧基羰基、正辛基氧基羰基、正癸基氧基羰基、正十二烷基氧基羰基、苯甲醯基、萘基羰基；(二)甲基胺基、(二)乙基胺基、直鏈或分支鏈之(二)丙基胺基、直鏈或分支鏈之(二)丁基胺基、直鏈或分支鏈之(二)戊基胺基、(二)正己基胺基、(二)環己基胺基、(二)正庚基胺基、(二)2-乙基己基胺基；氟原子、氯原子、溴原子；氰基、呋喃基、糠基、四氫呋喃基、四氫糠基、烷硫基、三甲基甲矽烷基、三氟甲基、羧基、噻吩基、嗎啉代基、嗎啉代基羰基等。 Further, as the above substituent, a methyl group, an ethyl group, a propyl group of a straight chain or a branched chain, a butyl group of a straight chain or a branched chain, a pentyl group of a straight or branched chain, a n-hexyl group, a cyclohexyl group, and the like are particularly preferable. N-heptyl, 2-ethylhexyl, n-octyl, n-decyl, n-dodecyl, methyloxy, ethyloxy, propyloxy, straight or branched chains, straight or branched Butyloxy, linear or branched pentyloxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, 2-ethylhexyloxy, n-octyloxy, n-decyl Oxy, n-dodecyloxy, benzyl, phenethyl, naphthylmethyl, naphthylethyl, phenyl, naphthyl, methylcarbonyloxy, ethylcarbonyloxy, straight chain or branched a propylcarbonyloxy group of a chain, a butylcarbonyloxy group of a straight or branched chain, a pentylcarbonyloxy group of a straight or branched chain, a n-hexylcarbonyloxy group, a cyclohexylcarbonyloxy group, a n-heptylcarbonyloxy group , 2-ethylhexylcarbonyloxy, n-octylcarbonyloxy, n-decylcarbonyloxy, n-dodecylcarbonyloxy, methylcarbonyl (ethenyl), ethylcarbonyl, straight chain or branched The cyclopropylcarbonyl, straight or branched chains butylcarbonyl group, a straight-chain Or a branched chain of pentylcarbonyl, n-hexylcarbonyl, cyclohexylcarbonyl, n-heptylcarbonyl, 2-ethylhexylcarbonyl, n-octylcarbonyl, n-decylcarbonyl, n-dodecylcarbonyl, methyloxycarbonyl Ethyloxycarbonyl, propyloxycarbonyl group of a straight or branched chain, butyloxycarbonyl group of a straight or branched chain, pentyloxycarbonyl group of a straight or branched chain, n-hexyloxycarbonyl group, ring Hexyloxycarbonyl, n-heptyloxycarbonyl, 2-ethylhexyloxycarbonyl, n-octyloxycarbonyl, n-decyloxycarbonyl, n-dodecyloxycarbonyl, benzhydryl, naphthalene (2) methylamino, (di)ethylamino, linear or branched (di)propylamino, linear or branched (di)butylamino, linear or a branched chain of (di)pentylamino, (di)n-hexylamino, (di)cyclohexylamino, (di)n-heptylamino, (di)2-ethylhexylamino; fluorine atom, Chlorine atom, bromine atom; cyano group, furyl group, fluorenyl group, tetrahydrofuranyl group, tetrahydroindenyl group, alkylthio group, trimethylcarbinyl group, trifluoromethyl group, carboxyl group, thienyl group, morpholino group, Porphyrin Carbonyl group and the like.
此外，此等取代基可經上述取代基進一步取代。其中，由於醇系羥基有時會使玻璃化轉變溫度(Tg)降低，因此自較佳之取代基之例子中排除。 Further, such substituents may be further substituted by the above substituents. Among them, since the alcoholic hydroxyl group sometimes lowers the glass transition temperature (Tg), it is excluded from the example of the preferable substituent.
此外，(甲基)丙烯腈、(甲基)巴豆腈可作為特別較佳之共聚成分(共聚單體)之例子而例舉。 Further, (meth)acrylonitrile or (meth)crotononitrile can be exemplified as an example of a particularly preferable copolymerization component (comonomer).
作為上述共聚成分，作為其他具有親水性之單體，含有磷酸、磷酸酯、四級銨鹽、伸乙基氧基鏈、伸丙基氧基鏈、磺酸及其鹽、嗎啉代基乙基等之單體等為有用的。 As the above-mentioned copolymerization component, as another monomer having hydrophilicity, it contains phosphoric acid, a phosphate ester, a quaternary ammonium salt, an extended ethyloxy chain, a propyloxy chain, a sulfonic acid and a salt thereof, and a morpholino group B. A monomer or the like of a base or the like is useful.
上述磺酸基、羧酸基可來自金屬鹽。 The above sulfonic acid group or carboxylic acid group may be derived from a metal salt.
在本發明之黏合劑中，共聚之單體之種類、數量沒有特別限制，較佳為1~12種，更佳為1~8種，特別較佳為1~5種。 In the binder of the present invention, the type and amount of the monomer to be copolymerized are not particularly limited, and are preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 5.
以下，用化學式1-1~化學式1-24表示本發明之化學式1之形態的黏合劑之具體例，但本發明不限於此。 In the following, a specific example of the binder of the chemical formula 1 of the present invention is shown by Chemical Formula 1-1 to Chemical Formula 1-24, but the present invention is not limited thereto.
[化學式1-1]
[化學式1-6]玻璃化轉變溫度(Tg)=150℃
[化學式1-11]玻璃化轉變溫度(Tg)=140℃
[化學式1-16]玻璃化轉變溫度(Tg)=140℃
接下來，本發明之包含量子點之固化性組合物能夠包含化學式2之黏合劑，玻璃化轉變溫度可為-20~250℃。 Next, the curable composition containing the quantum dots of the present invention can contain the binder of Chemical Formula 2, and the glass transition temperature can be -20 to 250 °C.
藉由含有化學式2所表示之化合物，能夠提高光(射線)照射時之固化性，能夠形成固化度高之圖案。因此，為高解析度的，且藉由在量子點之表面起到免受POB工序中產生之自由基的影響之保護基團之作用，能夠表現優異之亮度特性。 By containing the compound represented by Chemical Formula 2, the curability at the time of light (ray) irradiation can be improved, and a pattern having a high degree of curing can be formed. Therefore, it is high-resolution and can exhibit excellent brightness characteristics by acting as a protective group on the surface of the quantum dot which is protected from the radical generated in the POB process.
化學式2中，R5及R6各自獨立地彼此相同或不同，且表示氫或C1-C6烷基。 In Chemical Formula 2, R 5 and R 6 are each independently the same or different from each other, and represent hydrogen or a C1-C6 alkyl group.
R7表示氧、-NH-或基。 R 7 represents oxygen, -NH- or base.
R8表示C1-C30伸烷基、C1-C30伸烷基氧基或C1-C30乙基氧基羰基胺基乙基。 R 8 represents a C1-C30 alkylene group, a C1-C30 alkyleneoxy group or a C1-C30 ethyloxycarbonylaminoethyl group.
上述R8所表示之伸烷基、伸烷基氧基及乙基氧基羰基胺基乙基之中，較佳均為C1~C25之基團，更佳為C1~C20之基團，特別較佳亞甲基、伸乙基、伸丙基、伸丁基、伸乙基氧基、二伸乙基氧基、三伸乙基氧基、乙基氧基羰基胺基乙基。此等基團可具有取代基。作為上述R8之取代基，較佳為C1~C20烷基或OH基，其中，更佳為C1~C15烷基或OH基，進一步較佳為C1~C10烷基或OH基，特別較佳為C1~C7烷基或OH基。其中，考慮到原料及合成適合性等，最佳為甲基、乙基、分支鏈或直鏈之丙基、丁基、戊基、己基、OH基。 The alkylene group, the alkyleneoxy group and the ethyloxycarbonylaminoethyl group represented by the above R 8 are preferably a group of C1 to C25, more preferably a group of C1 to C20, particularly Preferred are methylene, ethyl, propyl, butyl, ethyl ethoxy, diethyloxy, triethyloxy, ethyloxycarbonylaminoethyl. These groups may have a substituent. The substituent of R 8 is preferably a C1 to C20 alkyl group or an OH group, more preferably a C1 to C15 alkyl group or an OH group, further preferably a C1 to C10 alkyl group or an OH group, particularly preferably It is a C1~C7 alkyl group or an OH group. Among them, a methyl group, an ethyl group, a branched chain or a linear propyl group, a butyl group, a pentyl group, a hexyl group or an OH group is preferable in view of the raw material, the synthetic suitability and the like.
R9表示含有不飽和雙鍵之基團。 R 9 represents a group containing an unsaturated double bond.
上述R9表示含有不飽和雙鍵之基團，較佳為選自由乙烯基氧基、烯丙基氧基、(甲基)丙烯醯基氧基、4-乙烯基苯基氧基、4-乙烯基苯基甲基氧基、苯乙烯基、乙烯基酯基及乙烯基醚基組成之群之基團。其中，更佳為乙烯基氧基、烯丙基氧基、(甲基)丙烯醯基氧基、4-乙烯基苯基甲基氧基、乙烯基酯基，特別較佳為烯丙基氧基、(甲基)丙烯醯基氧基、4-乙烯基苯基甲基氧基。 R 9 above represents a group containing an unsaturated double bond, and is preferably selected from the group consisting of vinyloxy group, allyloxy group, (meth) acryloyloxy group, 4-vinylphenyloxy group, 4- a group consisting of a group consisting of a vinyl phenylmethyloxy group, a styryl group, a vinyl ester group, and a vinyl ether group. More preferably, it is a vinyloxy group, an allyloxy group, a (meth) propylene fluorenyloxy group, a 4-vinyl phenylmethyloxy group, a vinyl ester group, and an allyyl oxygen is especially preferable. Base, (meth) propylene decyloxy, 4-vinyl phenylmethyloxy.
上述X表示0<X<100之值。更佳地，X能夠考慮膜之強度、彈性模數、黏彈性、耐熱性、合成適合性、聚合物之玻璃化轉變溫度(Tg)、溶解性、顯影性、合成適合性、膜之顯影性、顯影液之濃度、與量子點及其他成分之相互作用強度等而適當選擇。其中，X較佳為5~95之值，更佳為10~90之值，特別較佳為15~85之值。 The above X represents a value of 0 < X < 100. More preferably, X can take into consideration the strength of the film, the modulus of elasticity, the viscoelasticity, the heat resistance, the suitability for synthesis, the glass transition temperature (Tg) of the polymer, the solubility, the developability, the suitability for synthesis, and the developability of the film. The concentration of the developer, the strength of interaction with quantum dots and other components, and the like are appropriately selected. Wherein, X is preferably a value of 5 to 95, more preferably a value of 10 to 90, and particularly preferably a value of 15 to 85.
作為上述化學式2所表示之化合物之分子量，以重量平均分子量計，較佳為500~10,000,000Da(道爾頓：分子量單位)，更佳為100~5,000,000Da，特別較佳為2,000~5,000,000Da。 The molecular weight of the compound represented by the above Chemical Formula 2 is preferably 500 to 10,000,000 Da (Dalton: molecular weight unit), more preferably 100 to 5,000,000 Da, and particularly preferably 2,000 to 5,000,000 Da, based on the weight average molecular weight.
上述黏合劑尤其較佳為水溶性或鹼溶性。在此，鹼溶性係指， 可溶於下述鹼性化合物之水溶液、或與水具有混合性之任意有機溶劑及該鹼性化合物的水溶液混合而成之溶液。 The above binder is particularly preferably water-soluble or alkali-soluble. Here, alkali solubility means A solution which is soluble in an aqueous solution of the following basic compound or an aqueous solution of any organic solvent which is miscible with water and an aqueous solution of the basic compound.
以下，例舉上述化學式2所表示之化合物之具體例，但本發明不限於此。 Specific examples of the compound represented by the above Chemical Formula 2 are exemplified below, but the present invention is not limited thereto.
包含上述化學式1或化學式2所表示之化合物之黏合劑相對於包含量子點的固化性組合物之全部固體成分(質量)較佳為10~90質量%，更佳為15~80質量%。 The binder containing the compound represented by the above Chemical Formula 1 or Chemical Formula 2 is preferably 10 to 90% by mass, and more preferably 15 to 80% by mass based on the total solid content (mass) of the curable composition containing the quantum dot.
若上述黏合劑之含量低於上述範圍，則由光(射線)之照射引起之固化度的提高效果不充分，有時會使耐熱性、解析度以及固化部之殘膜率、未固化部之顯影性等效果降低。此外，若超過上述範圍，則其他成分之含量過度降低，有時會使顯影性、著色性等受到損傷。 When the content of the above-mentioned binder is less than the above range, the effect of improving the degree of curing by light (ray) irradiation may be insufficient, and the heat resistance, the resolution, the residual film ratio of the cured portion, and the uncured portion may be insufficient. The effect such as developability is lowered. In addition, when it exceeds the above range, the content of the other components is excessively lowered, and the developability, the coloring property, and the like may be impaired.
本發明之固化性樹脂組合物包含光致發光量子點粒子。 The curable resin composition of the present invention contains photoluminescence quantum dot particles.
所謂量子點為奈米尺寸之半導體物質。原子形成分子，分子構 成諸如簇之小分子之集合體而形成奈米粒子。當此類奈米粒子尤其帶有半導體特性時，將其稱為量子點。當量子點自外部獲得能量而成為激發態時，會自行釋放符合相應能量帶隙之能量。 The quantum dots are semiconductor materials of nanometer size. Atom forming molecule Nanoparticles are formed into a collection of small molecules such as clusters. When such nanoparticles have, in particular, semiconductor properties, they are referred to as quantum dots. When a quantum dot acquires energy from the outside and becomes an excited state, it releases its own energy in accordance with the corresponding energy band gap.
本發明之固化性組合物包含此類光致發光量子點粒子，由其製造之濾色器能夠藉由光之照射而發光(光致發光)。在包括濾色器之習知影像顯示裝置中，白色光透過濾色器而表現顏色，在該過程中，光之一部分經濾色器吸收，因而光效率降低。然而，在包含由本發明之固化性組合物製造之濾色器的情況下，濾色器藉助光源之光而自行發光，因而能夠表現優異之光效率。此外，由於釋放具有顏色之光，因此顏色再現性優異，且由於藉由光致發光向全部方向釋放光，因此亦能夠改善視角。 The curable composition of the present invention contains such photoluminescent quantum dot particles, and a color filter manufactured therefrom can emit light (photoluminescence) by irradiation of light. In a conventional image display device including a color filter, white light passes through a color filter to express color, and in the process, a part of the light is absorbed by the color filter, and thus light efficiency is lowered. However, in the case of including the color filter manufactured from the curable composition of the present invention, the color filter self-illuminates by the light of the light source, and thus can exhibit excellent light efficiency. Further, since light having color is released, color reproducibility is excellent, and since light is emitted in all directions by photoluminescence, the viewing angle can also be improved.
