TWI772376B - A black colored photosensitive resin composition and display device produced using the same - Google Patents

Abstract

The present invention relates to a black photosensitive resin composition containing one or more photopolymerization initiators selected from the group consisting of compounds of Chemical Formula 1 and a display device manufactured using the same.

The black photosensitive resin composition of the present invention has an advantage that in the manufacture of an organic light emitting display device, dissolution of outgas components, which is fatal to the driving of the organic light emitting element, can be reduced during the high pressure deposition process.

In addition, the display device manufactured using the black photosensitive resin composition of the present invention has an advantage of being excellent in contrast and brightness.

(The definition of the substituent in the chemical formula is as described in the specification.)

Description

黑色感光性樹脂組合物及使用彼製造的顯示裝置 Black photosensitive resin composition and display device manufactured using the same

本發明係關於一種黑色感光性樹脂組合物及使用彼製造的顯示裝置。 The present invention relates to a black photosensitive resin composition and a display device manufactured using the same.

作為平板顯示裝置(Flat Panel Display Device)之一的有機發光顯示裝置為自發光型，因此與液晶顯示裝置(Liquid Crystal Display Device)相比，具有優異的視角、對比度(Contrast)等，由於不需要背光，因此可以為輕薄型，在電力消耗方面也有利。此外，可進行直流低電壓驅動，且回應速度快，由於構成的全部元件皆為固體，因此耐外部衝擊，不僅使用溫度範圍廣，而且也具有在製造成本方面便宜的優點。 The organic light-emitting display device, which is one of the flat panel display devices, is a self-luminous type, so compared with the liquid crystal display device (Liquid Crystal Display Device), it has excellent viewing angle, contrast (Contrast), etc. Therefore, the backlight can be thin and light, and it is also advantageous in terms of power consumption. In addition, it can be driven by low DC voltage and has a fast response speed. Since all the components are solid, it is resistant to external shocks, and not only has a wide operating temperature range, but also has the advantage of being cheap in terms of manufacturing costs.

特別地，有機發光顯示裝置的製造製程與液晶顯示裝置、PDP(Plasma Display Panel，電漿顯示面板)不同，其係藉由反覆的蒸鍍/蝕刻(Deposition/Etching)製程以及封裝(Encapsulation)製程來進行，因此具有製程非常單純的優點。 In particular, the manufacturing process of the organic light emitting display device is different from that of the liquid crystal display device and the PDP (Plasma Display Panel). Therefore, it has the advantage that the process is very simple.

這樣的有機發光顯示裝置包含劃分各畫素間的邊界 且使它們絕緣的畫素界定膜層(PDL，Pixel Defined Layer)及在該畫素界定膜的下部平坦地形成並具有絕緣特性的平坦化層。此時，該畫素界定膜層係藉由光刻製程而被精密地圖案化。 Such an organic light-emitting display device includes a Pixel Defined Layer (PDL) that divides and insulates boundaries between pixels, and a planarization layer that is formed flat and has insulating properties under the PDL layer. Floor. At this time, the pixel-defining film is precisely patterned by a photolithography process.

韓國公開專利第2015-0072581號係關於一種OLED顯示裝置用感光性樹脂組合物，其包含將至少一個矽氧烷(SiO_3/2)重複鍵結而成的聚矽氧烷，揭露如下內容：上述感光性樹脂組合物能夠作為PDL層及平坦化層使用，PDL層劃分OLED顯示裝置的各畫素間的邊界並且使它們絕緣，且平坦化層在上述PDL層的下部平坦地形成並且具有絕緣特性。 Korean Laid-Open Patent No. 2015-0072581 relates to a photosensitive resin composition for an OLED display device, which comprises a polysiloxane formed by repeatedly bonding at least one siloxane (SiO _3/2 ), and discloses the following contents: The above-mentioned photosensitive resin composition can be used as a PDL layer and a planarization layer, the PDL layer divides and insulates the boundaries between the pixels of the OLED display device, and the planarization layer is formed flatly under the PDL layer and has insulation. characteristic.

但是，由於上述感光性樹脂組合物為透明的組合物，因此在外部光明亮的情況下，對比度差，且因為有機發光元件的陰極面由反射率優異的金屬構成，因此存在如下問題：從外部進入有機發光元件的內部的光係在有機發光元件的陰極面反射從而與從發光層出來的光混合。 However, since the above-mentioned photosensitive resin composition is a transparent composition, when the external light is bright, the contrast ratio is poor, and since the cathode surface of the organic light-emitting element is made of a metal having excellent reflectivity, there is a problem that the The light entering the inside of the organic light-emitting element is reflected on the cathode surface of the organic light-emitting element and mixed with the light coming out of the light-emitting layer.

為了解決上述問題，現在幾乎所有的有機發光元件藉由在透明基板的下部形成圓偏光板(Circular polarizer)，從而減少陰極產生的外部入射光的反射。即，利用上述圓偏光板，在外部的光入射時，將其一半阻斷，剩餘的一半在陰極反射出來時被阻斷，從而能夠抑制外部光引起的對比度的降低。 In order to solve the above problems, almost all organic light-emitting elements now use a circular polarizer on the lower part of the transparent substrate to reduce the reflection of external incident light generated by the cathode. That is, with the above-described circular polarizer, when external light is incident, half of it is blocked, and the remaining half is blocked when reflected from the cathode, thereby suppressing a decrease in contrast caused by external light.

但是，如上所述以往在透明基板上附著有圓偏光板的有機發光元件係在使陰極產生的外部入射光的反射大幅地減少的同時，甚至將從有機發光層向外部發散的光阻斷，因此存在雖 然對比度提高但亮度減少50%以上的問題以及成本提高的問題。 However, in the conventional organic light-emitting element in which the circularly polarizing plate is attached to the transparent substrate as described above, the reflection of external incident light by the cathode is greatly reduced, and the light radiated to the outside from the organic light-emitting layer is even blocked. Therefore, although the contrast ratio is improved, there are problems that the brightness is reduced by more than 50%, and there are problems that the cost is increased.

因此，為了解決上述問題，能夠形成將外部入射光吸收而使對比度提高的黑色畫素界定膜。黑色畫素界定膜係藉由光刻製程而被精密地圖案化，並且在製作有機發光元件的畫素的高壓蒸鍍製程中對元件的驅動致命的逸氣成分不應溶出方面須具有可靠性。 Therefore, in order to solve the above-mentioned problems, it is possible to form a black pixel-defining film that absorbs external incident light and improves the contrast. The black pixel-defining film is precisely patterned by a photolithography process, and must be reliable in that the outgas components, which are fatal to the driving of the device, should not be eluted during the high-pressure evaporation process of making the pixels of the organic light-emitting device. .

但是，在現有的液晶顯示裝置中所使用的BM(Black Matrix，黑矩陣)用感光性樹脂組合物的情況下，在製作有機發光元件的畫素的高壓蒸鍍製程中容易溶出對有機發光元件的驅動致命的逸氣成分，因此存在有亮度降低，甚至不能驅動有機發光元件的問題。 However, in the case of the photosensitive resin composition for BM (Black Matrix) used in the conventional liquid crystal display device, the organic light-emitting element is easily eluted in the high-pressure vapor deposition process for producing the pixels of the organic light-emitting element. Therefore, there is a problem that the brightness is lowered and even the organic light-emitting element cannot be driven.

因此，在製造有機發光顯示裝置時，需要對具有下述特徵的感光性樹脂組合物進行研究：將高壓蒸鍍過程中對有機發光元件的驅動致命的逸氣成分的溶出最小化，且能夠製造具有優異的對比度及亮度的有機發光顯示裝置。 Therefore, when manufacturing an organic light-emitting display device, it is necessary to study a photosensitive resin composition that minimizes the elution of outgassing components that are fatal to the driving of the organic light-emitting element during high-pressure vapor deposition and can be manufactured An organic light-emitting display device with excellent contrast and brightness.

先前技術文獻 prior art literature

專利文獻 Patent Literature

(專利文獻1) 韓國公開專利第2015-0072581號 (2015.06.30.) (Patent Document 1) Korean Patent Publication No. 2015-0072581 (2015.06.30.)

本發明的目的在於提供一種黑色感光性樹脂組合 物，其在製造有機發光顯示裝置時，能夠使高壓蒸鍍過程中對有機發光元件的驅動致命的逸氣成分的溶出減少，能夠吸收外部入射光而使對比度及亮度提高。 An object of the present invention is to provide a black photosensitive resin composition capable of reducing the elution of outgassing components that are fatal to the driving of organic light-emitting elements during high-pressure vapor deposition and capable of absorbing external incident light when manufacturing an organic light-emitting display device The contrast and brightness are improved.

另外，本發明的目的在於提供一種包含使用上述黑色感光性樹脂組合物的畫素界定膜的顯示裝置。 Another object of the present invention is to provide a display device including a pixel-defining film using the above-mentioned black photosensitive resin composition.

用於實現上述目的之本發明的黑色感光性樹脂組合物，其特徵在於，光聚合引發劑包含選自下述的化學式1的化合物中之至少一者。 The black photosensitive resin composition of the present invention for achieving the above object is characterized in that the photopolymerization initiator contains at least one compound selected from the group consisting of the following chemical formula 1.

另外，本發明提供一種包含畫素界定膜的顯示裝置，該畫素界定膜包含上述的黑色感光性樹脂組合物的固化物。 In addition, the present invention provides a display device including a pixel-defining film including a cured product of the above-mentioned black photosensitive resin composition.

本發明的黑色感光性樹脂組合物能夠在有機發光元件或者量子點發光元件的畫素界定膜的形成中使用，且具有如下優點：在製造包含有機發光元件或者量子點發光元件的顯示裝置時，能夠減少高壓蒸鍍過程中對有機發光元件或者量子點發光元 件的驅動致命的逸氣成分的溶出。 The black photosensitive resin composition of the present invention can be used in the formation of a pixel-defining film of an organic light-emitting element or a quantum dot light-emitting element, and has the following advantages: when manufacturing a display device including an organic light-emitting element or a quantum dot light-emitting element, It is possible to reduce the elution of outgassing components that are fatal to the driving of the organic light-emitting element or the quantum dot light-emitting element during the high-pressure vapor deposition.

因此，包含利用本發明的黑色感光性樹脂組合物所製造的畫素界定膜的有機發光元件、量子點發光元件及包含上述有機發光元件或者量子點發光元件的顯示裝置具有亮度、驅動性及耐久性等優異的優點。 Therefore, the organic light-emitting element, the quantum dot light-emitting element and the display device comprising the above-mentioned organic light-emitting element or the quantum dot light-emitting element including the pixel-defining film produced using the black photosensitive resin composition of the present invention have brightness, drivability, and durability. Excellent advantages such as performance.

以下對本發明詳細地說明。 The present invention will be described in detail below.

本發明中，某構件位於另一構件「上」時，其不僅包含某構件與另一構件相接的情形，也包含在二個構件之間還存在其他構件的情形。 In the present invention, when a certain member is located "on" another member, it includes not only the case where a certain member is connected to another member, but also the case where there are other members between the two members.

本發明中，某部分「包含」某構成要素時，只要無特別地相反的記載，其意指能夠不排除其他構成要素，還可包含其他構成要素。 In the present invention, when a certain part "includes" a certain element, unless otherwise stated, it means that other elements may not be excluded, and other elements may be included.

<黑色感光性樹脂組合物> <Black photosensitive resin composition>

本發明的一實施態樣係關於黑色感光性樹脂組合物，其包含著色劑、黏結劑樹脂、光可聚合化合物、光聚合引發劑及溶劑，上述光聚合引發劑包含選自由下述的化學式1表示的化合物中之至少一者。較佳地，本發明的黑色感光性樹脂組合物能夠用於有機發光元件或者量子點發光元件的畫素界定膜的形成。 One aspect of the present invention relates to a black photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the photopolymerization initiator comprises a chemical formula 1 selected from the following at least one of the compounds represented. Preferably, the black photosensitive resin composition of the present invention can be used to form a pixel-defining film of an organic light-emitting element or a quantum dot light-emitting element.

