TW201942688A

TW201942688A - Method of forming cured film and curable composition

Info

Publication number: TW201942688A
Application number: TW108110851A
Authority: TW
Inventors: 石川暁; 和田光弘; 浜口仁
Original assignee: 日商Ｊｓｒ股份有限公司
Priority date: 2018-04-02
Filing date: 2019-03-28
Publication date: 2019-11-01
Also published as: KR20200138734A; WO2019193941A1; CN111902747A; JP2019182899A

Abstract

Provided is a method of forming a cured film that makes it possible to obtain a cured film which is excellent in coating property and patterning property and has good light blocking property, and also provided is a curable composition that makes it possible to obtain a cured film which is excellent in coating property and patterning property and has good light blocking property. The method of forming a cured film of the present invention comprises the steps of: (1) forming a template having projections on a substrate, (2) forming a coating film with a curable composition between the projections of the template, and (3) curing the film, wherein the curable composition includes a pigment which is a white pigment, a black pigment, or a combination thereof, a curable compound, and a solvent, the amount of the pigment with respect to all components except the solvent is 50%-90% by mass, and the dielectric constant of the solvent is 6.0 or less.

Description

硬化膜的形成方法及硬化性組成物Method for forming cured film and curable composition

本發明是有關於一種硬化膜的形成方法及硬化性組成物。The present invention relates to a method for forming a cured film and a curable composition.

顯示元件或固體攝像元件具備黑色矩陣、彩色濾光片、遮光膜等經圖案化的硬化膜。先前，此種硬化膜的形成廣泛藉由使用感放射線性組成物的光微影法來進行（參照專利文獻1、專利文獻2）。另外，所述黑色矩陣等中，為了發揮遮光性等而添加黑色顏料等顏料。The display element or the solid-state imaging element includes a patterned cured film such as a black matrix, a color filter, and a light-shielding film. Conventionally, the formation of such a cured film has been widely performed by a photolithography method using a radiation-sensitive composition (see Patent Documents 1 and 2). Moreover, in the said black matrix etc., pigments, such as a black pigment, are added in order to exhibit light-shielding properties.

另一方面，近年來推進開發被稱為微發光二極體（Light Emitting Diode，LED）顯示器等的配置有多個微LED的顯示裝置（參照專利文獻3）。
[現有技術文獻]
[專利文獻]On the other hand, in recent years, development of a display device including a plurality of micro LEDs, such as a light emitting diode (LED) display, has been advanced (see Patent Document 3).
[Prior Art Literature]
[Patent Literature]

[專利文獻1]日本專利特開2004-205862號公報
[專利文獻2]日本專利特開2003-302515號公報
[專利文獻3]日本專利特開2012-142489號公報[Patent Document 1] Japanese Patent Laid-Open No. 2004-205862
[Patent Document 2] Japanese Patent Laid-Open No. 2003-302515
[Patent Document 3] Japanese Patent Laid-Open No. 2012-142489

[發明所欲解決之課題]
於所述微LED顯示器中，設為分別配置發出紅色光的LED（R-LED）、發出綠色光的LED（G-LED）及發出藍色光的LED（B-LED）作為多個微LED的結構於實用化方面的技術性障礙高。相對於此，認為如圖1所示般的設為如下結構的微LED顯示器101的技術性障礙相對較低，所述結構是於薄膜電晶體（Thin Film Transistor，TFT）基板105上僅配置B-LED 102作為微LED，並將B-LED 102與波長變換層103a、波長變換層103b加以組合而成。具體而言，於圖1的微LED顯示器101中，於發出紅色光的區域將B-LED 102與使藍色光變換為紅色光的波長變換層103a加以組合。同樣地，於發出綠色光的區域將B-LED 102與使藍色光變換為綠色的波長變換層103b加以組合。於發出藍色光的區域不設置波長變換層而僅配置B-LED 102。再者，於各區域亦可進而設置彩色濾光片等。[Problems to be Solved by the Invention]
In the micro LED display, it is assumed that LEDs emitting red light (R-LED), LEDs emitting green light (G-LED), and LEDs emitting blue light (B-LED) are configured as a plurality of micro LEDs. The technical barriers to the practical application are high. In contrast, it is considered that the technical obstacle of the micro LED display 101 configured as shown in FIG. 1 is relatively low, and the structure is that only B is disposed on the thin film transistor (TFT) substrate 105 -LED 102 is a micro LED, and B-LED 102 is combined with a wavelength conversion layer 103a and a wavelength conversion layer 103b. Specifically, in the micro LED display 101 of FIG. 1, the B-LED 102 is combined with a wavelength conversion layer 103 a that converts blue light into red light in a region that emits red light. Similarly, the B-LED 102 and the wavelength conversion layer 103b that converts blue light to green are combined in a region that emits green light. A wavelength conversion layer is not provided in a region emitting blue light, and only the B-LED 102 is disposed. Furthermore, a color filter or the like may be further provided in each region.

如此，於在發光的各區域不僅僅設置LED而且設置波長變換層103a、波長變換層103b的情況下，尤其是於為了以充分的發光強度獲得經變換的紅色光、綠色光而提高波長變換層103a、波長變換層103b的膜厚的情況下，需要將隔開各區域的隔離壁104設置得高。通常，利用光微影法的隔離壁104的形成是藉由如下方式來進行：於透明基板106的其中一面（圖1中的下表面）上形成感放射線性組成物的塗膜，並經過曝光及顯影。另一方面，為了提高區域間的遮光性，需要提高隔離壁104中的顏料的濃度。但是，於欲藉由使用感放射線性組成物的光微影法來形成顏料濃度高的隔離壁104的情況下，照射光難以到達至塗膜的下部，因此難以形成具有高度的隔離壁。In this way, when not only the LED but also the wavelength conversion layer 103a and the wavelength conversion layer 103b are provided in each light-emitting area, the wavelength conversion layer is improved in order to obtain converted red light and green light with sufficient light emission intensity. When the film thickness of 103a and the wavelength conversion layer 103b is high, it is necessary to set the partition wall 104 separating each region to be high. Generally, the formation of the partition wall 104 by the photolithography method is performed by forming a coating film of a radiation-sensitive composition on one surface (the lower surface in FIG. 1) of the transparent substrate 106 and exposing it. And development. On the other hand, in order to improve the light-shielding property between regions, it is necessary to increase the concentration of the pigment in the partition wall 104. However, when a partition wall 104 having a high pigment concentration is to be formed by a photolithography method using a radiation-sensitive composition, it is difficult to reach the lower portion of the coating film with the irradiation light, and it is difficult to form a partition wall having a high height.

因此，發明者等人對使用成為隔離壁的模具的模板（template）（亦稱為預圖案（prepattern）等）的隔離壁的形成方法進行了研究。具體而言，首先，使用感放射線性組成物等來形成具有凸部的模板。繼而，於該模板的凸部間塗佈硬化性組成物而形成硬化性組成物的塗膜。使該塗膜硬化後，將模板的凸部去除，藉此可形成具有充分高度的隔離壁。但是，於此種方法中，於硬化性組成物的塗佈性及圖案化性等方面，亦並非可稱為充分者。Therefore, the inventors have studied a method of forming a partition wall using a template (also referred to as a “prepattern”, etc.) as a mold for the partition wall. Specifically, first, a template having convex portions is formed using a radiation-sensitive composition or the like. Then, a curable composition is applied between the convex portions of the template to form a coating film of the curable composition. After curing the coating film, the convex portion of the template is removed, whereby a partition wall having a sufficient height can be formed. However, in this method, the coating properties and patterning properties of the curable composition are not sufficient.

本發明是基於如以上般的情況而成者，其目的在於提供一種可獲得塗佈性及圖案化性優異且具有良好的遮光性的硬化膜的硬化膜的形成方法以及可獲得塗佈性及圖案化性優異且具有良好的遮光性的硬化膜的硬化性組成物。
[解決課題之手段]The present invention is based on the above-mentioned circumstances, and an object thereof is to provide a method for forming a cured film that can obtain a cured film that is excellent in coating properties and patterning properties and has good light-shielding properties, and that can obtain coating properties and A curable composition of a cured film that is excellent in patternability and has good light-shielding properties.
[Means for solving problems]

為了解決所述課題而成的發明為一種硬化膜的形成方法，其包括：（1）於基板上形成具有凸部的模板的步驟；（2）藉由硬化性組成物而於所述模板的凸部間形成塗膜的步驟；以及（3）使所述塗膜硬化的步驟，並且所述硬化性組成物包含白色顏料、黑色顏料或該些的組合的顏料；硬化性化合物；及溶媒，且所述顏料相對於所述溶媒除外的所有成分的含量為50質量%以上、90質量%以下，所述溶媒的相對介電常數為6.0以下。An invention made in order to solve the problem is a method for forming a cured film, which includes: (1) a step of forming a template having a convex portion on a substrate; and (2) a step of forming a template with a hardening composition on the template. A step of forming a coating film between the convex portions; and (3) a step of hardening the coating film, and the curable composition includes a white pigment, a black pigment, or a combination of these pigments; a curable compound; and a solvent, The content of the pigment with respect to all components except the solvent is 50% by mass or more and 90% by mass or less, and the relative dielectric constant of the solvent is 6.0 or less.

為了解決所述課題而成的另一發明為一種硬化性組成物，其包含：白色顏料、黑色顏料或該些的組合的顏料；硬化性化合物；及溶媒，且所述顏料相對於所述溶媒除外的所有成分的含量為50質量%以上、90質量%以下，所述溶媒的相對介電常數為6.0以下。
[發明的效果]Another invention made in order to solve the above problem is a curable composition including: a white pigment, a black pigment, or a combination of these pigments; a curable compound; and a solvent. The content of all components except 50% by mass to 90% by mass, and the relative dielectric constant of the solvent is 6.0 or less.
[Effect of the invention]

根據本發明，可提供一種可獲得塗佈性及圖案化性優異且具有良好的遮光性的硬化膜的硬化膜的形成方法以及可獲得塗佈性及圖案化性優異且具有良好的遮光性的硬化膜的硬化性組成物。According to the present invention, it is possible to provide a method for forming a cured film that can obtain a cured film that is excellent in coating properties and patterning properties and has good light-shielding properties, and can obtain A curable composition of a cured film.

以下，對本發明的一實施形態的硬化性組成物及硬化膜的形成方法進行詳細說明。Hereinafter, a method for forming a curable composition and a cured film according to an embodiment of the present invention will be described in detail.

＜硬化性組成物＞
本發明的一實施形態的硬化性組成物包含：
[A]白色顏料、黑色顏料或該些的組合的顏料；
[B]硬化性化合物；及
[C]溶媒。
於該硬化性組成物中，[A]顏料相對於[C]溶媒除外的所有成分的含量為50質量%以上、90質量%以下。另外，[C]溶媒的相對介電常數為6.0以下。＜ Sclerosing composition ＞
A curable composition according to an embodiment of the present invention includes:
[A] white pigment, black pigment, or a combination of these pigments;
[B] a hardening compound; and
[C] Solvent.
In this curable composition, the content of the [A] pigment with respect to all components except the [C] solvent is 50% by mass or more and 90% by mass or less. The relative dielectric constant of the [C] solvent is 6.0 or less.

該硬化性組成物可獲得塗佈性及圖案化性優異且具有良好的遮光性的硬化膜。具體而言，於藉由硬化性組成物的塗佈而於所述模板的凸部間形成塗膜，使該塗膜硬化，藉此獲得硬化膜的方法中，藉由使用該硬化性組成物，可較佳地顯現所述效果。再者，所謂圖案化性優異例如是指於經過顯影步驟而獲得經圖案化的硬化膜的情況下，可獲得硬化膜的剝離或裂紋的產生少且良好形狀的硬化膜等。該硬化性組成物可發揮所述效果的理由並不確定，但推測以下理由。若使用極性高的溶媒作為硬化性組成物的溶媒，則會溶解成為模具的模板，塗佈性或圖案化性變差。相對於此，於該硬化性組成物中，由於使用相對介電常數為6.0以下的極性低的[C]溶媒，因此不易產生模板的溶解，且塗佈性或圖案化性得到改善。另外，由於使用相對介電常數為6.0以下的極性低的[C]溶媒，因此該硬化性組成物於模板的凸部間的潤濕擴展亦良好。進而，由於該硬化性組成物中的[A]顏料的含量高，因此所獲得的硬化膜的遮光性良好。因此，根據該硬化性組成物，可有效地用作能夠較佳地應用於微LED顯示器等中的具有相對較高的高度的隔離壁等的形成材料。再者，由該硬化性組成物所獲得的硬化膜通常為白色、黑色或灰色。With this curable composition, a cured film having excellent coating properties and patterning properties and excellent light-shielding properties can be obtained. Specifically, in a method of obtaining a cured film by forming a coating film between the convex portions of the template by applying a curable composition, and curing the coating film, the curable composition is used. , Can better show the effect. The term “excellent patternability” means that when a patterned cured film is obtained through a development step, a cured film having a good shape with little peeling or cracking can be obtained. The reason why the curable composition can exert the above effects is not certain, but the following reason is presumed. When a highly polar solvent is used as a solvent for the curable composition, it will dissolve as a template for a mold, and the coating properties and patterning properties will deteriorate. In contrast, in this curable composition, since a [C] solvent having a low polarity and a relative dielectric constant of 6.0 or less is used, dissolution of a template is unlikely to occur, and coating properties and patterning properties are improved. In addition, since a low-polarity [C] solvent having a relative dielectric constant of 6.0 or less is used, the wetting spread of the curable composition between the convex portions of the template is also good. Furthermore, since the content of the [A] pigment in this curable composition is high, the light-shielding property of the obtained cured film is good. Therefore, according to this hardenable composition, it can be effectively used as a forming material for a partition wall or the like having a relatively high height that can be preferably applied to a micro LED display or the like. The cured film obtained from the curable composition is usually white, black, or gray.

該硬化性組成物除所述[A]成分～[C]成分以外，亦可進而包含其他成分。以下，對各成分進行詳細說明。The curable composition may further contain other components in addition to the components [A] to [C]. Hereinafter, each component is demonstrated in detail.

（[A]顏料）
[A]顏料為白色顏料、黑色顏料或該些的組合。遮光性可以光反射率或光密度（OD（Optical Density）值）的形式進行評價。[A]顏料可使用一種或兩種以上。([A] pigment)
[A] The pigment is a white pigment, a black pigment, or a combination thereof. The light-shielding property can be evaluated in the form of light reflectance or optical density (OD (Optical Density) value). [A] The pigment may be used alone or in combination of two or more.

（白色顏料）
作為白色顏料，例如可列舉：碳酸鈣、碳酸鉛、碳酸鋇、硫酸鋇、硫酸鉛、磷酸鉛、磷酸鋅、氧化鈦、氧化鋁、二氧化矽、氧化鋅、氧化銻、氧化鋯、氧化錫、硫化鋅、硫化鍶、鈦酸鍶、鎢酸鋇、偏矽酸鉛、滑石、高嶺土、黏土、氯氧化鉍、氫氧化鈣、中空氧化矽等。(White pigment)
Examples of the white pigment include calcium carbonate, lead carbonate, barium carbonate, barium sulfate, lead sulfate, lead phosphate, zinc phosphate, titanium oxide, aluminum oxide, silicon dioxide, zinc oxide, antimony oxide, zirconia, and tin oxide. , Zinc sulfide, strontium sulfide, strontium titanate, barium tungstate, lead metasilicate, talc, kaolin, clay, bismuth oxychloride, calcium hydroxide, hollow silicon oxide, etc.

作為白色顏料，例如可列舉於染料索引（Colour Index，C.I.；染料及色彩師學會（The Society of Dyers and Colourists）公司發行）中被分類為顏料（pigment）的化合物，即標註有如下述般的染料索引（C.I.）編號者。As the white pigment, for example, a compound classified as a pigment in the Colour Index (CI; issued by The Society of Dyers and Colourists) can be listed as follows: Dye Index (CI) number.

C.I.顏料白（pigment white）1、C.I.顏料白2、C.I.顏料白3、C.I.顏料白4、C.I.顏料白5、C.I.顏料白6、C.I.顏料白6：1、C.I.顏料白7、C.I.顏料白8、C.I.顏料白10、C.I.顏料白11、C.I.顏料白12、C.I.顏料白13、C.I.顏料白14、C.I.顏料白15、C.I.顏料白16、C.I.顏料白17、C.I.顏料白18、C.I.顏料白18：1、C.I.顏料白19、C.I.顏料白20、C.I.顏料白21、C.I.顏料白22、C.I.顏料白23、C.I.顏料白24、C.I.顏料白25、C.I.顏料白26、C.I.顏料白27、C.I.顏料白28、C.I.顏料白30、C.I.顏料白32、C.I.顏料白33。CI pigment white 1, CI pigment white 2, CI pigment white 3, CI pigment white 4, CI pigment white 5, CI pigment white 6, CI pigment white 6: 1, CI pigment white 7, CI pigment white 8 , CI Pigment White 10, CI Pigment White 11, CI Pigment White 12, CI Pigment White 13, CI Pigment White 14, CI Pigment White 15, CI Pigment White 16, CI Pigment White 17, CI Pigment White 18, CI Pigment White 18 : 1, CI Pigment White 19, CI Pigment White 20, CI Pigment White 21, CI Pigment White 22, CI Pigment White 23, CI Pigment White 24, CI Pigment White 25, CI Pigment White 26, CI Pigment White 27, CI Pigment White 28, CI Pigment White 30, CI Pigment White 32, CI Pigment White 33.

關於該些白色顏料，亦可利用氧化鋁、矽氧烷、氧化鋯、氧化鋅等其他金屬對其表面進行處理來使用。These white pigments can also be used by treating the surface with other metals such as alumina, silica, zirconia, and zinc oxide.

該些白色顏料中，就可有效地提高所獲得的硬化膜的遮光性（光反射性）等方面而言，較佳為氧化鈦及鈦酸鍶。氧化鈦的結晶型較佳為金紅石型。Among these white pigments, titanium oxide and strontium titanate are preferred in terms of effectively improving the light-shielding property (light reflectivity) of the obtained cured film. The crystal type of titanium oxide is preferably a rutile type.

（黑色顏料）
作為黑色顏料，可列舉：碳黑、鈦黑、乙炔黑、燈黑、骨黑、石墨、鐵黑、苯胺黑、花青黑、苝黑等。另外，作為黑色顏料，可組合使用多種有色顏料。(Black pigment)
Examples of the black pigment include carbon black, titanium black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and perylene black. In addition, as the black pigment, a plurality of colored pigments can be used in combination.

該些黑色顏料中，就可有效地提高所獲得的硬化膜的遮光性等方面而言，較佳為碳黑。Among these black pigments, carbon black is preferred in terms of effectively improving the light-shielding properties of the obtained cured film.

作為碳黑，可列舉如以下般的市售品。
三菱化學公司的MA7、MA8、MA11、MA77、MA100、MA100R、MA100S、MA220、MA230、MA600、MCF88、#5、#10、#20、#25、#30、#32、#33、#40、#44、#45、#47、#50、#52、#55、#650、#750、#850、#900、#950、#960、#970、#980、#990、#1000、#2200、#2300、#2350、#2400、#2600、#2650、#3030、#3050、#3150、#3250、#3400、#3600、#3750、#3950、#4000、#4010、OIL7B、OIL9B、OIL11B、OIL30B、OIL31B
德固賽（Degussa）公司的普林泰克斯（Printex）（註冊商標，以下相同）3、普林泰克斯（Printex）3OP、普林泰克斯（Printex）30、普林泰克斯（Printex）30OP、普林泰克斯（Printex）40、普林泰克斯（Printex）45、普林泰克斯（Printex）55、普林泰克斯（Printex）60、普林泰克斯（Printex）75、普林泰克斯（Printex）80、普林泰克斯（Printex）85、普林泰克斯（Printex）90、普林泰克斯（Printex）A、普林泰克斯（Printex）L、普林泰克斯（Printex）G、普林泰克斯（Printex）P、普林泰克斯（Printex）U、普林泰克斯（Printex）V、普林泰克斯（Printex）G、特種黑（SpecialBlack）550、特種黑（SpecialBlack）350、特種黑（SpecialBlack）250、特種黑（SpecialBlack）100、特種黑（SpecialBlack）6、特種黑（SpecialBlack）5、特種黑（SpecialBlack）4、色素碳黑（Color Black）FW1、色素碳黑（Color Black）FW2、色素碳黑（Color Black）FW2V、色素碳黑（Color Black）FW18、色素碳黑（Color Black）FW18、色素碳黑（Color Black）FW200、色素碳黑（Color Black）S160、色素碳黑（Color Black）S170
卡博特（CABOT）公司的芒那科（Monarch）（註冊商標，以下相同）120、芒那科（Monarch）280、芒那科（Monarch）460、芒那科（Monarch）800、芒那科（Monarch）880、芒那科（Monarch）900、芒那科（Monarch）1000、芒那科（Monarch）1100、芒那科（Monarch）1300、芒那科（Monarch）1400、芒那科（Monarch）4630、瑞格（REGAL）（註冊商標，以下相同）99、瑞格（REGAL）99R、瑞格（REGAL）415、瑞格（REGAL）415R、瑞格（REGAL）250、瑞格（REGAL）250R、瑞格（REGAL）330、瑞格（REGAL）400R、瑞格（REGAL）55R0、瑞格（REGAL）660R、黑珍珠（BLACK PEARLS）480、珍珠（PEARLS）130、伏爾甘（VULCAN）（註冊商標）XC72R、艾來福泰克斯（ELFTEX）（註冊商標）-8、TPK1099R、TPK1104R、TPK1227R
哥倫比亞碳（Columbia carbon）公司的雷文（RAVEN）（註冊商標，以下相同）11、雷文（RAVEN）14、雷文（RAVEN）15、雷文（RAVEN）16、雷文（RAVEN）22、雷文（RAVEN）30、雷文（RAVEN）35、雷文（RAVEN）40、雷文（RAVEN）410、雷文（RAVEN）420、雷文（RAVEN）450、雷文（RAVEN）500、雷文（RAVEN）780、雷文（RAVEN）850、雷文（RAVEN）890H、雷文（RAVEN）1000、雷文（RAVEN）1020、雷文（RAVEN）1040、雷文（RAVEN）1060U、雷文（RAVEN）1080U、雷文（RAVEN）1170、雷文（RAVEN）1190U、雷文（RAVEN）1250、雷文（RAVEN）1500、雷文（RAVEN）2000、雷文（RAVEN）2500U、雷文（RAVEN）3500、雷文（RAVEN）5000、雷文（RAVEN）5250、雷文（RAVEN）5750、雷文（RAVEN）7000Examples of the carbon black include commercially available products such as the following.
MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 900, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200 , # 2300, # 2350, # 2400, # 2600, # 2650, # 3030, # 3050, # 3150, # 3250, # 3400, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B
Degussa's Printex (registered trademark, the same below) 3, Printex 3OP, Printex 30, Printex 30OP , Printex 40, Printex 45, Printex 55, Printex 60, Printex 75, Printex (Printex) 80, Printex 85, Printex 90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, SpecialBlack 550, SpecialBlack 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black ) FW2, pigment carbon black (Colo r Black) FW2V, Pigment Carbon Black (Color Black) FW18, Pigment Carbon Black (Color Black) FW18, Pigment Carbon Black (Color Black) FW200, Pigment Carbon Black (Color Black) S160, Pigment Carbon Black (Color Black) S170
CABOT's Monarch (registered trademark, the same below) 120, Monarch 280, Monarch 460, Monarch 800, Monarch (Monarch) 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch ) 4630, REGAL (registered trademark, the same below) 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN (Registered trademark) XC72R, ELFTEX (registered trademark) -8, TPK1099R, TPK1104R, TPK1227R
Columbia Carbon's RAVEN (registered trademark, the same below) 11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 22, Raven 30, Raven 35, Raven 40, Raven 410, Raven 420, Raven 450, Raven 450, Raven 500, Raven RAVEN 780, RAVEN 850, RAVEN 890H, RAVEN 1000, RAVEN 1020, RAVEN 1040, RAVEN 1060U, RAVEN (RAVEN) 1080U, RAVEN 1170, RAVEN 1190U, RAVEN 1250, RAVEN 1500, RAVEN 2000, RAVEN 2500U, RAVEN ( RAVEN) 3500, RAVEN 5000, RAVEN 5250, RAVEN 5750, RAVEN 7000

作為其他黑色顏料，可較佳地使用國際公開第2017/110893號中記載的各黑色顏料。另外，關於組合使用多種有色顏料作為黑色顏料時的有色顏料，可使用國際公開第2017/110893號中記載的有機著色顏料等。As other black pigments, each of the black pigments described in International Publication No. 2017/110893 can be preferably used. In addition, as the colored pigment when a plurality of colored pigments are used in combination as a black pigment, an organic coloring pigment described in International Publication No. 2017/110893 and the like can be used.

