TWI751196B - Metal-containing nitride particles, dispersed composition, curable composition, cured film and their manufacturing method, color filter, solid-state imaging element, solid-state imaging device, infrared sensor - Google Patents

Metal-containing nitride particles, dispersed composition, curable composition, cured film and their manufacturing method, color filter, solid-state imaging element, solid-state imaging device, infrared sensor Download PDF

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TWI751196B
TWI751196B TW106131597A TW106131597A TWI751196B TW I751196 B TWI751196 B TW I751196B TW 106131597 A TW106131597 A TW 106131597A TW 106131597 A TW106131597 A TW 106131597A TW I751196 B TWI751196 B TW I751196B
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atom
containing nitride
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TW201815682A (en
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浜田大輔
久保田誠
田口貴規
坂本裕貴
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日商富士軟片股份有限公司
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Abstract

本發明提供一種含金屬氮化物粒子，其能夠用於具有優異之防沉降性及優異之經時穩定性且可得到具有優異之遮光性之硬化膜之硬化性組成物。含金屬氮化物粒子含有3~11族的過渡金屬的氮化物，平均一次粒徑為200nm以下，含有氮原子和原子T，原子T不是氧原子、氯原子及氮原子中的任意一者，並選自13~17族元素，當將藉由X射線光電子光譜分析檢測之原子T的質量基準的含量設為TE，並將藉由X射線螢光分析檢測之原子T的質量基準的含量設為TX時，滿足TE/TX<2.0。 The present invention provides a metal-containing nitride particle which can be used for a curable composition which has excellent anti-settling properties and excellent stability over time and can obtain a cured film having excellent light-shielding properties. The metal-containing nitride particles contain nitrides of transition metals of Groups 3 to 11, have an average primary particle diameter of 200 nm or less, contain nitrogen atoms and atomic T, and atomic T is not any one of oxygen atoms, chlorine atoms and nitrogen atoms, and is selected from group 13 to 17 element, when the content by mass of a reference atom detecting X-ray photoelectron spectroscopy is defined as T T E, and the content by mass of a reference atom T analysis and detection of the fluorescent X-ray is provided When it is T X , T E /T X <2.0 is satisfied.

Description

含金屬氮化物粒子、分散組成物、硬化性組成物、硬化膜及它們的製造方法以及彩色濾光片、固體攝影元件、固體攝像裝置、紅外線感測器Metal-containing nitride particles, dispersion composition, curable composition, cured film, and method for producing the same, color filter, solid-state imaging element, solid-state imaging device, and infrared sensor

本發明是有關一種含金屬氮化物粒子、分散組成物、硬化性組成物、硬化膜、彩色濾光片、固體攝影元件、固體攝像裝置、紅外線感測器、含金屬氮化物粒子的製造方法、分散組成物的製造方法、硬化性組成物的製造方法及硬化膜的製造方法。The present invention relates to a metal-containing nitride particle, a dispersion composition, a curable composition, a cured film, a color filter, a solid-state imaging element, a solid-state imaging device, an infrared sensor, and a method for producing metal-containing nitride particles, The manufacturing method of a dispersion composition, the manufacturing method of a curable composition, and the manufacturing method of a cured film.

一直以來，作為用於製造具有遮光性之硬化膜（以下，亦稱為「遮光膜」。）之組成物中所含有之粒子，已知有含金屬氮化物粒子。含金屬氮化物粒子用於各種用途，尤其含有含金屬氮化物粒子之組成物例如用於製作圖像顯示裝置（例如，液晶顯示裝置及有機EL（electro luminescence：電致發光）裝置等）及固體攝像裝置等所具備之遮光膜。 具體而言，圖像顯示裝置等所具備之彩色濾光片以遮蔽著色像素之間的光並提高對比度（contrast）等為目的而具備被稱作黑矩陣（black matrix）之遮光膜。 又，固體攝影元件以防止噪聲發生及提高畫質等為目的而具備遮光膜。當前，行動電話及PDA（Personal Digital Assistant：個人數位助理）等電子設備的行動終端中搭載有小型且薄型的固體攝像裝置。該種固體攝像裝置一般具備CCD（Charge Coupled Device：電荷耦合元件）影像感測器及CMOS（Complementary Metal-Oxide Semiconductor：互補金屬氧化物半導體）影像感測器等固體攝影元件和用於在固體攝影元件上形成被攝體像之透鏡。Conventionally, metal-containing nitride particles are known as particles contained in a composition for producing a light-shielding cured film (hereinafter, also referred to as a "light-shielding film"). Metal-containing nitride particles are used for various purposes, especially compositions containing metal-containing nitride particles are used for the production of image display devices (eg, liquid crystal display devices and organic EL (electro luminescence: electroluminescence) devices, etc.) and solid A light-shielding film for imaging devices, etc. Specifically, a color filter included in an image display device or the like includes a light-shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast. In addition, the solid-state imaging element includes a light-shielding film for the purpose of preventing noise generation, improving image quality, and the like. Currently, a small and thin solid-state imaging device is mounted in a mobile terminal of an electronic device such as a mobile phone and a PDA (Personal Digital Assistant). This type of solid-state imaging device generally includes a solid-state imaging element such as a CCD (Charge Coupled Device: Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor: Complementary Metal-Oxide Semiconductor) image sensor, and is used for solid-state imaging. The lens that forms the subject image on the element.

作為用於製造如上所述之硬化膜之組成物中所含有之粒子，例如專利文獻1中記載有鈦氮化物粒子與鈦碳化物粒子的質量組成比在80/20～20/80的範圍之遮光材料。 [先前技術文獻] [專利文獻]As particles contained in the composition for producing the above cured film, for example, Patent Document 1 describes that the mass composition ratio of titanium nitride particles to titanium carbide particles is within the range of 80/20 to 20/80 Shading material. [Prior Art Literature] [Patent Literature]

[專利文獻1]：日本特開2010-95716號公報[Patent Document 1]: Japanese Patent Laid-Open No. 2010-95716

本發明人等對專利文獻1中所記載之含有遮光材料之組成物進行了研究，其結果得到了所得到之硬化膜的遮光性以及組成物的防沉降性及經時穩定性未達到最近所要求之水準之見解。 另外，本說明書中，遮光性、防沉降性及經時穩定性是指藉由實施例中所記載之方法測定之遮光性、防沉降性及經時穩定性。The inventors of the present invention studied the composition containing the light-shielding material described in Patent Document 1, and as a result found that the light-shielding properties of the obtained cured film, the anti-settling properties and the stability over time of the composition were not as high as those achieved recently. Insights on the required level. In addition, in this specification, the light-shielding property, the anti-settling property, and the stability over time refer to the light-shielding property, the anti-settling property, and the stability over time measured by the methods described in the examples.

因此，本發明的課題在於提供一種能夠用於具有優異之防沉降性及優異之經時穩定性且可得到具有優異之遮光性之硬化膜之硬化性組成物之（以下，亦稱為「具有本發明的效果」。）含金屬氮化物粒子。 本發明的課題還在於提供一種分散組成物、硬化性組成物、硬化膜、彩色濾光片、固體攝影元件、固體攝像裝置、紅外線感測器、含金屬氮化物粒子的製造方法、分散組成物的製造方法、硬化性組成物的製造方法及硬化膜的製造方法。Therefore, the subject of the present invention is to provide a curable composition which can be used for a cured film having excellent anti-settling properties and excellent temporal stability and can obtain a cured film having excellent light-shielding properties (hereinafter, also referred to as "with Effects of the present invention".) containing metal nitride particles. Another object of the present invention is to provide a dispersion composition, a curable composition, a cured film, a color filter, a solid-state imaging element, a solid-state imaging device, an infrared sensor, a method for producing metal-containing nitride particles, and a dispersion composition The manufacturing method, the manufacturing method of a curable composition, and the manufacturing method of a cured film.

本發明人等為了達成上述課題而進行了深入研究，其結果發現，藉由以下的構成能夠達成上述課題。The inventors of the present invention have conducted intensive studies in order to achieve the above-mentioned problems, and as a result, found that the above-mentioned problems can be achieved by the following configurations.

[1]一種含金屬氮化物粒子，其含有3～11族的過渡金屬的氮化物，該含金屬氮化物粒子的平均一次粒徑為200nm以下，含有氮原子和原子T，原子T不是氧原子、氯原子及氮原子中的任意一者，並選自13～17族元素，當將藉由X射線光電子光譜分析檢測之含金屬氮化物粒子的表面上之原子T的質量基準的含量設為TE （質量%），並將藉由X射線螢光分析檢測之含金屬氮化物粒子中之原子T的質量基準的含量設為TX （質量%）時，滿足TE /TX ＜2.0所表示之關係。 [2]如[1]所述之含金屬氮化物粒子，其進一步含有氧原子。 [3]如[2]所述之含金屬氮化物粒子，其中氮原子的含量相對於氮化物所含有之過渡金屬原子的含量之含有原子數比X、氧原子的含量相對於氮化物所含有之過渡金屬原子的含量之含有原子數比Y及原子T的含量相對於氮化物所含有之過渡金屬原子的含量之含有原子數比Z分別超過0且小於2。 [4]如[3]所述之含金屬氮化物粒子，其中X、Y及Z之和超過0.4且小於1.6。 [5]如[1]至[4]中任一項所述之含金屬氮化物粒子，其中當由ε=ε’+ε”j表示在波長400～1200nm下之含金屬氮化物粒子的複介電常數ε時，ε’的最小值小於0。ε’表示複介電常數ε的實數部，ε”表示複介電常數ε的虛數部，j表示虛數單位。 [6]如[1]至[5]中任一項所述之含金屬氮化物粒子，其中原子T選自第2～6週期的元素中的鋁、鎵、銦、錫、鉈、鉛及鉍以外的元素。 [7]如[6]所述之含金屬氮化物粒子，其中原子T選自13～16族元素。 [8]如[1]至[7]中任一項所述之含金屬氮化物粒子，其中原子T是選自包括硼原子、碳原子、硫原子及磷原子之組群中之任意一種原子。 [9]如[1]至[8]中任一項所述之含金屬氮化物粒子，其中原子T是選自包括硼原子、硫原子及磷原子之組群中之任意一種原子。 [10]一種分散組成物，其含有[1]至[9]中任一項所述之含金屬氮化物粒子和樹脂。 [11]一種硬化性組成物，其含有[10]所述之分散組成物、聚合性化合物及聚合起始劑。 [12]一種硬化性組成物，其含有[1]至[9]中任一項所述之含金屬氮化物粒子、樹脂、聚合性化合物及聚合起始劑。 [13]如[11]或[12]所述之硬化性組成物，其進一步含有溶劑。 [14]一種硬化膜，其是將[11]至[13]中任一項所述之硬化性組成物進行硬化而得到。 [15]一種彩色濾光片，其含有[14]所述之硬化膜。 [16]一種固體攝影元件，其含有[14]所述之硬化膜。 [17]一種固體攝像裝置，其含有[14]所述之硬化膜。 [18]一種紅外線感測器，其含有[14]所述之硬化膜。 [19]一種含金屬氮化物粒子的製造方法，其是[1]至[9]中任一項所述之含金屬氮化物粒子的製造方法，包含以下製程：原材料準備製程，準備含有氮原子之原材料A及含有過渡金屬原子及原子T之原材料B、或者準備含有氮原子之原材料A、含有過渡金屬原子之原材料C及含有原子T之原材料D；將2種以上的原材料以氣相狀態進行混合而得到混合物之製程；及使氣相狀態的混合物凝縮而得到含金屬氮化物粒子之製程。 [20]一種分散組成物的製造方法，其是[10]所述之分散組成物的製造方法，包含以下製程：原材料準備製程，準備含有氮原子之原材料A及含有過渡金屬原子及原子T之原材料B、或者準備含有氮原子之原材料A、含有過渡金屬原子之原材料C及含有原子T之原材料D；將2種以上的原材料以氣相狀態進行混合而得到混合物之製程；使氣相狀態的混合物凝縮而得到含金屬氮化物粒子之製程；及混合含金屬氮化物粒子及樹脂而得到分散組成物之製程。 [21]一種硬化性組成物的製造方法，其是含有分散組成物、聚合性化合物及聚合起始劑之硬化性組成物的製造方法，包含[20]所述之分散組成物的製造方法。 [22]一種硬化膜的製造方法，其包含以下製程：硬化性組成物層形成製程，使用[11]至[13]中任一項所述之硬化性組成物而形成硬化性組成物層；曝光製程，經由具備圖案狀的開口部之光罩，向硬化性組成物層照射光化射線或放射線而進行曝光；及顯影製程，對曝光後的硬化性組成物層進行顯影而形成硬化膜。 [發明效果][1] A metal-containing nitride particle containing a nitride of a transition metal of Groups 3 to 11, the metal-containing nitride particle having an average primary particle diameter of 200 nm or less, and containing nitrogen atoms and atoms T, and the atoms T are not oxygen atoms , any one of chlorine atoms and nitrogen atoms, and selected from the elements of Groups 13 to 17, when the content of the atomic T on the surface of the metal-containing nitride particles detected by X-ray photoelectron spectroscopy analysis is based on the mass basis of content as T E (% by mass), and the content by mass of a reference metal-detecting fluorescent X-ray analysis of the nitride particles is defined as the atoms T T X (mass%), satisfies T E / T X <2.0 the relationship represented. [2] The metal-containing nitride particle according to [1], which further contains an oxygen atom. [3] The metal-containing nitride particles according to [2], wherein the content of nitrogen atoms relative to the content of transition metal atoms contained in the nitride has an atomic ratio X, and the content of oxygen atoms relative to that contained in the nitride The atomic ratio Y of the content of the transition metal atoms and the atomic ratio Z of the content of the atoms T to the content of the transition metal atoms contained in the nitride are more than 0 and less than 2, respectively. [4] The metal-containing nitride particles according to [3], wherein the sum of X, Y, and Z exceeds 0.4 and is less than 1.6. [5] The metal-containing nitride particle according to any one of [1] to [4], wherein the composite of the metal-containing nitride particle at a wavelength of 400 to 1200 nm is represented by ε=ε′+ε”j When the permittivity is ε, the minimum value of ε' is less than 0. ε' represents the real part of the complex permittivity ε, ε" represents the imaginary part of the complex permittivity ε, and j represents the imaginary unit. [6] The metal-containing nitride particle according to any one of [1] to [5], wherein the atom T is selected from the group consisting of aluminum, gallium, indium, tin, thallium, lead and Elements other than bismuth. [7] The metal-containing nitride particle according to [6], wherein the atom T is selected from elements of Groups 13 to 16. [8] The metal-containing nitride particle according to any one of [1] to [7], wherein the atom T is any one atom selected from the group consisting of a boron atom, a carbon atom, a sulfur atom and a phosphorus atom . [9] The metal-containing nitride particle according to any one of [1] to [8], wherein the atom T is any one atom selected from the group consisting of a boron atom, a sulfur atom, and a phosphorus atom. [10] A dispersion composition comprising the metal nitride-containing particles according to any one of [1] to [9] and a resin. [11] A curable composition comprising the dispersion composition described in [10], a polymerizable compound, and a polymerization initiator. [12] A curable composition comprising the metal-containing nitride particles according to any one of [1] to [9], a resin, a polymerizable compound, and a polymerization initiator. [13] The curable composition according to [11] or [12], which further contains a solvent. [14] A cured film obtained by curing the curable composition according to any one of [11] to [13]. [15] A color filter comprising the cured film described in [14]. [16] A solid-state imaging element comprising the cured film described in [14]. [17] A solid-state imaging device comprising the cured film described in [14]. [18] An infrared sensor comprising the cured film described in [14]. [19] A method for producing metal-containing nitride particles, which is the method for producing metal-containing nitride particles according to any one of [1] to [9], comprising the following process: a raw material preparation process, preparing a nitrogen atom-containing particle Raw material A and raw material B containing transition metal atom and atom T, or prepare raw material A containing nitrogen atom, raw material C containing transition metal atom and raw material D containing atom T; A process of mixing to obtain a mixture; and a process of condensing the mixture in the gas phase to obtain metal-containing nitride particles. [20] A method for producing a dispersed composition, which is the method for producing a dispersed composition described in [10], comprising the following process: a raw material preparation process, preparing a raw material A containing nitrogen atoms and a raw material A containing transition metal atoms and atoms T Raw material B, or preparing raw material A containing nitrogen atom, raw material C containing transition metal atom, and raw material D containing atom T; the process of mixing two or more kinds of raw materials in gas phase to obtain a mixture; The process of condensing the mixture to obtain metal-containing nitride particles; and the process of mixing the metal-containing nitride particles and resin to obtain a dispersion composition. [21] A method for producing a curable composition comprising a dispersion composition, a polymerizable compound, and a polymerization initiator, comprising the method for producing the dispersion composition described in [20]. [22] A method for producing a cured film, comprising the following process: a process for forming a curable composition layer, and a curable composition layer is formed using the curable composition described in any one of [11] to [13]; In the exposure process, the curable composition layer is irradiated with actinic rays or radiation through a mask with a patterned opening to expose; and in the development process, the exposed curable composition layer is developed to form a cured film. [Inventive effect]

依本發明，能夠提供一種能夠用於具有優異之防沉降性及優異之經時穩定性且可形成具有優異之遮光性之硬化膜之硬化性組成物之含金屬氮化物粒子。 依本發明，還能夠提供分散組成物、硬化性組成物、硬化膜、彩色濾光片、固體攝影元件、固體攝像裝置、紅外線感測器、含金屬氮化物粒子的製造方法、分散組成物的製造方法、硬化性組成物的製造方法及硬化膜的製造方法。According to the present invention, it is possible to provide metal-containing nitride particles which can be used for a curable composition having excellent anti-settling properties and excellent stability over time, and which can form a cured film having excellent light-shielding properties. According to the present invention, a dispersion composition, a curable composition, a cured film, a color filter, a solid-state imaging element, a solid-state imaging device, an infrared sensor, a method for producing metal-containing nitride particles, and a dispersion composition can also be provided. The manufacturing method, the manufacturing method of a curable composition, and the manufacturing method of a cured film.

以下，對本發明進行詳細說明。 以下所記載之構成要件的說明有時基於本發明的代表性實施態樣來進行，但本發明並不限定於該種實施態樣。 本說明書中，使用「～」表示之數值範圍是指將「～」的前後所記載之數值作為下限值及上限值而包含之範圍。 本說明書中之基團（原子團）的標記中，未標有經取代及未經取代之標記包含不含有取代基者，並且還包含含有取代基者。例如，「烷基」不僅包含不含有取代基之烷基（未經取代之烷基），而且還包含含有取代基之烷基（經取代之烷基）。 本說明書中之「光化射線」或「放射線」例如是指遠紫外線、極紫外線（EUV：Extreme ultraviolet lithography光）、X射線及電子束等。本說明書中，光是指光化射線及放射線。本說明書中之「曝光」只要沒有特別指定，則不僅包含使用遠紫外線、X射線及EUV光等進行之曝光，而且還包含使用電子束及離子束等粒子線進行之描畫。 本說明書中，「（甲基）丙烯酸酯」表示丙烯酸酯及甲基丙烯酸酯。本說明書中，「（甲基）丙烯酸」表示丙烯酸及甲基丙烯酸。本說明書中，「（甲基）丙烯醯基」表示丙烯醯基及甲基丙烯醯基。本說明書中，「（甲基）丙烯醯胺」表示丙烯醯胺及甲基丙烯醯胺。本說明書中，「單量體」的含義與「單體」的含義相同。單量體被區分為寡聚物及聚合物，是指重量平均分子量為2,000以下的化合物。本說明書中，聚合性化合物是指含有聚合性基之化合物，可以是單量體，亦可以是聚合物。聚合性基是指參與聚合反應之基團。Hereinafter, the present invention will be described in detail. The description of the constituent requirements described below may be based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment. In this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In the notation of groups (atomic groups) in this specification, the notation that is not substituted and unsubstituted includes those without a substituent and those with a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). In this specification, "actinic rays" or "radiation rays" refer to, for example, far ultraviolet rays, extreme ultraviolet rays (EUV: Extreme ultraviolet lithography light), X-rays, electron beams, and the like. In this specification, light refers to actinic rays and radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure using extreme ultraviolet rays, X-rays, EUV light, etc., but also drawing using particle beams such as electron beams and ion beams. In this specification, "(meth)acrylate" means acrylate and methacrylate. In this specification, "(meth)acrylic acid" means acrylic acid and methacrylic acid. In this specification, "(meth)acryloyl group" means an acryl group and a methacryloyl group. In this specification, "(meth)acrylamide" means acrylamide and methacrylamide. In this specification, "monomer" has the same meaning as "monomer". Monomers are classified into oligomers and polymers, and refer to compounds having a weight average molecular weight of 2,000 or less. In this specification, the polymerizable compound refers to a compound containing a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.

[含金屬氮化物粒子] 本發明的實施形態之含金屬氮化物粒子含有特定的過渡金屬的氮化物（含有氮原子）及特定的原子T。 當將藉由X射線光電子光譜分析（以下亦稱為「ESCA」。另外，ESCA為Electron Spectroscopy for Chemical Analysis的略語。）檢測之含金屬氮化物粒子的表面上之原子T的質量基準的含量設為TE （質量%）、並將藉由X射線螢光分析（以下亦稱為「XRF」。另外，XRF為X-ray Fluorescence的略語。）檢測之含金屬氮化物粒子中之原子T的質量基準的含量設為TX （質量%）時，含金屬氮化物粒子滿足下述式（1）所表示之關係。 式（1） TE /TX ＜2.0[Metal-Containing Nitride Particles] The metal-containing nitride particles according to the embodiment of the present invention contain a specific transition metal nitride (containing a nitrogen atom) and a specific atom T. The mass-based content of the atomic T on the surface of the metal-containing nitride particles detected by X-ray photoelectron spectroscopy analysis (hereinafter, also referred to as "ESCA". ESCA is an abbreviation for Electron Spectroscopy for Chemical Analysis) is set to be is T E (% by mass), and analyzed by X-ray fluorescence (hereinafter, also referred to as "XRF." Further, as X-ray fluorescence XRF abbreviations.) T is the detection of a metal-containing nitride particles of atoms The metal-containing nitride particles satisfy the relationship represented by the following formula (1) when the content on the basis of mass is T X (mass %). Formula (1) T E /T X <2.0

本說明書中，ESCA是指，藉由向測定對象物照射X射線，並測定所產生之光電子的固有能量來分析存在於測定對象物（含金屬氮化物粒子）的表面之各原子的含量（各原子的原子數基準的含量：原子（atomic）%）之方法，是指利用以下的條件進行之分析方法。 ・裝置：PHI公司製造之Quantera-SXM（商品名稱）裝置 ・X射線源：單色化Al Kα射線（1486.6eV、25W、15kV、光束直徑200μmφ） ・測定區域：200μmφ ・測定條件：通過能量（Pass Energy）=140eV、步長（step）=0.1eV、累積次數4～8次 ・測定方法：使用壓機擠壓粒子而得到較薄的顆粒狀的測定試料。將該測定試料固定於上述裝置中，將光電子取出角設為10度而進行測定。In this specification, ESCA refers to analyzing the content of each atom present on the surface of the object to be measured (metal-containing nitride particles) by irradiating the object with X-rays and measuring the intrinsic energy of the generated photoelectrons (each The content of atoms based on the atomic number: atomic (atomic)%) is an analysis method using the following conditions.・Apparatus: Quantera-SXM (trade name) apparatus manufactured by PHI Corporation ・X-ray source: Monochromatic Al Kα rays (1486.6eV, 25W, 15kV, beam diameter 200μmφ) ・Measurement area: 200μmφ ・Measurement conditions: Pass energy ( Pass Energy) = 140 eV, step size (step) = 0.1 eV, accumulation times 4 to 8 times - Measurement method: Use a press to extrude particles to obtain a thin granular measurement sample. The measurement sample was fixed in the above-mentioned apparatus, and the photoelectron extraction angle was set to 10 degrees, and the measurement was performed.

依ESCA，能夠測定含金屬氮化物粒子的表面上之後述之原子T的含量（原子%），能夠根據該測定值得到含金屬氮化物粒子的表面上之原子T的質量基準的含量TE （質量%）。 另外，本說明書中，含金屬氮化物粒子的表面是指，從含金屬氮化物粒子的最表面朝向含金屬氮化物粒子的中心方向在深度5nm以內的區域。According to ESCA, the content (at %) of atomic T, which will be described later, on the surface of the metal-containing nitride particle can be measured, and the mass-based content T E of the atomic T on the surface of the metal-containing nitride particle can be obtained from the measured value ( quality%). In addition, in this specification, the surface of a metal-containing nitride particle means the area|region within 5 nm of depth from the outermost surface of a metal-containing nitride particle toward the center direction of a metal-containing nitride particle.

本說明書中，XRF是指，向測定對象物照射X射線，根據所產生之螢光X射線的能量及強度來分析測定對象物（含金屬氮化物粒子）中的各原子的含量（質量%）之方法，是指利用以下的條件進行之分析方法。 ・裝置：Rigaku製造之ZSM PrimusII型XRF ・X射線源：Rh 30-50 kV，48-80 mA ・測定區域：10μmφ ・測定時間：10-240 deg/min（deg為度（degree）的略語。） ・試料：使用壓機擠壓粒子而得到較薄的顆粒狀的測定試料。將該測定試料固定於上述裝置中進行測定。In this specification, XRF refers to irradiating an object to be measured with X-rays, and analyzing the content (mass %) of each atom in the object to be measured (metal-containing nitride particles) based on the energy and intensity of the generated fluorescent X-rays. The method refers to an analysis method using the following conditions.・Equipment: ZSM Primus II XRF manufactured by Rigaku ・X-ray source: Rh 30-50 kV, 48-80 mA ・Measurement area: 10μmφ ・Measurement time: 10-240 deg/min (deg is an abbreviation for degree. ) ・Sample: Use a press to extrude particles to obtain a thin granular measurement sample. The measurement sample was fixed in the above-mentioned apparatus, and the measurement was performed.

依XRF，能夠得到含金屬氮化物粒子中之後述之原子T的質量基準的含量TX （質量%）。 According to XRF, the content T X (mass %) based on the mass of the atomic T described later in the metal-containing nitride particles can be obtained.

含金屬氮化物粒子的特徵為，TE 及TX 滿足下述式（1）所表示之關係。 式（1） TE /TX ＜2.0Metal-containing nitride particles wherein, T E and T X satisfy the relationship represented by the following formula (1). Formula (1) T E /T X <2.0

具有上述特徴之含金屬氮化物粒子是特定的過渡金屬與特定的原子T的複合體，原子T存在於含金屬氮化物粒子的表面及內部。 其中，在含金屬氮化物粒子具有更加優異之本發明的效果之觀點上，TE /Tx 小於1.1為較佳。亦即，原子T更加均勻地存在於表面及內部狀態為較佳。TE /Tx 的下限並沒有特別限制，0.5以上的情況較多。 另外，含金屬氮化物粒子中，原子T亦可以形成成為與其他成分例如過渡金屬的氮化物獨立之晶體之共晶體、完全融合之固溶體及化合物等中的任意一種狀態。The metal-containing nitride particles having the above-mentioned characteristics are complexes of a specific transition metal and a specific atom T, and the atom T is present on the surface and inside of the metal-containing nitride particle. Among them, from the viewpoint that the metal-containing nitride particles have more excellent effects of the present invention, T E /T x is preferably less than 1.1. That is, it is preferable that the atoms T exist more uniformly on the surface and inside. The lower limit of T E /T x is not particularly limited, but it is often 0.5 or more. In addition, in the metal-containing nitride particles, the atoms T may be in any state of a eutectic crystal, a completely fused solid solution, a compound, etc., which are independent crystals with other components such as transition metal nitrides.

〔原子T〕 含金屬氮化物粒子含有原子T。 原子T不是氧原子、氯原子及氮原子中的任意一者，並選自週期表的13～17族的元素，並沒有特別限制。 在含金屬氮化物粒子具有更加優異之本發明的效果之觀點上，作為原子T，選自週期表的第2～6週期的元素為較佳，其中選自除鋁、鎵、銦、錫、鉈、鉛及鉍以外的元素為更佳。換言之，作為原子T，選自包括硼原子、碳原子、氧原子、氟原子、矽原子、磷原子、硫原子、鍺原子、砷原子、硒原子、溴原子、銻原子、碲原子、碘原子、釙原子及砈原子之組群中之任意一種原子為更佳。 在含金屬氮化物粒子具有進一步優異之本發明的效果之觀點上，作為原子T，選自包括硼原子、碳原子、硫原子、矽原子、磷原子及氟原子之組群中之任意一種原子為進一步較佳。 其中，在含金屬氮化物粒子具有特別優異之本發明的效果之觀點上，原子T選自週期表的13～16族的元素為特佳，選自包括硼原子、碳原子、硫原子及磷原子之組群中之任意一種原子為最佳，選自包括硼原子、硫原子及磷原子之組群中之任意一種原子為特佳。[Atomic T] The metal-containing nitride particles contain atomic T. The atom T is not any one of an oxygen atom, a chlorine atom, and a nitrogen atom, and is selected from the elements of Groups 13 to 17 of the periodic table, and is not particularly limited. From the viewpoint that the metal-containing nitride particles have more excellent effects of the present invention, as the atom T, elements selected from the 2nd to 6th periods of the periodic table are preferably selected from among the group consisting of aluminum, gallium, indium, tin, Elements other than thallium, lead and bismuth are more preferable. In other words, the atom T is selected from the group consisting of boron atom, carbon atom, oxygen atom, fluorine atom, silicon atom, phosphorus atom, sulfur atom, germanium atom, arsenic atom, selenium atom, bromine atom, antimony atom, tellurium atom, iodine atom Any one of the group of , polonium atoms and polonium atoms is more preferable. From the viewpoint that the metal-containing nitride particles have further excellent effects of the present invention, the atom T is any atom selected from the group consisting of a boron atom, a carbon atom, a sulfur atom, a silicon atom, a phosphorus atom, and a fluorine atom. for further better. Among them, from the viewpoint that the metal-containing nitride particles have particularly excellent effects of the present invention, the atom T is preferably selected from elements of Groups 13 to 16 of the periodic table, and is selected from the group consisting of boron atom, carbon atom, sulfur atom and phosphorus. Any atom in the group of atoms is most preferred, and any atom selected from the group including boron atom, sulfur atom and phosphorus atom is particularly preferred.

另外，含金屬氮化物粒子中之原子T的含量並沒有特別限制，相對於含金屬氮化物粒子的總質量，是0.05～40質量%為較佳，0.5～20質量%為更佳。 原子T可以單獨使用1種，亦可以併用2種以上。當併用2種以上的原子T時，合計含量在上述範圍內為較佳。The content of atomic T in the metal-containing nitride particles is not particularly limited, but is preferably 0.05 to 40 mass %, more preferably 0.5 to 20 mass %, relative to the total mass of the metal-containing nitride particles. Atom T may be used individually by 1 type, and may use 2 or more types together. When two or more kinds of atoms T are used in combination, the total content is preferably within the above range.

〔3～11族的過渡金屬的氮化物〕 上述含金屬氮化物粒子含有3～11族的過渡金屬（以下，簡稱為「過渡金屬」。）的氮化物。 作為上述過渡金屬，在含金屬氮化物粒子具有更加優異之本發明的效果之觀點上，電負性為1.22～2.36的過渡金屬為較佳。 作為上述過渡金屬（括弧內為電負性），例如可以舉出3族的過渡元素的Sc（1.36）、Y（1.22）、Dy（1.22）、Ho（1.23）、Er（1.24）、Tm（1.25）、Lu（1.27）、Th（1.3）、Pa（1.5）、U（1.38）、Np（1.36）、Pu（1.28）、Am（1.3）、Cm（1.3）、Bk（1.3）、Cf（1.3）、Es（1.3）、Fm（1.3）、Md（1.3）、No（1.3）、Lr（1.3）；4族的Ti（1.54）、Zr（1.33）、Hf（1.3）；5族的V（1.63）、Nb（1.6）、Ta（1.5）；6族的Cr（1.66）、Mo（2.16）、W（2.36）；7族的Mn（1.55）、Tc（1.9）、Re（1.9）；8族的Fe（1.83）、Ru（2.2）、Os（2.2）；9族的Co（1.88）、Rh（2.28）、Ir（2.2）；10族的Ni（1.91）、Pd（2.2）、Pt（2.28）；11族的Cu（1.9）、Ag（1.93）。 其中，在含金屬氮化物粒子具有更加優異之本發明的效果之觀點上，Sc、V、Cr、Mn、Fe、Co、Ni、Cu、Y、Ti、Zr、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Hf、Ta、W、Re、Os、Ir或Pt為較佳，Ti、Zr、V、Nb、Hf、Cr、W、Ta、Y或Re為更佳，Ti、Zr、V、Hf、Cr、W、Ta、Y或Re為進一步較佳，Ti、Zr、V、Hf、Cr或W為進一步更佳，Ti、Zr或Cr為特佳，Ti為最佳。[Nitrides of Transition Metals of Groups 3 to 11] The metal-containing nitride particles contain nitrides of transition metals of Groups 3 to 11 (hereinafter, simply referred to as "transition metals"). As the transition metal, a transition metal having an electronegativity of 1.22 to 2.36 is preferable from the viewpoint that the metal-containing nitride particles have more excellent effects of the present invention. As said transition metal (in parenthesis, electronegativity), for example, Sc (1.36), Y (1.22), Dy (1.22), Ho (1.23), Er (1.24), Tm ( 1.25), Lu (1.27), Th (1.3), Pa (1.5), U (1.38), Np (1.36), Pu (1.28), Am (1.3), Cm (1.3), Bk (1.3), Cf ( 1.3), Es (1.3), Fm (1.3), Md (1.3), No (1.3), Lr (1.3); Group 4 Ti (1.54), Zr (1.33), Hf (1.3); Group 5 V (1.63), Nb (1.6), Ta (1.5); Cr (1.66), Mo (2.16), W (2.36) of Group 6; Mn (1.55), Tc (1.9), Re (1.9) of Group 7; Group 8 Fe (1.83), Ru (2.2), Os (2.2); Group 9 Co (1.88), Rh (2.28), Ir (2.2); Group 10 Ni (1.91), Pd (2.2), Pt (2.28); Cu (1.9), Ag (1.93) of group 11. Among them, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Ti, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir or Pt are preferred, Ti, Zr, V, Nb, Hf, Cr, W, Ta, Y or Re are more preferred, Ti, Zr, V, Hf, Cr, W, Ta, Y or Re is further preferred, Ti, Zr, V, Hf, Cr or W is further preferred, Ti, Zr or Cr is particularly preferred, and Ti is most preferred.

含金屬氮化物粒子中的過渡金屬原子的含量並沒有特別限制，相對於含金屬氮化物粒子的總質量，是10質量%～99質量%為較佳，30～90質量%為更佳，40～70質量%為進一步較佳。含金屬氮化物粒子中之過渡金屬原子的含量能夠藉由X射線螢光分析裝置進行分析。 過渡金屬可以單獨使用1種，亦可以併用2種以上。當併用2種以上的過渡金屬時，合計含量在上述範圍內為較佳。The content of transition metal atoms in the metal-containing nitride particles is not particularly limited, but relative to the total mass of the metal-containing nitride particles, it is preferably 10% by mass to 99% by mass, more preferably 30% by mass to 90% by mass, and 40% by mass. -70 mass % is more preferable. The content of transition metal atoms in the metal-containing nitride particles can be analyzed by an X-ray fluorescence analyzer. A transition metal may be used individually by 1 type, and may use 2 or more types together. When two or more transition metals are used in combination, the total content is preferably within the above range.

〔氮原子〕 含金屬氮化物粒子含有氮原子。 含金屬氮化物粒子中之氮原子的形態並沒有特別限制，例如可以舉出與已說明之過渡金屬鍵結而形成過渡金屬的氮化物之形態。 含金屬氮化物粒子中的氮原子（N原子）的含量並沒有特別限制，相對於含金屬氮化物粒子的總質量，是0.1～80質量%為較佳，5～70質量%為更佳，20～50質量%為進一步較佳。氮原子的含量能夠藉由X射線螢光分析裝置進行分析。[Nitrogen Atom] The metal-containing nitride particles contain nitrogen atoms. The form of the nitrogen atom in the metal-containing nitride particles is not particularly limited, and for example, the form of a nitride that forms a transition metal by bonding with the transition metal described above is exemplified. The content of nitrogen atoms (N atoms) in the metal-containing nitride particles is not particularly limited, but is preferably 0.1 to 80% by mass, more preferably 5 to 70% by mass relative to the total mass of the metal-containing nitride particles, 20-50 mass % is more preferable. The content of nitrogen atoms can be analyzed by an X-ray fluorescence analyzer.

〔氧原子〕 含金屬氮化物粒子含有氧原子為較佳。 含金屬氮化物粒子中之氧原子的形態並沒有特別限制，可以是在含金屬氮化物粒子的製造製程中有意圖地添加者，亦可以是在含金屬氮化物粒子的製造製程中沒有意圖地混入者。 含金屬氮化物粒子中的氧原子的含量並沒有特別限制，相對於含金屬氮化物粒子的總質量，是0.01～50質量%為較佳，1～20質量%為更佳。氧原子的含量能夠藉由X射線螢光分析裝置進行分析。[Oxygen Atom] It is preferable that the metal-containing nitride particles contain oxygen atoms. The form of oxygen atoms in the metal-containing nitride particles is not particularly limited, and may be intentionally added during the manufacturing process of the metal-containing nitride particles, or may be unintentionally added during the manufacturing process of the metal-containing nitride particles. Mixer. The content of oxygen atoms in the metal-containing nitride particles is not particularly limited, but is preferably 0.01 to 50 mass %, more preferably 1 to 20 mass %, relative to the total mass of the metal-containing nitride particles. The content of oxygen atoms can be analyzed by an X-ray fluorescence analyzer.

含金屬氮化物粒子中氮原子的含量相對於氮化物所含有之過渡金屬原子（以下，簡稱為「過渡金屬原子」。）的含量之含有原子數比X、氧原子的含量相對於過渡金屬原子的含量之含有原子數比Y及原子T的含量相對於過渡金屬原子的含量之含有原子數比Z分別超過0且小於2為較佳。The content of nitrogen atoms in the metal-containing nitride particles relative to the content of transition metal atoms (hereinafter, simply referred to as "transition metal atoms") contained in the nitride is the atomic number ratio X, and the content of oxygen atoms relative to the transition metal atoms It is preferable that the content of the content of the atomic number ratio Y and the content of the atomic number of T with respect to the content of the transition metal atom of the content of the content of the atomic number ratio Z is more than 0 and less than 2, respectively.

含金屬氮化物粒子中氮原子的含量相對於過渡金屬原子的含量之含有原子數比X的下限值超過0.3為更佳，0.4以上為進一步較佳，0.64以上為特佳。上限值小於1.3為更佳，1.2以下為進一步較佳，小於1.2為特佳。 若X為0.4以上，則含有含金屬氮化物粒子之硬化性組成物具有更加優異之防沉降性及經時穩定性。 若X小於1.3，則由含有含金屬氮化物粒子之硬化性組成物得到之硬化膜具有更加優異之遮光性。若X為1.2以下，則由含有含金屬氮化物粒子之硬化性組成物得到之硬化膜具有進一步優異之遮光性。若X小於1.2，則含有含金屬氮化物粒子之硬化性組成物具有更加優異之經時穩定性。The lower limit of the atomic number ratio X of the content of nitrogen atoms to the content of transition metal atoms in the metal-containing nitride particles is more preferably more than 0.3, more preferably 0.4 or more, and particularly preferably 0.64 or more. The upper limit is more preferably less than 1.3, further preferably less than 1.2, and particularly preferably less than 1.2. When X is 0.4 or more, the curable composition containing metal-containing nitride particles has more excellent anti-settling properties and stability over time. When X is less than 1.3, the cured film obtained from the curable composition containing metal nitride particles has more excellent light-shielding properties. If X is 1.2 or less, the cured film obtained from the curable composition containing metal nitride particle|grains will have more excellent light-shielding property. When X is less than 1.2, the curable composition containing metal-containing nitride particles has more excellent stability over time.

含金屬氮化物粒子中氧原子的含量相對於過渡金屬原子的含量之含有原子數比Y的下限值超過0.03為更佳，0.05以上為進一步較佳，0.08以上為特佳。上限值小於0.25為更佳，0.2以下為進一步較佳。 若Y為0.05以上，則含有含金屬氮化物粒子之硬化性組成物具有更加優異之防沉降性及經時穩定性。 若Y為0.2以下，則含有含金屬氮化物粒子之硬化性組成物具有更加優異之經時穩定性，又，所得到之遮光膜具有更加優異之遮光性。The lower limit of the atomic number ratio Y of the content of oxygen atoms to the content of transition metal atoms in the metal-containing nitride particles is more preferably more than 0.03, more preferably 0.05 or more, and particularly preferably 0.08 or more. It is more preferable that the upper limit is less than 0.25, and it is more preferable that it is 0.2 or less. When Y is 0.05 or more, the curable composition containing metal-containing nitride particles has more excellent anti-settling properties and stability over time. When Y is 0.2 or less, the curable composition containing metal-containing nitride particles has more excellent stability over time, and the obtained light-shielding film has more excellent light-shielding properties.

含金屬氮化物粒子中原子T的含量相對於過渡金屬原子的含量之含有原子數比Z的下限值超過0.03為更佳，0.05以上為進一步較佳，0.08以上為特佳。上限值小於1.2為更佳，0.5以下為進一步較佳。 若Z為0.05以上，則含有含金屬氮化物粒子之硬化性組成物具有更加優異之防沉降性及經時穩定性。 若Y為0.5以下，則含有含金屬氮化物粒子之硬化性組成物具有更加優異之經時穩定性，又，所得到之遮光膜具有更加優異之遮光性。The lower limit of the atomic ratio Z of the content of atoms T relative to the content of transition metal atoms in the metal-containing nitride particles is more preferably more than 0.03, more preferably 0.05 or more, and particularly preferably 0.08 or more. It is more preferable that the upper limit is less than 1.2, and it is more preferable that it is 0.5 or less. When Z is 0.05 or more, the curable composition containing metal-containing nitride particles has more excellent anti-settling properties and stability over time. When Y is 0.5 or less, the curable composition containing the metal-containing nitride particles has more excellent stability over time, and the obtained light-shielding film has more excellent light-shielding properties.