[化學式1]

[Chemical formula 1]

於化學式1中，R¹、R²、R³及R⁴各自獨立地為氫、C₁至C₂₀烷基、OR¹⁵、鹵素或NO₂；或者R¹與R²、R²與R³、及R³與R⁴各自獨立地一起為

，與其所連接的碳原子一起形成六員環；R¹¹、R¹²、R¹³及R¹⁴各自獨立地為氫、未被取代或者被至少一個鹵素、苯基、CN、OH、SH、C₁至C₄-烷氧基、(CO)OH取代或者被(CO)O(C₁至C₄烷基)取代的C₁至C₂₀烷基；或者R¹¹、R¹²、R¹³及R¹⁴各自獨立地為未被取代的苯基或者被至少一個C₁至C₆烷基、鹵素、CN、OR¹⁵或者被NR¹⁷R¹⁸取代的苯基；或者R¹¹、R¹²、R¹³及R¹⁴各自獨立地為鹵素、CN、OR¹⁵、SR¹⁶、SOR¹⁶、SO₂R¹⁶或NR¹⁷R¹⁸，其中取代基OR¹⁵、SR¹⁶或NR¹⁷R¹⁸任意地與萘基環的碳原子中的一個一起藉由基團R¹⁵、R¹⁶、R¹⁷及/或R¹⁸而形成五員環或六員環；R⁵為未被取代或者被至少一個鹵素、R¹⁵、COOR¹⁵、OR¹⁵、SR¹⁶、CONR¹⁷R¹⁸、NR¹⁷R¹⁸取代的C₁至C₂₀烷基； 或者R⁵為被至少一個O、S、SO、SO₂、NR²³或CO***其間的C₂至C₂₀烷基，或者為未被***或被至少一個O、CO或NR²³***其間的C₂至C₁₂烯基，其中，被***的C₂至C₂₀烷基及未被***或被***的C₂至C₁₂烯基未被取代或者被至少一個鹵素取代；或者R⁵為C₄至C₈環烯基、C₂至C₁₂炔基、或者未被***或被至少一個O、S、CO或NR²³***其間的C₃至C₁₀環烷基；或者R⁵為苯基或萘基，該等各自未被取代或者被至少一個OR¹⁵、SR¹⁶、NR¹⁷R¹⁸、COR²²、CN、NO₂、鹵素、C₁至C₂₀烷基、C₁至C₄鹵代烷基、被至少一個O、S、CO或NR²³***其間的C₂至C₂₀烷基取代或者該等各自被C₃至C₁₀環烷基、或者被至少一個O、S、CO或NR²⁴***其間的C₃至C₁₀環烷基取代；R⁶、R⁷、R⁸、R⁹及R¹⁰為氫、苯基-C₁至C₃烷基、未被取代或者被至少一個鹵素、OH、SH、CN、C₃至C₆烯氧基、OCH₂CH₂CN、OCH₂CH₂(CO)O(C₁至C₄烷基)、O(CO)-(C₁至C₄烷基)、O(CO)-(C₂至C₄烯基)、O(CO)-苯基、(CO)OH、(CO)O(C₁至C₄烷基)、C₃至C₂₀環烷基、SO₂-(C₁至C₄鹵代烷基)、O(C₁至C₄鹵代烷基)或者被至少一個O***其間的C₃至C₂₀環烷基取代的C₁至C₂₀烷基；或者R⁶、R⁷、R⁸、R⁹及R¹⁰為被至少一個O、S或NR²⁴***其間的C₂至C₂₀烷基；或者R⁶、R⁷、R⁸、R⁹及R¹⁰為(CH₂CH₂O)_n+1H、(CH₂CH₂O)_n(CO)-(C₁至C₈烷基)、C₁至C₈烷醯基、C₂至C₁₂烯基、 C₃至C₆烯醯基、或者未被***或被至少一個O、S、CO或NR²³***其間的C₃至C₂₀環烷基；或者R⁶、R⁷、R⁸、R⁹及R¹⁰為未被***或被至少一個O***其間的C₁至C₈烷基-C₃至C₁₀環烷基；或者R⁶、R⁷、R⁸、R⁹及R¹⁰為未被取代或者被至少一個C₁至C₆烷基、鹵素、OH或C₁至C₃烷氧基取代的苯甲醯基；或者R⁶、R⁷、R⁸、R⁹及R¹⁰為苯基、萘基或C₃至C₂₀雜芳基，該等各自未被取代或者被至少一個鹵素、OH、C₁至C₁₂烷基、C₁至C₁₂烷氧基、CN、NO₂、苯基-C₁至C₃烷氧基、苯氧基、C₁至C₁₂烷基硫烷基、苯基硫烷基、N(C₁至C₁₂烷基)₂、二苯胺基取代；R¹⁵為氫、苯基-C₁至C₃烷基、未被取代或者被至少一個鹵素、OH、SH、CN、C₃至C₆烯氧基、OCH₂CH₂CN、OCH₂CH₂(CO)O(C₁至C₄烷基)、O(CO)-(C₁至C₄烷基)、O(CO)-(C₂至C₄烯基)、O(CO)-苯基、(CO)OH、(CO)O(C₁至C₄烷基)、C₃至C₂₀環烷基、SO₂-(C₁至C₄鹵代烷基)、O(C₁至C₄鹵代烷基)或者被至少一個O***其間的C₃至C₂₀環烷基取代的C₁至C₂₀烷基；或者R¹⁵為被至少一個O、S或NR²³***其間的C₂至C₂₀烷基；或者R¹⁵為(CH₂CH₂O)_n+1H、(CH₂CH₂O)_n(CO)-(C₁至C₈烷基)、C₁至C₈烷醯基、C₂至C₁₂烯基、C₃至C₆烯醯基、或者未被***或被至少一個O、S、CO或NR²³***其間的C₃至C₂₀環烷基；或者R¹⁵為未被***或者被至少一個O***其間的C₁至C₈ 烷基-C₃至C₁₀環烷基；或者R¹⁵為未被取代或者被至少一個C₁至C₆烷基、鹵素、OH或C₁至C₃烷氧基取代的苯甲醯基；或者R¹⁵為苯基、萘基或C₃至C₂₀雜芳基，該等各自未被取代或者被至少一個鹵素、OH、C₁至C₁₂烷基、C₁至C₁₂烷氧基、CN、NO₂、苯基-C₁至C₃烷氧基、苯氧基、C₁至C₁₂烷基硫烷基、苯基硫烷基、N(C₁至C₁₂烷基)₂、二苯胺基或

取代；R¹⁶為氫、C₂至C₁₂烯基、C₃至C₂₀環烷基或苯基-C₁至C₃烷基，其中C₂至C₁₂烯基、C₃至C₂₀環烷基或苯基-C₁至C₃烷基未被***或者被至少一個O、S、CO、NR²³或COOR¹⁵***其間；或者R¹⁶為未被取代或者被至少一個OH、SH、CN、C₃至C₆烯氧基、OCH₂CH₂CN、OCH₂CH₂(CO)O(C₁至C₄烷基)、O(CO)-(C₂至C₄烯基)、O(CO)-(C₁至C₄烷基)、O(CO)-苯基或(CO)OR¹⁵取代的C₁至C₂₀烷基；或者R¹⁶為被至少一個O、S、CO、NR²³或COOR¹⁵***其間的C₂至C₂₀烷基；或者R¹⁶為(CH₂CH₂O)_nH、(CH₂CH₂O)_n(CO)-(C₁至C₈烷基)、C₂至C₈烷醯基或C₃至C₆烯醯基；或者R¹⁶為未被取代或者被至少一個C₁至C₆烷基、鹵素、OH、C₁至C₄烷氧基或C₁至C₄烷基硫烷基取代的苯甲醯基； 或者R¹⁶為苯基、萘基或C₃至C₂₀雜芳基，該等各自未被取代或者被至少一個鹵素、C₁至C₁₂烷基、C₁至C₄鹵代烷基、C₁至C₁₂烷氧基、CN、NO₂、苯基-C₁至C₃烷氧基、苯氧基、C₁至C₁₂烷基硫烷基、苯基硫烷基、N(C₁至C₁₂烷基)₂、二苯胺基、(CO)O(C₁至C₈烷基)、(CO)-C₁至C₈烷基、(CO)N(C₁至C₈烷基)₂或

取代；R¹⁷及R¹⁸各自獨立地為氫、C₁至C₂₀烷基、C₂至C₄羥基烷基、C₂至C₁₀烷氧基烷基、C₂至C₅烯基、C₃至C₂₀環烷基、苯基-C₁至C₃烷基、C₁至C₈烷醯基、C₁至C₈烷醯氧基、C₃至C₁₂烯醯基、SO₂-(C₁至C₄鹵代烷基)或者苯甲醯基；或者R¹⁷及R¹⁸為苯基、萘基或C₃至C₂₀雜芳基，該等各自未被取代或者被至少一個鹵素、C₁至C₄鹵代烷基、C₁至C₂₀烷氧基、C₁至C₁₂烷基、苯甲醯基或C₁至C₁₂烷氧基取代；或者R¹⁷及R¹⁸與其所連接的N-原子一起形成未被***或者O、S或NR¹⁵***其間的五員或六員飽和或不飽和環，該五員或六員飽和或不飽和環未被取代或者被至少一個C₁至C₂₀烷基、C₁至C₂₀烷氧基、=O、OR¹⁵、SR¹⁶、NR¹⁹R²⁰、(CO)R²¹、NO₂、鹵素、C₁至C₄-鹵代烷基、CN、苯基取代或者被未被***或被至少一個O、S、CO或NR¹⁵***其間的C₃至C₂₀環烷基取代；或者R¹⁷及R¹⁸與其所連接的N-原子一起形成未被取代或者被至少一個C₁至C₂₀烷基、C₁至C₄鹵代烷基、C₁至C₂₀烷氧基、= O、OR¹⁵、SR¹⁶、NR¹⁹R²⁰、(CO)R²¹、鹵素、NO₂、CN、苯基或者被未被***或被至少一個O、S、CO或NR¹⁵***其間的C₃至C₂₀環烷基取代的雜芳香族環系；R¹⁹及R²⁰各自獨立地為氫、C₁至C₂₀烷基、C₁至C₄鹵代烷基、C₃至C₁₀環烷基或苯基；或者R¹⁹及R²⁰與其所連接的N-原子一起形成未被***或者被O、S或NR²³***其間的五員或六員飽和或不飽和環，上述五員或六員飽和或不飽和環未被稠合或者使苯環稠合於該五員或六員飽和或不飽和環；R²¹為氫、OH、C₁至C₂₀烷基、C₁至C₄鹵代烷基、未被***或者被至少一個O、CO或NR²⁴***其間的C₂至C₂₀烷基、未被***或者O、S、CO或NR²⁴***其間的C₃至C₂₀環烷基，或者R²¹為苯基、萘基、苯基-C₁至C₄烷基、OR¹⁵、SR¹⁶或NR¹⁹R²⁰；R²²為C₆至C₂₀芳基或者C₃至C₂₀雜芳基，該等各自未被取代或者被至少一個苯基、鹵素、C₁至C₄鹵代烷基、CN、NO₂、OR¹⁵、SR¹⁶、NR¹⁷R¹⁸、或者被至少一個O、S或NR²³***其間的C₁至C₂₀烷基取代，或者該等各自未被取代或者被經至少一個鹵素、COOR¹⁵、CONR¹⁷R¹⁸、苯基、C₃至C₈環烷基、C₃至C₂₀雜芳基、C₆至C₂₀芳氧基羰基、C₃至C₂₀雜芳氧基羰基、OR¹⁵、SR¹⁶或NR¹⁷R¹⁸取代的至少一個C₁至C₂₀烷基所取代；或者R²²為氫、未被取代或者被至少一個鹵素、苯基、OH、 SH、CN、C₃至C₆烯氧基、OCH₂CH₂CN、OCH₂CH₂(CO)O(C₁至C₄烷基)、O(CO)-(C₁至C₄烷基)、O(CO)-苯基、(CO)OH或(CO)O(C₁至C₄烷基)取代的C₁至C₂₀烷基；或者R²²為被至少一個O、S或NR²⁴***其間的C₂至C₁₂烷基；或者R²²為(CH₂CH₂O)_n+1H、(CH₂CH₂O)_n(CO)-(C₁至C₈烷基)、C₂至C₁₂烯基或C₃至C₈環烷基；或者R²²為被SR¹⁶取代的苯基，其中，基團R¹⁶表示對於COR²²基所連接的咔唑部分的苯基或萘基環的直接結合；n為1至20；R²³為氫、C₁至C₂₀烷基、C₁至C₄鹵代烷基、被至少一個O或CO***其間的C₂至C₂₀烷基，或者為苯基-C₁至C₄烷基、未被***或者被至少一個O或CO***其間的C₃至C₈環烷基，或者為(CO)R¹⁷，或者為未被取代或被至少一個C₁至C₂₀烷基、鹵素、C₁至C₄鹵代烷基、OR¹⁵、SR¹⁶、NR¹⁷R¹⁸或