[A]顏料的平均粒徑的下限亦有時較佳為30 nm，較佳為50 nm，更佳為100 nm，進而佳為200 nm。另一方面，其上限亦有時較佳為700 nm，更佳為500 nm，進而佳為400 nm，尤佳為200 nm。再者，於[A]顏料為白色顏料的情況下，存在平均粒徑以相對較大者為宜的傾向。另一方面，於[A]顏料為黑色顏料的情況下，存在平均粒徑以相對較小者為宜的傾向。The lower limit of the average particle diameter of the [A] pigment is also preferably 30 nm, preferably 50 nm, more preferably 100 nm, and even more preferably 200 nm. On the other hand, the upper limit is sometimes preferably 700 nm, more preferably 500 nm, still more preferably 400 nm, and even more preferably 200 nm. When the [A] pigment is a white pigment, the average particle diameter tends to be relatively large. On the other hand, when the [A] pigment is a black pigment, the average particle diameter tends to be relatively small.

[A]顏料可藉由再結晶法、再沈澱法、溶劑清洗法、昇華法、真空加熱法或該些的組合進行精製而使用。另外，顏料視需要亦可利用樹脂等對其粒子表面進行改質而使用。作為對顏料的粒子表面進行改質的樹脂，例如可列舉：日本專利特開2001-108817號公報中記載的媒介（vehicle）樹脂、或市售的各種顏料分散用的樹脂。另外，顏料亦可藉由所謂的鹽磨（salt milling）將一次粒子加以微細化而使用。作為鹽磨的方法，例如可採用日本專利特開平08-179111號公報中所揭示的方法。[A] The pigment can be purified by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof. In addition, the pigment can also be used by modifying the surface of its particles with a resin or the like if necessary. Examples of the resin for modifying the particle surface of a pigment include a vehicle resin described in Japanese Patent Laid-Open No. 2001-108817, and various commercially available resins for dispersing pigments. In addition, the pigment can be used by miniaturizing the primary particles by a so-called salt milling. As a method of salt milling, for example, the method disclosed in Japanese Patent Laid-Open No. 08-179111 can be used.

[A]顏料相對於該硬化性組成物中的[C]溶媒除外的所有成分的含量、即固體成分中的含量的下限為50質量%，較佳為60質量%，更佳為70質量%。藉由將[A]顏料的含量設為所述下限以上，可提高所獲得的硬化膜的遮光性。另一方面，[A]顏料的含量的上限為90質量%，較佳為85質量%。藉由將[A]顏料的含量設為所述上限以下，可顯現出良好的圖案化性或硬化性。The lower limit of the content of the [A] pigment with respect to all components except the [C] solvent in the curable composition, that is, the content in the solid content is 50% by mass, preferably 60% by mass, and more preferably 70% by mass . When the content of the [A] pigment is at least the above lower limit, the light-shielding property of the obtained cured film can be improved. On the other hand, the upper limit of the content of the [A] pigment is 90% by mass, and preferably 85% by mass. When the content of the [A] pigment is equal to or less than the above-mentioned upper limit, good patternability or hardenability can be exhibited.

（[B]硬化性化合物）
所謂[B]硬化性化合物為可硬化的化合物。該硬化性組成物含有[B]硬化性化合物，因此可發揮良好的硬化性及圖案化性。作為[B]硬化性化合物，較佳為具有一個或兩個以上的聚合性基的化合物，更佳為具有兩個以上的聚合性基的化合物。作為聚合性基，例如可列舉：氧雜環丙基、氧雜環丁基等環狀醚基、(甲基)丙烯醯基、乙烯基、N-烷氧基甲基胺基等。該些中，較佳為環員數3～5的環狀醚基，更佳為氧雜環丙基及氧雜環丁基。即，[B]硬化性化合物較佳為具有氧雜環丙基、氧雜環丁基或該些的組合。[B]硬化性化合物可使用一種或兩種以上。[B]硬化性化合物可為[B1]樹脂（聚合物），亦可為樹脂以外的[B2]化合物（單量體）。亦可併用[B1]樹脂與[B2]化合物。([B] hardening compound)
The [B] hardenable compound is a hardenable compound. Since this hardenable composition contains a [B] hardenable compound, it can exhibit favorable hardenability and patternability. [B] The curable compound is preferably a compound having one or two or more polymerizable groups, and more preferably a compound having two or more polymerizable groups. Examples of the polymerizable group include a cyclic ether group such as an oxepropyl group and an oxetanyl group, a (meth) acrylfluorenyl group, a vinyl group, and an N-alkoxymethylamino group. Among these, a cyclic ether group having 3 to 5 ring members is preferable, and an oxetanyl group and an oxetanyl group are more preferable. That is, the [B] curable compound preferably has an oxetanyl group, an oxetanyl group, or a combination thereof. [B] The hardening compound may be used alone or in combination of two or more. The [B] curable compound may be a [B1] resin (polymer), or a [B2] compound (monomer) other than a resin. [B1] resin and [B2] compound can also be used together.

（[B1]樹脂）
[B1]樹脂為可硬化的聚合物。[B1]樹脂較佳為一種或多種乙烯性不飽和單量體（具有不飽和雙鍵的單量體）的聚合物。[B1]樹脂可使用一種或兩種以上。作為[B1]樹脂，可列舉含有具有聚合性基的結構單元（I）的聚合物。([B1] resin)
[B1] The resin is a hardenable polymer. [B1] The resin is preferably a polymer of one or more ethylenically unsaturated singly bodies (single bodies having unsaturated double bonds). [B1] The resin may be used alone or in combination of two or more. Examples of the [B1] resin include polymers containing a structural unit (I) having a polymerizable group.

（結構單元（I））
結構單元（I）為具有聚合性基的結構單元。該聚合性基的具體例如上所述。(Structural unit (I))
The structural unit (I) is a structural unit having a polymerizable group. Specific examples of the polymerizable group are as described above.

作為提供結構單元（I）的單量體，例如可列舉：丙烯酸縮水甘油酯、丙烯酸-3,4-環氧環己酯、丙烯酸-3,4-環氧環己基甲酯、丙烯酸-3,4-環氧三環[5.2.1.0^2,6 ]癸酯、丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯、丙烯酸-2-(乙烯氧基乙氧基)乙酯等丙烯酸酯；甲基丙烯酸縮水甘油酯、甲基丙烯酸-3,4-環氧環己酯、甲基丙烯酸-3,4-環氧環己基甲酯、甲基丙烯酸-3,4-環氧三環[5.2.1.0^2,6 ]癸酯、甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯、甲基丙烯酸-2-(乙烯氧基乙氧基)乙酯等甲基丙烯酸酯；乙烯基縮水甘油醚等乙烯基醚化合物等。該些單量體可使用一種或兩種以上。Examples of the unit that provides the structural unit (I) include glycidyl acrylate, -3,4-epoxycyclohexyl acrylate, -3,4-epoxy cyclohexyl methyl acrylate, and -3, 4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ester, (3-ethyloxetane-3-yl) acrylate, 2- (vinyloxyethoxy) ethyl acrylate And other acrylic esters; glycidyl methacrylate, cyclohexyl methacrylate-3,4-epoxy, cyclohexyl methyl methacrylate-3,4-epoxy Tricyclo [5.2.1.0 ^2,6 ] decyl ester, (3-ethyloxetane-3-yl) methacrylate, 2- (vinyloxyethoxy) ethyl methacrylate And other methacrylates; vinyl ether compounds such as vinyl glycidyl ether and the like. These single bodies can be used alone or in combination of two or more.

結構單元（I）亦可藉由如下方式來獲得：使聚合物中的結構單元所具有的特定基與具有和所述特定基反應的基及作為聚合性基的(甲基)丙烯醯基或乙烯基的化合物進行反應。例如可列舉：（1）使具有羧基的聚合物與含氧雜環丙基或氧雜環丁基的不飽和化合物等進行反應的方法；（2）使具有氧雜環丙基或氧雜環丁基的聚合物與(甲基)丙烯酸等進行反應的方法；（3）使具有羥基的聚合物與具有異氰酸酯基的(甲基)丙烯酸酯或乙烯基化合物進行反應的方法；（4）使具有酸酐部位的聚合物與(甲基)丙烯酸等進行反應的方法等。藉由此種方法，可導入具有作為聚合性基的(甲基)丙烯醯基或乙烯基的結構單元（I）。The structural unit (I) can also be obtained by causing a specific group of the structural unit in the polymer to react with the specific group and a (meth) acrylfluorenyl group as a polymerizable group or The vinyl compound reacts. Examples include: (1) a method of reacting a polymer having a carboxyl group with an unsaturated compound containing an oxetanyl group or an oxetanyl group; and (2) reacting a polymer having an oxetanyl group or an oxetanyl group; A method of reacting a butyl polymer with (meth) acrylic acid, etc .; (3) A method of reacting a polymer having a hydroxyl group with a (meth) acrylate or vinyl compound having an isocyanate group; (4) A method of reacting A method of reacting a polymer having an acid anhydride site with (meth) acrylic acid and the like. According to this method, the structural unit (I) having a (meth) acrylfluorenyl group or a vinyl group as a polymerizable group can be introduced.

作為結構單元（I），較佳為包含環員數3～5的環狀醚基的結構單元，更佳為包含氧雜環丙基或氧雜環丁基的結構單元，進而佳為包含氧雜環丙基的結構單元。另外，作為結構單元（I），較佳為源自(甲基)丙烯酸酯的結構單元，更佳為源自(甲基)丙烯酸縮水甘油酯的結構單元。The structural unit (I) is preferably a structural unit containing a cyclic ether group having 3 to 5 ring members, more preferably a structural unit containing an oxetanyl group or an oxetanyl group, and even more preferably an oxygen group. The structural unit of heterocyclyl. The structural unit (I) is preferably a structural unit derived from a (meth) acrylate, and more preferably a structural unit derived from a glycidyl (meth) acrylate.

結構單元（I）相對於[B1]樹脂的所有結構單元的含量的下限較佳為2莫耳%，更佳為5莫耳%。另一方面，該結構單元（I）的含量的上限亦有時較佳為60莫耳%，更佳為50莫耳%，進而佳為35莫耳%或25莫耳%。The lower limit of the content of the structural unit (I) relative to all the structural units of the [B1] resin is preferably 2 mol%, and more preferably 5 mol%. On the other hand, the upper limit of the content of the structural unit (I) is sometimes preferably 60 mol%, more preferably 50 mol%, and even more preferably 35 mol% or 25 mol%.

（結構單元（II））
[B1]樹脂較佳為含有具有碳數8以上、30以下的烴基的結構單元（II）。藉由[B1]樹脂含有結構單元（II），[B1]樹脂於[C]溶媒中的溶解性提高。因此，該硬化性組成物藉由包含含有結構單元（II）的[B1]樹脂，塗佈性等提高。(Structural Unit (II))
[B1] The resin preferably contains a structural unit (II) having a hydrocarbon group having 8 or more and 30 or less carbon atoms. When the [B1] resin contains the structural unit (II), the solubility of the [B1] resin in the [C] solvent is improved. Therefore, the curable composition improves the coatability and the like by including the [B1] resin containing the structural unit (II).

作為碳數8以上、30以下的烴基，可列舉脂肪族鏈狀烴基及脂肪族環狀烴基等碳數8以上、30以下的脂肪族烴基以及碳數8以上、30以下的芳香族烴基。Examples of the hydrocarbon group having 8 or more and 30 carbon atoms include aliphatic hydrocarbon groups having 8 or more and 30 carbon atoms such as aliphatic chain hydrocarbon groups and aliphatic cyclic hydrocarbon groups, and aromatic hydrocarbon groups having 8 or more and 30 carbon atoms.

作為碳數8以上、30以下的脂肪族鏈狀烴基，可列舉：
辛基、壬基、癸基、十二烷基、十五烷基、十八烷基（硬脂基）、二十四烷基等烷基；
辛烯基、癸烯基、十八烯基等烯基；
辛炔基、癸炔基、十八炔基等炔基等。Examples of the aliphatic chain hydrocarbon group having 8 or more and 30 or less carbon atoms include:
Alkyl such as octyl, nonyl, decyl, dodecyl, pentadecyl, stearyl, stearyl, etc .;
Alkenyl such as octenyl, decenyl, octadecyl;
Alkynyl, such as octynyl, decynyl, octadecynyl, etc.

作為碳數8以上、30以下的脂肪族環狀烴基，可列舉：環十六烷基等環烷基、環烯基、環炔基等。Examples of the aliphatic cyclic hydrocarbon group having 8 or more and 30 or less carbon atoms include cycloalkyl such as cyclohexadecyl, cycloalkenyl, and cycloalkynyl.

作為碳數8以上、30以下的芳香族烴基，可列舉：萘基、蒽基、二甲苯基等。Examples of the aromatic hydrocarbon group having 8 or more and 30 or less carbon atoms include naphthyl, anthracenyl, and xylyl.

該些中，較佳為脂肪族烴基，更佳為脂肪族鏈狀烴基，進而佳為烷基。另外，作為該烴基的碳數的下限，較佳為12，更佳為15。另一方面，作為該碳數的上限，較佳為25，更佳為20。Among these, an aliphatic hydrocarbon group is preferable, an aliphatic chain hydrocarbon group is more preferable, and an alkyl group is more preferable. The lower limit of the number of carbons in the hydrocarbon group is preferably 12, and more preferably 15. On the other hand, the upper limit of the carbon number is preferably 25, and more preferably 20.

作為提供結構單元（II）的單量體，例如可列舉：丙烯酸辛酯、丙烯酸癸酯、丙烯酸十八烷基酯（丙烯酸硬脂酯）、丙烯酸二十四烷基酯、丙烯酸萘酯等丙烯酸酯；甲基丙烯酸辛酯、甲基丙烯酸癸酯、甲基丙烯酸十八烷基酯（甲基丙烯酸硬脂酯）、甲基丙烯酸二十四烷基酯、甲基丙烯酸萘酯等甲基丙烯酸酯；十八烷基乙烯基醚等乙烯基醚化合物等。該些單量體可使用一種或兩種以上。Examples of the single body that provides the structural unit (II) include acrylic acid such as octyl acrylate, decyl acrylate, octadecyl acrylate (stearyl acrylate), behenyl acrylate, and naphthyl acrylate. Esters; methacrylic acid such as octyl methacrylate, decyl methacrylate, stearyl methacrylate (stearyl methacrylate), behenyl methacrylate, naphthyl methacrylate, etc. Esters; vinyl ether compounds such as octadecyl vinyl ether and the like. These single bodies can be used alone or in combination of two or more.

結構單元（II）相對於[B1]樹脂的所有結構單元的含量的下限較佳為20莫耳%，更佳為40莫耳%，進而佳為50莫耳%。另一方面，該結構單元（II）的含量的上限較佳為85莫耳%，更佳為75莫耳%，進而佳為70莫耳%。The lower limit of the content of the structural unit (II) relative to all the structural units of the [B1] resin is preferably 20 mol%, more preferably 40 mol%, and even more preferably 50 mol%. On the other hand, the upper limit of the content of the structural unit (II) is preferably 85 mol%, more preferably 75 mol%, and even more preferably 70 mol%.

（結構單元（III））
[B1]樹脂較佳為進而含有具有羧基或羥基的結構單元（III）。藉由[B1]樹脂含有結構單元（III），有時可實現進一步改善圖案化性等。作為結構單元（III），更佳為具有羧基的結構單元。(Construction unit (III))
[B1] The resin preferably further contains a structural unit (III) having a carboxyl group or a hydroxyl group. When the [B1] resin contains the structural unit (III), further improvement in patternability and the like may be achieved. The structural unit (III) is more preferably a structural unit having a carboxyl group.

作為提供結構單元（III）的單量體，例如可列舉：丙烯酸、甲基丙烯酸、巴豆酸、4-乙烯基苯甲酸等不飽和單羧酸；
馬來酸、富馬酸、檸康酸、中康酸、衣康酸等不飽和二羧酸；
所述不飽和二羧酸的酸酐；
(甲基)丙烯酸-4-羥基苯酯、(甲基)丙烯酸-2-羥基乙酯等具有羥基的(甲基)丙烯酸酯；
對羥基-α-甲基苯乙烯、對羥基苯乙烯、4-(乙烯基苯基)甲醇等具有羥基的乙烯基化合物等。該些單量體可使用一種或兩種以上。Examples of the monounit that provides the structural unit (III) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and 4-vinylbenzoic acid;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
The anhydride of the unsaturated dicarboxylic acid;
(Meth) acrylic acid esters having a hydroxyl group, such as 4-hydroxyphenyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate;
Vinyl compounds having a hydroxyl group, such as p-hydroxy-α-methylstyrene, p-hydroxystyrene, 4- (vinylphenyl) methanol, and the like. These single bodies can be used alone or in combination of two or more.

結構單元（III）相對於[B1]樹脂的所有結構單元的含量的下限較佳為1莫耳%，更佳為5莫耳%。另一方面，該結構單元（III）的含量的上限較佳為30莫耳%，更佳為20莫耳%。The lower limit of the content of the structural unit (III) with respect to all the structural units of the [B1] resin is preferably 1 mole%, more preferably 5 mole%. On the other hand, the upper limit of the content of the structural unit (III) is preferably 30 mol%, and more preferably 20 mol%.

（結構單元（IV））
[B1]樹脂較佳為進而含有所述結構單元（I）～結構單元（III）以外的具有碳數1以上、7以下的烴基的結構單元（IV）。藉由[B1]樹脂含有結構單元（IV），可實現進一步改善塗佈性或圖案化性等。(Construction unit (IV))
[B1] The resin preferably further contains a structural unit (IV) having a hydrocarbon group having 1 to 7 carbon atoms other than the structural units (I) to (III). By containing the structural unit (IV) in the [B1] resin, it is possible to further improve coating properties, patterning properties, and the like.

碳數1以上、7以下的烴基可為脂肪族烴基及芳香族烴基的任一者。作為碳數1以上、7以下的烴基，可列舉：碳數1以上、7以下的脂肪族鏈狀烴基、碳數3以上、7以下的脂肪族環狀烴基及碳數6以上、7以下的芳香族烴基。The hydrocarbon group having 1 to 7 carbon atoms may be any of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Examples of the hydrocarbon group having 1 or more and 7 carbon atoms include aliphatic chain hydrocarbon groups having 1 or more and 7 carbon atoms, aliphatic cyclic hydrocarbon groups having 3 or more and 7 carbon atoms, and hydrocarbon groups having 6 or more and 7 carbon atoms. Aromatic hydrocarbon group.

作為碳數1以上、7以下的脂肪族鏈狀烴基，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基等烷基；乙烯基等烯基；乙炔基等炔基等。Examples of the aliphatic chain hydrocarbon group having a carbon number of 1 to 7 include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and third butyl; vinyl groups; And other alkenyl groups; ethynyl and other alkynyl groups.

作為碳數3以上、7以下的脂肪族環狀烴基，可列舉環戊基、環己基等。Examples of the aliphatic cyclic hydrocarbon group having 3 to 7 carbon atoms include a cyclopentyl group and a cyclohexyl group.

作為碳數6以上、7以下的芳香族烴基，可列舉苯基、苄基等。Examples of the aromatic hydrocarbon group having 6 to 7 carbon atoms include a phenyl group and a benzyl group.

該些中，較佳為脂肪族烴基，更佳為脂肪族鏈狀烴基，進而佳為烷基。另外，亦較佳為三級烴基。作為該烴基的碳數的下限，較佳為2，更佳為3，進而佳為4。另一方面，作為該碳數的上限，較佳為6，更佳為5，進而佳為4。Among these, an aliphatic hydrocarbon group is preferable, an aliphatic chain hydrocarbon group is more preferable, and an alkyl group is more preferable. A tertiary hydrocarbon group is also preferred. The lower limit of the carbon number of the hydrocarbon group is preferably 2, more preferably 3, and even more preferably 4. On the other hand, the upper limit of the carbon number is preferably 6, more preferably 5 and even more preferably 4.

作為提供結構單元（IV）的單量體，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、苯乙烯等。該些單量體可使用一種或兩種以上。Examples of the single body that provides the structural unit (IV) include methyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth) acrylate. Esters, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, styrene, and the like. These single bodies can be used alone or in combination of two or more.

結構單元（IV）相對於[B1]樹脂的所有結構單元的含量的下限較佳為1莫耳%，更佳為5莫耳%。另一方面，該結構單元（IV）的含量的上限較佳為30莫耳%，更佳為20莫耳%。The lower limit of the content of the structural unit (IV) relative to all the structural units of the [B1] resin is preferably 1 mole%, and more preferably 5 mole%. On the other hand, the upper limit of the content of the structural unit (IV) is preferably 30 mol%, and more preferably 20 mol%.

（結構單元（V））
[B1]樹脂亦可進而含有所述結構單元（I）～結構單元（IV）以外的結構單元（V）。(Structural unit (V))
[B1] The resin may further contain a structural unit (V) other than the structural unit (I) to the structural unit (IV).

作為提供結構單元（V）的單量體，例如可列舉：N-苯基馬來醯亞胺、N-環己基馬來醯亞胺等馬來醯亞胺化合物、聚乙二醇甲醚(甲基)丙烯酸酯、聚丙二醇甲醚(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯等。該些單量體可使用一種或兩種以上。Examples of the unit that provides the structural unit (V) include maleimide compounds such as N-phenylmaleimide and N-cyclohexylmaleimide, and polyethylene glycol methyl ether ( (Meth) acrylates, polypropylene glycol methyl ether (meth) acrylates, polyethylene glycol mono (meth) acrylates, polypropylene glycol mono (meth) acrylates, and the like. These single bodies can be used alone or in combination of two or more.