本發明之量子點粒子只要為能夠藉由光之刺激而發光的量子點粒子，就沒有特別限制，能夠選自由例如II-VI族半導體化合物；III-V族半導體化合物；IV-VI族半導體化合物；IV族元素或包含其之化合物；及其組合組成之群。其能夠單獨使用或混合2種以上使用。上述II-VI族半導體化合物能夠選自由如下物質組成之群：選自由CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe及其混合物組成之群之二元素化合物，選自由CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe及其混合物組成之群之三元素化合物，及選自由CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe、HgZnSTe及其的混合物組成之群之四元素化合物；上述III-V族半導體化合物能夠選自由如下物質組成之群：選自由GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb及其混合物組成之群之二元素化合物，選自由GaNP、GaNAs、 GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP及其混合物組成之群之三元素化合物，及選自由GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs、InAlPSb及其混合物組成之群之四元素化合物；上述IV-VI族半導體化合物能夠選自由如下物質組成之群：選自由SnS、SnSe、SnTe、PbS、PbSe、PbTe及其混合物組成之群之二元素化合物，選自由SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe及其混合物組成之群之三元素化合物，及選自由SnPbSSe、SnPbSeTe、SnPbSTe及其混合物組成之群之四元素化合物；上述IV族元素或包含其之化合物能夠選自由如下物質組成之群：選自由Si、Ge及其混合物組成之群之元素化合物，及選自由SiC、SiGe及其混合物組成之群之二元素化合物。 The quantum dot particles of the present invention are not particularly limited as long as they are light-emitting, and can be selected from, for example, a Group II-VI semiconductor compound; a Group III-V semiconductor compound; and a Group IV-VI semiconductor compound. a Group IV element or a compound comprising the same; and a combination thereof. These can be used individually or in mixture of 2 or more types. The above Group II-VI semiconductor compound can be selected from the group consisting of a group of two-element compounds selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof, selected from a tri-element compound consisting of CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, and mixtures thereof, and selected from CdZnSeS a four-element compound composed of a group consisting of CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and a mixture thereof; the above III-V semiconductor compound can be selected from the group consisting of GaN, GaP, a two-element compound consisting of GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof, selected from the group consisting of GaNP, GaNAs, a tri-element compound consisting of GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof, and selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP a four-element compound of a group consisting of GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and a mixture thereof; the above IV-VI semiconductor compound can be selected from the group consisting of: SnS, SnSe a two-element compound consisting of SnTe, PbS, PbSe, PbTe, and a mixture thereof, selected from the group consisting of three elements of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof, and a four-element compound selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and a mixture thereof; the above-mentioned Group IV element or a compound containing the same can be selected from the group consisting of elemental compounds selected from the group consisting of Si, Ge, and mixtures thereof. And a di-element compound selected from the group consisting of SiC, SiGe, and mixtures thereof.
量子點粒子可為均質之(homogeneous)單一結構，核殼(core-shell)、梯度(gradient)結構等二重結構，或其混合結構。在核殼(core-shell)二重結構中，形成各個核(core)及殼(shell)之物質能夠由上述提及之彼此不同的半導體化合物形成。例如，上述核能夠包含選自由CdSe、CdS、ZnS、ZnSe、CdTe、CdSeTe、CdZnS、PbSe、AgInZnS及ZnO組成之群之一種以上物質，但不限於此。上述殼能夠包含選自由CdSe、ZnSe、ZnS、ZnTe、CdTe、PbS、TiO、SrSe及HgSe組成之群之一種以上物質，但不限於此。通常用於濾色器製造之著色感光性樹脂組合物，為了表現顏色，會包含紅色、綠色、藍色著色劑，與此相同，光致發光量子點粒子亦可分為紅色量子點粒子、綠色量子點粒子及藍色量子點粒子，本發明之量子點粒子可為紅色量子點粒子、綠色量子點粒子或藍色量子點粒子。 The quantum dot particles may be a homogenous single structure, a core-shell, a gradient structure, or the like, or a mixed structure thereof. In a core-shell double structure, substances forming respective cores and shells can be formed of semiconductor compounds different from each other mentioned above. For example, the core may include one or more selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS, and ZnO, but is not limited thereto. The shell may include one or more selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto. The colored photosensitive resin composition generally used for color filter manufacturing contains red, green, and blue colorants in order to express color. Similarly, photoluminescent quantum dot particles can be classified into red quantum dot particles and green. The quantum dot particles and the blue quantum dot particles, the quantum dot particles of the present invention may be red quantum dot particles, green quantum dot particles or blue quantum dot particles.
量子點粒子能夠藉由濕式化學製程(wet chemical process)、有機 金屬化學沈積製程或分子束外延製程合成。濕式化學製程為向有機溶劑加入前驅體物質而使粒子生長之方法。當結晶生長時，有機溶劑自然地配位於量子點結晶之表面來起到分散劑之作用，從而調節結晶之生長，因此與有機金屬化學沈積(MOCVD，metal organic chemical vapor deposition)、分子束外延(MBE，molecular beam epitaxy)等氣相沈積法相比，能夠藉由更加容易且廉價之製程來控制奈米粒子之生長。 Quantum dot particles can be wet chemical processes, organic Metal chemical deposition process or molecular beam epitaxy process synthesis. The wet chemical process is a method of growing particles by adding a precursor substance to an organic solvent. When the crystal grows, the organic solvent is naturally located on the surface of the quantum dot crystal to act as a dispersing agent, thereby regulating the growth of the crystal, and thus metal organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MOCVD) Compared with vapor deposition methods such as MBE, molecular beam epitaxy, the growth of nanoparticles can be controlled by an easier and cheaper process.
本發明之量子點粒子之含量沒有特別限制，例如在感光性樹脂組合物之固體成分之總重量中，較佳以3~80重量%包含，更佳以5~70重量%包含。若上述量子點粒子之含量低於上述範圍，則發光效率非常弱，若超過上述範圍，則存在其他組成之含量相對不足而難以形成像素圖案之問題。 The content of the quantum dot particles of the present invention is not particularly limited. For example, the total weight of the solid components of the photosensitive resin composition is preferably 3 to 80% by weight, more preferably 5 to 70% by weight. When the content of the above-mentioned quantum dot particles is less than the above range, the luminous efficiency is extremely weak. When the content exceeds the above range, there is a problem that the content of other components is relatively insufficient and it is difficult to form a pixel pattern.
本發明之包含量子點之固化性組合物可進一步包含能夠與上述化學式1或化學式2所表示之化合物併用之其他黏合劑。 The curable composition containing a quantum dot of the present invention may further contain another binder which can be used in combination with the compound represented by the above Chemical Formula 1 or Chemical Formula 2.
作為其他黏合劑，只要為鹼溶性就沒有特別限制，較佳自耐熱性、顯影性、獲得性等方面選擇。 The other binder is not particularly limited as long as it is alkali-soluble, and is preferably selected from the viewpoints of heat resistance, developability, and availability.
作為上述鹼溶性黏合劑，較佳為線型有機高分子聚合物，即在有機溶劑中為可溶性，能夠在弱鹼水溶液中顯影之物質。作為此類線型有機高分子聚合物，可利用側鏈具有羧酸之聚合物，例如日本特開昭59-44615號、日本特公昭54-34327號、日本特公昭58-12577號、日本特公昭54-25957號、日本特開昭59-53836號、日本特開昭59-71048號公報中記載之甲基丙烯酸共聚物、丙烯酸共聚物、衣康酸共聚物、巴豆酸共聚物、順丁烯二酸共聚物、部分酯化順丁烯二酸共聚物等；側鏈具有羧酸之酸性纖維素衍生物。 The alkali-soluble binder is preferably a linear organic polymer, that is, a substance which is soluble in an organic solvent and can be developed in a weakly alkaline aqueous solution. As such a linear organic high molecular polymer, a polymer having a carboxylic acid in a side chain can be used, for example, JP-A-59-44615, JP-A-54-34327, JP-A-58-12577, and JP-A-2013 A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid described in JP-A-59-53848, JP-A-59-71048, and JP-A-59-71048 A diacid copolymer, a partially esterified maleic acid copolymer or the like; an acid cellulose derivative having a side chain having a carboxylic acid.
除此之外，使酸酐與具有羥基之聚合物加成之物質等，聚羥基苯乙烯系樹脂、聚矽氧烷系樹脂、聚(2-羥基乙基(甲基)丙烯酸酯)、 聚乙烯基吡咯啶酮、聚環氧乙烷、聚乙烯醇等亦有用。 In addition to the above, a substance obtained by adding an acid anhydride to a polymer having a hydroxyl group, a polyhydroxystyrene resin, a polyoxyalkylene resin, or a poly(2-hydroxyethyl (meth)acrylate), Polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful.
此外，在第1方式中，可有用地使用由上述化學式1所表示之結構單元以及構成本發明之黏合劑的成分(即，共聚成分)形成之黏合劑。 Further, in the first aspect, a binder formed of the structural unit represented by the above Chemical Formula 1 and a component (that is, a copolymerization component) constituting the binder of the present invention can be used.
此外，亦可為將具有親水性之單體共聚而成之物質，可舉出例如烷氧基烷基(甲基)丙烯酸酯、羥基烷基(甲基)丙烯酸酯、甘油(甲基)丙烯酸酯、(甲基)丙烯醯胺、N-羥甲基丙烯醯胺、第二或第三烷基丙烯醯胺、二烷基胺基烷基(甲基)丙烯酸酯、嗎啉(甲基)丙烯酸酯、N-乙烯基吡咯啶酮、N-乙烯基己內醯胺、乙烯基咪唑、乙烯基***、甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、分支鏈或直鏈之丙基(甲基)丙烯酸酯、分支鏈或直鏈之丁基(甲基)丙烯酸酯、苯氧基羥基丙基(甲基)丙烯酸酯等，其他含有四氫糠基、磷酸、磷酸酯、四級銨鹽、乙基氧基鏈、伸丙基氧基鏈、磺酸及其鹽、嗎啉代基乙基等之單體等。 Further, a substance obtained by copolymerizing a monomer having hydrophilicity may, for example, be an alkoxyalkyl (meth) acrylate, a hydroxyalkyl (meth) acrylate or a glycerin (meth) acrylate. Ester, (meth) acrylamide, N-methylol acrylamide, second or third alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (methyl) Acrylate, N-vinylpyrrolidone, N-vinyl caprolactam, vinyl imidazole, vinyl triazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched chain or Linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxy hydroxy propyl (meth) acrylate, etc., other containing tetrahydroindenyl, phosphoric acid, a phosphate, a quaternary ammonium salt, an ethyloxy chain, a propyloxy chain, a sulfonic acid and a salt thereof, a monomer such as a morpholinoethyl group, and the like.
在第1方式中，含有化學式1所表示之結構單元之物質的玻璃化轉變溫度(Tg)處於-20~250℃之範圍，與本發明之黏合劑併用之其他黏合劑在能夠以期望的範圍維持體系之黏彈性、玻璃化轉變溫度(Tg)時亦可含有醇系羥基。 In the first aspect, the glass transition temperature (Tg) of the substance containing the structural unit represented by Chemical Formula 1 is in the range of -20 to 250 ° C, and other binders used in combination with the adhesive of the present invention can be in a desired range. The alcoholic hydroxyl group may also be contained in maintaining the viscoelasticity and glass transition temperature (Tg) of the system.
此外，在本發明中，自提高交聯效率之觀點出發，可在側鏈具有聚合性基團，在側鏈具有烯丙基、(甲基)丙烯酸基、烯丙基氧基烷基等之聚合物等亦為有用的。作為在側鏈具有聚合性基團之聚合物之例子，可例舉KS RESIST-106(大阪有機化學工業株式會社製品)、CYCLOMER P系列(DAICEL化學工業株式會社製品)等。 Further, in the present invention, from the viewpoint of improving the crosslinking efficiency, a polymerizable group may be present in the side chain, and an allyl group, a (meth)acryl group, an allyloxyalkyl group or the like may be present in the side chain. Polymers and the like are also useful. Examples of the polymer having a polymerizable group in the side chain include KS RESIST-106 (product of Osaka Organic Chemical Industry Co., Ltd.), CYCLOMER P series (product of DAICEL Chemical Industry Co., Ltd.), and the like.
此外，自進一步提高固化被膜之強度之觀點出發，醇溶性耐綸、2,2-雙-(4-羥基苯基)-丙烷與表氯醇之聚醚等亦為有用的。 Further, from the viewpoint of further increasing the strength of the cured film, a alcohol-soluble nylon, a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin, and the like are also useful.
此等各種各樣之黏合劑之中，自耐熱性之觀點出發，較佳為聚 羥基苯乙烯系樹脂、聚矽氧烷系樹脂、丙烯酸系樹脂、丙烯醯胺系樹脂、丙烯酸/丙烯醯胺共聚物樹脂，自控制顯影性之觀點出發，較佳為丙烯酸系樹脂、丙烯醯胺系樹脂、丙烯酸/丙烯醯胺共聚物樹脂。此外，在與第1觀點之黏合劑一同使用之情況下，較佳為由化學式1所表示之結構單元以及構成高分子化合物之成分(即，共聚成分)形成黏合劑。 Among these various adhesives, from the viewpoint of heat resistance, it is preferred to be agglomerated The hydroxystyrene resin, the polyoxyalkylene resin, the acrylic resin, the acrylamide resin, and the acrylic acid/acrylamide copolymer resin are preferably an acrylic resin or an acrylamide from the viewpoint of controlling developability. Resin, acrylic acid / acrylamide copolymer resin. Further, when it is used together with the binder of the first aspect, it is preferred that the structural unit represented by Chemical Formula 1 and the component constituting the polymer compound (that is, a copolymerization component) form a binder.
作為上述丙烯酸系樹脂，較佳為由選自苄基(甲基)丙烯酸酯、(甲基)丙烯酸、羥基乙基(甲基)丙烯酸酯、(甲基)丙烯醯胺等之單體形成之共聚物以及KS RESIST-106(大阪有機化學工業株式會社製品)、CYCLOMER P系列等。 The acrylic resin is preferably formed of a monomer selected from the group consisting of benzyl (meth) acrylate, (meth) acryl, hydroxyethyl (meth) acrylate, and (meth) acrylamide. Copolymer, KS RESIST-106 (product of Osaka Organic Chemical Industry Co., Ltd.), CYCLOMER P series, and the like.
此外，鹼溶性苯酚樹脂亦為有用的。作為上述鹼溶性苯酚樹脂，可舉出例如酚醛清漆樹脂或乙烯基聚合物等。 Further, an alkali-soluble phenol resin is also useful. The alkali-soluble phenol resin may, for example, be a novolak resin or a vinyl polymer.