取代的苯基；R²⁴為氫、C₁至C₂₀烷基、C₁至C₄鹵代烷基、被至少一個O或CO***其間的C₂至C₂₀烷基，或者為苯基-C₁至C₄烷基、未被***或者被至少一個O或CO***其間的C₃至C₈環烷基，或者為(CO)R¹⁷，或者為未取代或者被至少一個C₁至C₂₀烷基、鹵素、C₁至C₄鹵代烷基、OR¹⁵、SR¹⁶、NR¹⁷R¹⁸或

取代 的苯基。 In Chemical Formula 1, R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, C ₁ to C ₂₀ alkyl, OR ¹⁵ , halogen or NO ₂ ; or R ¹ and R ² , R ² and R ³ , and R ³ and R ⁴ are each independently taken together

, together with the carbon atom to which it is attached to form a six-membered ring; R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently hydrogen, unsubstituted or replaced by at least one halogen, phenyl, CN, OH, SH, C ₁ to C ₄ -alkoxy, (CO)OH substituted or C ₁ to C ₂₀ alkyl substituted with (CO)O (C ₁ to C ₄ alkyl); or R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently unsubstituted phenyl or phenyl substituted with at least one C ₁ to C ₆ alkyl, halogen, CN, OR ¹⁵ or NR ¹⁷ R ¹⁸ ; or R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is each independently halogen, CN, OR ¹⁵ , SR ¹⁶ , SOR ¹⁶ , SO ₂ R ¹⁶ or NR ¹⁷ R ¹⁸ , wherein the substituents OR ¹⁵ , SR ¹⁶ or NR ¹⁷ R ¹⁸ are optionally associated with a carbon atom of the naphthyl ring One of them forms a five- or six-membered ring together by the groups R ¹⁵ , R ¹⁶ , R ¹⁷ and/or R ¹⁸ ; R ⁵ is unsubstituted or by at least one halogen, R ¹⁵ , COOR ¹⁵ , OR ¹⁵ , SR ¹⁶ , CONR ¹⁷ R ¹⁸ , NR ¹⁷ R ¹⁸ substituted C ₁ to C ₂₀ alkyl; or R ⁵ is C ₂ to C 20 intervened by at least one O, S, SO, SO ₂ , NR ²³ or CO C ₂₀ alkyl, or C ₂ to C ₁₂ alkenyl not inserted or intervened by at least one O, CO or NR ²³ , wherein the inserted C ₂ to C ₂₀ alkyl and uninserted or inserted The C ₂ to C ₁₂ alkenyl is unsubstituted or substituted by at least one halogen; or R ⁵ is C ₄ to C ₈ cycloalkenyl, C ₂ to C ₁₂ alkynyl, or uninterrupted or substituted by at least one O, S , CO or NR ²³ intervening C ₃ to C ₁₀ cycloalkyl; or R ⁵ is phenyl or naphthyl, each of which is unsubstituted or replaced by at least one OR ¹⁵ , SR ¹⁶ , NR ¹⁷ R ¹⁸ , COR ²² , CN, NO ₂ , halogen, C ₁ to C ₂₀ alkyl, C ₁ to C ₄ haloalkyl, C ₂ to C ₂₀ alkyl substituted with at least one O, S, CO or NR ²³ intervening or each of these substituted by C ₃ to C ₁₀ cycloalkyl, or C ₃ to C ₁₀ cycloalkyl with at least one O, S, CO or NR ²⁴ interposed therebetween; R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are Hydrogen, phenyl-C ₁ to C ₃ alkyl, unsubstituted or by at least one halogen, OH, SH, CN, C ₃ to C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O(C ₁ to C ₄ alkyl), O(CO)-(C ₁ to C ₄ alkyl), O(CO)-(C ₂ to C ₄ alkenyl), O(CO)-phenyl, (CO)OH, (CO)O(C ₁ to C ₄ alkyl), C ₃ to C ₂₀ cycloalkyl, SO ₂ -(C ₁ to C ₄ haloalkyl), O (C ₁ to C ₄ haloalkyl), or C ₁ to C ₂₀ alkyl substituted with at least one C ₃ to C ₂₀ cycloalkyl with at least one O intervening therebetween; or R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are C ₂ to C ₂₀ alkyl intervened by at least one O, S or NR ²⁴ ; or R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are (CH ₂ CH ₂ O) _{n +1} H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ to C ₈ alkyl), C ₁ to C ₈ alkanyl, C ₂ to C ₁₂ alkenyl, C ₃ to C ₆ alkenyl radical, or a C3 to _C20 cycloalkyl group that is not intervened or intervened by at least one O, S, CO, or ^NR23 _; or that ^R6 , ^R7 , ^R8 , ^R9 , and ^R10 are not intercalated or C ₁ to C ₈ alkyl-C ₃ to C ₁₀ cycloalkyl intervened by at least one O; or R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are unsubstituted or by at least one C ₁ to C ₆ alkyl, halogen, OH or C ₁ to C ₃ alkoxy substituted benzyl; or R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are phenyl, naphthyl or C ₃ to C ₂₀ heteroaryl groups, each _of which is unsubstituted or substituted by at least one halogen, OH, _C1 to C12 alkyl, _C1 to _C12 alkoxy, CN, NO2, phenyl _{- C1} to C3 _alkane Oxy, phenoxy, C ₁ to C ₁₂ alkylsulfanyl, phenylsulfanyl, N(C ₁ to C ₁₂ alkyl) ₂ , diphenylamino substituted; R ¹⁵ is hydrogen, phenyl-C ₁ to _C3 alkyl, unsubstituted or by at least one halogen, OH, SH, CN, _C3 to _C6 alkenyloxy, OCH2CH2CN, _{OCH2CH2 ( CO )} O( _C1 to C ₄ alkyl), O(CO)-(C ₁ to C ₄ alkyl), O(CO)-(C ₂ to C ₄ alkenyl), O(CO)-phenyl, (CO)OH, (CO ) O(C ₁ to C ₄ alkyl), C ₃ to C ₂₀ cycloalkyl, SO ₂ -(C ₁ to C ₄ haloalkyl), O(C ₁ to C ₄ haloalkyl) or inserted by at least one O C ₁ to C ₂₀ alkyl substituted with C ₃ to C ₂₀ cycloalkyl therebetween; or R ¹⁵ is C ₂ to C ₂₀ alkyl intervened by at least one O, S or NR ²³ ; or R ¹⁵ is (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ to C ₈ alkyl), C ₁ to C ₈ alkanoyl, C ₂ to C ₁₂ alkenyl, C ₃ to C ₆ alkenyl, or C ₃ to C ₂₀ cycloalkyl not inserted or intervened by at least one O, S, CO or NR ²³ ; or R ¹⁵ is C ₁ not intervened or intervened by at least one O to _C8 alkyl _- C3 to _C10 cycloalkyl; or ^R15 is benzyl unsubstituted or substituted with at least one _C1 to _C6 alkyl, halogen, OH or _C1 to _C3 alkoxy Acyl; or R ¹⁵ is phenyl, naphthyl, or C ₃ to C ₂₀ heteroaryl, each of which is unsubstituted or substituted by at least one halogen, OH, C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ alkane Oxy, CN, NO ₂ , phenyl-C ₁ to C ₃ alkoxy, phenoxy, C ₁ to C ₁₂ alkylsulfanyl, phenylsulfanyl, N(C ₁ to C ₁₂ alkyl ) ₂ , diphenylamine or

Substituted; R ¹⁶ is hydrogen, C ₂ to C ₁₂ alkenyl, C ₃ to C ₂₀ cycloalkyl, or phenyl-C ₁ to C ₃ alkyl, wherein C ₂ to C ₁₂ alkenyl, C ₃ to C ₂₀ cyclo Alkyl or phenyl-C ₁ to C ₃ alkyl is not inserted or is intervened by at least one O, S, CO, NR ²³ or COOR ¹⁵ ; or R ¹⁶ is unsubstituted or by at least one OH, SH, CN , C ₃ to C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O (C ₁ to C ₄ alkyl), O(CO)-(C ₂ to C ₄ alkenyl), O (CO)-(C ₁ to C ₄ alkyl), O(CO)-phenyl or (CO)OR ¹⁵ substituted C ₁ to C ₂₀ alkyl; or R ¹⁶ is at least one O, S, CO, C ₂ to C ₂₀ alkyl with NR ²³ or COOR ¹⁵ intervening; or R ¹⁶ is (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ to C ₈ alkyl ), C ₂ to C ₈ alkyl or C ₃ to C ₆ alkenyl; or R ¹⁶ is unsubstituted or by at least one C ₁ to C ₆ alkyl, halogen, OH, C ₁ to C ₄ alkoxy or C ₁ to C ₄ alkylsulfanyl substituted benzyl; or R ¹⁶ is phenyl, naphthyl, or C ₃ to C ₂₀ heteroaryl, each of which is unsubstituted or substituted by at least one halogen, C ₁ to C ₁₂ alkyl, C ₁ to C ₄ haloalkyl, C ₁ to C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ to C ₃ alkoxy, phenoxy, C ₁ to C ₁₂ alkylsulfanyl, phenylsulfanyl, N(C ₁ to C ₁₂ alkyl) ₂ , diphenylamino, (CO)O(C ₁ to C ₈ alkyl), (CO)-C ₁ to C ₈ alkyl, (CO)N(C ₁ to C ₈ alkyl) ₂ or