在含金屬氮化物粒子具有更加優異之本發明的效果之觀點上，氮原子的含量相對於過渡金屬原子的含量之含有原子數比X、氧原子的含量相對於過渡金屬原子的含量之含有原子數比Y及原子T的含量相對於過渡金屬原子的含量之含有原子數比Z之和（以下亦稱為「X、Y及Z之和」或「X+Y+Z」。）超過0.4且小於1.6為較佳。 若X+Y+Z小於1.6，則由含有含金屬氮化物粒子之硬化性組成物得到之硬化膜具有更加優異之遮光性。 若X+Y+Z超過0.4，則含有含金屬氮化物粒子之硬化性組成物具有更加優異之防沉降性及經時穩定性。From the viewpoint that the metal-containing nitride particles have more excellent effects of the present invention, the atomic ratio X of the content of nitrogen atoms to the content of transition metal atoms, and the atomic ratio of the content of oxygen atoms to the content of transition metal atoms The sum of the number ratio Y and the content of the atomic T with respect to the content of the transition metal atoms with respect to the content of the atomic number ratio Z (hereinafter also referred to as "the sum of X, Y and Z" or "X+Y+Z") exceeds 0.4 and Less than 1.6 is better. When X+Y+Z is less than 1.6, the cured film obtained from the curable composition containing metal nitride particles has more excellent light-shielding properties. When X+Y+Z exceeds 0.4, the curable composition containing metal-containing nitride particles has more excellent anti-settling properties and stability over time.

在含金屬氮化物粒子具有更加優異之本發明的效果之觀點上，X、Y及Z之和的下限值是0.5以上為更佳，0.8以上為進一步較佳，1.0以上為特佳。上限值是1.5以下為更佳。 若X、Y及Z之和為0.5以上，則含有含金屬氮化物粒子之硬化性組成物具有更加優異之防沉降性及經時穩定性。 若X、Y及Z之和為1.5以下，則含有含金屬氮化物粒子之硬化性組成物具有更加優異之經時穩定性，又，所得到之遮光膜具有更加優異之遮光性。From the viewpoint that the metal-containing nitride particles have more excellent effects of the present invention, the lower limit of the sum of X, Y and Z is more preferably 0.5 or more, more preferably 0.8 or more, and particularly preferably 1.0 or more. The upper limit is more preferably 1.5 or less. When the sum of X, Y, and Z is 0.5 or more, the curable composition containing metal-containing nitride particles has more excellent anti-settling properties and stability over time. When the sum of X, Y, and Z is 1.5 or less, the curable composition containing the metal-containing nitride particles has more excellent stability over time, and the obtained light-shielding film has more excellent light-shielding properties.

〔含金屬氮化物粒子的物性〕 以下，對含金屬氮化物粒子的物性進行說明。[Physical Properties of Metal-Containing Nitride Particles] Hereinafter, the physical properties of the metal-containing nitride particles will be described.

＜平均一次粒徑＞ 含金屬氮化物粒子的平均一次粒徑為200nm以下，在具有更加優異之本發明的效果之觀點上，80nm以下為較佳，小於80nm為更佳。 若含金屬氮化物粒子的平均一次粒徑為200nm以下，則硬化性組成物具有優異之經時穩定性。若含金屬氮化物粒子的平均一次粒徑小於80nm，則硬化性組成物具有更加優異之經時穩定性。 含金屬氮化物粒子的平均一次粒徑的下限值並沒有特別限制，一般是1.0nm以上為較佳。若平均一次粒徑為1.0nm以上，則可抑制含金屬氮化物粒子間的相互作用，含金屬氮化物粒子難以凝聚，其結果，硬化性組成物具有更加優異之經時穩定性。 另外，本說明書中，平均一次粒徑是指將使用透射型電子顯微鏡（TEM：Transmission Electron Microscope）對400個含金屬氮化物粒子評價之圓換算的直徑進行算術平均而求出之平均一次粒徑，試驗方法如實施例所記載。<Average Primary Particle Size> The average primary particle size of the metal-containing nitride particles is 200 nm or less, and from the viewpoint of having more excellent effects of the present invention, 80 nm or less is preferable, and less than 80 nm is more preferable. When the average primary particle diameter of the metal-containing nitride particles is 200 nm or less, the curable composition has excellent stability over time. When the average primary particle size of the metal-containing nitride particles is less than 80 nm, the curable composition has more excellent stability over time. The lower limit of the average primary particle size of the metal-containing nitride particles is not particularly limited, but generally 1.0 nm or more is preferable. When the average primary particle size is 1.0 nm or more, the interaction between the metal-containing nitride particles can be suppressed, the metal-containing nitride particles are less likely to aggregate, and as a result, the curable composition has more excellent stability over time. In addition, in this specification, the average primary particle size refers to the average primary particle size obtained by arithmetically averaging the circle-converted diameters of 400 metal-containing nitride particles evaluated using a transmission electron microscope (TEM: Transmission Electron Microscope). , the test method is as described in the examples.

＜複介電常數的實數部＞ 當由ε=ε’+ε”j表示含金屬氮化物粒子的複介電常數ε時，在波長400～1200nm下之ε’的最小值並沒有特別限制，小於0為較佳，在由含有含金屬氮化物粒子之硬化性組成物得到之硬化膜具有更加優異之遮光性之觀點上，ε’的最小值是-0.5以下為較佳。 ε’的最小值的下限值並沒有特別限制，-20左右的情況較多。 另外，ε’表示複介電常數ε的實數部，ε”表示複介電常數ε的虛數部，j表示虛數單位。又，本說明書中，複介電常數的實數部ε’的最小值是指與400～1200nm的各波長相對應之複介電常數的實數部ε’中最小的值。<Real part of complex permittivity> When the complex permittivity ε of the metal-containing nitride particles is represented by ε=ε'+ε"j, the minimum value of ε' at a wavelength of 400 to 1200 nm is not particularly limited, It is preferably less than 0, and the minimum value of ε' is preferably -0.5 or less, from the viewpoint that the cured film obtained from the curable composition containing metal nitride particles has more excellent light-shielding properties. The lower limit of the value is not particularly limited, but is often around -20. In addition, ε' represents the real part of the complex permittivity ε, ε" represents the imaginary part of the complex permittivity ε, and j represents an imaginary unit. In this specification, the minimum value of the real part ε' of the complex permittivity refers to the smallest value among the real parts ε' of the complex permittivity corresponding to wavelengths of 400 to 1200 nm.

本說明書中，複介電常數的實數部ε’是指藉由以下方法測定出之值。首先，使用含有含金屬氮化物粒子之組成物，在矽晶片上形成0.3μm厚度的膜。然後，使用分光橢圓偏光計，藉由實施例中所記載之方法對所形成之膜測定複介電常數。 另外，在形成膜時，組成物包含聚合性化合物之組成物的情況下，對形成於矽晶片上之塗膜實施硬化處理而形成成為測定對象之膜。In this specification, the real part ε' of the complex permittivity refers to a value measured by the following method. First, a film having a thickness of 0.3 μm was formed on a silicon wafer using a composition containing metal-containing nitride particles. Then, the complex permittivity of the formed film was measured by the method described in the Examples using a spectroscopic ellipsometry. In addition, when forming a film, when a composition contains the composition of a polymerizable compound, the coating film formed on the silicon wafer is subjected to a curing treatment to form a film to be measured.

[含金屬氮化物粒子的製造方法] 作為含金屬氮化物粒子的製造方法並沒有特別限制，能夠使用公知的方法。作為含金屬氮化物粒子的製造方法，例如可以舉出氣相反應法。作為氣相反應法，可以舉出電爐法及熱電漿法等，在雜質的混入較少、粒徑容易齊勻、又生產率較高的觀點上，熱電漿法為較佳。 在熱電漿法中，產生熱電漿之方法並沒有特別限制，可以舉出直流電弧放電、多層電弧放電、高頻（RF）電漿及混合電漿（hybrid plasma）等。 作為基於熱電漿法之含金屬氮化物粒子的具體製造方法並沒有特別限制，例如作為含有鈦作為過渡金屬之含金屬氮化物粒子的製造方法，可以舉出在電漿焰中使四氯化鈦和氨氣反應之方法（日本特開平2-22110號公報）；利用高頻熱電漿使鈦粉末蒸發，以氮為載氣導入，使其在冷卻過程中氮化而進行合成之方法（日本特開昭61-11140號公報）；及向電漿的周緣部吹入氨氣之方法（日本特開昭63-85007號）等。[Method for Producing Metal-Containing Nitride Particles] The method for producing metal-containing nitride particles is not particularly limited, and a known method can be used. As a method for producing the metal-containing nitride particles, for example, a gas phase reaction method can be mentioned. As the gas-phase reaction method, an electric furnace method, a thermoplasma method, etc. are mentioned, and the thermoplasma method is preferable from the viewpoint of less contamination of impurities, easy uniformity of particle size, and high productivity. In the thermoplasma method, the method for generating thermoplasm is not particularly limited, and examples thereof include DC arc discharge, multilayer arc discharge, high frequency (RF) plasma, and hybrid plasma. The specific method for producing the metal-containing nitride particles by the thermoplasma method is not particularly limited. For example, as a method for producing the metal-containing nitride particles containing titanium as a transition metal, titanium tetrachloride is prepared in a plasma flame. A method of reacting with ammonia gas (Japanese Patent Laid-Open No. 2-22110); a method of evaporating titanium powder by high-frequency thermoplasma, introducing nitrogen as a carrier gas, and nitriding it during cooling (Japanese special Unexamined Publication No. 61-11140); and a method of blowing ammonia gas into the peripheral edge of the plasma (Japanese Patent Laid-Open No. 63-85007).

但是，含金屬氮化物粒子的製造方法只要可得到具有所希望之物性之含金屬氮化物粒子，則沒有限制。 又，在藉由熱電漿法製造含金屬氮化物粒子時，為了將其原材料以所希望之流量供給至電漿焰中，可以適當對原材料進行加熱或冷卻。However, the method for producing metal-containing nitride particles is not limited as long as metal-containing nitride particles having desired physical properties can be obtained. In addition, when the metal-containing nitride particles are produced by the thermoplasma method, in order to supply the raw material to the plasma flame at a desired flow rate, the raw material may be appropriately heated or cooled.

＜含金屬氮化物粒子的製造方法的較佳形態＞ 作為含金屬氮化物粒子的製造方法，包含以下的各製程之製造方法為較佳。 （a）準備含有氮原子之原材料A及含有過渡金屬原子及原子T之原材料B、或者準備含有氮原子之原材料A、含有過渡金屬原子之原材料C及含有原子T之原材料D之製程（原材料準備製程） （b）將2種以上的原材料以氣相狀態進行混合而得到混合物之製程（混合製程） （c）使氣相狀態的混合物凝縮而得到含金屬氮化物粒子之製程（凝縮製程） 以下，對上述各製程進行詳細敘述。另外，在以下的各製程中，原材料、混合物及凝縮物中可以沒有意圖地混入氧原子。<Preferable form of the manufacturing method of a metal-containing nitride particle> As a manufacturing method of a metal-containing nitride particle, the manufacturing method which includes each of the following processes is preferable. (a) The process of preparing raw material A containing nitrogen atom and raw material B containing transition metal atom and atom T, or preparing raw material A containing nitrogen atom, raw material C containing transition metal atom and raw material D containing atom T (raw material preparation Process) (b) A process of mixing two or more raw materials in a gaseous state to obtain a mixture (mixing process) (c) A process of condensing the mixture in a gaseous state to obtain metal-containing nitride particles (condensation process) The following , the above-mentioned processes are described in detail. In addition, in each of the following processes, an oxygen atom may be unintentionally mixed into the raw material, the mixture, and the condensate.

（a）原材料準備製程 原材料準備製程是準備以下組合的2種以上的原材料之製程。 ・含有氮原子之原材料A及含有過渡金屬原子及原子T之原材料B、或者 ・含有氮原子之原材料A、含有過渡金屬原子之原材料C及含有原子T之原材料D 原材料A含有氮原子，例如可以舉出氮氣等。原材料B含有過渡金屬原子及原子T，例如可以舉出四氯化鈦等。原材料C含有過渡金屬原子，可以舉出過渡金屬粉末等。原材料D可以舉出含有原子T之固體、液體或氣體等。 準備原材料之方法並沒有特別限制，可以舉出藉由購入等而供應原材料及藉由合成而得到原材料等方法。 另外，在原材料準備製程中，只要準備上述組合的2種以上的原材料，則並沒有特別限制，可以一併準備其他原材料。(a) Raw material preparation process The raw material preparation process is a process for preparing two or more kinds of raw materials in the following combinations.・raw material A containing nitrogen atom and raw material B containing transition metal atom and atom T, or ・raw material A containing nitrogen atom, raw material C containing transition metal atom and raw material D containing atom T Raw material A contains nitrogen atom, for example, Nitrogen etc. are mentioned. The raw material B contains a transition metal atom and an atom T, and examples thereof include titanium tetrachloride and the like. The raw material C contains transition metal atoms, and examples thereof include transition metal powders and the like. The raw material D includes a solid, liquid, or gas containing atoms T, and the like. The method of preparing a raw material is not specifically limited, The method of supplying a raw material by purchasing etc., and obtaining a raw material by synthesis, etc. are mentioned. In addition, in the raw material preparation process, as long as two or more kinds of raw materials in the above-mentioned combination are prepared, there is no particular limitation, and other raw materials may be prepared together.

各原材料的形態並沒有特別限制，可以是固體（包含昇華性固體）、液體及氣體中的任意一種。又，原材料可以是日本特開2005-170760號公報的0024及0025段中所記載之漿液。 又，在本製程中準備之原材料的種類的上限並沒有特別限制，一般是10種以下為較佳。The form of each raw material is not particularly limited, and may be any of a solid (including a sublimable solid), a liquid, and a gas. In addition, the raw material may be the slurry described in paragraphs 0024 and 0025 of Japanese Patent Application Laid-Open No. 2005-170760. In addition, the upper limit of the types of raw materials prepared in this process is not particularly limited, and generally 10 or less are preferably used.

（b）混合製程 混合製程是將包含（a）原材料準備製程中準備之任意一種原材料之2種以上的原材料以氣相狀態進行混合而得到混合物之製程。混合製程可以是將（a）原材料準備製程中準備之所有原材料、亦即原材料A及原材料B、或原材料A、原材料C及原材料D以氣相狀態進行混合而得到混合物之製程。將2種以上的原材料以氣相狀態進行混合之方法並沒有特別限制，將原材料供給至熱電漿而使原材料蒸發並以氣相狀態進行混合之熱電漿法為較佳。 藉由熱電漿法混合氣相狀態的原材料之方法並沒有特別限制，能夠使用公知的方法。作為公知的方法，例如可以舉出日本特開2005-170760號公報的0015～0037段中所記載之方法、日本特開2015-227282號公報的0038～0086段及日本特開2005-343784號公報的0017～0047段中所記載之方法等。 其中，在可得到具有更加優異之本發明的效果之含金屬氮化物粒子之觀點上，藉由電弧放電產生熱電漿並將原材料導入到熱電漿中之方法為較佳。 藉由電弧放電產生熱電漿並將原材料導入到熱電漿中之方法並沒有特別限制，能夠使用公知的方法。(b) Mixing process The mixing process is a process in which two or more raw materials including any one of the raw materials prepared in the (a) raw material preparation process are mixed in a gaseous state to obtain a mixture. The mixing process can be a process of mixing all the raw materials prepared in the (a) raw material preparation process, namely raw material A and raw material B, or raw material A, raw material C and raw material D in a gas phase state to obtain a mixture. The method of mixing two or more kinds of raw materials in a gas phase state is not particularly limited, and a thermoplasma method in which the raw materials are supplied to a thermoplasmic plasma to evaporate the raw materials and mixed in a gaseous phase state is preferable. The method of mixing the raw materials in the gas phase by the thermoplasma method is not particularly limited, and a known method can be used. Examples of known methods include the method described in paragraphs 0015 to 0037 of JP 2005-170760 A, paragraphs 0038 to 0086 of JP 2015-227282 A, and JP 2005-343784 A The methods described in paragraphs 0017 to 0047, etc. Among them, a method of generating a thermoplasma by arc discharge and introducing a raw material into the thermoplasma is preferable from the viewpoint of obtaining metal-containing nitride particles having more excellent effects of the present invention. The method of generating the thermoplasm by arc discharge and introducing the raw material into the thermoplasm is not particularly limited, and a known method can be used.

基於熱電漿法之含金屬氮化物粒子的具體製造方法可以舉出使用日本特開2005-343784號公報的0042段及圖1中所記載之裝置、以及日本特開2005-170760號公報的0019及0020段中所記載之原材料供給裝置等之方法。Specific methods for producing metal-containing nitride particles by the thermoplasma method include the use of the apparatus described in paragraph 0042 and FIG. 1 of JP 2005-343784 A, and 0019 and JP 2005-170760 A. The method of the raw material supply device, etc. described in paragraph 0020.

（c）凝縮製程 凝縮製程是使氣相狀態的混合物凝縮而得到含金屬氮化物粒子之製程。得到凝縮物之方法並沒有特別限制，能夠使用公知的方法。作為得到含金屬氮化物粒子之方法，例如可以舉出使氣相狀態的混合物與裝置內壁接觸而使其急冷之方法等。(c) Condensation process The condensation process is a process of condensing the mixture in the gas phase to obtain metal-containing nitride particles. The method in particular of obtaining a condensate is not restrict|limited, A well-known method can be used. As a method of obtaining a metal-containing nitride particle, the method of making the mixture in a gas phase state contact with an apparatus inner wall, and making it quench|quench, etc. are mentioned, for example.

（加熱製程） 含金屬氮化物粒子的製造方法進一步包括對利用上述製造方法製作出之含金屬氮化物粒子進行加熱而揮發去除雜質之製程（加熱製程）為較佳。 經加熱製程而製作出之含金屬氮化物粒子，在波長400～1200nm下之複介電常數的實數部ε’的最小值容易小於0。 加熱製程中之加熱溫度並沒有特別限制，一般是150～500℃為較佳。加熱時間並沒有特別限制，一般是1小時～3日為較佳。加熱中的環境並沒有特別限制，氧小於200ppm的氮環境等為較佳。又，加熱中可以進行減壓。(Heating Process) Preferably, the manufacturing method of the metal-containing nitride particles further includes a process (heating process) for volatilizing and removing impurities by heating the metal-containing nitride particles manufactured by the above-mentioned manufacturing method. For the metal-containing nitride particles produced by the heating process, the minimum value of the real part ε' of the complex permittivity at a wavelength of 400 to 1200 nm is likely to be less than 0. The heating temperature in the heating process is not particularly limited, and is generally preferably 150-500°C. The heating time is not particularly limited, but generally 1 hour to 3 days is preferable. The environment during heating is not particularly limited, but a nitrogen environment in which oxygen is less than 200 ppm is preferable. In addition, decompression may be performed during heating.

（靜置製程） 含金屬氮化物粒子的製造方法進一步包括在氮氣環境下靜置利用上述製造方法製作出之含金屬氮化物粒子之靜置製程為較佳。 靜置的方法並沒有特別限制，能夠使用公知的方法。(Standing Process) The manufacturing method of the metal-containing nitride particles further includes a resting process of leaving the metal-containing nitride particles produced by the above manufacturing method in a nitrogen atmosphere. The method of leaving still is not particularly limited, and a known method can be used.

[分散組成物] 本發明的實施形態之分散組成物含有含金屬氮化物粒子和樹脂。以下，對分散組成物所含有之各成分進行詳細敘述。[Dispersion composition] The dispersion composition of the embodiment of the present invention contains metal-containing nitride particles and a resin. Hereinafter, each component contained in the dispersion composition will be described in detail.

〔含金屬氮化物粒子〕 作為分散組成物所含有之含金屬氮化物粒子，如作為含金屬氮化物粒子的形態而已說明那樣。分散組成物中之含金屬氮化物粒子的含量並沒有特別限制，相對於分散組成物的總固體成分，一般是10～90質量%為較佳，20～80質量%為更佳。含金屬氮化物粒子可以單獨使用1種，亦可以併用2種以上。當併用2種以上的含金屬氮化物粒子時，合計含量在上述範圍內為較佳。[Metal-Containing Nitride Particles] The metal-containing nitride particles contained in the dispersion composition are as described above as the form of the metal-containing nitride particles. The content of the metal-containing nitride particles in the dispersion composition is not particularly limited, but is generally preferably 10 to 90% by mass, more preferably 20 to 80% by mass relative to the total solid content of the dispersion composition. The metal-containing nitride particles may be used alone or in combination of two or more. When two or more kinds of metal-containing nitride particles are used in combination, the total content is preferably within the above range.

〔樹脂〕 分散組成物含有樹脂。作為樹脂，例如可以舉出分散劑及鹼可溶性樹脂等。 分散組成物中之樹脂的含量並沒有特別限制，相對於分散組成物的總固體成分，一般是5～40質量%為較佳。樹脂可以單獨使用1種，亦可以併用2種以上。當併用2種以上的樹脂時，合計含量在上述範圍內為較佳。[Resin] The dispersion composition contains resin. As resin, a dispersing agent, an alkali-soluble resin, etc. are mentioned, for example. The content of the resin in the dispersion composition is not particularly limited, but is generally preferably 5 to 40% by mass relative to the total solid content of the dispersion composition. A resin may be used individually by 1 type, and may use 2 or more types together. When two or more resins are used in combination, the total content is preferably within the above range.

＜分散劑＞ 分散組成物含有分散劑（相當於樹脂）為較佳。另外，本說明書中，分散劑是指與後述之鹼可溶性樹脂不同之化合物。 組成物中之分散劑的含量並沒有特別限制，相對於組成物的總固體成分，一般是5～40質量%為較佳，5～30質量%為更佳。 分散劑可以單獨使用1種，亦可以併用2種以上。當併用2種以上的分散劑時，合計含量在上述範圍內為較佳。<Dispersant> It is preferable that the dispersion composition contains a dispersant (corresponding to resin). In addition, in this specification, a dispersing agent means the compound different from the alkali-soluble resin mentioned later. The content of the dispersant in the composition is not particularly limited, but is generally preferably 5 to 40% by mass, more preferably 5 to 30% by mass relative to the total solid content of the composition. A dispersing agent may be used individually by 1 type, and may use 2 or more types together. When two or more types of dispersants are used in combination, the total content is preferably within the above range.

分散劑例如能夠適當選擇使用公知的分散劑。其中，高分子化合物為較佳。 作為分散劑，能夠舉出高分子分散劑（例如，聚醯胺胺及其鹽、聚羧酸及其鹽、高分子量不飽和酸酯、改質聚氨酯、改質聚酯、改質聚（甲基）丙烯酸酯、（甲基）丙烯酸系共聚物、萘磺酸福馬林縮合物）、聚氧乙烯烷基磷酸酯、聚氧乙烯烷基胺及顏料衍生物等。 高分子化合物根據其結構能夠進一步分類為直鏈狀高分子、末端改質型高分子、接枝型高分子及嵌段型高分子。As the dispersing agent, for example, a known dispersing agent can be appropriately selected and used. Among them, polymer compounds are preferred. Examples of the dispersing agent include polymer dispersing agents (for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly(methyl) base) acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formalin condensate), polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine and pigment derivatives, etc. The polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft-type polymers, and block-type polymers according to their structures.

（高分子化合物） 高分子化合物以吸附於含金屬氮化物粒子（以下，有時亦稱為「顏料」。）的表面而防止被分散體的再凝聚之方式起作用。因此，含有對顏料表面之黏固（anchor）部位之末端改質型高分子、接枝型（含有高分子鏈）高分子及嵌段型高分子為較佳。(Polymer compound) The polymer compound acts so as to be adsorbed on the surface of metal-containing nitride particles (hereinafter, also referred to as "pigment" in some cases) to prevent reagglomeration of the dispersion. Therefore, terminal-modified polymers, graft-type (containing a polymer chain) polymer, and block-type polymers containing an anchor portion on the surface of the pigment are preferred.

高分子化合物可以含有硬化性基。 作為硬化性基，例如可以舉出乙烯性不飽和基（例如，（甲基）丙烯醯基、乙烯基及苯乙烯基等）及環狀醚基（例如，環氧基及氧雜環丁基等）等，但並不限定於該等。 其中，在能夠藉由自由基反應來進行聚合控制之觀點上，作為硬化性基，乙烯性不飽和基為較佳。乙烯性不飽和基是（甲基）丙烯醯基為更佳。The polymer compound may contain a sclerosing group. Examples of curable groups include ethylenically unsaturated groups (for example, (meth)acryloyl groups, vinyl groups, styryl groups, etc.) and cyclic ether groups (for example, epoxy groups and oxetanyl groups) etc.), etc., but not limited to such. Among them, an ethylenically unsaturated group is preferable as a curable group from the viewpoint that the polymerization can be controlled by a radical reaction. More preferably, the ethylenically unsaturated group is a (meth)acryloyl group.

含有硬化性基之樹脂含有選自包括聚酯結構及聚醚結構之組群中之至少1種為較佳。在該情況下，主鏈中可以含有聚酯結構和/或聚醚結構，如後述那樣，當上述樹脂包含含有接枝鏈之結構單元時，上述高分子鏈可以含有聚酯結構和/或聚醚結構。 上述樹脂中，上述高分子鏈含有聚酯結構為更佳。The curable group-containing resin preferably contains at least one selected from the group consisting of a polyester structure and a polyether structure. In this case, the main chain may contain a polyester structure and/or a polyether structure. As will be described later, when the resin contains a structural unit containing a graft chain, the polymer chain may contain a polyester structure and/or a polyether structure. ether structure. In the above-mentioned resin, it is more preferable that the above-mentioned polymer chain contains a polyester structure.

高分子化合物包含含有接枝鏈之結構單元為較佳。另外，本說明書中，「結構單元」的含義與「重複單元」的含義相同。 該種包含含有接枝鏈之結構單元之高分子化合物藉由接枝鏈而具有與溶劑之親和性，因此是含金屬氮化物粒子等的分散性及經時後的分散穩定性（經時穩定性）優異者。又，藉由接枝鏈的存在，包含含有接枝鏈之結構單元之高分子化合物具有與聚合性化合物或其他可併用之樹脂等之親和性。其結果，在鹼顯影中難以產生殘渣。 若接枝鏈變長，則立體排斥效果變高，含金屬氮化物粒子等的分散性得到提高。另一方面，若接枝鏈過長，則具有對含金屬氮化物粒子等之吸附力下降而含金屬氮化物粒子等的分散性下降之傾向。因此，接枝鏈的除氫原子以外的原子數為40～10000者為較佳，50～2000者為更佳，60～500者為進一步較佳。 在此，接枝鏈表示自共聚物的主鏈的根部（在從主鏈分支之基團中鍵結於主鏈之原子）至從主鏈分支之基團的末端為止。Preferably, the polymer compound contains a structural unit containing a graft chain. In addition, in this specification, the meaning of a "structural unit" is the same as that of a "repeating unit". The polymer compound including the structural unit containing the graft chain has an affinity with the solvent due to the graft chain, so the dispersibility of the metal-containing nitride particles and the like and the dispersion stability over time (stable over time) sex) excellent. Furthermore, by the presence of the graft chain, the polymer compound including the structural unit containing the graft chain has an affinity with a polymerizable compound or other resins that can be used in combination. As a result, it becomes difficult to generate a residue in alkali image development. When the graft chain becomes longer, the steric repulsion effect becomes high, and the dispersibility of metal-containing nitride particles and the like improves. On the other hand, when the graft chain is too long, the adsorption force to the metal-containing nitride particles and the like decreases, and the dispersibility of the metal-containing nitride particles and the like tends to decrease. Therefore, the number of atoms other than hydrogen atoms in the graft chain is preferably 40 to 10,000, more preferably 50 to 2,000, and even more preferably 60 to 500. Here, the graft chain means from the root of the main chain of the copolymer (the atom bonded to the main chain in the group branched from the main chain) to the end of the group branched from the main chain.

接枝鏈含有聚合物結構為較佳，作為該種聚合物結構，例如能夠舉出聚（甲基）丙烯酸酯結構（例如，聚（甲基）丙烯酸結構）、聚酯結構、聚氨酯結構、聚脲結構、聚醯胺結構及聚醚結構等。 為了提高接枝鏈與溶劑的相互作用性，藉此提高含金屬氮化物粒子等的分散性，接枝鏈是含有選自包括聚酯結構、聚醚結構及聚（甲基）丙烯酸酯結構中之組群中之至少1種之接枝鏈為較佳，含有聚酯結構及聚醚結構中的至少任意一種之接枝鏈為更佳。It is preferable that the graft chain contains a polymer structure. Examples of such a polymer structure include a poly(meth)acrylate structure (for example, a poly(meth)acrylic structure), a polyester structure, a polyurethane structure, a poly(meth)acrylate structure, and a poly(meth)acrylate structure. Urea structure, polyamide structure and polyether structure, etc. In order to improve the interaction between the grafted chain and the solvent, thereby improving the dispersibility of metal-containing nitride particles, etc., the grafted chain is selected from the group consisting of polyester structure, polyether structure and poly(meth)acrylate structure. The graft chain of at least one kind in the group is preferred, and the graft chain containing at least any one of a polyester structure and a polyether structure is more preferred.

含有該種接枝鏈之大分子單體（具有聚合物結構且鍵結於共聚物的主鏈而構成接枝鏈之單體）並沒有特別限定，能夠較佳地使用含有反應性雙鍵性基之大分子單體。The macromonomer containing such a graft chain (a monomer having a polymer structure and being bound to the main chain of the copolymer to form a graft chain) is not particularly limited, and a reactive double bond can be preferably used. base macromonomer.

作為對應於含有高分子化合物所含有之接枝鏈之結構單元且較佳地用於高分子化合物的合成之市售的大分子單體，可以使用AA-6（商品名稱，TOAGOSEI CO.,LTD.製造）、AA-10（商品名稱，TOAGOSEI CO.,LTD.製造）、AB-6（商品名稱，TOAGOSEI CO.,LTD.製造）、AS-6（商品名稱，TOAGOSEI CO.,LTD.製造）、AN-6（商品名稱，TOAGOSEI CO.,LTD.製造）、AW-6（商品名稱，TOAGOSEI CO.,LTD.製造）、AA-714（商品名稱，TOAGOSEI CO.,LTD.製造）、AY-707（商品名稱，TOAGOSEI CO.,LTD.製造）、AY-714（商品名稱，TOAGOSEI CO.,LTD.製造）、AK-5（商品名稱，TOAGOSEI CO.,LTD.製造）、AK-30（商品名稱，TOAGOSEI CO.,LTD.製造）、AK-32（商品名稱，TOAGOSEI CO.,LTD.製造）、BLEMMER PP-100（商品名稱，NOF CORPORATION製造）、BLEMMER PP-500（商品名稱，NOF CORPORATION製造）、BLEMMER PP-800（商品名稱，NOF CORPORATION製造）、BLEMMER PP-1000（商品名稱，NOF CORPORATION製造）、BLEMMER 55-PET-800（商品名稱，NOF CORPORATION製造）、BLEMMER PME-4000（商品名稱，NOF CORPORATION製造）、BLEMMER PSE-400（商品名稱，NOF CORPORATION製造）、BLEMMER PSE-1300（商品名稱，NOF CORPORATION製造）、BLEMMER 43PAPE-600B（商品名稱，NOF CORPORATION製造）等。其中，較佳為使用AA-6（商品名稱，TOAGOSEI CO.,LTD.製造）、AA-10（商品名稱，TOAGOSEI CO.,LTD.製造）、AB-6（商品名稱，TOAGOSEI CO.,LTD.製造）、AS-6（商品名稱，TOAGOSEI CO.,LTD.製造）、AN-6（商品名稱，TOAGOSEI CO.,LTD.製造）及BLEMMER PME-4000（商品名稱，NOF CORPORATION製造）等。As a commercially available macromonomer that corresponds to a structural unit containing a graft chain contained in a polymer compound and is preferably used for the synthesis of a polymer compound, AA-6 (trade name, TOAGOSEI CO., LTD.) can be used. .manufactured), AA-10 (trade name, manufactured by TOAGOSEI CO., LTD.), AB-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AS-6 (trade name, manufactured by TOAGOSEI CO., LTD. ), AN-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AW-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AA-714 (trade name, manufactured by TOAGOSEI CO., LTD.), AY-707 (trade name, manufactured by TOAGOSEI CO., LTD.), AY-714 (trade name, manufactured by TOAGOSEI CO., LTD.), AK-5 (trade name, manufactured by TOAGOSEI CO., LTD.), AK- 30 (trade name, manufactured by TOAGOSEI CO., LTD.), AK-32 (trade name, manufactured by TOAGOSEI CO., LTD.), BLEMMER PP-100 (trade name, manufactured by NOF CORPORATION), BLEMMER PP-500 (trade name, manufactured by NOF CORPORATION) , manufactured by NOF CORPORATION), BLEMMER PP-800 (trade name, manufactured by NOF CORPORATION), BLEMMER PP-1000 (trade name, manufactured by NOF CORPORATION), BLEMMER 55-PET-800 (trade name, manufactured by NOF CORPORATION), BLEMMER PME- 4000 (trade name, manufactured by NOF CORPORATION), BLEMMER PSE-400 (trade name, manufactured by NOF CORPORATION), BLEMMER PSE-1300 (trade name, manufactured by NOF CORPORATION), BLEMMER 43PAPE-600B (trade name, manufactured by NOF CORPORATION), etc. Among them, it is preferable to use AA-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AA-10 (trade name, manufactured by TOAGOSEI CO., LTD.), AB-6 (trade name, manufactured by TOAGOSEI CO., LTD.) .manufactured), AS-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AN-6 (trade name, manufactured by TOAGOSEI CO., LTD.) and BLEMMER PME-4000 (trade name, manufactured by NOF CORPORATION).

分散劑含有選自包括聚丙烯酸甲酯、聚甲基丙烯酸甲酯及環狀或鏈狀的聚酯之組群中之至少1種結構為較佳。分散劑含有選自包括聚丙烯酸甲酯、聚甲基丙烯酸甲酯及鏈狀的聚酯之組群中之至少1種結構為更佳。分散劑含有選自包括聚丙烯酸甲酯結構、聚甲基丙烯酸甲酯結構、聚己內酯結構及聚戊內酯結構之組群中之至少1種結構為進一步較佳。分散劑可以是在一分散劑中單獨含有上述結構者，亦可以是在一分散劑中含有複數個該等結構者。 在此，聚己內酯結構是指含有ε-己內酯開環之結構作為重複單元者。聚戊內酯結構是指含有δ-戊內酯開環之結構作為重複單元者。 作為含有聚己內酯結構之分散劑的具體例，可以舉出下述式（1）及下述式（2）中之j及k為5者。作為含有聚戊內酯結構之分散劑的具體例，可以舉出下述式（1）及下述式（2）中之j及k為4者。 作為含有聚丙烯酸甲酯結構之分散劑的具體例，可以舉出下述式（4）中之X5 為氫原子且R4 為甲基者。作為含有聚甲基丙烯酸甲酯結構之分散劑的具體例，可以舉出下述式（4）中之X5 為甲基且R4 為甲基者。Preferably, the dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate and chain polyester. It is further preferable that the dispersant contains at least one structure selected from the group consisting of a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure and a polyvalerolactone structure. The dispersing agent may contain the above-mentioned structures alone in one dispersing agent, or may contain a plurality of these structures in one dispersing agent. Here, the polycaprolactone structure refers to a structure containing an ε-caprolactone ring-opened structure as a repeating unit. The polyvalerolactone structure refers to a structure containing a ring-opened structure of delta-valerolactone as a repeating unit. As a specific example of the dispersing agent containing a polycaprolactone structure, the thing in which j and k in following formula (1) and following formula (2) are 5 is mentioned. As a specific example of the dispersing agent containing a polyvalerolactone structure, the thing in which j and k in following formula (1) and following formula (2) are 4 is mentioned. As a specific example of the dispersing agent containing a polymethyl acrylate structure, in the following formula (4), X 5 is a hydrogen atom, and R 4 is a methyl group. As a specific example of the dispersing agent containing a polymethyl methacrylate structure, in the following formula (4), X 5 is a methyl group, and R 4 is a methyl group.

・含有接枝鏈之結構單元 高分子化合物含有下述式（1）～式（4）中的任意一個所表示之結構單元作為含有接枝鏈之結構單元為較佳，含有下述式（1A）、下述式（2A）、下述式（3A）、下述式（3B）及下述式（4）中的任意一個所表示之結構單元為更佳。・Structural unit containing a graft chain The polymer compound preferably contains a structural unit represented by any one of the following formulae (1) to (4) as a structural unit containing a graft chain, and contains the following formula (1A ), the following formula (2A), the following formula (3A), the following formula (3B), and the structural unit represented by any one of the following formula (4) is more preferable.

[化學式1]

Figure 02_image001
[Chemical formula 1]
Figure 02_image001

式（1）～式（4）中，W1 、W2 、W3 及W4 分別獨立地表示氧原子或NH。W1 、W2 、W3 及W4 是氧原子為較佳。 式（1）～式（4）中，X1 、X2 、X3 、X4 及X5 分別獨立地表示氫原子或1價的有機基。從合成上的制約的觀點而言，X1 、X2 、X3 、X4 及X5 分別獨立地是氫原子或碳數（碳原子數）1～12的烷基為較佳，分別獨立地是氫原子或甲基為更佳，甲基為進一步較佳。In Formulas (1) to (4), W 1 , W 2 , W 3 and W 4 each independently represent an oxygen atom or NH. Preferably, W 1 , W 2 , W 3 and W 4 are oxygen atoms. In formulas (1) to (4), X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of synthetic constraints, it is preferable that X 1 , X 2 , X 3 , X 4 and X 5 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms), each independently The ground is more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group.

式（1）～式（4）中，Y1 、Y2 、Y3 及Y4 分別獨立地表示2價的連結基，連結基在結構上並沒有特別的制約。作為Y1 、Y2 、Y3 及Y4 所表示之2價的連結基，具體而言，可以舉出下述（Y-1）～（Y-21）的連結基等。下述所示之結構中，A、B分別是指鍵結部位。在下述所示之結構之中，從合成的簡便性而言，（Y-2）或（Y-13）為更佳。In Formulas (1) to (4), Y 1 , Y 2 , Y 3 and Y 4 each independently represent a divalent linking group, and the linking group is not particularly restricted in terms of structure. Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 and Y 4 include the following linking groups (Y-1) to (Y-21). In the structures shown below, A and B respectively refer to bonding sites. Among the structures shown below, (Y-2) or (Y-13) are more preferable from the viewpoint of ease of synthesis.

[化學式2]

Figure 02_image003
[Chemical formula 2]
Figure 02_image003

式（1）～式（4）中，Z1 、Z2 、Z3 及Z4 分別獨立地表示1價的有機基。有機基的結構並沒有特別限定，具體而言，可以舉出烷基、羥基、烷氧基、芳氧基、雜芳氧基、烷硫基醚基、芳硫基醚基、雜芳硫基醚基及胺基等。在該等之中，尤其從提高分散性之觀點而言，Z1 、Z2 、Z3 及Z4 所表示之有機基具有立體排斥效果者為較佳，各自獨立地是碳數5～24的烷基或烷氧基為更佳，各自獨立地是碳數5～24的分支烷基、碳數5～24的環狀烷基或碳數5～24的烷氧基為進一步較佳。另外，烷氧基中所包含之烷基可以是直鏈狀、支鏈狀及環狀中的任意一種。In Formulas (1) to (4), Z 1 , Z 2 , Z 3 and Z 4 each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, and specific examples thereof include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio ether group, an arylthio ether group, and a heteroarylthio group. ether and amine groups. Among them, in particular, from the viewpoint of improving dispersibility, the organic groups represented by Z 1 , Z 2 , Z 3 and Z 4 are preferably those having a steric repulsion effect, each independently having 5 to 24 carbon atoms. The alkyl group or alkoxy group is more preferably, and each independently is a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms. In addition, the alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

式（1）～式（4）中，n、m、p及q分別獨立地為1～500的整數。 式（1）及式（2）中，j及k分別獨立地表示2～8的整數。從組成物的經時穩定性及顯影性的觀點而言，式（1）及式（2）中之j及k是4～6的整數為更佳，5為進一步較佳。 又，式（1）及式（2）中，n及m是10以上的整數為較佳，20以上的整數為更佳。又，當分散劑含有聚己內酯結構及聚戊內酯結構時，作為聚己內酯結構的重複數與聚戊內酯的重複數之和，10以上的整數為較佳，20以上的整數為更佳。In Formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500. In Formula (1) and Formula (2), j and k each independently represent an integer of 2 to 8. It is more preferable that j and k in Formula (1) and Formula (2) are integers of 4-6, and 5 is more preferable from the viewpoint of the stability over time and developability of the composition. Moreover, in Formula (1) and Formula (2), n and m are preferably an integer of 10 or more, and more preferably an integer of 20 or more. Also, when the dispersant contains a polycaprolactone structure and a polyvalerolactone structure, as the sum of the repeating number of the polycaprolactone structure and the repeating number of the polyvalerolactone, an integer of 10 or more is preferable, and an integer of 20 or more is preferable. Integers are better.

式（3）中，R3 表示支鏈狀或直鏈狀的伸烷基，碳數1～10的伸烷基為較佳，碳數2或3的伸烷基為更佳。當p為2～500時，存在複數個之R3 彼此可以相同亦可以不同。 式（4）中，R4 表示氫原子或1價的有機基，該1價的有機基在結構上並沒有特別的限定。作為R4 ，較佳為可以舉出氫原子、烷基、芳基或雜芳基，更佳為氫原子或烷基。當R4 為烷基時，碳數1～20的直鏈狀烷基、碳數3～20的支鏈狀烷基或碳數5～20的環狀烷基為較佳，碳數1～20的直鏈狀烷基為更佳，碳數1～6的直鏈狀烷基為進一步較佳。式（4）中，當q為2～500時，在接枝共聚物中存在複數個之X5 及R4 彼此可以相同亦可以不同。In formula (3), R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, R 3 in plural may be the same or different from each other. In formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. Preferable examples of R 4 include a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R 4 is an alkyl group, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms is preferred. A straight-chain alkyl group of 20 is more preferable, and a straight-chain alkyl group having 1 to 6 carbon atoms is further preferable. In formula (4), when q is 2 to 500, X 5 and R 4 which are present in plural in the graft copolymer may be the same or different from each other.