結構單元（V）相對於[B1]樹脂的所有結構單元的含量的上限亦有時較佳為30莫耳%，更佳為10莫耳%，進而佳為3莫耳%。The upper limit of the content of the structural unit (V) relative to all the structural units of the [B1] resin is sometimes preferably 30 mol%, more preferably 10 mol%, and even more preferably 3 mol%.

[B1]樹脂例如可藉由利用自由基聚合等公知的方法來使所述各單量體聚合而獲得。[B1] The resin can be obtained, for example, by polymerizing the respective monomers by a known method such as radical polymerization.

（[B2]化合物）
[B2]化合物為聚合物以外的可硬化的化合物。[B2]化合物較佳為具有一個或兩個以上的聚合性基。聚合性基的具體例如上所述。作為[B2]化合物所具有的聚合性基，特佳為氧雜環丁基。[B2]化合物可使用一種或兩種以上。([B2] compound)
[B2] The compound is a hardenable compound other than a polymer. [B2] The compound preferably has one or two or more polymerizable groups. Specific examples of the polymerizable group are as described above. The polymerizable group possessed by the [B2] compound is particularly preferably an oxetanyl group. [B2] The compound may be used alone or in combination of two or more.

作為[B2]化合物，較佳為具有環員數3～5的環狀醚基或(甲基)丙烯醯基的化合物，更佳為具有氧雜環丙基或氧雜環丁基的化合物，進而佳為具有氧雜環丁基的結構單元。The [B2] compound is preferably a compound having a cyclic ether group or a (meth) acrylfluorenyl group having 3 to 5 ring members, more preferably a compound having an oxetanyl group or an oxetanyl group, Furthermore, a structural unit having an oxetanyl group is preferred.

作為具有氧雜環丙基的化合物，例如可列舉：
丁基縮水甘油醚、戊基縮水甘油醚、己基縮水甘油醚等縮水甘油醚類；
(甲基)丙烯酸縮水甘油酯等縮水甘油酯類；
雙酚A二縮水甘油醚、雙酚F二縮水甘油醚、雙酚S二縮水甘油醚等雙酚型二縮水甘油醚類；
1,4-丁二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、甘油三縮水甘油醚等多元醇的聚縮水甘油醚類等。Examples of the compound having an oxetanyl group include:
Glycidyl ethers such as butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether;
(Glycidyl acrylate) and other glycidyl esters;
Bisphenol type diglycidyl ethers such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether;
Polyglycidyl ethers of polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and glycerol triglycidyl ether.

作為具有氧雜環丁基的化合物，例如可列舉：
3,3-二甲基氧雜環丁烷、3,3-二乙基氧雜環丁烷、3-乙基-3-羥基甲基氧雜環丁烷、3-甲基-3-甲氧基甲基氧雜環丁烷、3-乙基-3-[(2-乙基己氧基)甲基]氧雜環丁烷、伸二甲苯基雙氧雜環丁烷、3-乙基-3{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}氧雜環丁烷、間苯二甲酸雙[(3-乙基氧雜環丁烷-3-基)甲基]酯、1,4-雙[(3-乙基氧雜環丁烷-3-基)甲氧基甲基]苯、1,3-雙[(3-乙基-3-氧雜環丁基甲氧基)甲基]丙烷、乙二醇雙(3-乙基-3-氧雜環丁基甲基)醚等。Examples of the compound having an oxetanyl group include:
3,3-dimethyloxetane, 3,3-diethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-methyl Oxymethyloxetane, 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane, xylyldioxetane, 3-ethyl -3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane, isophthalic acid bis [(3-ethyloxetane-3 -Yl) methyl] ester, 1,4-bis [(3-ethyloxetane-3-yl) methoxymethyl] benzene, 1,3-bis [(3-ethyl-3 -Oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, and the like.

另外，作為具有氧雜環丙基或氧雜環丁基的化合物，亦可使用：
3-(全氟丙基)丙烯-1,2-氧化物、3-(全氟己基)丙烯-1,2-氧化物等具有氟化烴基的化合物；
2-縮水甘油氧基乙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷等矽烷化合物等。In addition, as a compound having an oxetanyl group or an oxetanyl group, it is also possible to use:
Compounds having a fluorinated hydrocarbon group such as 3- (perfluoropropyl) propylene-1,2-oxide, 3- (perfluorohexyl) propylene-1,2-oxide;
Silane compounds such as 2-glycidyloxyethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and the like.

具有氧雜環丁基的化合物中，更佳為3-乙基-3-[(2-乙基己氧基)甲基]氧雜環丁烷、3-乙基-3{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}氧雜環丁烷等具有醚鍵（-O-）的化合物，更佳為包含氧雜環丁基、烴基及醚鍵的化合物。Among the compounds having an oxetanyl group, 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane, 3-ethyl-3 {[((3- Compounds having an ether bond (-O-) such as ethyloxetane-3-yl) methoxy] methyl} oxetane, more preferably containing an oxetanyl group, a hydrocarbon group, and an ether bond compound of.

作為具有(甲基)丙烯醯基的化合物，例如可列舉：
乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、二丙烯二(甲基)丙烯酸酯、三丙烯二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三丙二醇二丙烯酸酯、三環[5.2.1.0^2,6 ]癸烷二甲醇二(甲基)丙烯酸酯等二(甲基)丙烯酸酯化合物；
三(2-羥基乙基)異氰脲酸酯三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯等三(甲基)丙烯酸酯化合物；
季戊四醇四(甲基)丙烯酸酯等四(甲基)丙烯酸酯化合物；
二季戊四醇五(甲基)丙烯酸酯等五(甲基)丙烯酸酯化合物等。Examples of the compound having a (meth) acrylfluorenyl group include:
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene di (meth) acrylate ) Acrylate, tripropylene di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediene Alcohol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol diacrylate, tricyclic [5.2.1.0 ^2,6 ] decane dimethanol di (meth) acrylate, etc. (Meth) acrylate compounds;
Tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and other tri (meth) acrylates Compound
Tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate;
Penta (meth) acrylate compounds such as dipentaerythritol penta (meth) acrylate and the like.

另外，所述提供[B1]樹脂的各結構單元的單量體中的、作為(甲基)丙烯酸酯類所例示的化合物亦可用作具有(甲基)丙烯醯基的化合物。In addition, the compounds exemplified as (meth) acrylic acid esters in the unit body of each structural unit providing the [B1] resin can also be used as a compound having a (meth) acrylfluorenyl group.

作為[B2]化合物於一分子中所具有的聚合性基的數量，較佳為1～3，更佳為1及2，進而佳為2。The number of polymerizable groups that the [B2] compound has in one molecule is preferably 1 to 3, more preferably 1 and 2, and even more preferably 2.

作為[B]硬化性化合物相對於該硬化性組成物中的[C]溶媒除外的所有成分的含量、即固體成分中的含量的下限，亦有時較佳為3質量%，更佳為5質量%，進而佳為10質量%、15質量%或20質量%。另一方面，作為該[B]硬化性化合物的含量的上限，亦有時較佳為40質量%，更佳為30質量%，進而佳為20質量%或10質量%。藉由將[B]硬化性化合物的含量設為所述範圍，可顯現出良好的硬化性，另外，所獲得的硬化膜的圖案形狀亦充分。再者，於使用白色顏料作為[A]顏料的情況下，存在[B]硬化性化合物的含量以相對較多者為宜的傾向。另一方面，於使用黑色顏料作為[A]顏料的情況下，存在[B]硬化性化合物的含量以相對較少者為宜的傾向。The lower limit of the content of the [B] curable compound with respect to all components except the [C] solvent in the curable composition, that is, the content in the solid content, is preferably 3% by mass, and more preferably 5 Mass%, more preferably 10 mass%, 15 mass%, or 20 mass%. On the other hand, the upper limit of the content of the [B] curable compound is preferably 40% by mass, more preferably 30% by mass, and even more preferably 20% by mass or 10% by mass. When the content of the [B] curable compound is within the above range, good curability can be exhibited, and the pattern shape of the obtained cured film is also sufficient. When a white pigment is used as the [A] pigment, the content of the [B] curable compound tends to be relatively large. On the other hand, in the case where a black pigment is used as the [A] pigment, the content of the [B] curable compound tends to be relatively small.

（[C]溶媒）
[C]溶媒為相對介電常數為6.0以下的溶媒。作為[C]溶媒的相對介電常數的上限，較佳為5，更佳為3。另一方面，該相對介電常數的下限，例如為1.0，亦可為1.5。[C]溶媒可僅使用一種，亦可混合使用兩種以上。於混合使用兩種以上的溶媒作為[C]溶媒的情況下，相對介電常數設為所有溶媒的加權平均值。([C] Solvent)
[C] The solvent is a solvent having a relative dielectric constant of 6.0 or less. The upper limit of the relative dielectric constant of the [C] solvent is preferably 5, more preferably 3. On the other hand, the lower limit of the relative dielectric constant is, for example, 1.0 or 1.5. [C] The solvent may be used singly or in combination of two or more kinds. In a case where two or more solvents are used as a [C] solvent in a mixture, the relative dielectric constant is a weighted average of all the solvents.

作為[C]溶媒，例如可列舉烴。作為烴，可為脂肪族烴及芳香族烴的任一者。Examples of the [C] solvent include hydrocarbons. The hydrocarbon may be any of an aliphatic hydrocarbon and an aromatic hydrocarbon.

作為脂肪族烴，可列舉：
戊烷、己烷、庚烷、辛烷、壬烷、癸烷、十一烷、十二烷、十三烷、十四烷、十五烷、十六烷、二十烷等烷烴；庚烯、辛烯、十二烯、十四烯、二十烯等烯烴等脂肪族鏈狀烴；
環戊烷、環己烷、環庚烷、環辛烷、環癸烷、環十四烷、環二十烷、甲基環己烷等環烷烴；環庚烯、環十四烯等環烯烴等脂肪族環狀烴。Examples of the aliphatic hydrocarbon include:
Alkanes such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, eicosane; heptene Aliphatic chain hydrocarbons such as olefins such as octene, dodecene, tetradecene, eicosene, etc .;
Cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclotetradecane, cycloicosesane, methylcyclohexane and other cycloalkanes; cycloheptene, cyclotetradecene and other cycloolefins And other aliphatic cyclic hydrocarbons.

作為芳香族烴，可列舉：苯、甲苯、二甲苯等。Examples of the aromatic hydrocarbon include benzene, toluene, and xylene.

該些中，較佳為脂肪族烴，更佳為烷烴及環烷烴，進而佳為烷烴。Among these, an aliphatic hydrocarbon is preferable, an alkane and a cycloalkane are more preferable, and an alkane is more preferable.

另外，作為[C]溶媒的碳數的下限，較佳為5，更佳為8，進而佳為12。另一方面，作為該碳數的上限，較佳為20，更佳為16。藉由使用碳數為所述範圍的溶媒，揮發性、塗佈性等更良好。The lower limit of the number of carbons in the [C] solvent is preferably 5, more preferably 8 and even more preferably 12. On the other hand, the upper limit of the carbon number is preferably 20, and more preferably 16. By using a solvent having a carbon number within the above range, volatility, coating properties, and the like are better.

該硬化性組成物中的[C]溶媒的含量並無特別限定。作為該硬化性組成物中的固體成分濃度（[C]溶媒除外的各成分的合計濃度）的下限，較佳為20質量%，更佳為40質量%，進而佳為50質量%，尤佳為60質量%。另一方面，作為該固體成分濃度的上限，較佳為80質量%，更佳為70質量%。藉由將固體成分濃度設為所述範圍，塗佈性、尤其是利用噴墨法進行塗佈時的塗佈性等更良好。The content of the [C] solvent in the curable composition is not particularly limited. The lower limit of the solid content concentration (total concentration of each component excluding the [C] solvent) in the curable composition is preferably 20% by mass, more preferably 40% by mass, even more preferably 50% by mass, and even more preferably It is 60% by mass. On the other hand, the upper limit of the solid content concentration is preferably 80% by mass, and more preferably 70% by mass. By setting the solid content concentration to the above range, the applicability, especially the applicability when applying by the inkjet method, and the like are better.

（[D]聚合起始劑）
該硬化性組成物較佳為進而包含[D]聚合起始劑。該[D]聚合起始劑較佳為熱酸產生劑、熱自由基產生劑或該些的組合。藉由該硬化性組成物進而包含[D]聚合起始劑，有效地推進塗膜中的[B]硬化性化合物的硬化反應（聚合反應）等，藉此可形成圖案化性等更優異且良好的硬化膜。([D] Polymerization initiator)
The curable composition preferably further contains a [D] polymerization initiator. The [D] polymerization initiator is preferably a thermal acid generator, a thermal radical generator, or a combination thereof. By including the [D] polymerization initiator in this hardenable composition, the hardening reaction (polymerization reaction) and the like of the [B] hardenable compound in the coating film is effectively promoted, so that patterning properties and the like can be more excellent and Good hardened film.

作為熱酸產生劑，可列舉：鋶鹽、苯并噻唑鎓鹽、銨鹽、鏻鹽等鎓鹽等離子性熱酸產生劑；或含鹵素的化合物、二偶氮甲烷化合物、碸化合物、磺酸酯化合物、羧酸酯化合物、磷酸酯化合物、磺醯亞胺化合物、碸苯并***化合物等非離子性熱酸產生劑。作為熱酸產生劑，較佳為離子性熱酸產生劑。Examples of the thermal acid generator include ionic thermal acid generators such as sulfonium salts, benzothiazolium salts, ammonium salts, and sulfonium salts; or halogen-containing compounds, diazomethane compounds, sulfonium compounds, and sulfonic acids. Non-ionic thermal acid generators such as ester compounds, carboxylic acid ester compounds, phosphate ester compounds, sulfonylimine compounds, and benzobenzotriazole compounds. The thermal acid generator is preferably an ionic thermal acid generator.

作為離子性熱酸產生劑的具體例，可列舉：三苯基鋶、1-二甲硫基萘、1-二甲硫基-4-羥基萘、1-二甲硫基-4,7-二羥基萘、4-羥基苯基-二甲基鋶、4-羥基苯基-甲基-苄基鋶、2-甲基苄基-4-羥基苯基甲基鋶、2-甲基苄基-4-乙醯基苯基甲基鋶、2-甲基苄基-4-苯甲醯氧基苯基甲基鋶、N,N-二甲基苯銨、N,N-二乙基苯銨等甲磺酸鹽、三氟甲磺酸鹽、樟腦磺酸鹽、對甲苯磺酸鹽、六氟膦酸鹽、四氟硼酸鹽、四苯基硼酸鹽、四(五氟苯基)硼酸鹽、六氟磷酸、三(五氟乙基)三氟磷酸鹽等。Specific examples of the ionic thermal acid generator include triphenylsulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, and 1-dimethylthio-4,7- Dihydroxynaphthalene, 4-hydroxyphenyl-dimethylfluorene, 4-hydroxyphenyl-methyl-benzylfluorene, 2-methylbenzyl-4-hydroxyphenylmethylfluorene, 2-methylbenzyl 4-Ethylphenylphenylmethylfluorene, 2-methylbenzyl-4-benzyloxyphenylmethylfluorene, N, N-dimethylaniline, N, N-diethylbenzene Mesylate, triflate, camphor sulfonate, p-toluenesulfonate, hexafluorophosphonate, tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate Salt, hexafluorophosphoric acid, tris (pentafluoroethyl) trifluorophosphate, and the like.

作為熱自由基產生劑，可列舉：烷基過氧化物、醯基過氧化物、酮過氧化物、烷基氫過氧化物、過氧化二碳酸鹽、磺醯基過氧化物等有機過氧化物類；無機過氧化物類；偶氮腈等偶氮化合物類；亞磺酸類；雙疊氮類；二偶氮化合物等。Examples of the thermal radical generator include organic peroxides such as alkyl peroxide, fluorenyl peroxide, ketone peroxide, alkyl hydroperoxide, peroxydicarbonate, and sulfonyl peroxide. Substances; inorganic peroxides; azo compounds such as azonitrile; sulfinic acids; diazides; diazo compounds.

作為熱自由基產生劑的具體例，可較佳地使用枯烯氫過氧化物、第三丁基氫過氧化物、二枯基過氧化物、二-第三丁基過氧化物、過氧化苯甲醯、過氧化月桂醯、過氧二硫酸鹽（peroxodisulfate）、過氧化氫、過硫酸鉀、過硫酸銨、過硼酸鹽、2,2'-偶氮雙異丁腈、1,1'-偶氮雙(1-環己烷-1-甲腈)、二甲基-2,2'-偶氮異雙丁酸酯、2,2'-偶氮雙(2-甲基丁腈)、2,2'-偶氮雙(2-脒基丙烷)二碳酸鹽、偶氮雙氰基戊酸鈉、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙[2-(2-咪唑啉-2-基)丙烷]、2,2'-偶氮雙{2-甲基-N-[1,1-雙(羥基甲基)-2-羥基乙基]丙醯胺}、2,2'-偶氮雙{2-甲基-N-[1,1-雙(羥基甲基)乙基]丙醯胺}、2,2'-偶氮雙[2-甲基-N-(2-羥基乙基)丙醯胺]、2,2'-偶氮雙(2-氰基丙醇)、2,2'-偶氮雙(2,4,4-三甲基戊烷)、對甲苯亞磺酸鈉、2,2'-偶氮雙(異丁酸甲酯)等。As specific examples of the thermal radical generator, cumene hydroperoxide, third butyl hydroperoxide, dicumyl peroxide, di-third butyl peroxide, and peroxide can be preferably used. Benzamidine, lauryl peroxide, peroxodisulfate, hydrogen peroxide, potassium persulfate, ammonium persulfate, perborate, 2,2'-azobisisobutyronitrile, 1,1 ' -Azobis (1-cyclohexane-1-carbonitrile), dimethyl-2,2'-azoisobisbutyrate, 2,2'-azobis (2-methylbutyronitrile) , 2,2'-azobis (2-fluorenylpropane) dicarbonate, sodium azobiscyanovalerate, 2,2'-azobis (2,4-dimethylvaleronitrile), 2 , 2'-Azobis [2- (2-imidazolin-2-yl) propane], 2,2'-Azobis {2-methyl-N- [1,1-bis (hydroxymethyl) 2-Hydroxyethyl] propanamidin}, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propanamidin}, 2,2 '-Azobis [2-methyl-N- (2-hydroxyethyl) propanamine], 2,2'-azobis (2-cyanopropanol), 2,2'-azobis (2,4,4-trimethylpentane), sodium p-toluene sulfinate, 2,2'-azobis (isobutyric acid methyl ester), and the like.

作為[D]聚合起始劑相對於該硬化性組成物中的[C]溶媒除外的所有成分的含量、即固體成分中的含量的下限，較佳為0.01質量%，更佳為0.05質量%。另一方面，作為該[D]聚合起始劑的含量的上限，較佳為5質量%，更佳為3質量%。另外，作為[D]聚合起始劑相對於[B]硬化性化合物的含量，例如較佳為1質量%以上、20質量%以下。藉由將[D]聚合起始劑的含量設為所述範圍，可顯現出良好的圖案化性及硬化性，所獲得的硬化膜的圖案形狀亦充分。The lower limit of the content of the [D] polymerization initiator relative to all components except the [C] solvent in the curable composition, that is, the content in the solid content, is preferably 0.01% by mass, and more preferably 0.05% by mass. . On the other hand, the upper limit of the content of the [D] polymerization initiator is preferably 5% by mass, and more preferably 3% by mass. The content of the [D] polymerization initiator relative to the [B] curable compound is preferably, for example, 1% by mass or more and 20% by mass or less. By setting the content of the [D] polymerization initiator to the above range, good patternability and hardenability can be exhibited, and the pattern shape of the obtained cured film is also sufficient.

（[E]氟樹脂）
該硬化性組成物較佳為進而包含[E]氟樹脂。藉由該硬化性組成物包含[E]氟樹脂，可提高所獲得的硬化膜的撥液性。再者，於硬化膜的撥液性高的情況下，可實現提高藉由塗佈而於作為隔離壁的硬化膜間形成波長變換層等層時的塗佈性、使塗佈後的硬化膜的形狀良好等。[E]氟樹脂包含具有含有氟的基的結構單元（VI）。[E]氟樹脂較佳為一種或多種乙烯性不飽和單量體（具有不飽和雙鍵的單量體）的聚合物。[E]氟樹脂可使用一種或兩種以上。([E] Fluoro resin)
The curable composition preferably further contains [E] a fluororesin. When the curable composition contains [E] fluororesin, the liquid repellency of the obtained cured film can be improved. Further, when the liquid-repellent property of the cured film is high, it is possible to improve the applicability when a layer such as a wavelength conversion layer is formed between the cured films that serve as the partition wall by coating, and the cured film after coating can be achieved. The shape is good and so on. [E] The fluororesin includes a structural unit (VI) having a fluorine-containing group. [E] The fluororesin is preferably a polymer of one or more ethylenically unsaturated singly bodies (single bodies having unsaturated double bonds). [E] The fluororesin may be used alone or in combination of two or more.

（結構單元（VI））
結構單元（VI）為具有含有氟的基的結構單元。作為含有氟的基，可列舉至少一個氫原子經氟原子取代的烴基，較佳為至少一個氫原子經氟原子取代的碳數1以上、20以下的烷基、及至少一個氫原子經氟原子取代的碳數4以上、20以下的一價環烷基，更佳為至少一個氫原子經氟原子取代的碳數1以上、20以下的烷基。(Structural Unit (VI))
The structural unit (VI) is a structural unit having a fluorine-containing group. Examples of the fluorine-containing group include a hydrocarbon group in which at least one hydrogen atom is replaced with a fluorine atom, and an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is replaced with a fluorine atom, and at least one hydrogen atom through a fluorine atom is preferred. The substituted monovalent cycloalkyl group having 4 to 20 carbon atoms is more preferably an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is replaced with a fluorine atom.

作為含有氟的基的碳數的下限，較佳為4，更佳為6。作為其上限，較佳為16，更佳為12。含有氟的基的氟數的下限為1，較佳為3，更佳為5。作為其上限，例如為30，亦可為20。The lower limit of the number of carbons of the fluorine-containing group is preferably 4, and more preferably 6. The upper limit thereof is preferably 16 and more preferably 12. The lower limit of the fluorine number of the fluorine-containing group is 1, preferably 3, and more preferably 5. The upper limit is, for example, 30 or 20.

作為至少一個氫原子經氟原子取代的碳數1以上、20以下的烷基，可列舉所述烷基中的碳數為1以上、20以下者中的氫原子的至少一個被氟原子取代的部分氟化烷基、全氟烷基等。Examples of the alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom include at least one hydrogen atom in the alkyl group having 1 to 20 carbon atoms being substituted with a fluorine atom. Partially fluorinated alkyl, perfluoroalkyl and the like.