Substituted; R ¹⁷ and R ¹⁸ are each independently hydrogen, C ₁ to C ₂₀ alkyl, C ₂ to C ₄ hydroxyalkyl, C ₂ to C ₁₀ alkoxyalkyl, C ₂ to C ₅ alkenyl, C ₃ to C ₂₀ cycloalkyl, phenyl-C ₁ to C ₃ alkyl, C ₁ to C ₈ alkanoyl, C ₁ to C ₈ alkanoyloxy, C ₃ to C ₁₂ alkenyl, SO ₂ - (C ₁ to C ₄ haloalkyl) or benzyl; or R ¹⁷ and R ¹⁸ are phenyl, naphthyl, or C ₃ to C ₂₀ heteroaryl, each of which is unsubstituted or substituted by at least one halogen, C ₁ to C ₄ haloalkyl, C ₁ to C ₂₀ alkoxy, C ₁ to C ₁₂ alkyl, benzyl or C ₁ to C ₁₂ alkoxy substituted; or R ¹⁷ and R ¹⁸ and the N to which they are attached - atoms together form a five- or six-membered saturated or unsaturated ring not intervening or O, S or NR ¹⁵ intervening, the five- or six-membered saturated or unsaturated ring being unsubstituted or replaced by at least one C ₁ to C ₂₀ alkyl, C ₁ to C ₂₀ alkoxy, =O, OR ¹⁵ , SR ¹⁶ , NR ¹⁹ R ²⁰ , (CO)R ²¹ , NO ₂ , halogen, C ₁ to C ₄ -haloalkyl, CN, benzene substituted with C3 to _C20 cycloalkyl groups either uninterrupted or substituted with at least one O, S, CO or NR ¹⁵ intervening; or _R ¹⁷ and R ¹⁸ together with the N-atom to which they are attached form an unsubstituted or by at least one C ₁ to C ₂₀ alkyl, C ₁ to C ₄ haloalkyl, C ₁ to C ₂₀ alkoxy, =O, OR ¹⁵ , SR ¹⁶ , NR ¹⁹ R ²⁰ , (CO)R ²¹ , halogen , NO ₂ , CN, phenyl, or a heteroaromatic ring system substituted with C ₃ to C ₂₀ cycloalkyl not intervening or intervening with at least one O, S, CO or NR ¹⁵ ; R ¹⁹ and R ²⁰ each independently hydrogen, C ₁ to C ₂₀ alkyl, C ₁ to C ₄ haloalkyl, C ₃ to C ₁₀ cycloalkyl, or phenyl; or R ¹⁹ and R ²⁰ together with the N-atom to which they are attached form an unrestricted A five-membered or six-membered saturated or unsaturated ring inserted or inserted between by O, S or NR ²³ , the above-mentioned five-membered or six-membered saturated or unsaturated ring is not fused or the benzene ring is fused to the five-membered or six-membered saturated or unsaturated ring Saturated or unsaturated ring; R ²¹ is hydrogen, OH, C ₁ to C ₂₀ alkyl, C ₁ to C ₄ haloalkyl, C ₂ to C not intercalated or intervened by at least one O, CO or NR ²⁴ ₂₀ alkyl, C ₃ to C ₂₀ cycloalkyl not intercalated or with O, S, CO or NR ²⁴ intervening, or R ²¹ is phenyl, naphthyl, phenyl-C ₁ to C ₄ alkyl, OR ¹⁵ , SR ¹⁶ or NR ¹⁹ R ²⁰ ; R ²² is C ₆ to C ₂₀ aryl or C ₃ to C ₂₀ heteroaryl, each of which is unsubstituted or by at least one phenyl, halogen, C ₁ to C ₄ haloalkyl, CN, NO ₂ , OR ¹⁵ , SR ¹⁶ , NR ¹⁷ R ¹⁸ , or C ₁ to C ₂₀ alkane intervened by at least one O, S or NR ²³ substituted, each of which is unsubstituted or substituted with at least one halogen, COOR ¹⁵ , CONR ¹⁷ R ¹⁸ , phenyl, C ₃ to C ₈ cycloalkyl, C ₃ to C ₂₀ heteroaryl, C ₆ to C ₂₀ aryloxycarbonyl, C ₃ to C ₂₀ heteroaryloxycarbonyl, OR ¹⁵ , SR ¹⁶ or NR ¹⁷ R ¹⁸ substituted at least one C ₁ to C ₂₀ alkyl substituted; or R ²² is hydrogen, unsubstituted or by at least one halogen, phenyl, OH, SH, CN, _C3 to _C6 alkenyloxy, OCH2CH2CN, _{OCH2CH2 ( CO )} O( _C1 to _C4 alkyl), O( CO)-( _C1 to _C4 alkyl), O(CO)-phenyl, (CO)OH or (CO)O( _C1 to _C4 alkyl) substituted _C1 to _C20 alkyl; or R ²² is C ₂ to C ₁₂ alkyl intervened by at least one O, S or NR ²⁴ ; or R ²² is (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO) -(C ₁ to C ₈ alkyl), C ₂ to C ₁₂ alkenyl or C ₃ to C ₈ cycloalkyl; or R ²² is phenyl substituted by SR ¹⁶ , wherein the group R ¹⁶ represents for COR ²² A direct bond of the phenyl or naphthyl ring of the carbazole moiety to which the radical is attached; n is 1 to 20; R ²³ is hydrogen, C ₁ to C ₂₀ alkyl, C ₁ to C ₄ haloalkyl, replaced by at least one O or _C2 to _C20 alkyl with CO intervening, or phenyl _{- C1} to _C4 alkyl, C3 to _C8 cycloalkyl not intercalated or intervened by at least one O or CO, or ( CO)R ¹⁷ , or unsubstituted or substituted with at least one C ₁ to C ₂₀ alkyl, halogen, C ₁ to C ₄ haloalkyl, OR ¹⁵ , SR ¹⁶ , NR ¹⁷ R ¹⁸ or

Substituted phenyl; R ²⁴ is hydrogen, C ₁ to C ₂₀ alkyl, C ₁ to C ₄ haloalkyl, C ₂ to C ₂₀ alkyl intervened by at least one O or CO, or phenyl-C ₁ to _C4 alkyl, _C3 to _C8 cycloalkyl not intercalated or intervened by at least one O or CO, or (CO) ^R17 , or unsubstituted or intervened by at least one _C1 to _C20 alkane radical, halogen, C ₁ to C ₄ haloalkyl, OR ¹⁵ , SR ¹⁶ , NR ¹⁷ R ¹⁸ or

Substituted phenyl.

上述光聚合引發劑較佳包含在化學式1中R¹、R²、R³及R⁴各自獨立地為氫、C₁至C₂₀烷基、OR¹⁵、鹵素或NO₂的化合物。 The above-mentioned photopolymerization initiator preferably includes a compound in Chemical Formula 1 wherein R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, C ₁ to C ₂₀ alkyl, OR ¹⁵ , halogen or NO ₂ .

上述光聚合引發劑較佳包含在化學式1中R¹與R²、R²與R³、及R³與R⁴各自獨立地一起為

、與其所連接的碳原子一起形成六員環的化合物。 The above-mentioned photopolymerization initiator is preferably included in the chemical formula 1. R ¹ and R ² , R ² and R ³ , and R ³ and R ⁴ are each independently taken together.

, which together with the carbon atom to which it is attached form a six-membered ring.

上述光聚合引發劑較佳包含：在化學式1中R¹、R²、R³及R⁴各自獨立地為氫、C₁至C₂₀烷基、OR¹⁵、鹵素或NO₂的化合物；以及R¹與R²、R²與R³、及R³與R⁴各自獨立地一起為

、與其所連接的碳原子一起形成六員環的化合物。 The above-mentioned photopolymerization initiator preferably comprises: in Chemical Formula 1, R ¹ , R ² , R ³ and R ⁴ are each independently a compound in which hydrogen, C ₁ to C ₂₀ alkyl, OR ¹⁵ , halogen or NO ₂ ; and R ¹ and R ² , R ² and R ³ , and R ³ and R ⁴ are each independently taken together to be

, which together with the carbon atom to which it is attached form a six-membered ring.

相對於黑色感光性樹脂組合物的總重量，這樣的光聚合引發劑能夠以0.01至10重量%的量使用，較佳以0.01至5重量%使用。這樣的含量範圍是考慮了光可聚合化合物的光聚合速度及最終得到的塗膜的物性而確定的，如果低於上述範圍，則光聚合速度低，因此將延長全部的製程時間，相反地，超過上述範圍的情況下，由於過度的反應，塗膜的物性反而會降低，因此較佳在上述範圍內適當地使用。 Such a photopolymerization initiator can be used in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight, relative to the total weight of the black photosensitive resin composition. Such a content range is determined in consideration of the photopolymerization speed of the photopolymerizable compound and the physical properties of the final coating film. If it is lower than the above range, the photopolymerization speed will be low, so the entire process time will be prolonged. On the contrary, When it exceeds the said range, since the physical property of a coating film will fall on the contrary by an excessive reaction, it is preferable to use suitably within the said range.

進一步而言，本發明的黑色感光性樹脂組合物可更包含光聚合引發輔助劑，較佳地可將選自胺系化合物及羧酸系的化合物中之至少一種化合物用於光聚合引發輔助劑。 Further, the black photosensitive resin composition of the present invention may further comprise a photopolymerization initiation adjuvant, preferably at least one compound selected from amine-based compounds and carboxylic acid-based compounds may be used as the photopolymerization initiation adjuvant .

胺系化合物之實例可為：脂肪族胺化合物，如三乙醇胺、甲基二乙醇胺及三異丙醇胺等；芳香族胺化合物，如4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、4-二甲基胺基苯甲酸2-乙基己酯、苯甲酸2-二甲基胺基乙酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲基胺基)二苯甲酮及4,4'-雙(二乙基胺基)二苯甲酮等，其中較佳為芳香族胺化合物。 Examples of the amine compound include: aliphatic amine compounds, such as triethanolamine, methyldiethanolamine, and triisopropanolamine, etc.; aromatic amine compounds, such as 4-dimethylaminobenzoic acid methyl ester, 4-diethanolamine Ethyl methylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-Dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone, etc. Preferred are aromatic amine compounds.

羧酸系化合物之實例可為芳香族雜醋酸類等，芳香族雜醋酸類如苯硫基醋酸、甲基苯硫基醋酸、乙基苯硫基醋酸、甲基乙基苯硫基醋酸、二甲基苯硫基醋酸、甲氧基苯硫基醋酸、二甲氧基苯硫基醋酸、氯苯硫基醋酸、二氯苯硫基醋酸、N-苯基甘氨酸、苯氧基醋酸、萘硫基醋酸、N-萘基甘氨酸及萘氧基醋酸等。 Examples of carboxylic acid-based compounds may be aromatic heteroacetic acids, etc., aromatic heteroacetic acids such as thiophenylacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, Methylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, thionaphthalene acetic acid, N-naphthylglycine and naphthyloxyacetic acid.

使用該等光聚合引發輔助劑的情況下，相對於光聚合引發劑1莫耳，光聚合引發輔助劑通常使用10莫耳以下，較佳在0.01至5莫耳的範圍內使用。如果在上述的範圍內，則黑色感光性樹脂組合物的感光度進一步提高，且使用該組合物形成的畫素界定膜的生產率有提高的傾向，因此係合宜的。 When these photopolymerization initiation adjuvants are used, the photopolymerization initiation adjuvant is usually used in a range of 10 mol or less, preferably within a range of 0.01 to 5 mol, relative to 1 mol of the photopolymerization initiator. Within the above-mentioned range, the sensitivity of the black photosensitive resin composition is further improved, and the productivity of the pixel-defining film formed using the composition tends to be improved, so it is preferable.

在本發明的黑色感光性樹脂組合物的一實施態樣中，黑色感光性樹脂組合物更包含選自著色劑、黏結劑樹脂、光可聚合化合物、溶劑及添加劑中之至少一種成分。以下對這些成分具體地說明。 In an embodiment of the black photosensitive resin composition of the present invention, the black photosensitive resin composition further comprises at least one component selected from the group consisting of colorants, binder resins, photopolymerizable compounds, solvents and additives. These components will be specifically described below.

著色劑 Colorant

本發明中所使用的著色劑可包含選自黑色顏料或染料及有機顏料或染料中之至少一者。 The colorant used in the present invention may include at least one selected from black pigments or dyes and organic pigments or dyes.

本發明中所使用的著色劑可為自身即為黑色，如黑色顏料或染料，也包含將多種顏料或染料混合而獲得黑色的情形。著色劑只要在可見光線中存在遮光性，則並無特別限制。 The coloring agent used in the present invention may be black by itself, such as a black pigment or dye, and may also include a case where a plurality of pigments or dyes are mixed to obtain black. The colorant is not particularly limited as long as it has light-shielding properties in visible light.

上述黑色顏料，可使用習知的黑色顏料，並無特別限制，具體地，可使用苯胺黑、內醯胺黑、苝黑、碳黑、氧化鉻、氧化鐵及鈦黑等，該等可單獨使用或以二或更多者之組合使用。上述碳黑，例如可為槽法碳黑、爐法碳黑、熱裂法碳黑、燈煙法碳黑等。 The above-mentioned black pigments can be conventional black pigments without particular limitation. Specifically, aniline black, lactamide black, perylene black, carbon black, chromium oxide, iron oxide and titanium black can be used, and these can be used independently used or used in combination of two or more. The above-mentioned carbon black may be, for example, channel carbon black, furnace carbon black, thermal carbon black, lamp smoke carbon black, or the like.

在必要的情況下，為了電絕緣性，可使用在表面被覆有樹脂的碳黑。該被覆有樹脂的碳黑與未被覆樹脂的碳黑相比，導電性低，因此具有在形成黑矩陣或畫素界定膜時能夠賦予優異的電絕緣性的優點。 If necessary, for the purpose of electrical insulation, carbon black whose surface is coated with resin can be used. Since this resin-coated carbon black has lower electrical conductivity than carbon black not covered with resin, it has an advantage of being able to impart excellent electrical insulating properties when forming a black matrix or a pixel-defining film.

為符合畫素界定膜所需要的性質，可調整著色劑中所使用的黑色顏料或染料及有機顏料或染料的含量。以黑色感光性樹脂組合物全體100重量%計，著色劑可含有1至50重量%，較佳含有5至40重量%。在著色劑的含量低於上述範圍的情況下，遮光性不充足，在超過上述範圍的情況下，圖案化後所得到的圖案的品質有可能降低。 In order to meet the desired properties of the pixel-defining film, the content of black pigment or dye and organic pigment or dye used in the colorant can be adjusted. The colorant may be contained in 1 to 50% by weight, preferably 5 to 40% by weight, based on 100% by weight of the entire black photosensitive resin composition. When the content of the colorant is less than the above-mentioned range, the light-shielding property is insufficient, and when the content of the colorant exceeds the above-mentioned range, the quality of the pattern obtained after patterning may be deteriorated.

除此之外，本發明的黑色感光性樹脂組合物可進一 步包含選自本領域中通常所使用的黏結劑樹脂、光可聚合化合物、溶劑及添加劑中之至少一者。 In addition to this, the black photosensitive resin composition of the present invention may further comprise at least one selected from the group consisting of binder resins, photopolymerizable compounds, solvents and additives commonly used in the art.