又，高分子化合物能夠含有2種以上的結構不同之含有接枝鏈之結構單元。亦即，在高分子化合物的分子中可以包含彼此結構不同之式（1）～式（4）所表示之結構單元，又，式（1）～式（4）中，當n、m、p及q分別表示2以上的整數時，式（1）及式（2）中，在側鏈中可以包含j及k彼此不同之結構，式（3）及式（4）中，在分子內存在複數個之R3 、R4 及X5 彼此可以相同亦可以不同。In addition, the polymer compound can contain two or more structural units containing a graft chain that are different in structure. That is, structural units represented by formulas (1) to (4) whose structures are different from each other may be contained in the molecule of the polymer compound, and in formulas (1) to (4), when n, m, and p and q respectively represent an integer of 2 or more, in the formulas (1) and (2), a structure in which j and k are different from each other may be included in the side chain, and in the formulas (3) and (4), the structure exists in the molecule A plurality of R 3 , R 4 and X 5 may be the same or different from each other.

從組成物的經時穩定性及顯影性的觀點而言，式（1）所表示之結構單元是下述式（1A）所表示之結構單元為更佳。 從組成物的經時穩定性及顯影性的觀點而言，式（2）所表示之結構單元是下述式（2A）所表示之結構單元為更佳。It is more preferable that the structural unit represented by formula (1) is a structural unit represented by the following formula (1A) from the viewpoint of the stability over time and developability of the composition. It is more preferable that the structural unit represented by the formula (2) is the structural unit represented by the following formula (2A) from the viewpoints of the stability over time and developability of the composition.

[化學式3]

Figure 02_image005
[Chemical formula 3]
Figure 02_image005

式（1A）中，X1 、Y1 、Z1 及n的含義與式（1）中之X1 、Y1 、Z1 及n的含義相同，較佳的範圍亦相同。式（2A）中，X2 、Y2 、Z2 及m的含義與式（2）中之X2 、Y2 、Z2 及m的含義相同，較佳的範圍亦相同。In the formula (1A), X 1, 1 , Y 1, Z 1 and n have the same meaning as Y 1, Z 1 and n are as defined in the formula (1) in the X, preferred ranges are also the same. In formula (2A), X 2, Y 2, 2, Y 2, Z 2 and m are the same meaning as Z 2 and m are as defined for the formula (2) in the X, preferred ranges are also the same.

從組成物的經時穩定性及顯影性的觀點而言，式（3）所表示之結構單元是下述式（3A）或式（3B）所表示之結構單元為更佳。It is more preferable that the structural unit represented by formula (3) is a structural unit represented by the following formula (3A) or formula (3B) from the viewpoints of the stability over time and developability of the composition.

[化學式4]

Figure 02_image007
[Chemical formula 4]
Figure 02_image007

式（3A）或（3B）中，X3 、Y3 、Z3 及p的含義與式（3）中之X3 、Y3 、Z3 及p的含義相同，較佳的範圍亦相同。Formula (3A) or (3B) in, X 3, 3, Y 3 , Z 3 and p have the same meaning of Y 3, Z 3 and p meaning as in formula (3) in the X, preferred ranges are also the same.

高分子化合物含有式（1A）所表示之結構單元作為含有接枝鏈之結構單元為更佳。More preferably, the polymer compound contains the structural unit represented by the formula (1A) as the structural unit containing the graft chain.

在高分子化合物中，以質量換算計，相對於高分子化合物的總質量，在2～90%的範圍包含含有接枝鏈之結構單元（例如，上述式（1）～式（4）所表示之結構單元）為較佳，在5～30%的範圍包含為更佳。若在該範圍包含含有接枝鏈之結構單元，則含金屬氮化物粒子的分散性變高，形成硬化膜時的顯影性良好。In the polymer compound, the structural unit (for example, represented by the above formula (1) to formula (4)) is contained in the range of 2 to 90% with respect to the total mass of the polymer compound in terms of mass. The structural unit) is better, and it is more preferably included in the range of 5-30%. When the structural unit containing a graft chain is included in this range, the dispersibility of metal-containing nitride particles becomes high, and the developability at the time of forming a cured film becomes favorable.

・疏水性結構單元 又，高分子化合物含有與含有接枝鏈之結構單元不同（亦即，並不相當於含有接枝鏈之結構單元）之疏水性結構單元為較佳。其中，本說明書中，疏水性結構單元是不具有酸基（例如，羧酸基、磺酸基、磷酸基、酚性羥基等）之結構單元。・Hydrophobic structural unit In addition, it is preferable that the polymer compound contains a hydrophobic structural unit different from the structural unit containing the graft chain (that is, not equivalent to the structural unit containing the graft chain). However, in this specification, a hydrophobic structural unit is a structural unit which does not have an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).

疏水性結構單元較佳為源自（對應於）ClogP值為1.2以上的化合物（單體）之結構單元，更佳為源自ClogP值為1.2～8的化合物之結構單元。藉此，能夠更加確實地顯現本發明的效果。The hydrophobic structural unit is preferably a structural unit derived from (corresponds to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably a structural unit derived from a compound having a ClogP value of 1.2 to 8. Thereby, the effect of this invention can be exhibited more reliably.

ClogP值是由能夠從Daylight Chemical Information System，Inc.獲得之程式「CLOGP」計算出之值。該程式提供藉由Hansch，Leo的片段法（fragment approach）（參閱下述文獻）計算之「計算logP」的值。片段法是基於化合物的化學結構，將化學結構分割為部分結構（片段），並將對該片段分配之logP貢獻值進行合計，藉此推算化合物的logP值。其詳細內容記載於以下文獻中。本說明書中，ClogP值是指藉由程式CLOGP v4.82計算出之值。 A. J. Leo，Comprehensive Medicinal Chemistry，Vol.4，C. Hansch，P. G. Sammnens，J. B. Taylor and C. A. Ramsden，Eds.，p.295，Pergamon Press，1990 C. Hansch & A. J. Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A.J. Leo. Calculating logPoct from structure. Chem. Rev.，93，1281-1306，1993。The ClogP value is a value calculated by the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides "calculated logP" values calculated by the fragment approach of Hansch, Leo (see below). The fragment method is based on the chemical structure of the compound, divides the chemical structure into partial structures (fragments), and sums up the logP contribution values assigned to the fragments, thereby estimating the logP value of the compound. The details are described in the following documents. In this specification, the ClogP value refers to the value calculated by the program CLOGP v4.82. AJ Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, PG Sammnens, JB Taylor and CA Ramsden, Eds., p.295, Pergamon Press, 1990 C. Hansch & AJ Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. AJ Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.

logP是指分配係數P（Partition Coefficient）的常用對數，是以定量的數值表示某有機化合物在油（一般而言為1-辛醇）與水的兩相系的平衡下如何分配之物性值，由以下的式表示。 logP=log（Coil/Cwater） 式中，Coil表示油相中的化合物的莫耳濃度，Cwater表示水相中的化合物的莫耳濃度。 若logP的值以0為中心向正數變大，則指油溶性增加，若為負數且絕對值變大，則指水溶性增加，與有機化合物的水溶性具有負的相關關係，被廣泛利用為評估有機化合物的親疏水性之參數。logP refers to the common logarithm of the partition coefficient P (Partition Coefficient), which is a quantitative value indicating how an organic compound is distributed under the equilibrium of the two-phase system of oil (generally 1-octanol) and water. It is represented by the following formula. logP=log(Coil/Cwater) In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the water phase. If the value of logP increases toward a positive number around 0, it means that the oil solubility increases, and if it is a negative number and the absolute value increases, it means an increase in water solubility, which has a negative correlation with the water solubility of organic compounds, and is widely used as Parameter for evaluating the hydrophilicity and hydrophobicity of organic compounds.

高分子化合物含有選自源自下述式（i）～（iii）所表示之單量體之結構單元中之1種以上的結構單元作為疏水性結構單元為較佳。The polymer compound preferably contains, as the hydrophobic structural unit, one or more structural units selected from structural units derived from the monomers represented by the following formulae (i) to (iii).

[化學式5]

Figure 02_image009
[Chemical formula 5]
Figure 02_image009

上述式（i）～（iii）中，R1 、R2 及R3 分別獨立地表示氫原子、鹵素原子（例如，氟原子、氯原子、溴原子等）或碳數為1～6的烷基（例如，甲基、乙基、丙基等）。 R1 、R2 及R3 較佳為氫原子或碳數為1～3的烷基，更佳為氫原子或甲基。R2 及R3 是氫原子為進一步較佳。 X表示氧原子（-O-）或亞胺基（-NH-），氧原子為較佳。In the above formulae (i) to (iii), R 1 , R 2 and R 3 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkane having 1 to 6 carbon atoms. group (eg, methyl, ethyl, propyl, etc.). R 1 , R 2 and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. It is further preferable that R 2 and R 3 are hydrogen atoms. X represents an oxygen atom (-O-) or an imino group (-NH-), and an oxygen atom is preferred.

L為單鍵或2價的連結基。作為2價的連結基，可以舉出2價的脂肪族基（例如，伸烷基、經取代之伸烷基、伸烯基、經取代之伸烯基、伸炔基、經取代之伸炔基）、2價的芳香族基（例如，伸芳基、經取代之伸芳基）、2價的雜環基、氧原子（-O-）、硫原子（-S-）、亞胺基（-NH-）、經取代之亞胺基（-NR31 -，其中R31 為脂肪族基、芳香族基或雜環基）、羰基（-CO-）及該等的組合等。L is a single bond or a divalent linking group. The divalent linking group includes a divalent aliphatic group (for example, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, substituted alkyne base), 2-valent aromatic group (for example, aryl extended group, substituted aryl extended group), 2-valent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino (-NR 31 -, wherein R 31 is aliphatic, aromatic or heterocyclic), carbonyl (-CO-) and combinations thereof and the like.

2價的脂肪族基可以具有環狀結構或分支結構。脂肪族基的碳數是1～20為較佳，1～15為更佳，1～10為進一步較佳。脂肪族基可以是不飽和脂肪族基，亦可以是飽和脂肪族基，但飽和脂肪族基為較佳。脂肪族基可以具有取代基。取代基的例子可以舉出鹵素原子、芳香族基及雜環基等。The divalent aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but a saturated aliphatic group is preferred. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, a heterocyclic group, and the like.

2價的芳香族基的碳數是6～20為較佳，6～15為更佳，6～10為進一步較佳。芳香族基可以具有取代基。取代基的例子可以舉出鹵素原子、脂肪族基、芳香族基及雜環基等。The number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, and the like.

2價的雜環基含有5員環或6員環作為雜環為較佳。雜環中可以縮合有其他雜環、脂肪族環或芳香族環。雜環基可以具有取代基。作為取代基的例子，可以舉出鹵素原子、羥基、側氧基（oxo group）（=O）、硫基（thioxo group）（=S）、亞胺基（=NH）、經取代之亞胺基（=N-R32 ，其中R32 為脂肪族基、芳香族基或雜環基）、脂肪族基、芳香族基或雜環基。The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocyclic ring. The heterocyclic ring may be condensed with other heterocyclic rings, aliphatic rings or aromatic rings. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (=O), a thioxo group (=S), an imino group (=NH), and a substituted imine. group (=NR 32 , wherein R 32 is aliphatic, aromatic or heterocyclic), aliphatic, aromatic or heterocyclic.

L是單鍵、伸烷基或含有氧化烯結構之2價的連結基為較佳。氧化烯結構是氧乙烯基結構或氧丙烯基結構為更佳。L可以包含重複含有2個以上的氧化烯結構之聚氧化烯結構。作為聚氧化烯結構，聚氧乙烯基結構或聚氧丙烯基結構為較佳。聚氧乙烯基結構由-（OCH2 CH2 ）n-表示，n是2以上的整數為較佳，2～10的整數為更佳。L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. More preferably, the oxyalkylene structure is an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure in which two or more oxyalkylene structures are repeatedly contained. As the polyoxyalkylene structure, a polyoxyethylene-based structure or a polyoxypropylene-based structure is preferable. The polyoxyethylene structure is represented by -(OCH 2 CH 2 )n-, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.

作為Z，可以舉出脂肪族基（例如，烷基、經取代之烷基、不飽和烷基、取代不飽和烷基、）、芳香族基（例如，芳基、經取代之芳基、伸芳基、經取代之伸芳基）、雜環基或該等的組合。該等基團中可以包含氧原子（-O-）、硫原子（-S-）、亞胺基（-NH-）、經取代之亞胺基（-NR31 -，其中R31 為脂肪族基、芳香族基或雜環基）或羰基（-CO-）。As Z, an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group, etc.), an aromatic group (for example, an aryl group, a substituted aryl group, an extended aryl, substituted aryl), heterocyclyl, or a combination of these. These groups may contain oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino group (-NR 31 -, wherein R 31 is aliphatic group, aromatic group or heterocyclic group) or carbonyl group (-CO-).

脂肪族基可以具有環狀結構或分支結構。脂肪族基的碳數是1～20為較佳，1～15為更佳，1～10為進一步較佳。脂肪族基中進一步包含環集合烴基、交聯環式烴基，作為環集合烴基的例子，包含雙環己基、全氫萘基（perhydronaphthalenyl）、聯苯基及4-環己基苯基等。作為交聯環式烴環，例如可以舉出蒎烷（pinane）、莰烷（bornane）、降蒎烷（norpinane）、降莰烷（norbornane）、雙環辛烷環（雙環[2.2.2]辛烷環及雙環[3.2.1]辛烷環等）等2環式烴環、高布雷烷、金剛烷、三環[5.2.1.02,6 ]癸烷及三環[4.3.1.12,5 ]十一烷環等3環式烴環、以及四環[4.4.0.12,5 .17,10 ]十二烷及全氫-1,4-甲橋（methano）-5,8-甲橋萘環等4環式烴環等。交聯環式烴環中亦包含稠環式烴環，例如全氫萘（十氫萘）、全氫蒽、全氫菲、全氫苊、全氫茀、全氫茚及全氫葩環等5～8員環烷烴環複數個縮合而得到之稠環。 與不飽和脂肪族基相比，脂肪族基是飽和脂肪族基為較佳。脂肪族基可以具有取代基。作為取代基的例子，可以舉出鹵素原子、芳香族基及雜環基。但是，脂肪族基並不具有酸基作為取代基。The aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group further includes a ring-assembled hydrocarbon group and a cross-linked cyclic hydrocarbon group, and examples of the ring-assembled hydrocarbon group include bicyclohexyl, perhydronaphthalenyl, biphenyl, 4-cyclohexylphenyl, and the like. Examples of the crosslinked cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, bicyclooctane (bicyclo[2.2.2]octane) 2-cyclic hydrocarbon rings such as alkane ring and bicyclo[3.2.1]octane ring, etc.), homobreane, adamantane, tricyclo[5.2.1.0 2,6 ] decane and tricyclo[4.3.1.1 2,5 ] 3-cyclic hydrocarbon rings such as undecane ring, tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodecane and perhydro-1,4-methano-5,8-methano Bridged naphthalene ring and other 4-cyclic hydrocarbon rings, etc. The cross-linked cyclic hydrocarbon ring also includes fused cyclic hydrocarbon rings, such as perhydronaphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydroindene, perhydroindene, and perhydropaline, etc. A fused ring obtained by the condensation of multiple 5-8 membered cycloalkane rings. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. As an example of a substituent, a halogen atom, an aromatic group, and a heterocyclic group are mentioned. However, the aliphatic group does not have an acid group as a substituent.

芳香族基的碳數是6～20為較佳，6～15為更佳，6～10為進一步較佳。芳香族基可以具有取代基。取代基的例子可以舉出鹵素原子、脂肪族基、芳香族基及雜環基。其中，芳香族基並不具有酸基作為取代基。The number of carbon atoms in the aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include halogen atoms, aliphatic groups, aromatic groups, and heterocyclic groups. Among them, the aromatic group does not have an acid group as a substituent.

雜環基含有5員環或6員環作為雜環為較佳。雜環上可以縮合有其他雜環、脂肪族環或芳香族環。雜環基可以具有取代基。作為取代基的例子，可以舉出鹵素原子、羥基、側氧基（=O）、硫基（=S）、亞胺基（=NH）、經取代之亞胺基（=N-R32 ，其中R32 為脂肪族基、芳香族基或雜環基）、脂肪族基、芳香族基及雜環基。但是，雜環基並不具有酸基作為取代基。The heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocyclic ring. The heterocycle may be condensed with other heterocycles, aliphatic rings or aromatic rings. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a pendant oxy group (=O), a thio group (=S), an imino group (=NH), a substituted imino group (=NR 32 , wherein R 32 is aliphatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.

上述式（iii）中，R4 、R5 及R6 分別獨立地表示氫原子、鹵素原子（例如，氟原子、氯原子、溴原子等）、碳數為1～6的烷基（例如，甲基、乙基、丙基等）、Z或L-Z。在此，L及Z的含義與上述中者的含義相同。作為R4 、R5 及R6 ，氫原子或碳數為1～3的烷基為較佳，氫原子為更佳。In the above formula (iii), R 4 , R 5 and R 6 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, propyl, etc.), Z or LZ. Here, the meanings of L and Z are the same as those described above. As R 4 , R 5 and R 6 , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

作為上述式（i）所表示之單量體，R1 、R2 及R3 為氫原子或甲基、L為單鍵或伸烷基或含有氧化烯結構之2價的連結基、X為氧原子或亞胺基、且Z為脂肪族基、雜環基或芳香族基的化合物為較佳。 作為上述式（ii）所表示之單量體，R1 為氫原子或甲基、L為伸烷基、且Z為脂肪族基、雜環基或芳香族基的化合物為較佳。作為上述式（iii）所表示之單量體，R4 、R5 及R6 為氫原子或甲基、且Z為脂肪族基、雜環基或芳香族基的化合物為較佳。As the monomer represented by the above formula (i), R 1 , R 2 and R 3 are hydrogen atoms or methyl groups, L is a single bond or an alkylene group or a divalent linking group containing an oxyalkylene structure, and X is A compound in which an oxygen atom or an imino group and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable. The monomer represented by the above formula (ii) is preferably a compound in which R 1 is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group or an aromatic group. The monomer represented by the above formula (iii) is preferably a compound in which R 4 , R 5 and R 6 are hydrogen atoms or methyl groups, and Z is an aliphatic group, a heterocyclic group or an aromatic group.

作為式（i）～（iii）所表示之代表性化合物的例子，可以舉出選自丙烯酸酯類、甲基丙烯酸酯類及苯乙烯類等中之自由基聚合性化合物。 另外，作為式（i）～（iii）所表示之代表性化合物的例子，能夠參閱日本特開2013-249417號公報的0089～0093段中所記載之化合物，該等內容被併入本說明書中。Examples of representative compounds represented by formulae (i) to (iii) include radically polymerizable compounds selected from acrylates, methacrylates, styrenes, and the like. In addition, as examples of the representative compounds represented by the formulae (i) to (iii), the compounds described in paragraphs 0089 to 0093 of JP-A-2013-249417 can be referred to, and these contents are incorporated into the present specification .

在高分子化合物中，以質量換算計，相對於高分子化合物的總質量，在10～90%的範圍包含疏水性結構單元為較佳，在20～80%的範圍包含為更佳。含量在上述範圍內時可得到充分的圖案形成性。In the polymer compound, the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably in a range of 20 to 80%, based on the total mass of the polymer compound in terms of mass. When the content is within the above range, sufficient pattern formability can be obtained.

・能夠與含金屬氮化物粒子等形成相互作用之官能基 高分子化合物能夠導入能夠與含金屬氮化物粒子等形成相互作用之官能基。在此，高分子化合物進一步包含含有能夠與含金屬氮化物粒子等形成相互作用之官能基之結構單元為較佳。 作為該能夠與含金屬氮化物粒子等形成相互作用之官能基，例如可以舉出酸基、鹼性基、配位性基及具有反應性之官能基等。 當高分子化合物含有酸基、鹼性基、配位性基或具有反應性之官能基時，分別包含含有酸基之結構單元、含有鹼性基之結構單元、含有配位性基之結構單元或具有反應性之結構單元為較佳。 尤其，藉由高分子化合物進一步含有羧酸基等鹼可溶性基作為酸基，能夠對高分子化合物賦予用於藉由鹼顯影形成圖案之顯影性。 亦即，藉由在高分子化合物中導入鹼可溶性基，上述組成物中，作為有助於含金屬氮化物粒子等的分散之分散劑之高分子化合物會具有鹼可溶性。含有該種高分子化合物之組成物成為曝光部的遮光性優異者，且未曝光部的鹼顯影性得到提高。 又，藉由高分子化合物包含含有酸基之結構單元，具有高分子化合物容易與溶劑親和，且塗佈性亦得到提高之傾向。 推測這是由於，含有酸基之結構單元中之酸基容易與含金屬氮化物粒子等相互作用，高分子化合物使含金屬氮化物粒子等穩定地分散，並且使含金屬氮化物粒子等分散之高分子化合物的黏度降低，從而高分子化合物本身亦容易穩定地被分散。・Functional groups capable of interacting with metal-containing nitride particles, etc. Functional groups capable of interacting with metal-containing nitride particles, etc. can be introduced into polymer compounds. Here, it is preferable that the polymer compound further contains a structural unit containing a functional group capable of interacting with the metal-containing nitride particles and the like. Examples of the functional group capable of interacting with the metal-containing nitride particles and the like include an acid group, a basic group, a coordinating group, and a reactive functional group. When the polymer compound contains an acid group, a basic group, a coordinating group or a reactive functional group, it contains a structural unit containing an acid group, a structural unit containing a basic group, and a structural unit containing a coordinating group, respectively. Or a reactive structural unit is preferred. In particular, when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be provided with developability for forming a pattern by alkali development. That is, by introducing an alkali-soluble group into the polymer compound, in the above-mentioned composition, the polymer compound serving as a dispersant that contributes to the dispersion of metal-containing nitride particles and the like becomes alkali-soluble. The composition containing such a polymer compound is excellent in the light-shielding property of the exposed part, and the alkali developability of the unexposed part is improved. In addition, since the polymer compound contains a structural unit containing an acid group, the polymer compound tends to have an affinity with a solvent, and the applicability tends to be improved. This is presumably because the acid group in the acid group-containing structural unit easily interacts with the metal-containing nitride particles and the like, and the polymer compound stably disperses the metal-containing nitride particles and the like, and disperses the metal-containing nitride particles and the like. The viscosity of the polymer compound is lowered, so that the polymer compound itself is easily and stably dispersed.

其中，含有作為酸基之鹼可溶性基之結構單元可以是與上述含有接枝鏈之結構單元相同之結構單元，亦可以是不同之結構單元，但含有作為酸基之鹼可溶性基之結構單元是與上述疏水性結構單元不同之結構單元（亦即，並不相當於上述疏水性結構單元）。Among them, the structural unit containing the alkali-soluble group as the acid group may be the same structural unit as the above-mentioned structural unit containing the graft chain, or it may be a different structural unit, but the structural unit containing the alkali-soluble group as the acid group is A structural unit different from the above-mentioned hydrophobic structural unit (that is, not equivalent to the above-mentioned hydrophobic structural unit).

作為能夠與含金屬氮化物粒子等形成相互作用之官能基亦即酸基，例如有羧酸基、磺酸基、磷酸基或酚性羥基等，較佳為羧酸基、磺酸基及磷酸基中的至少1種，在對含金屬氮化物粒子等之吸附力良好且分散性較高的觀點上，更佳為羧酸基。 亦即，高分子化合物進一步包含含有羧酸基、磺酸基及磷酸基中的至少1種之結構單元為較佳。Examples of functional groups that can interact with metal-containing nitride particles, that is, acid groups include carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, phenolic hydroxyl groups, and the like, preferably carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups. At least one of the groups is more preferably a carboxylic acid group from the viewpoint of good adsorption force to metal-containing nitride particles and the like and high dispersibility. That is, it is preferable that the polymer compound further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

高分子化合物可以具有1種或2種以上的含有酸基之結構單元。 高分子化合物可以包含或不包含含有酸基之結構單元，當含有時，含有酸基之結構單元的含量以質量換算計，相對於高分子化合物的總質量，較佳為5～80%，從抑制由鹼顯影引起之圖像強度的損失之觀點而言，更佳為10～60%。The polymer compound may have one or two or more structural units containing an acid group. The polymer compound may or may not contain a structural unit containing an acid group. When it does, the content of the structural unit containing an acid group is calculated in terms of mass, relative to the total mass of the polymer compound, preferably 5 to 80%. From the viewpoint of suppressing the loss of image strength due to alkali development, it is more preferably 10 to 60%.

作為能夠與含金屬氮化物粒子等形成相互作用之官能基亦即鹼性基，例如有一級胺基、二級胺基、三級胺基、含有N原子之雜環及醯胺基等，在對含金屬氮化物粒子等之吸附力良好且分散性較高的觀點上，較佳的是三級胺基。高分子化合物能夠含有1種或2種以上的該等鹼性基。 高分子化合物可以包含或不包含含有鹼性基之結構單元，當含有時，含有鹼性基之結構單元的含量以質量換算計，相對於高分子化合物的總質量，較佳為0.01%以上且50%以下，從抑制顯影性阻礙之觀點而言，更佳為0.01%以上且30%以下。Examples of functional groups capable of interacting with metal-containing nitride particles, that is, basic groups, include primary amine groups, secondary amine groups, tertiary amine groups, heterocycles containing N atoms, and amide groups. A tertiary amine group is preferable from the viewpoint of good adsorption force to metal-containing nitride particles and the like and high dispersibility. The polymer compound can contain one kind or two or more kinds of these basic groups. The polymer compound may or may not contain a structural unit containing a basic group. When it does, the content of the structural unit containing a basic group is preferably 0.01% or more relative to the total mass of the polymer compound in terms of mass conversion. 50% or less is more preferably 0.01% or more and 30% or less from the viewpoint of suppressing the developmental hindrance.

作為能夠與含金屬氮化物粒子等形成相互作用之官能基亦即配位性基及具有反應性之官能基，例如可以舉出乙醯基乙醯氧基、三烷氧基矽基、異氰酸酯基、酸酐及醯氯等。在對含金屬氮化物粒子等之吸附力良好且含金屬氮化物粒子等的分散性較高的觀點上，較佳者為乙醯基乙醯氧基。高分子化合物可以具有1種或2種以上的該種基團。 高分子化合物可以包含或不包含含有配位性基之結構單元或含有具有反應性之官能基之結構單元，當含有時，該等結構單元的含量以質量換算計，相對於高分子化合物的總質量，較佳為10%以上且80%以下，從抑制顯影性的阻礙之觀點而言，更佳為20%以上且60%以下。Examples of functional groups capable of interacting with metal-containing nitride particles, ie, coordinating groups and reactive functional groups include acetylacetoxyl groups, trialkoxysilyl groups, and isocyanate groups. , acid anhydride and acyl chloride, etc. From the viewpoints of good adsorption force to the metal-containing nitride particles and the like and high dispersibility of the metal-containing nitride particles and the like, acetylacetoxyl is preferable. The polymer compound may have one kind or two or more kinds of such groups. The polymer compound may or may not contain a structural unit containing a coordinating group or a structural unit containing a reactive functional group. The mass is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less, from the viewpoint of suppressing the inhibition of developability.

當上述高分子化合物除了接枝鏈以外還含有能夠與含金屬氮化物粒子等形成相互作用之官能基時，含有上述各種能夠與含金屬氮化物粒子等形成相互作用之官能基即可，關於該等官能基以哪種方式被導入並沒有特別限定，高分子化合物含有選自源自下述式（iv）～（vi）所表示之單量體之結構單元中之1種以上的結構單元為較佳。When the polymer compound contains a functional group capable of interacting with metal-containing nitride particles and the like in addition to the graft chain, it is sufficient to contain the above-mentioned various functional groups capable of interacting with metal-containing nitride particles and the like. It is not particularly limited in which way the functional groups such as the equivalence are introduced, and the polymer compound contains one or more structural units selected from the structural units derived from the monomers represented by the following formulae (iv) to (vi): better.

[化學式6]

Figure 02_image011
[Chemical formula 6]
Figure 02_image011

式（iv）～式（vi）中，R11 、R12 及R13 分別獨立地表示氫原子、鹵素原子（例如，氟原子、氯原子、溴原子等）或碳數為1～6的烷基（例如，甲基、乙基、丙基等）。 式（iv）～式（vi）中，R11 、R12 及R13 較佳為分別獨立地是氫原子或碳數為1～3的烷基，更佳為分別獨立地是氫原子或甲基。通式（iv）中，R12 及R13 分別是氫原子為特佳。In formulas (iv) to (vi), R 11 , R 12 and R 13 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkane having 1 to 6 carbon atoms. group (eg, methyl, ethyl, propyl, etc.). In formulas (iv) to (vi), R 11 , R 12 and R 13 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably each independently a hydrogen atom or a methyl group. base. In the general formula (iv), it is particularly preferred that R 12 and R 13 are each a hydrogen atom.

式（iv）中的X1 表示氧原子（-O-）或亞胺基（-NH-），氧原子為較佳。 式（v）中的Y表示次甲基或氮原子。 X 1 in the formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), and an oxygen atom is preferable. Y in formula (v) represents a methine group or a nitrogen atom.

式（iv）～式（v）中的L1 表示單鍵或2價的連結基。2價的連結基的定義與上述式（i）中的L所表示之2價的連結基的定義相同。 L 1 in formulas (iv) to (v) represents a single bond or a divalent linking group. The definition of the divalent linking group is the same as the definition of the divalent linking group represented by L in the above formula (i).

L1 是單鍵、伸烷基或含有氧化烯結構之2價的連結基為較佳。氧化烯結構是氧乙烯基結構或氧丙烯基結構為更佳。L1 可以包含重複含有2個以上的氧化烯結構之聚氧化烯結構。作為聚氧化烯結構，聚氧乙烯基結構或聚氧丙烯基結構為較佳。聚氧乙烯基結構由-（OCH2 CH2 ）n-表示，n是2以上的整數為較佳，2～10的整數為更佳。L 1 is preferably a single bond, an alkylene group, or a divalent linking group containing an oxyalkylene structure. More preferably, the oxyalkylene structure is an oxyethylene structure or an oxypropylene structure. L 1 may contain a polyoxyalkylene structure repeatedly containing two or more oxyalkylene structures. As the polyoxyalkylene structure, a polyoxyethylene-based structure or a polyoxypropylene-based structure is preferable. The polyoxyethylene structure is represented by -(OCH 2 CH 2 )n-, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.

式（iv）～式（vi）中，Z1 表示接枝鏈以外能夠與含金屬氮化物粒子等形成相互作用之官能基，羧酸基及三級胺基為較佳，羧酸基為更佳。In formulas (iv) to (vi), Z 1 represents a functional group other than the graft chain that can interact with the metal-containing nitride particles, etc., carboxylic acid groups and tertiary amine groups are preferred, and carboxylic acid groups are more preferred. good.

式（vi）中，R14 、R15 及R16 分別獨立地表示氫原子、鹵素原子（例如，氟原子、氯原子、溴原子等）、碳數為1～6的烷基（例如，甲基、乙基、丙基等）、-Z1 或L1 -Z1 。在此，L1 及Z1 的含義與上述中之L1 及Z1 的含義相同，較佳的例子亦相同。作為R14 、R15 及R16 ，分別獨立地是氫原子或碳數為1～3的烷基為較佳，氫原子為更佳。In formula (vi), R 14 , R 15 and R 16 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group). , ethyl, propyl, etc.), - Z 1 or L 1 -Z 1. Here, L 1 and Z 1 have the meaning and the meaning of L 1 and Z 1 is the same as above, preferred examples are also the same. As R 14 , R 15 and R 16 , each independently is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

作為式（iv）所表示之單量體，R11 、R12 及R13 分別獨立地為氫原子或甲基、L1 為伸烷基或含有氧化烯結構之2價的連結基、X1 為氧原子或亞胺基、且Z1 為羧酸基的化合物為較佳。 作為式（v）所表示之單量體，R11 為氫原子或甲基、L1 為伸烷基、Z1 為羧酸基、且Y為次甲基的化合物為較佳。 作為式（vi）所表示之單量體，R14 、R15 及R16 分別獨立地為氫原子或甲基、L1 為單鍵或伸烷基、且Z1 為羧酸基的化合物為較佳。As the monomer represented by the formula (iv), R 11 , R 12 and R 13 are each independently a hydrogen atom or a methyl group, L 1 is an alkylene group or a divalent linking group containing an oxyalkylene structure, X 1 The compound which is an oxygen atom or an imino group and Z 1 is a carboxylic acid group is preferable. The monomer represented by the formula (v) is preferably a compound in which R 11 is a hydrogen atom or a methyl group, L 1 is an alkylene group, Z 1 is a carboxylic acid group, and Y is a methine group. As the monomer represented by the formula (vi), the compound in which R 14 , R 15 and R 16 are each independently a hydrogen atom or a methyl group, L 1 is a single bond or an alkylene group, and Z 1 is a carboxylic acid group is: better.

以下，示出式（iv）～式（vi）所表示之單量體（化合物）的代表性例。 作為單量體的例子，可以舉出甲基丙烯酸、巴豆酸、異巴豆酸、在分子內含有加成聚合性雙鍵及羥基之化合物（例如，甲基丙烯酸2-羥基乙酯）與琥珀酸酐的反應物、在分子內含有加成聚合性雙鍵及羥基之化合物與鄰苯二甲酸酐的反應物、在分子內含有加成聚合性雙鍵及羥基之化合物與四羥基鄰苯二甲酸酐的反應物、在分子內含有加成聚合性雙鍵及羥基之化合物與偏苯三酸酐的反應物、在分子內含有加成聚合性雙鍵及羥基之化合物與均苯四甲酸酐的反應物、丙烯酸、丙烯酸二聚物、丙烯酸寡聚物、順丁烯二酸、衣康酸、反丁烯二酸、4-乙烯基苯甲酸、乙烯基苯酚及4-羥基苯基甲基丙烯醯胺等。Representative examples of the monomers (compounds) represented by the formulae (iv) to (vi) are shown below. Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, compounds containing an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate), and succinic anhydride The reactant of the compound, the compound containing the addition polymerizable double bond and the hydroxyl group in the molecule and the phthalic anhydride, the compound containing the addition polymerizable double bond and the hydroxyl group in the molecule and the tetrahydroxyphthalic anhydride Reactants of compounds containing addition polymerizable double bonds and hydroxyl groups in the molecule and trimellitic anhydride, compounds containing addition polymerizable double bonds and hydroxyl groups in the molecules and pyromellitic anhydride reactants, acrylic acid, Acrylic acid dimer, acrylic oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinyl benzoic acid, vinyl phenol and 4-hydroxyphenyl methacrylamide, etc.

從與含金屬氮化物粒子等之相互作用、經時穩定性及對顯影液之滲透性的觀點而言，含有能夠與含金屬氮化物粒子等形成相互作用之官能基之結構單元的含量相對於高分子化合物的總質量，是0.05質量%～90質量%為較佳，1.0質量%～80質量%為更佳，10質量%～70質量%為進一步較佳。From the viewpoints of interaction with metal-containing nitride particles and the like, stability over time, and permeability to developing solutions, the content of the structural unit containing a functional group capable of forming an interaction with metal-containing nitride particles and the like is relative to The total mass of the polymer compound is preferably 0.05% by mass to 90% by mass, more preferably 1.0% by mass to 80% by mass, and even more preferably 10% by mass to 70% by mass.

・其他結構單元 以提高圖像強度等諸多性能為目的，只要不損害本發明的效果，則高分子化合物可以進一步具有與含有接枝鏈之結構單元、疏水性結構單元及含有能夠與含金屬氮化物粒子等形成相互作用之官能基之結構單元不同之、具有各種功能之其他結構單元（例如，含有具有與用於分散組成物之溶劑之親和性之官能基等之結構單元）。 作為該種其他結構單元，例如可以舉出源自選自丙烯腈類及甲基丙烯腈類等中之自由基聚合性化合物之結構單元。 高分子化合物能夠使用1種或2種以上的該等其他結構單元，其含量以質量換算計，相對於高分子化合物的總質量，較佳為0%～80%，更佳為10%～60%。含量在上述範圍之情況下，可維持充分的圖案形成性。・Other structural units For the purpose of improving various properties such as image strength, as long as the effect of the present invention is not impaired, the polymer compound may further have a structural unit containing a graft chain, a hydrophobic structural unit, and a structural unit capable of interacting with metal nitrogen Other structural units having various functions (for example, structural units containing functional groups having affinity with the solvent used to disperse the composition, etc.), which are different from the structural units that form functional groups that interact with chemical particles, etc. As such other structural unit, the structural unit derived from the radically polymerizable compound chosen from acrylonitrile, methacrylonitrile, etc. is mentioned, for example. The polymer compound can use one or more of these other structural units, and its content is calculated by mass conversion, relative to the total mass of the polymer compound, preferably 0% to 80%, more preferably 10% to 60% %. When the content is within the above range, sufficient pattern formability can be maintained.

・高分子化合物的物性 高分子化合物的酸值在0mgKOH/g以上且250mgKOH/g以下的範圍為較佳，更佳為10mgKOH/g以上且200mgKOH/g以下的範圍，進一步較佳為20mgKOH/g以上且120mgKOH/g以下的範圍。 若高分子化合物的酸值為250mgKOH/g以下，則可更有效地抑制形成硬化膜時的顯影時之圖案剝離。若高分子化合物的酸值為10mgKOH/g以上，則鹼顯影性變得更加良好。若高分子化合物的酸值為20mgKOH/g以上，則能夠進一步抑制含金屬氮化物粒子等的沉降，能夠使粗大粒子數量變得更少，從而能夠進一步提高組成物的經時穩定性。・Physical properties of polymer compound The acid value of the polymer compound is preferably in the range of 0 mgKOH/g or more and 250 mgKOH/g or less, more preferably 10 mgKOH/g or more and 200 mgKOH/g or less, and still more preferably 20 mgKOH/g More than the range of 120 mgKOH/g or less. Pattern peeling at the time of image development at the time of forming a cured film can be suppressed more effectively as the acid value of a polymer compound is 250 mgKOH/g or less. When the acid value of the polymer compound is 10 mgKOH/g or more, the alkali developability becomes more favorable. When the acid value of the polymer compound is 20 mgKOH/g or more, precipitation of metal-containing nitride particles and the like can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the composition can be further improved.

高分子化合物的酸值例如能夠根據高分子化合物中之酸基的平均含量進行計算。藉由改變作為高分子化合物的構成成分之含有酸基之結構單元的含量，能夠得到具有所希望之酸值之樹脂。The acid value of the polymer compound can be calculated from, for example, the average content of acid groups in the polymer compound. A resin having a desired acid value can be obtained by changing the content of the acid group-containing structural unit as a constituent of the polymer compound.

從形成硬化膜時抑制顯影時的圖案剝離和顯影性的觀點而言，高分子化合物的重量平均分子量以藉由GPC（Gel Permeation Chromatography：凝膠滲透層析）法之聚苯乙烯換算值計，是4,000以上且300,000以下為較佳，5,000以上且200,000以下為更佳，6,000以上且100,000以下為進一步較佳，10,000以上且50,000以下為特佳。 GPC法基於如下方法：使用HLC-8020GPC（TOSOH CORPORATION製造），使用TSKgel SuperHZM-H、TSKgel SuperHZ4000、TSKgel SuperHZ2000（TOSOH CORPORATION製造，4.6mmID×15cm）作為管柱，並使用THF（四氫呋喃）作為洗提液。 高分子化合物能夠基於公知的方法進行合成。The weight-average molecular weight of the polymer compound is in terms of polystyrene by the GPC (Gel Permeation Chromatography) method, from the viewpoint of suppressing pattern peeling and developability during development when forming a cured film. It is preferably 4,000 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, more preferably 6,000 or more and 100,000 or less, and particularly preferably 10,000 or more and 50,000 or less. The GPC method is based on a method using HLC-8020GPC (manufactured by TOSOH CORPORATION), using TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6 mmID×15 cm) as a column, and using THF (tetrahydrofuran) as an eluent liquid. The polymer compound can be synthesized based on a known method.