作為至少一個氫原子經氟原子取代的碳數4以上、20以下的一價環烷基，可列舉所述環烷基中的碳數為4以上、20以下者中的氫原子的至少一個被氟原子取代的部分氟化環烷基、全氟環烷基等。Examples of the monovalent cycloalkyl group having 4 or more and 20 or less carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom include at least one hydrogen atom in the cycloalkyl group having 4 or more and 20 or less carbon atoms. Partially fluorinated cycloalkyl, perfluorocycloalkyl, etc. substituted with a fluorine atom.

作為提供結構單元（VI）的單量體，可列舉：(甲基)丙烯酸三氟甲酯、(甲基)丙烯酸-2,2,2-三氟乙酯、(甲基)丙烯酸全氟乙酯、(甲基)丙烯酸全氟正丙酯、(甲基)丙烯酸全氟異丙酯、(甲基)丙烯酸全氟正丁酯、(甲基)丙烯酸全氟異丁酯、(甲基)丙烯酸全氟第三丁酯、(甲基)丙烯酸-2-(1,1,1,3,3,3-六氟丙基)酯、(甲基)丙烯酸-1-(2,2,3,3,4,4,5,5-八氟戊基)酯、(甲基)丙烯酸全氟環己基甲酯、(甲基)丙烯酸-1-(2,2,3,3,3-五氟丙基)酯、(甲基)丙烯酸-1-(3,3,4,4,5,5,6,6,7,7,8,8,8-十三烷氟辛基)酯、(甲基)丙烯酸-1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-十七氟癸基)酯、(甲基)丙烯酸-1-(5-三氟甲基-3,3,4,4,5,6,6,6-八氟己基)酯等(甲基)丙烯酸氟化烴酯等。該些單量體可使用一種或兩種以上。Examples of the single body that provides the structural unit (VI) include trifluoromethyl (meth) acrylate, -2,2,2-trifluoroethyl (meth) acrylate, and perfluoroethyl (meth) acrylate. Ester, perfluoron-propyl (meth) acrylate, perfluoroisopropyl (meth) acrylate, perfluoron-butyl (meth) acrylate, perfluoroisobutyl (meth) acrylate, (meth) Perfluorotributyl acrylate, 2- (1,1,1,3,3,3-hexafluoropropyl) (meth) acrylate, 1- (2,2,3) (meth) acrylate , 3,4,4,5,5-octafluoropentyl) ester, perfluorocyclohexyl methyl (meth) acrylate, 1- (2,2,3,3,3-penta (meth) acrylate Fluoropropyl) ester, (meth) acrylic acid 1- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecanefluorooctyl) ester, (Meth) acrylic acid-1- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl) ester And (meth) acrylic acid fluorinated hydrocarbon esters such as (meth) acrylic acid 1- (5-trifluoromethyl-3,3,4,4,5,6,6,6-octafluorohexyl) ester. These single bodies can be used alone or in combination of two or more.

結構單元（VI）相對於[E]氟樹脂的所有結構單元的含量的下限較佳為5莫耳%，更佳為10莫耳%，進而佳為20莫耳%。另一方面，該結構單元（II）的含量的上限較佳為60莫耳%，更佳為50莫耳%，進而佳為40莫耳%。The lower limit of the content of the structural unit (VI) relative to all the structural units of the [E] fluororesin is preferably 5 mol%, more preferably 10 mol%, and even more preferably 20 mol%. On the other hand, the upper limit of the content of the structural unit (II) is preferably 60 mol%, more preferably 50 mol%, and even more preferably 40 mol%.

（結構單元（I））
[E]氟樹脂較佳為含有具有聚合性基的結構單元（I）。再者，於該硬化性組成物中，於併用[B1]樹脂與[E]氟樹脂的情況下，含有具有聚合性基的結構單元（I）與結構單元（IV）的樹脂設為與[E]氟樹脂相符者，所述結構單元（IV）具有含有氟的基。另一方面，於含有具有聚合性基的結構單元（I）的樹脂僅為含有氟的樹脂的情況下，該樹脂為[B1]樹脂。藉由[E]氟樹脂含有結構單元（I），該硬化性組成物的硬化性或圖案化性進一步提高。該結構單元（I）的具體態樣及較佳態樣與作為[B1]樹脂的結構單元（I）所說明者相同。(Structural unit (I))
[E] The fluororesin preferably contains a structural unit (I) having a polymerizable group. In addition, in this curable composition, when [B1] resin and [E] fluororesin are used in combination, a resin containing a structural unit (I) and a structural unit (IV) having a polymerizable group is used as [ E] In the case of a fluororesin, the structural unit (IV) has a fluorine-containing group. On the other hand, when the resin containing the structural unit (I) having a polymerizable group is only a resin containing fluorine, the resin is a [B1] resin. When the [E] fluororesin contains the structural unit (I), the curability or patternability of the curable composition is further improved. The specific aspect and preferred aspect of the structural unit (I) are the same as those described as the structural unit (I) of the [B1] resin.

結構單元（I）相對於[E]氟樹脂的所有結構單元的含量的下限較佳為5莫耳%，更佳為10莫耳%。另一方面，該結構單元（I）的含量的上限較佳為50莫耳%，更佳為40莫耳%，進而佳為25莫耳%。The lower limit of the content of the structural unit (I) relative to all the structural units of the [E] fluororesin is preferably 5 mol%, and more preferably 10 mol%. On the other hand, the upper limit of the content of the structural unit (I) is preferably 50 mol%, more preferably 40 mol%, and even more preferably 25 mol%.

（結構單元（II））
[E]氟樹脂較佳為含有具有碳數8以上、30以下的烴基的結構單元（II）。藉由[E]氟樹脂含有結構單元（II），[E]氟樹脂的溶解性降低，因此該硬化性組成物的圖案化性等提高。該結構單元（II）的具體態樣及較佳態樣與作為[B1]樹脂的結構單元（II）所說明者相同。(Structural Unit (II))
[E] The fluororesin preferably contains a structural unit (II) having a hydrocarbon group having 8 or more and 30 or less carbon atoms. Since the [E] fluororesin contains the structural unit (II), the solubility of the [E] fluororesin decreases, and thus the patternability and the like of the curable composition are improved. The specific aspect and preferred aspect of the structural unit (II) are the same as those described as the structural unit (II) of the [B1] resin.

結構單元（II）相對於[E]氟樹脂的所有結構單元的含量的下限較佳為10莫耳%，更佳為20莫耳%，進而佳為30莫耳%。另一方面，該結構單元（II）的含量的上限較佳為70莫耳%，更佳為60莫耳%，進而佳為50莫耳%。The lower limit of the content of the structural unit (II) relative to all the structural units of the [E] fluororesin is preferably 10 mol%, more preferably 20 mol%, and even more preferably 30 mol%. On the other hand, the upper limit of the content of the structural unit (II) is preferably 70 mol%, more preferably 60 mol%, and even more preferably 50 mol%.

（結構單元（III））
[E]氟樹脂較佳為進而含有具有羧基或羥基的結構單元（III）。藉由[E]氟樹脂含有結構單元（III），可實現進一步改善塗佈性或圖案化性等。該結構單元（III）的具體態樣及較佳態樣與作為[B1]樹脂的結構單元（III）所說明者相同。(Construction unit (III))
[E] The fluororesin preferably further contains a structural unit (III) having a carboxyl group or a hydroxyl group. By containing the structural unit (III) in the [E] fluororesin, it is possible to further improve coating properties, patterning properties, and the like. The specific aspect and preferred aspect of the structural unit (III) are the same as those described as the structural unit (III) of the [B1] resin.

結構單元（III）相對於[E]氟樹脂的所有結構單元的含量的下限較佳為2莫耳%，更佳為5莫耳%。另一方面，該結構單元（III）的含量的上限較佳為30莫耳%，進而佳為20莫耳%。The lower limit of the content of the structural unit (III) relative to all the structural units of the [E] fluororesin is preferably 2 mol%, more preferably 5 mol%. On the other hand, the upper limit of the content of the structural unit (III) is preferably 30 mol%, more preferably 20 mol%.

（其他結構單元）
[E]氟樹脂可進而含有其他結構單元。作為此種結構單元，可列舉[B1]樹脂中的結構單元（IV）或結構單元（V）。(Other structural units)
[E] The fluororesin may further contain other structural units. Examples of such a structural unit include a structural unit (IV) or a structural unit (V) in the [B1] resin.

其他結構單元相對於[E]氟樹脂的所有結構單元的含量的下限可為0莫耳%，亦可為1莫耳%。其上限亦有時較佳為30莫耳%，更佳為10莫耳%，進而佳為3莫耳%。The lower limit of the content of the other structural units with respect to all the structural units of the [E] fluororesin may be 0 mol% or 1 mol%. The upper limit is sometimes preferably 30 mol%, more preferably 10 mol%, and even more preferably 3 mol%.

[E]氟樹脂例如可藉由利用自由基聚合等公知的方法來使所述各單量體聚合而獲得。[E] The fluororesin can be obtained, for example, by polymerizing the respective monomers by a known method such as radical polymerization.

作為[E]氟樹脂相對於該硬化性組成物中的[C]溶媒除外的所有成分的含量、即固體成分中的含量的下限，較佳為0.1質量%，更佳為0.5質量%，進而佳為1質量%。另一方面，作為該[E]氟樹脂的含量的上限，較佳為10質量%，更佳為5質量%，進而佳為3質量%。The lower limit of the content of the [E] fluororesin with respect to all components except the [C] solvent in the curable composition, that is, the content in the solid content, is preferably 0.1% by mass, more preferably 0.5% by mass, and further It is preferably 1% by mass. On the other hand, the upper limit of the content of the [E] fluororesin is preferably 10% by mass, more preferably 5% by mass, and even more preferably 3% by mass.

（[F]分散劑）
該硬化性組成物亦可進而包含[F]分散劑。藉由該硬化性組成物進而包含[F]分散劑，[A]顏料的分散性提高，可進一步提高所獲得的硬化膜的遮光性等。([F] Dispersant)
The curable composition may further contain a [F] dispersant. When the curable composition further contains a [F] dispersant, the dispersibility of the [A] pigment is improved, and the light-shielding property of the obtained cured film can be further improved.

作為[F]分散劑，可列舉：公知的聚酯系分散劑、聚胺基甲酸酯系分散劑、非離子系界面活性劑分散劑、聚醚系分散劑、磷酸酯系分散劑等。[F]分散劑可使用一種或兩種以上。Examples of the [F] dispersant include known polyester-based dispersants, polyurethane-based dispersants, non-ionic surfactant dispersants, polyether-based dispersants, and phosphate-based dispersants. [F] The dispersant may be used alone or in combination of two or more.

作為分散劑的市售品，例如可使用：迪斯帕畢克（Disperbyk）-108、迪斯帕畢克（Disperbyk）-109、迪斯帕畢克（Disperbyk）-2055、安提泰拉路（ANTI-TERRAR）-204、BYK-W966（以上，畢克化學（BYK）公司製造）；或阿吉斯帕（Ajisper）PN411、阿吉斯帕（Ajisper）PA111（以上，味之素精密技術（Ajinomoto Fine-techno）公司製造）等。As a commercially available product as a dispersant, for example, Disperbyk-108, Disperbyk-109, Disperbyk-2055, Antitila Road can be used. (ANTI-TERRAR) -204, BYK-W966 (above, manufactured by BYK); or Ajisper PN411, Ajisper PA111 (above, Ajinomoto Precision Technology (Manufactured by Ajinomoto Fine-techno).

作為[F]分散劑相對於該硬化性組成物中的[A]顏料100質量份的含量的含量的下限，較佳為0.5質量份，更佳為2質量份。另一方面，作為該含量的上限，較佳為50質量份，更佳為30質量份。The lower limit of the content of the [F] dispersant with respect to 100 parts by mass of the [A] pigment in the curable composition is preferably 0.5 parts by mass, and more preferably 2 parts by mass. On the other hand, the upper limit of the content is preferably 50 parts by mass, and more preferably 30 parts by mass.

（其他添加劑）
該硬化性組成物視需要亦可包含[A]成分～[F]成分以外的其他添加劑。作為添加劑，例如可列舉：[A]顏料以外的著色劑、界面活性劑、密接促進劑、抗氧化劑、紫外線吸收劑、抗凝聚劑、殘渣改善劑、顯影性改善劑等。但是，作為所述其他添加劑相對於該硬化性組成物中的[C]溶媒除外的所有成分的含量的上限，亦有時較佳為10質量%，還有時更佳為1質量%。(Other additives)
This curable composition may contain other additives other than [A] component [F] component as needed. Examples of the additives include coloring agents other than [A] pigments, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anticoagulants, residue improvers, and developability improvers. However, the upper limit of the content of the other additives with respect to all components other than the [C] solvent in the curable composition is preferably 10% by mass, and even more preferably 1% by mass.

作為[A]顏料以外的著色劑，可列舉：螢光染料、藍色染料、紫色染料、紅色染料等染料。關於所述染料，根據其結構而可分類為苝染料、蒽醌染料、三芳基甲烷染料、酞菁染料、呫噸染料、二吡咯亞甲基染料等。Examples of the coloring agent other than the [A] pigment include dyes such as a fluorescent dye, a blue dye, a purple dye, and a red dye. The dyes can be classified into perylene dyes, anthraquinone dyes, triarylmethane dyes, phthalocyanine dyes, xanthene dyes, dipyrromethene dyes, and the like according to their structures.

作為苝染料，例如可列舉：C.I.溶劑橙（Solvent Orange）55以及路摩根黃（Lumogen Yellow）083、路摩根橙（Lumogen Orange）240、路摩根紅（Lumogen Red）305（以上，巴斯夫（BASF）公司製造）。作為蒽醌染料，例如可列舉日本專利特開2013-053292號公報的段落[0049]～段落[0064]中記載的化合物，其中，較佳為C.I.溶劑藍（Solvent Blue）35、C.I.溶劑藍45、C.I.酸性藍（Acid Blue）80、C.I.溶劑藍104、C.I.溶劑藍122。作為三芳基甲烷染料，例如可列舉日本專利特開2013-144724號公報的段落[0048]～段落[0064]中記載的化合物。作為酞菁染料，例如可列舉日本專利特開2007-094181號公報的段落[0100]～段落[0188]中記載的化合物，其中，較佳為C.I.溶劑藍38、C.I.溶劑藍70。作為呫噸染料，例如可列舉日本專利特開2013-053292號公報的段落[0010]～段落[0048]中記載的化合物，其中，較佳為酸性呫噸染料。作為二吡咯亞甲基染料，例如可列舉：日本專利特開2010-085454號公報的段落[0017]～段落[0105]中記載的化合物、日本專利特開2011-164594號公報的段落[0014]～段落[0095]中記載的化合物、日本專利特開2012-140586號公報的段落[0025]～段落[0058]中記載的化合物。再者，所謂「酸性染料」是指陰離子部成為顯色團的離子性染料，並設為形成有分子內鹽的離子性染料亦包含於酸性染料中者。例如，所謂「酸性呫噸染料」是指呫噸顯色團為陰離子性且具有抗衡陽離子的化合物，或者呫噸顯色團形成分子內鹽的化合物。Examples of vat dyes include CI Solvent Orange 55 and Lumogen Yellow 083, Lumogen Orange 240, Lumogen Red 305 (above, BASF) Company). Examples of the anthraquinone dye include compounds described in paragraphs [0049] to [0064] of Japanese Patent Laid-Open No. 2013-053292. Among them, CI Solvent Blue 35 and CI Solvent Blue 45 are preferred. , CI Acid Blue 80, CI Solvent Blue 104, CI Solvent Blue 122. Examples of the triarylmethane dye include compounds described in paragraphs [0048] to [0064] of Japanese Patent Laid-Open No. 2013-144724. Examples of the phthalocyanine dye include compounds described in paragraphs [0100] to [0188] of Japanese Patent Laid-Open No. 2007-094181. Among them, C.I. Solvent Blue 38 and C.I. Solvent Blue 70 are preferred. Examples of xanthene dyes include compounds described in paragraphs [0010] to [0048] of Japanese Patent Laid-Open No. 2013-053292, and among these, acidic xanthene dyes are preferred. Examples of the dipyrromethene dye include compounds described in paragraphs [0017] to [0105] of Japanese Patent Laid-Open No. 2010-085454, and paragraphs [0014] of Japanese Patent Laid-Open No. 2011-164594. ~ The compound described in paragraph [0095], and the compound described in paragraph [0025]-paragraph [0058] of Japanese Patent Laid-Open No. 2012-140586. The "acid dye" refers to an ionic dye in which the anion portion becomes a chromophore, and an ionic dye in which an intramolecular salt is formed is also included in the acid dye. For example, the "acid xanthene dye" refers to a compound in which the xanthene chromophore is anionic and has a counter cation, or a compound in which the xanthene chromophore forms an intramolecular salt.

該硬化性組成物可實質上不具有感放射線性（藉由放射線的照射而硬化的性質）。即，該硬化性組成物可不包含例如光酸產生劑、光自由基產生劑等光聚合起始劑。但是，該硬化性組成物可促進經放射線照射的部分的硬化。This curable composition may not substantially have radiation sensitivity (the property of being hardened by irradiation of radiation). That is, the curable composition may not include a photopolymerization initiator such as a photoacid generator and a photoradical generator. However, this curable composition can accelerate the hardening of the radiation-irradiated portion.

（製備方法）
作為該硬化性組成物的製備方法，並無特別限定，可藉由將各成分混合來製備。例如，可藉由以下方法來製備。首先，對[A]顏料於[C]溶媒中且於[F]分散劑的存在下進行粉碎並加以混合及分散而獲得顏料分散液。該操作例如可使用珠磨機、輥磨機等進行。藉由於所獲得的顏料分散液中添加其他成分以及視需要的進一步的[C]溶媒並加以混合，可獲得該硬化性組成物。該硬化性組成物視需要可實施過濾處理而去除凝聚物。(Preparation)
The method for preparing the curable composition is not particularly limited, and it can be prepared by mixing the components. For example, it can be prepared by the following method. First, the [A] pigment is pulverized in a [C] solvent and in the presence of a [F] dispersant, mixed and dispersed to obtain a pigment dispersion liquid. This operation can be performed using, for example, a bead mill, a roll mill, or the like. The hardening composition can be obtained by adding and mixing other components and a further [C] solvent as needed in the obtained pigment dispersion. This hardening composition can be filtered to remove agglomerates if necessary.

（用途）
該硬化性組成物可獲得塗佈性及圖案化性優異且具有良好的遮光性的硬化膜。因此，該硬化性組成物可較佳地用作硬化膜的形成材料，且可更佳地用作顯示元件或固體攝像元件的硬化膜的形成材料。該顯示元件或固體攝像元件的硬化膜中，可特佳地用作隔離壁的形成材料。(use)
With this curable composition, a cured film having excellent coating properties and patterning properties and excellent light-shielding properties can be obtained. Therefore, the curable composition can be preferably used as a material for forming a cured film, and can be more preferably used as a material for forming a cured film of a display element or a solid-state imaging element. This hardened film of a display element or a solid-state imaging element can be particularly suitably used as a material for forming a partition wall.

所述顯示元件或固體攝像元件的作為硬化膜的隔離壁亦被稱為堤（bank）、黑色矩陣等。作為所述隔離壁，可列舉：微LED顯示器中的設置於各微LED、波長變換層等之間的隔離壁（參照圖1）、液晶顯示元件中的設置於各彩色濾光片等之間的隔離壁、固體攝像元件中的各發光二極體、彩色濾光片等之間等的隔離壁等。該些中，可較佳地用作微LED顯示器中的隔離壁。進而，於微LED顯示器中，可更佳地用作各區域具有由包含微LED與波長變換層的結構構成的區域的區域間所設置的隔離壁（參照圖1）。於該微LED顯示器中，於包含所述微LED與波長變換層的隔離壁間的區域中亦可進而設置彩色濾光片層等其他層。The partition wall of the display element or the solid-state imaging element as a cured film is also called a bank, a black matrix, or the like. Examples of the partition wall include a partition wall (see FIG. 1) provided between micro LEDs, a wavelength conversion layer, and the like in a micro LED display, and a color filter and the like provided in a liquid crystal display element. Partition walls, partitions between light emitting diodes, color filters, etc. in solid-state imaging devices. Among these, it can be preferably used as a partition wall in a micro LED display. Furthermore, in the micro LED display, it can be more preferably used as a partition wall provided between regions having a region including a structure including a micro LED and a wavelength conversion layer in each region (see FIG. 1). In the micro LED display, another layer such as a color filter layer may be further provided in a region including the micro LED and a partition wall of the wavelength conversion layer.

（硬化膜的形成方法）
使用該硬化性組成物的硬化膜的形成方法的一例包括：
（1）於基板上形成具有凸部的模板的步驟；
（2）藉由該硬化性組成物而於所述模板的凸部間形成塗膜的步驟；以及
（3）使所述塗膜硬化的步驟。
該硬化膜的形成方法較佳為進而包括：
（4）將所述模板的凸部去除的步驟。(How to form a hardened film)
An example of a method for forming a cured film using the curable composition includes:
(1) a step of forming a template having a convex portion on a substrate;
(2) a step of forming a coating film between the convex portions of the template using the curable composition; and (3) a step of hardening the coating film.
The method for forming the cured film preferably further includes:
(4) a step of removing the convex portion of the template.

根據使用該硬化性組成物的硬化膜的形成方法，可獲得塗佈性及圖案化性優異且具有良好的遮光性的硬化膜。According to the method for forming a cured film using this curable composition, a cured film having excellent coating properties and patterning properties and excellent light-shielding properties can be obtained.

（1）模板形成步驟
凸部及具有其的模板通常以樹脂為主成分，且較佳為由以樹脂為主成分的感放射線性組成物形成。於基板上形成具有凸部的模板的步驟較佳為包括：
（1-1）藉由感放射線性組成物而形成模板用塗膜的步驟；
（1-2）照射放射線的步驟；以及
（1-3）藉由顯影而獲得模板的步驟。(1) Template forming step The convex portion and the template having the same generally include a resin as a main component, and preferably are formed of a radiation-sensitive composition having a resin as a main component. The step of forming a template with a convex portion on the substrate preferably includes:
(1-1) a step of forming a coating film for a template by using a radiation-sensitive composition;
(1-2) a step of irradiating radiation; and (1-3) a step of obtaining a template by development.

（1-1）模板用塗膜形成步驟
模板用塗膜形成步驟為藉由感放射線性組成物而形成具有撥液性表面的模板用塗膜的步驟。感放射線性組成物通常包含具有酸解離性基的聚合物（以下亦稱為「[a]聚合物」）及感放射線性酸產生劑（以下亦稱為「[b]酸產生劑」）。所謂酸解離性基例如是指對酚性羥基、羧基、磺酸基等酸性官能基中的氫原子進行取代而成的基，且是指於酸的存在下解離的基。關於該感放射線性組成物將於以後進行詳述。關於步驟（1-1），具體而言，如圖2（a）所示，藉由於基板10表面塗佈感放射線性組成物來形成模板用塗膜11。(1-1) Coating film forming step for template The coating film forming step for template is a step of forming a coating film for template having a liquid-repellent surface by using a radiation-sensitive composition. The radiation-sensitive composition usually includes a polymer having an acid dissociable group (hereinafter also referred to as "[a] polymer") and a radiation-sensitive acid generator (hereinafter also referred to as "[b] acid generator"). The acid-dissociable group refers to, for example, a group obtained by substituting a hydrogen atom in an acidic functional group such as a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group, and refers to a group that dissociates in the presence of an acid. This radiation-sensitive composition will be described in detail later. Regarding step (1-1), specifically, as shown in FIG. 2 (a), a coating film 11 for a template is formed by applying a radiation-sensitive composition to the surface of the substrate 10.