黏結劑樹脂 Binder resin

在本發明的一實施態樣中，黏結劑樹脂可包含藉由含有下述的化學式2的化合物(以下稱為A1)的共聚反應而得到的共聚物。 In one embodiment of the present invention, the binder resin may include a copolymer obtained by a copolymerization reaction containing a compound of the following Chemical Formula 2 (hereinafter referred to as A1).

於化學式2中，R²⁵為氫原子；或者被羥基取代或未被取代的C₁至C₄的烷基，R²⁶為單鍵；或者含有或不含雜原子的C₁至C₂₀的脂肪族或芳香族烴基。 In Chemical Formula 2, R ²⁵ is a hydrogen atom; or a C ₁ to C ₄ alkyl group substituted or unsubstituted by a hydroxyl group, and R ²⁶ is a single bond; or a C ₁ to C ₂₀ aliphatic with or without a hetero atom aromatic or aromatic hydrocarbon group.

本發明中，烷基可為直鏈或分支鏈，例如可為甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、二級丁基，但並不限定於此。 In the present invention, the alkyl group can be straight chain or branched chain, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, tertiary butyl, but It is not limited to this.

本發明中，雜原子可選自N、O及S。 In the present invention, the heteroatom may be selected from N, O and S.

本發明中，脂肪族烴基可包含直鏈脂肪族烴基及支鏈脂肪族烴基、飽和脂肪族烴基及不飽和脂肪族烴基。例如：烷基，如甲基、乙基、正丙基、異丙基、正丁基、二級丁基、異丁基、三級丁基、戊基、己基等；具有雙鍵的烯基，如乙烯基；及具有三鍵的炔基，如乙炔基，但並不限定於此。 In the present invention, the aliphatic hydrocarbon group may include a straight-chain aliphatic hydrocarbon group, a branched-chain aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group, and an unsaturated aliphatic hydrocarbon group. For example: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, isobutyl, tertiary butyl, pentyl, hexyl, etc.; alkenyl with double bonds , such as vinyl; and alkynyl with triple bonds, such as ethynyl, but not limited thereto.

本發明中，芳香族烴基之實例可為：單環式芳香族環，如苯基、聯苯基、三聯苯基等；及多環式芳香族環等，如萘基、蒽基、芘基、苝基等，但並不限定於此。 In the present invention, examples of the aromatic hydrocarbon group can be: monocyclic aromatic rings, such as phenyl, biphenyl, terphenyl, etc.; and polycyclic aromatic rings, such as naphthyl, anthracenyl, pyrenyl, etc. , perylene group, etc., but not limited thereto.

在本發明的另一實施態樣中，黏結劑樹脂可包含共聚物，該共聚物係藉由包含化學式2的化合物(A1)及進一步包含選自以下之至少一者並透過共聚反應而得到：含有不飽和羧酸的單體(以下稱為A2)、以及可與化學式2的化合物(A1)及含有不飽和羧酸的單體(A2)共聚並具有不飽和鍵的化合物(以下稱為A3)。 In another aspect of the present invention, the binder resin may comprise a copolymer obtained by comprising the compound (A1) of Chemical Formula 2 and further comprising at least one selected from the following and through a copolymerization reaction: A monomer containing an unsaturated carboxylic acid (hereinafter referred to as A2), and a compound (hereinafter referred to as A3) which can be copolymerized with the compound (A1) of the chemical formula 2 and the monomer (A2) containing an unsaturated carboxylic acid and has an unsaturated bond ).

相對於黏結劑樹脂(A)的結構單元的總莫耳數，上述衍生自(A1)的結構單元的比例較佳為20至90莫耳%，更佳可含有40至70莫耳%。在上述(A1)的含量低於20莫耳%的情況下，使逸氣產生量減少的效果不足，在超過90莫耳%的情況下，對於顯影液的溶解度降低，產生圖案的形成困難的問題，因此係不合宜的。 The ratio of the above-mentioned structural unit derived from (A1) is preferably 20 to 90 mol %, more preferably 40 to 70 mol %, with respect to the total molar number of structural units of the binder resin (A). When the content of the above-mentioned (A1) is less than 20 mol %, the effect of reducing the amount of outgassing is insufficient, and when it exceeds 90 mol %, the solubility in the developing solution is reduced, and pattern formation is difficult. problem and therefore inappropriate.

在黏結劑樹脂(A)中含有上述(A2)的情況下，相對於黏結劑樹脂(A)的結構單元的總莫耳數，上述衍生自(A2)的結構單元的比例較佳為超過0且為70莫耳%以下。在黏結劑樹脂(A)中含有上述(A3)的情況下，相對於黏結劑樹脂(A)的結構單元的總莫耳數，上述衍生自(A3)的結構單元的比例較佳為超過0且為70莫耳%以下。在上述範圍內含有上述(A2)及(A3)的情況下，對於顯影液的溶解度升高，具有圖案的形成容易的優 點，因此係合宜的。 When the binder resin (A) contains the above-mentioned (A2), the ratio of the structural unit derived from the above-mentioned (A2) is preferably more than 0 with respect to the total number of moles of structural units of the binder resin (A). And it is 70 mol% or less. When the binder resin (A) contains the above-mentioned (A3), the ratio of the above-mentioned structural unit derived from (A3) is preferably more than 0 with respect to the total number of moles of structural units of the binder resin (A). And it is 70 mol% or less. When the above-mentioned (A2) and (A3) are contained within the above-mentioned range, the solubility in the developing solution is increased, and there is an advantage that the formation of a pattern is easy, which is preferable.

黏結劑樹脂(A)意指具有基於光、熱作用的反應性及鹼溶解性，作為以著色劑為首的固體成分的分散介質而發揮作用，發揮黏結劑樹脂的功能。 The binder resin (A) means that it has reactivity and alkali solubility due to the action of light and heat, and it functions as a dispersion medium of solid components including a colorant, and functions as a binder resin.

含有羧基的不飽和單體(A2)之實例可為在分子中具有至少一個羧基的不飽和羧酸等，如不飽和單羧酸、不飽和二羧酸、不飽和三羧酸等。 Examples of the carboxyl group-containing unsaturated monomer (A2) may be unsaturated carboxylic acids having at least one carboxyl group in the molecule, and the like, such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated tricarboxylic acids, and the like.

不飽和單羧酸可為例如丙烯酸、甲基丙烯酸、巴豆酸、α-氯丙烯酸、肉桂酸等。 The unsaturated monocarboxylic acid can be, for example, acrylic acid, methacrylic acid, crotonic acid, alpha-chloroacrylic acid, cinnamic acid, and the like.

不飽和二羧酸可為例如馬來酸、富馬酸、伊康酸、檸康酸、中康酸等。 The unsaturated dicarboxylic acid can be, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like.

不飽和多元羧酸可為酸酐，具體例如馬來酸酐、伊康酸酐、檸康酸酐等。另外，不飽和多元羧酸可為其單(2-甲基丙烯醯氧基烷基)酯，例如琥珀酸單(2-丙烯醯氧基乙基)酯、琥珀酸單(2-甲基丙烯醯氧基乙基)酯、鄰苯二甲酸單(2-丙烯醯氧基乙基)酯、鄰苯二甲酸單(2-甲基丙烯醯氧基乙基)酯等。不飽和多元羧酸可為在其兩末端具有二羧酸聚合物的單(甲基)丙烯酸酯，例如ω-羧基聚己內酯單丙烯酸酯、ω-羧基聚己內酯單甲基丙烯酸酯等。 The unsaturated polycarboxylic acid can be an acid anhydride, such as maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. In addition, the unsaturated polycarboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, such as mono(2-acryloyloxyethyl) succinate, mono(2-methacryloyl succinate) Acryloyloxyethyl) ester, mono(2-acryloyloxyethyl) phthalate, mono(2-methacryloyloxyethyl) phthalate, and the like. The unsaturated polycarboxylic acid may be a mono(meth)acrylate having a dicarboxylic acid polymer at both ends thereof, such as ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate Wait.

含有羧基的單體可各自單獨地使用或者以二或更多者之組合使用。 The carboxyl group-containing monomers may be used each alone or in combination of two or more.

作為可與上述(A1)及(A2)共聚的具有不飽和鍵 的化合物(A3)，例如可為：芳香族乙烯基化合物，如苯乙烯、α-甲基苯乙烯、鄰乙烯基甲苯、間乙烯基甲苯、對乙烯基甲苯、對氯苯乙烯、鄰甲氧基苯乙烯、間甲氧基苯乙烯、對甲氧基苯乙烯、鄰乙烯基苄基甲基醚、間乙烯基苄基甲基醚、對乙烯基苄基甲基醚、鄰乙烯基苄基縮水甘油基醚、間乙烯基苄基縮水甘油基醚、對乙烯基苄基縮水甘油基醚、茚等；不飽和羧酸酯類，如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸異丙酯、甲基丙烯酸異丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸異丁酯、甲基丙烯酸異丁酯、丙烯酸二級丁酯、甲基丙烯酸二級丁酯、丙烯酸三級丁酯、甲基丙烯酸三級丁酯、丙烯酸-2-羥基乙酯、甲基丙烯酸-2-羥基乙酯、丙烯酸-2-羥基丙酯、甲基丙烯酸-2-羥基丙酯、丙烯酸-3-羥基丙酯、甲基丙烯酸-3-羥基丙酯、丙烯酸-2-羥基丁酯、甲基丙烯酸-2-羥基丁酯、丙烯酸-3-羥基丁酯、甲基丙烯酸-3-羥基丁酯、丙烯酸-4-羥基丁酯、甲基丙烯酸-4-羥基丁酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸環己酯、甲基丙烯酸環己酯、丙烯酸苯酯、甲基丙烯酸苯酯、丙烯酸-2-甲氧基乙酯、甲基丙烯酸-2-甲氧基乙酯、丙烯酸-2-苯氧基乙酯、甲基丙烯酸-2-苯氧基乙酯、甲氧基二甘醇丙烯酸酯、甲氧基二甘醇甲基丙烯酸酯、甲氧基三甘醇丙烯酸酯、甲氧基三甘醇甲基丙烯酸酯、甲氧基丙二醇丙烯酸酯、甲氧基丙二醇甲基丙烯酸酯、甲氧基二丙二醇丙烯酸酯、甲氧基二丙二醇甲基丙烯酸酯、丙烯酸 異冰片酯、甲基丙烯酸異冰片酯、丙烯酸雙環戊二烯酯、甲基丙烯酸雙環戊二烯酯、丙烯酸-2-羥基-3-苯氧基丙酯、甲基丙烯酸-2-羥基-3-苯氧基丙酯、甘油單丙烯酸酯、甘油單甲基丙烯酸酯等；不飽和羧酸胺基烷基酯類，如丙烯酸-2-胺基乙酯、甲基丙烯酸-2-胺基乙酯、丙烯酸-2-二甲基胺基乙酯、甲基丙烯酸-2-二甲基胺基乙酯、丙烯酸-2-胺基丙酯、甲基丙烯酸-2-胺基丙酯、丙烯酸-2-二甲基胺基丙酯、甲基丙烯酸-2-二甲基胺基丙酯、丙烯酸-3-胺基丙酯、甲基丙烯酸-3-胺基丙酯、丙烯酸-3-二甲基胺基丙酯、甲基丙烯酸-3-二甲基胺基丙酯等；不飽和羧酸縮水甘油酯類，如丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯等；羧酸乙烯酯類，如醋酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、苯甲酸乙烯酯等；不飽和醚類，如乙烯基甲基醚、乙烯基乙基醚、烯丙基縮水甘油基醚等；乙烯基氰化合物，如丙烯腈、甲基丙烯腈、α-氯丙烯腈、二氰亞乙烯等；不飽和醯胺類，如丙烯醯胺、甲基丙烯醯胺、α-氯丙烯醯胺、N-2-羥基乙基丙烯醯胺、N-2-羥基乙基甲基丙烯醯胺等；不飽和醯亞胺類，如馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺等；脂肪族共軛二烯類，如1,3-丁二烯、異戊二烯、氯丁二烯等；以及在下列聚合物的分子鏈的末端具有單丙烯醯基或單甲基丙烯醯基的大分子單體：聚苯乙烯、聚丙烯酸甲酯、聚甲基丙烯酸甲酯、聚丙烯酸正丁酯、聚甲基丙烯酸正丁酯、聚矽氧烷。該等單體可各自單獨使用或以二或更多者之組合使用。 As the compound (A3) having an unsaturated bond that can be copolymerized with the above (A1) and (A2), for example, aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m Vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl Ethyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, indene, etc.; unsaturated carboxylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate ester, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, acrylic acid -2-Hydroxyethyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxy methacrylate Propyl, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, methacrylic acid -4-Hydroxybutyl, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate , 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene Alcohol acrylate, Methoxydiethylene glycol methacrylate, Methoxytriethylene glycol acrylate, Methoxytriethylene glycol methacrylate, Methoxypropanediol acrylate, Methoxypropanediol methacrylate , Methoxydipropylene glycol acrylate, Methoxydipropylene glycol methacrylate, Isobornyl acrylate, Isobornyl methacrylate, Dicyclopentadienyl acrylate, Dicyclopentadienyl methacrylate, Acrylic acid-2 -Hydroxy-3-phenoxypropyl ester, methacrylate-2-hydroxy-3-phenoxypropyl ester, glycerol monoacrylate, glycerol monomethacrylate, etc.; unsaturated carboxylic acid amino alkyl esters , such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, acrylic acid- 2-aminopropyl methacrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-amino acrylate propyl ester, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, etc.; glycidyl unsaturated carboxylic acid esters, Such as glycidyl acrylate, glycidyl methacrylate, etc.; vinyl carboxylates, such as vinyl acetate, vinyl propionate esters, vinyl butyrate, vinyl benzoate, etc.; unsaturated ethers, such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, etc.; vinyl cyanide compounds, such as acrylonitrile, methyl Acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, etc; , N-2-hydroxyethyl methacrylimide, etc.; Unsaturated imide, such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc.; Aliphatic conjugated dienes, such as 1,3-butadiene, isoprene, chloroprene, etc.; and a monoacryloyl group or a monomethacryloyl group at the end of the molecular chain of the following polymers Macromonomers: polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane. These monomers may each be used alone or in combination of two or more.