作為上述酚醛清漆樹脂，可舉出例如酚類與醛類在酸催化劑之存在下縮合而得之物質。作為酚類，可舉出例如苯酚、甲酚、乙基苯酚、丁基苯酚、二甲苯酚、苯基苯酚、鄰苯二酚、間苯二酚、鄰苯三酚、萘酚、雙酚A等。此等酚類能夠單獨使用或縮合2種以上使用。作為醛類，可舉出例如甲醛、低聚甲醛、乙醛、丙醛、苯甲醛等。 Examples of the novolak resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethyl phenol, butyl phenol, xylenol, phenylphenol, catechol, resorcin, pyrogallol, naphthol, and bisphenol A. Wait. These phenols can be used alone or in combination of two or more. Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and the like.
作為上述酚醛清漆樹脂之具體例，可例舉間甲酚、對甲酚或其混合物與福爾馬林之縮合生成物。此等酚醛清漆樹脂可使用分離等方法來調節分子量分佈。此外，亦可將雙酚C或雙酚A等具有酚性羥基之低分子量成分與上述酚醛清漆樹脂混合。 Specific examples of the novolac resin include a condensation product of m-cresol, p-cresol or a mixture thereof with formalin. These novolak resins can be adjusted to have a molecular weight distribution by a method such as separation. Further, a low molecular weight component having a phenolic hydroxyl group such as bisphenol C or bisphenol A may be mixed with the above novolak resin.
作為上述其他黏合劑之重量平均分子量(用GPC法測定之聚苯乙烯換算值)，較佳為500~10,000,000Da(道爾頓：分子量單位)，更佳為1,000~5,000,000Da，特別較佳為2,000~5,000,000Da。 The weight average molecular weight (polystyrene equivalent value measured by GPC method) of the above other binder is preferably 500 to 10,000,000 Da (Dalton: molecular weight unit), more preferably 1,000 to 5,000,000 Da, and particularly preferably 2,000~5,000,000 Da.
此外，上述其他黏合劑為能夠與本發明之黏合劑併用而使用之物質，在僅使用本發明之黏合劑就能夠充分發揮效能之情況下，亦可 不使用。 Further, the above-mentioned other binder is a substance which can be used in combination with the binder of the present invention, and can be sufficiently used only when the binder of the present invention is used. Do not use.
此外，在將本發明之化學式1或化學式2所表示之黏合劑與其他黏合劑併用的情況下，上述其他黏合劑在本發明之包含量子點之固化性組合物中之使用量相對於組合物中之全部固體成分較佳為0~90質量%，更佳為0~80質量%，特別較佳為0~70質量%。 Further, when the binder represented by Chemical Formula 1 or Chemical Formula 2 of the present invention is used in combination with another binder, the amount of the other binder used in the curable composition containing quantum dots of the present invention is relative to the composition. The solid content in all is preferably from 0 to 90% by mass, more preferably from 0 to 80% by mass, particularly preferably from 0 to 70% by mass.
本發明之包含量子點之固化性組合物能夠進一步包含交聯劑，以便能夠以更高靈敏度得到固化之膜。 The curable composition containing the quantum dots of the present invention can further contain a crosslinking agent so that a cured film can be obtained with higher sensitivity.
作為本發明中能夠使用之交聯劑，只要為藉由交聯反應進行膜固化之物質就沒有特別限制，可舉出例如經選自環氧樹脂(a)、羥甲基(b)、烷氧基甲基及醯基氧基甲基之一種以上取代基取代之三聚氰胺化合物、胍胺化合物、甘脲化合物或脲化合物，經選自羥甲基(c)、烷氧基甲基及醯基氧基甲基之1種以上取代基取代之苯酚化合物、萘酚化合物或羥基蒽化合物。其中，較佳為多官能環氧樹脂。 The crosslinking agent which can be used in the present invention is not particularly limited as long as it is a film which is cured by a crosslinking reaction, and examples thereof include an epoxy resin (a), a methylol group (b), and an alkyl group. a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with one or more substituents of an oxymethyl group and a decyloxymethyl group, which are selected from the group consisting of hydroxymethyl (c), alkoxymethyl and fluorenyl A phenol compound, a naphthol compound or a hydroxy hydrazine compound substituted with one or more substituents of an oxymethyl group. Among them, a polyfunctional epoxy resin is preferred.
作為上述交聯劑(a)，具有環氧基且具有交聯性之物質均可，例如，可為雙酚A二縮水甘油醚、乙二醇二縮水甘油醚、丁二醇二縮水甘油醚、己二醇二縮水甘油醚、二羥基聯苯基二縮水甘油醚、鄰苯二甲酸二縮水甘油酯、N,N-二縮水甘油基苯胺等含有2員縮水甘油基之低分子化合物，同一方式下以三羥甲基丙烷三縮水甘油醚、三羥甲基苯酚三縮水甘油醚、TrisP-PA三縮水甘油醚等為代表之含有3員縮水甘油基之低分子化合物，同一方式下以異戊四醇四縮水甘油醚、四羥甲基雙酚A四縮水甘油醚等為代表之含有4員縮水甘油基之低分子化合物，同一方式下二異戊四醇五縮水甘油基醚、二異戊四醇六縮水甘油醚等含有多員縮水甘油基之低分子化合物，以聚縮水甘油基(甲基)丙烯酸酯、2,2-雙(羥基甲基)-1-丁醇之1,2-環氧-4-(2-環氧乙烷基)環己烷加成物等為代表之含有縮水甘油基的高分子化合物等。 As the crosslinking agent (a), those having an epoxy group and having crosslinkability may be, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. a low molecular compound containing 2 members of glycidyl group, such as hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, or N,N-diglycidyl aniline. A low molecular compound containing 3 members of glycidyl group represented by trimethylolpropane triglycidyl ether, trimethylol phenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., in the same manner a low molecular compound containing 4 members of glycidyl group represented by pentaerythritol tetraglycidyl ether, tetrakis hydroxy bisphenol A tetraglycidyl ether, etc., in the same manner, diisopentyl pentoxide pentacyl glyceryl ether, diiso a low molecular weight compound containing a glycidyl group such as pentaerythritol hexahydroglyceryl ether, which is a polyglycidyl (meth) acrylate or a 2,2-bis(hydroxymethyl)-1-butanol 1,2 -epoxy-4-(2-oxiranyl)cyclohexane adduct, etc. Oil-based polymer compound.
作為上述交聯劑(b)所含有之羥甲基、烷氧基甲基、醯基氧基甲 基之取代數量，在三聚氰胺化合物之情況下，為2~6，在甘脲化合物、胍胺化合物、脲化合物之情況下，為2~4，在三聚氰胺化合物之情況下，較佳為5~6，在甘脲化合物、胍胺化合物、脲化合物之情況下，較佳為3~4。 As the above-mentioned crosslinking agent (b), a methylol group, an alkoxymethyl group or a mercaptooxy group The substitution amount of the base is 2 to 6 in the case of the melamine compound, 2 to 4 in the case of the glycoluril compound, the indoleamine compound, and the urea compound, and preferably 5 to 6 in the case of the melamine compound. In the case of a glycoluril compound, a guanamine compound, or a urea compound, it is preferably from 3 to 4.
以下，上述交聯劑(b)之三聚氰胺化合物、胍胺化合物、甘脲化合物及脲化合物一般稱為關於交聯劑(b)之(含有羥甲基、烷氧基甲基或醯基氧基甲基之)化合物。 Hereinafter, the melamine compound, the guanamine compound, the glycoluril compound, and the urea compound of the above crosslinking agent (b) are generally referred to as the crosslinking agent (b) (containing a methylol group, an alkoxymethyl group or a decyloxy group). a compound of methyl).
上述關於交聯劑(b)之含有羥甲基之化合物可藉由將關於交聯劑(b)的含有烷氧基甲基之化合物在醇中、在鹽酸、硫酸、硝酸、甲烷磺酸等酸催化劑之存在下加熱而得到。上述關於交聯劑(b)之含有醯基氧基甲基之化合物可藉由將關於交聯劑(b)的含有羥甲基之化合物在鹼性催化劑之存在下與醯基氯混合攪拌而得到。 The above-mentioned methylol group-containing compound for the crosslinking agent (b) can be obtained by using an alkoxymethyl group-containing compound for the crosslinking agent (b) in an alcohol, hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. It is obtained by heating in the presence of an acid catalyst. The above-mentioned compound containing a mercaptooxymethyl group as the crosslinking agent (b) can be obtained by mixing and stirring a methylol group-containing compound having a crosslinking agent (b) with a mercapto chloride in the presence of a basic catalyst. get.
以下，例舉具有上述取代基之關於交聯劑(b)之化合物的具體例。 Specific examples of the compound having the above substituent with respect to the crosslinking agent (b) are exemplified below.
作為上述三聚氰胺化合物，可舉出例如六羥甲基三聚氰胺、六甲氧基甲基三聚氰胺、六羥甲基三聚氰胺之羥甲基中之1~5個經甲氧基甲基化的化合物或其混合物、六甲氧基乙基三聚氰胺、六醯基氧基甲基三聚氰胺、六羥甲基三聚氰胺之羥甲基中之1~5個經醯基氧基甲基化的化合物或其混合物等。 The melamine compound may, for example, be one to five methoxymethylated compounds of a hydroxymethyl group of hexamethylol melamine, hexamethoxymethyl melamine or hexamethylol melamine or a mixture thereof. 1 to 5 fluorenyloxymethylated compounds of hexamethoxyethyl melamine, hexamethyleneoxymethyl melamine, hexamethylol melamine, or a mixture thereof, or the like.
作為上述胍胺化合物，可舉出例如四羥甲基胍胺、四甲氧基甲基胍胺、四羥甲基胍胺之1~3個羥甲基經甲氧基甲基化之化合物或其混合物、四甲氧基乙基胍胺、四醯基氧基甲基胍胺、四羥甲基胍胺之1~3個羥甲基經醯基氧基甲基化之化合物或其混合物等。 Examples of the above guanamine compound include a compound in which one to three methylol groups of tetramethylolguanamine, tetramethoxymethylguanamine, and tetrahydroxymethylguanamine are methoxymethylated or a mixture thereof, tetramethoxyethyl decylamine, tetradecyloxymethyl decylamine, tetramethylol decylamine, 1 to 3 methylol groups, methylated methoxymethylated compounds or mixtures thereof .
作為上述甘脲化合物，可舉出例如四羥甲基甘脲、四甲氧基甲基甘脲、四羥甲基甘脲之羥甲基中之1~3個經甲氧基甲基化的化合物或其混合物、四羥甲基甘脲之羥甲基中之1~3個經醯基氧基甲基化的 化合物或其混合物等。 Examples of the above-mentioned glycoluril compound include methoxymethylated ones of hydroxymethyl groups of tetramethylol glycoluril, tetramethoxymethyl glycoluril, and tetramethylol glycoluril. 1 to 3 of the compound or a mixture thereof, methylol group of tetramethylol glycoluril, methylated by a mercaptooxy group a compound or a mixture thereof or the like.
作為上述脲化合物，可舉出例如四羥甲基脲、四甲氧基甲基脲、四羥甲基脲之1~3個羥甲基經甲氧基甲基化之化合物或其混合物、四甲氧基乙基脲等。 The urea compound may, for example, be a compound of tetramethylolurea, tetramethoxymethylurea or tetramethylolurea methoxymethylated by methoxymethylation or a mixture thereof, or Methoxyethyl urea and the like.
此等關於交聯劑(b)之化合物可單獨使用，亦可組合使用。上述交聯劑(c)即經選自羥甲基、烷氧基甲基及醯基氧基甲基之一種以上基團取代之苯酚化合物、萘酚化合物或羥基蒽化合物與上述交聯劑(b)之情況相同為抑制與藉由熱交聯而經外覆(overcoat)的光致抗蝕劑之混雜(intermixing)，且進一步提高膜強度之物質。以下，有時將此等化合物一般稱為關於交聯劑(c)之含有羥甲基、烷氧基甲基或醯基氧基甲基之化合物。 These compounds for the crosslinking agent (b) may be used singly or in combination. The above crosslinking agent (c) is a phenol compound, a naphthol compound or a hydroxy hydrazine compound substituted with one or more groups selected from a methylol group, an alkoxymethyl group and a mercaptooxymethyl group, and the above crosslinking agent ( The case of b) is the same as the substance which suppresses the intermixing of the overcoated photoresist by thermal crosslinking and further increases the film strength. Hereinafter, such compounds are generally referred to as compounds containing a methylol group, an alkoxymethyl group or a mercaptooxymethyl group as the crosslinking agent (c).
作為上述交聯劑(c)所含有之羥甲基、醯基氧基甲基或烷氧基甲基之數量，每1分子最少需要2個，自熱交聯性及保存穩定性之觀點出發，較佳作為骨架之苯酚化合物之2位、4位全部經取代的化合物。此外，作為骨架之萘酚化合物、羥基蒽化合物亦較佳OH基之鄰位、對位全部經取代之化合物。上述苯酚化合物之3位或5位可未經取代，亦可具有取代基。在上述萘酚化合物中，除了OH基之鄰位以外，可未經取代，亦可具有取代基。 The amount of the methylol group, the mercaptooxymethyl group or the alkoxymethyl group contained in the crosslinking agent (c) is required to be at least two per molecule, from the viewpoint of thermal crosslinkability and storage stability. It is preferably a compound in which all of the 2-position and 4-position of the phenol compound of the skeleton are substituted. Further, as the skeleton naphthol compound or hydroxyanthracene compound, a compound in which the ortho and para positions of the OH group are all substituted are preferred. The 3- or 5-position of the above phenol compound may be unsubstituted or may have a substituent. The naphthol compound may be unsubstituted or may have a substituent in addition to the ortho position of the OH group.
上述關於交聯劑(c)之含有羥甲基之化合物可藉由將酚性OH基之2位或4位為氫原子之化合物用作原料，且使其在氫氧化鈉、氫氧化鉀、氨水、四烷基氫氧化銨等鹼性催化劑之存在下與福爾馬林反應而得到。 The above-mentioned methylol group-containing compound for the crosslinking agent (c) can be used as a raw material by using a compound having a hydrogen atom at the 2- or 4-position of the phenolic OH group, and is made to be sodium hydroxide or potassium hydroxide. It is obtained by reacting with formalin in the presence of a basic catalyst such as ammonia water or tetraalkylammonium hydroxide.
上述關於交聯劑(c)之含有烷氧基甲基之化合物可藉由將關於交聯劑(c)之含有羥甲基之化合物在醇中、在鹽酸、硫酸、硝酸、甲烷磺酸等酸催化劑之存在下加熱而得到。 The above-mentioned alkoxymethyl group-containing compound for the crosslinking agent (c) can be obtained by using a compound containing a methylol group as the crosslinking agent (c) in an alcohol, hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. It is obtained by heating in the presence of an acid catalyst.