作為基板10的材質，例如可列舉：玻璃、石英、矽、樹脂等。作為樹脂，可列舉：聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、聚醚碸、聚碳酸酯、聚醯亞胺、環狀烯烴的開環聚合物（ROMP聚合物）、聚丙烯酸酯、丙烯腈-丁二烯-苯乙烯（Acrylonitrile-Butadiene-Styrene，ABS）樹脂、丙烯腈-乙烯-苯乙烯（Acrylonitrile-Ethylene-Styrene，AES）樹脂等。Examples of the material of the substrate 10 include glass, quartz, silicon, and resin. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyether fluorene, polycarbonate, polyimide, and cyclic olefin. Ring polymer (ROMP polymer), polyacrylate, Acrylonitrile-Butadiene-Styrene (ABS) resin, Acrylonitrile-Ethylene-Styrene (AES) resin Wait.

作為基板10，較佳為現有的樹脂製基板、玻璃基板及半導體基板。藉由使用此種基板，可將所獲得的積層圖案直接用於液晶顯示元件或固體攝像元件等光學用途等。The substrate 10 is preferably a conventional resin substrate, a glass substrate, and a semiconductor substrate. By using such a substrate, the obtained laminated pattern can be directly used for optical applications such as a liquid crystal display element and a solid-state imaging element.

再者，於對基板10塗佈感放射線性組成物之前，視需要亦可對基板10表面實施前處理。作為前處理，可列舉清洗、表面粗糙化處理等。Furthermore, before applying the radiation-sensitive composition to the substrate 10, if necessary, a surface of the substrate 10 may be subjected to a pretreatment. Examples of the pretreatment include cleaning, surface roughening, and the like.

作為感放射線性組成物的塗佈方法，並無特別限定，可列舉：使用毛刷或刷子的塗佈法、浸漬法、噴霧法、輥塗佈法、旋轉塗佈法（旋塗法）、狹縫模塗佈法、棒塗佈法、柔性印刷、平板印刷、噴墨印刷、分配法等公知的方法。The method for applying the radiation-sensitive composition is not particularly limited, and examples thereof include a coating method using a brush or a brush, a dipping method, a spray method, a roll coating method, a spin coating method (spin coating method), Well-known methods such as a slit die coating method, a bar coating method, flexographic printing, lithographic printing, inkjet printing, and a dispensing method.

於感放射線性組成物的塗佈後，較佳為對模板用塗膜11進行加熱（預烘烤）。加熱條件視感放射線性組成物的組成等而不同，例如為60℃以上、120℃以下且1分鐘以上、10分鐘以下的程度。After the application of the radiation-sensitive composition, the template coating film 11 is preferably heated (pre-baked). The heating conditions differ depending on the composition of the radiation-sensitive composition and the like, and are, for example, about 60 ° C. or higher and 120 ° C. or lower and about 1 minute or more and 10 minutes or less.

所獲得的模板用塗膜11的平均厚度可根據用途等而適宜調整，作為其下限，較佳為0.05 μm，更佳為0.1 μm。另一方面，作為其上限，較佳為30 μm，更佳為15 μm。The average thickness of the obtained coating film 11 for a template can be appropriately adjusted depending on the application and the like, and as a lower limit thereof, it is preferably 0.05 μm, and more preferably 0.1 μm. On the other hand, the upper limit is preferably 30 μm, and more preferably 15 μm.

（1-2）放射線照射步驟
如圖2（b）所示，放射線照射步驟為對模板用塗膜11的一部分的表面區域照射（曝光）放射線（hν）的步驟。藉此可形成包含親液性表面的層12。再者，由感放射線性組成物所獲得的模板用塗膜11的表面具有撥液性，經放射線照射的區域成為包含親液性表面的層12。另外，該模板用塗膜11中的包含親液性表面的層12為鹼可溶性層。另一方面，未經放射線照射的區域為包含撥液性表面的層13。(1-2) Radiation irradiation step As shown in FIG. 2 (b), the radiation irradiation step is a step of irradiating (exposing) radiation (hν) to a part of a surface area of the template coating film 11. Thereby, a layer 12 including a lyophilic surface can be formed. The surface of the coating film 11 for a template obtained from the radiation-sensitive composition has liquid repellency, and the area irradiated with the radiation becomes the layer 12 including the lyophilic surface. The lyophilic surface-containing layer 12 in the coating film 11 for a template is an alkali-soluble layer. On the other hand, the area not irradiated with radiation is the layer 13 including a liquid-repellent surface.

再者，所謂包含親液性表面的層例如是指對於十四烷的接觸角比撥液性表面對於十四烷的接觸角小30°以上的區域。若存在此種接觸角差，則包含親液性表面的層無需為源自模板用塗膜的區域。即，於藉由顯影而將模板用塗膜去除來使基板表面露出的情況下，基板表面成為包含親液性表面的層。基板表面的露出可為全部，但一部分成為親液性表面的情況亦較佳。The layer containing a lyophilic surface means, for example, a region having a contact angle with tetradecane that is 30 ° or more smaller than a contact angle with liquid-repellent surfaces with tetradecane. If such a contact angle difference exists, the layer containing the lyophilic surface need not be a region derived from the coating film for a template. That is, when the coating film for a template is removed by development to expose the substrate surface, the substrate surface becomes a layer containing a lyophilic surface. Although the entire surface of the substrate may be exposed, it is also preferable that a part of the substrate becomes a lyophilic surface.

藉由放射線的照射而形成包含親液性表面的層12的理由如下所述。藉由放射線的照射，自感放射線性組成物中的感放射線性酸產生劑產生酸，藉此，聚合物所具有的酸解離性基解離。藉由酸解離性基的解離，經照射的區域的表面能量發生變化，潤濕性提高。尤其是於酸解離性基具有氟原子的情況下，自該撥液性向親液性的變化顯著。The reason why the layer 12 including the lyophilic surface is formed by irradiation of radiation is as follows. The radiation-sensitive acid generator in the self-sensitive radiation composition generates an acid upon irradiation with radiation, whereby the acid-dissociable group contained in the polymer is dissociated. By dissociation of the acid dissociable group, the surface energy of the irradiated area changes, and the wettability is improved. In particular, when the acid-dissociable group has a fluorine atom, the change from the liquid repellency to the lyophilic property is significant.

放射線的照射（曝光）可以形成與所欲形成的硬化膜的圖案形狀為相同形狀的包含親液性表面的層12的方式介隔具有規定圖案的光罩來進行。藉由介隔光罩進行曝光，即便於形成複雜的圖案的情況下亦可有效率地進行照射。此外，亦可使用直接描繪方式曝光機等對規定圖案進行描繪曝光。Radiation irradiation (exposure) can be performed through a photomask having a predetermined pattern so that the layer 12 including the lyophilic surface has the same shape as the pattern shape of the cured film to be formed. Exposure through a reticle enables efficient irradiation even when a complicated pattern is formed. In addition, a direct drawing type exposure machine or the like may be used to perform drawing exposure on a predetermined pattern.

於本步驟（1-2）中，作為所照射的放射線，可使用可見光線、紫外線、遠紫外線、帶電粒子束、X射線等。該些中，較佳為波長處於190 nm以上、450 nm以下的範圍內的放射線，更佳為包含365 nm的波長的紫外線的放射線。In this step (1-2), as the radiation to be irradiated, visible rays, ultraviolet rays, extreme ultraviolet rays, charged particle beams, X-rays, and the like can be used. Among these, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation including ultraviolet rays having a wavelength of 365 nm is more preferable.

作為本步驟（1-2）中的放射線的曝光量，只要於產生充分的酸解離性基的解離的範圍內適宜設定即可。作為該曝光量的下限，以放射線的波長365 nm中的強度計，較佳為10 mJ/cm² ，更佳為20 mJ/cm² 。另一方面，作為其上限，較佳為1000 mJ/cm² ，更佳為500 mJ/cm² 。The radiation exposure amount in this step (1-2) may be appropriately set within a range in which sufficient dissociation of the acid dissociable group is generated. The lower limit of the exposure amount is preferably 10 mJ / cm ² and more preferably 20 mJ / cm ² in terms of intensity at a wavelength of 365 nm of the radiation. On the other hand, the upper limit is preferably 1000 mJ / cm ² , and more preferably 500 mJ / cm ² .

所形成的包含親液性表面的層12的尺寸及形狀與所期望的圖案的尺寸及形狀對應，可設為寬度為100 μm以下的線狀，較佳為可設為0.1 μm～50 μm的線狀。The size and shape of the formed layer 12 including the lyophilic surface corresponds to the size and shape of a desired pattern, and can be set to a line shape with a width of 100 μm or less, preferably 0.1 μm to 50 μm. Linear.

於對模板用塗膜11曝光後，亦可對模板用塗膜11進行加熱。加熱條件視感放射線性組成物的組成等而不同，例如為50℃以上、120℃以下且1分鐘以上、20分鐘以下的程度。After the template coating film 11 is exposed, the template coating film 11 may be heated. The heating conditions vary depending on the composition of the radiation-sensitive composition and the like, and are, for example, about 50 ° C. or higher and 120 ° C. or lower and about 1 minute or longer and 20 minutes or shorter.

（1-3）顯影步驟
顯影步驟為對經放射線照射的模板用塗膜11進行顯影的步驟。藉由該顯影，可於經放射線照射的區域（包含親液性表面的層12）中使酸解離性基解離。藉此，經放射線照射的部分成為包含親液性表面的層，藉由顯影液而被去除。藉此，基板表面露出，藉此基板10成為包含親液性表面的層。藉由經過該顯影步驟，如圖2（c）所示，可形成具有凸部14的模板15。該模板15包含多個凸部14，且為殘留有模板用塗膜11的包含撥液性表面的層13者。即，模板15的各凸部14的表面為撥液性。(1-3) Development Step The development step is a step of developing the radiation-applied template coating film 11. By this development, the acid-dissociable group can be dissociated in the radiation-irradiated region (the layer 12 including the lyophilic surface). Thereby, the radiation-irradiated part becomes a layer containing a lyophilic surface, and is removed by a developing solution. Thereby, the surface of the substrate is exposed, whereby the substrate 10 becomes a layer containing a lyophilic surface. By going through this developing step, as shown in FIG. 2 (c), a template 15 having a convex portion 14 can be formed. The template 15 includes a plurality of convex portions 14 and is a layer 13 including a liquid-repellent surface in which the coating film 11 for the template remains. That is, the surface of each convex portion 14 of the template 15 is liquid-repellent.

作為顯影中所使用的顯影液，例如可使用溶解有氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨、四甲基氫氧化銨、四乙基氫氧化銨等鹼性化合物的至少一種的水溶液。亦可於該些鹼性化合物的水溶液中添加適量的甲醇、乙醇等水溶性有機溶媒來使用。As a developing solution used for development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like can be used. An aqueous solution of at least one of the basic compounds. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol may be added to the aqueous solution of these basic compounds and used.

作為顯影方法，例如可列舉：覆液法、浸漬法、搖動浸漬法、噴霧法等。顯影時間視硬化膜形成用組成物的組成而不同，作為其顯影時間的下限，較佳為5秒，更佳為10秒。另外，作為顯影時間的上限，較佳為300秒，更佳為180秒。緊接著顯影處理，例如以30秒以上、90秒以下的時間進行流水清洗後，利用壓縮空氣或壓縮氮氣使其乾燥，藉此可獲得所期望的模板的圖案。Examples of the development method include a liquid coating method, a dipping method, a shaking dipping method, and a spray method. The development time varies depending on the composition of the composition for forming a cured film, and the lower limit of the development time is preferably 5 seconds, and more preferably 10 seconds. The upper limit of the development time is preferably 300 seconds, and more preferably 180 seconds. Immediately after the development process, for example, after washing with flowing water for 30 seconds or more and 90 seconds or less, it is dried with compressed air or compressed nitrogen to obtain a desired pattern of the template.

以所述方式形成的凸部14（包含撥液性表面的層13）的表面與包含親液性表面的層（於圖2（c）中為基板10）的表面的對於十四烷的接觸角差（撥液性表面的接觸角-親液性表面的接觸角）較佳為30°以上，更佳為40°以上，進而佳為50°以上。作為該接觸角差的上限，例如為70°。Contact of the surface of the convex portion 14 (the layer 13 containing the liquid-repellent surface) formed in the manner described above with the surface of the layer containing the lyophilic surface (the substrate 10 in FIG. 2 (c)) with tetradecane The angular difference (contact angle of the liquid-repellent surface-contact angle of the lyophilic surface) is preferably 30 ° or more, more preferably 40 ° or more, and even more preferably 50 ° or more. The upper limit of the contact angle difference is, for example, 70 °.

另外，凸部14（包含撥液性表面的層13）的表面對於十四烷的接觸角較佳為40°以上，更佳為50°以上。該接觸角的上限例如為80℃。另外，凸部14（包含撥液性表面的層13）的表面對於水的接觸角較佳為80°以上，更佳為90°以上。該接觸角的上限例如為140℃。藉由形成此種撥液性高的凸部14，與模板15的凸部14接觸的硬化性組成物容易移動至凸部14間（基板10，即包含親液性表面的層的表面），可較佳地進行沿著模板15的凸部14間的形狀的硬化膜的形成。The contact angle of the surface of the convex portion 14 (the layer 13 including the liquid-repellent surface) with tetradecane is preferably 40 ° or more, and more preferably 50 ° or more. The upper limit of the contact angle is, for example, 80 ° C. The contact angle of the surface of the convex portion 14 (the layer 13 including the liquid-repellent surface) with respect to water is preferably 80 ° or more, and more preferably 90 ° or more. The upper limit of the contact angle is, for example, 140 ° C. By forming such a high liquid-repellent convex portion 14, the hardening composition that is in contact with the convex portion 14 of the template 15 can easily move between the convex portions 14 (the surface of the substrate 10, that is, the layer containing the lyophilic surface), The formation of a cured film along the shape between the convex portions 14 of the template 15 can be preferably performed.

經過此種顯影步驟，可獲得包括凸部14的模板15，所述凸部14包括包含撥液性表面的層。再者，於該模板中，模板用塗膜的包含親液性表面的層12亦可殘留於凸部14間（參照圖2（d））。但是，就所獲得的硬化膜的密接性等觀點而言，較佳為如圖2（c）般實質僅由凸部14構成模板15。After such a developing step, a template 15 including a convex portion 14 including a layer including a liquid-repellent surface can be obtained. Furthermore, in this template, the layer 12 including the lyophilic surface of the coating film for the template may remain between the convex portions 14 (see FIG. 2 (d)). However, from the viewpoint of the adhesiveness of the obtained cured film and the like, it is preferable that the template 15 is substantially composed of only the convex portions 14 as shown in FIG. 2 (c).

（2）硬化性組成物塗膜形成步驟
硬化性組成物塗膜形成步驟為藉由該硬化性組成物而於模板15的凸部14間形成塗膜16的步驟（參照圖3（a））。該塗膜16的形成可藉由對形成於基板10上的模板15塗佈硬化性組成物來進行。(2) Hardening composition coating film forming step The hardening composition coating film forming step is a step of forming a coating film 16 between the convex portions 14 of the template 15 by using the hardening composition (see FIG. 3 (a)). . The coating film 16 can be formed by applying a hardenable composition to the template 15 formed on the substrate 10.

硬化性組成物的塗佈可利用公知的方法來進行。具體而言，可列舉：使用毛刷或刷子的塗佈法、浸漬法、噴霧法、輥塗佈法、旋轉塗佈法（旋塗法）、狹縫模塗佈法、棒塗佈法、柔性印刷、平板印刷、噴墨印刷、分配法等。The coating of the curable composition can be performed by a known method. Specific examples include a coating method using a brush or a brush, a dipping method, a spray method, a roll coating method, a spin coating method (spin coating method), a slot die coating method, a bar coating method, Flexible printing, lithographic printing, inkjet printing, dispensing method, etc.

該些中，較佳為噴墨法。藉由利用噴墨法來塗佈硬化性組成物而進行塗膜的形成，藉此能夠實現硬化組成物的省液化且可容易將硬化組成物塗佈於所期望的位置。Among these, the inkjet method is preferred. By forming the coating film by applying the curable composition by an inkjet method, it is possible to achieve liquid saving of the cured composition, and it is possible to easily apply the cured composition to a desired position.

於對形成於基板10上的模板15塗佈硬化性組成物的情況下，硬化性組成物被凸部14（包含撥液性表面的層13）排斥而流入至作為凸部14間（凹部）的基板10表面（親液性表面）。藉此，可沿著凸部14間而形成硬化性組成物的塗膜16。尤其是，該硬化性組成物的塗佈性優異，因此硬化性組成物沿著凸部14間良好地流動而難以填充。另外，根據該硬化性組成物，可抑制模板15的侵蝕。When the hardening composition is applied to the template 15 formed on the substrate 10, the hardening composition is repelled by the convex portions 14 (the layer 13 including the liquid-repellent surface) and flows between the convex portions 14 (concave portions). The surface of the substrate 10 (lyophilic surface). Thereby, the coating film 16 of a hardening composition can be formed along between the convex parts 14. In particular, since the hardenable composition has excellent coatability, the hardenable composition flows well between the convex portions 14 and is difficult to fill. In addition, the hardening composition can suppress erosion of the template 15.

（3）硬化步驟
硬化步驟為藉由加熱而使形成於凸部14間的硬化性組成物的塗膜16硬化的步驟。(3) Hardening step The hardening step is a step of hardening the coating film 16 of the hardening composition formed between the convex portions 14 by heating.

作為該加熱方法，並無特別限定，可列舉使用加熱板、烘箱、乾燥機等進行加熱的方法。此外，亦可藉由真空烘烤進行加熱。加熱條件亦無特別限定，例如可設為50℃以上、200℃以下且1分鐘以上、120分鐘以下。The heating method is not particularly limited, and examples thereof include a method of heating using a hot plate, an oven, a dryer, and the like. In addition, heating may be performed by vacuum baking. The heating conditions are not particularly limited, and may be, for example, 50 ° C. or higher, 200 ° C. or lower, and 1 minute or longer and 120 minutes or shorter.

（4）去除步驟
去除步驟為將模板15的凸部14去除的步驟。藉由經過該步驟，如圖3（c）所示，可獲得形成有規定圖案的硬化膜17。該去除步驟可藉由顯影或蝕刻來進行，較佳為藉由顯影來進行。(4) Removal Step The removal step is a step of removing the convex portion 14 of the template 15. By going through this step, as shown in FIG. 3 (c), a cured film 17 having a predetermined pattern can be obtained. This removing step can be performed by development or etching, and is preferably performed by development.

去除步驟較佳為包括：
（4-1）照射放射線的步驟；以及
（4-2）藉由顯影而將模板的凸部去除的步驟。The removing step preferably includes:
(4-1) a step of radiating radiation; and (4-2) a step of removing the convex portion of the template by development.

（4-1）放射線照射步驟
（4-1）放射線照射步驟為對基板10的塗佈有硬化性組成物的一側照射放射線（hν）的步驟（參照圖3（b））。於該情況下，亦可介隔光罩進行曝光，亦可不使用光罩進行曝光。於該情況下，藉由放射線的照射，所露出的模板15的凸部14的酸解離性基解離，因此成為鹼可溶性（親水性）。(4-1) Radiation irradiation step (4-1) The radiation irradiation step is a step of irradiating radiation (hν) to the side of the substrate 10 on which the curable composition is applied (see FIG. 3 (b)). In this case, exposure may be performed through a photomask, or exposure may be performed without using a photomask. In this case, the acid-dissociable group of the convex portion 14 of the exposed template 15 is dissociated by irradiation of the radiation, and thus becomes alkali-soluble (hydrophilic).

於本步驟中，所照射的放射線的具體例及較佳例與所述（1-2）步驟相同。另外，本步驟中的放射線的曝光量亦可設為與（1-2）步驟相同。再者，於放射線的照射後，亦可對硬化性組成物的塗膜16進行加熱。In this step, specific examples and preferred examples of the irradiated radiation are the same as the step (1-2). In addition, the exposure amount of the radiation in this step may be the same as that in the step (1-2). After the radiation, the coating film 16 of the curable composition may be heated.

（4-2）顯影步驟
顯影步驟為對經過所述（4-1）放射線照射步驟的硬化性組成物的塗膜16進行顯影的步驟。藉由經過所述（4-1）放射線照射步驟，模板15的凸部14成為鹼可溶性。因此，藉由利用鹼性水溶液進行顯影，可去除模板15的凸部14（參照圖3（b）、圖3（c））。本步驟中的顯影液或顯影方法的具體例及較佳例與所述（1-3）步驟相同。(4-2) Development Step The development step is a step of developing the coating film 16 of the curable composition that has undergone the (4-1) radiation irradiation step. By passing through the (4-1) radiation irradiation step, the convex portion 14 of the template 15 becomes alkali-soluble. Therefore, by developing with an alkaline aqueous solution, the convex portion 14 of the template 15 can be removed (see FIGS. 3 (b) and 3 (c)). Specific examples and preferred examples of the developing solution or the developing method in this step are the same as those in the step (1-3).

藉由此種形成方法，如圖3（c）所示，可獲得圖案化為規定形狀的硬化膜17。於該形成方法中，由於使用該硬化性組成物，因此可獲得塗佈性及圖案化性優異且具有良好的遮光性的硬化膜。根據該形成方法，可獲得倒錐形狀（是指上大下小的朝下的梯形或T字型的形狀）的硬化膜。With this formation method, as shown in FIG. 3 (c), a cured film 17 patterned into a predetermined shape can be obtained. In this forming method, since the curable composition is used, a cured film having excellent coating properties and patterning properties and excellent light-shielding properties can be obtained. According to this forming method, a hardened film having an inverted cone shape (a trapezoidal shape or a T-shaped shape that faces upwards, downwards, and downwards) can be obtained.

該形成方法可較佳地用作顯示元件或固體攝像元件的硬化膜的形成方法。尤其是，顯示元件或固體攝像元件的硬化膜中，該形成方法可較佳地用作顯示元件或固體攝像元件的隔離壁的形成方法。This formation method is preferably used as a formation method of a cured film of a display element or a solid-state imaging element. In particular, in a cured film of a display element or a solid-state imaging element, this formation method can be preferably used as a method for forming a partition wall of a display element or a solid-state imaging element.