以黑色感光性樹脂組合物的總量100重量%計，可使 用5至80重量%的黏結劑樹脂(A)，較佳可使用5至50重量%的黏結劑樹脂(A)。此含量是多方考慮對於顯影液的溶解度及圖案形成等而選擇的範圍，在上述範圍內使用的情況下，對於顯影液的溶解性係足夠的，因此圖案的形成容易，顯影時防止曝光部分的畫素部分的膜減少，非畫素部分的脫落性變得良好。 The binder resin (A) can be used in an amount of 5 to 80% by weight, preferably 5 to 50% by weight, based on 100% by weight of the total amount of the black photosensitive resin composition. This content is a range selected in consideration of the solubility in the developing solution and pattern formation, etc. When used within the above range, the solubility in the developing solution is sufficient, so that the formation of the pattern is easy, and the exposure of the exposed part is prevented during development. The film of the pixel portion was reduced, and the peelability of the non-pixel portion was improved.

另外，在本發明的另一實施態樣中，黏結劑樹脂可使用該技術領域中一般所使用的咔哚系(cardo-based)樹脂。具體地，咔哚系樹脂可由以下而得到：雙(4-羥基苯基)碸、雙(4-羥基-3,5-二甲基苯基)碸與雙(4-羥基-3,5-二氯苯基)碸、雙(4-羥基苯基)六氟丙烷、雙(4-羥基-3,5-二甲基苯基)六氟丙烷與雙(4-羥基-3,5-二氯苯基)六氟丙烷、雙(4-羥基苯基)二甲基矽烷、雙(4-羥基-3,5-二甲基苯基)二甲基矽烷與雙(4-羥基-3,5-二氯苯基)二甲基矽烷、雙(4-羥基苯基)甲烷、雙(4-羥基-3,5-二氯苯基)甲烷與雙(4-羥基-3,5-二溴苯基)甲烷、2,2-雙(4-羥基苯基)丙烷、2,2-雙(4-羥基-3,5-二甲基苯基)丙烷、2,2-雙(4-羥基-3,5-二氯苯基)丙烷、2,2-雙(4-羥基-3-甲基苯基)丙烷與2,2-雙(4-羥基-3-氯苯基)丙烷、雙(4-羥基苯基)醚、雙(4-羥基-3,5-二甲基苯基)醚與雙(4-羥基-3,5-二氯苯基)醚、9,9-雙(4-羥基苯基)茀、9,9-雙(4-羥基-3-甲基苯基)茀、9,9-雙(4-羥基-3-氯苯基)茀、9,9-雙(4-羥基-3-溴苯基)茀、9,9-雙(4-羥基-3-氟苯基)茀、9,9-雙(4-羥基-3-甲氧基苯基)茀、9,9-雙(4-羥基-3,5-二甲基苯基)茀、9,9-雙(4-羥基-3,5-二氯苯基)茀以及9,9-雙(4-羥 基-3,5-二溴苯基)茀等，但並不限定於此。 In addition, in another embodiment of the present invention, a cardo-based resin generally used in this technical field can be used as the binder resin. Specifically, the carbdol-based resins can be obtained from bis(4-hydroxyphenyl) bis(4-hydroxy-3,5-dimethylphenyl) bis(4-hydroxy-3,5-dimethylphenyl) bis(4-hydroxy-3,5- Dichlorophenyl) bismuth, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane and bis(4-hydroxy-3,5-difluoropropane) chlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane and bis(4-hydroxy-3, 5-Dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane and bis(4-hydroxy-3,5-dichlorophenyl) bromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4- Hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane and 2,2-bis(4-hydroxy-3-chlorophenyl)propane, Bis(4-hydroxyphenyl) ether, bis(4-hydroxy-3,5-dimethylphenyl) ether and bis(4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis(4-hydroxy-3,5-dichlorophenyl) ether (4-Hydroxyphenyl) fluoride, 9,9-bis(4-hydroxy-3-methylphenyl) fluoride, 9,9-bis(4-hydroxy-3-chlorophenyl) fluoride, 9,9- Bis(4-hydroxy-3-bromophenyl) fluoride, 9,9-bis(4-hydroxy-3-fluorophenyl) fluoride, 9,9-bis(4-hydroxy-3-methoxyphenyl) Fluorine, 9,9-bis(4-hydroxy-3,5-dimethylphenyl) fluoride, 9,9-bis(4-hydroxy-3,5-dichlorophenyl) fluoride and 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluoride etc., but it is not limited to this.

將咔哚系樹脂作為黏結劑樹脂使用的情況下，以本發明黑色感光性樹脂組合物的固體成分總重量計，黏結劑樹脂的含量較佳可使用10至80重量%，更佳地可使用10至70重量%。在黏結劑樹脂的含量滿足10至80重量%範圍的情況下，顯影液的溶解性係足夠的，因此圖案的形成容易，顯影時防止曝光部分的畫素部分的膜減少，非畫素部分的脫落性變得良好，因此係合宜的。 In the case of using a carbodol-based resin as the binder resin, the content of the binder resin is preferably 10 to 80% by weight based on the total solid weight of the black photosensitive resin composition of the present invention, and more preferably 10 to 70% by weight. When the content of the binder resin satisfies the range of 10 to 80% by weight, the solubility of the developer solution is sufficient, so that the pattern formation is easy, the film reduction of the pixel part of the exposed part is prevented during development, and the non-pixel part of the film is prevented from being reduced. The detachability becomes good, so it is suitable.

光可聚合化合物 photopolymerizable compounds

對光可聚合化合物並無特別限定，可使用選自以下群組之至少一者：含有羧基的不飽和單體的聚合物、含有羧基的不飽和單體及可與其共聚的具有不飽和鍵的單體的共聚物、及其組合。 The photopolymerizable compound is not particularly limited, and at least one selected from the group consisting of: a polymer of a carboxyl group-containing unsaturated monomer, a carboxyl group-containing unsaturated monomer, and a polymer having an unsaturated bond copolymerizable therewith may be used. Copolymers of monomers, and combinations thereof.

含有羧基的不飽和單體可為不飽和單羧酸、不飽和二羧酸、不飽和三羧酸等。具體地，不飽和單羧酸，例如可為丙烯酸、甲基丙烯酸、巴豆酸、α-氯丙烯酸、肉桂酸等。不飽和二羧酸，例如可為富馬酸、中康酸、伊康酸、檸康酸等。不飽和多元羧酸可為酸酐，具體地，例如馬來酸酐、伊康酸酐、檸康酸酐等。另外，不飽和多元羧酸可為ω-羧基聚己內酯單(甲基)丙烯酸酯等兩末端具有羧基與羥基的聚合物的單(甲基)丙烯酸酯類、單甲基馬來酸、5-降冰片烯-2-羧酸、鄰苯二甲酸單-2-((甲基)丙烯醯氧基)乙酯、琥珀酸單-2-((甲基)丙烯醯氧基)乙酯等。這些具有不飽和羧基的化合物能夠各自單獨地使用或者以二或更 多者之組合使用，其中，丙烯酸及甲基丙烯酸係具有優異的共聚反應性及對於顯影液的溶解性，因此較佳可使用該等。 The carboxyl group-containing unsaturated monomer may be unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated tricarboxylic acid, and the like. Specifically, the unsaturated monocarboxylic acid can be, for example, acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like. The unsaturated dicarboxylic acid can be, for example, fumaric acid, mesaconic acid, itaconic acid, citraconic acid and the like. The unsaturated polycarboxylic acid may be an acid anhydride, specifically, maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. In addition, the unsaturated polycarboxylic acid may be mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate, monomethylmaleic acid, 5-Norbornene-2-carboxylic acid, mono-2-((meth)acryloyloxy)ethyl phthalate, mono-2-((meth)acryloyloxy)ethyl succinate Wait. These compounds having an unsaturated carboxyl group can each be used alone or in combination of two or more, and among them, acrylic acid and methacrylic acid have excellent copolymerization reactivity and solubility in developing solutions, so they are preferably used such.

另外，作為可與含有羧基的不飽和單體共聚的單體，可為芳香族乙烯基化合物、不飽和羧酸酯化合物、不飽和胺基烷基羧酸酯化合物、乙烯基氰化合物、不飽和氧雜環丁烷羧酸酯化合物等，該等可單獨地使用或者以二或更多者之組合使用。 In addition, as the monomer copolymerizable with the carboxyl group-containing unsaturated monomer, aromatic vinyl compounds, unsaturated carboxylate compounds, unsaturated amino alkyl carboxylate compounds, vinyl cyanide compounds, unsaturated Oxetane carboxylate compounds and the like, which may be used alone or in combination of two or more.

上述可共聚的單體之具體實例為：芳香族乙烯基化合物，如苯乙烯、α-甲基苯乙烯、乙烯基甲苯等；不飽和羧酸酯化合物，如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸-2-羥基乙酯、甲基丙烯酸-2-羥基乙酯、丙烯酸苄酯、甲基丙烯酸苄酯等；不飽和胺基烷基羧酸酯化合物，如丙烯酸胺基乙酯等；不飽和羧酸縮水甘油酯化合物，如甲基丙烯酸縮水甘油酯等；羧酸乙烯酯化合物，如乙酸乙烯酯、丙酸乙烯酯等；乙烯基氰化合物，如丙烯腈、甲基丙烯腈、α-氯丙烯腈等；氧雜環丁烷不飽和羧酸酯化合物，如3-甲基-3-丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-丙烯醯氧基乙基氧雜環丁烷、3-甲基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基乙基氧雜環丁烷等；以及其他。 Specific examples of the above-mentioned copolymerizable monomers are: aromatic vinyl compounds, such as styrene, α-methylstyrene, vinyltoluene, etc.; unsaturated carboxylate compounds, such as methyl acrylate, methyl methacrylate, etc. , ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, etc.; Unsaturated amino alkyl carboxylate compounds, such as aminoethyl acrylate, etc.; unsaturated glycidyl carboxylate compounds, such as glycidyl methacrylate, etc.; carboxylate vinyl ester compounds, such as vinyl acetate, propionic acid Vinyl esters, etc.; vinyl cyanide compounds, such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc.; oxetane unsaturated carboxylate compounds, such as 3-methyl-3-acryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane, 3-ethyl Alkyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-propenyloxyethyl oxetane, 3-methyl-3-methacryloyloxy Ethyl oxetane, 3-ethyl-3-propenyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and the like; and other.