上述關於交聯劑(c)之含有醯基氧基甲基之化合物可藉由將關於 交聯劑(c)的含有羥甲基之化合物在鹼性催化劑之存在下與醯基氯反應而得到。 The above-mentioned compound containing a mercaptooxymethyl group as the crosslinking agent (c) can be The methylol group-containing compound of the crosslinking agent (c) is obtained by reacting with mercapto chloride in the presence of a basic catalyst.
作為交聯劑(c)中之骨架化合物，可例舉酚性OH基之鄰位或對位為未經取代之苯酚化合物、萘酚、羥基蒽化合物等，例如，可使用苯酚、甲酚之各異構體，2,3-二甲苯酚、2,5-二甲苯酚、3,4-二甲苯酚、3,5-二甲苯酚、雙酚A等雙酚類，4,4'-雙羥基聯苯、TrisPPA(本州化學工業株式會社製品)、萘酚、二羥基萘、2,7-二羥基蒽等。 The skeleton compound in the crosslinking agent (c) may, for example, be an unsubstituted phenol compound, a naphthol or a hydroxy hydrazine compound in the ortho or para position of the phenolic OH group. For example, phenol or cresol may be used. Each isomer, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenol A and other bisphenols, 4,4'- Dihydroxybiphenyl, TrisPPA (product of Honshu Chemical Industry Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyindole, and the like.
作為上述交聯劑(c)之具體例，作為苯酚化合物，例如，可為三羥甲基苯酚、三(甲氧基甲基)苯酚、三羥甲基苯酚之1~2個羥甲基經甲氧基甲基化之化合物、三羥甲基-3-甲酚、三(甲氧基甲基)-3-甲酚、三羥甲基-3-甲酚之1~2個羥甲基經甲氧基甲基化之化合物、2,6-二羥甲基-4-甲酚等二羥甲基甲酚、四羥甲基雙酚A、四甲氧基甲基雙酚A、四羥甲基雙酚A之1~3個羥甲基經甲氧基甲基化之化合物、四羥甲基-4,4'-雙羥基聯苯、四甲氧基甲基-4,4'-雙羥基聯苯、TrisP-PA之六羥甲基體、TrisP-PA之六甲氧基甲基體、TrisP-PA之六羥甲基體之1~5個羥甲基經甲氧基甲基化的化合物、雙羥基甲基萘二醇等。 Specific examples of the crosslinking agent (c) include, as a phenol compound, 1 to 2 methylol groups of trimethylolphenol, tris(methoxymethyl)phenol, and trimethylolphenol. Methoxymethylated compound, trimethylol-3-methylphenol, tris(methoxymethyl)-3-cresol, trimethylol-3-methylphenol 1~2 hydroxymethyl a methoxymethylated compound, dimethylol cresol such as 2,6-dimethylol-4-methylphenol, tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, and tetra a methoxymethylated compound of hydroxymethyl bisphenol A with 1 to 3 methylol groups, tetramethylol-4,4'-bishydroxybiphenyl, tetramethoxymethyl-4,4' - bishydroxybiphenyl, hexamethylol of TrisP-PA, hexamethoxymethyl of TrisP-PA, hexamethylol of TrisP-PA, 1 to 5 hydroxymethyl groups via methoxymethyl Compound, bishydroxymethylnaphthalenediol, and the like.
此外，作為羥基蒽化合物，可舉出例如1,6-二羥基甲基-2,7-二羥基蒽等，作為含有醯基氧基甲基之化合物，可舉出例如上述含有羥甲基之化合物之羥甲基之一部分或全部經醯基氧基甲基化的化合物等。 In addition, examples of the hydroxy hydrazine compound include 1,6-dihydroxymethyl-2,7-dihydroxyindole, and the like, and examples of the compound containing a mercaptooxymethyl group include the above-described hydroxymethyl group. A compound in which a part or all of a methylol group of a compound is methylated by a mercaptooxy group.
作為此等化合物中之較佳化合物，可為三羥甲基苯酚、雙羥基甲基對甲酚、四羥甲基雙酚A、TrisP-PA(本州化學工業株式會社製品)之六羥甲基體或其羥甲基經烷氧基甲基以及羥甲基及烷氧基甲基此兩者取代之苯酚化合物。 Preferred compounds among these compounds may be hexamethylol of trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylol bisphenol A, or TrisP-PA (product of Honshu Chemical Industry Co., Ltd.). A phenolic compound in which the compound or its methylol group is substituted with an alkoxymethyl group and both a methylol group and an alkoxymethyl group.
此等關於交聯劑(c)之化合物可單獨使用，亦可組合使用。 These compounds for the crosslinking agent (c) may be used singly or in combination.
在本發明中，無需一定含有上述交聯劑。在含有時，交聯劑(a)~(c)在包含量子點之固化性組合物中之整體含量因材料的不同而不 同，相對於上述固化性組合物之固體成分(質量)，較佳為0~70重量%，更佳為0~50重量%，最佳為0~30重量%。 In the present invention, it is not necessary to necessarily contain the above crosslinking agent. When contained, the overall content of the crosslinking agents (a) to (c) in the curable composition containing quantum dots is different depending on the materials. The solid content (mass) of the curable composition is preferably 0 to 70% by weight, more preferably 0 to 50% by weight, most preferably 0 to 30% by weight.
本發明之包含量子點之固化性組合物可進一步包含具有1個以上乙烯性不飽和基團之單體或低聚物。 The quantum dot-containing curable composition of the present invention may further comprise a monomer or oligomer having one or more ethylenically unsaturated groups.
作為具有1個以上乙烯性不飽和基團之單體或低聚物，較佳為具有1個以上能夠加成聚合之乙烯性雙鍵的、常壓下具有100℃以上沸點之化合物。藉由與後述之光聚合引發劑等一同含有，能夠以負型構成本發明之包含量子點之固化性組合物，此外，自進一步提高固化性之觀點出發，可在包含正型量子點之固化性組合物中含有。 The monomer or oligomer having one or more ethylenically unsaturated groups is preferably a compound having one or more ethylenic double bonds capable of addition polymerization and having a boiling point of 100 ° C or higher at normal pressure. By containing together with a photopolymerization initiator or the like to be described later, the curable composition containing the quantum dots of the present invention can be formed in a negative form, and from the viewpoint of further improving the curability, the curing can be carried out including positive quantum dots. Contained in the composition.
作為其例子，可例舉聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、苯氧基乙基(甲基)丙烯酸酯等單官能之丙烯酸酯、甲基丙烯酸酯；聚乙二醇二(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、異戊四醇三(甲基)丙烯酸酯、異戊四醇四(甲基)丙烯酸酯、二異戊四醇五(甲基)丙烯酸酯、二異戊四醇六(甲基)丙烯酸酯、己二醇(甲基)丙烯酸酯、三羥甲基丙烷三(丙烯醯基氧基丙基)醚、三(丙烯醯基氧基乙基)異氰脲酸酯、甘油、三羥甲基乙烷等使環氧乙烷、環氧丙烷與多官能醇加成後(甲基)丙烯酸酯化之物質，日本特公昭48-41708號、日本特公昭50-6034號、日本特開昭51-37193號各公報中記載之胺基甲酸酯丙烯酸酯類、日本特開昭48-64183號、日本特公昭49-43191號、日本特公昭52-30490號各公報中記載之聚酯丙烯酸酯類、作為環氧樹脂與(甲基)丙烯酸之反應生成物的環氧丙烯酸酯類等多官能丙烯酸酯、甲基丙烯酸酯及其混合物。此外，可例舉日本接著協會志Vol.20、No.7之300~308頁中作為光固化性單體及低聚物而介紹之物質。 Examples thereof include monofunctional acrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate, and methacrylic acid. Ester; polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylic acid Ester, pentaerythritol tetra (meth) acrylate, diisopentyl pentoxide penta (meth) acrylate, diisopentaerythritol hexa (meth) acrylate, hexane diol (meth) acrylate, Trimethylolpropane tris(propylene decyloxypropyl) ether, tris(propylene decyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. to make ethylene oxide, epoxy Alkyl group which is described in each of the publications of the Japanese Patent Publication No. Sho 48-41708, Japanese Patent Publication No. Sho 50-6034, and JP-A-51-37193 Polyester acrylates described in the respective publications of the Japanese Patent Publication No. Sho 49-43183, Japanese Patent Publication No. Sho 49-43191, and Japanese Patent Publication No. Sho 52-30490, as epoxy acrylates Epoxy acrylates with (meth) acrylic acid and the product of polyfunctional acrylates, methacrylates and mixtures thereof. In addition, a substance which is introduced as a photocurable monomer and an oligomer in the following Japanese Association Association Vol. 20, No. 7 on pages 300 to 308 can be exemplified.
本發明之包含量子點之固化性組合物能夠進一步包含光聚合引發劑。 The curable composition containing a quantum dot of the present invention can further comprise a photopolymerization initiator.
關於光聚合引發劑，在以負型構成本發明之含有染料之固化性組合物的情況下，可與上述單體等一同含有，此外，在以正型構成之情況下，可根據需要含有。作為光聚合引發劑，只要為能夠使上述單體或低聚物聚合之物質就沒有特別限制，較佳自特性、引發效率、吸收波長、獲得性、費用等觀點出發進行選擇。 When the photopolymerization initiator contains the dye-containing curable composition of the present invention in a negative form, it may be contained together with the above-mentioned monomer or the like, and when it is a positive type, it may be contained as needed. The photopolymerization initiator is not particularly limited as long as it can polymerize the monomer or the oligomer, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
作為上述光聚合引發劑，例如選自鹵代甲基噁二唑化合物及鹵代甲基均三嗪化合物之一種以上活性鹵素化合物、3-芳基-取代香豆素化合物、咯吩二聚物、二苯甲酮化合物、苯乙酮化合物及其衍生物、環戊二烯-苯-鐵錯合物及其鹽、肟系化合物等。 The photopolymerization initiator is, for example, one or more active halogen compounds selected from the group consisting of a halogenated methyl oxadiazole compound and a halogenated methyl s-triazine compound, a 3-aryl-substituted coumarin compound, and a porphin dimer. , benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, lanthanide compounds and the like.
作為鹵代甲基噁二唑化合物之活性鹵素化合物，為日本特公昭57-6096號公報記載之2-鹵代甲基-5-乙烯基-1,3,4-噁二唑化合物等、2-三氯甲基-5-苯乙烯基-1,3,4-噁二唑、2-三氯甲基-5-(對氰基苯乙烯基)-1,3,4-噁二唑、2-三氯甲基-5-(對甲氧基苯乙烯基)-1,3,4-噁二唑等。 The active halogen compound of the halogenated methyl oxadiazole compound is a 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound described in JP-A-57-6096, 2 -trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, and the like.
作為鹵代甲基均三嗪系化合物之活性鹵素化合物，為日本特公昭59-1281號公報中記載之乙烯基鹵代甲基均三嗪化合物、日本特開昭53-133428號公報中記載之2-(萘-1-基)-4,6-雙鹵代甲基均三嗪化合物及4-(對胺基苯基)-2,6-二鹵代甲基均三嗪化合物等。 The active halogen compound of the halogenated methyl-s-triazine-based compound is described in JP-A-59-1281, which is described in JP-A-59-1281, and JP-A-53-133428. 2-(naphthalen-1-yl)-4,6-dihalomethyls-triazine compound and 4-(p-aminophenyl)-2,6-dihalomethyls-triazine compound and the like.