作為高分子化合物的具體例，可以舉出Kusumoto Chemicals, Ltd.製造之「DA-7301」、BYK Chemie GmbH製造之「Disperbyk-101（聚醯胺胺磷酸鹽）、107（羧酸酯）、110（含有酸基之共聚物）、111（磷酸系分散劑）、130（聚醯胺）、161、162、163、164、165、166、170、190（高分子共聚物）」、「BYK-P104、P105（高分子量不飽和聚羧酸）」、EFKA公司製造之「EFKA4047、4050～4010～4165（聚氨酯系）、EFKA4330～4340（嵌段共聚物）、4400～4402（改質聚丙烯酸酯）、5010（聚酯醯胺）、5765（高分子量聚羧酸鹽）、6220（脂肪酸聚酯）、6745（酞菁衍生物）、6750（偶氮顏料衍生物）」、Ajinomoto Fine-Techno Co.,Inc.製造之「Ajisper PB821、PB822、PB880、PB881」、Kyoeisha chemical Co.,Ltd.製造之「Flowlen TG-710（胺基甲酸酯寡聚物）」、「Polyflow No.50E、No.300（丙烯酸系共聚物）」、Kusumoto Chemicals, Ltd.製造之「Disparlon KS-860、873SN、874、#2150（脂肪族多元羧酸）、#7004（聚醚酯）、DA-703-50、DA-705、DA-725」、Kao Corporation製造之「Demol RN、N（萘磺酸福馬林縮聚物）、MS、C、SN-B（芳香族磺酸福馬林縮聚物）」、「Homogenol L-18（高分子聚羧酸）」、「Emulgen 920、930、935、985（聚氧乙烯壬基苯基醚）」、「Acetamin 86（硬脂基胺乙酸酯）」、Japan Lubrizol Corporation製造之「Solsperse 5000（酞菁衍生物）、22000（偶氮顏料衍生物）、13240（聚酯胺）、3000、12000、17000、20000、27000（末端部含有功能部之高分子）、24000、28000、32000、38500（接枝共聚物）」、Nikko Chemicals Co.,Ltd.製造之「Nikkol T106（聚氧乙烯脫水山梨糖醇單油酸酯）、MYS-IEX（聚氧乙烯單硬脂酸酯）」、Kawaken Fine Chemicals Co.,Ltd製造之Hinoact T-8000E等、Shin-Etsu Chemical Co.,Ltd.製造之有機矽氧烷聚合物KP341、Yusho Co.,Ltd.「W001：陽離子系界面活性劑」、聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、脫水山梨糖醇脂肪酸酯等非離子系界面活性劑、「W004、W005、W017」等陰離子系界面活性劑、MORISHITA & CO.,LTD.製造之「EFKA-46、EFKA-47、EFKA-47EA、EFKA聚合物100、EFKA聚合物400、EFKA聚合物401、EFKA聚合物450」、SAN NOPCO LIMITED製造之「Disperse Aid 6、Disperse Aid 8、Disperse Aid 15、Disperse Aid 9100」等高分子分散劑、ADEKA製造之「Adeka Pluronic L31、F38、L42、L44、L61、L64、F68、L72、P95、F77、P84、F87、P94、L101、P103、F108、L121、P-123」及SANYO KASEI CO.,LTD.製造之「Ionet（商品名稱）S-20」等。又，亦能夠使用Acrybase FFS-6752、Acrybase FFS-187、Acrycure-RD-F8及Cyclomer P。 作為兩性樹脂的市售品，例如可以舉出BYK Chemie GmbH製造之DISPERBYK-130、DISPERBYK-140、DISPERBYK-142、DISPERBYK-145、DISPERBYK-180、DISPERBYK-187、DISPERBYK-191、DISPERBYK-2001、DISPERBYK-2010、DISPERBYK-2012、DISPERBYK-2025、BYK-9076、Ajinomoto Fine-Techno Co.,Inc.製造之Ajisper PB821、Ajisper PB822及Ajisper PB881等。 該等高分子化合物可以單獨使用1種，亦可以併用2種以上。Specific examples of the polymer compound include "DA-7301" manufactured by Kusumoto Chemicals, Ltd., "Disperbyk-101 (polyamidoamine phosphate) manufactured by BYK Chemie GmbH, 107 (carboxylate), 110 (acid group-containing copolymer), 111 (phosphoric acid-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer)", "BYK- P104, P105 (high molecular weight unsaturated polycarboxylic acid)", "EFKA4047, 4050～4010～4165 (polyurethane type), EFKA4330～4340 (block copolymer), 4400～4402 (modified polyacrylate) manufactured by EFKA ), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)”, Ajinomoto Fine-Techno Co. "Ajisper PB821, PB822, PB880, PB881" manufactured by ., Inc., "Flowlen TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., Ltd., "Polyflow No.50E, No. .300 (acrylic copolymer)", "Disparlon KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyetherester), DA-703-50 manufactured by Kusumoto Chemicals, Ltd. , DA-705, DA-725", "Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (Aromatic sulfonic acid formalin polycondensate)", "Homogenol" manufactured by Kao Corporation L-18 (polymer polycarboxylic acid), "Emulgen 920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether)", "Acetamin 86 (stearylamine acetate)", Japan Lubrizol Corporation "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymer with functional part at the end), 24000, 28000, 32000, 38500 (graft copolymers)", "Nikkol T106 (polyoxyethylene sorbitan monooleate) manufactured by Nikko Chemicals Co., Ltd., MYS-IEX (polyoxyethylene monostearic acid) ester)", Kawa Hinoact T-8000E manufactured by ken Fine Chemicals Co., Ltd, etc., organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd., Yusho Co., Ltd. "W001: Cationic surfactant", Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyoxyethylene Nonionic surfactants such as ethylene glycol distearate and sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", "EFKA- 46. EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450", "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse" manufactured by SAN NOPCO LIMITED Aid 9100" and other polymer dispersants, "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P -123" and "Ionet (trade name) S-20" manufactured by SANYO KASEI CO., LTD., etc. In addition, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can also be used. Examples of commercially available amphoteric resins include DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK manufactured by BYK Chemie GmbH -2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajisper PB821, Ajisper PB822 and Ajisper PB881 manufactured by Ajinomoto Fine-Techno Co., Inc. These polymer compounds may be used alone or in combination of two or more.

另外，作為高分子化合物的具體例，能夠參閱日本特開2013-249417號公報的0127～0129段中所記載之高分子化合物，該等內容被併入本說明書中。In addition, as specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP-A No. 2013-249417 can be referred to, and these contents are incorporated in the present specification.

作為分散劑，除了上述高分子化合物以外，能夠使用日本特開2010-106268號公報的0037～0115段（對應之US2011/0124824的0075～0133段）的接枝共聚物，能夠援用該等內容，並被併入本說明書中。 除了上述以外，能夠使用日本特開2011-153283號公報的0028～0084段（對應之US2011/0279759的0075～0133段）的包含含有酸性基經由連結基鍵結而成之側鏈結構之構成成分之高分子化合物，能夠援用該等內容，並被併入本說明書中。As the dispersant, in addition to the above-mentioned polymer compounds, the graft copolymers of paragraphs 0037 to 0115 of JP-A-2010-106268 (corresponding to paragraphs 0075 to 0133 of US 2011/0124824 ) can be used, and these contents can be cited, and incorporated into this specification. In addition to the above, it is possible to use the constituent components of the paragraphs 0028 to 0084 of JP-A No. 2011-153283 (corresponding to the paragraphs 0075 to 0133 of US 2011/0279759 ) containing a side chain structure having an acidic group bound via a linking group. For the polymer compound, these contents can be cited and incorporated into this specification.

作為分散劑，亦能夠使用日本特開2016-109763號公報的0033～0049段中所記載之樹脂，該內容被併入本說明書中。As the dispersing agent, the resins described in paragraphs 0033 to 0049 of JP-A-2016-109763 can also be used, and the contents are incorporated in this specification.

＜鹼可溶性樹脂＞ 分散組成物含有鹼可溶性樹脂（相當於樹脂）為較佳。本說明書中，鹼可溶性樹脂是指含有促進鹼可溶性之基團（鹼可溶性基）之樹脂，是指與已說明之分散劑不同之樹脂。 分散組成物中之鹼可溶性樹脂的含量並沒有特別限制，相對於分散組成物的總固體成分，一般是1～30質量%為較佳，在分散組成物具有更加優異之本發明的效果之觀點上，1～15質量%為更佳。 鹼可溶性樹脂可以單獨使用1種，亦可以併用2種以上。當併用2種以上的鹼可溶性樹脂時，合計含量在上述範圍內為較佳。<Alkali-soluble resin> It is preferable that the dispersion composition contains an alkali-soluble resin (corresponding to resin). In this specification, the alkali-soluble resin refers to a resin containing a group for promoting alkali solubility (alkali-soluble group), and refers to a resin different from the dispersant described above. The content of the alkali-soluble resin in the dispersion composition is not particularly limited, but generally 1 to 30% by mass relative to the total solid content of the dispersion composition is preferable, and the dispersion composition has a viewpoint that the effect of the present invention is more excellent On the other hand, 1 to 15% by mass is more preferable. Alkali-soluble resin may be used individually by 1 type, and may use 2 or more types together. When two or more alkali-soluble resins are used in combination, the total content is preferably within the above-mentioned range.

作為鹼可溶性樹脂，可以舉出在分子中含有至少1個鹼可溶性基之樹脂，例如可以舉出聚羥基苯乙烯樹脂、聚矽氧烷樹脂、（甲基）丙烯酸樹脂、（甲基）丙烯醯胺樹脂、（甲基）丙烯酸/（甲基）丙烯醯胺共聚合樹脂、環氧系樹脂及聚醯亞胺樹脂等。Examples of the alkali-soluble resin include resins containing at least one alkali-soluble group in the molecule, for example, polyhydroxystyrene resins, polysiloxane resins, (meth)acrylic resins, and (meth)acrylonitrile Amine resin, (meth)acrylic acid/(meth)acrylamide copolymer resin, epoxy resin and polyimide resin, etc.

作為鹼可溶性樹脂的具體例，可以舉出不飽和羧酸與乙烯性不飽和化合物的共聚物。 不飽和羧酸並沒有特別限制，可以舉出（甲基）丙烯酸、巴豆酸及乙酸乙烯酯等單羧酸類；衣康酸、順丁烯二酸及反丁烯二酸等二羧酸或其酸酐；鄰苯二甲酸單（2-（甲基）丙烯醯氧基乙基）等多元羧酸單酯類；等。Specific examples of the alkali-soluble resin include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds. The unsaturated carboxylic acid is not particularly limited, and examples thereof include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and vinyl acetate; and dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, or the like. Acid anhydrides; phthalic acid mono(2-(meth)acryloyloxyethyl) and other polycarboxylic acid monoesters; etc.

作為能夠共聚合之乙烯性不飽和化合物，可以舉出（甲基）丙烯酸甲酯等。又，亦能夠使用日本特開2010-97210號公報的0027段及日本特開2015-68893號公報的0036～0037段中所記載之化合物，上述內容被併入本說明書中。Methyl (meth)acrylate etc. are mentioned as an ethylenically unsaturated compound which can be copolymerized. In addition, the compounds described in paragraph 0027 of JP-A-2010-97210 and paragraphs 0036-0037 of JP-A-2015-68893 can also be used, the contents of which are incorporated in the present specification.

又，亦可以將作為能夠共聚合之乙烯性不飽和化合物之在側鏈中含有乙烯性不飽和基之化合物組合使用。作為乙烯性不飽和基，（甲基）丙烯酸基為較佳。在側鏈中具有乙烯性不飽和基之丙烯酸樹脂例如能夠藉由使含有縮水甘油基或脂環式環氧基之乙烯性不飽和化合物與含有羧酸基之丙烯酸樹脂的羧酸基進行加成反應而得到。Moreover, you may use together the compound which has an ethylenically unsaturated group in a side chain as a copolymerizable ethylenically unsaturated compound. As the ethylenically unsaturated group, a (meth)acrylic group is preferable. The acrylic resin having an ethylenically unsaturated group in the side chain can be added, for example, by adding an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to the carboxylic acid group of the carboxylic acid group-containing acrylic resin obtained by the reaction.

作為鹼可溶性樹脂，例如能夠使用日本特開昭59-44615號、日本特公昭54-34327號、日本特公昭58-12577號、日本特公昭54-25957號、日本特開昭54-92723號、日本特開昭59-53836號及日本特開昭59-71048號中所記載之在側鏈中含有羧酸基之自由基聚合物；歐洲專利第993966號、歐洲專利第1204000號及日本特開2001-318463號等的各公報中所記載之含有鹼可溶性基之縮醛改質聚乙烯醇系黏合劑樹脂；聚乙烯吡咯啶酮；聚環氧乙烷；醇可溶性尼龍及2,2-雙-（4-羥基苯基）-丙烷與表氯醇的反應物之聚醚等；國際公開第2008/123097號中所記載之聚醯亞胺樹脂；等。As the alkali-soluble resin, for example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Laid-Open No. 54-34327, Japanese Patent Laid-Open No. 58-12577, Japanese Patent Laid-Open No. 54-25957, Japanese Patent Laid-Open No. 54-92723, Radical polymers containing carboxylic acid groups in side chains described in Japanese Patent Laid-Open No. 59-53836 and Japanese Patent Laid-Open No. 59-71048; European Patent No. 993966, European Patent No. 1204000 and Japanese Patent Laid-Open No. 993966 Alkali-soluble group-containing acetal-modified polyvinyl alcohol-based binder resins described in publications such as No. 2001-318463; polyvinylpyrrolidone; polyethylene oxide; alcohol-soluble nylon and 2,2-bis -(4-hydroxyphenyl)-propane and epichlorohydrin reactant polyethers, etc.; polyimide resins described in International Publication No. 2008/123097; etc.

作為鹼可溶性樹脂，例如亦能夠使用日本特開2016-75845號公報的0225～0245段中所記載之化合物，上述內容被併入本說明書中。As the alkali-soluble resin, for example, the compounds described in paragraphs 0225 to 0245 of JP 2016-75845 A can also be used, and the above-mentioned contents are incorporated in the present specification.

作為鹼可溶性樹脂，亦能夠使用聚醯亞胺前驅物。聚醯亞胺前驅物是指使含有酸酐基之化合物和二胺化合物於40～100℃下進行加成聚合反應而得到之樹脂。 作為聚醯亞胺前驅物，例如可以舉出含有下述式（1）所表示之重複單元之樹脂。作為聚醯亞胺前驅物的結構，例如可以舉出含有下述式（2）所表示之醯胺酸結構、醯胺酸結構一部分醯亞胺閉環而成之下述式（3）和/或全部進行醯亞胺閉環之下述式（4）所表示之醯亞胺結構者。 另外，本說明書中，有時將具有醯胺酸結構之聚醯亞胺前驅物稱為聚醯胺酸。As the alkali-soluble resin, a polyimide precursor can also be used. The polyimide precursor refers to a resin obtained by subjecting an acid anhydride group-containing compound and a diamine compound to an addition polymerization reaction at 40 to 100°C. As a polyimide precursor, the resin containing the repeating unit represented by following formula (1) is mentioned, for example. Examples of the structure of the polyimide precursor include the following formula (3) and/or the following formula (3) including an amide structure represented by the following formula (2), a part of the amide acid structure, and a ring-closed amide. The imide structure represented by the following formula (4) in which all of the imide rings are closed. In addition, in this specification, the polyimide precursor which has an amide acid structure may be called a polyamide acid.

[化學式7]

Figure 02_image013
[Chemical formula 7]
Figure 02_image013

[化學式8]

Figure 02_image015
[Chemical formula 8]
Figure 02_image015

[化學式9]

Figure 02_image017
[Chemical formula 9]
Figure 02_image017

[化學式10]

Figure 02_image019
[Chemical formula 10]
Figure 02_image019

上述式（1）～（4）中，R1 表示碳數2～22的4價的有機基，R2 表示碳數1～22的2價的有機基，n表示1或2。In the above formulae (1) to (4), R 1 represents a tetravalent organic group having 2 to 22 carbon atoms, R 2 represents a divalent organic group having 1 to 22 carbon atoms, and n represents 1 or 2.

作為上述聚醯亞胺前驅物的具體例，可以舉出日本特開2008-106250號公報的0011～0031段中所記載之化合物、日本特開2016-122101號公報的0022～0039段中所記載之化合物及日本特開2016-68401號公報的0061～0092段中所記載之化合物等，上述內容被併入本說明書中。Specific examples of the above-mentioned polyimide precursor include compounds described in paragraphs 0011 to 0031 of JP 2008-106250 A, and compounds described in paragraphs 0022 to 0039 of JP 2016-122101 A and the compounds described in paragraphs 0061 to 0092 of JP-A No. 2016-68401, the contents of which are incorporated into the present specification.

在使用分散組成物得到之圖案狀的硬化膜的圖案形狀更加優異之觀點上，鹼可溶性樹脂含有選自包括聚醯亞胺樹脂及聚醯亞胺前驅物之組群中之至少1種為較佳。 含有鹼可溶性基之聚醯亞胺樹脂並沒有特別限制，能夠使用公知的含有鹼可溶性基之聚醯亞胺樹脂。作為上述聚醯亞胺樹脂，例如可以舉出日本特開2014-137523號公報的0050段中所記載之樹脂、日本特開2015-187676號公報的0058段中所記載之樹脂及日本特開2014-106326號公報的0012～0013段中所記載之樹脂等，上述內容被併入本說明書中。From the viewpoint that the pattern shape of the patterned cured film obtained by using the dispersion composition is more excellent, it is preferable that the alkali-soluble resin contains at least one selected from the group consisting of a polyimide resin and a polyimide precursor. good. The alkali-soluble group-containing polyimide resin is not particularly limited, and known alkali-soluble group-containing polyimide resins can be used. Examples of the above-mentioned polyimide resin include resins described in paragraph 0050 of JP 2014-137523 A, resins described in paragraph 0058 of JP 2015-187676 A, and JP 2014 - For resins and the like described in paragraphs 0012 to 0013 of Gazette No. 106326, the above-mentioned contents are incorporated into this specification.

〔任意成分〕 上述分散組成物可以在發揮本發明的效果之範圍內含有其他成分。作為其他成分，例如可以舉出作為聚合抑制劑、溶劑、著色劑及後述之硬化性組成物的任意成分而說明者等。以下，對分散組成物中所含有之任意成分進行詳細敘述。[Optional Components] The above-mentioned dispersion composition may contain other components within the range in which the effects of the present invention are exhibited. Examples of other components include those described as a polymerization inhibitor, a solvent, a colorant, and an arbitrary component of a curable composition to be described later. Hereinafter, the optional components contained in the dispersion composition will be described in detail.

＜聚合抑制劑＞ 聚合抑制劑並沒有特別限制，能夠使用公知的聚合抑制劑。作為聚合抑制劑，例如可以舉出酚系聚合抑制劑（例如，對甲氧基苯酚、2,5-二-第三丁基-4-甲基苯酚、2,6-二-第三丁基-4-甲基苯酚、4,4’-硫代雙（3-甲基-6-第三丁基苯酚）、2,2’-亞甲基雙（4-甲基-6-第三丁基苯酚）及4-甲氧基萘酚等）；對苯二酚系聚合抑制劑（例如，對苯二酚及2,6-二-第三丁基對苯二酚等）；醌系聚合抑制劑（例如，苯醌等）；自由基（free radical）系聚合抑制劑（例如，2,2,6,6-四甲基哌啶1-氧基自由基及4-羥基-2,2,6,6-四甲基哌啶1-氧基自由基等）；硝基苯系聚合抑制劑（例如，硝基苯及4-硝基甲苯等）；啡噻嗪系聚合抑制劑（例如，啡噻嗪及2-甲氧基啡噻嗪等）；等。 其中，在硬化性組成物具有更加優異之本發明的效果之觀點上，酚系聚合抑制劑或自由基系聚合抑制劑為較佳。 另外，聚合抑制劑可以在製備分散組成物時與其他成分一同混合，亦可以是用於上述樹脂的合成等者與上述樹脂一同混合於分散組成物中。<Polymerization inhibitor> The polymerization inhibitor is not particularly limited, and a known polymerization inhibitor can be used. Examples of the polymerization inhibitor include phenolic polymerization inhibitors (for example, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl -4-Methylphenol, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) Hydroquinone-based polymerization inhibitors (for example, hydroquinone and 2,6-di-tert-butylhydroquinone, etc.); quinone-based polymerization Inhibitors (eg, benzoquinone, etc.); free radical polymerization inhibitors (eg, 2,2,6,6-tetramethylpiperidine 1-oxyl radical and 4-hydroxy-2,2 ,6,6-tetramethylpiperidine 1-oxyl radical, etc.); nitrobenzene-based polymerization inhibitors (such as nitrobenzene and 4-nitrotoluene, etc.); phenothiazine-based polymerization inhibitors (such as , phenothiazine and 2-methoxyphenothiazine, etc.); etc. Among them, a phenol-based polymerization inhibitor or a radical-based polymerization inhibitor is preferable from the viewpoint that the curable composition has more excellent effects of the present invention. In addition, the polymerization inhibitor may be mixed with other components at the time of preparation of the dispersion composition, or may be used in the synthesis of the above-mentioned resin or the like and may be mixed with the above-mentioned resin in the dispersion composition.

分散組成物中之聚合抑制劑的含量並沒有特別限制，在分散組成物具有更加優異之經時穩定性之觀點及後述之硬化性組成物具有更加優異之硬化性之觀點上，相對於分散組成物的總固體成分，是0.0001～1質量%為較佳。 聚合抑制劑可以單獨使用1種，亦可以併用2種以上。當併用2種以上的聚合抑制劑時，合計含量在上述範圍內為較佳。 聚合抑制劑在與含有硬化性基之樹脂一同使用時其效果顯著。例如，在分散組成物的製作中；分散組成物的製作後；後述之硬化性組成物的製作中；硬化性組成物製作後；等、分散組成物和/或硬化性組成物成為高溫或者長期保管等而擔心進行含有硬化性基之樹脂的聚合之情況下，亦能夠毫無問題地進行使用。The content of the polymerization inhibitor in the dispersion composition is not particularly limited. From the viewpoint of the dispersion composition having more excellent temporal stability and the later-mentioned curable composition having more excellent curability, the dispersion composition is relatively The total solid content of the product is preferably 0.0001 to 1% by mass. A polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together. When two or more kinds of polymerization inhibitors are used in combination, the total content is preferably within the above range. The effect of the polymerization inhibitor is remarkable when used together with a resin containing a curable group. For example, during the preparation of the dispersion composition; after the preparation of the dispersion composition; during the preparation of the curable composition described later; after the preparation of the curable composition; It can be used without any problem even when there is concern about polymerization of the resin containing a curable group during storage or the like.

＜溶劑＞ 分散組成物可以含有溶劑。 溶劑並沒有特別限制，能夠使用公知的溶劑。 分散組成物中之溶劑的含量並沒有特別限制，一般調整為分散組成物的固體成分成為10～90質量%為較佳，調整為成為20～90質量%之為更佳。 溶劑可以單獨使用1種，亦可以併用2種以上。當併用2種以上的溶劑時，調整組成物的總固體成分在上述範圍內為較佳。<Solvent> The dispersion composition may contain a solvent. The solvent is not particularly limited, and known solvents can be used. The content of the solvent in the dispersion composition is not particularly limited, but it is generally adjusted so that the solid content of the dispersion composition is preferably 10 to 90% by mass, and more preferably 20 to 90% by mass. A solvent may be used individually by 1 type, and may use 2 or more types together. When two or more kinds of solvents are used in combination, it is preferable to adjust the total solid content of the composition within the above-mentioned range.

作為溶劑，例如可以舉出水或有機溶劑。 作為有機溶劑，例如可以舉出丙酮、甲基乙基酮、環己烷、乙酸乙酯、二氯乙烷、四氫呋喃、甲苯、乙二醇單甲醚、乙二醇單***、乙二醇二甲醚、丙二醇單甲醚、丙二醇單***、乙醯基丙酮、環己酮、環戊酮、二丙酮醇、乙二醇單甲醚乙酸酯、乙二醇***乙酸酯、乙二醇單異丙醚、乙二醇單丁醚乙酸酯、3-甲氧基丙醇、甲氧基甲氧基乙醇、二乙二醇單甲醚、二乙二醇單***、二乙二醇二甲醚、二乙二醇二***、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、3-甲氧基丙基乙酸酯、N,N-二甲基甲醯胺、二甲基亞碸、γ-丁內酯、乙酸乙酯、乙酸丁酯、乳酸甲酯、N-甲基-2-吡咯啶酮及乳酸乙酯等，但並不限定於該等。As a solvent, water or an organic solvent is mentioned, for example. Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol diethyl ether. Methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol Monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl ether Ethylene, γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, ethyl lactate, etc., but not limited to these.

＜著色劑＞ 分散組成物可以含有著色劑。本說明書中，著色劑是指與含金屬氮化物粒子不同之化合物。<Colorant> The dispersion composition may contain a colorant. In this specification, the colorant refers to a compound different from the metal-containing nitride particles.

作為著色劑，能夠使用各種公知的顏料（著色顏料）及染料（著色染料）。作為顏料，可以舉出無機顏料及有機顏料。 當含有著色劑時，其含量能夠根據進行硬化而得到之遮光膜的光學特性來決定。著色劑可以單獨使用1種，亦可以併用2種以上。As a coloring agent, various well-known pigments (coloring pigments) and dyes (coloring dyes) can be used. As a pigment, an inorganic pigment and an organic pigment are mentioned. When a colorant is contained, the content can be determined according to the optical properties of the light-shielding film obtained by curing. A coloring agent may be used individually by 1 type, and may use 2 or more types together.

（無機顏料） 無機顏料並沒有特別限制，能夠使用公知的無機顏料。 作為無機顏料，例如可以舉出碳黑、二氧化矽、鋅白、鉛白、鋅鋇白、氧化鈦、氧化鉻、氧化鐵、沉降性硫酸鋇、及重晶石粉、鉛丹、氧化鐵紅、黃鉛、鋅黃（鋅黃1種、鋅黃2種）、群青（ultramarin blue）、普魯士藍（亞鐵氰化鉀（potassium ferrocyanide））、鋯石灰（zircon grey）、鐠黃（Praseodymium yellow）、鉻鈦黃、鉻綠、孔雀綠、維多利亞綠（victoria green）、鐵藍（iron blue）（與普魯士藍無關）、釩鋯藍（vanadium zirconium blue）、鉻錫紅（chrome tin pink）、錳紅（manganese pink）、橙紅（salmon pink）等。又，黑色的無機顏料為較佳，作為無機顏料，在含量至少為可得到能夠形成具有較高的光學密度之硬化膜之組成物之觀點上，碳黑及金屬顏料等（以下，亦稱為「黑色顏料」。）為較佳。作為金屬顏料，例如可以舉出包含選自包括Nb、V、Co、Cr、Cu、Mn、Ru、Fe、Ni、Sn、Ti及Ag之組群中之1種或2種以上的金屬元素之金屬氧化物及金屬碳化物（例如TiC等）等。 作為無機顏料，含有選自包括含有銀之金屬顏料、含有錫之金屬顏料及含有銀及錫之金屬顏料之組群中之至少1種為較佳。無機顏料可以單獨使用1種，亦可以併用2種以上。(Inorganic Pigment) The inorganic pigment is not particularly limited, and known inorganic pigments can be used. Examples of inorganic pigments include carbon black, silicon dioxide, zinc white, lead white, zinc white, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate, barite powder, lead red, and red iron oxide. , yellow lead, zinc yellow (1 type of zinc yellow, 2 types of zinc yellow), ultramarin blue, Prussian blue (potassium ferrocyanide), zircon grey, Praseodymium yellow ), chrome titanium yellow, chrome green, malachite green, victoria green, iron blue (not related to Prussian blue), vanadium zirconium blue, chrome tin pink, Manganese red (manganese pink), orange red (salmon pink), etc. In addition, black inorganic pigments are preferred, and as inorganic pigments, carbon black and metallic pigments (hereinafter, also referred to as “hereinafter referred to as "Black paint".) is preferred. As the metal pigment, for example, one containing one or two or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag can be mentioned. Metal oxides and metal carbides (such as TiC, etc.), etc. As the inorganic pigment, it is preferable to contain at least one selected from the group consisting of a silver-containing metallic pigment, a tin-containing metallic pigment, and a silver- and tin-containing metallic pigment. An inorganic pigment may be used individually by 1 type, and may use 2 or more types together.

作為著色劑，例如亦能夠使用日本特開2014-42375號公報的0027～0200段、日本特開2008-260927號公報的0031段及日本特開2015-68893號公報的0015～0025段中所記載之著色劑，上述內容被併入本說明書中。As the colorant, for example, those described in paragraphs 0027 to 0200 of JP 2014-42375 A, paragraph 0031 of JP 2008-260927 A, and paragraphs 0015 to 0025 of JP 2015-68893 A can also be used. For colorants, the above content is incorporated into this specification.

作為著色劑，亦能夠使用具有紅外線吸收性之顏料。 作為具有紅外線吸收性之顏料，鎢化合物及金屬硼化物等為較佳，其中，從紅外區域的波長下之遮光性優異之觀點而言，鎢化合物為較佳。尤其，從與基於曝光之硬化效率有關之肟系聚合起始劑的光吸收波長區域和可視光區域的透光性優異之觀點而言，鎢化合物為較佳。As the colorant, a pigment having infrared absorption properties can also be used. As pigments having infrared absorption properties, tungsten compounds, metal borides, and the like are preferred, and among them, tungsten compounds are preferred from the viewpoint of being excellent in light-shielding properties at wavelengths in the infrared region. In particular, a tungsten compound is preferable from the viewpoint of excellent light transmittance in the light absorption wavelength region and visible light region of the oxime-based polymerization initiator regarding curing efficiency by exposure.

該等顏料可以併用2種以上，又亦可以與後述之染料併用。為了調整色調及為了提高所希望之波長區域的遮光性，例如可以舉出在黑色或具有紅外線遮光性之顏料中混合紅色、綠色、黃色、橙色、紫色及藍色等彩色顏料或後述之染料之形態。在黑色或具有紅外線遮光性之顏料中混合紅色顏料或染料、或者紫色顏料或染料為較佳，在黑色或具有紅外線遮光性之顏料中混合紅色顏料為更佳。 可以進一步加入後述之近紅外線吸收劑、紅外線吸收劑。These pigments may be used in combination of two or more, and may be used in combination with the dyes described later. In order to adjust the color tone and improve the light-shielding properties in a desired wavelength region, for example, black or a pigment having infrared light-shielding properties can be mixed with color pigments such as red, green, yellow, orange, violet, and blue, or dyes described later. form. It is preferable to mix red pigment or dye, or purple pigment or dye with black or pigment with infrared light-shielding property, and it is more preferable to mix red pigment with black or pigment with infrared light-shielding property. A near-infrared absorber and an infrared absorber to be described later may be further added.

・有機顏料 作為有機顏料，例如可以舉出如下： 比色指數（C.I.）顏料黃1、2、3、4、5、6、10、11、12、13、14、15、16、17、18、20、24、31、32、34、35、35:1、36、36:1、37、37:1、40、42、43、53、55、60、61、62、63、65、73、74、77、81、83、86、93、94、95、97、98、100、101、104、106、108、109、110、113、114、115、116、117、118、119、120、123、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、161、162、164、166、167、168、169、170、171、172、173、174、175、176、177、179、180、181、182、185、187、188、193、194、199、213、214等； C.I.顏料橙2、5、13、16、17:1、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、71、73等； C.I.顏料紅1、2、3、4、5、6、7、9、10、14、17、22、23、31、38、41、48:1、48:2、48:3、48:4、49、49:1、49:2、52:1、52:2、53:1、57:1、60:1、63:1、66、67、81:1、81:2、81:3、83、88、90、105、112、119、122、123、144、146、149、150、155、166、168、169、170、171、172、175、176、177、178、179、184、185、187、188、190、200、202、206、207、208、209、210、216、220、224、226、242、246、254、255、264、270、272、279等； C.I.顏料綠7、10、36、37、58、59等； C.I.顏料紫1、19、23、27、32、37、42等；及 C.I.顏料藍1、2、15、15:1、15:2、15:3、15:4、15:6、16、22、60、64、66、79、80等。 顏料可以單獨使用1種，亦可以併用2種以上。・Organic pigments Examples of organic pigments include the following: Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18 , 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73 , 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120 , 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169 , 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc.; CI Pigment Orange 2, 5, 13 , 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc.; CI Pigment Red 1, 2 , 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1 , 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90 , 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188 , 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc.; CI Pigment Green 7, 10, 36 , 37, 58, 59, etc.; CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc.; and CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15: 4, 15:6, 16, 22, 60, 64, 66, 79, 80, etc. A pigment may be used individually by 1 type, and may use 2 or more types together.

（染料） 作為染料，例如能夠使用日本特開昭64-90403號公報、日本特開昭64-91102號公報、日本特開平1-94301號公報、日本特開平6-11614號公報、日本特登2592207號、美國專利4808501號說明書、美國專利5667920號說明書、美國專利505950號說明書、日本特開平5-333207號公報、日本特開平6-35183號公報、日本特開平6-51115號公報及日本特開平6-194828號公報等中所揭示之色素。若以化學結構的形式來區分，則能夠使用吡唑偶氮化合物、吡咯亞甲基化合物、苯胺基偶氮化合物、三苯基甲烷化合物、蒽醌化合物、苯亞甲基化合物、氧雜菁（oxonol）化合物、吡唑并***偶氮化合物、吡啶酮偶氮化合物、花青化合物、啡噻嗪化合物、及吡咯并吡唑次甲基偶氮（pyrrolopyrazole azomethine）化合物等。作為染料，可以使用色素多聚體。作為色素多聚體，可以舉出日本特開2011-213925號公報、日本特開2013-041097號公報中所記載之化合物。亦可以使用在分子內具有聚合性基之聚合性染料，作為市售品，例如可以舉出Wako Pure Chemical Co.,Ltd.製造之RDW系列。(Dye) As the dye, for example, Japanese Patent Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. 1-94301, Japanese Patent Laid-Open No. 6-11614, and Japanese Patent Laid-Open No. 6-11614 can be used. No. 2,592,207, US Patent No. 4,808,501, US Patent No. 5,667,920, US Patent No. 5,059,50, Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6-51115, and Japanese Patent Laid-Open No. 5-333207 The pigment disclosed in Kokai Publication No. 6-194828 and the like. In terms of chemical structures, pyrazole azo compounds, pyrrole methylene compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxocyanines ( oxonol) compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, and pyrrolopyrazole azomethine compounds and the like. As the dye, a dye polymer can be used. Examples of the dye multimer include compounds described in JP 2011-213925 A and JP 2013-041097 A. A polymerizable dye having a polymerizable group in the molecule can also be used, and as a commercial item, for example, the RDW series manufactured by Wako Pure Chemical Co., Ltd. can be mentioned.

（紅外線吸收劑） 上述著色劑可以進一步含有紅外線吸收劑。 紅外線吸收劑是指在紅外區域（較佳為波長650～1300nm）的波長區域具有吸收之化合物。作為紅外線吸收劑，在波長675～900nm的波長區域具有極大吸收波長之化合物為較佳。 作為具有該種分光特性之著色劑，例如可以舉出吡咯并吡咯化合物、銅化合物、花青化合物、酞菁化合物、亞銨（iminium）化合物、硫醇錯合物系化合物、過渡金屬氧化物系化合物、方酸菁（squarylium）化合物、萘酞菁化合物、夸特銳烯（quaterrylene）化合物、二硫醇金屬錯合物系化合物及克酮鎓（croconium）化合物等。 酞菁化合物、萘酞菁化合物、亞銨化合物、花青化合物、方酸菁化合物及克酮鎓化合物可以使用日本特開2010-111750號公報的0010～0081段中所揭示之化合物，該內容被併入本說明書中。花青化合物例如能夠參閱《功能性色素，大河原信/松岡賢/北尾悌次郎/平嶋恆亮著，Kodansha Scientific Ltd.》，該內容被併入本說明書中。(Infrared absorber) The said coloring agent may further contain an infrared absorber. The infrared absorber refers to a compound having absorption in the wavelength region of the infrared region (preferably, wavelengths of 650 to 1300 nm). As the infrared absorber, a compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferred. Examples of colorants having such spectroscopic properties include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, and transition metal oxide compounds. Compounds, squarylium compounds, naphthalocyanine compounds, quaterrylene compounds, dithiol metal complex compounds, croconium compounds, and the like. For the phthalocyanine compound, naphthalocyanine compound, imino compound, cyanine compound, squaraine compound, and ketonium compound, compounds disclosed in paragraphs 0010 to 0081 of JP-A No. 2010-111750 can be used. incorporated into this specification. The cyanine compound can be referred to, for example, "Functional Pigment, Nobu Ogawara / Ken Matsuoka / Tejiro Kitao / Ryo Hirashima, Kodansha Scientific Ltd.", the contents of which are incorporated into this specification.

作為具有上述分光特性之著色劑，亦能夠使用日本特開平07-164729號公報的0004～0016段中所揭示之化合物和/或日本特開2002-146254號公報的0027～0062段中所揭示之化合物、日本特開2011-164583號公報的0034～0067段中所揭示之包括包含Cu和/或P之氧化物的微晶且數量平均凝聚粒徑為5～200nm的近紅外線吸收粒子。As the coloring agent having the above-mentioned spectroscopic properties, compounds disclosed in paragraphs 0004 to 0016 of JP-A No. 07-164729 and/or those disclosed in paragraphs 0027 to 0062 of JP-A No. 2002-146254 can also be used The compound and the near-infrared absorbing particles disclosed in paragraphs 0034 to 0067 of JP 2011-164583 A include crystallites of oxides of Cu and/or P and have a number-average aggregated particle diameter of 5 to 200 nm.

作為在波長675～900nm的波長區域具有極大吸收波長之化合物，選自包括花青化合物、吡咯并吡咯化合物、方酸菁化合物、酞菁化合物及萘酞菁化合物之組群中之至少1種為較佳。 又，紅外線吸收劑是在25℃的水中溶解1質量%以上之化合物為較佳，在25℃的水中溶解10質量%以上之化合物為更佳。藉由使用該種化合物，耐溶劑性變得良好。 吡咯并吡咯化合物能够參閱日本特開2010-222557號公報的0049～0062段，該內容被併入本說明書中。花青化合物及方酸菁化合物能夠參閱國際公開2014/088063號公報的0022～0063段、國際公開2014/030628號公報的0053～0118段、日本特開2014-59550號公報的0028～0074段、國際公開2012/169447號公報的0013～0091段、日本特開2015-176046號公報的0019～0033段、日本特開2014-63144號公報的0053～0099段、日本特開2014-52431號公報的0085～0150段、日本特開2014-44301號公報的0076～0124段、日本特開2012-8532號公報的0045～0078段、日本特開2015-172102號公報的0027～0067段、日本特開2015-172004號公報的0029～0067段、日本特開2015-40895號公報的0029～0085段、日本特開2014-126642號公報的0022～0036段、日本特開2014-148567號公報的0011～0017段、日本特開2015-157893號公報的0010～0025段、日本特開2014-095007號公報的0013～0026段、日本特開2014-80487號公報的0013～0047段及日本特開2013-227403號公報的0007～0028段等，該內容被併入本說明書中。At least one compound selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squaraine compound, a phthalocyanine compound, and a naphthalocyanine compound as a compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is better. Moreover, it is preferable that the infrared absorber is a compound which melt|dissolved 1 mass % or more in the water of 25 degreeC, and it is more preferable that it melt|dissolved 10 mass % or more in the water of 25 degreeC. Solvent resistance becomes favorable by using such a compound. For the pyrrolopyrrole compound, reference can be made to paragraphs 0049 to 0062 of JP 2010-222557 A, the contents of which are incorporated in the present specification. For cyanine compounds and squaraine compounds, refer to paragraphs 0022 to 0063 of International Publication No. WO 2014/088063, paragraphs 0053 to 0118 of International Publication No. 2014/030628, and paragraphs 0028 to 0074 of JP 2014-59550 A. Paragraphs 0013 to 0091 of International Publication No. 2012/169447, Paragraphs 0019 to 0033 of JP 2015-176046 A, paragraphs 0053 to 0099 of JP 2014-63144 A, and JP 2014-52431 A Paragraphs 0085 to 0150, paragraphs 0076 to 0124 of JP 2014-44301 A, paragraphs 0045 to 0078 of JP 2012-8532 A, paragraphs 0027 to 0067 of JP 2015-172102 A, JP 2012-8532 A Paragraphs 0029 to 0067 of JP 2015-172004 A, paragraphs 0029 to 0085 of JP 2015-40895 A, paragraphs 0022 to 0036 of JP 2014-126642 A, and JP 2014-148567 A Paragraph 0017, Paragraphs 0010 to 0025 of JP 2015-157893 A, paragraphs 0013 to 0026 of JP 2014-095007 A, paragraphs 0013 to 0047 of JP 2014-80487 A, and JP 2013- Paragraphs 0007 to 0028 of Gazette No. 227403 and the like are incorporated into this specification.

[分散組成物的製造方法] 分散組成物能夠藉由公知的混合方法（例如，使用了攪拌機、均質器、高壓乳化裝置、濕式粉碎機及濕式分散機等之混合方法）混合上述各成分而進行製備。[Manufacturing method of dispersion composition] The dispersion composition can be mixed with each of the above-mentioned components by a known mixing method (for example, a mixing method using a mixer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, or the like) to prepare.

分散組成物的製造方法包含以下的製程為較佳。 ・準備含有氮原子之原材料A及含有過渡金屬原子及原子T之原材料B、或者準備含有氮原子之原材料A、含有過渡金屬原子之原材料C及含有原子T之原材料D之製程（原材料準備製程） ・將2種以上的原材料以氣相狀態進行混合而得到混合物之製程（混合製程） ・使氣相狀態的混合物凝縮而得到含金屬氮化物粒子之製程（凝縮製程） ・混合含金屬氮化物粒子及樹脂而得到分散組成物之製程（分散製程）The manufacturing method of the dispersion composition preferably includes the following processes.・Process for preparing raw material A containing nitrogen atom and raw material B containing transition metal atom and atom T, or preparing raw material A containing nitrogen atom, raw material C containing transition metal atom and raw material D containing atom T (raw material preparation process)・Process of mixing two or more raw materials in gas phase to obtain a mixture (mixing process) ・Process of condensing the mixture in gas phase to obtain metal-containing nitride particles (condensation process) ・Mixing of metal-containing nitride particles and resin to obtain the process of dispersion composition (dispersion process)

上述中，關於原材料準備製程、混合製程及凝縮製程，如在含金屬氮化物粒子的製造方法中已說明那樣。In the above, the raw material preparation process, the mixing process, and the condensation process are as described in the method for producing metal-containing nitride particles.

（分散製程） 分散製程是混合含金屬氮化物粒子和樹脂而得到分散組成物之製程。作為混合含金屬氮化物粒子和樹脂之方法，如已說明那樣。另外，在分散製程中，可以一併混合上述以外的任意成分。(Dispersion process) The dispersion process is a process of mixing metal-containing nitride particles and resin to obtain a dispersion composition. The method for mixing the metal-containing nitride particles and the resin is as described above. In addition, in the dispersion process, optional components other than the above may be mixed together.

[硬化性組成物] 本發明的實施形態之硬化性組成物含有含金屬氮化物粒子、樹脂、聚合性化合物及聚合起始劑。以下，對上述各成分進行詳細敘述。[Curable composition] The curable composition of the embodiment of the present invention contains metal-containing nitride particles, a resin, a polymerizable compound, and a polymerization initiator. Hereinafter, each of the above-mentioned components will be described in detail.

〔含金屬氮化物粒子〕 作為硬化性組成物所含有之含金屬氮化物粒子的形態，如作為含金屬氮化物粒子的形態而已說明那樣。硬化性組成物中之含金屬氮化物粒子的含量並沒有特別限制，相對於硬化性組成物的總固體成分，一般是30～80質量%為較佳。含金屬氮化物粒子可以單獨使用1種，亦可以併用2種以上。當併用2種以上的含金屬氮化物粒子時，合計含量在上述範圍內為較佳。[Metal-Containing Nitride Particles] The form of the metal-containing nitride particles contained in the curable composition is as described above as the form of the metal-containing nitride particles. The content of the metal-containing nitride particles in the curable composition is not particularly limited, but is generally preferably 30 to 80% by mass relative to the total solid content of the curable composition. The metal-containing nitride particles may be used alone or in combination of two or more. When two or more kinds of metal-containing nitride particles are used in combination, the total content is preferably within the above range.

〔樹脂〕 作為硬化性組成物所含有之樹脂的形態，如作為分散組成物所含有之樹脂的形態而已說明那樣。 硬化性組成物中之樹脂的含量並沒有特別限制，相對於硬化性組成物的總固體成分，一般是3～60質量%為較佳，5～40質量%為更佳。樹脂可以單獨使用1種，亦可以併用2種以上。當併用2種以上的樹脂時，合計含量在上述範圍內為較佳。[Resin] The form of the resin contained in the curable composition is as described above as the form of the resin contained in the dispersion composition. The content of the resin in the curable composition is not particularly limited, but is generally preferably 3 to 60 mass %, more preferably 5 to 40 mass % with respect to the total solid content of the curable composition. A resin may be used individually by 1 type, and may use 2 or more types together. When two or more resins are used in combination, the total content is preferably within the above range.