例如，於藉由該形成方法而獲得的硬化膜為作為顯示元件的一例的微LED顯示器的隔離壁的情況下，可於隔離壁間的規定區域積層波長變換層。作為波長變換層，可以含有量子點、螢光劑等的層的形式形成。波長變換層可藉由塗佈包含量子點、螢光劑等及黏合劑樹脂等的波長變換層形成用組成物並加以硬化等來形成。再者，於藉由該形成方法而獲得的硬化膜的撥液性高的情況下，所述波長變換膜形成用組成物的塗佈性提高。另外，於隔離壁間，亦可進而配置彩色濾光片層等，還可配置透明層。彩色濾光片層或透明層亦可與波長變換層同樣地藉由用以形成該些層的組成物的塗敷來形成。For example, when the cured film obtained by this forming method is a partition wall of a micro LED display as an example of a display element, a wavelength conversion layer may be laminated in a predetermined region between the partition walls. The wavelength conversion layer may be formed as a layer containing a quantum dot, a phosphor, or the like. The wavelength conversion layer can be formed by applying a composition for forming a wavelength conversion layer containing a quantum dot, a phosphor, and the like, a binder resin, and the like, and curing the composition. When the liquid-repellent property of the cured film obtained by the forming method is high, the coatability of the composition for forming a wavelength conversion film is improved. In addition, a color filter layer or the like may be further disposed between the partition walls, and a transparent layer may be disposed. Similar to the wavelength conversion layer, the color filter layer or the transparent layer may be formed by coating the composition for forming these layers.

＜感放射線性組成物＞
以下，對硬化膜的形成方法中的形成模板的感放射線性組成物的較佳形態進行說明。如上所述，所述感放射線性組成物通常包含[a]聚合物及[b]酸產生劑。所述感放射線性組成物較佳為進而包含溶媒（以下亦稱為「[c]溶媒」）。＜ Radiation-sensitive composition ＞
Hereinafter, a preferred embodiment of the radiation-sensitive composition for forming a template in the method for forming a cured film will be described. As described above, the radiation-sensitive composition usually contains [a] a polymer and [b] an acid generator. The radiation-sensitive composition preferably further contains a solvent (hereinafter also referred to as "[c] solvent").

（[a]聚合物）
[a]聚合物為含有具有藉由酸而解離的性質的基的聚合物。作為酸解離性基，較佳為含有氟原子的基。藉由[a]聚合物具有此種基，可形成撥液性的塗膜，且藉由經過曝光及顯影而可獲得具有良好的圖案形狀的模板。([A] polymer)
[a] The polymer is a polymer containing a group having a property of being dissociated by an acid. The acid-dissociable group is preferably a group containing a fluorine atom. When the polymer [a] has such a base, a liquid-repellent coating film can be formed, and a template having a good pattern shape can be obtained by exposure and development.

作為酸解離性基，就可製造精細的模板等方面而言，更佳為具有含有縮醛鍵、半縮醛酯鍵或包含該些的組合的鍵的基的基。作為此種基，較佳為下述式（1-1）所表示的基或下述式（1-2）所表示的基。The acid-dissociable group is more preferably a group having a group containing an acetal bond, a hemiacetal ester bond, or a bond containing a combination of these in terms of making a fine template and the like. Such a group is preferably a group represented by the following formula (1-1) or a group represented by the following formula (1-2).

[化1]
[Chemical 1]

式（1-1）及式（1-2）中，R¹ 及R² 分別獨立地為氫原子或甲基。Rf分別獨立地為具有氟原子的有機基。*表示鍵結部位。In the formula (1-1) and the formula (1-2), R ¹ and R ² are each independently a hydrogen atom or a methyl group. Rf is each independently an organic group having a fluorine atom. * Indicates a bonding site.

作為所述Rf，較佳為碳數1～20的氟化烴基，更佳為下述式（1-1）～式（1-33）所表示的基、2,2,2-三氟乙基及1,2,2-三氟乙烯基。The Rf is preferably a fluorinated hydrocarbon group having 1 to 20 carbon atoms, more preferably a group represented by the following formulae (1-1) to (1-33) and 2,2,2-trifluoroethyl And 1,2,2-trifluorovinyl.

[化2]

[Chemical 2]

[化3]

[Chemical 3]

[化4]
[Chemical 4]

[a]聚合物較佳為具有如下結構的化合物，所述結構是於作為前驅物的具有羥基的化合物的羥基中導入源自下述式（1）所表示的乙烯基醚化合物（以下亦稱為「化合物（1）」）的酸解離性基而成。另外，[a]聚合物亦可為具有如下結構的化合物，所述結構是於作為前驅物的具有羧基的化合物的羧基中導入源自化合物（1）的酸解離性基而成。[a] The polymer is preferably a compound having a structure in which a hydroxyl group derived from a vinyl ether compound represented by the following formula (1) is introduced into a hydroxyl group of a compound having a hydroxyl group as a precursor (hereinafter also referred to as "Compound (1)"). The polymer [a] may be a compound having a structure in which an acid-dissociable group derived from the compound (1) is introduced into a carboxyl group of a compound having a carboxyl group as a precursor.

[化5]
[Chemical 5]

式（1）中，R⁰ 表示氫原子或甲基。式（1）中，R^A 分別獨立地表示亞甲基、碳數2～12的伸烷基、碳數2～12的伸烯基、碳數6～13的經取代或未經取代的芳香族烴基、碳數4～12的經取代或未經取代的脂環式烴基、或者該些基的一個以上的氫原子經氟原子取代的基。In formula (1), R ⁰ represents a hydrogen atom or a methyl group. In formula (1), R ^A and R each independently represent a methylene group, an alkylene group having 2 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and a substituted or unsubstituted aromatic group having 6 to 13 carbon atoms. Group hydrocarbon group, substituted or unsubstituted alicyclic hydrocarbon group having 4 to 12 carbon atoms, or a group in which one or more hydrogen atoms of these groups are substituted with a fluorine atom.

式（1）中，R^B 表示烴基的一個以上的氫原子經氟原子取代的基。式（1）中，R^B 較佳為碳數1～20的氟化烴基，具體而言，可列舉所述Rf中的式（1-1）～式（1-33）所表示的基、2,2,2-三氟乙基、1,2,2-三氟乙烯基等。In formula (1), R ^B represents a group in which one or more hydrogen atoms of a hydrocarbon group are substituted with a fluorine atom. In the formula (1), R ^{B is} preferably a fluorinated hydrocarbon group having 1 to 20 carbon atoms, and specifically, a group represented by the formula (1-1) to (1-33) in the Rf, 2,2,2-trifluoroethyl, 1,2,2-trifluorovinyl and the like.

式（1）中，x表示0～12的整數，較佳為0～9的整數，更佳為0。In the formula (1), x represents an integer of 0 to 12, preferably an integer of 0 to 9, and more preferably 0.

其次，對用以獲得[a]聚合物的方法進行說明。作為用以獲得[a]聚合物的方法，可為使用聚合物作為成為前驅物的化合物的方法、與使用單體作為成為前驅物的化合物的方法這兩種方法。Next, a method for obtaining [a] polymer will be described. As a method for obtaining the [a] polymer, there may be two methods, a method using a polymer as a compound to be a precursor, and a method using a monomer as a compound to be a precursor.

使用聚合物作為成為前驅物的化合物的方法中，成為前驅物的聚合物於分子內含有羥基或羧基，使成為前驅物的聚合物的羥基或羧基與所述化合物（1）反應，藉此可獲得[a]聚合物。另外，使用單體作為成為前驅物的化合物的方法中，成為前驅物的單體於分子內含有羥基或羧基，使成為前驅物的單體的羥基或羧基與所述化合物（1）反應後，使所獲得的單體聚合，藉此可獲得[a]聚合物。以下，對用以獲得[a]聚合物的兩種方法更具體地進行說明。In the method of using a polymer as a compound to be a precursor, the polymer to be a precursor contains a hydroxyl group or a carboxyl group in a molecule, and a hydroxyl group or a carboxyl group of the polymer to be a precursor is reacted with the compound (1), whereby [A] polymer was obtained. In the method using a monomer as a compound to be a precursor, the monomer to be a precursor contains a hydroxyl group or a carboxyl group in the molecule, and after reacting the hydroxyl group or the carboxyl group of the monomer to be a precursor with the compound (1), By polymerizing the obtained monomer, a [a] polymer can be obtained. Hereinafter, two methods for obtaining the [a] polymer will be described more specifically.

（1）使用聚合物作為成為前驅物的化合物的方法
該方法中，可使具有羥基或羧基的單體聚合而獲得具有羥基或羧基的聚合物（前驅物），其後，使成為前驅物的聚合物的羥基或羧基與所述化合物（1）反應而獲得[a]聚合物。(1) Method using a polymer as a precursor compound In this method, a monomer having a hydroxyl group or a carboxyl group can be polymerized to obtain a polymer (precursor) having a hydroxyl group or a carboxyl group, and thereafter, a precursor having a hydroxyl group or a carboxyl group can be obtained. A hydroxyl group or a carboxyl group of the polymer is reacted with the compound (1) to obtain a [a] polymer.

作為所述具有羥基的單體，較佳為(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-2-羥基丁酯、(甲基)丙烯酸-4-羥基苯酯、4-羥基苄基丙烯醯胺、3,5-二甲基-4-羥基苄基丙烯醯胺等。The monomer having a hydroxyl group is preferably a (meth) acrylate, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (methyl) ) 2-hydroxybutyl acrylate, 4-hydroxyphenyl (meth) acrylate, 4-hydroxybenzylacrylamide, 3,5-dimethyl-4-hydroxybenzylacrylamide, and the like.

再者，作為具有羥基的單體，較佳為所述(甲基)丙烯酸酯，除該化合物以外，亦可使用異丙烯基苯酚等具有羥基及不飽和鍵的化合物。具有羥基的單體可單獨使用一種，亦可使用兩種以上。In addition, as the monomer having a hydroxyl group, the (meth) acrylate is preferably used. In addition to the compound, a compound having a hydroxyl group and an unsaturated bond such as isopropenylphenol can also be used. The monomer having a hydroxyl group may be used alone, or two or more kinds may be used.

作為所述具有羧基的單體，例如可列舉：(甲基)丙烯酸、琥珀酸-2-(甲基)丙烯醯氧基乙酯、鄰苯二甲酸-2-(甲基)丙烯醯氧基乙酯、(甲基)丙烯酸-4-羧基苯酯等。具有羧基的單體可單獨使用一種，亦可使用兩種以上。Examples of the monomer having a carboxyl group include (meth) acrylic acid, 2- (meth) acryloxyethyl succinate, and 2- (meth) acryloxy phthalate Ethyl ester, 4-carboxyphenyl (meth) acrylate and the like. The monomer having a carboxyl group may be used alone or in combination of two or more.

成為[a]聚合物的前驅物的、具有羥基或羧基的聚合物可僅使用所述具有羥基或羧基的單體來獲得，此外亦可使所述具有羥基或羧基的單體、與具有羥基或羧基的單體以外的單體共聚來獲得。The polymer having a hydroxyl group or a carboxyl group which is a precursor of the polymer [a] can be obtained by using only the monomer having a hydroxyl group or a carboxyl group. Or it is obtained by copolymerizing a monomer other than a carboxyl monomer.

作為具有羥基或羧基的單體以外的單體，可列舉：(甲基)丙烯酸鏈狀烷基酯、(甲基)丙烯酸環狀烷基酯、(甲基)丙烯酸芳基酯、不飽和芳香族化合物、共軛二烯、含有四氫呋喃骨架的不飽和化合物、馬來醯亞胺及該些以外的單體。具有羥基或羧基的單體以外的單體可單獨使用一種，亦可使用兩種以上。具體而言，可使用國際公開第2014/178279號中記載的不飽和化合物。Examples of the monomer other than the monomer having a hydroxyl group or a carboxyl group include a chain alkyl (meth) acrylate, a cyclic alkyl (meth) acrylate, an aryl (meth) acrylate, and an unsaturated aromatic group. Group compounds, conjugated dienes, unsaturated compounds containing a tetrahydrofuran skeleton, maleimide, and monomers other than these. A monomer other than the monomer having a hydroxyl group or a carboxyl group may be used alone, or two or more kinds may be used. Specifically, an unsaturated compound described in International Publication No. 2014/178279 can be used.

其次，使具有羥基或羧基的聚合物的羥基或羧基與所述化合物（1）反應而獲得[a]聚合物的方法可藉由國際公開第2014/178279號中記載的方法來進行。Next, a method of obtaining a [a] polymer by reacting a hydroxy group or a carboxyl group of a polymer having a hydroxy group or a carboxyl group with the compound (1) can be performed by a method described in International Publication No. 2014/178279.

（2）使用單體作為成為前驅物的化合物的方法
該方法中，使具有羥基或羧基的單體的羥基或羧基與所述化合物（1）反應而獲得加成物，並使該些聚合，藉此獲得[a]聚合物。此種獲得[a]聚合物的方法可參考公知的方法。(2) Method using a monomer as a precursor compound In this method, a hydroxyl group or a carboxyl group of a monomer having a hydroxyl group or a carboxyl group is reacted with the compound (1) to obtain an adduct, and polymerize these, Thereby, [a] a polymer was obtained. As such a method for obtaining the [a] polymer, a known method can be referred to.

例如，如日本專利特開2005-187609號公報中所記載般，由具有羥基的單體的羥基與化合物（1）的乙烯基醚基生成縮醛鍵，或由具有羧基的單體的羧基與所述化合物（1）的乙烯基醚基生成半縮醛酯鍵，從而形成加成物。For example, as described in Japanese Patent Laid-Open No. 2005-187609, an acetal bond is formed from a hydroxyl group of a monomer having a hydroxyl group and a vinyl ether group of the compound (1), or a carboxyl group of a monomer having a carboxyl group and The vinyl ether group of the compound (1) forms a hemiacetal ester bond, thereby forming an adduct.

繼而，使用所獲得的單體，與所述具有羥基或羧基的聚合物的製造方法同樣地進行，可獲得[a]聚合物。Then, using the obtained monomer, it carried out similarly to the manufacturing method of the said polymer which has a hydroxyl group or a carboxyl group, and [a] polymer was obtained.

[a]聚合物亦可進而含有具有酸解離性基的結構單元以外的結構單元。但是，作為[a]聚合物中的具有酸解離性基的結構單元的含有比例的下限，較佳為5莫耳%，更佳為10莫耳%，進而佳為20莫耳%。另一方面，該含有比例的上限可為100莫耳%，亦可為80莫耳%，還可為70莫耳%。[a] The polymer may further contain a structural unit other than a structural unit having an acid-dissociable group. However, as the lower limit of the content ratio of the structural unit having an acid-dissociable group in the [a] polymer, it is preferably 5 mol%, more preferably 10 mol%, and even more preferably 20 mol%. On the other hand, the upper limit of the content ratio may be 100 mol%, 80 mol%, or 70 mol%.

[a]聚合物可單獨使用一種，亦可使用兩種以上。[a] The polymer may be used singly or in combination of two or more kinds.

（[b]酸產生劑）
[b]酸產生劑為至少藉由放射線的照射而產生酸的化合物。即，[b]酸產生劑為感放射線性酸產生劑。藉由感放射線性組成物包含[b]酸產生劑，可使酸解離性基自[a]聚合物解離。([B] acid generator)
[b] The acid generator is a compound that generates an acid by at least radiation. That is, the [b] acid generator is a radiation-sensitive acid generator. By including the [b] acid generator in the radiation-sensitive composition, the acid-dissociable group can be dissociated from the [a] polymer.

作為[b]酸產生劑，例如可列舉：肟磺酸酯化合物、鎓鹽、磺醯亞胺化合物、含鹵素的化合物、二偶氮甲烷化合物、碸化合物、磺酸酯化合物、羧酸酯化合物等。[b]酸產生劑可使用一種或兩種以上。作為[b]酸產生劑，可使用國際公開第2014/178279號中記載的酸產生劑。Examples of the [b] acid generator include oxime sulfonate compounds, onium salts, sulfonylimine compounds, halogen-containing compounds, diazomethane compounds, sulfonium compounds, sulfonate compounds, and carboxylic acid ester compounds. Wait. [b] One or two or more acid generators can be used. [B] As the acid generator, an acid generator described in International Publication No. 2014/178279 can be used.

作為[b]酸產生劑的含量的下限，相對於[a]聚合物100質量份，較佳為0.1質量份，更佳為1質量份。另外，作為該含量的上限，較佳為10質量份，更佳為5質量份。The lower limit of the content of the [b] acid generator is preferably 0.1 parts by mass, and more preferably 1 part by mass based on 100 parts by mass of the polymer [a]. The upper limit of the content is preferably 10 parts by mass, and more preferably 5 parts by mass.

（[c]溶媒）
作為[c]溶媒，並無特別限定，較佳為可使[a]聚合物、[b]酸產生劑及任意成分的聚合性化合物等各成分均勻地溶解或分散的溶劑。([C] Solvent)
The [c] solvent is not particularly limited, and a solvent capable of uniformly dissolving or dispersing each component such as the [a] polymer, the [b] acid generator, and a polymerizable compound of an arbitrary component is preferable.

作為較佳的[c]溶媒，可列舉：醇系溶劑、醚類、二乙二醇烷基醚類、乙二醇烷基醚乙酸酯類、丙二醇單烷基醚乙酸酯類、丙二醇單烷基醚丙酸酯類、脂肪族烴類、芳香族烴類、酮類及酯類等。[c]溶媒可使用一種或兩種以上。Preferred [c] solvents include alcohol solvents, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether acetates, and propylene glycol monoalkane. Ether ether propionates, aliphatic hydrocarbons, aromatic hydrocarbons, ketones and esters. [c] One or two or more solvents can be used.

作為[c]溶媒的含量的下限，相對於感放射線性組成物的溶劑除外的成分100質量份，較佳為100質量份，更佳為200質量份。另一方面，作為該含量的上限，較佳為1000質量份，進而佳為500質量份。The lower limit of the content of the [c] solvent is preferably 100 parts by mass, and more preferably 200 parts by mass with respect to 100 parts by mass of the components excluding the solvent of the radiation-sensitive composition. On the other hand, the upper limit of the content is preferably 1,000 parts by mass, and more preferably 500 parts by mass.

（其他任意成分）
所述感放射線性組成物亦可進而包含增感劑、酸擴散抑制劑（淬滅劑）、聚合性化合物、感放射線性聚合起始劑、界面活性劑、保存穩定劑、接著助劑、耐熱性提高劑等任意成分。該些任意成分的具體例、調配例可參考國際公開第2014/178279號中記載的具體例、調配例。(Other optional ingredients)
The radiation-sensitive composition may further include a sensitizer, an acid diffusion inhibitor (quenching agent), a polymerizable compound, a radiation-sensitive polymerization initiator, a surfactant, a storage stabilizer, an adhesion promoter, and heat resistance. An optional component such as a property improving agent. For specific examples and formulation examples of these optional components, refer to the specific examples and formulation examples described in International Publication No. 2014/178279.

＜其他實施形態＞
本發明並不限定於所述實施形態，亦可於不變更本發明的主旨的範圍內對其構成進行變更。例如，本發明的硬化性組成物亦可用於利用不使用模板的方法的硬化膜的形成中。
[實施例]＜ Other embodiments ＞
The present invention is not limited to the above-mentioned embodiments, and the configuration may be changed within a range not changing the gist of the present invention. For example, the curable composition of the present invention can also be used for forming a cured film by a method that does not use a template.
[Example]

以下，基於實施例對本發明進行具體說明，但本發明並不限定於該些實施例。再者，實施例等中的測定是藉由以下方法來進行。Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In addition, the measurement in an Example etc. was performed by the following method.

（顏料的平均粒徑）
利用所使用的溶媒將製備例中所獲得的顏料分散液稀釋為10倍，使用粒度分佈計（堀場（HORIBA）公司的「L-500」）來求出顏料的平均粒徑。(Average particle size of pigment)
The pigment dispersion liquid obtained in the preparation example was diluted 10-fold with the solvent used, and the average particle diameter of the pigment was determined using a particle size distribution meter ("L-500" by HORIBA).

（重量平均分子量（Mw）及分子量分佈（Mw/Mn））
聚合物的聚苯乙烯換算的重量平均分子量（Mw）及分子量分佈（Mw/Mn）是於以下條件下進行測定。
·測定方法：凝膠滲透層析（Gel Permeation Chromatography，GPC）法
·標準物質：聚苯乙烯換算
·裝置：東曹（TOSOH）公司的「HLC-8220」
·管柱：將東曹（TOSOH）公司的保護管柱「HXL-H」、「TSK gel G7000HXL」、「TSK gel GMHXL」2根及「TSK gel G2000HXL」依次連結而成者
·溶媒：四氫呋喃
·樣品濃度：0.7質量%
·注入量：70 μL
·流速：1 mL/min(Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn))
The polystyrene-equivalent weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were measured under the following conditions.
· Measurement method: Gel Permeation Chromatography (GPC) method · Standard material: Polystyrene conversion · Apparatus: "HLC-8220" of Tosoh Corporation
· Columns: Tosoh (TOSOH) protective column "HXL-H", "TSK gel G7000HXL", "TSK gel GMHXL" and "TSK gel G2000HXL" are connected in sequence. Solvent: tetrahydrofuran. Sample concentration: 0.7% by mass
· Injection volume: 70 μL
Flow rate: 1 mL / min

（¹ H-核磁共振（¹ H-Nuclear Magnetic Resonance，¹ H-NMR）的測定）
¹ H-NMR是使用CDCl₃ 作為溶媒並使用核磁共振裝置（布魯克（Bruker）公司的「AVANCEIII AV400N」）於溫度25℃的條件下進行測定。 ⁽¹ H- Nuclear Magnetic Resonance ^{(1 H-Nuclear Magnetic Resonance,} 1 H-NMR) ) of
¹ H-NMR was measured using CDCl ₃ as a solvent and a nuclear magnetic resonance apparatus ("AVANCEIII AV400N" from Bruker) at a temperature of 25 ° C.

[合成例1]樹脂1的合成
於具備冷卻管及攪拌機的燒瓶中，投入8質量份的2,2'-偶氮雙(2,4-二甲基戊腈)、78質量份的甲基丙烯酸硬脂酯、22質量份的甲基丙烯酸縮水甘油酯及300質量份的十四烷。於氮氣環境下，緩慢地攪拌，並且使溶液的溫度上昇至80℃，將該溫度保持6小時並進行聚合，藉此獲得含有作為共聚物的樹脂1的溶液。繼而，將所獲得的反應溶液滴加至大量過剩的甲醇/異丙醇（質量比1：1）中，藉此進行再沈澱精製。其後，進行乾燥而以78%的產率獲得白色固體狀的下述式所表示的樹脂1。再者，以下的各結構單元的比表示莫耳比（以下相同）。[Synthesis Example 1] Synthesis of Resin 1 In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 78 parts by mass of methyl were charged. Stearyl acrylate, 22 parts by mass of glycidyl methacrylate, and 300 parts by mass of tetradecane. Under a nitrogen environment, the solution was slowly stirred and the temperature of the solution was raised to 80 ° C., and the temperature was maintained for 6 hours to perform polymerization, thereby obtaining a solution containing the resin 1 as a copolymer. Then, the obtained reaction solution was added dropwise to a large excess of methanol / isopropanol (mass ratio 1: 1), thereby performing reprecipitation purification. Thereafter, drying was performed to obtain a resin 1 represented by the following formula as a white solid in a yield of 78%. In addition, the ratio of each structural unit shown below shows a molar ratio (the same applies hereinafter).