具體而言，有2,4-雙(三氯甲基)-6-對甲氧基苯乙烯基均三嗪、2,6-雙(三氯甲基)-4-(3,4-亞甲基二氧基苯基)-1,3,5-三嗪、2,6-雙(三氯甲基)-4-(4-甲氧基苯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(1-對二甲基胺基苯基-1,3-丁二烯基)均三嗪、2-三氯甲基-4-胺基6-對甲氧基苯乙烯基均三嗪、2-(萘-1-基)-4,6-雙-三氯甲基均三嗪、2-(4-甲氧基-萘-1-基)-4,6-雙-三氯甲基均三嗪、2-(4-乙氧基-萘-1-基)-4,6-雙-三氯甲基均三嗪、2-(4-丁氧基-萘-1-基)-4,6-雙-三氯甲基均三嗪、2-[4-(2-甲氧基乙基)-萘-1-基]-4,6-雙-三氯甲基均三嗪、2-[4-(2-乙氧基乙基)-萘-1-基]-4,6-雙-三氯甲基均三嗪、2-[4-(2-丁氧基乙基)-萘-1-基]-4,6-雙-三 氯甲基均三嗪、2-(2-甲氧基-萘-1-基)-4,6-雙-三氯甲基均三嗪、2-(6-甲氧基-5-甲基-萘-2-基)-4,6-雙-三氯甲基均三嗪、2-(6-甲氧基萘-2-基)-4,6-雙-三氯甲基均三嗪、2-(5-甲氧基-萘-1-基)-4,6-雙-三氯甲基均三嗪、2-(4,7-二甲氧基-萘-1-基)-4,6-雙-三氯甲基均三嗪、2-(6-乙氧基-萘-2-基)-4,6-雙-三氯甲基均三嗪、2-(4,5-二甲氧基-萘-1-基)-4,6-雙-三氯甲基均三嗪、4-[對N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[鄰甲基-對N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[對N,N-二(氯乙基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[鄰甲基-對N,N-二(氯乙基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-(對N-氯乙基胺基苯基)-2,6-二(三氯甲基)均三嗪、4-(對N-乙氧基羰基甲基胺基苯基)-2,6-二(三氯甲基)均三嗪、4-[對N,N-二(苯基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-(對N-氯乙基羰基胺基苯基)-2,6-二(三氯甲基)均三嗪、4-[對N-(對甲氧基苯基)羰基胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[間N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[間溴-對N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[間氯-對N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[間氟-對N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[鄰溴-對N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[鄰氯-對N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[鄰氟-對N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[鄰溴-對N,N-二(氯乙基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[鄰氯-對N,N-二(氯乙基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[鄰氟-對N,N-二(氯乙基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[間溴-對N,N-二(氯乙基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[間氯-對N,N-二(氯乙基)胺基苯基]-2,6-二(三氯甲基)均三嗪、4-[間氟-對N-二(氯乙基)胺基苯基]- 2,6-二(三氯甲基)均三嗪、4-(間溴-對N-乙氧基羰基甲基胺基苯基)-2,6-二(三氯甲基)均三嗪、4-(間氯-對N-乙氧基羰基甲基胺基苯基)-2,6-二(三氯甲基)均三嗪、4-(間氟-對N-乙氧基羰基甲基胺基苯基)-2,6-二(三氯甲基)均三嗪、4-(鄰溴-對N-乙氧基羰基甲基胺基苯基)-2,6-二(三氯甲基)均三嗪、4-(鄰氯-對N-乙氧基羰基甲基胺基苯基)-2,6-二(三氯甲基)均三嗪、4-(鄰氟-對N-乙氧基羰基甲基胺基苯基)-2,6-二(三氯甲基)均三嗪、4-(間溴-對N-氯乙基胺基苯基)-2,6-二(三氯甲基)均三嗪、4-(間氯-對N-氯乙基胺基苯基)-2,6-二(三氯甲基)均三嗪、4-(間氟-對N-氯乙基胺基苯基)-2,6-二(三氯甲基)均三嗪、4-(鄰溴-對N-氯乙基胺基苯基)-2,6-二(三氯甲基)均三嗪、4-(鄰氯-對N-氯乙基胺基苯基)-2,6-二(三氯甲基)均三嗪、4-(鄰氟-對N-氯乙基胺基苯基)-2,6-二(三氯甲基)均三嗪等。 Specifically, there are 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine, 2,6-bis(trichloromethyl)-4-(3,4-A) Methyldioxyphenyl)-1,3,5-triazine, 2,6-bis(trichloromethyl)-4-(4-methoxyphenyl)-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl) s-triazine, 2-trichloromethyl-4-amine 6-p-methoxystyryl-s-triazine, 2-(naphthalen-1-yl)-4,6-bis-trichloromethyl-s-triazine, 2-(4-methoxy-naphthalene-1 -yl)-4,6-bis-trichloromethyls-triazine, 2-(4-ethoxy-naphthalen-1-yl)-4,6-bis-trichloromethyls-triazine, 2- (4-Butoxy-naphthalen-1-yl)-4,6-bis-trichloromethyls-triazine, 2-[4-(2-methoxyethyl)-naphthalen-1-yl]- 4,6-bis-trichloromethyl-s-triazine, 2-[4-(2-ethoxyethyl)-naphthalen-1-yl]-4,6-bis-trichloromethyl s-triazine, 2-[4-(2-butoxyethyl)-naphthalen-1-yl]-4,6-bis-three Chloromethyl-s-triazine, 2-(2-methoxy-naphthalen-1-yl)-4,6-bis-trichloromethyls-triazine, 2-(6-methoxy-5-methyl -naphthalen-2-yl)-4,6-bis-trichloromethyl s-triazine, 2-(6-methoxynaphthalen-2-yl)-4,6-bis-trichloromethyl s-triazine , 2-(5-methoxy-naphthalen-1-yl)-4,6-bis-trichloromethyls-triazine, 2-(4,7-dimethoxy-naphthalen-1-yl)- 4,6-bis-trichloromethyls-triazine, 2-(6-ethoxy-naphthalen-2-yl)-4,6-bis-trichloromethyls-triazine, 2-(4,5 -dimethoxy-naphthalen-1-yl)-4,6-bis-trichloromethyls-triazine, 4-[p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]- 2,6-bis(trichloromethyl)s-triazine, 4-[o-methyl-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloro) Methyl)s-triazine, 4-[p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)s-triazine, 4-[o-methyl-pair N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)s-triazine, 4-(p-N-chloroethylaminophenyl)-2,6- Bis(trichloromethyl)s-triazine, 4-(p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)s-triazine, 4-[N, N-bis(phenyl)aminophenyl]-2,6-bis(trichloromethyl)s-triazine, 4-(p-N-chloroethyl) Aminophenyl)-2,6-bis(trichloromethyl)s-triazine, 4-[p-N-(p-methoxyphenyl)carbonylaminophenyl]-2,6-di(III Chloromethyl)-s-triazine, 4-[inter-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)s-triazine, 4-[ Bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)s-triazine, 4-[m-chloro-p-N,N-di ( Ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)s-triazine, 4-[m-fluoro-p-N,N-bis(ethoxycarbonylmethyl)amino group Phenyl]-2,6-bis(trichloromethyl)s-triazine, 4-[o-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di (trichloromethyl)-s-triazine, 4-[o-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)s-triazine 4-[o-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)s-triazine, 4-[o-bromo-p-N ,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)s-triazine, 4-[o-chloro-p-N,N-bis(chloroethyl)aminobenzene -2,6-bis(trichloromethyl)-s-triazine, 4-[o-fluoro-p-N,N-di(chloroethyl)aminophenyl]-2,6-di(trichloromethyl) Triazine, 4-[interbromine- N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)s-triazine, 4-[m-chloro-p-N,N-di(chloroethyl)amino group Phenyl]-2,6-bis(trichloromethyl)s-triazine, 4-[m-fluoro-p-N-bis(chloroethyl)aminophenyl]- 2,6-bis(trichloromethyl)s-triazine, 4-(m-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)s-triazine , 4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)s-triazine, 4-(m-fluoro-p-N-ethoxycarbonyl) Methylaminophenyl)-2,6-bis(trichloromethyl)s-triazine, 4-(o-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di ( Trichloromethyl)-s-triazine, 4-(o-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)s-triazine, 4-(o-fluoride) -p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)s-triazine, 4-(m-bromo-p-N-chloroethylaminophenyl)-2 ,6-bis(trichloromethyl)s-triazine, 4-(m-chloro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)s-triazine, 4-( m-fluoro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)s-triazine, 4-(o-bromo-p-N-chloroethylaminophenyl)-2, 6-bis(trichloromethyl)s-triazine, 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)s-triazine, 4-(o- Fluorine-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)s-triazine or the like.
除此之外，亦可有用地使用Midori化學株式會社製之TAZ系列(例如，TAZ-107、TAZ-110、TAZ-104、TAZ-109、TAZ-140、TAZ-204、TAZ-113、TAZ-123)、PANCHIM公司製之T系列(例如，T-OMS、T-BMP、T-R、T-B)、汽巴嘉基公司製之IRGACURE系列(例如，IRGACURE651、IRGACURE184、IRGACURE500、IRGACURE1000、IRGACURE149、IRGACURE819、IRGACURE261)、Darocur系列(例如，Darocur1173)、4,4'-雙(二乙基胺基)-二苯甲酮、2-(鄰苯甲醯基肟)-1-[4-(苯基硫基)苯基]-1,2-辛二酮、2-苄基-2-二甲基胺基-4-嗎啉代基丁醯苯、2,2-二甲氧基-2-苯基苯乙酮、2-(鄰氯苯基)-4,5-二苯基咪唑基二聚物、2-(鄰氟苯基)-4,5-二苯基咪唑基二聚物、2-(鄰甲氧基苯基)-4,5-二苯基咪唑基二聚物、2-(對甲氧基苯基)-4,5-二苯基咪唑基二聚物、2-(對二甲氧基苯基)-4,5-二苯基咪唑基二聚物、2-(2,4-二甲氧基苯基)-4,5-二苯基咪唑基二聚物、2-(對甲基巰基苯基)-4,5-二苯基咪唑基二聚物、苯偶姻異丙基醚等。 In addition, the TAZ series manufactured by Midori Chemical Co., Ltd. (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ) can also be used usefully. -123), T series made by PANCHIM (for example, T-OMS, T-BMP, TR, TB), and IRGACURE series made by Cibajiaji (for example, IRGACURE651, IRGACURE184, IRGACURE500, IRGACURE1000, IRGACURE149, IRGACURE819, IRGACURE 261), Darocur series (eg, Darocur 1173), 4,4'-bis(diethylamino)-benzophenone, 2-(o-benzylidene fluorenyl)-1-[4-(phenyl thio Phenyl]-1,2-octanedione, 2-benzyl-2-dimethylamino-4-morpholinobutenylbenzene, 2,2-dimethoxy-2-phenyl Acetophenone, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl)-4,5-diphenylimidazolyl dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazolyl dimer, 2-(pair Dimethoxyphenyl)-4,5-diphenylimidazolyl dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazolyl dimer, 2 -(p-methylmercaptophenyl)-4,5-diphenylimidazolyl Dimer, benzoin isopropyl ether and the like.
在此等光聚合引發劑中，能夠併用增敏劑、光穩定劑。 Among these photopolymerization initiators, a sensitizer and a light stabilizer can be used in combination.
作為其具體例，可例舉苯偶姻、苯偶姻甲醚、9-茀酮、2-氯-9-茀酮、2-甲基-9-茀酮、9-蒽酮、2-溴-9-蒽酮、2-乙基-9-蒽酮、9,10-蒽醌、2-乙基-9,10-蒽醌、2-第三丁基-9,10-蒽醌、2,6-二氯-9,10-蒽醌、氧雜蒽酮(xanthone)、2-甲基氧雜蒽酮、2-甲氧基氧雜蒽酮、2-乙氧基氧雜蒽酮、硫代氧雜蒽酮、2,4-二乙基硫代氧雜蒽酮、吖啶酮、10-丁基-2-氯吖啶酮、二苯基乙二酮、二苄叉丙酮、對(二甲基胺基)苯基苯乙烯基酮、對(二甲基胺基)苯基-對甲基苯乙烯基酮、二苯甲酮、對(二甲基胺基)二苯甲酮(或米蚩酮)、對(二乙基胺基)二苯甲酮、苯并蒽酮等、日本特公昭51-48516號公報中記載之苯并噻唑系化合物等、TINUVIN1130、TINUVIN400等。 Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-fluorenone, and 2-bromo. -9-fluorenone, 2-ethyl-9-fluorenone, 9,10-fluorene, 2-ethyl-9,10-fluorene, 2-tert-butyl-9,10-fluorene, 2 ,6-dichloro-9,10-fluorene, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-ethoxyxanthone, Thiooxanone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, diphenylethylenedione, dibenzylideneacetone, pair (Dimethylamino)phenylstyryl ketone, p-(dimethylamino)phenyl-p-methylstyryl ketone, benzophenone, p-(dimethylamino)benzophenone (or Michler's ketone), p-(diethylamino)benzophenone, benzoxanthone, etc., benzothiazole-based compounds, such as those described in JP-A-51-48516, TINUVIN 1130, TINUVIN 400, and the like.
本發明之包含量子點之固化性組合物中，除了前述光聚合引發劑以外能夠使用其他公知引發劑。 In the curable composition containing quantum dots of the present invention, other known initiators can be used in addition to the photopolymerization initiator.
具體而言，可例舉美國專利第2,367,660號說明書中揭示之連位聚醛酮基(vicinal polyketaldonyl)化合物、美國專利第2,367,661號及美國專利第2,367,670號說明書中揭示之α-羰基化合物、美國專利第2,448,828號說明書中揭示之偶姻醚、美國專利第2,722,512號說明書中揭示之經α-烴取代的芳族偶姻化合物、美國專利第3,046,127號及美國專利第2,951,758號說明書中揭示之多核醌化合物、美國專利第3,549,367號說明書中揭示之三烯丙基咪唑二聚物/對胺基苯基酮之組合、日本特公昭51-48516號公報中揭示之苯并噻唑系化合物/三鹵代甲基均三嗪系化合物等。 Specifically, the vicinal polyketaldonyl compound disclosed in the specification of U.S. Patent No. 2,367,660, the α-carbonyl compound disclosed in the specification of U.S. Patent No. 2,367,661, and the U.S. Patent No. 2,367,670, and the U.S. Patent. The affixed ether disclosed in the specification of No. 2,448,828, the alpha-hydrocarbon-substituted aromatic acyloin compound disclosed in the specification of U.S. Patent No. 2,722,512, the polynuclear ruthenium compound disclosed in the specification of U.S. Patent No. 3,046,127 and U.S. Patent No. 2,951,758. The combination of triallyl imidazole dimer/p-aminophenyl ketone disclosed in the specification of U.S. Patent No. 3,549,367, the benzothiazole compound/trihalomethyl group disclosed in Japanese Patent Publication No. Sho 51-48516 A s-triazine-based compound or the like.
上述光聚合引發劑相對於本發明之包含量子點之固化性組合物中的固體成分之整體重量較佳為0.01~50重量%，更佳為1~30重量%，特別較佳為1~20重量%。在光聚合引發劑低於上述範圍之情況下，難以進行聚合，若超過上述範圍，則雖然聚合率變大，但分子量變低， 有時膜強度變弱。 The total weight of the photopolymerization initiator relative to the solid content of the quantum dot-containing curable composition of the present invention is preferably from 0.01 to 50% by weight, more preferably from 1 to 30% by weight, particularly preferably from 1 to 20%. weight%. When the photopolymerization initiator is less than the above range, it is difficult to carry out polymerization, and if it exceeds the above range, the polymerization rate is increased, but the molecular weight is lowered. Sometimes the film strength is weak.
本發明之包含量子點之固化性組合物能夠進一步包含熱聚合抑制劑。例如有氫醌、對甲氧基苯酚、二-第三丁基-對甲酚、鄰苯三酚、第三丁基鄰苯二酚、苯醌、4,4'-硫代雙(3-甲基-6-第三丁基苯酚)、2,2'-亞甲基雙(4-甲基-6-第三丁基苯酚)、2-巰基苯并咪唑等。 The curable composition containing quantum dots of the present invention can further comprise a thermal polymerization inhibitor. For example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-thiobis (3- Methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, and the like.
關於本發明之包含量子點之固化性組合物，在以正型構成包含量子點之固化性組合物之情況下，能夠進一步包含萘醌二疊氮基化合物。作為萘醌二疊氮基化合物，例如有鄰萘醌二疊氮基-5-磺酸酯或磺醯胺或鄰萘醌二疊氮基-4-磺酸酯或磺醯胺等。此等酯或醯胺能夠使用例如日本特開平2-84650號公報及日本特開平3-49437號公報中以化學式1記載之苯酚化合物等且藉由公知之方法製造。 In the curable composition containing a quantum dot of the present invention, when a curable composition containing a quantum dot is formed in a positive form, a naphthoquinonediazide compound can be further contained. Examples of the naphthoquinonediazide compound include o-naphthoquinonediazide-5-sulfonate or sulfonamide or o-naphthoquinonediazide-4-sulfonate or sulfonamide. For example, the phenol compound or the like described in Chemical Formula 1 of JP-A-4-84650 and JP-A-3-49437 can be produced by a known method.
上述鹼溶性苯酚樹脂及交聯劑通常相對於溶劑中之整體質量分別以2~50重量%及2~30重量%程度之比率溶解。此外，上述萘醌二疊氮基化合物及染料通常相對於含有上述鹼溶性樹脂及交聯劑之溶液分別以2~30重量%及2~50重量%程度之比率添加。此外，在濾色器用抗蝕劑組合物中，能夠進一步添加例如用於提供均勻塗佈性之平滑劑等彼等上述技術領域中應用之各種添加劑。 The alkali-soluble phenol resin and the crosslinking agent are usually dissolved in a ratio of 2 to 50% by weight and 2 to 30% by weight, based on the total mass of the solvent. Further, the naphthoquinonediazide compound and the dye are usually added in a ratio of 2 to 30% by weight and 2 to 50% by weight, based on the solution containing the alkali-soluble resin and the crosslinking agent, respectively. Further, in the resist composition for a color filter, various additives such as those used in the above technical fields such as a smoothing agent for providing uniform coating properties can be further added.