硬化性組成物含有作為樹脂之分散劑和鹼可溶性樹脂為較佳。作為分散劑及鹼可溶性樹脂的形態，如作為分散組成物所含有之分散劑及鹼可溶性樹脂的形態而已說明那樣。 硬化性組成物中之分散劑的含量並沒有特別限制，相對於硬化性組成物的總固體成分，一般是2～40質量%為較佳，5～30質量%為更佳。分散劑可以單獨使用1種，亦可以併用2種以上。當併用2種以上的分散劑時，合計含量在上述範圍內為較佳。 硬化性組成物中之鹼可溶性樹脂的含量並沒有特別限制，相對於硬化性組成物的總固體成分，一般是1～30質量%為較佳。鹼可溶性樹脂可以單獨使用1種，亦可以併用2種以上。當併用2種以上的鹼可溶性樹脂時，合計含量在上述範圍內為較佳。The curable composition preferably contains a dispersant as a resin and an alkali-soluble resin. The form of the dispersant and the alkali-soluble resin is as described above as the form of the dispersant and the alkali-soluble resin contained in the dispersion composition. The content of the dispersant in the curable composition is not particularly limited, but is generally preferably 2 to 40% by mass, more preferably 5 to 30% by mass relative to the total solid content of the curable composition. A dispersing agent may be used individually by 1 type, and may use 2 or more types together. When two or more types of dispersants are used in combination, the total content is preferably within the above range. The content of the alkali-soluble resin in the curable composition is not particularly limited, but is generally preferably 1 to 30% by mass relative to the total solid content of the curable composition. Alkali-soluble resin may be used individually by 1 type, and may use 2 or more types together. When two or more alkali-soluble resins are used in combination, the total content is preferably within the above-mentioned range.

〔聚合性化合物〕 硬化性組成物含有聚合性化合物。本說明書中，聚合性化合物是指含有聚合性基之化合物，是指與分散劑及鹼可溶性樹脂不同之成分。[Polymerizable compound] The curable composition contains a polymerizable compound. In this specification, the polymerizable compound refers to a compound containing a polymerizable group, and refers to a component different from a dispersant and an alkali-soluble resin.

硬化性組成物中之聚合性化合物的含量並沒有特別限制，相對於硬化性組成物的總固體成分，一般是5～30質量%為較佳。聚合性化合物可以單獨使用1種，亦可以併用2種以上。當併用2種以上的聚合性化合物時，合計含量在上述範圍內為較佳。The content of the polymerizable compound in the curable composition is not particularly limited, but is generally preferably 5 to 30% by mass relative to the total solid content of the curable composition. A polymerizable compound may be used individually by 1 type, and may use 2 or more types together. When two or more types of polymerizable compounds are used in combination, the total content is preferably within the above range.

聚合性化合物是含有1個以上含有乙烯性不飽和鍵之基團之化合物為較佳，含有2個以上之化合物為更佳，含有3個以上為進一步較佳，含有5個以上為特佳。上限例如為15個以下。作為含有乙烯性不飽和鍵之基團，例如可以舉出乙烯基、（甲基）烯丙基及（甲基）丙烯醯基等。The polymerizable compound is preferably a compound containing one or more ethylenically unsaturated bond-containing groups, more preferably two or more, more preferably three or more, and particularly preferably five or more. The upper limit is, for example, 15 or less. As a group containing an ethylenically unsaturated bond, a vinyl group, a (meth)allyl group, a (meth)acryloyl group, etc. are mentioned, for example.

作為聚合性化合物，例如能夠使用日本特開2008-260927號公報的0050段及日本特開2015-68893號公報的0040段中所記載之化合物，上述內容被併入本說明書中。As the polymerizable compound, for example, compounds described in paragraph 0050 of JP 2008-260927 A and paragraph 0040 of JP 2015-68893 A can be used, the contents of which are incorporated in the present specification.

聚合性化合物例如可以是單體、預聚物、寡聚物及該等的混合物、以及該等的多聚體等化學形態中的任意一種。 聚合性化合物是3～15官能的（甲基）丙烯酸酯化合物為較佳，3～6官能的（甲基）丙烯酸酯化合物為更佳。The polymerizable compound may be, for example, any of chemical forms such as monomers, prepolymers, oligomers, mixtures of these, and polymers of these. The polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, and more preferably a 3- to 6-functional (meth)acrylate compound.

聚合性化合物是含有1個以上含有乙烯性不飽和鍵之基團之、在常壓下具有100℃以上的沸點之化合物亦較佳。例如，能夠參閱日本特開2013-29760號公報的0227段、日本特開2008-292970號公報的0254～0257段中所記載之化合物，該內容被併入本說明書中。It is also preferable that the polymerizable compound contains one or more groups containing an ethylenically unsaturated bond and has a boiling point of 100° C. or higher under normal pressure. For example, reference can be made to the compounds described in paragraph 0227 of JP-A-2013-29760 and paragraphs 0254-0257 of JP-A-2008-292970, the contents of which are incorporated in the present specification.

聚合性化合物是二新戊四醇三丙烯酸酯（作為市售品為KAYARAD D-330；Nippon Kayaku Co.,Ltd.製造）、二新戊四醇四丙烯酸酯（作為市售品為KAYARAD D-320；Nippon Kayaku Co.,Ltd.製造）、二新戊四醇五（甲基）丙烯酸酯（作為市售品為KAYARAD D-310；Nippon Kayaku Co.,Ltd.製造）、二新戊四醇六（甲基）丙烯酸酯（作為市售品為KAYARAD DPHA；Nippon Kayaku Co.,Ltd.製造，A-DPH-12E；Shin-Nakamura Chemical Co.,Ltd.製造）及該等的（甲基）丙烯醯基介隔乙二醇殘基或丙二醇殘基之結構（例如，由Sartomer Company, Inc.市售之SR454、SR499）為較佳。亦能夠使用該等的寡聚物類型。又，亦能夠使用NK Ester A-TMMT（新戊四醇四丙烯酸酯，Shin-Nakamura Chemical Co.,Ltd.製造）及KAYARAD RP-1040（Nippon Kayaku Co.,Ltd.製造）等。 以下示出較佳的聚合性化合物的態樣。The polymerizable compounds were dipeotaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipivalerythritol tetraacrylate (commercially available as KAYARAD D- 320; manufactured by Nippon Kayaku Co., Ltd.), dipeptaerythritol penta(meth)acrylate (available as a commercial item: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipivoerythritol Hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and these (methyl) Structures in which an acrylyl group intervenes ethylene glycol residues or propylene glycol residues (eg, SR454, SR499 commercially available from Sartomer Company, Inc.) are preferred. These oligomer types can also be used. In addition, NK Ester A-TMMT (neopentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), and the like can also be used. The aspect of a preferable polymerizable compound is shown below.

聚合性化合物可以具有羧酸基、磺酸基及磷酸基等酸基。作為含有酸基之聚合性化合物，脂肪族聚羥基化合物與不飽和羧酸的酯為較佳，使非芳香族羧酸酐與脂肪族聚羥基化合物的未反應的羥基進行反應而具有酸基之聚合性化合物為更佳，進一步較佳為在該酯之中脂肪族聚羥基化合物為新戊四醇和/或二新戊四醇者。作為市售品，例如可以舉出TOAGOSEI CO.,LTD.製造之ARONIX TO-2349、M-305、M-510及M-520等。The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. As the polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride reacts with an unreacted hydroxyl group of an aliphatic polyhydroxy compound to polymerize an acid group. The compound is more preferable, and it is further preferable that the aliphatic polyhydroxy compound in the ester is neopentaerythritol and/or dipepentaerythritol. As a commercial item, ARONIX TO-2349 by TOAGOSEI CO., LTD., M-305, M-510, and M-520 etc. are mentioned, for example.

含有酸基之聚合性化合物的較佳的酸值為0.1～40mgKOH/g，更佳為5～30mgKOH/g。若聚合性化合物的酸值為0.1mgKOH/g以上，則顯影溶解特性良好，若為40mgKOH/g以下，則在製造和/或處理方面有利。進而，光聚合性能良好，硬化性優異。The acid value of the acid group-containing polymerizable compound is preferably 0.1 to 40 mgKOH/g, more preferably 5 to 30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, development and dissolution properties are favorable, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and/or handling. Furthermore, the photopolymerization performance is good, and the curability is excellent.

關於聚合性化合物，含有己內酯結構之化合物亦是較佳的態樣。 作為含有己內酯結構之化合物，只要在分子內含有己內酯結構，則並沒有特別限定，例如能夠舉出ε-己內酯改質多官能（甲基）丙烯酸酯，該ε-己內酯改質多官能（甲基）丙烯酸酯藉由將三羥甲基乙烷、二-三羥甲基乙烷、三羥甲基丙烷、二-三羥甲基丙烷、新戊四醇、二新戊四醇、三新戊四醇、甘油、二丙三醇、三羥甲基三聚氰胺等多元醇和（甲基）丙烯酸及ε-己內酯進行酯化而得到。其中，含有下述式（Z-1）所表示之己內酯結構之化合物為較佳。Regarding the polymerizable compound, a compound containing a caprolactone structure is also a preferable aspect. The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule. For example, ε-caprolactone-modified polyfunctional (meth)acrylate, the Ester-modified polyfunctional (meth)acrylates were prepared by mixing trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, neopentylerythritol, It is obtained by esterifying polyhydric alcohols, such as neopentaerythritol, tri-pivalerythritol, glycerin, diglycerol, and trimethylol melamine, with (meth)acrylic acid, and ε-caprolactone. Among them, a compound containing a caprolactone structure represented by the following formula (Z-1) is preferable.

[化學式11]

Figure 02_image021
[Chemical formula 11]
Figure 02_image021

式（Z-1）中，6個R全部為下述式（Z-2）所表示之基團，或者6個R中1～5個為下述式（Z-2）所表示之基團，其餘為下述式（Z-3）所表示之基團。In formula (Z-1), all 6 Rs are groups represented by the following formula (Z-2), or 1 to 5 of the 6 Rs are groups represented by the following formula (Z-2) , and the rest are groups represented by the following formula (Z-3).

[化學式12]

Figure 02_image023
[Chemical formula 12]
Figure 02_image023

式（Z-2）中，R1 表示氫原子或甲基，m表示1或2的數，「*」表示鍵結鍵。In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond.

[化學式13]

Figure 02_image025
[Chemical formula 13]
Figure 02_image025

式（Z-3）中，R1 表示氫原子或甲基，「*」表示鍵結鍵。In formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and "*" represents a bond.

含有己內酯結構之聚合性化合物例如由Nippon Kayaku Co.,Ltd.作為KAYARAD DPCA系列而市售，可以舉出DPCA-20（上述式（Z-1）～（Z-3）中，m=1、式（Z-2）所表示之基團的數量=2、R1 全部為氫原子的化合物）、DPCA-30（上述式（Z-1）～（Z-3），m=1、式（Z-2）所表示之基團的數量=3、R1 全部為氫原子的化合物）、DPCA-60（上述式（Z-1）～（Z-3），m=1、式（Z-2）所表示之基團的數量=6、R1 全部為氫原子的化合物）、DPCA-120（上述式（Z-1）～（Z-3）中，m=2、式（Z-2）所表示之基團的數量=6、R1 全部為氫原子的化合物）等。The polymerizable compound containing a caprolactone structure is marketed as KAYARAD DPCA series from, for example, Nippon Kayaku Co., Ltd., and examples thereof include DPCA-20 (in the above formulae (Z-1) to (Z-3), m= 1. The number of groups represented by formula (Z-2) = 2, and R 1 is a compound in which all hydrogen atoms are used), DPCA-30 (the above formulas (Z-1) to (Z-3), m=1, The number of groups represented by the formula (Z-2) = 3, and R 1 is a compound with all hydrogen atoms), DPCA-60 (the above formulas (Z-1) to (Z-3), m=1, formula ( The number of groups represented by Z-2) = 6, the compound in which all R 1 are hydrogen atoms), DPCA-120 (in the above formulas (Z-1) to (Z-3), m=2, formula (Z-1) -2) The number of groups represented = 6, compounds in which all R 1 are hydrogen atoms), etc.

聚合性化合物亦能夠使用下述式（Z-4）或（Z-5）所表示之化合物。As the polymerizable compound, a compound represented by the following formula (Z-4) or (Z-5) can also be used.

[化學式14]

Figure 02_image027
[Chemical formula 14]
Figure 02_image027

式（Z-4）及（Z-5）中，E各自獨立地表示-（（CH2 ）y CH2 O）-或-（（CH2 ）y CH（CH3 ）O）-，y各自獨立地表示0～10的整數，X各自獨立地表示（甲基）丙烯醯基、氫原子或羧酸基。 式（Z-4）中，（甲基）丙烯醯基的合計為3個或4個，m各自獨立地表示0～10的整數，各m的合計為0～40的整數。 式（Z-5）中，（甲基）丙烯醯基的合計為5個或6個，n各自獨立地表示0～10的整數，各n的合計為0～60的整數。In formulas (Z-4) and (Z-5), E each independently represents -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)-, and y each independently Each independently represents an integer of 0 to 10, and X each independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxylic acid group. In formula (Z-4), the total of (meth)acryloyl groups is 3 or 4, m each independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. In formula (Z-5), the total of (meth)acryloyl groups is 5 or 6, n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

式（Z-4）中，m是0～6的整數為較佳，0～4的整數為更佳。 各m的合計是2～40的整數為較佳，2～16的整數為更佳，4～8的整數為進一步較佳。 式（Z-5）中，n是0～6的整數為較佳，0～4的整數為更佳。各n的合計是3～60的整數為較佳，3～24的整數為更佳，6～12的整數為進一步較佳。 式（Z-4）或式（Z-5）中的-（（CH2 ）y CH2 O）-或-（（CH2 ）y CH（CH3 ）O）-是氧原子側的末端鍵結於X之形態為較佳。In formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8. In formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12. -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)- in formula (Z-4) or formula (Z-5) is a terminal bond on the oxygen atom side The shape of the knot in the X is better.

式（Z-4）或式（Z-5）所表示之化合物可以單獨使用1種，亦可以併用2種以上。尤其，式（Z-5）中6個X全部為丙烯醯基之形態、式（Z-5）中6個X全部為丙烯醯基之化合物與6個X中至少1個為氫原子的化合物的混合物的態樣為較佳。藉由設為該種構成，能夠進一步提高顯影性。The compound represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, compounds in which all 6 Xs in formula (Z-5) are acrylyl groups, compounds in which all 6 Xs in formula (Z-5) are acrylyl groups, and compounds in which at least one of 6 Xs is a hydrogen atom The state of the mixture is better. By setting it as such a structure, developability can be improved further.

式（Z-4）或式（Z-5）所表示之化合物在聚合性化合物中之總含量，是20質量%以上為較佳，50質量%以上為更佳。 在式（Z-4）或式（Z-5）所表示之化合物之中，新戊四醇衍生物和/或二新戊四醇衍生物為更佳。The total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, more preferably 50% by mass or more. Among the compounds represented by the formula (Z-4) or the formula (Z-5), the neopentaerythritol derivatives and/or the dipeotaerythritol derivatives are more preferable.

聚合性化合物可以含有卡多（cardo）骨架。 作為含有卡多骨架之聚合性化合物，含有9,9-雙芳基茀骨架之聚合性化合物為較佳。 作為含有卡多骨架之聚合性化合物並沒有限定，例如可以舉出ONCOAT EX系列（NAGASE & CO.,LTD.製造）及OGSOL（Osaka Gas Chemicals Co.,Ltd.製造）等。The polymerizable compound may contain a cardo skeleton. As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-bisarylpyridinium skeleton is preferable. The polymerizable compound containing a cardo skeleton is not limited, and examples thereof include ONCOAT EX series (manufactured by NAGASE & CO., LTD.) and OGSOL (manufactured by Osaka Gas Chemicals Co., Ltd.).

〔聚合起始劑〕 硬化性組成物含有聚合起始劑。 聚合起始劑並沒有特別限制，能夠使用公知的聚合起始劑。作為聚合起始劑，例如可以舉出光聚合起始劑及熱聚合起始劑等，光聚合起始劑為較佳。另外，作為聚合起始劑，所謂的自由基聚合起始劑為較佳。 硬化性組成物中之聚合起始劑的含量並沒有特別限制，相對於硬化性組成物的總固體成分，一般是0.5～20質量%為較佳。聚合起始劑可以單獨使用1種，亦可以併用2種以上。當併用2種以上的聚合起始劑時，合計含量在上述範圍內為較佳。[Polymerization Initiator] The curable composition contains a polymerization initiator. The polymerization initiator is not particularly limited, and known polymerization initiators can be used. As a polymerization initiator, a photoinitiator, a thermal polymerization initiator, etc. are mentioned, for example, A photoinitiator is preferable. Moreover, as a polymerization initiator, what is called a radical polymerization initiator is preferable. The content of the polymerization initiator in the curable composition is not particularly limited, but is generally preferably 0.5 to 20% by mass relative to the total solid content of the curable composition. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together. When two or more kinds of polymerization initiators are used in combination, the total content is preferably within the above range.

作為熱聚合起始劑，例如可以舉出2,2’-偶氮雙異丁腈（AIBN）、3-羧基丙腈、偶氮雙丙二腈及二甲基-（2,2’）-偶氮雙（2-甲基丙酸酯）[V-601]等偶氮化合物、以及過氧化苯甲醯、過氧化月桂醯及過硫酸鉀等有機過氧化物。 作為聚合起始劑的具體例，例如能夠舉出加藤清視著《紫外線硬化系統》（株式會社綜合技術中心發行：平成元年）的第65～148頁中所記載之聚合起始劑等。As the thermal polymerization initiator, for example, 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalononitrile, and dimethyl-(2,2')- Azo compounds such as azobis(2-methylpropionate) [V-601], and organic peroxides such as benzyl peroxide, lauryl peroxide and potassium persulfate. Specific examples of the polymerization initiator include those described in pages 65 to 148 of Kiyoshi Kato's "Ultraviolet Curing System" (published by the General Technology Center Co., Ltd.: Heisei 1).

＜光聚合起始劑＞ 上述硬化性組成物含有光聚合起始劑為較佳。 作為光聚合起始劑，只要能夠引發聚合性化合物的聚合，則並沒有特別限制，能夠使用公知的光聚合起始劑。作為光聚合起始劑，例如是對紫外線區域至可視光區域具有感光性者為較佳。又，可以是與被光激發之增感劑產生某種作用而生成活性自由基之活性劑，亦可以是根據聚合性化合物的種類引發陽離子聚合之起始劑。 又，光聚合起始劑含有至少1種在約300nm～800nm（330nm～500nm為更佳。）的範圍內具有至少約50莫耳吸光係數之化合物為較佳。<Photopolymerization initiator> It is preferable that the said curable composition contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can initiate the polymerization of the polymerizable compound, and known photopolymerization initiators can be used. As the photopolymerization initiator, for example, one having photosensitivity in the ultraviolet region to the visible light region is preferred. Moreover, it may be an activator which produces|generates active radicals by some action with the sensitizer excited by light, and may be an initiator which initiates cationic polymerization according to the kind of polymerizable compound. Furthermore, it is preferable that the photopolymerization initiator contains at least one compound having an absorption coefficient of at least about 50 molar in the range of about 300 nm to 800 nm (preferably 330 nm to 500 nm).

硬化性組成物中之光聚合起始劑的含量並沒有特別限制，相對於硬化性組成物的總固體成分，一般是0.5～20質量%為較佳。光聚合起始劑可以單獨使用1種，亦可以併用2種以上。當併用2種以上的光聚合起始劑時，合計含量在上述範圍內為較佳。The content of the photopolymerization initiator in the curable composition is not particularly limited, but is generally preferably 0.5 to 20% by mass relative to the total solid content of the curable composition. A photopolymerization initiator may be used individually by 1 type, and may use 2 or more types together. When two or more types of photopolymerization initiators are used in combination, the total content is preferably within the above range.

作為光聚合起始劑，例如可以舉出鹵化烴衍生物（例如，含有三嗪骨架者、含有噁二唑骨架者等）、醯基氧化膦等醯基膦化合物、六芳基聯咪唑、肟衍生物等肟化合物、有機過氧化物、硫代化合物、酮化合物、芳香族鎓鹽、胺基苯乙酮化合物及羥基苯乙酮等。 作為光聚合起始劑的具體例，能夠參閱日本特開2013-29760號公報的0265～0268段，該內容被併入本說明書中。Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton, those containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oximes. Oxime compounds such as derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, hydroxyacetophenone and the like. Specific examples of the photopolymerization initiator can be referred to in paragraphs 0265 to 0268 of JP 2013-29760 A, the contents of which are incorporated in the present specification.

作為光聚合起始劑，更具體而言，例如亦能夠使用日本特開平10-291969號公報中所記載之胺基苯乙酮系起始劑及日本專利第4225898號公報中所記載之醯基膦系起始劑。 作為羥基苯乙酮化合物，能夠使用IRGACURE-184、DAROCUR-1173、IRGACURE-500、IRGACURE-2959及IRGACURE-127（商品名稱：均為BASF公司製造）。 作為胺基苯乙酮化合物，能夠使用作為市售品之IRGACURE-907、IRGACURE-369或IRGACURE-379EG（商品名稱：均為BASF公司製造）。作為胺基苯乙酮化合物，亦能夠使用吸收波長與365nm或405nm等的長波光源匹配之日本特開2009-191179公報中所記載之化合物。 作為醯基膦化合物，能夠使用作為市售品之IRGACURE-819或IRGACURE-TPO（商品名稱：均為BASF公司製造）。As the photopolymerization initiator, more specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and the acyl group described in Japanese Patent No. 4225898 can also be used. Phosphine-based initiator. As the hydroxyacetophenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF Corporation) can be used. As the aminoacetophenone compound, commercially available IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade names: all manufactured by BASF) can be used. As an aminoacetophenone compound, the compound described in Unexamined-Japanese-Patent No. 2009-191179 whose absorption wavelength is matched with a long-wave light source, such as 365 nm or 405 nm, can also be used. As the acylphosphine compound, commercially available IRGACURE-819 or IRGACURE-TPO (trade name: both manufactured by BASF Corporation) can be used.

（肟化合物） 作為光聚合起始劑，更佳為可以舉出肟酯系聚合起始劑（肟化合物）。尤其，肟化合物是高靈敏度且聚合效率較高、能夠不依賴於硬化性組成物中之含金屬氮化物粒子的含量濃度而使硬化性組成物層進行硬化、容易將含金屬氮化物粒子的含量設計成較高，因此較佳。 作為肟化合物的具體例，能夠使用日本特開2001-233842號公報中所記載之化合物、日本特開2000-80068號公報中所記載之化合物或日本特開2006-342166號公報中所記載之化合物。 作為肟化合物，例如可以舉出3-苯甲醯氧基亞胺基丁烷-2-酮、3-乙醯氧基亞胺基丁烷-2-酮、3-丙醯氧基亞胺基丁烷-2-酮、2-乙醯氧基亞胺基戊烷-3-酮、2-乙醯氧基亞胺基-1-苯基丙烷-1-酮、2-苯甲醯氧基亞胺基-1-苯基丙烷-1-酮、3-（4-甲苯磺醯氧基）亞胺基丁烷-2-酮及2-乙氧基羰氧基亞胺基-1-苯基丙烷-1-酮等。 又，亦可以舉出J.C.S.Perkin II（1979年）pp.1653-1660、J.C.S.Perkin II（1979年）pp.156-162、光聚合物科學與技術雜誌（Journal of Photopolymer Science and Technology）（1995年）pp.202-232、日本特開2000-66385號公報中所記載之化合物、日本特開2000-80068號公報、日本特表2004-534797號公報及日本特開2006-342166號公報的各公報中所記載之化合物等。 在市售品中，亦可以較佳地使用IRGACURE-OXE01（BASF公司製造）、IRGACURE-OXE02（BASF公司製造）、IRGACURE-OXE03（BASF公司製造）或IRGACURE-OXE04（BASF公司製造）。又，亦能夠使用TR-PBG-304（Changzhou Tronly New Electronic Materials CO.,LTD.製造）、ADEKA ARKLS NCI-831及ADEKA ARKLS NCI-930（ADEKA CORPORATION製造）或N-1919（含有咔唑・肟酯骨架之光起始劑（ADEKA CORPORATION製造）。(Oxime compound) As a photopolymerization initiator, an oxime ester type|system|group polymerization initiator (oxime compound) is mentioned more preferably. In particular, the oxime compound has high sensitivity and high polymerization efficiency, can harden the curable composition layer independently of the content concentration of the metal-containing nitride particles in the curable composition, and can easily adjust the content of the metal-containing nitride particles. It is designed to be higher, so it is better. As specific examples of the oxime compound, the compound described in JP 2001-233842 A, the compound described in JP 2000-80068 A, or the compound described in JP 2006-342166 A can be used . Examples of the oxime compound include 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionoxyiminobutan-2-one. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzyloxy Imino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyloxyimino-1-benzene propan-1-one, etc. Also, JCS Perkin II (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) ) pp. 202-232, compounds described in JP 2000-66385 A, JP 2000-80068 A, JP 2004-534797, and JP 2006-342166 A. Compounds described in etc. Among the commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Trolly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831, ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), or N-1919 (carbazole-oxime-containing Ester skeleton light initiator (manufactured by ADEKA CORPORATION).

作為上述以外的肟化合物，可以使用在咔唑N位上連結有肟之日本特表2009-519904號公報中所記載之化合物；在二苯甲酮部位上導入有雜（hetero）取代基之美國專利第7626957號公報中所記載之化合物；在色素部位導入有硝基之日本特開2010-15025號公報及美國專利公開2009-292039號公報中所記載之化合物；國際公開專利2009-131189號公報中所記載之酮肟化合物；在同一分子內含有三嗪骨架和肟骨架之美國專利7556910號公報中所記載之化合物；在405nm處具有吸收極大且對g射線光源具有良好的靈敏度之日本特開2009-221114號公報中所記載之化合物；等。 較佳為例如能夠參閱日本特開2013-29760號公報的0274～0275段，該內容被併入本說明書中。 具體而言，作為肟化合物，下述式（OX-1）所表示之化合物為較佳。另外，可以是肟化合物的N-O鍵為（E）體的肟化合物，亦可以是（Z）體的肟化合物，亦可以是（E）體與（Z）體的混合物。As the oxime compound other than the above, the compounds described in JP-A No. 2009-519904 in which an oxime is linked to the N-position of carbazole; Compounds described in Patent No. 7626957; Compounds described in JP-A-2010-15025 and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced into a pigment site; International Patent Publication No. 2009-131189 The ketoxime compound described in; the compound described in the US Patent No. 7556910 Gazette containing a triazine skeleton and an oxime skeleton in the same molecule; the Japanese Patent Laid-Open Publication with the highest absorption at 405nm and good sensitivity to g-ray light source Compounds described in the 2009-221114 Bulletin; etc. For example, it is preferable to refer to paragraphs 0274 to 0275 of JP 2013-29760 A, the contents of which are incorporated in the present specification. Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. In addition, the oxime compound may be an oxime compound in which the N-O bond of the oxime compound is an (E) form, an oxime compound in a (Z) form, or a mixture of the (E) form and the (Z) form.

[化學式15]

Figure 02_image029
[Chemical formula 15]
Figure 02_image029

式（OX-1）中，R及B各自獨立地表示一價的取代基，A表示二價的有機基，Ar表示芳基。 式（OX-1）中，作為R所表示之一價的取代基，一價的非金屬原子團為較佳。 作為一價的非金屬原子團，可以舉出烷基、芳基、醯基、烷氧基羰基、芳氧基羰基、雜環基、烷硫基羰基及芳硫基羰基等。又，該等基團可以具有1個以上的取代基。又，前述取代基可以進一步經其他取代基取代。 作為取代基，可以舉出鹵素原子、芳氧基、烷氧基羰基或芳氧基羰基、醯氧基、醯基、烷基及芳基等。 式（OX-1）中，作為B所表示之一價的取代基，芳基、雜環基、芳基羰基或雜環羰基為較佳，芳基或雜環基為較佳。該等基團可以具有1個以上的取代基。作為取代基，可以舉出前述取代基。 式（OX-1）中，作為A所表示之二價的有機基，碳數1～12的伸烷基、伸環烷基或伸炔基為較佳。該等基團可以具有1個以上的取代基。作為取代基，可以舉出前述取代基。In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. In the formula (OX-1), as the monovalent substituent represented by R, a monovalent non-metallic atomic group is preferable. Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, an arylthiocarbonyl group, and the like. Moreover, these groups may have one or more substituents. In addition, the aforementioned substituents may be further substituted with other substituents. As a substituent, a halogen atom, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryloxy group, an aryl group, an alkyl group, an aryl group, etc. are mentioned. In formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group, and more preferably an aryl group or a heterocyclic group. These groups may have one or more substituents. Examples of the substituent include the aforementioned substituents. In the formula (OX-1), the divalent organic group represented by A is preferably an alkylene group, a cycloalkylene group or an alkynylene group having 1 to 12 carbon atoms. These groups may have one or more substituents. Examples of the substituent include the aforementioned substituents.

作為光聚合起始劑，亦能夠使用含有氟原子之肟化合物。作為含有氟原子之肟化合物的具體例，可以舉出日本特開2010-262028號公報中所記載之化合物；日本特表2014-500852號公報中所記載之化合物24、36～40；日本特開2013-164471號公報中所記載之化合物（C-3）；等。該內容被併入本說明書中。As a photopolymerization initiator, an oxime compound containing a fluorine atom can also be used. Specific examples of the fluorine atom-containing oxime compound include compounds described in JP 2010-262028 A; compounds 24, 36 to 40 described in JP 2014-500852 A; Compound (C-3) described in 2013-164471 Bulletin; etc. This content is incorporated into this specification.

作為光聚合起始劑，亦能夠使用下述通式（1）～（4）所表示之化合物。As the photopolymerization initiator, compounds represented by the following general formulae (1) to (4) can also be used.

[化學式16]

Figure 02_image031
[Chemical formula 16]
Figure 02_image031

[化學式17]

Figure 02_image033
[Chemical formula 17]
Figure 02_image033

式（1）中，R1 及R2 分別獨立地表示碳數1～20的烷基、碳數4～20的脂環式烴基、碳數6～30的芳基或碳數7～30的芳基烷基，當R1 及R2 為苯基時，苯基彼此可以鍵結而形成茀基，R3 及R4 分別獨立地表示氫原子、碳數1～20的烷基、碳數6～30的芳基、碳數7～30的芳基烷基或碳數4～20的雜環基，X表示直接鍵或羰基。In formula (1), R 1 and R 2 each independently represent an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkyl group having 7 to 30 carbon atoms. Arylalkyl, when R 1 and R 2 are phenyl groups, the phenyl groups can be bonded to each other to form a perylene group, and R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number An aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

式（2）中，R1 、R2 、R3 及R4 的含義與式（1）中之R1 、R2 、R3 及R4 的含義相同，R5 表示-R6 、-OR6 、-SR6 、-COR6 、-CONR6 R6 、-NR6 COR6 、-OCOR6 、-COOR6 、-SCOR6 、-OCSR6 、-COSR6 、-CSOR6 、-CN、鹵素原子或羥基，R6 表示碳數1～20的烷基、碳數6～30的芳基、碳數7～30的芳基烷基或碳數4～20的雜環基，X表示直接鍵或羰基，a表示0～4的整數。In the formula (2), R 1, R 2, R 3 and R meaning as in formula (1) 4 R 1, R 2, the same meaning as R 3 and R 4, R 5 represents -R 6, -OR 6 , -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6 , -CN, halogen Atom or hydroxyl group, R 6 represents an alkyl group with 1 to 20 carbons, an aryl group with 6 to 30 carbons, an arylalkyl group with 7 to 30 carbons or a heterocyclic group with 4 to 20 carbons, X represents a direct bond or a carbonyl group, and a represents an integer of 0-4.

式（3）中，R1 表示碳數1～20的烷基、碳數4～20的脂環式烴基、碳數6～30的芳基或碳數7～30的芳基烷基，R3 及R4 分別獨立地表示氫原子、碳數1～20的烷基、碳數6～30的芳基、碳數7～30的芳基烷基或碳數4～20的雜環基，X表示直接鍵或羰基。In formula (3), R 1 represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms, and R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms. X represents a direct bond or a carbonyl group.

式（4）中，R1 、R3 及R4 的含義與式（3）中之R1 、R3 及R4 的含義相同，R5 表示、-R6 、-OR6 、-SR6 、-COR6 、-CONR6 R6 、-NR6 COR6 、-OCOR6 、-COOR6 、-SCOR6 、-OCSR6 、-COSR6 、-CSOR6 、-CN、鹵素原子或羥基，R6 表示碳數1～20的烷基、碳數6～30的芳基、碳數7～30的芳基烷基或碳數4～20的雜環基，X表示直接鍵或羰基，a表示0～4的整數。Formula (4), R 1, R 3 and R 4 defined for the formula (3) in the R 1, the same meaning as R 3 and R 4, R 5 represent, -R 6, -OR 6, -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6 , -CN, halogen atom or hydroxyl group, R 6 represents an alkyl group with a carbon number of 1-20, an aryl group with a carbon number of 6-30, an arylalkyl group with a carbon number of 7-30 or a heterocyclic group with a carbon number of 4-20, X represents a direct bond or a carbonyl group, a represents An integer from 0 to 4.

上述式（1）及式（2）中，R1 及R2 分別獨立地是甲基、乙基、正丙基、異丙基、環己基或苯基為較佳。R3 是甲基、乙基、苯基、甲苯基或二甲苯基為較佳。R4 是碳數1～6的烷基或苯基為較佳。R5 是甲基、乙基、苯基、甲苯基或萘基為較佳。X是直接鍵為較佳。 上述式（3）及式（4）中，R1 分別獨立地是甲基、乙基、正丙基、異丙基、環己基或苯基為較佳。R3 是甲基、乙基、苯基、甲苯基或二甲苯基為較佳。R4 是碳數1～6的烷基或苯基為較佳。R5 是甲基、乙基、苯基、甲苯基或萘基為較佳。X是直接鍵為較佳。 作為式（1）及式（2）所表示之化合物的具體例，可以舉出日本特開2014-137466號公報的0076～0079段中所記載之化合物。該內容被併入本說明書中。In the above formulas (1) and (2), it is preferable that R 1 and R 2 are each independently methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl. R 3 is preferably methyl, ethyl, phenyl, tolyl or xylyl. R 4 is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R 5 is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond. In the above formulas (3) and (4), it is preferable that R 1 is each independently methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl. R 3 is preferably methyl, ethyl, phenyl, tolyl or xylyl. R 4 is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R 5 is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond. Specific examples of the compounds represented by formula (1) and formula (2) include compounds described in paragraphs 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated into this specification.

以下，示出硬化性組成物中可較佳地使用之肟化合物的具體例。又，作為肟化合物，亦能夠使用國際公開第2015-036910號的表1中所記載之化合物，上述內容被併入本說明書中。Below, the specific example of the oxime compound which can be used suitably in a curable composition is shown. Moreover, as an oxime compound, the compound described in Table 1 of International Publication No. 2015-036910 can also be used, and the above-mentioned content is incorporated in this specification.

[化學式18]

Figure 02_image035
[化學式19]
Figure 02_image037
[Chemical formula 18]
Figure 02_image035
[Chemical formula 19]
Figure 02_image037

肟化合物是在350nm～500nm的波長區域具有極大吸收波長者為較佳，在360nm～480nm的波長區域具有極大吸收波長者為更佳，365nm及405nm的吸光度較者為進一步較佳。 從靈敏度的觀點而言，肟化合物在365nm或405nm下之莫耳吸光係數是1,000～300,000為較佳，2,000～300,000為更佳，5,000～200,000為進一步較佳。 化合物的莫耳吸光係數能夠使用公知的方法進行測定,例如藉由紫外可視分光光度計（Varian公司製造之Cary-5 spectrophotometer：分光光度計），使用乙酸乙酯溶劑在0.01g/L的濃度下進行測定為較佳。 光聚合起始劑根據需要可以將2種以上組合使用。The oxime compound is preferably the one with the maximum absorption wavelength in the wavelength region of 350nm-500nm, more preferably the one with the maximum absorption wavelength in the wavelength region of 360nm-480nm, and the absorbance of 365nm and 405nm is more preferable. From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 200,000. The molar absorptivity of the compound can be measured using a known method, for example, by a UV-visible spectrophotometer (Cary-5 spectrophotometer: spectrophotometer manufactured by Varian), using an ethyl acetate solvent at a concentration of 0.01 g/L It is better to perform the measurement. A photopolymerization initiator can be used in combination of 2 or more types as needed.

又，作為光聚合起始劑，亦能夠使用日本特開第2008-260927號公報的0052段、日本特開第2010-97210號公報的0033～0037段、日本特開第2015-68893號公報的0044段中所記載之化合物，上述內容被併入本說明書中。In addition, as the photopolymerization initiator, paragraph 0052 of JP 2008-260927 A, paragraphs 0033 to 0037 of JP 2010-97210 A, and JP 2015-68893 A can also be used. For the compounds described in paragraph 0044, the above content is incorporated into this specification.

〔任意成分〕 硬化性組成物可以在發揮本發明的效果之範圍內含有上述以外的成分。作為上述以外的成分，例如可以舉出聚合抑制劑、溶劑、著色劑、界面活性劑、紫外線吸收劑、矽烷偶合劑及密合性改良劑等。以下，對硬化性組成物中所含有之任意成分進行詳細敘述。[Optional Components] The curable composition may contain components other than those described above within the range in which the effects of the present invention are exhibited. Examples of components other than the above include polymerization inhibitors, solvents, colorants, surfactants, ultraviolet absorbers, silane coupling agents, and adhesion improvers. Hereinafter, the optional components contained in the curable composition will be described in detail.

＜聚合抑制劑＞ 硬化性組成物含有聚合抑制劑為較佳。 硬化性組成物中之聚合抑制劑的含量並沒有特別限制，相對於硬化性組成物的總固體成分，一般是0.0001～0.5質量%為較佳，0.001～0.2質量%為更佳。聚合抑制劑可以單獨使用1種，亦可以併用2種以上。當併用2種以上的聚合抑制劑時，合計含量在上述範圍內為較佳。 作為聚合抑制劑，如作為分散組成物可含有之聚合抑制劑而已說明那樣。<Polymerization inhibitor> It is preferable that the curable composition contains a polymerization inhibitor. The content of the polymerization inhibitor in the curable composition is not particularly limited, but is generally preferably 0.0001 to 0.5 mass %, more preferably 0.001 to 0.2 mass % relative to the total solid content of the curable composition. A polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together. When two or more kinds of polymerization inhibitors are used in combination, the total content is preferably within the above range. The polymerization inhibitor is as described above as the polymerization inhibitor that can be contained in the dispersion composition.

＜溶劑＞ 硬化性組成物含有溶劑為較佳。 硬化性組成物中之溶劑的含量並沒有特別限制，一般調整為硬化性組成物的固體成分成為20～90質量%為較佳，調整為成為30～90質量%為更佳。溶劑可以單獨使用1種，亦可以併用2種以上。當併用2種以上的溶劑時，硬化性組成物的固體成分的合計含量在上述範圍內為較佳。 作為溶劑，如作為分散組成物可含有之溶劑而已說明那樣。<Solvent> It is preferable that the curable composition contains a solvent. The content of the solvent in the curable composition is not particularly limited, but is generally adjusted so that the solid content of the curable composition is preferably 20 to 90% by mass, and more preferably 30 to 90% by mass. A solvent may be used individually by 1 type, and may use 2 or more types together. When two or more solvents are used in combination, it is preferable that the total content of the solid content of the curable composition is within the above range. The solvent is as described above as the solvent that can be contained in the dispersion composition.

＜著色劑＞ 硬化性組成物可以含有著色劑。 硬化性組成物中之著色劑的含量並沒有特別限制，相對於硬化性組成物的總固體成分，一般是0.0001～70質量%為較佳。著色劑可以單獨使用1種，亦可以併用2種以上。當併用2種以上的著色劑時，合計含量在上述範圍內為較佳。 作為著色劑，如作為分散組成物可含有之溶劑而已說明那樣。<Colorant> The curable composition may contain a colorant. The content of the colorant in the curable composition is not particularly limited, but is generally preferably 0.0001 to 70% by mass relative to the total solid content of the curable composition. A coloring agent may be used individually by 1 type, and may use 2 or more types together. When two or more colorants are used in combination, the total content is preferably within the above range. As the coloring agent, it has been described as the solvent which can be contained in the dispersion composition.

＜界面活性劑＞ 硬化性組成物可以含有界面活性劑。界面活性劑有助於提高硬化性組成物的塗佈性。 當上述硬化性組成物含有界面活性劑時，界面活性劑的含量相對於硬化性組成物的總固體成分，是0.001～2.0質量%為較佳。 界面活性劑可以單獨使用1種，亦可以併用2種以上。當併用2種以上的界面活性劑時，合計量在上述範圍內為較佳。<Surfactant> The curable composition may contain a surfactant. The surfactant contributes to improving the coatability of the curable composition. When the curable composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass % with respect to the total solid content of the curable composition. Surfactant may be used individually by 1 type, and may use 2 or more types together. When two or more surfactants are used in combination, the total amount is preferably within the above range.

作為界面活性劑，例如可以舉出氟系界面活性劑、非離子系界面活性劑、陽離子系界面活性劑、陰離子系界面活性劑及矽氧系界面活性劑等。As the surfactant, for example, a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a silicone-based surfactant, and the like can be mentioned.

例如，藉由硬化性組成物含有氟系界面活性劑，硬化性組成物的溶液特性（尤其是流動性）得到進一步提高。亦即，當使用含有氟系界面活性劑之硬化性組成物來形成膜時，藉由使被塗佈面與塗佈液的界面張力下降而對被塗佈面之潤濕性得到改善，從而對被塗佈面之塗佈性得到提高。因此，即使在以少量的溶液量形成了數μm左右的薄膜之情況下，亦能夠更佳地進行厚度不均勻少的均勻厚度的膜形成之觀點上有效。For example, when the curable composition contains a fluorine-based surfactant, the solution properties (especially fluidity) of the curable composition are further improved. That is, when a film is formed using a curable composition containing a fluorine-based surfactant, the wettability of the surface to be coated is improved by reducing the interfacial tension between the surface to be coated and the coating liquid, thereby improving the wettability of the surface to be coated. The coatability to the coated surface is improved. Therefore, even when a thin film of about several μm is formed with a small amount of solution, it is effective in that the film formation of a uniform thickness with less thickness unevenness can be performed more preferably.