[化6]
[Chemical 6]

[合成例2]樹脂2的合成
於具備冷卻管及攪拌機的燒瓶中，投入8質量份的2,2'-偶氮雙(2,4-二甲基戊腈)、78.4質量份的甲基丙烯酸硬脂酯、16.4質量份的甲基丙烯酸縮水甘油酯、5.2質量份的(4-乙烯基苯基)甲醇及300質量份的十四烷。於氮氣環境下，緩慢地攪拌，並且使溶液的溫度上昇至80℃，將該溫度保持6小時並進行聚合，藉此獲得含有作為共聚物的樹脂2的溶液。繼而，將所獲得的反應溶液滴加至大量過剩的甲醇/異丙醇（質量比1：1）中，藉此進行再沈澱精製。其後，進行乾燥而以75%的產率獲得白色固體狀的下述式所表示的樹脂2。[Synthesis Example 2] Synthesis of Resin 2 In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 78.4 parts by mass of methyl were charged. Stearyl acrylate, 16.4 parts by mass of glycidyl methacrylate, 5.2 parts by mass of (4-vinylphenyl) methanol, and 300 parts by mass of tetradecane. Under a nitrogen atmosphere, the solution was slowly stirred and the temperature of the solution was raised to 80 ° C., and the temperature was maintained for 6 hours to perform polymerization, thereby obtaining a solution containing the resin 2 as a copolymer. Then, the obtained reaction solution was added dropwise to a large excess of methanol / isopropanol (mass ratio 1: 1), thereby performing reprecipitation purification. Thereafter, drying was performed to obtain a resin 2 represented by the following formula as a white solid in a yield of 75%.

[化7]
[Chemical 7]

[合成例3]樹脂3的合成
於具備冷卻管及攪拌機的燒瓶中，投入8質量份的2,2'-偶氮雙(2,4-二甲基戊腈)、79.9質量份的甲基丙烯酸硬脂酯、11.1質量份的甲基丙烯酸縮水甘油酯、3.4質量份的甲基丙烯酸、5.6質量份的甲基丙烯酸第三丁酯及300質量份的十四烷。於氮氣環境下，緩慢地攪拌，並且使溶液的溫度上昇至80℃，將該溫度保持6小時並進行聚合，藉此獲得含有作為共聚物的樹脂3的溶液。繼而，將所獲得的反應溶液滴加至大量過剩的甲醇/異丙醇（質量比1：1）中，藉此進行再沈澱精製。其後，進行乾燥而以80%的產率獲得白色固體狀的下述式所表示的樹脂3。[Synthesis Example 3] Synthesis of Resin 3 In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 79.9 parts by mass of methyl were charged. Stearyl acrylate, 11.1 parts by mass of glycidyl methacrylate, 3.4 parts by mass of methacrylic acid, 5.6 parts by mass of third butyl methacrylate, and 300 parts by mass of tetradecane. Under a nitrogen environment, the solution was slowly stirred, and the temperature of the solution was raised to 80 ° C., and the temperature was maintained for 6 hours to perform polymerization, thereby obtaining a solution containing the resin 3 as a copolymer. Then, the obtained reaction solution was added dropwise to a large excess of methanol / isopropanol (mass ratio 1: 1), thereby performing reprecipitation purification. Thereafter, drying was performed to obtain a resin 3 represented by the following formula as a white solid in a yield of 80%.

[化8]
[Chemical 8]

[合成例4]氟樹脂1的合成
於具備冷卻管及攪拌機的燒瓶中，投入8質量份的2,2'-偶氮雙(2,4-二甲基戊腈)、44質量份的甲基丙烯酸硬脂酯、14質量份的甲基丙烯酸縮水甘油酯、42質量份的甲基丙烯酸-2-(全氟己基)乙酯（凱米諾斯（CHEMINOX）FAMAC6尤尼馬泰克（UNIMATEC）公司製造）及300質量份的十四烷。於氮氣環境下，緩慢地攪拌，並且使溶液的溫度上昇至80℃，將該溫度保持6小時並進行聚合，藉此獲得含有作為共聚物的氟樹脂1的溶液。繼而，將所獲得的反應溶液滴加至大量過剩的甲醇/異丙醇（質量比1：1）中，藉此進行再沈澱精製。其後，進行乾燥而以75%的產率獲得白色固體狀的下述式所表示的氟樹脂1。[Synthesis Example 4] Synthesis of fluororesin 1 In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 44 parts by mass of formazan were charged. Stearyl acrylate, 14 parts by mass of glycidyl methacrylate, 42 parts by mass of 2- (perfluorohexyl) ethyl methacrylate (CHEMINOX FAMAC6 UNIMATEC) Company) and 300 parts by mass of tetradecane. Under a nitrogen atmosphere, the solution was slowly stirred and the temperature of the solution was raised to 80 ° C., and the temperature was maintained for 6 hours to perform polymerization, thereby obtaining a solution containing a fluororesin 1 as a copolymer. Then, the obtained reaction solution was added dropwise to a large excess of methanol / isopropanol (mass ratio 1: 1), thereby performing reprecipitation purification. Thereafter, drying was performed to obtain a fluororesin 1 represented by the following formula as a white solid in a yield of 75%.

[化9]
[Chemical 9]

[合成例5]氟樹脂2的合成
於具備冷卻管及攪拌機的燒瓶中，投入8質量份的2,2'-偶氮雙(2,4-二甲基戊腈)、44質量份的甲基丙烯酸硬脂酯、9.2質量份的甲基丙烯酸縮水甘油酯、42質量份的甲基丙烯酸-2-(全氟己基)乙酯（凱米諾斯（CHEMINOX）FAMAC6尤尼馬泰克（UNIMATEC）公司製造）、4.8質量份的甲基丙烯酸第三丁酯及300質量份的十四烷。於氮氣環境下，緩慢地攪拌，並且使溶液的溫度上昇至80℃，將該溫度保持6小時並進行聚合，藉此獲得含有作為共聚物的氟樹脂2的溶液。繼而，將所獲得的反應溶液滴加至大量過剩的甲醇/異丙醇（質量比1：1）中，藉此進行再沈澱精製。其後，進行乾燥而以75%的產率獲得白色固體狀的下述式所表示的氟樹脂2。[Synthesis Example 5] Synthesis of fluororesin 2 In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 44 parts by mass of formazan were charged. Stearyl acrylate, 9.2 parts by mass of glycidyl methacrylate, 42 parts by mass of 2- (perfluorohexyl) ethyl methacrylate (CHEMINOX) FAMAC6 UNIMATEC (Manufactured by the company), 4.8 parts by mass of third butyl methacrylate, and 300 parts by mass of tetradecane. Under a nitrogen environment, the solution was slowly stirred and the temperature of the solution was raised to 80 ° C., and the temperature was maintained for 6 hours to perform polymerization, thereby obtaining a solution containing a fluororesin 2 as a copolymer. Then, the obtained reaction solution was added dropwise to a large excess of methanol / isopropanol (mass ratio 1: 1), thereby performing reprecipitation purification. Thereafter, drying was performed to obtain a fluororesin 2 represented by the following formula as a white solid in a yield of 75%.

[化10]
[Chemical 10]

[合成例6]氟樹脂3
於具備冷卻管及攪拌機的燒瓶中，投入8質量份的2,2'-偶氮雙(2,4-二甲基戊腈)、44質量份的甲基丙烯酸硬脂酯、9質量份的甲基丙烯酸縮水甘油酯、42質量份的甲基丙烯酸-2-(全氟己基)乙酯（凱米諾斯（CHEMINOX）FAMAC6尤尼馬泰克（UNIMATEC）公司製造）、5質量份的(4-乙烯基苯基)甲醇及300質量份的十四烷。於氮氣環境下，緩慢地攪拌，並且使溶液的溫度上昇至80℃，將該溫度保持6小時並進行聚合，藉此獲得含有作為共聚物的氟樹脂3的溶液。繼而，將所獲得的反應溶液滴加至大量過剩的甲醇/異丙醇（質量比1：1）中，藉此進行再沈澱精製。其後，進行乾燥而以82%的產率獲得白色固體狀的下述式所表示的氟樹脂3。[Synthesis example 6] fluororesin 3
In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 44 parts by mass of stearyl methacrylate, and 9 parts by mass of Glycidyl methacrylate, 42 parts by mass of 2- (perfluorohexyl) ethyl methacrylate (CHEMINOX FAMAC6 manufactured by UNIMATEC), 5 parts by mass (4 -Vinylphenyl) methanol and 300 parts by mass of tetradecane. Under a nitrogen atmosphere, the solution was slowly stirred, and the temperature of the solution was raised to 80 ° C., and the temperature was maintained for 6 hours to perform polymerization, thereby obtaining a solution containing a fluororesin 3 as a copolymer. Then, the obtained reaction solution was added dropwise to a large excess of methanol / isopropanol (mass ratio 1: 1), thereby performing reprecipitation purification. Thereafter, drying was performed to obtain a fluororesin 3 represented by the following formula as a white solid in a yield of 82%.

[化11]
[Chemical 11]

[合成例7]氟樹脂4
於具備冷卻管及攪拌機的燒瓶中，投入8質量份的2,2'-偶氮雙(2,4-二甲基戊腈)、45質量份的甲基丙烯酸硬脂酯、9.5質量份的甲基丙烯酸縮水甘油酯、45質量份的甲基丙烯酸-2-(全氟己基)乙酯（凱米諾斯（CHEMINOX）FAMAC6尤尼馬泰克（UNIMATEC）公司製造）、3質量份的甲基丙烯酸及300質量份的十四烷。於氮氣環境下，緩慢地攪拌，並且使溶液的溫度上昇至80℃，將該溫度保持6小時並進行聚合，藉此獲得含有作為共聚物的氟樹脂4的溶液。繼而，將所獲得的反應溶液滴加至大量過剩的甲醇/異丙醇（質量比1：1）中，藉此進行再沈澱精製。其後，進行乾燥而以84%的產率獲得白色固體狀的下述式所表示的氟樹脂4。[Synthesis Example 7] Fluororesin 4
In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 45 parts by mass of stearyl methacrylate, and 9.5 parts by mass of Glycidyl methacrylate, 45 parts by mass of 2- (perfluorohexyl) ethyl methacrylate (CHEMINOX FAMAC6 manufactured by UNIMATEC), 3 parts by mass of methyl Acrylic acid and 300 parts by mass of tetradecane. Under a nitrogen environment, the solution was slowly stirred, and the temperature of the solution was raised to 80 ° C., and the temperature was maintained for 6 hours to perform polymerization, thereby obtaining a solution containing a fluororesin 4 as a copolymer. Then, the obtained reaction solution was added dropwise to a large excess of methanol / isopropanol (mass ratio 1: 1), thereby performing reprecipitation purification. Thereafter, drying was performed to obtain a fluororesin 4 represented by the following formula as a white solid in a yield of 84%.

[化12]
[Chemical 12]

以下，示出實施例及比較例中所使用的各成分。
（顏料）
×顏料1（白色顏料）：利用氧化鋁對表面進行了修飾的氧化鈦（C.I.顏料白6：1）
×顏料2（黑色顏料）：碳黑（卡博特（CABOT）公司製造的「TPK1099R」）Hereinafter, each component used in an Example and a comparative example is shown.
(pigment)
× Pigment 1 (white pigment): Titanium oxide whose surface is modified with alumina (CI Pigment White 6: 1)
× Pigment 2 (black pigment): carbon black ("TPK1099R" manufactured by CABOT)

（硬化性化合物及非硬化性化合物）
×樹脂1：合成例1中所合成的樹脂1
×樹脂2：合成例2中所合成的樹脂2
×樹脂3：合成例3中所合成的樹脂3
×樹脂4：兩末端羥基氫化聚丁二烯（日本曹達公司的「Nisso-PB GI-3000」）（再者，樹脂4為非硬化性化合物）
×化合物1：下述式（1）所表示的3-乙基-3-[(2-乙基己氧基)甲基]氧雜環丁烷（東亞合成公司的「OXT-212」）
×化合物2：下述式（2）所表示的3-乙基-3{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}氧雜環丁烷（東亞合成公司的「OXT-221」）
×化合物3：下述式（3）所表示的3-縮水甘油氧基丙基三甲氧基矽烷（信越矽酮公司的「KBM-403」）
×化合物4：下述式（4）所表示的3-(全氟己基)丙烯-1,2-氧化物（尤尼馬泰克（UNIMATEC）公司的「凱米諾斯（CHEMINOX）FAEP-6」）
×化合物5：下述式（5）所表示的三環[5.2.1.0^2,6 ]癸烷二甲醇二丙烯酸酯（新中村化學公司的「NK酯（ESTER）A-DCP」）(Hardening compound and non-hardening compound)
× Resin 1: Resin 1 synthesized in Synthesis Example 1
× Resin 2: Resin 2 synthesized in Synthesis Example 2
× Resin 3: Resin 3 synthesized in Synthesis Example 3
× Resin 4: Hydrogenated polybutadiene at both ends ("Nisso-PB GI-3000" of Japan Soda Co., Ltd.) (Further, resin 4 is a non-hardening compound)
× Compound 1: 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane represented by the following formula (1) ("OXT-212" from Toa Synthetic Corporation)
× Compound 2: 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (East Asia Synthetic Corporation's "OXT-221")
× Compound 3: 3-glycidoxypropyltrimethoxysilane represented by the following formula (3) ("KBM-403" of Shin-Etsu Silicone)
× Compound 4: 3- (perfluorohexyl) propene-1,2-oxide represented by the following formula (4) ("CHEMINOX FAEP-6" by UNIMATEC) )
× Compound 5: Tricyclic [5.2.1.0 ^2,6 ] decanedimethanol diacrylate represented by the following formula (5) ("NK ester (ESTER) A-DCP" by Shin Nakamura Chemical Co., Ltd.)

[化13]
[Chemical 13]

（溶媒）
×溶媒1：正癸烷（相對介電常數1.99）
×溶媒2：十四烷（相對介電常數2.04）
×溶媒3：丙二醇單甲醚乙酸酯（相對介電常數8）(Solvent)
× Solvent 1: n-decane (relative permittivity 1.99)
× Solvent 2: Tetradecane (relative permittivity 2.04)
× Solvent 3: Propylene glycol monomethyl ether acetate (relative dielectric constant 8)

（聚合起始劑）
×起始劑1：下述式（1）所表示的N,N-二甲基苯銨四(五氟苯基)硼酸酯
×起始劑2：下述式（2）所表示的4-羥基苯基-甲基-苄基鋶三(五氟乙基)三氟磷酸酯
×起始劑3：下述式（3）所表示的2,2'-偶氮雙(異丁酸甲酯)(Polymerization initiator)
× Starter 1: N, N-dimethylaniline tetrakis (pentafluorophenyl) borate represented by the following formula (1) × Starter 2: 4 represented by the following formula (2) -Hydroxyphenyl-methyl-benzylsulfonium tris (pentafluoroethyl) trifluorophosphate × starter 3: 2,2'-azobis (isobutyrate methyl) represented by the following formula (3) ester)

[化14]
[Chemical 14]

（氟樹脂）
×氟樹脂1：合成例4中所合成的氟樹脂1
×氟樹脂2：合成例5中所合成的氟樹脂2
×氟樹脂3：合成例6中所合成的氟樹脂3
×氟樹脂4：合成例7中所合成的氟樹脂4(Fluorine resin)
× fluororesin 1: fluororesin 1 synthesized in Synthesis Example 4
× fluororesin 2: fluororesin 2 synthesized in Synthesis Example 5
× fluororesin 3: fluororesin 3 synthesized in Synthesis Example 6
× Fluororesin 4: Fluororesin 4 synthesized in Synthesis Example 7

[製備例1]
以固體成分濃度成為62.4質量%的方式使用60質量份的顏料1、2.4質量份的作為分散劑的味之素精密技術（Ajinomoto Fine-techno）公司製造的「阿吉斯帕（Ajisper）PN411」及溶媒1，並利用珠磨機進行12小時混合×分散，從而製備顏料分散液（A-1）。顏料分散液（A-1）中的顏料1的平均粒徑為280 nm。[Preparation Example 1]
"Ajisper PN411" manufactured by Ajinomoto Fine-techno Corporation (Ajinomoto Fine-techno) as a dispersant was used so that the solid content concentration became 62.4% by mass, 60 parts by mass of pigment 1, and 2.4 parts by mass of Ajinomoto Fine-techno. And solvent 1, and mixed and dispersed in a bead mill for 12 hours to prepare a pigment dispersion liquid (A-1). The average particle diameter of the pigment 1 in the pigment dispersion liquid (A-1) was 280 nm.

[製備例2]
使用畢克化學（BYK）公司的「迪斯帕畢克（Disperbyk）-108」作為分散劑，並使用溶媒2作為溶媒，除此以外，與製備例1同樣地製備顏料分散液（A-2）。顏料分散液（A-2）中的顏料1的平均粒徑為320 nm。[Preparation Example 2]
A pigment dispersion liquid (A-2) was prepared in the same manner as in Preparation Example 1 except that "Disperbyk-108" of BYK was used as a dispersant and solvent 2 was used as a solvent. ). The average particle diameter of the pigment 1 in the pigment dispersion liquid (A-2) was 320 nm.

[製備例3]
以固體成分濃度成為65.0質量%的方式使用55質量份的顏料2、10.0質量份的作為分散劑的味之素精密技術（Ajinomoto Fine-techno）公司製造的「阿吉斯帕（Ajisper）PN411」及溶媒1，並利用珠磨機進行12小時混合×分散，從而製備顏料分散液（A-3）。顏料分散液（A-3）中的顏料2的平均粒徑為130 nm。[Preparation Example 3]
"Ajisper PN411" manufactured by Ajinomoto Fine-techno Corporation (Ajinomoto Fine-techno) as a dispersant was used so that 55 mass parts of pigment 2 and 10.0 mass parts were used as a dispersant so that the solid content concentration became 65.0 mass%. And solvent 1, and mixed and dispersed in a bead mill for 12 hours to prepare a pigment dispersion liquid (A-3). The average particle diameter of the pigment 2 in the pigment dispersion liquid (A-3) was 130 nm.

[製備例4]
使用溶媒2作為溶媒，除此以外，與製備例3同樣地製備顏料分散液（A-4）。顏料分散液（A-4）中的顏料2的平均粒徑為120 nm。[Preparation Example 4]
A pigment dispersion liquid (A-4) was prepared in the same manner as in Production Example 3, except that the solvent 2 was used as the solvent. The average particle diameter of the pigment 2 in the pigment dispersion liquid (A-4) was 120 nm.

[製備例5]
以固體成分濃度成為62.4質量%的方式使用60質量份的顏料1、2.4質量份的作為分散劑的味之素精密技術（Ajinomoto Fine-techno）公司製造的「阿吉斯帕（Ajisper）PN411」及溶媒3，並利用珠磨機進行12小時混合×分散，從而製備顏料分散液（A-5）。顏料分散液（A-5）中的顏料1的平均粒徑為260 nm。[Preparation Example 5]
"Ajisper PN411" manufactured by Ajinomoto Fine-techno Corporation (Ajinomoto Fine-techno) as a dispersant was used so that the solid content concentration became 62.4% by mass, 60 parts by mass of pigment 1, and 2.4 parts by mass of Ajinomoto Fine-techno. And solvent 3, and mixed and dispersed in a bead mill for 12 hours to prepare a pigment dispersion liquid (A-5). The average particle diameter of the pigment 1 in the pigment dispersion liquid (A-5) was 260 nm.

[實施例1]
以固體成分濃度成為65質量%的方式使用91.5質量份的顏料分散液（A-1）（包含55.0質量份的顏料1及2.1質量份的分散劑）、42.9質量份的樹脂1及溶媒1來製備硬化性組成物（S-1）。[Example 1]
91.5 parts by mass of pigment dispersion liquid (A-1) (containing 55.0 parts by mass of pigment 1 and 2.1 parts by mass of dispersant), 42.9 parts by mass of resin 1 and solvent 1 were used so that the solid content concentration became 65% by mass. A hardenable composition (S-1) was prepared.

[實施例2～實施例21及比較例1～比較例3]
如表1般變更各成分的種類及量，除此以外，與實施例1同樣地製備實施例2～實施例21的硬化性組成物（S-2）～硬化性組成物（S-21）及比較例1～比較例3的硬化性組成物（s-1）～硬化性組成物（s-3）。但是，任一硬化性組成物中，均以固體成分濃度成為65質量%的方式使用溶媒。再者，實施例1～實施例5、實施例7、實施例9～實施例15、實施例17及比較2、比較例3使用顏料分散液（A-1），實施例6、實施例8、實施例16使用顏料分散液（A-2），實施例18～實施例20使用顏料分散液（A-3），實施例21使用顏料分散液（A-4），比較例1使用顏料分散液（A-5）。另外，關於表1中的各成分的量，除溶媒以外，表示將溶媒除外的成分總量設為100質量%時的含量（質量%），關於溶媒，表示於所有溶媒中所佔的含量（質量%）。[Examples 2 to 21 and Comparative Examples 1 to 3]
Except that the types and amounts of the components were changed as in Table 1, the curable composition (S-2) to the curable composition (S-21) of Examples 2 to 21 were prepared in the same manner as in Example 1. And the curable composition (s-1) to the curable composition (s-3) of Comparative Examples 1 to 3. However, in any curable composition, a solvent was used so that solid content concentration might become 65 mass%. In addition, Example 1 to Example 5, Example 7, Example 9 to Example 15, Example 17, and Comparative 2, Comparative Example 3 used the pigment dispersion liquid (A-1), and Example 6 and Example 8 In Example 16, a pigment dispersion liquid (A-2) was used, in Examples 18 to 20, a pigment dispersion liquid (A-3) was used, in Example 21, a pigment dispersion liquid (A-4) was used, and in Comparative Example 1, a pigment dispersion was used. Fluid (A-5). In addition, the amounts of each component in Table 1 indicate the content (mass%) when the total amount of components except the solvent is 100% by mass, except for the solvent, and the content (%) of all solvents in the solvent ( quality%).

[合成例8]聚合物a（具有酸解離性基的聚合物）的合成
於具備冷卻管及攪拌機的燒瓶中，投入8質量份的二甲基-2,2'-偶氮雙(2-甲基丙酸酯)、2質量份的2,4-二苯基-4-甲基-1-戊烯及300質量份的丙二醇單甲醚乙酸酯。繼而，投入60質量份的甲基丙烯酸-4-羥基苯酯及40質量份的甲基丙烯酸甲酯，於氮氣環境下，緩慢地攪拌，並且使溶液的溫度上昇至80℃，將該溫度保持4小時並進行聚合，藉此獲得含有共聚物的溶液（固體成分濃度=26.1質量%、Mw=23000、Mw/Mn=2.6）。[Synthesis Example 8] Synthesis of polymer a (polymer having an acid dissociable group) In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of dimethyl-2,2'-azobis (2- Methyl propionate), 2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and 300 parts by mass of propylene glycol monomethyl ether acetate. Then, 60 parts by mass of 4-hydroxyphenyl methacrylate and 40 parts by mass of methyl methacrylate were added, and the solution was slowly stirred under a nitrogen atmosphere, and the temperature of the solution was raised to 80 ° C, and the temperature was maintained. Polymerization was performed for 4 hours, thereby obtaining a solution containing a copolymer (solid content concentration = 26.1% by mass, Mw = 23000, Mw / Mn = 2.6).