本發明之包含量子點之固化性組合物能夠包含溶劑，上述溶劑沒有特別限制，尤其較佳考慮量子點、黏合劑之溶解性、塗佈性、安全性而進行選擇。 The curable composition containing a quantum dot of the present invention can contain a solvent, and the solvent is not particularly limited, and it is particularly preferable to select a quantum dot, a solubility of a binder, a coating property, and safety.
作為上述溶劑，較佳為酯類，例如乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯，烷基酯類，乳酸甲酯、乳酸乙酯、氧基乙酸甲酯、氧基乙酸乙酯、氧基乙酸丁酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯等；3-氧基丙酸甲酯、3-氧基丙酸乙酯等3-氧基丙酸烷基酯類，例如3-甲 氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯等；2-氧基丙酸甲酯、2-氧基丙酸乙酯、2-氧基丙酸丙酯等2-氧基丙酸烷基酯類，例如2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-氧基-2-甲基丙酸甲酯、2-氧基-2-甲基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯等；丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-側氧基丁酸甲酯、2-側氧基丁酸乙酯等；醚類，例如二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單***、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚、丙二醇甲醚、丙二醇甲醚乙酸酯、丙二醇***乙酸酯、丙二醇丙醚乙酸酯等；酮類，例如甲乙酮、環己酮、2-庚酮、3-庚酮等；芳族烴類，例如甲苯、二甲苯等。 As the above solvent, preferred are esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, methoxy Ethyl acetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; 3-oxypropane methyl ester, ethyl 3-oxypropionate, etc. Acid alkyl esters, such as 3-methyl Methyl oxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.; methyl 2-oxypropionate, 2-oxygen Alkyl 2-oxopropionates such as ethyl propyl propionate and propyl 2-oxypropionate, for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methyl Propyl oxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropanoate, 2-oxy-2-methyl Ethyl propionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, etc.; methyl pyruvate, ethyl pyruvate, propyl pyruvate , ethyl acetate methyl acetate, ethyl acetate ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutyrate, etc.; ethers, such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene Alcohol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl Ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3- Heptanone or the like; an aromatic hydrocarbon such as toluene, xylene or the like.
其中，更較佳為3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙基溶纖劑乙酸酯、乳酸乙酯、二乙二醇二甲醚、乙酸丁酯、3-甲氧基丙酸甲酯、2-庚酮、環己酮、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇甲醚、丙二醇甲醚乙酸酯等。 Among them, more preferred are methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, and butyl acetate. Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, and the like.
本發明之包含量子點之固化性組合物能夠進一步包含各種添加物，例如填充劑、上述以外之高分子化合物、界面活性劑、密合促進劑、抗氧化劑、紫外線吸收劑、防凝劑等。 The curable composition containing a quantum dot of the present invention can further contain various additives such as a filler, a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-coagulant, and the like.
作為上述各種添加物之具體例，可例舉玻璃、氧化鋁等填充劑；聚乙烯醇、聚丙烯酸、聚乙二醇單烷基醚、聚氟烷基丙烯酸酯等黏接樹脂以外之高分子化合物；非離子系、陽離子系、陰離子系等之界面活性劑；乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基 矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷等密合促進劑；2,2-硫代雙(4-甲基-6-第三丁基苯酚)、2,6-二-第三丁基苯酚等抗氧化劑；2-(3-第三丁基-5-甲基-2-羥基苯基)-5-氯苯并***、烷氧基二苯甲酮等紫外線吸收劑；及聚丙烯酸鈉等防凝劑。 Specific examples of the various additives include a filler such as glass or alumina, and a polymer other than a binder resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether or polyfluoroalkyl acrylate. a compound; a surfactant such as a nonionic, cationic or anionic; vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, N-( 2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyl Triethoxy Decane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Decane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, etc. Adhesion promoter; 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and other antioxidants; 2-(3-third An ultraviolet absorber such as keto-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole or alkoxybenzophenone; and an anti-coagulant such as sodium polyacrylate.
此外，在為了促進非影像部之鹼溶解性，進一步提高本發明之含有染料的固化性組合物之顯影性之情況下，對於上述組合物，能夠進行有機羧酸、較佳為分子量1000以下之低分子量有機羧酸之添加。 Further, in order to promote the alkali solubility of the non-image portion and further improve the developability of the dye-containing curable composition of the present invention, the composition may be an organic carboxylic acid, preferably having a molecular weight of 1,000 or less. Addition of low molecular weight organic carboxylic acids.
具體而言，可舉出例如甲酸、乙酸、丙酸、丁酸、戊酸、特戊酸、己酸、二乙基乙酸、庚酸、辛酸等脂族單羧酸；乙二酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、巴西基酸、甲基丙二酸、乙基丙二酸、二甲基丙二酸、甲基琥珀酸、四甲基琥珀酸、檸康酸等脂族二羧酸；丙三酸、烏頭酸、樟腦三酸等脂族三羧酸；苯甲酸、苯乙酸、枯茗酸、二甲基苯甲酸、米林酸等芳族單羧酸；鄰苯二甲酸、間苯二甲酸、對苯二甲酸、偏苯三酸、均苯三酸、偏苯四酸、均苯四酸等芳族多羧酸；苯基乙酸、氫化阿托酸、氫化肉桂酸、苦杏仁酸、苯基琥珀酸、阿托酸、肉桂酸、肉桂酸甲酯、肉桂酸苄酯、肉桂叉乙酸、香豆酸、傘形酸等其他羧酸。 Specific examples thereof include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, heptanoic acid, and caprylic acid; oxalic acid and propylene glycol; Acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, basic acid, methylmalonic acid, ethylmalonic acid, dimethylpropane Aliphatic dicarboxylic acids such as acid, methyl succinic acid, tetramethyl succinic acid, citraconic acid; aliphatic tricarboxylic acids such as triglyceride, aconitic acid, camphoric acid; benzoic acid, phenylacetic acid, cumene, An aromatic monocarboxylic acid such as dimethylbenzoic acid or milinic acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, pyromellitic acid An aromatic polycarboxylic acid; phenylacetic acid, hydrogenated atropic acid, hydrogenated cinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamyl acetic acid, Other carboxylic acids such as coumaric acid and umbrella acid.
本發明提供由上述包含量子點之固化性組合物製造之濾色器。 The present invention provides a color filter manufactured from the above-described curable composition containing quantum dots.
本發明之濾色器在應用於影像顯示裝置之情況下，藉助顯示裝置光源之光而發光，因而能夠實現優異之光效率。此外，由於釋放帶有顏色之光，因而顏色再現性優異，且由於藉由光致發光來向全部方向釋放光，因此亦能夠改善視角。 When applied to an image display device, the color filter of the present invention emits light by means of light from a light source of the display device, thereby achieving excellent light efficiency. Further, since light with color is released, color reproducibility is excellent, and since light is emitted in all directions by photoluminescence, the viewing angle can also be improved.
濾色器包含基板及在上述基板之上部形成之圖案層。 The color filter includes a substrate and a pattern layer formed on an upper portion of the substrate.
關於基板，濾色器本身可為基板，或者亦可為顯示裝置等中濾色器所處之部位，沒有特別限制。上述基板可為玻璃基板、矽(Si)基板、矽氧化物(SiOx)基板或高分子基板，上述高分子基板可為聚醚碸(polyethersulfone，PES)或聚碳酸酯(polycarbonate，PC)等。 Regarding the substrate, the color filter itself may be a substrate, or may be a portion where the color filter is located in a display device or the like, and is not particularly limited. The substrate may be a glass substrate, a germanium (Si) substrate, a germanium oxide (SiO x ) substrate or a polymer substrate, and the polymer substrate may be a polyethersulfone (PES) or a polycarbonate (PC). .
圖案層為含有本發明之包含量子點之固化性組合物的層，可為塗佈上述包含量子點之固化性組合物，以預定之圖案曝光、顯影及熱固化而形成之層。 The pattern layer is a layer containing the curable composition containing quantum dots of the present invention, and may be a layer formed by applying the above-described curable composition containing quantum dots, exposing, developing, and thermally curing in a predetermined pattern.
由上述包含量子點之固化性組合物形成之圖案層可具備含有紅色量子點粒子之紅色圖案層、含有綠色量子點粒子之綠色圖案層及含有藍色量子點粒子之藍色圖案層。光照射時，紅色圖案層釋放紅色光，綠色圖案層釋放綠色光，藍色圖案層釋放藍色光。 The pattern layer formed of the above-described curable composition containing quantum dots may include a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles. When the light is irradiated, the red pattern layer releases red light, the green pattern layer releases green light, and the blue pattern layer releases blue light.
當以此類情況應用於影像顯示裝置時，光源之釋放光沒有特別限制，自優異之顏色再現性方面考慮，可使用釋放藍色光之光源。 When applied to the image display device in such a case, the light emitted from the light source is not particularly limited, and a light source that emits blue light can be used from the viewpoint of excellent color reproducibility.
根據本發明之另一實施方式，上述圖案層亦可僅具備紅色圖案層、綠色圖案層及藍色圖案層中之2種顏色之圖案層。在此類情況下，上述圖案層進一步具備不含有量子點粒子之透明圖案層。 According to another embodiment of the present invention, the pattern layer may include only a pattern layer of two colors of a red pattern layer, a green pattern layer, and a blue pattern layer. In such a case, the pattern layer further includes a transparent pattern layer that does not contain quantum dot particles.
在僅具備2種顏色之圖案層之情況下，可使用釋放表現出未包含之剩餘顏色之波長的光之光源。例如，在包含紅色圖案層及綠色圖案層之情況下，可使用釋放藍色光之光源。在此類情況下，紅色量子點粒子釋放紅色光，綠色量子點粒子釋放綠色光，透明圖案層直接透過藍色光而表現出藍色。 In the case of a pattern layer having only two colors, a light source that emits light that exhibits a wavelength of the remaining color not included may be used. For example, in the case of including a red pattern layer and a green pattern layer, a light source that emits blue light can be used. In such cases, the red quantum dot particles release red light, the green quantum dot particles release green light, and the transparent pattern layer directly transmits blue light to exhibit blue color.
上述包含基板及圖案層之濾色器可進一步包含在各圖案之間形成的隔板，亦可進一步包含黑矩陣。此外，亦可進一步包含形成於濾色器之圖案層之上部的保護膜。 The color filter including the substrate and the pattern layer may further include a spacer formed between the patterns, and may further include a black matrix. Further, a protective film formed on the upper portion of the pattern layer of the color filter may be further included.
此外，本發明提供包括上述濾色器之影像顯示裝置。 Further, the present invention provides an image display device including the above color filter.
本發明之濾色器不僅能夠應用於習知之液晶顯示裝置，亦能夠 應用於電致發光顯示裝置、電漿顯示裝置、場致發射顯示裝置等各種影像顯示裝置。 The color filter of the present invention can be applied not only to a conventional liquid crystal display device but also It is applied to various image display devices such as electroluminescence display devices, plasma display devices, and field emission display devices.
本發明之影像顯示裝置可具備濾色器，該濾色器包含含有紅色量子點粒子之紅色圖案層、含有綠色量子點粒子之綠色圖案層及含有藍色量子點粒子之藍色圖案層。在此類情況下，當應用於影像顯示裝置時，光源之釋放光沒有特別限制，自優異之顏色再現性方面考慮，較佳可使用釋放藍色光之光源。 The image display device of the present invention may be provided with a color filter including a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles. In such a case, when applied to an image display device, the light emitted from the light source is not particularly limited, and from the viewpoint of excellent color reproducibility, a light source that emits blue light is preferably used.
根據本發明之另一實施方式，本發明之影像顯示裝置可具備僅包含紅色圖案層、綠色圖案層及藍色圖案層中之2種顏色之圖案層的濾色器。在此類情況下，上述濾色器進一步具備不含有量子點粒子之透明圖案層。 According to another embodiment of the present invention, the image display device of the present invention may include a color filter including only a pattern layer of two colors of a red pattern layer, a green pattern layer, and a blue pattern layer. In such a case, the color filter further includes a transparent pattern layer that does not contain quantum dot particles.
在僅具備2種顏色之圖案層之情況下，可使用釋放表現出未包含之剩餘顏色之波長的光之光源。例如，在包含紅色圖案層及綠色圖案層之情況下，可使用釋放藍色光之光源。在此類情況下，紅色量子點粒子釋放紅色光，綠色量子點粒子釋放綠色光，透明圖案層直接透過藍色光而表現出藍色。 In the case of a pattern layer having only two colors, a light source that emits light that exhibits a wavelength of the remaining color not included may be used. For example, in the case of including a red pattern layer and a green pattern layer, a light source that emits blue light can be used. In such cases, the red quantum dot particles release red light, the green quantum dot particles release green light, and the transparent pattern layer directly transmits blue light to exhibit blue color.
本發明之影像顯示裝置之光效率優異，表現出高亮度，顏色再現性優異，具有寬視角。 The image display device of the present invention is excellent in light efficiency, exhibits high luminance, is excellent in color reproducibility, and has a wide viewing angle.
以下，為了有助於本發明之理解，提供較佳之實施例，但此等實施例僅例示本發明，不限制申請專利範圍，熟習此項技術者應當明確，在本發明之範疇及技術思想之範圍內，能夠進行針對實施例之多種變更及修改，此類變更及修改亦理應包括在申請專利範圍中。 In the following, in order to facilitate the understanding of the present invention, the preferred embodiments are provided, but these embodiments are merely illustrative of the present invention and are not intended to limit the scope of the claims. Those skilled in the art should clarify the scope and technical idea of the present invention. Many changes and modifications to the embodiments are possible within the scope of the invention, and such changes and modifications are also included in the scope of the patent application.
將CdO(0.4mmol)、乙酸鋅(Zinc acetate)(4mmol)及油酸(Oleic acid)(5.5mL)與1-十八烯(1-Octadecene)(20mL)一同加入反應器，加熱至150℃使其反應。之後，為了移除對鋅置換油酸而生成之乙酸 (acetic acid)，將上述反應物在100毫托之真空下置放20分鐘。然後，施加310℃之熱而獲得透明之混合物後，將其在310℃維持20分鐘後，將使0.4mmol之Se粉末及2.3mmol之S粉末溶解於3mL之三辛基膦(trioctylphosphine)而得的Se及S溶液快速注入裝有Cd(OA)2及ZN(OA)2溶液之反應器。使由此得到之混合物在310℃生長5分鐘後，利用冰浴(ice bath)使生長中斷。然後，用乙醇使其沈澱，利用離心分離機分離量子點，並利用氯仿(chloroform)及乙醇洗滌多餘之雜質，從而獲得由油酸穩定化的、分佈有核粒徑及殼厚度之和為3~5nm之粒子的CdSe(核)/ZnS(殼)結構之量子點粒子A。 CdO (0.4 mmol), zinc acetate (4 mmol) and oleic acid (5.5 mL) were added to the reactor together with 1-octadecene (20 mL) and heated to 150 ° C. Make it react. Thereafter, in order to remove the acetic acid formed by replacing the oleic acid with zinc, the above reactant was placed under a vacuum of 100 mTorr for 20 minutes. Then, after applying a heat of 310 ° C to obtain a transparent mixture, after maintaining at 310 ° C for 20 minutes, 0.4 mmol of Se powder and 2.3 mmol of S powder were dissolved in 3 mL of trioctylphosphine. The Se and S solutions were quickly injected into a reactor containing Cd(OA) 2 and ZN(OA) 2 solutions. After the thus obtained mixture was grown at 310 ° C for 5 minutes, growth was interrupted by an ice bath. Then, it was precipitated with ethanol, and the quantum dots were separated by a centrifugal separator, and excess impurities were washed with chloroform and ethanol to obtain a nucleus-stabilized, distributed nuclear particle size and shell thickness of 3 Quantum dot particles A of CdSe (nuclear)/ZnS (shell) structure of ~5 nm particles.