氟系界面活性劑中的氟含有率是3～40質量%為較佳，更佳為5～30質量%，進一步較佳為7～25質量%。氟含有率在該範圍內的氟系界面活性劑在塗佈膜的厚度的均勻性和/或省液性的觀點上有效果，在硬化性組成物中之溶解性亦良好。The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective from the viewpoint of uniformity of the thickness of the coating film and/or liquid saving, and also has good solubility in a curable composition.

作為氟系界面活性劑，例如可以舉出MEGAFAC F171、MEGAFAC F172、MEGAFAC F173、MEGAFAC F176、MEGAFAC F177、MEGAFAC F141、MEGAFAC F142、MEGAFAC F143、MEGAFAC F144、MEGAFAC R30、MEGAFAC F437、MEGAFAC F475、MEGAFAC F479、MEGAFAC F482、MEGAFAC F554、MEGAFAC F780（以上為DIC Corporation製造）、Fluorad FC430、Fluorad FC431、Fluorad FC171（以上為Sumitomo 3M Limited製造）、Surflon S-382、Surflon SC-101、Surflon SC-103、Surflon SC-104、Surflon SC-105、Surflon SC-1068、Surflon SC-381、Surflon SC-383、Surflon S-393、Surflon KH-40（以上為ASAHI GLASS CO.,LTD.製造）、PF636、PF656、PF6320、PF6520、PF7002（OMNOVA Solutions Inc.製造）。 作為氟系界面活性劑，亦能夠使用嵌段聚合物，作為具體例，可以舉出日本特開第2011-89090號公報中所記載之化合物。Examples of fluorine-based surfactants include MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F141, MEGAFAC F142, MEGAFAC F143, MEGAFAC F144, MEGAFAC R30, MEGAFAC F437, MEGAFAC F475, MEGAFAC F479, MEGAFAC F482, MEGAFAC F554, MEGAFAC F780 (the above are manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171 (the above are manufactured by Sumitomo 3M Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC -104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (the above are manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320 , PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.). As the fluorine-based surfactant, a block polymer can also be used, and specific examples thereof include compounds described in Japanese Patent Laid-Open No. 2011-89090.

＜紫外線吸收劑＞ 硬化性組成物可以含有紫外線吸收劑。藉此，能夠設為硬化膜的圖案的形狀更加優異之（精細）者。 作為紫外線吸收劑，能夠使用水楊酸系、二苯甲酮系、苯并***系、經取代之丙烯腈系及三嗪系的紫外線吸收劑。作為該等的具體例，能夠使用日本特開2012-068418號公報的0137～0142段（對應之US2012/0068292的0251～0254段）的化合物，該等內容被併入本說明書中。 此外，亦能夠較佳地使用二乙基胺基-苯基磺醯基系紫外線吸收劑（DAITO CHEMICAL CO.,LTD.製造，商品名稱：UV-503）等。 作為紫外線吸收劑，可以舉出日本特開2012-32556號公報的0134～0148段中所例示之化合物。 紫外線吸收劑的含量相對於硬化性組成物的總固體成分，是0.001～15質量%為較佳，0.01～10質量%為更佳，0.1～5質量%為進一步較佳。<Ultraviolet absorber> The curable composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of a cured film can be made the one which is more excellent (fine). As the ultraviolet absorber, salicylic acid-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. As such specific examples, the compounds of paragraphs 0137 to 0142 of JP 2012-068418 A (corresponding to paragraphs 0251 to 0254 of US 2012/0068292 ) can be used, and these contents are incorporated herein. In addition, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by DAITO CHEMICAL CO., LTD., trade name: UV-503) or the like can also be preferably used. Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP 2012-32556 A. The content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and even more preferably 0.1 to 5% by mass relative to the total solid content of the curable composition.

＜矽烷偶合劑＞ 硬化性組成物可以含有矽烷偶合劑。 矽烷偶合劑是指在分子中含有水解性基和其以外的官能基之化合物。另外，烷氧基等水解性基鍵結於矽原子。 水解性基是指直接鍵結於矽原子且能夠藉由水解反應和/或縮合反應產生矽氧烷鍵之取代基。作為水解性基，例如可以舉出鹵素原子、烷氧基、醯氧基及烯氧基。當水解性基含有碳原子時，其碳數是6以下為較佳，4以下為更佳。尤其，碳數4以下的烷氧基或碳數4以下的烯氧基為較佳。 又，當在基板上形成硬化膜時，為了提高基板與硬化膜之間的密合性，矽烷偶合劑不含氟原子及矽原子（但是，水解性基所鍵結之矽原子除外）為較佳，不含經氟原子、矽原子（但是，水解性基所鍵結之矽原子除外）、矽原子取代之伸烷基、碳數8以上的直鏈狀烷基及碳數3以上的支鏈狀烷基為較佳。<Silane coupling agent> The curable composition may contain a silane coupling agent. The silane coupling agent refers to a compound containing a hydrolyzable group and other functional groups in the molecule. In addition, a hydrolyzable group such as an alkoxy group is bonded to a silicon atom. The hydrolyzable group refers to a substituent directly bonded to a silicon atom and capable of generating a siloxane bond through a hydrolysis reaction and/or a condensation reaction. As a hydrolyzable group, a halogen atom, an alkoxy group, an alkenyloxy group, and an alkenyloxy group are mentioned, for example. When the hydrolyzable group contains carbon atoms, the number of carbon atoms is preferably 6 or less, more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable. In addition, when forming a cured film on a substrate, in order to improve the adhesion between the substrate and the cured film, the silane coupling agent does not contain fluorine atoms and silicon atoms (however, except for the silicon atoms bound by the hydrolyzable group), it is relatively low. Preferably, it does not contain fluorine atoms, silicon atoms (except for the silicon atoms bound by hydrolyzable groups), alkyl groups substituted with silicon atoms, straight-chain alkyl groups with 8 or more carbon atoms, and branched groups with 3 or more carbon atoms. Chain alkyl groups are preferred.

硬化性組成物中之矽烷偶合劑的含量相對於硬化性組成物中的總固體成分，是0.1～10質量%為較佳，0.5～8質量%為更佳，1.0～6質量%為進一步較佳。 硬化性組成物可以單獨包含1種矽烷偶合劑，亦可以包含2種以上。當硬化性組成物含有2種以上的矽烷偶合劑時，其合計在上述範圍內即可。The content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and even more preferably 1.0 to 6% by mass relative to the total solid content in the curable composition. good. The curable composition may contain one type of silane coupling agent alone, or may contain two or more types. When the curable composition contains two or more types of silane coupling agents, the total of the silane coupling agents may be within the above range.

＜密合性改良劑＞ 硬化性組成物可以含有矽烷偶合劑作為密合性改良劑。作為矽烷偶合劑，例如可以舉出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、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、乙烯基三甲氧基矽烷及乙烯基三乙氧基矽烷等。 密合性改良劑的含量並沒有特別限制，相對於硬化性組成物的總固體成分，是0.02～20質量%為較佳。<Adhesion Improver> The curable composition may contain a silane coupling agent as an adhesion improver. Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. Silane, 3-glycidoxypropylmethyldiethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane, etc. The content of the adhesion improver is not particularly limited, but is preferably 0.02 to 20% by mass relative to the total solid content of the curable composition.

〔硬化性組成物的另一形態〕 作為本發明的實施形態之硬化性組成物的另一形態，是已說明之含有分散組成物、聚合性化合物及聚合起始劑之硬化性組成物。 關於分散組成物、聚合性化合物及聚合起始劑，如已說明那樣。 關於硬化性組成物中之各成分的含量等，如已說明那樣。[Another form of the curable composition] Another form of the curable composition according to the embodiment of the present invention is the curable composition containing the dispersion composition, the polymerizable compound, and the polymerization initiator described above. The dispersion composition, the polymerizable compound, and the polymerization initiator are as described above. The content and the like of each component in the curable composition are as described above.

〔硬化性組成物中之含金屬氮化物粒子的體積平均粒徑〕 硬化性組成物中之含金屬氮化物粒子的體積平均粒徑並沒有特別限制，使用以動態光散射法為測定原理之粒度分佈計測定出之體積換算的累積90%粒徑（D90）小於0.5μm為較佳，小於0.2μm為更佳。 若硬化性組成物中之含金屬氮化物粒子的體積平均粒徑小於0.5μm，則硬化性組成物具有更加優異之本發明的效果。 D90的下限值並沒有特別限制，一般是0.01μm以上為較佳。[Volume-average particle size of metal-containing nitride particles in curable composition] The volume-average particle size of metal-containing nitride particles in the curable composition is not particularly limited, and the particle size determined by the dynamic light scattering method is used. The volume-converted cumulative 90% particle size (D90) measured by the distribution meter is preferably less than 0.5 μm, more preferably less than 0.2 μm. If the volume average particle diameter of the metal-containing nitride particles in the curable composition is less than 0.5 μm, the curable composition has more excellent effects of the present invention. The lower limit of D90 is not particularly limited, but generally 0.01 μm or more is preferable.

[硬化性組成物的製造方法] 硬化性組成物能夠藉由公知的混合方法（例如，使用了攪拌機、均質器、高壓乳化裝置、濕式粉碎機及濕式分散機等之混合方法）混合上述各成分而進行製備。硬化性組成物可以混合已說明之分散組成物和上述各成分而進行製備。又，硬化性組成物的製造方法可以包含已說明之分散組成物的製造方法。 在製備硬化性組成物時，可以一次性調配各成分，亦可以將各成分分別溶解或分散於溶劑中之後逐次調配。調配時的投入順序及作業條件並沒有特別限制。[Manufacturing method of curable composition] The curable composition can be mixed by a known mixing method (eg, a mixing method using a mixer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, etc.) each component is prepared. The curable composition can be prepared by mixing the above-described dispersion composition and the above-mentioned components. Moreover, the manufacturing method of a curable composition may include the manufacturing method of the dispersion composition already demonstrated. When preparing a curable composition, each component may be mixed at one time, or each component may be dissolved or dispersed in a solvent and then mixed sequentially. There are no particular restrictions on the input sequence and operating conditions at the time of deployment.

以去除異物或減少缺陷等為目的，利用過濾器對硬化性組成物進行過濾為較佳。作為過濾器，只要是一直以來用於過濾用途等者，則能夠無特別限定地進行使用。例如，可以舉出使用PTFE（聚四氟乙烯）等氟樹脂、尼龍等聚醯胺系樹脂及聚乙烯、聚丙烯（PP）等聚烯烴系樹脂（包含高密度、超高分子量）等製成之過濾器。在該等材料之中，聚丙烯（包含高密度聚丙烯）、尼龍為較佳。 過濾器的孔徑是0.1～7.0μm左右為適當，較佳為0.2～2.5μm左右，更佳為0.2～1.5μm左右，進一步較佳為0.3～0.7μm。藉由設在該範圍，能夠抑制顏料的過濾堵塞之同時，確實地去除顏料中所包含之雜質及凝聚物等微細的異物。 在使用過濾器時，可以組合不同之過濾器（例如第1過濾器和第2過濾器等）。此時，基於第1過濾器之過濾可以僅進行1次，亦可以進行2次以上。當組合不同之過濾器而進行2次以上過濾時，第2次以後的孔徑等於或大於第1次過濾的孔徑為較佳。亦可以組合在上述範圍內不同孔徑的第1過濾器。在此的孔徑能夠參閱過濾器廠商的標稱值。作為市售的過濾器，例如能夠從由NIHON PALL LTD.、Advantec Toyo Kaisha, Ltd.、Nihon Entegris K.K.（舊Japan Microlis Co.,Ltd.）或KITZ MICRO FILTER Corporation等提供之各種過濾器中選擇。 第2過濾器能夠使用由與上述第1過濾器相同之材料等形成者。第2過濾器的孔徑是0.2～10.0μm左右為適當，較佳為0.2～7.0μm左右，更佳為0.3～6.0μm左右。 硬化性組成物不含金屬、含鹵素之金屬鹽、酸、鹼等雜質為較佳。該等材料中所包含之雜質的含量是1ppm以下為較佳，1ppb以下為更佳，100ppt以下為進一步較佳，10ppt以下為特佳，實質上不含（測定裝置的檢測極限以下）為最佳。 另外，上述雜質能夠藉由感應耦合電漿質量分析裝置（Yokogawa Analytical Systems, Inc.製造，Agilent 7500cs型）進行測定。For the purpose of removing foreign matter or reducing defects, it is preferable to filter the curable composition with a filter. As a filter, as long as it is conventionally used for filtering purposes, it can be used without particular limitation. For example, fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP) can be used. the filter. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred. The pore diameter of the filter is appropriately about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and still more preferably about 0.3 to 0.7 μm. By setting it in this range, while suppressing the filter clogging of the pigment, it is possible to reliably remove impurities such as impurities and aggregates contained in the pigment. When using filters, you can combine different filters (eg 1st filter, 2nd filter, etc.). At this time, the filtering by the first filter may be performed only once, or may be performed twice or more. When filtration is performed two or more times by combining different filters, it is preferable that the pore size after the second filtration is equal to or larger than the pore size of the first filtration. It is also possible to combine the first filters with different pore diameters within the above range. The pore size here can refer to the filter manufacturer's nominal value. As commercially available filters, for example, it is possible to select from various filters provided by NIHON PALL LTD., Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (former Japan Microlis Co., Ltd.), KITZ MICRO FILTER Corporation, and the like. The second filter can be formed of the same material or the like as the above-mentioned first filter. The pore diameter of the second filter is suitably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm. Preferably, the curable composition does not contain impurities such as metals, halogen-containing metal salts, acids, and alkalis. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, further preferably 100 ppt or less, particularly preferably 10 ppt or less, and most preferably does not contain substantially (below the detection limit of the measuring device) good. In addition, the above-mentioned impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Inc., Agilent 7500cs model).

[硬化膜及硬化膜的製造方法] 本發明的實施形態之硬化膜是將上述硬化性組成物進行硬化而得到之硬化膜。硬化膜的厚度並沒有特別限制，一般是0.2～7μm為較佳，0.4～5μm為更佳。 上述厚度為平均厚度，是測定硬化膜的任意5處以上的厚度，並將該等進行算術平均而得到之值。THE MANUFACTURING METHOD OF A CURED FILM AND A CURED FILM The cured film which concerns on embodiment of this invention is a cured film obtained by hardening the said curable composition. The thickness of the cured film is not particularly limited, but is generally preferably 0.2 to 7 μm, more preferably 0.4 to 5 μm. The said thickness is an average thickness, and is the value obtained by measuring the thickness of arbitrary 5 or more places of a cured film, and arithmetically averaging these.

硬化膜的製造方法並沒有特別限制，可以舉出將上述硬化性組成物塗佈於基板上而形成塗膜，並對塗膜實施硬化處理而製造硬化膜之方法。 硬化處理的方法並沒有特別限制，可以舉出光硬化處理或熱硬化處理，從容易形成圖案之觀點而言，光硬化處理（尤其是藉由照射光化射線或放射線進行之硬化處理）為較佳。The manufacturing method in particular of a cured film is not restrict|limited, The said curable composition is apply|coated on a board|substrate, it forms a coating film, and the method of performing a curing process on a coating film, and manufacturing a cured film is mentioned. The method of curing treatment is not particularly limited, and photocuring treatment or thermal curing treatment can be mentioned. From the viewpoint of easy pattern formation, photocuring treatment (especially curing treatment by irradiation of actinic rays or radiation) is relatively good.

本發明的實施形態之硬化膜是將使用上述硬化性組成物形成之硬化性組成物層進行硬化而得到之硬化膜。 硬化膜的製造方法並沒有特別限制，包含以下製程為較佳。 ・硬化性組成物層形成製程 ・曝光製程 ・顯影製程 以下，對各製程進行說明。The cured film which concerns on embodiment of this invention is a cured film obtained by hardening the curable composition layer formed using the said curable composition. The manufacturing method of the cured film is not particularly limited, and it is preferable to include the following processes.・Curable composition layer forming process ・Exposure process ・Development process Next, each process will be explained.

＜硬化性組成物層形成製程＞ 硬化性組成物層形成製程是使用上述硬化性組成物形成硬化性組成物層之製程。作為使用硬化性組成物形成硬化性組成物層之製程，例如可以舉出在基板上塗佈硬化性組成物而形成硬化性組成物層之製程。 基板的種類並沒有特別限制，當用作固體攝影元件時，例如可以舉出矽基板，當用作彩色濾光片（包含固體攝影元件用彩色濾光片）時，可以舉出玻璃基板（玻璃晶片）等。 作為將硬化性組成物塗佈於基板上之方法，能夠適用旋塗（spin coat）、狹縫塗佈、噴墨法、噴霧塗佈、旋轉塗佈、流延塗佈、輥塗及網版印刷法等各種塗佈方法。 塗佈於基板上之硬化性組成物通常在70～150℃且1～4分鐘左右的條件下進行乾燥而形成硬化性組成物層。<The curable composition layer forming process> The curable composition layer forming process is a process of forming the curable composition layer using the above-mentioned curable composition. As a process of forming a curable composition layer using a curable composition, for example, a process of coating a curable composition on a substrate to form a curable composition layer can be exemplified. The type of the substrate is not particularly limited, and when used as a solid-state imaging device, for example, a silicon substrate can be used, and when used as a color filter (including color filters for solid-state imaging devices), a glass substrate (glass substrate) can be used. wafers) etc. As a method of applying the curable composition on the substrate, spin coating, slit coating, ink jet method, spray coating, spin coating, casting coating, roll coating, and screen printing can be applied Various coating methods such as printing method. The curable composition applied on the substrate is usually dried at 70 to 150° C. for about 1 to 4 minutes to form a curable composition layer.

＜曝光製程＞ 在曝光製程中，向在硬化性組成物層形成製程中形成之硬化性組成物層經由具備圖案狀的開口部之光罩照射光化射線或放射線而進行曝光，僅使被光照射之硬化性組成物層進行硬化。 曝光藉由放射線的照射來進行為較佳，作為曝光時能夠使用之放射線，尤其可以較佳地使用g射線、h射線及i射線等紫外線，作為光源，高壓水銀燈為較佳。照射強度是5～1500mJ/cm2 為較佳，10～1000mJ/cm2 為更佳。<Exposure process> In the exposure process, the curable composition layer formed in the curable composition layer forming process is exposed to actinic rays or radiation through a mask having a patterned opening, and only the exposed The irradiated curable composition layer is cured. Exposure is preferably carried out by irradiation with radiation. As radiation that can be used for exposure, ultraviolet rays such as g-rays, h-rays, and i-rays can be preferably used. As a light source, a high-pressure mercury lamp is preferable. The irradiation intensity is preferably 5 to 1500 mJ/cm 2 , more preferably 10 to 1000 mJ/cm 2 .

＜顯影製程＞ 接著曝光製程進行顯影處理（顯影製程），使在曝光製程中之光未照射部分溶出於顯影液中。藉此，僅保留經光硬化之部分。 作為顯影液，可以使用鹼顯影液。能夠使用無機鹼顯影液或有機鹼顯影液，但使用有機鹼顯影液為較佳。顯影溫度通常是20～40℃為較佳，顯影時間是20～180秒為較佳。 作為無機鹼顯影液，可以舉出將氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、矽酸鈉及偏矽酸鈉等鹼性化合物溶解成濃度成為0.001～10質量%、較佳為成為0.005～0.5質量%而得到之鹼水溶液。 作為有機鹼顯影液，可以舉出將氨水、乙胺、二乙胺、二甲基乙醇胺、四甲基氫氧化銨、四乙基氫氧化銨、四丙基氫氧化銨、四丁基氫氧化銨、苄基三甲基氫氧化銨、膽鹼、吡咯、哌啶及1,8-二氮雜雙環-[5,4,0]-7-十一碳烯等鹼性化合物溶解成濃度成為0.001～10質量%、較佳為成為0.005～0.5質量%而得到之鹼水溶液。 鹼水溶液中例如亦能夠添加適量甲醇、乙醇等水溶性有機溶劑和/或界面活性劑等。另外，當使用包括該種鹼水溶液之顯影液時，一般在顯影後利用純水清洗（沖洗）硬化膜。<Development process> The exposure process is followed by a development process (development process), so that the unirradiated part of the light in the exposure process is dissolved in the developing solution. Thereby, only the photohardened portion remains. As the developer, an alkali developer can be used. An inorganic alkali developer or an organic alkali developer can be used, but it is preferable to use an organic alkali developer. The development temperature is usually preferably 20 to 40°C, and the development time is preferably 20 to 180 seconds. Examples of the inorganic alkaline developer include dissolving alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate so that the concentration may be 0.001 to 10% by mass, preferably The alkaline aqueous solution obtained by being 0.005-0.5 mass %. As the organic alkali developer, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide can be mentioned. Basic compounds such as ammonium, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo-[5,4,0]-7-undecene are dissolved to a concentration of 0.001-10 mass %, Preferably it is the alkaline aqueous solution obtained by 0.005-0.5 mass %. For example, an appropriate amount of water-soluble organic solvents such as methanol and ethanol, and/or surfactants, etc. can be added to the aqueous alkali solution. In addition, when a developer including such an aqueous alkali solution is used, the cured film is generally washed (rinsed) with pure water after development.

另外，硬化膜的製造方法可以包括其他製程。 作為其他製程並沒有特別限制，根據需要能夠適當選擇。 作為其他製程，例如可以舉出基材的表面處理製程、預加熱製程（預烘烤製程）、後加熱製程（後烘烤製程）等。 預加熱製程及後加熱製程中之加熱溫度是80～300℃為較佳。上限是220℃以下為更佳。下限是90℃以上為更佳。 預加熱製程及後加熱製程中之加熱時間是30～300秒為較佳。In addition, the manufacturing method of the cured film may include other processes. There are no particular limitations on other processes, and can be appropriately selected according to needs. As other processes, for example, a surface treatment process of a substrate, a preheating process (pre-baking process), a post-heating process (post-baking process), and the like can be mentioned. The heating temperature in the pre-heating process and the post-heating process is preferably 80-300°C. The upper limit is more preferably 220°C or lower. The lower limit is more preferably 90°C or higher. The heating time in the pre-heating process and the post-heating process is preferably 30-300 seconds.

〔硬化膜的物性〕 ・OD（Optical Density：光學密度） 在具有更加優異之遮光性之觀點上，硬化膜在400～1200nm的波長區域中之每1.0μm膜厚的光學密度（OD：Optical Density）超過2.0為較佳，超過3.0為更佳。另外，上限值並沒有特別限制，一般是10以下為較佳。硬化膜能夠較佳地用作遮光膜。 另外，本說明書中，光學密度是指藉由實施例中所記載之方法測定出之光學密度。本說明書中，在400～1200nm的波長區域中之每1.0μm膜厚的光學密度超過3.0是指，在波長400～1200nm的整個區域中，每1.0μm膜厚的光學密度超過3.0。[Physical properties of cured film] ・OD (Optical Density: Optical Density) Optical density (OD: Optical Density) per 1.0 μm film thickness in the wavelength region of 400 to 1200 nm of the cured film from the viewpoint of having more excellent light-shielding properties ) more than 2.0 is better, more than 3.0 is better. In addition, the upper limit is not particularly limited, but generally 10 or less is preferable. The cured film can be preferably used as a light-shielding film. In addition, in this specification, an optical density means the optical density measured by the method as described in an Example. In this specification, the optical density per 1.0 μm film thickness in the wavelength region of 400 to 1200 nm exceeds 3.0 means that the optical density per 1.0 μm film thickness exceeds 3.0 in the entire wavelength region of 400 to 1200 nm.

硬化膜具有表面凹凸結構為較佳。藉此能夠降低遮光層的反射率。可以是在遮光層其本身的表面上具有凹凸結構者，亦可以在遮光層上設置另外的層而賦予凹凸結構。表面凹凸結構的形狀並沒有特別限定，但表面粗糙度在0.55μm以上且1.5μm以下的範圍為較佳。 遮光層的反射率是5%以下為較佳，3%以下為更佳，2%以下為進一步較佳。 製作表面凹凸結構之方法並沒有特別限定，可以是藉由利用使遮光層或其以外的層含有有機填料（filler）或無機填料之方法、利用了曝光顯影之微影法、蝕刻或濺射、奈米壓印法等將遮光層或其以外的層的表面進行粗面化之方法。 又，作為降低硬化膜的反射率之方法，除上述以外，可以舉出在遮光層上設置低折射率層之方法、進一步設置複數個折射率不同之層（例如，高折射率層）之方法、例如日本特開2015-1654號公報中所記載之形成低光學密度層和高光學密度層之方法（在該情況下，可以使用含有本發明的3～11族的過渡金屬的氮化物作為黑色顏料之含金屬氮化物粒子）。It is preferable that the cured film has a surface uneven structure. Thereby, the reflectance of the light shielding layer can be reduced. The light-shielding layer itself may have a concavo-convex structure on its surface, or another layer may be provided on the light-shielding layer to give the concavo-convex structure. The shape of the surface uneven structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 μm or more and 1.5 μm or less. The reflectance of the light shielding layer is preferably 5% or less, more preferably 3% or less, and further preferably 2% or less. The method for producing the surface uneven structure is not particularly limited, and may be a method of incorporating an organic filler or an inorganic filler in the light-shielding layer or layers other than it, a lithography method using exposure and development, etching or sputtering, A method of roughening the surface of a light shielding layer or other layers such as nanoimprinting. Moreover, as a method of reducing the reflectance of the cured film, in addition to the above, a method of providing a low refractive index layer on a light shielding layer, and a method of further providing a plurality of layers with different refractive indices (for example, a high refractive index layer) can be mentioned , For example, the method for forming a low optical density layer and a high optical density layer as described in Japanese Patent Laid-Open No. 2015-1654 (in this case, nitrides containing the transition metals of Groups 3 to 11 of the present invention can be used as black Pigment-containing metal nitride particles).

硬化膜適合於個人計算機、平板電腦（tablet）、行動電話、智慧型手機及數位相機等可攜式設備；列印複合機及掃描器等OA（Office Automation：辦公室自動化）設備；監控相機、條碼讀取器（barcoder reader）、自動櫃員機（ATM：automated teller machine）、高速相機及具有使用了面部圖像認證之個人認證功能之設備等產業用設備；車載用相機設備；內視鏡（endoscope）、膠囊式內視鏡（capsule endoscope）及導管（catheter）等醫療用相機設備；機體感測器、生物感測器（biosensor）、軍事偵察用相機、三維地圖用相機、氣象及海洋觀測相機、陸地資源探查相機、以及宇宙的天文及深太空目標用的探查相機等宇宙用設備；等中所使用之濾光器及模組的遮光構件及遮光膜、以及防反射構件及防反射膜。The hardened film is suitable for portable devices such as personal computers, tablet computers, mobile phones, smart phones and digital cameras; OA (Office Automation: Office Automation) equipment such as printers and scanners; surveillance cameras, barcodes Industrial equipment such as barcode readers, automated teller machines (ATMs), high-speed cameras, and equipment with a personal authentication function using facial image authentication; in-vehicle camera equipment; endoscopes , Capsule endoscope (capsule endoscope) and catheter (catheter) and other medical camera equipment; body sensor, biosensor (biosensor), military reconnaissance camera, three-dimensional map camera, meteorological and marine observation camera, Space equipment such as terrestrial resource exploration cameras, and exploration cameras for space astronomy and deep space targets; shading members and shading films, and anti-reflection members and anti-reflection films used in optical filters and modules.

硬化膜亦能夠用於微LED（Light Emitting Diode：發光二極體）及微OLED（Organic Light Emitting Diode：有機發光二極體）等用途。上述硬化膜除了微LED及微OLED中所使用之濾光器及光學膜以外，對賦予遮光功能或防反射功能之構件亦是適合的。 作為微LED及微OLED的例子，可以舉出日本特表2015-500562號及日本特表2014-533890中所記載者。The cured film can also be used for applications such as micro LED (Light Emitting Diode: light emitting diode) and micro OLED (Organic Light Emitting Diode: organic light emitting diode). The said cured film is suitable also for the member which provides a light-shielding function or an antireflection function in addition to the optical filter and optical film used for micro-LED and micro-OLED. Examples of micro LEDs and micro OLEDs include those described in JP 2015-500562 A and JP 2014-533890.

硬化膜適合作為量子點顯示器中所使用之濾光器及光學膜。又，適合作為賦予遮光功能及防反射功能之構件。 作為量子點顯示器的例子，可以舉出美國專利申請公開第2013/0335677號、美國專利申請公開第2014/0036536號、美國專利申請公開第2014/0036203號及美國專利申請公開第2014/0035960號中所記載者。The cured film is suitable as a filter and an optical film used in quantum dot displays. Moreover, it is suitable as a member which provides a light-shielding function and an antireflection function. Examples of quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960 recorded.

[固體攝像裝置及固體攝影元件] 本發明的實施形態之固體攝像裝置及固體攝影元件含有上述硬化膜。固體攝影元件含有硬化膜之形態並沒有特別限制，例如，可以舉出在基板上具有構成固體攝影元件（CCD影像感測器、CMOS影像感測器等）的受光區之複數個光二極體及包括多晶矽（polysilicon）等之受光元件，並且在支撐體的受光元件形成面側（例如，受光部以外的部分和/或顏色調整用像素等）或與該形成面相反之一側具備本發明的硬化膜而構成者。 固體攝像裝置含有上述固體攝影元件。[Solid-State Imaging Device and Solid-State Imaging Device] The solid-state imaging device and the solid-state imaging device according to the embodiment of the present invention contain the cured film described above. The form in which the solid-state imaging element includes a cured film is not particularly limited, and examples thereof include a plurality of photodiodes and A light-receiving element including polysilicon (polysilicon) or the like, and the light-receiving element of the present invention is provided on the side of the support body on which the light-receiving element is formed (for example, the portion other than the light-receiving portion and/or the pixel for color adjustment, etc.) or the side opposite to the forming surface. Made of hardened film. The solid-state imaging device includes the above-described solid-state imaging element.

參閱圖1～圖2，對固體攝像裝置及固體攝影元件的構成例進行說明。另外，圖1～圖2中，為了明確各部，忽視相互的厚度和/或寬度的比率而將一部分誇張顯示。 如圖1所示，固體攝像裝置100具備矩形狀的固體攝影元件101及保持於固體攝影元件101的上方並密封該固體攝影元件101之透明的蓋玻璃（cover glass）103。進而，在該蓋玻璃103上經由間隔件104重疊設置有透鏡層111。透鏡層111由支撐體113和透鏡材料112構成。透鏡層111亦可以是支撐體113和透鏡材料112成形為一體之構成。若雜散光入射到透鏡層111的周緣區域，則藉由光的擴散，透鏡材料112中之聚光的效果減弱，到達攝像部102之光減少。又，亦會產生由雜散光引起之干擾（noise）。因此，該透鏡層111的周緣區域設置遮光膜114而被遮光。本發明的實施形態之硬化膜亦能夠用作上述遮光膜114。1 to 2 , a configuration example of a solid-state imaging device and a solid-state imaging element will be described. In addition, in FIGS. 1-2, in order to clarify each part, the ratio of the thickness and/or width of each other is ignored, and a part is shown exaggeratedly. As shown in FIG. 1 , the solid-state imaging device 100 includes a rectangular solid-state imaging element 101 and a transparent cover glass 103 held above the solid-state imaging element 101 and sealing the solid-state imaging element 101 . Furthermore, the lens layer 111 is superposed on the cover glass 103 via the spacer 104 . The lens layer 111 is composed of a support body 113 and a lens material 112 . The lens layer 111 may also be a structure in which the support body 113 and the lens material 112 are integrally formed. When the stray light enters the peripheral region of the lens layer 111 , the light condensing effect in the lens material 112 is weakened due to light diffusion, and the light reaching the imaging unit 102 is reduced. In addition, noise caused by stray light is also generated. Therefore, the peripheral region of the lens layer 111 is provided with the light shielding film 114 to be shielded from light. The cured film of the embodiment of the present invention can also be used as the light-shielding film 114 described above.

固體攝影元件101對成像於成為其受光面之攝像部102之光學像進行光電轉換並作為圖像訊號而輸出。該固體攝影元件101具備2片基板積層而得到之積層基板105。積層基板105包括相同尺寸的矩形狀的芯片基板106及電路基板107，在芯片基板106的背面積層有電路基板107。The solid-state imaging element 101 photoelectrically converts the optical image formed on the imaging portion 102 serving as the light-receiving surface thereof, and outputs it as an image signal. The solid-state imaging element 101 includes a laminate substrate 105 obtained by laminating two substrates. The build-up substrate 105 includes a rectangular chip substrate 106 and a circuit substrate 107 of the same size, and the circuit substrate 107 is laminated on the backside of the chip substrate 106 .

用作芯片基板106之基板的材料並沒有特別限制，能夠使用公知的材料。The material used as the substrate of the chip substrate 106 is not particularly limited, and known materials can be used.

在芯片基板106的表面中央部設置有攝像部102。又，若雜散光入射到攝像部102的周緣區域，則從該周緣區域內的電路產生暗電流（干擾），因此該周緣區域設置遮光膜115而被遮光。本發明的實施形態之硬化膜能夠用作遮光膜115。The imaging unit 102 is provided in the center portion of the surface of the chip substrate 106 . Further, when stray light is incident on the peripheral region of the imaging unit 102 , dark current (interference) is generated from circuits in the peripheral region, so the peripheral region is shielded from light by providing the light shielding film 115 . The cured film of the embodiment of the present invention can be used as the light shielding film 115 .

在芯片基板106的表面緣部設置有複數個電極焊盤108。電極焊盤（electrode pad）108經由設置於芯片基板106的表面上之未圖示之訊號線（亦可以是接合線（bonding wire））與攝像部102電連接。A plurality of electrode pads 108 are provided on the edge of the surface of the chip substrate 106 . The electrode pads 108 are electrically connected to the imaging unit 102 via signal wires (which may also be bonding wires), which are not shown, provided on the surface of the chip substrate 106 .

在電路基板107的背面，於各電極焊盤108的大致下方位置分別設置有外部連接端子109。各外部連接端子109經由垂直貫穿積層基板105之貫穿電極110分別與電極焊盤108連接。又，各外部連接端子109經由未圖示之配線與控制固體攝影元件101的驅動之控制電路及對從固體攝影元件101輸出之攝像訊號實施圖像處理之圖像處理電路等連接。On the back surface of the circuit board 107 , external connection terminals 109 are respectively provided at positions substantially below the electrode pads 108 . The external connection terminals 109 are respectively connected to the electrode pads 108 via the through electrodes 110 vertically penetrating the laminate substrate 105 . Further, each external connection terminal 109 is connected to a control circuit for controlling the driving of the solid-state imaging element 101 , an image processing circuit for performing image processing on the imaging signal output from the solid-state imaging element 101 , and the like via wiring not shown.

如圖2所示，攝像部102由受光元件201、彩色濾光片202、微透鏡203等設置於基板204上之各部構成。彩色濾光片202具有藍色像素205b、紅色像素205r、綠色像素205g及黑矩陣205bm。本發明的實施形態之硬化膜亦能夠用作黑矩陣205bm。As shown in FIG. 2 , the imaging unit 102 is constituted by the light-receiving element 201 , the color filter 202 , the microlens 203 , and the like provided on the substrate 204 . The color filter 202 has blue pixels 205b, red pixels 205r, green pixels 205g, and a black matrix 205bm. The cured film of the embodiment of the present invention can also be used as the black matrix 205bm.

作為基板204的材料，能夠使用與前述芯片基板106相同之材料。在基板204的表層形成有p阱層206。在該p阱層26內以正方格子狀排列形成有受光元件201，該受光元件201包括n型層且藉由光電轉換生成訊號電荷並將其積蓄。As the material of the substrate 204, the same material as the aforementioned chip substrate 106 can be used. A p-well layer 206 is formed on the surface layer of the substrate 204 . In the p-well layer 26, light-receiving elements 201 are formed in a square lattice arrangement. The light-receiving elements 201 include an n-type layer and generate and store signal charges by photoelectric conversion.

在受光元件201的其中一方的側方，經由p阱層206的表層的讀出閘極部207形成有包括n型層之垂直傳輸路徑208。在受光元件201的另一方的側方，經由包括p型層之元件分離區域209形成有屬於相鄰像素之垂直傳輸路徑208。讀出閘極部207是用於將積蓄在受光元件201中之訊號電荷讀出於垂直傳輸路徑208之通道區域。On one side of the light-receiving element 201 , a vertical transmission path 208 including an n-type layer is formed via the readout gate portion 207 of the surface layer of the p-well layer 206 . On the other side of the light-receiving element 201, a vertical transfer path 208 belonging to an adjacent pixel is formed via an element isolation region 209 including a p-type layer. The readout gate portion 207 is a channel region for reading out the signal charges accumulated in the light-receiving element 201 to the vertical transmission path 208 .

在基板204的表面上形成有包括ONO（Oxide-Nitride-Oxide：氧化物-氮化物-氧化物）膜之閘極絕緣膜210。在該閘極絕緣膜210上，以覆蓋垂直傳輸路徑208、讀出閘極部207及元件分離區域209的大致正上方之方式，形成有包括多晶矽或非晶矽之垂直傳輸電極211。垂直傳輸電極211 作為驅動垂直傳輸路徑208使其進行電荷傳輸之驅動電極和驅動讀出閘極部207使其進行訊號電荷読出之読出電極發揮功能。訊號電荷從垂直傳輸路徑208依次傳輸至未圖示之水平傳輸路徑及輸出部（浮動擴散放大器（Floating Diffusion Amplifier））之後，作為電壓訊號而被輸出。A gate insulating film 210 including an Oxide-Nitride-Oxide (Oxide-Nitride-Oxide) film is formed on the surface of the substrate 204 . On the gate insulating film 210 , a vertical transfer electrode 211 including polysilicon or amorphous silicon is formed so as to cover the vertical transfer path 208 , the readout gate portion 207 and substantially directly above the element isolation region 209 . The vertical transfer electrode 211 functions as a drive electrode for driving the vertical transfer path 208 for charge transfer and as a readout electrode for driving the readout gate portion 207 for signal charge readout. The signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path and an output part (floating diffusion amplifier) (not shown), and then output as a voltage signal.

在垂直傳輸電極211上以覆蓋其表面之方式形成有遮光膜212。遮光膜212在受光元件201的正上方位置具有開口部，對其以外的區域進行遮光。本發明的實施形態之硬化膜亦能夠用作遮光膜212。 在遮光膜212上 設置有透明的中間層，該中間層包含包括BPSG（borophospho silicate glass：硼磷矽玻璃）之絕緣膜213、包括P-SiN之絕緣膜（鈍化膜）214及包括透明樹脂等之平坦化膜215。彩色濾光片202形成於中間層上。A light shielding film 212 is formed on the vertical transfer electrode 211 so as to cover the surface thereof. The light-shielding film 212 has an opening at a position directly above the light-receiving element 201, and shields the other regions from light. The cured film of the embodiment of the present invention can also be used as the light shielding film 212 . A transparent intermediate layer is provided on the light shielding film 212, and the intermediate layer includes an insulating film 213 including BPSG (borophospho silicate glass), an insulating film (passivation film) 214 including P-SiN, and a transparent resin, etc. the planarizing film 215. The color filter 202 is formed on the intermediate layer.

[黑矩陣] 黑矩陣含有本發明的實施形態之硬化膜。黑矩陣有時含於彩色濾光片、固體攝影元件及液晶顯示裝置中。 作為黑矩陣，可以舉出在上述中已說明者；設置於液晶顯示裝置等顯示裝置的周緣部之黑色的緣部；紅色、藍色及綠色像素間的格子狀和/或條狀的黑色部分；用於TFT（thin film transistor：薄膜電晶體）遮光之點狀和/或線狀的黑色圖案；等。關於該黑矩陣的定義，例如在菅野泰平著、《液晶顯示器製造裝置用語辭典》、第2版、NIKKAN KOGYO SHIMBUN,LTD.、1996年、p.64有記載。 為了提高顯示對比度（contrast）,又，在使用薄膜電晶體（TFT）之主動矩陣驅動方式的液晶顯示裝置的情況下，為了防止由光的電流洩漏引起之畫質下降，黑矩陣具有較高的遮光性（以光學密度OD計為3以上）為較佳。[Black Matrix] The black matrix contains the cured film of the embodiment of the present invention. Black matrices are sometimes included in color filters, solid-state imaging elements, and liquid crystal display devices. Examples of the black matrix include those described above; a black edge part provided on a peripheral part of a display device such as a liquid crystal display device; a grid-like and/or strip-like black portion between red, blue, and green pixels ; Dotted and/or linear black patterns for TFT (thin film transistor) shading; etc. The definition of this black matrix is described, for example, in Yasuhira Kanno, "Dictionary of Terms for Liquid Crystal Display Manufacturing Equipment", 2nd edition, NIKKAN KOGYO SHIMBUN, LTD., 1996, p.64. In order to improve the display contrast (contrast), and in the case of a liquid crystal display device using an active matrix driving method of thin film transistor (TFT), in order to prevent the degradation of image quality caused by the leakage of light current, the black matrix has a high The light-shielding property (3 or more in optical density OD) is preferable.

黑矩陣的製造方法並沒有特別限制，能夠藉由與上述硬化膜的製造方法相同之方法進行製造。具體而言，能夠藉由在基板上塗佈硬化性組成物而形成硬化性組成物層，並進行曝光及顯影而製造圖案狀的硬化膜（黑矩陣）。另外，作為用作黑矩陣之硬化膜的膜厚，0.1～4.0μm為較佳。The manufacturing method of a black matrix is not specifically limited, It can manufacture by the method similar to the manufacturing method of the said cured film. Specifically, a patterned cured film (black matrix) can be manufactured by apply|coating a curable composition on a board|substrate, forming a curable composition layer, exposing and developing. Moreover, as a film thickness of the cured film used as a black matrix, 0.1-4.0 micrometers is preferable.

作為基板的材料並沒有特別限制，對可視光（波長：400～800nm）具有80%以上的透射率為較佳。作為該種材料，具體而言，例如可以舉出鈉鈣玻璃、無鹼玻璃、石英玻璃及硼矽酸玻璃等玻璃；聚酯系樹脂及聚烯烴系樹脂等塑膠；等，從耐藥品性及耐熱性的觀點而言，無鹼玻璃或石英玻璃等為較佳。The material of the substrate is not particularly limited, but it is preferable to have a transmittance of 80% or more for visible light (wavelength: 400 to 800 nm). Specific examples of such materials include glass such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester-based resins and polyolefin-based resins; From the viewpoint of heat resistance, alkali-free glass, quartz glass, or the like is preferable.