繼而，於所獲得的共聚物中添加190質量份的丙二醇單甲醚乙酸酯、0.4質量份的吡啶鎓-對甲苯磺酸酯及155質量份的3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟-1-乙烯基氧基辛烷，於氮氣環境下且於80℃下反應2小時。將所獲得的反應溶液滴加至大量過剩的甲醇中，藉此進行再沈澱精製。其後，進行乾燥而獲得230質量份的白色固體狀的作為共聚物的聚合物a。針對所獲得的聚合物a，使用¹ H-NMR進行分析，確認到進行了縮醛化（化學位移：5.50 ppm、縮醛基C-H）。Then, 190 parts by mass of propylene glycol monomethyl ether acetate, 0.4 parts by mass of pyridinium-p-toluenesulfonate, and 155 parts by mass of 3,3,4,4,5,5 were added to the obtained copolymer. , 6,6,7,7,8,8,8-tridecylfluoro-1-vinyloxyoctane, and reacted at 80 ° C for 2 hours under a nitrogen atmosphere. The obtained reaction solution was dropped into a large amount of excess methanol, thereby performing reprecipitation purification. Thereafter, it was dried to obtain 230 parts by mass of a polymer a as a copolymer in the form of a white solid. The obtained polymer a was analyzed by ¹ H-NMR, and it was confirmed that acetalization (chemical shift: 5.50 ppm, acetal group CH) was performed.

[製備例5]感放射線性組成物的製備
添加100質量份的所述合成例8中所獲得的聚合物a、2質量份的作為酸產生劑的PA-528（賀利氏（HERAEUS）公司）、0.1質量份的作為淬滅劑的2-苯基苯并咪唑、0.1質量份的作為界面活性劑的珀利弗洛（Polyflow）No95（共榮社化學公司），且以固體成分濃度成為30質量%的方式添加作為溶媒的丙二醇單甲醚乙酸酯。其後，利用孔徑0.5 μm的微孔過濾器進行過濾，藉此製備感放射線性組成物（P-1）。[Preparation Example 5] Preparation of a radiation-sensitive composition 100 parts by mass of the polymer a obtained in the Synthesis Example 8 and 2 parts by mass of PA-528 (HERAEUS) as an acid generator were added. ), 0.1 parts by mass of 2-phenylbenzimidazole as a quencher, and 0.1 parts by mass of Polyflow No. 95 (Kyoeisha Chemical Co., Ltd.) as a surfactant, and the solid content concentration is 30 mass% of propylene glycol monomethyl ether acetate was added as a solvent. Thereafter, filtration was performed using a microporous filter having a pore diameter of 0.5 μm, thereby preparing a radiation-sensitive composition (P-1).

[評價]
實施以下的各評價。將評價結果示於表2中。[Evaluation]
The following evaluations were performed. The evaluation results are shown in Table 2.

（模板的製成）
於9.5 cm見方的無鹼玻璃基板（康寧（Corning）公司的「益格（EAGLE）-XG」、0.7 mm厚）上，利用旋轉器以成為10 μm的膜厚的方式塗佈所述製備的感放射線性組成物（P-1）後，於90℃的加熱板上預烘烤3分鐘，藉此形成塗膜。針對所獲得的塗膜，使用高壓水銀燈以300 mJ/cm² 的曝光量介隔光罩（線&空間=50 μm/450 μm）進行放射線照射。繼而，於90℃的加熱板上進行15分鐘烘烤。其後，使基板於2.38%四氫氧化銨水溶液中浸漬2分鐘，藉此將曝光部去除。其後，於90℃的加熱板上乾燥烘烤15分鐘。藉此獲得形成於基板上的包含凸部的撥液性的模板（T-1）。所殘留的膜上的水的接觸角為109°，十四烷的接觸角為60°，充分確認到撥液性。(Made of template)
The prepared 9.5 cm square alkali-free glass substrate ("EAGLE-XG" by Corning, 0.7 mm thick) was coated with a spinner so as to have a film thickness of 10 μm. After the radiation-sensitive composition (P-1), a coating film was formed by pre-baking for 3 minutes on a hot plate at 90 ° C. The obtained coating film was irradiated with radiation using a high-pressure mercury lamp at a light exposure of 300 mJ / cm ² through a light barrier (line & space = 50 μm / 450 μm). Then, it baked on the hot plate at 90 degreeC for 15 minutes. Thereafter, the exposed portion was removed by immersing the substrate in a 2.38% ammonium tetrahydroxide aqueous solution for 2 minutes. Thereafter, it was baked on a hot plate at 90 ° C for 15 minutes. Thereby, a liquid-repellent template (T-1) including a convex portion formed on the substrate was obtained. The contact angle of water on the remaining film was 109 °, and the contact angle of tetradecane was 60 °, and liquid repellency was fully confirmed.

（經圖案化的硬化膜的製成）
於使用感放射線性組成物（P-1）而獲得的模板（T-1）上注射塗佈實施例及比較例中所獲得的各硬化性組成物，結果硬化性組成物不殘留於模板（T-1）的凸部上而選擇性被塗佈於凸部間上。於70℃下加熱2分鐘而將一部分溶媒去除後，於130℃下加熱30分鐘而使硬化性組成物的塗膜硬化。其後，使用高壓水銀燈以500 mJ/cm² 的曝光量進行放射線照射。繼而，於70℃的加熱板上進行15分鐘烘烤。其後，使基板於2.38%四氫氧化銨水溶液中浸漬4分鐘，藉此將模板（T-1）去除，從而獲得經圖案化的硬化膜（圖案）。所獲得的圖案寬度為50 μm，形成了與模板寬度相適合的圖案。但是，比較例1由於產生模板的侵蝕等，因此無法實現選擇性塗佈於凸部間，從而無法形成圖案。另外，比較例2的密接性顯著差，無法形成圖案。(Made of patterned hardened film)
Each of the hardening compositions obtained in the examples and comparative examples was injection-coated on the template (T-1) obtained using the radiation-sensitive composition (P-1), and as a result, the hardening composition did not remain on the template ( T-1) is selectively applied to the convex portions. After heating at 70 ° C for 2 minutes to remove a part of the solvent, it was heated at 130 ° C for 30 minutes to harden the coating film of the curable composition. Thereafter, radiation was performed using a high-pressure mercury lamp at an exposure amount of 500 mJ / cm ² . Then, baking was performed on a hot plate at 70 ° C for 15 minutes. Thereafter, the substrate was immersed in a 2.38% ammonium tetrahydroxide aqueous solution for 4 minutes, thereby removing the template (T-1), thereby obtaining a patterned cured film (pattern). The obtained pattern width was 50 μm, and a pattern suitable for the template width was formed. However, Comparative Example 1 was unable to achieve selective coating between the convex portions due to the occurrence of erosion or the like of the template, and the pattern could not be formed. In addition, the adhesion of Comparative Example 2 was significantly poor, and a pattern could not be formed.

（塗佈性的評價）
關於在所述模板（T-1）上注射塗佈硬化性組成物時的塗佈性，就模板的侵蝕與於凸部間的潤濕擴展的觀點而言，以如下基準進行評價。
AA：模板未被硬化性組成物侵蝕，自塗佈起經過5秒後的硬化性組成物於凸部間的潤濕擴展為5 mm以上
A：雖不存在模板的侵蝕，但自塗佈起經過5秒後的硬化性組成物於凸部間的潤濕擴展未滿5 mm
C：模板被硬化性組成物侵蝕(Evaluation of coating properties)
The applicability when the hardenable composition was injection-coated on the template (T-1) was evaluated from the viewpoints of erosion of the template and spread of wetting between the convex portions on the following criteria.
AA: The template is not corroded by the hardening composition, and the wetting spread of the hardening composition between the protrusions after 5 seconds from the application is 5 mm or more
A: Although there is no erosion of the template, the wetting spread of the hardening composition between the convex parts after 5 seconds has elapsed is less than 5 mm.
C: The template is eroded by the hardening composition

（圖案化性的評價）
針對所獲得的硬化膜，利用掃描式電子顯微鏡（Scanning Electron Microscope，SEM）來確認裂紋（膜內部的龜裂或斷裂線）的有無及密接性（膜底部是否遠離基板面或不發生上浮地接地），並以如下基準進行評價。
AA：無裂紋且密接性亦良好
A：雖可確認到裂紋，但密接性良好
B：可確認到裂紋，且存在一部分密接性不良的部位
C：由於無法獲得經圖案化的硬化膜，因此無法實施SEM觀察(Evaluation of patternability)
Scanning electron microscope (Scanning Electron Microscope, SEM) was used to confirm the presence or absence of cracks (cracks or fracture lines inside the film) and adhesion (whether the bottom of the film is far away from the substrate surface or there is no floating grounding) ) And evaluated based on the following criteria.
AA: No cracks and good adhesion
A: Although cracks can be confirmed, the adhesion is good
B: Cracks can be confirmed, and there are some parts with poor adhesion.
C: SEM observation cannot be performed because a patterned cured film cannot be obtained

（硬化膜的製成）
使用旋塗機將實施例及比較例中所獲得的各硬化性組成物塗佈於9.5 cm見方的無鹼玻璃基板（康寧（Corning）公司的「益格（EAGLE）-XG」、0.7 mm厚）上。其後，利用加熱板於70℃下歷時2分鐘將一部分溶媒去除。繼而，於130℃下歷時30分鐘使硬化性組成物硬化，從而形成膜厚10 μm的硬化膜。(Made of hardened film)
Using a spin coater, each hardenable composition obtained in the examples and comparative examples was applied to a 9.5 cm square alkali-free glass substrate ("EAGLE-XG" from Corning, 0.7 mm thick )on. Thereafter, a part of the solvent was removed using a hot plate at 70 ° C. for 2 minutes. Then, the curable composition was cured at 130 ° C. for 30 minutes to form a cured film having a film thickness of 10 μm.

（遮光性的評價）
於使用白色顏料的實施例1～實施例17及比較例1～比較例3中，進行評價1（反射率），於使用黑色顏料的實施例18～實施例21中，進行評價2（OD值）。(Evaluation of light-shielding properties)
Evaluation 1 (reflectance) was performed in Examples 1 to 17 and Comparative Examples 1 to 3 using a white pigment, and Evaluation 2 (OD value) was performed in Examples 18 to 21 using a black pigment. ).

（遮光性的評價1：反射率）
使用紫外可見紅外絕對反射率測定裝置一式（分光光度計V-670、反射率測定單元ARN-731、均為日本分光公司製造）對所述形成的硬化膜的反射光進行測定。以由標準反射板（海洋光子學（Ocean photonics）公司的「斯百科陶拉龍（Spectralon）」（註冊商標））而得的相對反射率進行數值化。將波長700 nm的光下的標準反射板的反射光設為100%，以如下基準進行評價。
AA：75%以上
A：70%以上、未滿75%
C：未滿70%(Evaluation of light-shielding property 1: reflectance)
The reflected light of the formed cured film was measured using an ultraviolet-visible-infrared absolute reflectance measuring apparatus (spectrophotometer V-670, reflectance measuring unit ARN-731, all manufactured by Japan Spectroscopy Corporation). The relative reflectance obtained from a standard reflection plate ("Spectralon" (registered trademark) of Ocean photonics) was quantified. The reflected light of a standard reflection plate under light with a wavelength of 700 nm was set to 100%, and evaluated according to the following criteria.
AA: 75% or more
A: Above 70% and below 75%
C: less than 70%

（遮光性的評價2：OD值）
使用X-Rite公司的361T（V）透過濃度計（照明光源的色溫度：約2850 K（相當於CIE標準光源A）、光接收部的分光感度特性：ISO 5-3標準的ISO視覺密度（visual density）），對透過硬化膜的光於可見光區域的光密度（OD值）進行測定，進行膜厚換算而求出OD值（/μm），並以如下基準進行評價。
AA：每1 μm的OD值為4以上
A：每1 μm的OD值為3.5以上、未滿4
C：每1 μm的OD值未滿3.5(Evaluation of light-shielding property 2: OD value)
Using X-Rite's 361T (V) transmission densitometer (color temperature of illumination light source: about 2850 K (equivalent to CIE standard light source A)), spectral sensitivity characteristics of the light receiving section: ISO visual density according to ISO 5-3 ( visual density)), the optical density (OD value) of the light transmitted through the cured film in the visible light region was measured, and the OD value (/ μm) was calculated by converting the film thickness, and evaluated based on the following criteria.
AA: OD value of 4 or more per 1 μm
A: The OD value per 1 μm is 3.5 or more and less than 4
C: OD value is less than 3.5 per 1 μm

（撥液性的評價）
使用自動接觸角計（協和界面科學公司的「DM-501Hi」），於23℃、55%RH的環境下，將2.5 μL的丙二醇單甲醚乙酸酯滴加至所述形成的硬化膜上，以θ/2法來算出接觸角。以如下的基準來評價撥液性。
AA：50°以上
A：40°以上、未滿50°
B：未滿40°(Evaluation of liquid repellency)
Using an automatic contact angle meter ("DM-501Hi" of Kyowa Interface Science Co., Ltd.), 2.5 μL of propylene glycol monomethyl ether acetate was added dropwise to the formed hardened film at 23 ° C and 55% RH. Calculate the contact angle using the θ / 2 method. The liquid repellency was evaluated based on the following criteria.
AA: above 50 °
A: Above 40 ° and below 50 °
B: less than 40 °

[表1]

[Table 1]

[表2]

[Table 2]

如表2所示，實施例1～實施例21的各硬化性組成物的塗佈性及圖案化性優異且所獲得的硬化膜的遮光性亦良好。進而，得知：由包含氟樹脂的實施例13～實施例17的各硬化性組成物所獲得的硬化膜的撥液性亦優異。
[產業上的可利用性]As shown in Table 2, each of the curable compositions of Examples 1 to 21 was excellent in coatability and patterning property, and the light-shielding property of the obtained cured film was also good. Furthermore, it turned out that the cured film obtained from each curable composition of Examples 13 to 17 containing a fluororesin is also excellent in liquid repellency.
[Industrial availability]

本發明的硬化性組成物可較佳地用作顯示元件或固體攝像元件的硬化膜形成材料。The curable composition of the present invention can be preferably used as a cured film forming material for a display element or a solid-state imaging element.

10‧‧‧基板10‧‧‧ substrate

11‧‧‧模板用塗膜 11‧‧‧ Coating film

12‧‧‧包含親液性表面的層 12‧‧‧ Layer containing lyophilic surface

13‧‧‧包含撥液性表面的層 13‧‧‧ Layer containing liquid-repellent surface

14‧‧‧凸部 14‧‧‧ convex

15‧‧‧模板 15‧‧‧Template

16‧‧‧塗膜 16‧‧‧ Coating

17‧‧‧硬化膜 17‧‧‧hardened film

hν‧‧‧放射線 hν‧‧‧Radiation

101‧‧‧微LED顯示器 101‧‧‧Micro LED display

102‧‧‧B-LED 102‧‧‧B-LED

103a、103b‧‧‧波長變換層 103a, 103b‧‧‧ wavelength conversion layer

104‧‧‧隔離壁 104‧‧‧ wall

105‧‧‧TFT基板 105‧‧‧TFT substrate

106‧‧‧透明基板 106‧‧‧ transparent substrate

圖1是用以對微LED顯示器的結構的一例進行說明的示意說明圖。FIG. 1 is a schematic explanatory diagram for explaining an example of a structure of a micro LED display.

圖2（a）、圖2（b）、圖2（c）及圖2（d）是本發明的一實施形態中的硬化膜的形成方法的第1說明圖。 2 (a), 2 (b), 2 (c), and 2 (d) are first explanatory diagrams of a method for forming a cured film according to an embodiment of the present invention.

圖3（a）、圖3（b）及圖3（c）是本發明的一實施形態中的硬化膜的形成方法的第2說明圖。 3 (a), 3 (b), and 3 (c) are second explanatory diagrams of a method for forming a cured film according to an embodiment of the present invention.

Claims

一種硬化膜的形成方法，其包括：（1）於基板上形成具有凸部的模板的步驟；（2）藉由硬化性組成物而於所述模板的凸部間形成塗膜的步驟；以及（3）使所述塗膜硬化的步驟，並且所述硬化性組成物包含白色顏料、黑色顏料或該些的組合的顏料；硬化性化合物；及溶媒，且所述顏料相對於所述溶媒除外的所有成分的含量為50質量%以上、90質量%以下，所述溶媒的相對介電常數為6.0以下。A method for forming a hardened film includes: (1) a step of forming a template having a convex portion on a substrate; (2) a step of forming a coating film between the convex portions of the template with a curable composition; and (3) a step of hardening the coating film, and The curable composition includes a white pigment, a black pigment, or a combination of these pigments; a curable compound; and a solvent, and The content of the pigment relative to all components except the solvent is 50% by mass or more and 90% by mass or less, The relative dielectric constant of the solvent is 6.0 or less.

如申請專利範圍第1項所述的硬化膜的形成方法，其進而包括（4）將所述模板的凸部去除的步驟。The method for forming a cured film according to item 1 of the patent application scope, further comprising (4) a step of removing the convex portion of the template.

如申請專利範圍第1項或第2項所述的硬化膜的形成方法，其中，藉由利用噴墨法來塗佈所述硬化性組成物而進行所述塗膜的形成。The method for forming a cured film according to claim 1 or 2, wherein the coating film is formed by applying the curable composition by an inkjet method.

如申請專利範圍第1項、第2項或第3項所述的硬化膜的形成方法，其中，所述硬化膜為顯示元件或固體攝像元件的硬化膜。The method for forming a cured film according to claim 1, 2, or 3, wherein the cured film is a cured film of a display element or a solid-state imaging element.

如申請專利範圍第4項所述的硬化膜的形成方法，其中，所述顯示元件或固體攝像元件的硬化膜為隔離壁。The method for forming a cured film according to item 4 of the scope of patent application, wherein the cured film of the display element or the solid-state imaging element is a partition wall.

如申請專利範圍第1項至第5項中任一項所述的硬化膜的形成方法，其中，所述硬化性化合物為含有具有碳數8以上、30以下的烴基的結構單元的樹脂。The method for forming a cured film according to any one of claims 1 to 5, wherein the curable compound is a resin containing a structural unit having a hydrocarbon group of 8 to 30 carbon atoms.

如申請專利範圍第1項至第6項中任一項所述的硬化膜的形成方法，其中，所述硬化性化合物具有氧雜環丙基、氧雜環丁基或該些的組合。The method for forming a cured film according to any one of claims 1 to 6, wherein the curable compound has an oxetanyl group, an oxetanyl group, or a combination thereof.

如申請專利範圍第1項至第7項中任一項所述的硬化膜的形成方法，其中，所述硬化性組成物進而包含熱酸產生劑、熱自由基產生劑或該些的組合的聚合起始劑。The method for forming a cured film according to any one of claims 1 to 7, wherein the curable composition further comprises a thermal acid generator, a thermal radical generator, or a combination of these. Polymerization initiator.

如申請專利範圍第1項至第8項中任一項所述的硬化膜的形成方法，其中，所述硬化性組成物進而包含氟樹脂，所述氟樹脂包含具有含有氟的基的結構單元。The method for forming a cured film according to any one of claims 1 to 8, wherein the curable composition further includes a fluororesin, and the fluororesin includes a structural unit having a fluorine-containing group .

如申請專利範圍第9項所述的硬化膜的形成方法，其中，所述氟樹脂含有具有碳數8以上、30以下的烴基的結構單元。The method for forming a cured film according to item 9 of the patent application scope, wherein the fluororesin contains a structural unit having a hydrocarbon group having 8 or more and 30 or less carbon atoms.

如申請專利範圍第1項至第10項中任一項所述的硬化膜的形成方法，其中，所述溶媒為碳數5以上、20以下的脂肪族烴。The method for forming a cured film according to any one of claims 1 to 10, wherein the solvent is an aliphatic hydrocarbon having 5 or more and 20 or less carbon atoms.

一種硬化性組成物，其包含：白色顏料、黑色顏料或該些的組合的顏料；硬化性化合物；及溶媒，且所述顏料相對於所述溶媒除外的所有成分的含量為50質量%以上、90質量%以下，所述溶媒的相對介電常數為6.0以下。A hardening composition comprising: White pigment, black pigment or a combination of these pigments; Hardening compounds; and Solvent, and The content of the pigment relative to all components except the solvent is 50% by mass or more and 90% by mass or less, The relative dielectric constant of the solvent is 6.0 or less.

如申請專利範圍第12項所述的硬化性組成物，其中，所述硬化性化合物為含有具有碳數8以上、30以下的烴基的結構單元的樹脂。The curable composition according to claim 12 in the application scope, wherein the curable compound is a resin containing a structural unit having a hydrocarbon group having 8 or more and 30 or less carbon atoms.

如申請專利範圍第12項或第13項所述的硬化性組成物，其中，所述硬化性化合物具有氧雜環丙基、氧雜環丁基或該些的組合。The hardenable composition according to claim 12 or 13, wherein the hardenable compound has an oxetanyl group, an oxetanyl group, or a combination thereof.

如申請專利範圍第12項、第13項或第14項所述的硬化性組成物，其進而包含熱酸產生劑、熱自由基產生劑或該些的組合的聚合起始劑。The hardenable composition according to claim 12, 13, or 14, which further comprises A thermal acid generator, a thermal radical generator, or a combination of these as a polymerization initiator.

如申請專利範圍第12項至第15項中任一項所述的硬化性組成物，其進而包含氟樹脂，所述氟樹脂包含具有含有氟的基的結構單元。The curable composition according to any one of claims 12 to 15 of the scope of patent application, further comprising a fluororesin, The fluororesin includes a structural unit having a fluorine-containing group.

如申請專利範圍第16項所述的硬化性組成物，其中，所述氟樹脂含有具有碳數8以上、30以下的烴基的結構單元。The curable composition according to claim 16 in the patent application scope, wherein the fluororesin contains a structural unit having a hydrocarbon group having 8 or more and 30 or less carbon atoms.

如申請專利範圍第12項至第17項中任一項所述的硬化性組成物，其中，所述溶媒為碳數5以上、20以下的脂肪族烴。The hardenable composition according to any one of claims 12 to 17, in which the solvent is an aliphatic hydrocarbon having 5 or more and 20 or less carbon atoms.

如申請專利範圍第12項至第18項中任一項所述的硬化性組成物，其用於形成顯示元件或固體攝像元件的硬化膜。The curable composition according to any one of claims 12 to 18, which is used to form a cured film of a display element or a solid-state imaging element.

如申請專利範圍第19項所述的硬化性組成物，其中，所述硬化膜為隔離壁。The hardenable composition according to claim 19, wherein the hardened film is a partition wall.