向具備攪拌器、溫度計、回流冷凝管、滴液漏斗及氮氣導入管之燒瓶加入丙二醇單甲醚乙酸酯182g，將燒瓶內之氛圍自空氣填充成氮氣後，升溫至100℃，然後投入甲基丙烯酸68.8g、環己基甲基丙烯酸酯36.4g及丙二醇單甲醚乙酸酯136g，將添加了第三丁基過氧化-2-乙基己基碳酸酯3.2g之溶液自滴液漏斗經2小時滴入燒瓶，在100℃進一步進行5小時攪拌。接著，將燒瓶內之氛圍自氮氣置換成空氣，將縮水甘油基甲基丙烯酸酯71g、三(二甲基胺基甲基)苯酚0.9g及氫醌0.145g投入燒瓶內，在110℃繼續反應6小時，得到固體成分之酸值為100mgKOH/g之樹脂D-1。利用GPC測定之聚苯乙烯換算之重量平均分子量為17000，分子量分佈(Mw/Mn)為2.2。用差示掃描量熱計測定玻璃化轉變溫度，結果為120℃。 182 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was filled with nitrogen from air, and then heated to 100 ° C, and then charged into a flask. 68.8 g of acrylic acid, 36.4 g of cyclohexyl methacrylate and 136 g of propylene glycol monomethyl ether acetate, and a solution of 3.2 g of t-butylperoxy-2-ethylhexyl carbonate was added from the dropping funnel. The flask was dropped into the flask every hour, and further stirred at 100 ° C for 5 hours. Next, the atmosphere in the flask was replaced with air from nitrogen, and 71 g of glycidyl methacrylate, 0.9 g of tris(dimethylaminomethyl)phenol, and 0.145 g of hydroquinone were placed in a flask, and the reaction was continued at 110 ° C. After 6 hours, Resin D-1 having a solid content of 100 mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 17,000, and the molecular weight distribution (Mw/Mn) was 2.2. The glass transition temperature was measured by a differential scanning calorimeter and found to be 120 °C.
向具備攪拌器、溫度計、回流冷凝管、滴液漏斗及氮氣導入管之燒瓶加入丙二醇單甲醚乙酸酯182g，將燒瓶內之氛圍自空氣填充成氮氣後，升溫至100℃，然後投入甲基丙烯酸68.8g、三環癸烷骨架之單甲基丙烯酸酯(日立化成(株)製造FA-513M)44.0g及丙二醇單甲 醚乙酸酯136g，將添加了第三丁基過氧化-2-乙基己基碳酸酯3.2g之溶液自滴液漏斗經2小時滴入燒瓶，在100℃進一步進行5小時攪拌。接著，將燒瓶內之氛圍自氮氣置換成空氣，將縮水甘油基甲基丙烯酸酯71g、三(二甲基胺基甲基)苯酚0.9g及氫醌0.145g投入燒瓶內，在110℃繼續反應6小時，得到固體成分之酸值為110mgKOH/g之樹脂D-2。利用GPC測定之聚苯乙烯換算之重量平均分子量為15300，分子量分佈(Mw/Mn)為2.3。用差示掃描量熱計測定玻璃化轉變溫度，結果為130℃。 182 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was filled with nitrogen from air, and then heated to 100 ° C, and then charged into a flask. 68.8 g of acrylic acid and monomethacrylate of tricyclodecane skeleton (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) 44.0 g and propylene glycol monomethyl 136 g of an ether acetate, and a solution containing 3.2 g of a third butyl peroxy-2-ethylhexyl carbonate was added dropwise from the dropping funnel to the flask over 2 hours, and further stirred at 100 ° C for 5 hours. Next, the atmosphere in the flask was replaced with air from nitrogen, and 71 g of glycidyl methacrylate, 0.9 g of tris(dimethylaminomethyl)phenol, and 0.145 g of hydroquinone were placed in a flask, and the reaction was continued at 110 ° C. After 6 hours, Resin D-2 having a solid content of 110 mg KOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 15,300, and the molecular weight distribution (Mw/Mn) was 2.3. The glass transition temperature was measured by a differential scanning calorimeter and found to be 130 °C.
向具備攪拌器、溫度計、回流冷凝管、滴液漏斗及氮氣導入管之燒瓶加入丙二醇單甲醚乙酸酯182g，將燒瓶內之氛圍自空氣填充成氮氣後，升溫至100℃，然後投入甲基丙烯酸47.3g、1-丙烯醯基氧基-3-羥基金剛烷(奧德里奇(株))99.9g及丙二醇單甲醚乙酸酯300g，將添加了第三丁基過氧化-2-乙基己基碳酸酯3.2g之溶液自滴液漏斗經2小時滴入燒瓶，在100℃進一步進行5小時攪拌。接著，將燒瓶內之氛圍自氮氣置換成空氣，將縮水甘油基甲基丙烯酸酯35.5g、三(二甲基胺基甲基)苯酚0.9g及氫醌0.145g投入燒瓶內，在110℃繼續反應6小時，得到固體成分之酸值為95mgKOH/g之樹脂D-3。利用GPC測定之聚苯乙烯換算之重量平均分子量為18300，分子量分佈(Mw/Mn)為2.3。用差示掃描量熱計測定玻璃化轉變溫度，結果為160℃。 182 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was filled with nitrogen from air, and then heated to 100 ° C, and then charged into a flask. 47.3 g of acrylic acid, 99.9 g of 1-propenyloxy-3-hydroxyadamantane (Aldrich Co., Ltd.) and 300 g of propylene glycol monomethyl ether acetate, added with tert-butylperoxy-2- A solution of 3.2 g of ethylhexyl carbonate was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 100 ° C for 5 hours. Next, the atmosphere in the flask was replaced with air from nitrogen, and 35.5 g of glycidyl methacrylate, 0.9 g of tris(dimethylaminomethyl)phenol, and 0.145 g of hydroquinone were placed in a flask, and the reaction was continued at 110 ° C. After reacting for 6 hours, Resin D-3 having a solid content of 95 mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 18,300, and the molecular weight distribution (Mw/Mn) was 2.3. The glass transition temperature was measured by a differential scanning calorimeter and found to be 160 °C.
向具備攪拌器、溫度計、回流冷凝管、滴液漏斗及氮氣導入管之燒瓶加入丙二醇單甲醚乙酸酯250g，將燒瓶內之氛圍自空氣填充成氮氣後，升溫至100℃，然後投入甲基丙烯酸25.8g、1-丙烯醯基氧基-3-羥基金剛烷(奧德里奇(株))50.4g、烯丙醯苯56.7g及丙二醇單甲醚乙酸酯110g，將添加了偶氮二異丁腈3.6g之溶液自滴液漏斗經2小時滴入燒瓶，在100℃進一步進行5小時攪拌，得到固體成分之酸值為 115mgKOH/g之樹脂D-4。利用GPC測定之聚苯乙烯換算之重量平均分子量為19000，分子量分佈(Mw/Mn)為2.3。用差示掃描量熱計測定玻璃化轉變溫度，結果為160℃。 250 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was filled with nitrogen from air, and then heated to 100 ° C, and then charged into a flask. 25.8 g of acrylic acid, 50.4 g of 1-propenyloxy-3-hydroxyadamantane (Aldrich Co., Ltd.), 56.7 g of allylic benzene, and 110 g of propylene glycol monomethyl ether acetate, azo was added. A solution of 3.6 g of diisobutyronitrile was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 100 ° C for 5 hours to obtain an acid value of the solid component. 115 mg KOH/g of resin D-4. The weight average molecular weight in terms of polystyrene measured by GPC was 19,000, and the molecular weight distribution (Mw/Mn) was 2.3. The glass transition temperature was measured by a differential scanning calorimeter and found to be 160 °C.
向具備攪拌器、溫度計、回流冷凝管、滴液漏斗及氮氣導入管之燒瓶加入丙二醇單甲醚乙酸酯250g，將燒瓶內之氛圍自空氣填充成氮氣後，升溫至100℃，然後投入甲基丙烯酸25.8g、1-丙烯醯基氧基-3-羥基金剛烷(奧德里奇(株))44.4g、烯丙醯苯44.8g、甲基甲基丙烯酸10.0g及丙二醇單甲醚乙酸酯110g，將添加了偶氮二異丁腈3.6g之溶液自滴液漏斗經2小時滴入燒瓶，在100℃進一步進行5小時攪拌，得到固體成分之酸值為115mgKOH/g之樹脂D-5。利用GPC測定之聚苯乙烯換算之重量平均分子量為19000，分子量分佈(Mw/Mn)為2.2。用差示掃描量熱計測定玻璃化轉變溫度，結果為135℃。 250 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was filled with nitrogen from air, and then heated to 100 ° C, and then charged into a flask. 25.8 g of acrylonitrile, 44.4 g of 1-propenyloxy-3-hydroxyadamantane (Aldrich Co., Ltd.), 44.8 g of acrylonitrile, 10.0 g of methyl methacrylate, and propylene glycol monomethyl ether acetate 110 g of the ester, and a solution of 3.6 g of azobisisobutyronitrile was added dropwise from the dropping funnel to the flask over 2 hours, and further stirred at 100 ° C for 5 hours to obtain a resin D- having a solid content of 115 mg KOH/g. 5. The weight average molecular weight in terms of polystyrene measured by GPC was 19,000, and the molecular weight distribution (Mw/Mn) was 2.2. The glass transition temperature was measured by a differential scanning calorimeter and found to be 135 °C.
向具備攪拌器、溫度計、回流冷凝管、滴液漏斗及氮氣導入管之燒瓶加入丙二醇單甲醚乙酸酯250g，將燒瓶內之氛圍自空氣填充成氮氣後，升溫至100℃，然後投入甲基丙烯酸25.8g、2-降冰片烯18.8g、烯丙醯苯44.8g、甲基甲基丙烯酸10.0g及丙二醇單甲醚乙酸酯110g，將添加了偶氮二異丁腈3.6g之溶液自滴液漏斗經2小時滴入燒瓶，在100℃進一步進行5小時攪拌，得到固體成分之酸值為105mgKOH/g之樹脂D-6。利用GPC測定之聚苯乙烯換算之重量平均分子量為16300，分子量分佈(Mw/Mn)為2.4。用差示掃描量熱計測定玻璃化轉變溫度，結果為150℃。 250 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was filled with nitrogen from air, and then heated to 100 ° C, and then charged into a flask. 25.8 g of acrylic acid, 18.8 g of 2-norbornene, 44.8 g of allylic benzene, 10.0 g of methyl methacrylic acid and 110 g of propylene glycol monomethyl ether acetate, and a solution of 3.6 g of azobisisobutyronitrile was added. The flask was dropped from the dropping funnel over 2 hours, and further stirred at 100 ° C for 5 hours to obtain a resin D-6 having a solid content of 105 mg KOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 16,300, and the molecular weight distribution (Mw/Mn) was 2.4. The glass transition temperature was measured by a differential scanning calorimeter and found to be 150 °C.
向具備攪拌器、溫度計、回流冷凝管、滴液漏斗及氮氣導入管之燒瓶加入丙二醇單甲醚乙酸酯180g，將燒瓶內之氛圍自空氣填充 成氮氣後，升溫至80℃，然後投入甲基甲基丙烯酸20.0g、正丁基丙烯酸酯55.2g、縮水甘油基甲基丙烯酸酯30g及丙二醇單甲醚乙酸酯71g，將添加了第三丁基過氧化-2-乙基己基碳酸酯3.2g之溶液自滴液漏斗經2小時滴入燒瓶，在100℃進一步進行5小時攪拌。接著，將燒瓶內之氛圍自氮氣置換為空氣，將甲基丙烯酸36.0g、三(二甲基胺基甲基)苯酚0.9g及氫醌0.145g投入燒瓶內，在100℃反應6小時。之後，將反應液之溫度降至常溫，投入琥珀酸酐4.5份，在80℃反應6小時，得到固體成分之酸值為80mgKOH/g之樹脂D-7。利用GPC測定之聚苯乙烯換算之重量平均分子量為15200，分子量分佈(Mw/Mn)為2.1。用差示掃描量熱計測定玻璃化轉變溫度，結果為-1.3℃。 Add 180 g of propylene glycol monomethyl ether acetate to a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and fill the atmosphere in the flask from air. After nitrogen gas was introduced, the temperature was raised to 80 ° C, and then 20.0 g of methyl methacrylic acid, 55.2 g of n-butyl acrylate, 30 g of glycidyl methacrylate, and 71 g of propylene glycol monomethyl ether acetate were added, and a third was added. A solution of 3.2 g of butylperoxy-2-ethylhexyl carbonate was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 100 ° C for 5 hours. Next, the atmosphere in the flask was replaced with air from nitrogen, and 36.0 g of methacrylic acid, 0.9 g of tris(dimethylaminomethyl)phenol, and 0.145 g of hydroquinone were placed in a flask, and reacted at 100 ° C for 6 hours. Thereafter, the temperature of the reaction liquid was lowered to normal temperature, and 4.5 parts of succinic anhydride was added thereto, and the mixture was reacted at 80 ° C for 6 hours to obtain a resin D-7 having a solid content of 80 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 15,200, and the molecular weight distribution (Mw/Mn) was 2.1. The glass transition temperature was measured by a differential scanning calorimeter and found to be -1.3 °C.