上述例示的可與具有羧基的不飽和化合物共聚的其 他單體可各自單獨地使用或者以二或更多者之組合使用。 The other monomers copolymerizable with the unsaturated compound having a carboxyl group exemplified above may be used each alone or in combination of two or more.

溶劑 solvent

本發明的黑色感光性樹脂組合物中所含的溶劑並無特別限制，可使用黑色感光性樹脂組合物的領域中所使用的各種有機溶劑。其具體實例可為：乙二醇單烷基醚類，如乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚等；二甘醇二烷基醚類，如二甘醇二甲基醚、二甘醇二乙基醚、二甘醇二丙基醚、二甘醇二丁基醚等；乙二醇烷基醚乙酸酯類，如甲基賽路蘇乙酸酯及乙基賽路蘇乙酸酯等；伸烷基二醇烷基醚乙酸酯類，如丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、乙酸甲氧基丁酯及乙酸甲氧基戊酯等；芳香烴類，如苯、甲苯、二甲苯、均三甲苯等；酮類，如甲乙酮、丙酮、甲基戊基酮、甲基異丁基酮、環己酮等；醇類，如乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、甘油等；酯類，如3-乙氧基丙酸乙酯、3-甲氧基丙酸甲酯等；以及環狀酯類，如γ-丁內酯等。在上述溶劑中，從塗佈性、乾燥性等方面出發，較佳可為在上述溶劑中沸點為100℃至200℃的有機溶劑，更佳可為伸烷基二醇烷基醚乙酸酯類、酮類、3-乙氧基丙酸乙酯及3-甲氧基丙酸甲酯等酯類，進一步更佳地，可為丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、環己酮、3-乙氧基丙酸乙酯、3-甲氧基丙酸甲酯等。該等溶劑可各自單獨地使用或者以二或更多者之組合使用。 The solvent contained in the black photosensitive resin composition of the present invention is not particularly limited, and various organic solvents used in the field of the black photosensitive resin composition can be used. Specific examples thereof can be: ethylene glycol monoalkyl ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc.; Glycol dialkyl ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc.; glycol alkyl ether acetate Classes, such as methyl cyluthol acetate and ethyl cyluthol acetate, etc.; alkylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ethyl Acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxyamyl acetate, etc.; aromatic hydrocarbons, such as benzene, toluene, xylene, mesitylene, etc.; ketones, such as methyl ethyl ketone, Acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; alcohols, such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, etc.; esters, such as Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc.; and cyclic esters, such as γ-butyrolactone, etc. Among the above-mentioned solvents, from the viewpoints of coatability, drying properties, etc., organic solvents having a boiling point of 100°C to 200°C in the above-mentioned solvents are preferable, and alkylene glycol alkyl ether acetates are more preferable. , ketones, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetic acid ester, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. These solvents may each be used alone or in combination of two or more.

溶劑可作為餘量而含有以使得黑色感光性樹脂組合 物為100重量%。此含量是考慮組成的分散穩定性及製造製程中的製程容易性(例如塗佈性)而選擇的範圍。 The solvent may be contained as the remainder so that the black photosensitive resin composition is 100% by weight. This content is a range selected in consideration of dispersion stability of the composition and process easiness (eg, coatability) in the manufacturing process.

添加劑 Additives

在本發明的黑色感光性樹脂組合物中，也可根據需要添加填充劑、其他高分子化合物、顏料分散劑、密合促進劑、抗氧化劑、紫外線吸收劑、防凝聚劑等添加劑。 To the black photosensitive resin composition of the present invention, if necessary, additives such as fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-agglomeration agents may be added.

填料之具體實例可為玻璃、二氧化矽、氧化鋁等。其他的高分子化合物之具體實例可為：固化性樹脂，如環氧樹脂、馬來醯亞胺樹脂等；熱塑性樹脂，如聚乙烯醇、聚丙烯酸、聚乙二醇單烷基醚、聚丙烯酸氟烷基酯、聚酯、聚胺甲酸酯等；以及其他。顏料分散劑可使用市售的表面活性劑，例如矽系、氟系、酯系、陽離子系、陰離子系、非離子系、兩性等的表面活性劑等。該等可以各自單獨地使用或者以二或更多者之組合使用。 Specific examples of fillers may be glass, silica, alumina, and the like. Specific examples of other polymer compounds can be: curable resins, such as epoxy resins, maleimide resins, etc.; thermoplastic resins, such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyacrylic acid Fluoroalkyl esters, polyesters, polyurethanes, etc.; and others. As the pigment dispersant, commercially available surfactants such as silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants can be used. These may each be used alone or in combination of two or more.

表面活性劑之實例可為聚氧乙烯烷基醚類、聚氧乙烯烷基苯基醚類、聚乙二醇二酯類、山梨醇脂肪酸酯類、脂肪酸改性聚酯類、三級胺改性聚胺甲酸酯類、聚乙烯亞胺類等，除此以外，可包括以下商品：KP(信越化學工業股份有限公司製造)、POLYFLOW(共榮社化學股份有限公司製造)、EFTOP(托克產品(TOHKEM PRODUCTS)有限公司製造)、MEGAFAC(大日本油墨化學工業股份有限公司製造)、Flourad(住友3M股份有限公司製造)、Asahi guard、Surflon(旭硝子股份有限公司製造)、SOLSPERSE(捷利康(ZENECA)股份有限公司製造)、EFKA(埃 弗卡(EFKA)化學公司製造)及PB 821(味之素股份有限公司製造)等。 Examples of surfactants may be polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitol fatty acid esters, fatty acid modified polyesters, tertiary amine modified Polyurethanes, polyethyleneimine, etc., in addition to the following products: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (Tokyo Chemical Co., Ltd.) Products (manufactured by TOHKEM PRODUCTS Co., Ltd.), MEGAFAC (manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.), Flourad (manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (Zelecon ( ZENECA) Co., Ltd.), EFKA (Efka (EFKA) Chemical Co., Ltd.) and PB 821 (Ajinomoto Co., Ltd.) and so on.

密合促進劑之實例可為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-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油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。抗氧化劑之實例可為2,2'-硫代雙(4-甲基-6-三級-丁基苯酚)、2,6-二-三級-丁基-4-甲基苯酚等。 Examples of adhesion promoters may be vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3 -aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyl Glyceryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropyl Methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Examples of antioxidants may be 2,2'-thiobis(4-methyl-6-tertiary-butylphenol), 2,6-di-tertiary-butyl-4-methylphenol, and the like.

紫外線吸收劑之具體實例可為2-(3-三級-丁基-2-羥基-5-甲基苯基)-5-氯苯并***、烷氧基二苯甲酮等。 Specific examples of the ultraviolet absorber may be 2-(3-tertiary-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, and the like.

防凝聚劑之具體實例可為聚丙烯酸鈉等。 Specific examples of the anti-agglomeration agent may be sodium polyacrylate and the like.

該等添加劑能夠在不阻礙本發明的效果的範圍內由本領域技術人員適當地添加使用。 These additives can be appropriately added and used by those skilled in the art within a range that does not inhibit the effects of the present invention.

<顯示裝置> <Display device>

本發明的另一實施態樣係關於包含畫素界定膜的顯示裝置，該畫素界定膜包含上述黑色感光性樹脂組合物的固化物。本發明的顯示裝置可包含含有有機發光元件或者量子點發光元件的顯示裝置。 Another embodiment of the present invention relates to a display device including a pixel-defining film including a cured product of the black photosensitive resin composition. The display device of the present invention may include a display device including an organic light-emitting element or a quantum dot light-emitting element.

採用光刻方法形成畫素界定膜的圖案化製程通常包 含以下的步驟：a)將黑色感光性樹脂組合物塗佈於基板的步驟；b)將溶劑乾燥的預烘焙步驟；c)在得到的被膜上使光遮罩接觸，照射活性光線而使曝光部分固化的步驟；d)進行使用鹼性水溶液將未曝光部分溶解的顯影製程的步驟；及e)進行乾燥及後烘焙的步驟。 The patterning process of forming a pixel-defining film by photolithography usually includes the following steps: a) a step of coating the black photosensitive resin composition on a substrate; b) a pre-baking step of drying the solvent; c) after the obtained The photomask is brought into contact with the film, and the exposed parts are cured by irradiating active rays; d) the developing process of dissolving the unexposed parts with an aqueous alkaline solution is performed; and e) the drying and post-baking are performed.

為了得到所期望的厚度，上述塗佈採用其中使用輥塗機、旋塗機、狹縫旋塗機、狹縫塗佈機(有時也稱為模塗機)、噴墨等塗佈裝置的濕式塗佈法而進行。 In order to obtain a desired thickness, the above-mentioned coating adopts a coating apparatus in which a roll coater, a spin coater, a slit spin coater, a slit coater (sometimes also referred to as a die coater), an ink jet, or the like is used. by the wet coating method.

藉由用烘箱、熱板等進行加熱來進行預烘焙。此時，預烘焙中的加熱溫度及加熱時間係根據所使用的溶劑而適當地選擇，例如在80至150℃的溫度下進行1至30分鐘。 Prebaking is performed by heating with an oven, hot plate, or the like. At this time, the heating temperature and heating time in the prebaking are appropriately selected according to the solvent to be used, and for example, it is performed at a temperature of 80 to 150° C. for 1 to 30 minutes.

另外，採用曝光機進行在預烘焙後實施的曝光，經由光遮罩進行曝光，從而只使與圖案對應的部分感光。此時，照射的光可為例如可見光線、紫外線、X射線及電子束等。 In addition, exposure performed after prebaking was performed using an exposure machine, and exposure was performed through a photomask so that only a portion corresponding to the pattern was exposed to light. At this time, the irradiated light may be, for example, visible rays, ultraviolet rays, X-rays, and electron beams.

為了將非曝光部分的未被除去部分的感光性樹脂組合物除去，係進行曝光後的鹼顯影，藉由顯影，形成所期望的圖案。作為適於該鹼顯影的顯影液，例如可使用鹼金屬、鹼土族金屬的碳酸鹽的水溶液等。特別地，使用含有1至3重量%的碳酸鈉、碳酸鉀、碳酸鋰等碳酸鹽的鹼水溶液，在10至50℃、較佳在20至 40℃的溫度下利用顯影機或超聲波清洗機等進行。 In order to remove the photosensitive resin composition of the unremoved part of a non-exposed part, alkali development after exposure is performed, and a desired pattern is formed by image development. As a developer suitable for this alkali development, for example, an aqueous solution of an alkali metal or an alkaline earth metal carbonate can be used. In particular, using an alkaline aqueous solution containing 1 to 3% by weight of carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, etc., at a temperature of 10 to 50° C., preferably 20 to 40° C., using a developing machine or an ultrasonic cleaner or the like conduct.

為了提高圖案化的膜與基板的密合性而進行後烘焙，在80至220℃、10至120分鐘的條件下藉由熱處理而進行。後烘焙係與預烘焙同樣地，使用烘箱、熱板等進行。 In order to improve the adhesiveness of the patterned film and a board|substrate, post-baking is performed by heat processing on the conditions of 80-220 degreeC and 10-120 minutes. The post-baking system is performed using an oven, a hot plate, or the like in the same manner as the pre-baking.

用本發明的黑色感光性樹脂組合物製造的畫素界定膜不僅光學密度、密合性、電絕緣性、遮光性等物性優異，而且耐熱性及耐溶劑性等優異，因此能夠提高有機發光元件、量子點發光元件以及包含上述有機發光元件或量子點發光元件的顯示裝置的可靠度。 The pixel-defining film produced from the black photosensitive resin composition of the present invention is not only excellent in physical properties such as optical density, adhesiveness, electrical insulating properties, and light-shielding properties, but also excellent in heat resistance, solvent resistance, and the like, so that it is possible to improve organic light-emitting elements. , the reliability of a quantum dot light-emitting element and a display device comprising the above-mentioned organic light-emitting element or quantum dot light-emitting element.

在下文中，為了詳細解釋本發明，將參照實施例詳細描述本發明。然而，根據本發明之實施例可以各種不同的形式進行修改，並且本發明之範圍不應被視為限於下面將描述的實施例。提供本發明之例示性實施態樣是為了讓具有通常技術者更全面地理解本發明。另外，在下文中，除非另外特別定義，否則表示含量的「%」及「份」是基於重量。 Hereinafter, in order to explain the present invention in detail, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present invention may be modified in various different forms, and the scope of the present invention should not be construed as being limited to the embodiments to be described below. Illustrative embodiments of the present invention are provided so that those skilled in the art can more fully understand the present invention. In addition, in the following, unless otherwise specifically defined, "%" and "part" indicating the content are based on weight.