[彩色濾光片] 本發明的實施形態之彩色濾光片含有硬化膜。 作為彩色濾光片含有硬化膜之形態並沒有特別限制，可以舉出具備基板和上述黑矩陣之彩色濾光片。亦即，能夠例示出具備在形成於基板上之上述黑矩陣的開口部形成之紅色、綠色及藍色的著色像素之彩色濾光片。[COLOR FILTER] The color filter of the embodiment of the present invention contains a cured film. There is no restriction|limiting in particular as the form which contains a cured film as a color filter, The color filter provided with a board|substrate and the said black matrix is mentioned. That is, a color filter including red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate can be exemplified.

含有黑矩陣（硬化膜）之彩色濾光片例如能夠藉由以下方法進行製造。 首先，在形成於基板上之圖案狀的黑矩陣的開口部形成含有與彩色濾光片的各著色像素相對應之顏料之樹脂組成物的塗膜（樹脂組成物層）。另外，各顏色用樹脂組成物並沒有特別限制，能夠使用公知的樹脂組成物，在本發明的實施形態之硬化性組成物中，使用將含金屬氮化物粒子替換成與各像素相對應之著色劑之者為較佳。 接著，對樹脂組成物層經由具有與黑矩陣的開口部相對應之圖案之光罩進行曝光。接著，藉由顯影處理來去除未曝光部之後，進行烘烤，藉此能夠在黑矩陣的開口部形成著色像素。藉由例如使用含有紅色、綠色及藍色顏料之各顏色用樹脂組成物來進行一系列操作，能夠製造具有紅色、綠色及藍色像素之彩色濾光片。The color filter containing a black matrix (cured film) can be manufactured by the following method, for example. First, a coating film (resin composition layer) of a resin composition containing a pigment corresponding to each colored pixel of the color filter is formed in the opening of the patterned black matrix formed on the substrate. In addition, the resin composition for each color is not particularly limited, and a known resin composition can be used. In the curable composition of the embodiment of the present invention, a coloring corresponding to each pixel is used in which the metal-containing nitride particles are replaced. The one with the medicine is better. Next, the resin composition layer is exposed through a mask having a pattern corresponding to the opening of the black matrix. Next, after removing the unexposed portion by a development process, a colored pixel can be formed in the opening portion of the black matrix by baking. A color filter having red, green, and blue pixels can be manufactured by, for example, performing a series of operations using resin compositions for each color containing red, green, and blue pigments.

[液晶顯示裝置] 本發明的實施形態之液晶顯示裝置含有硬化膜。液晶顯示裝置含有硬化膜之形態並沒有特別限制，可以舉出包含含有已說明之黑矩陣（硬化膜）之彩色濾光片之形態。[Liquid Crystal Display Device] The liquid crystal display device of the embodiment of the present invention contains a cured film. There is no restriction|limiting in particular in the aspect which a liquid crystal display device contains a cured film, The aspect which consists of the color filter containing the black matrix (cured film) already demonstrated is mentioned.

作為本實施形態之液晶顯示裝置，例如可以舉出具備對向配置之一對基板和封入該等基板之間之液晶化合物之形態。作為上述基板，如作為黑矩陣用基板已說明那樣。As the liquid crystal display device of the present embodiment, for example, a form including a pair of substrates arranged to face each other and a liquid crystal compound enclosed between the substrates is exemplified. The above-mentioned substrate is as described above as the substrate for a black matrix.

作為上述液晶顯示裝置的具體形態，例如可以舉出從使用者側依次包括偏光板/基板/彩色濾光片/透明電極層/配向膜/液晶層/配向膜/透明電極層/TFT（Thin Film Transistor：薄膜電晶體）元件/基板/偏光板/背光單元之積層體。As a specific form of the above-mentioned liquid crystal display device, for example, a polarizing plate/substrate/color filter/transparent electrode layer/alignment film/liquid crystal layer/alignment film/transparent electrode layer/TFT (Thin Film Transistor: thin film transistor) component/substrate/polarizer/backlight unit laminate.

另外，作為本發明的實施形態之液晶顯示裝置，並不限於上述，例如可以舉出《電子顯示器器件（佐佐木昭夫著，Kogyo Chosakai Publishing Co.,Ltd，1990年發行）》、《顯示器器件（伊吹順章著，Sangyo-Tosho Publishing Co.,Ltd.，平成元年發行）》等中所記載之液晶顯示裝置。又，例如可以舉出《下一代液晶顯示器技術（內田龍男編輯，Kogyo Chosakai Publishing Co.,Ltd，1994年發行）》中所記載之液晶顯示裝置。In addition, the liquid crystal display device according to the embodiment of the present invention is not limited to the above, for example, "Electronic Display Device (Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd, published in 1990)", "Display Device (Ibuki)" The liquid crystal display device described in Shunzhang, Sangyo-Tosho Publishing Co., Ltd., published in the first year of Heisei), etc. Moreover, for example, the liquid crystal display device described in "Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd., published in 1994)" is mentioned.

[紅外線感測器] 本發明的實施形態之紅外線感測器含有上述硬化膜。 使用圖3對上述實施態樣之紅外線感測器進行說明。圖3所示之紅外線感測器300中，符號310為固體攝影元件。 設置於固體攝影元件310上之攝像區域是將紅外線吸收濾光片311和本發明的實施形態之彩色濾光片312組合而構成。 紅外線吸收濾光片311是使可視光區域的光（例如，波長400～700nm的光）透射，且遮蔽紅外區域的光（例如，波長800～1300nm的光，較佳為波長900～1200nm的光，更佳為波長900～1000nm的光）之膜，能夠使用含有紅外線吸收劑（作為紅外線吸收劑的形態，如已說明那樣。）作為著色劑之硬化膜。 彩色濾光片312是形成有透射及吸收可視光區域中之特定波長的光之像素之彩色濾光片，例如使用形成有紅色（R）、綠色（G）、藍色（B）的像素之彩色濾光片等，其形態如已說明那樣。 在紅外線透射濾光片313與固體攝影元件310之間配置有能夠使透射了紅外線透射濾光片313之波長的光透射之樹脂膜314（例如，透明樹脂膜等）。 紅外線透射濾光片313是具有可視光遮蔽性且使特定波長的紅外線透射之濾光片，能夠使用含有吸收可視光區域的光之著色劑（例如，苝化合物和/或雙苯并呋喃酮化合物等）和紅外線吸收劑（例如，吡咯并吡咯化合物、酞菁化合物、萘酞菁化合物及聚次甲基化合物等）之本發明的實施形態之硬化膜。紅外線透射濾光片313例如遮擋波長400～830nm的光並使波長900～1300nm的光透射為較佳。 在彩色濾光片312及紅外線透射濾光片313的入射光hν側配置有微透鏡315。以覆蓋微透鏡315之方式形成有平坦化膜316。 在圖3所示之實施形態中，配置有樹脂膜314，但亦可以形成紅外線透射濾光片313來代替樹脂膜314。亦即，在固體攝影元件310上可以形成紅外線透射濾光片313。 在圖3所示之實施形態中，彩色濾光片312的膜厚和紅外線透射濾光片313的膜厚相同，但兩者的膜厚亦可以不同。 在圖3所示之實施形態中，彩色濾光片312設置於比紅外線吸收濾光片311更靠入射光hν側，但亦可以將紅外線吸收濾光片311和彩色濾光片312的順序倒過來，將紅外線吸收濾光片311設置於比彩色濾光片312更靠入射光hν側。 在圖3所示之實施形態中，紅外線吸收濾光片311和彩色濾光片312相鄰積層，但兩個濾光片無需一定相鄰，在其之間可以設置有其他層。本發明的實施形態之硬化膜除了能夠用作紅外線吸收濾光片311的表面的端部或側面等的遮光膜以外，還能夠用於紅外線感測器的裝置內壁，藉此能夠防止內部反射或未意圖之光入射到受光部，並提高靈敏度。 依該紅外線感測器，能夠同時取入圖像資訊，因此能夠進行識別了感測動作之對象之動作感測（motion sensing）等。進而，由於能夠獲取距離資訊，因此還能夠進行包括3D資訊之圖像的攝影等。[Infrared Sensor] The infrared sensor of the embodiment of the present invention contains the above-mentioned cured film. The infrared sensor of the above-mentioned embodiment will be described with reference to FIG. 3 . In the infrared sensor 300 shown in FIG. 3, reference numeral 310 is a solid-state imaging element. The imaging region provided on the solid-state imaging element 310 is formed by combining the infrared absorption filter 311 and the color filter 312 according to the embodiment of the present invention. The infrared absorption filter 311 transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1300 nm, preferably light with a wavelength of 900 to 1200 nm). , more preferably a film of light having a wavelength of 900 to 1000 nm), and a cured film containing an infrared absorber (as a form of the infrared absorber, as described above) can be used as a colorant. The color filter 312 is a color filter formed with pixels that transmit and absorb light of a specific wavelength in the visible light region. For example, a pixel formed with red (R), green (G), and blue (B) pixels is used. The color filter and the like are as described above. A resin film 314 (eg, a transparent resin film or the like) that can transmit light having a wavelength transmitted through the infrared transmission filter 313 is disposed between the infrared transmission filter 313 and the solid-state imaging element 310 . The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength, and can use a coloring agent (for example, a perylene compound and/or a bisbenzofuranone compound) that absorbs light in the visible light region. etc.) and an infrared absorber (for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, a polymethine compound, etc.) The cured film of the embodiment of this invention. It is preferable that the infrared transmission filter 313, for example, blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1300 nm. A microlens 315 is arranged on the incident light hν side of the color filter 312 and the infrared transmission filter 313 . A planarization film 316 is formed so as to cover the microlenses 315 . In the embodiment shown in FIG. 3 , the resin film 314 is disposed, but an infrared transmission filter 313 may be formed instead of the resin film 314 . That is, the infrared transmission filter 313 may be formed on the solid-state imaging element 310 . In the embodiment shown in FIG. 3, the film thickness of the color filter 312 and the film thickness of the infrared transmission filter 313 are the same, but the film thicknesses may be different. In the embodiment shown in FIG. 3 , the color filter 312 is disposed on the side of the incident light hν relative to the infrared absorption filter 311, but the order of the infrared absorption filter 311 and the color filter 312 can also be reversed Then, the infrared absorption filter 311 is provided on the incident light hν side rather than the color filter 312 . In the embodiment shown in FIG. 3 , the infrared absorption filter 311 and the color filter 312 are laminated adjacently, but the two filters do not necessarily need to be adjacent, and other layers may be provided between them. The cured film according to the embodiment of the present invention can be used not only as a light-shielding film on the surface of the infrared absorption filter 311 , such as an end portion or a side surface, but also as a device inner wall of an infrared sensor, whereby internal reflection can be prevented. Or unintended light is incident on the light-receiving part, and the sensitivity is improved. According to the infrared sensor, image information can be simultaneously acquired, so that motion sensing and the like can be performed to identify the object whose motion is sensed. Furthermore, since distance information can be acquired, it is also possible to photograph images including 3D information.

接著，對適用了上述紅外線感測器之固體攝像裝置進行說明。 上述固體攝像裝置含有透鏡光學系統、固體攝影元件及紅外發光二極體等。另外，關於固體攝像裝置的各構成，能夠參閱日本特開2011-233983號公報的0032～0036段，該內容被併入本說明書中。 [實施例]Next, a solid-state imaging device to which the above-described infrared sensor is applied will be described. The above-mentioned solid-state imaging device includes a lens optical system, a solid-state imaging element, an infrared light-emitting diode, and the like. In addition, regarding each configuration of the solid-state imaging device, reference can be made to paragraphs 0032 to 0036 of Japanese Patent Application Laid-Open No. 2011-233983, the contents of which are incorporated in this specification. [Example]

以下，基於實施例對本發明進行進一步詳細的說明。以下實施例所示之材料、使用量、比例、處理內容及處理步驟等，只要不脫離本發明的趣旨，則能夠適當進行變更。因此，本發明的範圍不應藉由以下所示之實施例進行限定性解釋。Hereinafter, the present invention will be described in further detail based on examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly construed by the examples shown below.

[含金屬氮化物粒子P-1的製作] 藉由以下方法製作出含金屬氮化物粒子P-1。 製作中使用了日本特開2005-343784號公報的0042段及圖1中所記載之裝置。具體而言，使用將上述公報的圖1中之放電容器1作為不銹鋼製的真空腔室（FUKUSHIN KOGYO Co.,Ltd.製造）之裝置（以下，稱為「奈米粒子製造裝置」。）製作出含金屬氮化物粒子。首先，藉由排氣泵對真空腔室內的空氣進行排氣。接著，向真空腔室供給氦（He）氣（純度99.99%）及氬氣的混合氣體（標準狀態下之混合比50/50體積%）直至成為600托（79.99kPa）的壓力。[Production of Metal-Containing Nitride Particles P-1] Metal-containing nitride particles P-1 were produced by the following method. For the production, the apparatus described in paragraph 0042 of Japanese Patent Laid-Open No. 2005-343784 and FIG. 1 was used. Specifically, it was fabricated using an apparatus (hereinafter, referred to as "nanoparticle manufacturing apparatus") using the discharge vessel 1 in FIG. 1 of the above-mentioned publication as a vacuum chamber made of stainless steel (manufactured by FUKUSHIN KOGYO Co., Ltd.). Metal-containing nitride particles are produced. First, the air in the vacuum chamber is exhausted by the exhaust pump. Next, a mixed gas of helium (He) gas (purity 99.99%) and argon gas (mixing ratio of 50/50 volume % in a standard state) was supplied to the vacuum chamber until the pressure reached 600 Torr (79.99 kPa).

作為奈米粒子製造裝置的放電電極，使用了將鎢成形加工成長度500mm、直徑12mm及中空口徑6mm的中空結構的棒狀者。放電電極的配置設為與日本特開2005-343784號公報的圖1相同。具體而言，將12個放電電極每6個配置成2段。另外，上段與下段之間的距離設為約160mm。 中空結構的放電電極與原材料供給裝置連接，使得能夠從放電電極的中空部分向真空腔室內供給原料氣體。As the discharge electrode of the nanoparticle manufacturing apparatus, a rod-shaped one having a hollow structure of 500 mm in length, 12 mm in diameter, and 6 mm in hollow diameter was used by molding tungsten. The arrangement of the discharge electrodes was the same as that in FIG. 1 of Japanese Patent Laid-Open No. 2005-343784. Specifically, 12 discharge electrodes were arranged in two stages every six. In addition, the distance between the upper stage and the lower stage was set to about 160 mm. The discharge electrode of the hollow structure is connected to the raw material supply device so that the raw material gas can be supplied into the vacuum chamber from the hollow portion of the discharge electrode.

一邊對各放電電極施加存在相位差之交流（電壓20～40V、電流70～100A），一邊以使各放電電極的前端接觸之狀態開始放電。產生電弧放電之後，以使各放電電極的前端分開之方式向外方移動，並固定於相鄰之放電電極的前端之間的距離成為5～10mm之位置，繼續進行電弧放電。While applying alternating current (voltage 20 to 40 V, current 70 to 100 A) having a phase difference to each discharge electrode, discharge was started in a state where the tips of each discharge electrode were brought into contact with each other. After the arc discharge is generated, the distal ends of the discharge electrodes are moved outward so that the distal ends of the discharge electrodes are separated, and they are fixed at a position where the distance between the distal ends of the adjacent discharge electrodes becomes 5 to 10 mm, and the arc discharge is continued.

進行15分鐘電弧放電之後，對原材料供給裝置的供給罐進行加溫，將原料氣體導入到真空腔室內。首先，以0.5氣壓導入了NH3 氣（液化銨ECOAN，Showa Denko K.K.製造）、以0.1氣壓導入了H2 氣（氫氣，SHOWA DENKO GAS PRODUCTS CO.LTD.）、並以0.4氣壓導入了Ar氣（氬氣，TAIYO NIPPON SANSO CORPORATION）。接著，將供給罐加溫至210℃，並從放電電極以600氣壓導入了TiCl4 氣（TLT-1、TOHO TITANIUM CO.,LTD.製造）。在導入TiCl4 氣之同時，使用粉末供給裝置TP-99010FDR（JEOL Ltd.製造），利用氮氣供給了硫微粉末（微粉硫325目（mesh），Tsurumi Chemical Industry Co.,ltd.製造，相當於原子T。）。供給量調整為所得到之含金屬氮化物粒子中之TE /TX 成為如表2-1～2-9中所記載。向真空腔室內導入1小時混合有TiCl4 氣和硫微粉末之氮氣之後，停止從交流電源施加電壓，從而停止供給上述氣體。接著，回收了附著於真空腔室的內壁之粒子。After the arc discharge was performed for 15 minutes, the supply tank of the raw material supply device was heated, and the raw material gas was introduced into the vacuum chamber. First, NH 3 gas (liquefied ammonium ECOAN, manufactured by Showa Denko KK) was introduced at 0.5 atmosphere , H 2 gas (hydrogen gas, SHOWA DENKO GAS PRODUCTS CO.LTD.) was introduced at 0.1 atmosphere, and Ar gas was introduced at 0.4 atmosphere (Argon, TAIYO NIPPON SANSO CORPORATION). Next, the supply tank was heated to 210° C., and TiCl 4 gas (TLT-1, manufactured by TOHO TITANIUM CO., LTD.) was introduced from the discharge electrode at 600 atmosphere. Simultaneously with the introduction of TiCl 4 gas, a powder supply device TP-99010FDR (manufactured by JEOL Ltd.) was used to supply fine sulfur powder (fine powder sulfur 325 mesh, manufactured by Tsurumi Chemical Industry Co., Ltd., equivalent to atomic T.). The supply amount was adjusted to give the metal-containing particles of the nitride T E / T X becomes as given in Table 2-1 to 2-9 described. After introducing nitrogen gas mixed with TiCl 4 gas and fine sulfur powder into the vacuum chamber for 1 hour, the application of voltage from the AC power supply was stopped, and the supply of the above-mentioned gas was stopped. Next, the particles adhering to the inner wall of the vacuum chamber were recovered.

接著，將所得到之粒子放入導入有O2 含量及水分含量分別控制為100ppm以下之氮（N2 ）氣之密閉容器內，靜置了24小時。Next, the obtained particles were placed in an airtight container into which nitrogen (N 2 ) gas having an O 2 content and a moisture content controlled to be 100 ppm or less, respectively, was introduced, and allowed to stand for 24 hours.

＜加熱製程＞ 使用減壓烘箱VAC-101P（ESPEC Corp.製造）於200℃下對上述中所得到之粒子進行加熱而得到了含金屬氮化物粒子P-1。另外，加熱中的減壓烘箱的內壓設為1.0×103 Pa。<Heating process> The particle obtained above was heated at 200 degreeC using a reduced pressure oven VAC-101P (made by ESPEC Corp.), and the metal-containing nitride particle P-1 was obtained. In addition, the internal pressure of the reduced-pressure oven during heating was set to 1.0×10 3 Pa.

（含金屬氮化物粒子P-1中的Ti、S（原子T）、O及N的含量的測定） 藉由X射線螢光分析裝置測定了所得到之含金屬氮化物粒子P-1中的鈦原子（Ti）、硫原子（S）、氧原子（O）及氮原子（N）的含量。作為試料，準備了使用壓機將含金屬氮化物粒子P-1成形為顆粒狀者。對於上述試料，使用X射線螢光分析裝置在以下的條件下進行了測定。 ・裝置 Rigaku製造之ZSM PrimusII型XRF ・X射線 Rh 30-50 kV、48-80 mA ・測定區域 10μmφ ・測定時間 10-240deg/min(Measurement of Contents of Ti, S (atomic T), O, and N in Metal-Containing Nitride Particles P-1) The obtained metal-containing nitride particles P-1 were measured by an X-ray fluorescence analyzer. Contents of titanium atoms (Ti), sulfur atoms (S), oxygen atoms (O) and nitrogen atoms (N). As a sample, one prepared by molding the metal-containing nitride particles P-1 into pellets using a press was prepared. The above-mentioned samples were measured under the following conditions using an X-ray fluorescence analyzer.・Apparatus ZSM Primus II XRF manufactured by Rigaku ・X-ray Rh 30-50 kV, 48-80 mA ・Measurement area 10μmφ ・Measurement time 10-240deg/min

[含金屬氮化物粒子P-2～P-63的製作] 作為過渡金屬，使用以下所記載之各金屬來代替Ti，且作為原子T，使用表1中所記載之各原子來代替硫，除此以外，進行與含金屬氮化物粒子P-1相同之操作而製作出含金屬氮化物粒子P-2～P～63。 另外，在將各原材料導入到上述真空腔室時，若各原材料為粉末則使用上述粉末供給裝置，若為液體或昇華性固體則藉由帶狀加熱器（ribbon heater）對供給容器進行加熱，並供給了使原材料揮發後之氣體。 另外，使用X射線螢光分析裝置測定了各含金屬氮化物粒子中所含有之過渡金屬的含量。另外，測定條件如上所述。[Production of Metal-Containing Nitride Particles P-2 to P-63] As the transition metal, each of the metals described below was used in place of Ti, and as the atom T, each of the atoms described in Table 1 was used in place of sulfur, except Otherwise, the same operations as those of the metal-containing nitride particles P-1 were performed to produce metal-containing nitride particles P-2 to P-63. In addition, when each raw material is introduced into the above-mentioned vacuum chamber, if each raw material is a powder, the above-mentioned powder supply device is used, and if each raw material is a liquid or a sublimable solid, the supply container is heated by a ribbon heater, And supply the gas after volatilizing the raw material. In addition, the content of the transition metal contained in each metal-containing nitride particle was measured using an X-ray fluorescence analyzer. In addition, the measurement conditions are as described above.

・Nb粉：Mitsuwa Chemicals Co.,Ltd.製造之鈮（粉末）＜100-325目＞ ・V粉 ：TAIYO KOKO Co.,LTD.製造之金屬釩粉末VHO ・Zr粉：Wako Pure Chemical Industries, Ltd.製造之鋯粉末 ・鉭結節狀粉：Global Advanced Metal製造之鉭結節狀粉 ・Hf粉：Furuuchi Chemical Corporation製造之鉿粉末 ・Y粉：NIPPON YTTRIUM CO.,LTD.製造之釔粉末 ・Cr粉：KOHSEI Co.,Ltd.製造之脫氣電解金屬鉻粉 ・Re粉：Rhenium Alloys, Inc.製造之錸粉末 ・W粉：Eurotungsten製造之鎢粉末AW3110 ・Ag粉：Ag粉MITSUI MINING & SMELTING CO.,LTD.製造之SPQ03R・Nb powder: Niobium (powder) <100-325 mesh> manufactured by Mitsuwa Chemicals Co., Ltd. ・V powder: Metal vanadium powder VHO manufactured by TAIYO KOKO Co., LTD. ・Zr powder: Wako Pure Chemical Industries, Ltd .Manufactured zirconium powder・Tantalum nodular powder: Tantalum nodular powder manufactured by Global Advanced Metal・Hf powder: Hafnium powder manufactured by Furuuchi Chemical Corporation・Y powder: Yttrium powder・Cr powder manufactured by NIPPON YTTRIUM CO.,LTD.: Degassed electrolytic metal chromium powder manufactured by KOHSEI Co.,Ltd. ・Re powder: Rhenium powder manufactured by Rhenium Alloys, Inc. ・W powder: Tungsten powder AW3110 manufactured by Eurotungsten ・Ag powder: Ag powder MITSUI MINING & SMELTING CO., SPQ03R manufactured by LTD.

[表1]

Figure 106131597-A0304-0001
[Table 1]
Figure 106131597-A0304-0001

[含金屬氮化物粒子P-C1的製作] 在含金屬氮化物粒子P-1的製作中，未使用硫微粉末，除此以外，進行相同之操作而製作出含金屬氮化物粒子P-C1。[Production of Metal-Containing Nitride Particles P-C1] Metal-containing nitride particles P-C1 were produced in the same manner except that fine sulfur powder was not used in the production of metal-containing nitride particles P-1 .

[含金屬氮化物粒子P-C2的製作] 使用Ag粉（MITSUI MINING & SMELTING CO.,LTD.製造之「SPQ03R」）來代替硫微粉末，除此以外，進行與含金屬氮化物粒子P-1相同之操作而得到了含金屬氮化物粒子P-C2。[Preparation of metal-containing nitride particles P-C2] In addition to using Ag powder (“SPQ03R” manufactured by MITSUI MINING & SMELTING CO., LTD.) instead of the sulfur fine powder, the metal-containing nitride particles P-C2 1 The same operation was carried out to obtain metal-containing nitride particles P-C2.

[含金屬氮化物粒子P-C3的製作] 含金屬氮化物粒子P-C3使用了Nisshin Engineering Inc.製造之TiN奈米粉末。另外，在製作後述之分散組成物時，加入Hefei Kai’er公司製造之TiC奈米粉末作為著色劑。 另外，如以下那樣調整了分散組成物中之TiN奈米粉末與TiC奈米粉末的比率。 ・Nisshin Engineering Inc.製造，TiN奈米粉末：9.43質量份 ・Hefei Kai’er公司製造，TiC奈米粉末：2.35質量份[Preparation of Metal-Containing Nitride Particles P-C3] TiN nanopowders manufactured by Nisshin Engineering Inc. were used for the metal-nitride-containing particles P-C3. In addition, when preparing the dispersion composition described later, TiC nanopowder manufactured by Hefei Kai'er Co., Ltd. was added as a colorant. In addition, the ratio of TiN nanopowder and TiC nanopowder in the dispersion composition was adjusted as follows.・Made by Nisshin Engineering Inc., TiN nanopowder: 9.43 parts by mass ・Made by Hefei Kai’er Co., Ltd., TiC nanopowder: 2.35 parts by mass

[含金屬氮化物粒子P-C4的製作] 藉由以下方法製作出含金屬氮化物粒子P-C4。 稱取平均粒徑15nm的氧化鈦MT-150A（商品名稱：TAYCA CORPORATION製造）100g、BET（Brunauer，Emmett，Teller：布厄特）表面積300m2 /g的二氧化矽粒子AEROPERL（登録商標）300/30（EVONIK公司製造）25g及分散劑Disperbyk190（商品名稱：BYK Chemie GmbH製造）100g，加入離子電交換水71g，並使用行星式撹拌機（KURABO製造之MAZERUSTAR KK-400W）以公轉轉速1360rpm（rotation per minute：每分鐘轉速）、自轉轉速1047rpm攪拌20分鐘而得到了均勻的混合物。 該混合物填充至石英容器中，使用小型回轉窯（Motoyama Co.,Ltd.製造）在氧環境中加熱至920℃之後，用氮置換環境，並在相同溫度下使氨氣以100mL/min流過5小時，藉此進行了氮化還元處理。然後，利用乳缽對從石英容器中回收之粉末進行粉碎，得到了含有Si原子且粉末狀的比表面積73m2 /g的鈦黑〔含有鈦黑粒子及Si原子之被分散體〕。[Production of Metal-Containing Nitride Particles P-C4] Metal-containing nitride particles P-C4 were produced by the following method. 100 g of titanium oxide MT-150A (trade name: manufactured by TAYCA CORPORATION) having an average particle size of 15 nm and silica particles AEROPERL (registered trademark) 300 having a BET (Brunauer, Emmett, Teller: Buett) surface area of 300 m 2 /g were weighed /30 (manufactured by EVONIK) 25 g and dispersant Disperbyk190 (trade name: manufactured by BYK Chemie GmbH) 100 g, 71 g of ion-exchanged water was added, and a planetary stirrer (MAZERUSTAR KK-400W manufactured by KURABO) was used at a revolution speed of 1360 rpm ( rotation per minute: rotation per minute), the rotation speed of 1047rpm was stirred for 20 minutes to obtain a uniform mixture. This mixture was filled in a quartz container, and after heating to 920°C in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), the atmosphere was replaced with nitrogen, and ammonia gas was flowed at 100 mL/min at the same temperature. 5 hours, thereby performing nitridation reduction treatment. Then, the powder recovered from the quartz container was pulverized in a mortar to obtain powdery titanium black containing Si atoms and having a specific surface area of 73 m 2 /g (dispersed body containing titanium black particles and Si atoms).

[含金屬氮化物粒子P-C5的製作] 參閱日本特開2006-209102號公報的0189～0190段中所記載之＜製造例1＞，製作出含金屬氮化物粒子P-C5。具體的製作方法如以下所示。 首先，使以TiO2 換算為300g的含水二氧化鈦懸浮於1升水中而得到了漿液。接著，利用氫氧化鈉水溶液將漿液的pH調整為10，接著，將漿液溫度加溫至70℃。向加溫後的漿液中經2小時滴加了矽酸鈉水溶液。接著，將漿液溫度加溫至90℃。向加溫後的漿液中經2小時滴加稀硫酸，使漿液的pH中和至5。將中和後的漿液保持了30分鐘。接著，將漿液進行脫水，得到了固體成分。接著，清洗固體成分，將清洗後的固體成分在空氣中加溫至850℃，並燒成了5小時。藉由上述，得到了被覆有氧化矽（以SiO2 計為0.3質量%）之二氧化鈦。所得到之二氧化鈦為銳鈦礦型。 接著，將該被覆有氧化矽之二氧化鈦放入內徑7.5cm的石英管中。接著，一邊將氨氣以10L/min的流速通入石英管中，一邊將石英管在980℃的溫度下加熱6小時而得到了生成物。接著，將所得到之生成物在相同環境下冷卻至100℃，進而在大氣中自然冷卻至常溫，得到了組成式由TiN0.95 O0.20 ・0.01SiO2 表示之含金屬氮化物粒子P-C5。[Production of Metal-Containing Nitride Particles P-C5] With reference to <Production Example 1> described in paragraphs 0189 to 0190 of JP-A No. 2006-209102, metal-containing nitride particles P-C5 were produced. A specific production method is as follows. First, 300 g of hydrous titanium dioxide in terms of TiO 2 was suspended in 1 liter of water to obtain a slurry. Next, the pH of the slurry was adjusted to 10 with an aqueous sodium hydroxide solution, and then the temperature of the slurry was heated to 70°C. A sodium silicate aqueous solution was added dropwise to the heated slurry over 2 hours. Next, the temperature of the slurry was heated to 90°C. To the heated slurry, dilute sulfuric acid was added dropwise over 2 hours to neutralize the pH of the slurry to 5. The neutralized slurry was held for 30 minutes. Next, the slurry was dehydrated to obtain a solid content. Next, the solid content was washed, and the washed solid content was heated to 850° C. in the air and fired for 5 hours. In this way, titanium dioxide coated with silicon oxide (0.3 mass % in terms of SiO 2 ) was obtained. The obtained titanium dioxide is of anatase type. Next, the silica-coated titania was put into a quartz tube with an inner diameter of 7.5 cm. Next, the quartz tube was heated at a temperature of 980° C. for 6 hours while passing ammonia gas into the quartz tube at a flow rate of 10 L/min to obtain a product. Next, the obtained product was cooled to 100° C. in the same environment, and then naturally cooled to normal temperature in the atmosphere, to obtain metal-containing nitride particles P-C5 represented by the composition formula of TiN 0.95 O 0.20 ·0.01SiO 2 .

[含金屬氮化物粒子P-C6的製作] 參閱國際公開2007/102490號的0040段中所記載之方法，製作出含金屬氮化物粒子P-C6。具體的製作方法如以下所示。 向含金屬氮化物粒子P-1C中加入去離子水，得到了含金屬氮化物粒子P-1C的含量為100g/L的懸浮液。接著，將1升該懸浮液加熱至70℃。向加熱後的懸浮液中並行添加了50%氯化錫水溶液23.5g、將氯化銻1.3g溶解於35%鹽酸水溶液59g中而得到之溶液及17%的氫氧化鈉水溶液。另外，添加時將懸浮液的pH維持為2～3，添加時間設為60分鐘。接著，對懸浮液進行過濾，並清洗至濾液的比電阻成為50μS/cm而得到了固體成分。接著，將固體成分於120℃下乾燥一晝夜，並使用電爐將乾燥後的固體成分於600℃下燒成1小時而得到由銻固溶氧化錫的導電層被覆之含金屬氮化物粒子P-1C，將其設為含金屬氮化物粒子P-C6。[Production of Metal-Containing Nitride Particles P-C6] With reference to the method described in paragraph 0040 of International Publication No. 2007/102490, metal-containing nitride particles P-C6 were produced. A specific production method is as follows. Deionized water was added to the metal nitride-containing particles P-1C to obtain a suspension with a metal nitride-containing particle P-1C content of 100 g/L. Next, 1 liter of this suspension was heated to 70°C. To the heated suspension, 23.5 g of a 50% tin chloride aqueous solution, a solution obtained by dissolving 1.3 g of antimony chloride in 59 g of a 35% hydrochloric acid aqueous solution, and a 17% sodium hydroxide aqueous solution were added in parallel. In addition, the pH of the suspension was maintained at 2 to 3 during the addition, and the addition time was 60 minutes. Next, the suspension was filtered and washed until the specific resistance of the filtrate became 50 μS/cm to obtain a solid content. Next, the solid content was dried at 120° C. overnight, and the dried solid content was fired at 600° C. for 1 hour using an electric furnace to obtain metal-containing nitride particles P- 1C, let this be metal-containing nitride particle P-C6.

另外，關於含金屬氮化物粒子P-1～P-63及P-C1～P-C6的組成，總結示於表2-1～2-9。In addition, the compositions of the metal-containing nitride particles P-1 to P-63 and P-C1 to P-C6 are summarized in Tables 2-1 to 2-9.

[含金屬氮化物粒子的TE /TX 的測定] 藉由以下方法測定了含金屬氮化物粒子的TE /TX 。 使用壓機將各含金屬氮化物粒子成形為顆粒狀並作為試料。對於上述試料，使用X射線光電子光譜分析裝置及X射線螢光分析裝置在以下測定條件下測定了含金屬氮化物粒子的TE /TX 。利用以下的基準評價結果，並示於表2-1～2-9。 A：TE /TX 小於1.1。 B：TE /TX 為1.1以上且小於2.0。 C：TE /TX 為2.0以上或者無法計算TE /TX 的值。[Measurement of metal-containing nitride particles T E / T X] The following method was measured by the metal-nitride particles T E / T X. Each metal-containing nitride particle was molded into a pellet using a press, and used as a sample. For the above sample, the measured metal-containing nitride particles T E / T X under the following measurement conditions using an X-ray photoelectron spectroscopy apparatus and an X-ray fluorescence analyzer. The evaluation results were based on the following criteria, and are shown in Tables 2-1 to 2-9. A: T E /T X is less than 1.1. B: T E /T X is 1.1 or more and less than 2.0. C: T E /T X is 2.0 or more or the value of T E /T X cannot be calculated.

X射線光電子光譜分析（TE 的測定） ・裝置：PHI公司製造之Quantera-SXM（商品名稱）裝置 ・X射線源：單色化Al Kα射線（1486.6ev、25W、15kV、光束直徑200μmφ） ・測定區域：200μmφ ・測定條件：通過能量=140eV、步長=0.1eV、累積次數4～8次 ・測定方法：將試料固定於裝置中，將光電子取出角設為10度而進行了測定。X-ray photoelectron spectroscopy (measurement of T E) Apparatus: Quantera-SXM manufactured by PHI sum (trade name) means X-ray source: monochromatic Al Kα ray (1486.6ev, 25W, 15kV, a beam diameter 200μmφ) · Measurement area: 200 μmφ ・Measurement conditions: Energy = 140 eV, step = 0.1 eV, 4 to 8 times of accumulation ・Measurement method: The sample was fixed in the device, and the photoelectron extraction angle was set to 10 degrees and measured.

X射線螢光分析（TX 的測定） ・裝置 Rigaku製ZSM PrimusII型XRF ・X射線 Rh 30-50 kV，48-80 mA ・測定區域 10μmφ ・測定時間 10-240 deg/minX-ray fluorescence analysis ( measurement of T X ) ・Apparatus ZSM Primus II XRF manufactured by Rigaku ・X-ray Rh 30-50 kV, 48-80 mA ・Measurement area 10μmφ ・Measurement time 10-240 deg/min

[實施例1～85及比較例1～6的硬化性組成物的製備] 在製備實施例1～85的各硬化性組成物時，藉由以下方法將表2-1～2-9中所記載之各成分以以下的比率進行混合，並使含金屬氮化物粒子分散於表中所記載之各分散劑中而製備出分散組成物。另外，使用攪拌機（IKA公司製造之EUROSTAR）混合15分鐘而得到了混合物。[Preparation of Curable Compositions of Examples 1 to 85 and Comparative Examples 1 to 6] When preparing the curable compositions of Examples 1 to 85, the following methods were used to combine the curable compositions shown in Tables 2-1 to 2-9. The components described were mixed in the following ratios, and the metal-containing nitride particles were dispersed in the dispersants described in the table to prepare a dispersion composition. Moreover, the mixture was obtained by mixing for 15 minutes using a mixer (EUROSTAR manufactured by IKA Corporation).

〔分散劑A的合成〕 首先，藉由以下方法合成了分散劑A。[Synthesis of Dispersant A] First, the dispersant A was synthesized by the following method.

＜合成例A1：大分子單體A-1的合成＞ 向容量3000mL的三口燒瓶中導入ε-己內酯（1044.2g）、δ-戊內酯（184.3g）及2-乙基-1-己醇（71.6g）而得到了混合物。接著，一邊吹入氮，一邊攪拌了上述混合物。接著，向混合物中加入Disperbyk111（12.5g，BYK Chemie GmbH製造，磷酸樹脂），並將所得到之混合物加熱至90℃。6小時後，使用1 H-NMR（nuclear magnetic resonance：核磁共振）確認源自混合物中之2-乙基-1-己醇之訊號消失之後，將混合物加熱至110℃。在氮下於110℃下繼續進行12小時聚合反應之後，利用1 H-NMR確認源自ε-己內酯及δ-戊內酯之訊號的消失，並藉由GPC法（Gel permeation chromatography：凝膠滲透層析，基於後述之測定條件。）對所得到之化合物進行了分子量測定。確認到化合物的分子量已達到所希望之值之後，向含有上述化合物之混合物中添加2,6-二-第三丁基-4-甲基苯酚（0.35g）之後，進一步對所得到之混合物經30分鐘滴加了2-甲基丙烯醯氧基乙基異氰酸酯（87.0g）。滴加結束6小時後，藉由1 H-NMR確認源自2-甲基丙烯醯氧基乙基異氰酸酯（MOI）之訊號消失之後，將丙二醇單甲醚乙酸酯（PGMEA）（1387.0g）添加到混合物中，得到了濃度為50質量%的大分子單體A-1溶液（2770g）。所得到之大分子單體A-1的重量平均分子量為6,000。<Synthesis example A1: Synthesis of macromonomer A-1> ε-caprolactone (1044.2 g), δ-valerolactone (184.3 g) and 2-ethyl-1- were introduced into a three-necked flask with a capacity of 3000 mL. Hexanol (71.6 g) gave a mixture. Next, the above-mentioned mixture was stirred while blowing in nitrogen. Next, Disperbyk111 (12.5 g, manufactured by BYK Chemie GmbH, phosphoric acid resin) was added to the mixture, and the resulting mixture was heated to 90°C. After 6 hours, after confirming the disappearance of the signal derived from 2-ethyl-1-hexanol in the mixture using 1 H-NMR (nuclear magnetic resonance), the mixture was heated to 110°C. After the polymerization reaction was continued at 110°C for 12 hours under nitrogen, the disappearance of the signals derived from ε-caprolactone and δ-valerolactone was confirmed by 1 H-NMR, and the signals derived from ε-caprolactone and δ-valerolactone were confirmed by GPC (Gel permeation chromatography: condensation). Gel permeation chromatography, based on the measurement conditions described later.) The molecular weight of the obtained compound was measured. After confirming that the molecular weight of the compound had reached the desired value, 2,6-di-tert-butyl-4-methylphenol (0.35 g) was added to the mixture containing the above-mentioned compound, and the resulting mixture was further subjected to 2-Methacryloyloxyethyl isocyanate (87.0 g) was added dropwise over 30 minutes. Six hours after the completion of the dropwise addition, it was confirmed by 1 H-NMR that the signal derived from 2-methacryloyloxyethyl isocyanate (MOI) disappeared, and then propylene glycol monomethyl ether acetate (PGMEA) (1387.0 g) was added. It was added to the mixture to obtain a macromonomer A-1 solution (2770 g) having a concentration of 50% by mass. The weight average molecular weight of the obtained macromonomer A-1 was 6,000.

＜合成例P-1：分散劑A的合成＞ 向容量1000mL的三口燒瓶中導入大分子單體A-1（200.0g）、甲基丙烯酸（以下亦稱為「MAA」，60.0g，相當於用於得到結構單元B之聚合性單體。）、甲基丙烯酸苄酯（以下亦稱為「BzMA」，40.0g，相當於用於得到結構單元C之化合物。）、PGMEA（丙二醇1-單甲醚2-乙酸酯，366.7g）而得到了混合物。一邊吹入氮，一邊攪拌了上述混合物。接著，一邊使氮流向燒瓶內，一邊將混合物升溫至75℃。接著，向混合物中添加十二烷基硫醇（5.85g）、接著添加2,2’-偶氮雙（2-甲基丙酸甲酯）（1.48g，以下亦稱為「V-601」。），引發了聚合反應。將混合物於75℃下加熱2小時之後，進一步將V-601（1.48g）追加到混合物中。2小時後，進一步將V-601（1.48g）追加到混合物中。進一步反應2小時後，將混合物升溫至90℃，並攪拌了3小時。藉由上述操作，結束聚合反應，得到了分散劑A。<Synthesis Example P-1: Synthesis of Dispersant A> Macromonomer A-1 (200.0 g), methacrylic acid (hereinafter also referred to as "MAA", 60.0 g, equivalent to Polymerizable monomer for obtaining structural unit B.), benzyl methacrylate (hereinafter also referred to as "BzMA", 40.0 g, corresponding to the compound for obtaining structural unit C.), PGMEA (propylene glycol 1-mono methyl ether 2-acetate, 366.7 g) to give a mixture. The above mixture was stirred while blowing in nitrogen. Next, the temperature of the mixture was raised to 75°C while flowing nitrogen into the flask. Next, dodecyl mercaptan (5.85 g) was added to the mixture, followed by addition of 2,2'-azobis(methyl 2-methylpropionate) (1.48 g, hereinafter also referred to as "V-601" .), which initiated the polymerization reaction. After the mixture was heated at 75°C for 2 hours, V-601 (1.48 g) was further added to the mixture. After 2 hours, V-601 (1.48 g) was further added to the mixture. After further reacting for 2 hours, the mixture was warmed to 90°C and stirred for 3 hours. By the above operation, the polymerization reaction was completed, and the dispersant A was obtained.