向具備攪拌器、溫度計、回流冷凝管、滴液漏斗及氮氣導入管之燒瓶加入丙二醇單甲醚乙酸酯180g，將燒瓶內之氛圍自空氣填充成氮氣後，升溫至80℃，然後投入甲基甲基丙烯酸20.0g、2-乙基己基丙烯酸酯55.2g、縮水甘油基甲基丙烯酸酯30g及丙二醇單甲醚乙酸酯71g，將添加了第三丁基過氧化-2-乙基己基碳酸酯3.2g之溶液自滴液漏斗經2小時滴入燒瓶，在100℃進一步進行5小時攪拌。接著，將燒瓶內之氛圍自氮氣置換成空氣，將甲基丙烯酸36.0g、三(二甲基胺基甲基)苯酚0.9g及氫醌0.145g投入燒瓶內，在100℃反應6小時。之後，將反應液之溫度降至常溫，投入琥珀酸酐4.5份，在80℃反應6小時，得到固體成分之酸值為45mgKOH/g之樹脂D-8。利用GPC測定之聚苯乙烯換算之重量平均分子量為7500，分子量分佈(Mw/Mn)為2.1。用差示掃描量熱計測定玻璃化轉變溫度，結果為-19.3℃。 180 g of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was filled with nitrogen from air, and then heated to 80 ° C, and then injected into a flask. 20.0 g of methacrylic acid, 55.2 g of 2-ethylhexyl acrylate, 30 g of glycidyl methacrylate, and 71 g of propylene glycol monomethyl ether acetate, to which a third butylperoxy-2-ethylhexyl group was added A solution of 3.2 g of carbonate was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 100 ° C for 5 hours. Next, the atmosphere in the flask was replaced with air from nitrogen, and 36.0 g of methacrylic acid, 0.9 g of tris(dimethylaminomethyl)phenol, and 0.145 g of hydroquinone were placed in a flask, and reacted at 100 ° C for 6 hours. Thereafter, the temperature of the reaction liquid was lowered to normal temperature, and 4.5 parts of succinic anhydride was added thereto, and the mixture was reacted at 80 ° C for 6 hours to obtain a resin D-8 having a solid content of 45 mg KOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 7,500, and the molecular weight distribution (Mw/Mn) was 2.1. The glass transition temperature was measured by a differential scanning calorimeter and found to be -19.3 °C.
向具備攪拌器、溫度計、回流冷凝管、滴液漏斗及氮氣導入管之燒瓶加入丙二醇單甲醚乙酸酯182g，將燒瓶內之氛圍自空氣填充 成氮氣後，升溫至100℃，然後投入苄基甲基丙烯酸酯105.7g、甲基丙烯酸17.2g、2-羥基乙基甲基丙烯酸26.0g及丙二醇單甲醚乙酸酯136g，將添加了偶氮二異丁腈3.6g之溶液自滴液漏斗經2小時滴入燒瓶，在100℃進一步進行3小時攪拌，得到固體成分之酸值為60mgKOH/g之樹脂D-9。利用GPC測定之聚苯乙烯換算之重量平均分子量為18000，分子量分佈(Mw/Mn)為2.2。用差示掃描量熱計測定玻璃化轉變溫度，結果為80℃。 182 g of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was filled with air. After nitrogen gas was introduced, the temperature was raised to 100 ° C, and then 105.7 g of benzyl methacrylate, 17.2 g of methacrylic acid, 26.0 g of 2-hydroxyethyl methacrylic acid, and 136 g of propylene glycol monomethyl ether acetate were added. A solution of 3.6 g of nitrogen diisobutyronitrile was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 100 ° C for 3 hours to obtain a resin D-9 having a solid content of 60 mg KOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 18,000, and the molecular weight distribution (Mw/Mn) was 2.2. The glass transition temperature was measured by a differential scanning calorimeter and found to be 80 °C.
向具備攪拌器、溫度計、回流冷凝管、滴液漏斗及氮氣導入管之燒瓶加入丙二醇單甲醚乙酸酯182g，將燒瓶內之氛圍自空氣填充成氮氣後，升溫至100℃，然後投入苄基甲基丙烯酸酯105.7g、甲基丙烯酸34.4g及丙二醇單甲醚乙酸酯136g，將添加了偶氮二異丁腈3.6g之溶液自滴液漏斗經2小時滴入燒瓶，在100℃進一步進行3小時攪拌，得到固體成分之酸值為130mgKOH/g之樹脂D-10。利用GPC測定之聚苯乙烯換算之重量平均分子量為17000，分子量分佈(Mw/Mn)為2.2。用差示掃描量熱計測定玻璃化轉變溫度，結果為100℃。 182 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was filled with nitrogen from air, and then the temperature was raised to 100 ° C, and then benzyl was introduced. 105.7 g of methacrylic acid ester, 34.4 g of methacrylic acid and 136 g of propylene glycol monomethyl ether acetate, and a solution of 3.6 g of azobisisobutyronitrile was added dropwise from the dropping funnel to the flask over 2 hours at 100 ° C. Further, stirring was carried out for 3 hours to obtain a resin D-10 having a solid content of 130 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 17,000, and the molecular weight distribution (Mw/Mn) was 2.2. The glass transition temperature was measured by a differential scanning calorimeter and found to be 100 °C.
向具備攪拌器、溫度計、回流冷凝管、滴液漏斗及氮氣導入管之燒瓶加入丙二醇單甲醚乙酸酯182g，將燒瓶內之氛圍自空氣填充成氮氣後，升溫至100℃，然後投入正丁基甲基丙烯酸酯76.8g、甲基丙烯酸17.2g、2-羥基乙基甲基丙烯酸26.0g及丙二醇單甲醚乙酸酯136g，將添加了偶氮二異丁腈3.6g之溶液自滴液漏斗經2小時滴入燒瓶，在100℃進一步進行3小時攪拌，得到固體成分之酸值為62mgKOH/g之樹脂D-11。利用GPC測定之聚苯乙烯換算之重量平均分子量為15500，分子量分佈(Mw/Mn)為2.2。用差示掃描量熱計測定玻璃化轉變溫度，結果為-20℃。 182 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was filled with nitrogen from air, and then heated to 100 ° C, and then put into positive 76.8 g of butyl methacrylate, 17.2 g of methacrylic acid, 26.0 g of 2-hydroxyethyl methacrylic acid, and 136 g of propylene glycol monomethyl ether acetate, and a solution of 3.6 g of azobisisobutyronitrile was added from the dropping funnel. The flask was dropped into the flask over 2 hours, and further stirred at 100 ° C for 3 hours to obtain a resin D-11 having a solid content of 62 mg KOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 15,500, and the molecular weight distribution (Mw/Mn) was 2.2. The glass transition temperature was measured by a differential scanning calorimeter and found to be -20 °C.
向具備攪拌器、溫度計、回流冷凝管、滴液漏斗及氮氣導入管之燒瓶加入丙二醇單甲醚乙酸酯100g，將燒瓶內之氛圍自空氣填充成氮氣後，升溫至80℃，然後投入2-乙基己基丙烯酸酯10.2g、4-甲基苯乙烯0.7g、縮水甘油基甲基丙烯酸酯76g、正十二烷基硫醇3g及丙二醇單甲醚100g，將添加了偶氮二異丁腈5g之溶液自滴液漏斗經2小時滴入燒瓶，在80℃進一步進行4小時攪拌。接著，將燒瓶內之氛圍自氮氣置換為空氣，將三乙胺0.2g、4-甲氧基苯酚0.1g、丙烯酸10.4g投入燒瓶內，在100℃反應6小時。之後，將反應液之溫度降至常溫，投入琥珀酸酐2.7g，在80℃反應6小時，得到固體成分之酸值為16.45mgKOH/g之樹脂D-12。利用GPC測定之聚苯乙烯換算之重量平均分子量為5450，分子量分佈(Mw/Mn)為2.1。用差示掃描量熱計測定玻璃化轉變溫度，結果為-28.4℃。 100 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was filled with nitrogen from air, and then heated to 80 ° C, and then charged. - 10.5% of ethylhexyl acrylate, 0.7 g of 4-methylstyrene, 76 g of glycidyl methacrylate, 3 g of n-dodecyl mercaptan and 100 g of propylene glycol monomethyl ether, azobisisobutyl A solution of 5 g of nitrile was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 80 ° C for 4 hours. Next, the atmosphere in the flask was replaced with air from nitrogen, and 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol, and 10.4 g of acrylic acid were placed in a flask, and reacted at 100 ° C for 6 hours. Thereafter, the temperature of the reaction liquid was lowered to normal temperature, and 2.7 g of succinic anhydride was added thereto, and the mixture was reacted at 80 ° C for 6 hours to obtain a resin D-12 having a solid content of 16.45 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 5,450, and the molecular weight distribution (Mw/Mn) was 2.1. The glass transition temperature was measured by a differential scanning calorimeter and found to be -28.4 °C.
如下述表1及表2所記載，將各個成分混合後，用丙二醇單甲醚乙酸酯稀釋，以使全部固體成分為20重量%，然後充分攪拌，得到自發光型感光性樹脂組合物。 Each of the components was mixed and then diluted with propylene glycol monomethyl ether acetate so as to have a total solid content of 20% by weight, and then sufficiently stirred to obtain a self-luminous photosensitive resin composition, as described in the following Tables 1 and 2.
利用由上述實施例1~8及比較例1~4製造之自發光型感光性樹脂組合物製造濾色器。即，將上述各個自發光型感光性樹脂組合物用旋塗法塗佈於玻璃基板上，然後置放於加熱板上，以100℃之溫度維持3分鐘，形成薄膜。接著，在上述薄膜上置放具有長×寬20mm×20mm之正方形透過圖案及1μm~100μm之線/間隙圖案的試驗光罩，以 與試驗光罩之間隔為100μm照射紫外線。 A color filter was produced using the self-luminous photosensitive resin compositions produced in the above Examples 1 to 8 and Comparative Examples 1 to 4. Specifically, each of the above self-luminous photosensitive resin compositions was applied onto a glass substrate by a spin coating method, placed on a hot plate, and maintained at a temperature of 100 ° C for 3 minutes to form a film. Next, a test mask having a square transmission pattern of length × width 20 mm × 20 mm and a line/gap pattern of 1 μm to 100 μm is placed on the film to Ultraviolet rays were irradiated with a distance of 100 μm from the test reticle.
此時、紫外線光源利用USHIO電機(株)製之超高壓水銀燈(商品名USH-250D)，在大氣氛圍下以200mJ/cm2之曝光量(365nm)進行光照射，沒有使用特別之光學過濾器。將上述照射了紫外線之薄膜浸入pH為10.5之KOH水溶液顯影溶液80秒以顯影。將附有該薄膜之玻璃板使用蒸餾水洗滌後，吹送氮氣進行乾燥，在150℃之加熱烘箱中加熱10分鐘，從而製造濾色器圖案。上述製造之自發光有色圖案之膜厚度為3.0μm。 At this time, the ultraviolet light source was irradiated with an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by USHIO Electric Co., Ltd. at an exposure amount (365 nm) of 200 mJ/cm 2 in an atmospheric atmosphere, and no special optical filter was used. . The above ultraviolet ray-irradiated film was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 80 seconds to develop. The glass plate to which the film was attached was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150 ° C for 10 minutes to produce a color filter pattern. The film thickness of the self-luminous colored pattern produced above was 3.0 μm.
對於形成有上述自發光像素之濾色器之中隔著100μm的線/間隙圖案遮罩而得到之圖案之尺寸，由OM設備(ECLIPSE LV100POL，尼康公司製造)測定圖案尺寸。 The pattern size was measured by an OM apparatus (ECLIPSE LV100POL, manufactured by Nikon Corporation) for the size of the pattern obtained by masking the 100 μm line/gap pattern among the color filters in which the self-luminous pixels were formed.
微細圖案(△μm)=(線/間隙圖案遮罩尺寸、100μm)-(測定之像素圖案尺寸) Fine pattern (Δμm) = (line/gap pattern mask size, 100 μm) - (measured pixel pattern size)
若微細圖案之值大於10μm，則難以實現微細像素，若具有負值，則能夠引起工序不良。 When the value of the fine pattern is larger than 10 μm, it is difficult to realize fine pixels, and if it has a negative value, process defects can be caused.
對於形成有上述自發光像素之濾色器之中由20mm×20mm的正方形圖案形成之圖案(Pattern)部，由365nm管型4W UV照射器(VL-4LC，VILBER LOURMAT)測定光變化之區域，利用分光儀(Spectrum meter)(Ocean Optics公司製)測定實施例1~8及比較例1~4之550nm區域之發光強度(Intensity)。可判斷，所測定之發光強度(Intensity)越高，越發揮優異之自發光特性，發光強度(Intensity)之測定結果示於下述表3。此外，以230℃進行60分鐘硬烘烤(hard bake)，測定硬烘烤前之發光強度(Intensity)及硬烘烤後之發光強度(Intensity)，確認維持發光效率之等級，在表3中以發光強度維持率表示。 For a pattern portion formed of a square pattern of 20 mm × 20 mm among the color filters in which the self-luminous pixels are formed, a region of light change is measured by a 365 nm tubular type 4W UV irradiator (VL-4LC, VILBER LOURMAT), The luminescence intensity (Intensity) of the 550 nm regions of Examples 1 to 8 and Comparative Examples 1 to 4 was measured by a spectrometer (manufactured by Ocean Optics Co., Ltd.). It can be judged that the higher the luminescence intensity (Intensity) measured, the more excellent the self-luminous property is exhibited, and the measurement results of the luminescence intensity (Intensity) are shown in Table 3 below. Further, hard bake was performed at 230 ° C for 60 minutes, and the intensity of the intensity before the hard baking and the intensity of the intensity after the hard baking were measured, and the level of the luminous efficiency was confirmed. It is expressed by the luminous intensity maintenance rate.
如表3所示，本發明藉由包含提供之實施例1~實施例8中使用之黏合劑，發光強度及發光強度維持率增加，能夠製作微細圖案，能夠得到能夠製作高解析度之濾色器之優異的感光性樹脂組合物。 As shown in Table 3, in the present invention, by providing the binders used in Examples 1 to 8, the luminous intensity and the luminous intensity maintenance ratio are increased, and a fine pattern can be produced, and a high-resolution color filter can be obtained. An excellent photosensitive resin composition.
參照比較例1~3及實施例1~8，在使用末端具有雙鍵、具有交聯能力、與量子點及量子點表面之配體具有相溶性之黏合劑的情況下，能夠確認如下效果：在量子點表面起到保護基團之作用，從而在工序中具有優異之發光強度，消光幅度少。此外，參照比較例4及實施例7~8，能夠確認即使發光強度高，在玻璃化轉變溫度(Tg)為-20℃以下時亦不能夠形成高解析度之微細圖案，因此不能夠應用。 With reference to Comparative Examples 1 to 3 and Examples 1 to 8, when an adhesive having a double bond at the terminal and having crosslinkability and compatibility with a quantum dot and a ligand on the surface of a quantum dot was used, the following effects can be confirmed: It acts as a protective group on the surface of the quantum dot, so that it has excellent luminescence intensity in the process, and the extinction amplitude is small. Further, with reference to Comparative Example 4 and Examples 7 to 8, it was confirmed that even if the luminescence intensity is high, a high-resolution fine pattern cannot be formed when the glass transition temperature (Tg) is -20 ° C or lower, and therefore it cannot be applied.
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| JP7069543B2 (en) * | 2017-01-31 | 2022-05-18 | 大日本印刷株式会社 | Light wavelength conversion composition, light wavelength conversion member, light wavelength conversion sheet, backlight device, and image display device |
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