製造例：黏結劑樹脂A的合成 Production Example: Synthesis of Binder Resin A

準備裝備有攪拌機、溫度計、回流冷凝管、滴液漏斗及氮氣導入管的燒瓶。作為單體滴液漏斗，添加20份的以莫耳比50：50混合而成的(甲基)丙烯酸-3,4-環氧三環癸烷-8-基酯及(甲基)丙烯酸-3,4-環氧三環癸烷-9-基酯的混合物、30份的丙烯酸、80份的環己基馬來醯亞胺、70份的甲基丙烯酸-2-羥基乙酯、4份的過氧化-2-乙基己酸三級丁酯、40份的丙二醇單甲基醚乙酸酯 (PGMEA)，並攪拌。作為鏈轉移劑滴液漏斗，添加6份的正十二硫醇、24份的PGMEA，並攪拌。然後，在燒瓶中添加395份的PGMEA，使燒瓶內的氣氛從空氣置換為氮氣後，攪拌並使燒瓶的溫度升溫至90℃。然後，從滴液漏斗開始滴入單體及鏈轉移劑。在90℃下分別進行滴液2小時，1小時後，升溫至110℃，維持5小時，得到了固體成分的酸值為100毫克KOH/公克的樹脂。由GPC所量測的聚苯乙烯換算重量平均分子量為10100，分子量分佈(Mw/Mn)為2.2。 Prepare a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube. As a monomer dropping funnel, 20 parts of (meth)acrylic acid-3,4-epoxytricyclodecan-8-yl ester and (meth)acrylic acid- Mixture of 3,4-epoxytricyclodecan-9-yl esters, 30 parts of acrylic acid, 80 parts of cyclohexylmaleimide, 70 parts of 2-hydroxyethyl methacrylate, 4 parts of Tertiary butyl peroxy-2-ethylhexanoate, 40 parts of propylene glycol monomethyl ether acetate (PGMEA), and stirring. As a chain transfer agent dropping funnel, 6 parts of n-dodecanethiol and 24 parts of PGMEA were added and stirred. Then, after adding 395 parts of PGMEA to the flask and replacing the atmosphere in the flask with nitrogen, the temperature of the flask was raised to 90°C with stirring. Then, the monomer and the chain transfer agent were dripped from the dropping funnel. Dropping was performed at 90° C. for 2 hours, and after 1 hour, the temperature was raised to 110° C. and maintained for 5 hours to obtain a resin having an acid value of solid content of 100 mg KOH/g. The polystyrene-equivalent weight average molecular weight measured by GPC was 10,100, and the molecular weight distribution (Mw/Mn) was 2.2.

實施例1至3及比較例1至3：黑色感光性樹脂組合物的製備 Examples 1 to 3 and Comparative Examples 1 to 3: Preparation of Black Photosensitive Resin Compositions

以下表1中記載的組成及含量製備黑色感光性樹脂組合物。 A black photosensitive resin composition was prepared according to the composition and content described in Table 1 below.

在上述表1中記載的各成分中，相對於顏料、顏料分散劑及丙二醇單甲基醚乙酸酯的混合物，預先以作為著色材料的顏料及作為添加劑的顏料分散劑的合計量為20質量%的方式進行混合，利用珠磨機使顏料充分地分散後，將珠磨機分離，進一步添加包含丙二醇單甲基醚乙酸酯的餘量的剩餘成分，進行混合，得到了著色感光性樹脂組合物。 Among the components described in Table 1 above, the total amount of the pigment as a coloring material and the pigment dispersant as an additive is 20 mass in advance with respect to the mixture of the pigment, the pigment dispersant, and propylene glycol monomethyl ether acetate. %, the pigment was sufficiently dispersed by a bead mill, and then the bead mill was separated, and the remaining components including the balance of propylene glycol monomethyl ether acetate were added and mixed to obtain a colored photosensitive resin. combination.

實驗例：逸氣性質的評估 Experimental Example: Evaluation of Outgassing Properties

(1)著色基板的製造 (1) Manufacture of colored substrates

將5公分×5公分的玻璃基板(康寧公司)用中性洗滌劑及水洗淨，然後乾燥。在玻璃基板上將實施例及比較例中所製造的黑色感光性樹脂組合物分別旋塗以使最終膜厚成為1.5微米，在80至120℃下進行預烘焙，乾燥1至2分鐘，將溶劑除去。然後，用曝光量40至100毫焦耳/平方公分(mJ/cm²)進行曝光，形成1公分×3公分的圖案，使用鹼性水溶液將非曝光部分除去。然後在220℃進行20分鐘後烘焙，製得著色基板。 A 5 cm x 5 cm glass substrate (Corning Corporation) was washed with a neutral detergent and water, and then dried. The black photosensitive resin compositions produced in the Examples and Comparative Examples were spin-coated on a glass substrate so that the final film thickness was 1.5 μm, pre-baked at 80 to 120° C., dried for 1 to 2 minutes, and the solvent remove. Then, exposure is performed with an exposure amount of 40 to 100 millijoules/square centimeter (mJ/cm ² ) to form a pattern of 1 cm×3 cm, and the non-exposed portion is removed using an alkaline aqueous solution. Then, post-baking was performed at 220° C. for 20 minutes to obtain a colored substrate.

(2)逸氣的評估 (2) Evaluation of outgassing

採用以下方法實施逸氣的評估：在230℃下使上述製得的著色基板熱分解30分鐘，在此期間用Py-GC/MS分析所收集的化合物。分析結果示於下述表2中。 The evaluation of outgassing was carried out by thermally decomposing the colored substrate prepared above at 230° C. for 30 minutes, during which time the collected compounds were analyzed by Py-GC/MS. The analysis results are shown in Table 2 below.

如由上述表2可得知，使用實施例1至3的本發明黑色感光性樹脂組合物製造的情形，與利用比較例1至3的感光性樹脂組合物製造的情形相比，溶出的逸氣量顯著減少。 As can be seen from Table 2 above, in the case of manufacturing using the black photosensitive resin compositions of the present invention of Examples 1 to 3, compared with the cases of manufacturing using the photosensitive resin compositions of Comparative Examples 1 to 3, the elution rate of Air volume is significantly reduced.

Claims (9)

一種用於形成黑矩陣或畫素界定膜之黑色感光性樹脂組合物，其具有減少逸氣產生的效果，其以黑色感光性樹脂組合物全體100重量%計，包含1至50重量%的著色劑、5至80重量%的黏結劑樹脂、1至30重量%的光可聚合化合物、0.01至10重量%的光聚合引發劑以及餘量的溶劑，其中該著色劑包含黑色顏料或染料，其中該光聚合引發劑包含選自由下述化學式1表示的化合物中之至少一者：

於化學式1中，R¹、R²、R³及R⁴各自獨立地為氫、NO₂或

；或者R¹與R²、R²與R³以及R³與R⁴中至少一對各自獨立地一起為

，與其所連接的碳原子一起形成六員環；其中R¹¹、R¹²、R¹³及R¹⁴為氫；其中R⁵為未被取代的C₁至C₂₀烷基； R⁶、R⁷、R⁸、R⁹及R¹⁰各自獨立為氫、或被至少一個氧或至少一個鹵素取代的C₁至C₂₀烷基。 A black photosensitive resin composition for forming a black matrix or a pixel-defining film, which has the effect of reducing outgassing, and contains 1 to 50% by weight of coloring based on 100% by weight of the entire black photosensitive resin composition agent, 5 to 80% by weight of a binder resin, 1 to 30% by weight of a photopolymerizable compound, 0.01 to 10% by weight of a photopolymerization initiator, and the balance of a solvent, wherein the colorant comprises a black pigment or dye, wherein The photopolymerization initiator includes at least one compound selected from the group consisting of compounds represented by the following Chemical Formula 1:

In Chemical Formula 1, R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, NO ₂ or

; or at least one pair of R ¹ and R ² , R ² and R ³ , and R ³ and R ⁴ are each independently taken together

, form a six-membered ring together with the carbon atom to which it is attached; wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are hydrogen; wherein R ⁵ is an unsubstituted C ₁ to C ₂₀ alkyl; R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen, or C ₁ to C ₂₀ alkyl substituted with at least one oxygen or at least one halogen. 如請求項1所述的用於形成黑矩陣或畫素界定膜之黑色感光性樹脂組合物，其中，該光聚合引發劑包含：在化學式1中R¹、R²、R³及R⁴各自獨立地為氫、NO₂或

的化合物；以及在化學式1中R¹與R²、R²與R³及R³與R⁴中至少一對各自獨立地一起為

、與其所連接的碳原子一起形成六員環的化合物。 The black photosensitive resin composition for forming a black matrix or a pixel-defining film according to claim 1, wherein the photopolymerization initiator comprises: each of R ¹ , R ² , R ³ and R ⁴ in Chemical Formula 1 independently _hydrogen , NO or

and at least one pair of R ¹ and R ² , R ² and R ³ , and R ³ and R ⁴ in Chemical Formula 1 are each independently taken together

, which together with the carbon atom to which it is attached form a six-membered ring. 如請求項1所述的用於形成黑矩陣或畫素界定膜之黑色感光性樹脂組合物，其更包含光聚合引發輔助劑。 The black photosensitive resin composition for forming a black matrix or a pixel-defining film according to claim 1, further comprising a photopolymerization initiation adjuvant. 如請求項3所述的用於形成黑矩陣或畫素界定膜之黑色感光性樹脂組合物，其中，該光聚合引發輔助劑包含選自胺系化合物以及羧酸系化合物之至少一者。 The black photosensitive resin composition for forming a black matrix or a pixel-defining film according to claim 3, wherein the photopolymerization initiation adjuvant comprises at least one selected from the group consisting of amine-based compounds and carboxylic acid-based compounds. 如請求項1所述的用於形成黑矩陣或畫素界定膜之黑色感光性樹脂組合物，其中，更包含添加劑。 The black photosensitive resin composition for forming a black matrix or a pixel-defining film according to claim 1, further comprising an additive. 如請求項1所述的用於形成黑矩陣或畫素界定膜之黑色感光性樹脂組合物，其中，該黏結劑樹脂包含由含有下述的化學式2的化合物的共聚反應所得到的共聚物：[化學式2]

於化學式2中，R²⁵為氫原子；或者被羥基取代或未被取代的C₁至C₄的烷基，R²⁶為單鍵；或者含雜原子或不含雜原子的C₁至C₂₀的脂肪族或芳香族烴基。 The black photosensitive resin composition for forming a black matrix or a pixel-defining film according to claim 1, wherein the binder resin comprises a copolymer obtained by a copolymerization reaction of a compound containing the following chemical formula 2: [Chemical formula 2]

In Chemical Formula 2, R ²⁵ is a hydrogen atom; or a C ₁ to C ₄ alkyl group substituted or unsubstituted by a hydroxyl group, and R ²⁶ is a single bond; or a hetero atom-containing or heteroatom-free C ₁ to C ₂₀ aliphatic or aromatic hydrocarbon groups. 如請求項6所述的用於形成黑矩陣或畫素界定膜之黑色感光性樹脂組合物，其中，該黏結劑樹脂包含共聚物，該共聚物係藉由進一步包含選自含有不飽和羧酸的單體、以及可與化學式2的化合物及含有不飽和羧酸的單體共聚並具有不飽和鍵的化合物之至少一者，透過共聚反應而得到。 The black photosensitive resin composition for forming a black matrix or a pixel-defining film as claimed in claim 6, wherein the binder resin comprises a copolymer, which is obtained by further comprising an unsaturated carboxylic acid selected from the group consisting of The monomer and at least one of the compound which can be copolymerized with the compound of Chemical Formula 2 and the unsaturated carboxylic acid-containing monomer and have an unsaturated bond are obtained through a copolymerization reaction. 一種顯示裝置，其包含含有如請求項1至7中任一項所述的黑色感光性樹脂組合物的固化物的畫素界定膜。 A display device comprising a pixel-defining film containing the cured product of the black photosensitive resin composition according to any one of claims 1 to 7. 如請求項8所述的顯示裝置，其中，該顯示裝置包含有機發光元件或量子點發光元件。 The display device according to claim 8, wherein the display device includes an organic light-emitting element or a quantum dot light-emitting element.