〔分散組成物的組成〕 ・（表2-1～2-9中所記載之）各含金屬氮化物粒子：11.79質量份 ・分散劑A的丙二醇單甲醚乙酸酯30質量%溶液：11.79質量份 ・丙二醇單甲醚乙酸酯：23.58質量份 混合上述成分，接著，使用Shinmaru Enterprises Corporation製造之NPM-Pilot使所得到之混合物在下述條件下分散而得到了分散組成物。[Composition of Dispersion Composition] ・(described in Tables 2-1 to 2-9) Metal-containing nitride particles: 11.79 parts by mass ・ 30 mass % solution of propylene glycol monomethyl ether acetate of dispersant A: 11.79 Parts by mass ・Propylene glycol monomethyl ether acetate: 23.58 parts by mass, the above components were mixed, and then the resulting mixture was dispersed under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Corporation to obtain a dispersion composition.

（分散條件） ・珠徑：φ0.05mm（Nikkato Corporation製造之氧化鋯珠，YTZ） ・珠填充率：65體積% ・研磨圓周速度：10m/sec ・分離器（seperator）圓周速度：13m/s ・分散處理之混合液量：15kg ・循環流量（泵供給量）：90kg/hour ・處理液溫度：19～21℃ ・冷卻水：水 ・處理時間：22小時(Dispersion conditions) ・Bead diameter: φ0.05mm (Zirconium oxide beads manufactured by Nikkato Corporation, YTZ) ・Bead filling rate: 65% by volume ・Peripheral grinding speed: 10m/sec ・Separator peripheral speed: 13m/s・Amount of mixed liquid for dispersion treatment: 15kg ・Circulation flow rate (pump supply rate): 90kg/hour ・Temperature of treatment liquid: 19～21℃ ・Cooling water: water ・Treatment time: 22 hours

〔硬化性組成物的組成〕 接著，混合上述分散組成物、鹼可溶性樹脂、聚合起始劑、聚合性化合物、界面活性劑、聚合抑制劑及有機溶劑而得到了各實施例之硬化性組成物。 以下示出各硬化性組成物中所含有之成分的含量（質量%）。[Composition of Curable Composition] Next, the above-mentioned dispersion composition, alkali-soluble resin, polymerization initiator, polymerizable compound, surfactant, polymerization inhibitor, and organic solvent were mixed to obtain curable compositions of each example. . The content (mass %) of the components contained in each curable composition is shown below.

・上述中製備出之分散組成物：73.00質量份・Dispersion composition prepared above: 73.00 parts by mass

・鹼可溶性樹脂A-1（「Acrycure RD-F8」，Nippon Shokubai Co.,Ltd.製造，固體成分40%，溶劑：丙二醇單甲醚）：8.32質量份・Alkali-soluble resin A-1 ("Acrycure RD-F8", manufactured by Nippon Shokubai Co., Ltd., solid content 40%, solvent: propylene glycol monomethyl ether): 8.32 parts by mass

・聚合起始劑：下述之式（I-1）所表示之化合物：1.96質量份・Polymerization initiator: a compound represented by the following formula (I-1): 1.96 parts by mass

・聚合性化合物M1（「KAYARAD DPHA」，Nippon Kayaku Co.,Ltd.製造，6官能聚合性化合物（乙烯性不飽和基的量：10.4mmol/g）及5官能聚合性化合物（乙烯性不飽和基的量：9.5mmol/g）的混合物）：6.82質量份・Polymerizable compound M1 (“KAYARAD DPHA”, manufactured by Nippon Kayaku Co., Ltd., hexafunctional polymerizable compound (amount of ethylenically unsaturated group: 10.4 mmol/g) and pentafunctional polymerizable compound (ethylenically unsaturated group) Amount of base: 9.5 mmol/g) mixture): 6.82 parts by mass

・界面活性劑1：由下述式表示之界面活性劑（重量平均分子量（Mw）=15311） 其中，下述式中，式中（A）及（B）所表示之結構單元分別為62莫耳%、38莫耳%。式（B）所表示之結構單元中，a、b、c分別滿足a+c=14、b=17的關係。・Surfactant 1: Surfactant represented by the following formula (weight average molecular weight (Mw)=15311) In the following formula, the structural units represented by (A) and (B) are 62 moles, respectively Ear%, 38 mole%. In the structural unit represented by the formula (B), a, b, and c satisfy the relationships of a+c=14 and b=17, respectively.

[化學式20]

Figure 02_image039
[Chemical formula 20]
Figure 02_image039

・聚合抑制劑（對甲氧基苯酚）（PI-1）：0.00025質量份・Polymerization inhibitor (p-methoxyphenol) (PI-1): 0.00025 parts by mass

・溶劑（丙二醇單甲醚乙酸酯）：7.82質量份・Solvent (propylene glycol monomethyl ether acetate): 7.82 parts by mass

另外，藉由以下方法合成了實施例64中所使用之分散劑B。In addition, the dispersant B used in Example 64 was synthesized by the following method.

〔分散劑B的合成〕 在空氣下，對分散劑A加入四丁基溴化銨（TBAB，7.5g）和對甲氧基苯酚（MEHQ，0.13g）之後，滴加了甲基丙烯酸縮水甘油酯（以下，亦稱為「GMA」，66.1g）。滴加結束後，在空氣下繼續進行7小時反應之後，藉由酸值測定確認了反應結束。藉由向所得到之混合物中追加PGMEA（643.6g）而得到了分散劑B的20質量%溶液。所得到之分散劑B的重量平均分子量為35000，酸值為50mgKOH/mg。[Synthesis of Dispersant B] Tetrabutylammonium bromide (TBAB, 7.5 g) and p-methoxyphenol (MEHQ, 0.13 g) were added to Dispersant A under air, and then glycidyl methacrylate was added dropwise. Ester (hereinafter, also referred to as "GMA", 66.1 g). After completion of the dropwise addition, the reaction was continued under air for 7 hours, and the completion of the reaction was confirmed by the measurement of the acid value. A 20 mass % solution of dispersant B was obtained by adding PGMEA (643.6 g) to the obtained mixture. The weight average molecular weight of the obtained dispersant B was 35000, and the acid value was 50 mgKOH/mg.

上述以外的表2-1～2-9中的各成分表示以下的化合物。 ・分散劑C～I [化學式21]

Figure 02_image041
[化學式22]
Figure 02_image043
Figure 02_image045
Each component in Tables 2-1 to 2-9 other than the above represents the following compounds.・Dispersants C to I [Chemical formula 21]
Figure 02_image041
[Chemical formula 22]
Figure 02_image043
Figure 02_image045

・分散劑J： 與4,4’-二胺基甲苯醯苯胺161.3g、N-甲基-2-吡咯啶酮527g一同裝入而得到了混合液。向上述混合液中添加3,3’，4,4’-聯苯四羧酸二酐439.1g，並於70℃下反應3小時之後，添加鄰苯二甲酸酐2.2g，進一步於70℃下反應2小時而得到了20質量%的分散劑J溶液（分散劑J相當於聚醯胺酸）。・Dispersant J: 161.3 g of 4,4'-diaminotoluaniline and 527 g of N-methyl-2-pyrrolidone were charged together to obtain a mixed solution. After adding 439.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride to the above-mentioned liquid mixture, and reacting at 70°C for 3 hours, 2.2 g of phthalic anhydride was added, and the mixture was further heated at 70°C. A 20 mass % solution of dispersing agent J was obtained by reacting for 2 hours (dispersing agent J corresponds to polyamic acid).

・分散劑K： 將3’-二胺基二苯基碸176.7g及雙（3-胺基丙基）四甲基二矽氧烷18.6g與γ-丁內酯2667g、N-甲基-2-吡咯啶酮527g一同裝入而得到了混合液。向上述混合液中添加3,3’,4,4’-聯苯四羧酸二酐439.1g，並於70℃下反應3小時之後，添加鄰苯二甲酸酐2.2g，進一步於70℃下反應2小時而得到了20質量%的分散劑K溶液（分散劑K相當於聚醯胺酸。）。・Dispersant K: 176.7 g of 3'-diaminodiphenyl sulfone, 18.6 g of bis(3-aminopropyl)tetramethyldisiloxane, 2667 g of γ-butyrolactone, N-methyl- 527 g of 2-pyrrolidone was charged together to obtain a mixed solution. After adding 439.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride to the above-mentioned liquid mixture, and reacting at 70°C for 3 hours, 2.2 g of phthalic anhydride was added, and the mixture was further heated at 70°C. A 20 mass % solution of dispersant K was obtained by reacting for 2 hours (dispersant K corresponds to polyamic acid.).

・鹼可溶性樹脂A-2 將4,4’-二胺基二苯基醚95.1g及雙（3-胺基丙基）四甲基二矽氧烷6.2g與γ-丁內酯525g、N-甲基-2-吡咯啶酮220g一同裝入而得到了混合液。向上述混合液中添加3,3’,4,4’-聯苯四羧酸二酐144.1g，並於70℃下反應3小時之後，添加鄰苯二甲酸酐3.0g，進一步於70℃下反應2小時而得到了25質量%的樹脂A-2溶液（樹脂A-2相當於聚醯胺酸。）。・Alkali-soluble resin A-2 95.1 g of 4,4'-diaminodiphenyl ether, 6.2 g of bis(3-aminopropyl)tetramethyldisiloxane, 525 g of γ-butyrolactone, N -220 g of methyl-2-pyrrolidone was charged together to obtain a mixed solution. After adding 144.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride to the above-mentioned mixed solution, and reacting at 70°C for 3 hours, 3.0 g of phthalic anhydride was added, and the mixture was further heated at 70°C. A 25 mass % solution of resin A-2 was obtained by reacting for 2 hours (resin A-2 corresponds to polyamic acid.).

・聚合性化合物M2：Shin-Nakamura Chemical Co.,Ltd.製造，商品名稱「U-15HA」 ・聚合性化合物M3：Nippon Kayaku Co.,Ltd.製造，商品名稱「KAYARAD RP-1040」 [化學式23]

Figure 02_image047
・Polymerizable compound M2: manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “U-15HA” ・Polymerizable compound M3: manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD RP-1040” [Chemical formula 23 ]
Figure 02_image047

・聚合性化合物M4： 下述式所表示之化合物（參閱日本特開2009-169049號公報進行了合成。） [化學式24]

Figure 02_image049
・Polymerizable compound M4: A compound represented by the following formula (Synthesized with reference to JP 2009-169049 A.) [Chemical formula 24]
Figure 02_image049

・聚合起始劑I-1：下述式（I-1）的聚合起始劑 ・聚合起始劑I-2：Irgacure OXE01（商品名稱，BASF Japan Ltd.製造，上述式（C-7）的聚合起始劑） ・聚合起始劑I-3：Irgacure OXE02（商品名稱，BASF Japan Ltd.製造，上述式（C-11）的聚合起始劑） ・聚合起始劑I-4：下述式（I-4）的聚合起始劑 ・聚合起始劑I-5：下述式（I-5）的聚合起始劑 ・聚合起始劑I-6：下述式（I-6）的聚合起始劑 ・聚合起始劑I-7：ADEKA ARKLS NCI-831（商品名稱，ADEKA CORPORATION製造） ・聚合起始劑I-8：N-1919（商品名稱，ADEKA CORPORATION製造）・Polymerization initiator I-1: Polymerization initiator of the following formula (I-1) ・Polymerization initiator I-2: Irgacure OXE01 (trade name, manufactured by BASF Japan Ltd., the above formula (C-7) polymerization initiator) ・Polymerization initiator I-3: Irgacure OXE02 (trade name, manufactured by BASF Japan Ltd., polymerization initiator of the above formula (C-11)) ・Polymerization initiator I-4: the following Polymerization initiator of the above formula (I-4)・Polymerization initiator I-5: Polymerization initiator of the following formula (I-5)・Polymerization initiator I-6: The following formula (I-6) ) ・Polymerization initiator I-7: ADEKA ARKLS NCI-831 (trade name, manufactured by ADEKA CORPORATION) ・Polymerization initiator I-8: N-1919 (trade name, manufactured by ADEKA CORPORATION)

[化學式25]

Figure 02_image051
[Chemical formula 25]
Figure 02_image051

[評價] 〔含金屬氮化物粒子的複介電常數的實數部〕 藉由以下方法測定了各硬化性組成物中所含有之含金屬氮化物粒子的複介電常數的實數部。 藉由旋塗，將硬化性組成物以膜厚成為0.3μm之轉速塗佈於8英吋的矽晶片上而得到了硬化性組成物層。將帶硬化性組成物層之矽晶片以使矽晶片面朝下之方式載置於加熱板，並於100℃下加熱2分鐘而使硬化性組成物層乾燥。接著，使用i射線步進機曝光裝置FPA-3000i5+（Canon Inc.製造），在365nm的波長下透過2cm×2cm的區域被曝光之光罩（reticle）（photomask）以500mJ/cm2 的曝光量將硬化性組成物層進行曝光。接著，將形成有曝光後的硬化性組成物層之矽晶片載置於旋轉噴淋顯影機（DW-30型，Chemitronics Co.,Ltd.製造）的水平旋轉台上，並使用CD-2000（FUJIFILM Electronic Materials Co.,Ltd.製造，有機鹼顯影液），於23℃下進行了60秒鐘浸置顯影。接著，將浸置顯影後的矽晶片以真空卡盤方式固定於上述水平旋轉台，藉由旋轉裝置一邊使矽晶片以轉速50rpm旋轉，一邊從其旋轉中心的上方由噴出噴嘴以噴淋狀供給純水而進行了沖洗處理，得到了具備2cm×2cm的圖案狀的硬化膜之矽晶片。使用潔淨烘箱（clean oven）（High-Temperature Clean Oven：高溫潔淨烘箱 CLH-300S，Koyo Thermo Systems Co.,Ltd.製造）將所得到之矽晶片於220℃下熱處理了1小時。另外，為了得到厚度0.3μm的膜，將所使用之硬化性組成物適當利用PGMEA（propyleneglycol monomethyl ether acetate：丙二醇單甲醚乙酸酯）進行了稀釋。 藉由分光橢圓偏光計（M-2000XI-210：J.A.Woollam公司製造之分光橢圓偏光計），對所得到之硬化膜得到了在波長400～1200 nm下之p偏光（平行）與s偏光（垂直）的相位差Δ和振幅比Ψ的光譜。對所得到之（Δ，Ψ）光譜，使用Bruggeman的有效媒質近似（EMA；Effective medium approximation）模型進行擬合（Fitting）分析，求出了膜中所含有之真的含金屬氮化物粒子的介電常數。（EMA模型中所使用之含金屬氮化物粒子的含量使用了配方值，但亦可以藉由下述方法分離出硬化膜中的含金屬氮化物粒子，並實測硬化膜中的含金屬氮化物粒子的含量。）。根據所得到之複介電常數，利用以下的基準評價了複介電常數的實數部。結果示於表2-1～2-9。 從硬化性組成物中分離出含金屬氮化物粒子之方法： 首先，向硬化性組成物中添加含有氯仿之有機溶劑，使含金屬氮化物粒子以外的成分溶解而得到溶解液。對上述溶解液進行離心分離而得到沉澱物。接著，對上述沉澱物進行加熱而使其濃縮，得到含金屬氮化物粒子。 A：複介電常數的實數部的最小值小於0。 B：複介電常數的實數部的最小值為0以上。[Evaluation] [Real Part of Complex Permittivity of Metal-Containing Nitride Particles] The real part of the complex permittivity of the metal-containing nitride particles contained in each curable composition was measured by the following method. By spin coating, the curable composition was applied on an 8-inch silicon wafer at a rotational speed of 0.3 μm in film thickness to obtain a curable composition layer. The silicon wafer with the curable composition layer was placed on a hot plate with the silicon wafer facing down, and the curable composition layer was dried by heating at 100° C. for 2 minutes. Next, using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), at a wavelength of 365 nm, a reticle (photomask) exposed through an area of 2 cm × 2 cm was exposed at an exposure amount of 500 mJ/cm 2 The curable composition layer is exposed to light. Next, the silicon wafer on which the exposed curable composition layer was formed was placed on a horizontal rotary table of a rotary shower developer (Model DW-30, manufactured by Chemitronics Co., Ltd.), and a CD-2000 ( FUJIFILM Electronic Materials Co., Ltd. product, organic alkali developer), and immersion development was performed at 23° C. for 60 seconds. Next, the silicon wafer after immersion development was fixed on the above-mentioned horizontal rotary table by a vacuum chuck, and the silicon wafer was rotated at a rotational speed of 50 rpm by a rotating device, and was supplied in a spray form from a spray nozzle from above the rotation center. It rinsed with pure water, and obtained the silicon wafer provided with the patterned cured film of 2 cm x 2 cm. The obtained silicon wafer was heat-treated at 220° C. for 1 hour using a clean oven (High-Temperature Clean Oven: CLH-300S, manufactured by Koyo Thermo Systems Co., Ltd.). In addition, in order to obtain a film with a thickness of 0.3 μm, the curable composition used was appropriately diluted with PGMEA (propylene glycol monomethyl ether acetate: propylene glycol monomethyl ether acetate). Using a spectroscopic ellipsometry (M-2000XI-210: spectroscopic ellipsometry manufactured by JAWoollam), p-polarized light (parallel) and s-polarized light (vertical) at wavelengths of 400 to 1200 nm were obtained for the obtained cured film. The phase difference Δ and amplitude ratio Ψ of the spectrum. The obtained (Δ, Ψ) spectrum was subjected to fitting analysis using Bruggeman's Effective medium approximation (EMA; Effective medium approximation) model, and the medium of the actual metal-containing nitride particles contained in the film was obtained. Electric constant. (The content of the metal-containing nitride particles used in the EMA model uses the formula value, but the metal-containing nitride particles in the cured film can also be separated by the following method, and the metal-containing nitride particles in the cured film can be measured. content.). Based on the obtained complex permittivity, the real part of the complex permittivity was evaluated by the following criteria. The results are shown in Tables 2-1 to 2-9. Method for separating metal nitride-containing particles from curable composition: First, an organic solvent containing chloroform is added to the curable composition, and components other than the metal-containing nitride particles are dissolved to obtain a solution. The above-mentioned dissolved solution was centrifuged to obtain a precipitate. Next, the above-mentioned precipitate is heated and concentrated to obtain metal-containing nitride particles. A: The minimum value of the real part of the complex permittivity is less than 0. B: The minimum value of the real part of the complex permittivity is 0 or more.

〔含金屬氮化物粒子的平均一次粒徑〕 藉由以下方法測定了各硬化性組成物中所含有之含金屬氮化物粒子的平均一次粒徑。 試料：利用PGMEA（propyleneglycol monomethyl ether acetate：丙二醇單甲醚乙酸酯）將各硬化性組成物稀釋100倍而得到了稀釋液。接著，將稀釋液滴加到碳箔上，進行乾燥而得到者作為試料。 使用透射型電子顯微鏡（TEM：Transmission Electron Microscope）以2萬倍的倍率觀察上述試料而得到了圖像。接著，藉由圖像處理計算出所得到之圖像中的含金屬氮化物粒子的面積。接著，計算出將所得到之面積換算成圓時的直徑，將對400個粒子評價之圓換算的直徑進行算術平均而求出。利用以下的基準評價結果，並示於表2-1～2-9。另外，各實施例及比較例之含金屬氮化物粒子的平均一次粒徑全部為1nm以上。 A：含金屬氮化物粒子的平均一次粒徑小於80nm。 B：含金屬氮化物粒子的平均一次粒徑為80nm以上且200nm以下。 C：含金屬氮化物粒子的平均一次粒徑超過200nm。[Average Primary Particle Size of Metal-Containing Nitride Particles] The average primary particle size of the metal-containing nitride particles contained in each curable composition was measured by the following method. Sample: Each curable composition was diluted 100 times with PGMEA (propyleneglycol monomethyl ether acetate) to obtain a diluted solution. Next, the diluted solution was dropped on carbon foil and dried to obtain a sample. The image was obtained by observing the above-mentioned sample at a magnification of 20,000 times using a transmission electron microscope (TEM: Transmission Electron Microscope). Next, the area of the metal-containing nitride particles in the obtained image is calculated by image processing. Next, the diameter when the obtained area was converted into a circle was calculated, and the circle-converted diameter of the evaluation of 400 particles was arithmetically averaged to obtain it. The evaluation results were based on the following criteria, and are shown in Tables 2-1 to 2-9. In addition, the average primary particle size of the metal-containing nitride particles in each of the Examples and Comparative Examples was all 1 nm or more. A: The average primary particle diameter of the metal-containing nitride particles is less than 80 nm. B: The average primary particle diameter of the metal-containing nitride particles is 80 nm or more and 200 nm or less. C: The average primary particle diameter of the metal-containing nitride particles exceeds 200 nm.

〔含金屬氮化物粒子的體積平均粒徑D90〕 藉由以下方法測定了各硬化性組成物中所含有之含金屬氮化物粒子的體積平均粒徑D90。 試料：利用丙二醇單甲醚乙酸酯將各硬化性組成物稀釋80倍，將所得到之稀釋液作為試料。 使用以動態光散射法為測定原理之Nikkiso Co.,Ltd.製造之NANOTRAC UPA-EX150，對上述試料進行測定，計算出含金屬氮化物粒子的體積平均粒徑D90。利用以下的基準評價結果，並示於表2-1～2-9。 A：含金屬氮化物粒子的體積平均粒徑D90小於0.2μm。 B：含金屬氮化物粒子的體積平均粒徑D90為0.2μm以上且小於0.5μm。 C：含金屬氮化物粒子的體積平均粒徑D90為0.5μm以上。[Volume Average Particle Size D90 of Metal-Containing Nitride Particles] The volume average particle size D90 of the metal-containing nitride particles contained in each curable composition was measured by the following method. Sample: Each curable composition was diluted 80 times with propylene glycol monomethyl ether acetate, and the obtained diluted solution was used as a sample. The above-mentioned sample was measured using NANOTRAC UPA-EX150 manufactured by Nikkiso Co., Ltd. using the dynamic light scattering method as the measurement principle, and the volume average particle diameter D90 of the metal-containing nitride particles was calculated. The evaluation results were based on the following criteria, and are shown in Tables 2-1 to 2-9. A: The volume average particle diameter D90 of the metal-containing nitride particles is less than 0.2 μm. B: The volume average particle diameter D90 of the metal-containing nitride particles is 0.2 μm or more and less than 0.5 μm. C: The volume average particle diameter D90 of the metal-containing nitride particles is 0.5 μm or more.

〔防沉降性〕 藉由以下方法評價了各硬化性組成物的防沉降性。 首先，利用丙二醇單甲醚乙酸酯將硬化性組成物稀釋2倍而得到了稀釋液。接著，採取稀釋液20mL，將所採取之稀釋液放入50mL的樹脂製容器中，在23℃的環境中靜置了6個月。靜置後，採取從樹脂製容器中的稀釋液的液面起深度1cm為止的上清液5g，並測定了固體成分含量。 比較上述上清液的固體成分含量和剛製備後的各硬化性組成物的固體成分含量，計算出固體成分含量的變化量。利用以下的基準評價結果，並示於表2-1～2-9。該固體成分含量的變化量越小，在硬化性組成物中含金屬氮化物粒子越不易沉降。 另外，利用以下方法計算出固體成分含量。亦即，稱取硬化性組成物1g，在165℃的烘箱中加熱60分鐘而得到了固體成分。測定該固體成分的質量，計算出固體成分含量[質量%]=（固體成分的質量/硬化性組成物的質量（1g））×100。 A：固體成分濃度的變化量小於1%。 B：固體成分濃度的變化量為1%以上且小於2%。 C：固體成分濃度的變化量為2%以上且小於3%。 D：固體成分濃度的變化量為3%以上。[Anti-settling property] The anti-settling property of each curable composition was evaluated by the following method. First, a diluent was obtained by diluting the curable composition twice with propylene glycol monomethyl ether acetate. Next, 20 mL of the diluted solution was collected, and the collected diluted solution was placed in a 50 mL resin container, and left to stand in an environment of 23° C. for 6 months. After standing still, 5 g of the supernatant liquid up to a depth of 1 cm from the liquid surface of the diluent in the resin container was collected, and the solid content was measured. The amount of change in the solid content was calculated by comparing the solid content of the supernatant with the solid content of each curable composition immediately after preparation. The evaluation results were based on the following criteria, and are shown in Tables 2-1 to 2-9. The smaller the amount of change in the solid content, the less likely the metal-containing nitride particles are to settle in the curable composition. In addition, the solid content content was calculated by the following method. That is, 1 g of the curable composition was weighed, and the solid content was obtained by heating in an oven at 165° C. for 60 minutes. The mass of the solid content was measured, and solid content content [mass %]=(mass of solid content/mass of curable composition (1 g))×100 was calculated. A: The amount of change in solid content concentration is less than 1%. B: The amount of change in solid content concentration is 1% or more and less than 2%. C: The amount of change in solid content concentration is 2% or more and less than 3%. D: The amount of change in solid content concentration is 3% or more.

〔經時穩定性〕 藉由以下方法評價了硬化性組成物的經時穩定性。 首先，將各硬化性組成物50g封入玻璃製的100mL容器中。接著，將上述容器保持為45℃，靜置7天之後，保持為-20℃，靜置了10天。靜置後，採取了從容器的底部起深度1cm為止的硬化性組成物。利用旋塗法，將所採取之硬化性組成物塗佈於玻璃基板上而得到了硬化性組成物層。接著，將上述玻璃基板以使玻璃基板面朝下之方式載置於加熱板上，並於100℃下加熱了2分鐘。接著，將加熱後的硬化性組成物層於常溫下放置了3日。接著，使用光學顯微鏡MT-3600LW（FLOVEL製造）觀察了放置後的硬化性組成物層的面狀。藉由放置後的硬化性組成物內的異物的產生狀況來評價了硬化性組成物的經時穩定性。異物越少，可以說硬化性組成物的經時穩定性越良好。實用上，「C」以上為較佳。[Stability over time] The stability over time of the curable composition was evaluated by the following method. First, 50 g of each curable composition was sealed in a 100 mL container made of glass. Next, the above-mentioned container was kept at 45°C and left to stand for 7 days, and then kept at -20°C and left to stand for 10 days. After standing, a curable composition having a depth of 1 cm from the bottom of the container was collected. The collected curable composition was applied on a glass substrate by spin coating to obtain a curable composition layer. Next, the said glass substrate was mounted on the hotplate so that the glass substrate may face down, and it heated at 100 degreeC for 2 minutes. Next, the heated curable composition layer was left at room temperature for 3 days. Next, the surface shape of the curable composition layer after being left to stand was observed using an optical microscope MT-3600LW (manufactured by FLOVEL). The temporal stability of the curable composition was evaluated based on the generation state of foreign matter in the curable composition after being left to stand. It can be said that the less foreign matter is, the better the temporal stability of the curable composition is. Practically, "C" or above is preferable.

（評價基準） AA：在硬化性組成物層內未觀察到異物。 A：在硬化性組成物層內觀察到幾個異物。 B：在硬化性組成物層內構成到幾十個異物。 C：在硬化性組成物層內觀察到幾百個異物，但在硬化性組成物層的面內存在異物的產生較少的部位。 D：在硬化性組成物層內的整個面上觀察到異物。(Evaluation Criteria) AA: No foreign matter was observed in the curable composition layer. A: Several foreign substances were observed in the curable composition layer. B: Several tens of foreign substances were formed in the curable composition layer. C: Hundreds of foreign substances were observed in the curable composition layer, but there were places where the occurrence of foreign substances was small on the surface of the curable composition layer. D: Foreign matter was observed on the entire surface in the curable composition layer.

〔遮光性〕 藉由以下方法評價了硬化膜的遮光性。 首先，利用旋塗法，將各硬化性組成物塗佈於厚度0.7mm、大小10cm見方的玻璃基板（EagleXG，Corning Incorporated製造）上而得到了硬化性組成物層。另外，此時調整了旋塗機的轉速，以使乾燥後的硬化性組成物層的厚度成為1.0μm。 接著，將上述玻璃基板以使玻璃基板面朝下之方式載置於加熱板上，並於100℃下熱處理2分鐘而使硬化性組成物層乾燥。 接著，使用i射線步進機曝光裝置FPA-3000i5+（Canon Inc.製造），在365nm的波長、500mJ/cm2 的曝光量下，將硬化性組成物層進行了曝光。接著，將形成有曝光後的硬化性組成物層之玻璃基板載置於旋轉噴淋顯影機（DW-30型，Chemitronics Co.,Ltd.製造）的水平旋轉台上，使用CD-2000（FUJIFILM Electronic Materials Co.,Ltd.製造，有機鹼顯影液），於23℃下進行了60秒鐘浸置顯影。接著，將浸置顯影後的矽晶片以真空卡盤方式固定於上述水平旋轉台，藉由旋轉裝置一邊使矽晶片以轉速50rpm旋轉，一邊從其旋轉中心的上方由噴出噴嘴以噴淋狀供給純水而進行沖洗處理，得到了硬化膜。 使用透過濃度計（X-rite 361T（visual）densitometer）對所得到之硬化膜測定了OD（optical density：光學密度）。利用以下的基準評價結果，並示於表2-1～2-9。另外，表2-1～2-9中的OD值是在波長400～1200nm下之最小值。亦即，各實施例的硬化膜（膜厚1.0μm）在波長400～1200nm的整個區域具有表中所示之OD值以上的OD值。 A：OD超過3.0。 B：OD超過2.0且3.0以下。 C：OD為2.0以下。[Light-shielding property] The light-shielding property of the cured film was evaluated by the following method. First, each curable composition was coated on a glass substrate (EagleXG, manufactured by Corning Incorporated) with a thickness of 0.7 mm and a size of 10 cm by a spin coating method to obtain a curable composition layer. In addition, at this time, the rotational speed of the spin coater was adjusted so that the thickness of the curable composition layer after drying would be 1.0 μm. Next, the said glass substrate was mounted on a hotplate so that the glass substrate may face down, and it heat-processed for 2 minutes at 100 degreeC, and the curable composition layer was dried. Next, the curable composition layer was exposed at a wavelength of 365 nm and an exposure amount of 500 mJ/cm 2 using an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.). Next, the glass substrate on which the exposed curable composition layer was formed was placed on a horizontal rotary table of a rotary shower developer (Model DW-30, manufactured by Chemitronics Co., Ltd.), and a CD-2000 (FUJIFILM) was used. Electronic Materials Co., Ltd. product, organic alkali developer), and immersion development was performed at 23° C. for 60 seconds. Next, the silicon wafer after immersion development was fixed on the above-mentioned horizontal rotary table by a vacuum chuck, and the silicon wafer was rotated at a rotational speed of 50 rpm by a rotating device, and was supplied in a spray form from a spray nozzle from above the rotation center. The rinsing process was performed with pure water, and a cured film was obtained. The OD (optical density: optical density) of the obtained cured film was measured using a permeation densitometer (X-rite 361T (visual) densitometer). The evaluation results were based on the following criteria, and are shown in Tables 2-1 to 2-9. In addition, the OD values in Tables 2-1 to 2-9 are the minimum values at wavelengths of 400 to 1200 nm. That is, the cured film (film thickness 1.0 micrometer) of each Example has the OD value more than the OD value shown in the table|surface in the whole area|region of wavelength 400-1200 nm. A: OD exceeds 3.0. B: OD exceeds 2.0 and 3.0 or less. C: OD is 2.0 or less.

[表2-1]

Figure 106131597-A0304-0002
另外，表2-1～2-9中，「/」表示併用。 [表2-2]
Figure 106131597-A0304-0003
 [表2-3]
Figure 106131597-A0304-0004
 [表2-4]
Figure 106131597-A0304-0005
 [表2-5]
Figure 106131597-A0304-0006
 [表2-6]
Figure 106131597-A0304-0007
 [表2-7]
Figure 106131597-A0304-0008
 [表2-8]
Figure 106131597-A0304-0009
 [表2-9]
Figure 106131597-A0304-0010
 [table 2-1]
Figure 106131597-A0304-0002
 In addition, in Tables 2-1 to 2-9, "/" indicates that they are used together. [Table 2-2]
Figure 106131597-A0304-0003
 [Table 2-3]
Figure 106131597-A0304-0004
 [Table 2-4]
Figure 106131597-A0304-0005
 [Table 2-5]
Figure 106131597-A0304-0006
 [Table 2-6]
Figure 106131597-A0304-0007
 [Table 2-7]
Figure 106131597-A0304-0008
 [Table 2-8]
Figure 106131597-A0304-0009
 [Table 2-9]
Figure 106131597-A0304-0010

根據表2-1～2-9所示之結果，實施例1～85的硬化性組成物具有本發明的效果。另一方面，比較例1～6的硬化性組成物不具有本發明的效果。 與實施例61的硬化性組成物相比，X、Y及Z分別超過0且小於2的實施例1的硬化性組成物具有更加優異之防沉降性及更加優異之經時穩定性。 與實施例50的硬化性組成物相比，X、Y及Z之和超過0.4且小於1.6的實施例1的硬化性組成物具有更加優異之防沉降性及更加優異之經時穩定性。又，與實施例55的硬化性組成物相比，實施例1的硬化性組成物具有更加優異之經時穩定性，由上述硬化性組成物得到之硬化膜具有更加優異之遮光性。 與實施例63的硬化性組成物相比，在波長400～1200nm下之含金屬氮化物粒子的複介電常數的虛數部ε’的最小值小於0的實施例1的硬化性組成物具有更加優異之遮光性。 與實施例9～12的硬化性組成物相比，原子T選自第2～6週期的元素中的鋁、鎵、銦、錫、鉈、鉛及鉍以外的元素中之實施例1的硬化性組成物具有更加優異之防沉降性及經時穩定性。 與實施例6～8的硬化性組成物相比，原子T選自13～16族元素中之實施例1的硬化性組成物具有更加優異之防沉降性及更加優異之經時穩定性。 依原子T為選自包括硼原子、碳原子、硫原子及磷原子之組群中之任意一種原子的實施例1的硬化性組成物，與實施例5的硬化性組成物相比，具有更加優異之經時穩定性。 與實施例3的硬化性組成物相比，原子T為選自包括硼原子、硫原子及磷原子之組群中之任意一種原子的實施例1的硬化性組成物具有更加優異之經時穩定性。 與實施例65及實施例66的硬化性組成物相比，具有聚己內酯結構和/或聚戊內酯結構、聚己內酯結構和聚戊內酯結構的重複數之和為10以上的、含有分散劑A之實施例1的硬化性組成物、含有分散劑B之實施例64的硬化性組成物、含有分散劑E之實施例67的硬化性組成物及含有分散劑F之實施例68的硬化性組成物具有更加優異之防沉降性。 又，與實施例79、實施例81及實施例82的硬化性組成物相比，式（OX-1）中，B所表示之一價的取代基為芳基或雜環基的、含有聚合起始劑I-1之實施例1的硬化性組成物、含有聚合起始劑I-3之實施例80的硬化性組成物、含有聚合起始劑I-6之實施例83的硬化性組成物、含有聚合起始劑I-7之實施例84的硬化性組成物及含有聚合起始劑I-8之實施例85的硬化性組成物具有更加優異之經時穩定性。From the results shown in Tables 2-1 to 2-9, the curable compositions of Examples 1 to 85 have the effects of the present invention. On the other hand, the curable compositions of Comparative Examples 1 to 6 did not have the effects of the present invention. Compared with the curable composition of Example 61, the curable composition of Example 1 in which X, Y, and Z are more than 0 and less than 2, respectively, has more excellent anti-settling properties and more excellent stability over time. Compared with the curable composition of Example 50, the curable composition of Example 1 in which the sum of X, Y and Z exceeds 0.4 and less than 1.6 has more excellent anti-settling properties and more excellent stability over time. Moreover, compared with the curable composition of Example 55, the curable composition of Example 1 has more excellent time-dependent stability, and the cured film obtained from the said curable composition has more excellent light-shielding property. Compared with the curable composition of Example 63, the curable composition of Example 1 in which the minimum value of the imaginary part ε' of the complex permittivity of the metal-containing nitride particles at a wavelength of 400 to 1200 nm is less than 0 has more Excellent shading. Compared with the curable compositions of Examples 9 to 12, the atomic T is selected from the elements other than aluminum, gallium, indium, tin, thallium, lead, and bismuth among the elements of the second to sixth periods. The synthetic composition has more excellent anti-settling properties and stability over time. Compared with the curable compositions of Examples 6 to 8, the curable composition of Example 1 in which atomic T is selected from elements of Groups 13 to 16 has more excellent anti-settling properties and more excellent stability over time. Compared with the curable composition of Example 5, the curable composition of Example 1, in which the atom T is any one atom selected from the group consisting of boron atom, carbon atom, sulfur atom and phosphorus atom, has more advantages. Excellent stability over time. Compared with the curable composition of Example 3, the curable composition of Example 1 in which the atom T is any one selected from the group consisting of boron atoms, sulfur atoms and phosphorus atoms has more excellent stability over time. sex. Compared with the curable compositions of Examples 65 and 66, the total number of repetitions of a polycaprolactone structure and/or a polyvalerolactone structure, a polycaprolactone structure and a polyvalerolactone structure is 10 or more The curable composition of Example 1 containing dispersant A, the curable composition of Example 64 containing dispersant B, the curable composition of Example 67 containing dispersant E, and the embodiment containing dispersant F The curable composition of Example 68 has more excellent anti-settling properties. Moreover, compared with the curable compositions of Example 79, Example 81, and Example 82, in the formula (OX-1), the monovalent substituent represented by B is an aryl group or a heterocyclic group, and contains a polymer Curable composition of Example 1 of initiator I-1, curable composition of Example 80 containing polymerization initiator I-3, curable composition of Example 83 containing polymerization initiator I-6 The curable composition of Example 84 containing the polymerization initiator I-7 and the curable composition of Example 85 containing the polymerization initiator I-8 had more excellent stability over time.

[實施例1-WL：晶片級透鏡用硬化膜的製作及評價] 藉由以下方法，製作出具備將實施例1的硬化性組成物進行硬化而得到之硬化膜作為遮光膜之晶片級透鏡，並評價了其性能。[Example 1-WL: Preparation and evaluation of cured film for wafer-level lens] The wafer-level lens provided with the cured film obtained by curing the curable composition of Example 1 as a light-shielding film was prepared by the following method, and evaluated its performance.

首先，藉由以下的操作形成了透鏡膜。 〔熱硬化性硬化膜的形成〕 將透鏡用硬化性組成物（向脂環式環氧樹脂（Daicel Corporation製EHPE-3150）中添加了芳基鋶鹽衍生物（ADEKA CORPORATION製造之SP-172）1質量%之組成物）（2mL）塗佈於5×5cm的玻璃基板（厚度1mm，Schott公司製造，BK7）上，並將塗膜於200℃下加熱1分鐘而使其硬化，形成了能夠評價透鏡上的殘渣之膜。First, a lens film was formed by the following operations. [Formation of a thermosetting cured film] A curable composition for lenses (a cycloaliphatic epoxy resin (EHPE-3150 manufactured by Daicel Corporation) was added with an aryl perionate derivative (SP-172 manufactured by ADEKA CORPORATION) 1 mass % of the composition) (2 mL) was applied on a 5×5 cm glass substrate (thickness 1 mm, manufactured by Schott Corporation, BK7), and the coating film was heated at 200° C. for 1 minute to harden, forming a The film of residue on the lens was evaluated.

在形成有上述透鏡膜之玻璃晶片上塗佈實施例1的硬化性組成物而得到了硬化性組成物層。接著，將上述玻璃晶片載置於加熱板上，並於120℃下加熱了120秒鐘。加熱後的硬化性組成物層的厚度為2.0μm。（硬化性組成物層形成製程） 接著，使用高壓水銀燈將加熱後的硬化性組成物層進行了曝光。經由具有10mm的孔圖案之光罩進行曝光，曝光量為500mJ/cm2 。（曝光製程） 接著，使用四甲基氫氧化銨0.3%水溶液，將曝光後的硬化性組成物層於23℃的溫度下進行60秒鐘浸置顯影而得到了圖案狀的硬化膜（遮光膜）。接著，使用旋轉噴淋沖洗遮光膜，進一步使用純水清洗了遮光膜。（顯影製程）The curable composition of Example 1 was apply|coated to the glass wafer on which the said lens film was formed, and the curable composition layer was obtained. Next, the above-mentioned glass wafer was placed on a hot plate and heated at 120° C. for 120 seconds. The thickness of the curable composition layer after heating was 2.0 μm. (Curable Composition Layer Formation Process) Next, the heated curable composition layer was exposed to light using a high pressure mercury lamp. Exposure was performed through a photomask with a hole pattern of 10 mm at an exposure level of 500 mJ/cm 2 . (Exposure process) Next, using tetramethylammonium hydroxide 0.3% aqueous solution, the curable composition layer after exposure was subjected to immersion development at a temperature of 23° C. for 60 seconds to obtain a patterned cured film (light-shielding film). ). Next, the light-shielding film was rinsed with a rotary shower, and the light-shielding film was further washed with pure water. (Development process)

〔固體攝像裝置的製作及評價〕 使用透鏡用硬化性組成物（向脂環式環氧樹脂（Daicel Corporation製造之EHPE-3150）中添加了芳基鋶鹽衍生物（ADEKA CORPORATION製造之SP-172）1質量%之組成物），在形成有上述中製作出之遮光膜之玻璃晶片上形成硬化性樹脂層，利用具有透鏡形狀之石英模具轉印形狀，並藉由高壓水銀燈以400mJ/cm2 的曝光量進行硬化，藉此製作出具有複數個晶片級透鏡之晶片級透鏡陣列。 切斷所製作出之晶片級透鏡陣列，並使用所得到之晶片級透鏡製作透鏡模組之後，安裝攝影元件及感測器基板，製作出攝像單元（固體攝像裝置）。 所得到之晶片級透鏡是，在透鏡開口部無殘渣物，具有良好的透射性，且關於遮光層，塗佈面的均勻性較高，遮光性較高者。[Fabrication and evaluation of solid-state imaging device] A curable composition for lenses (a cycloaliphatic epoxy resin (EHPE-3150, manufactured by Daicel Corporation) was added with an aryl perionate derivative (SP-172, manufactured by ADEKA CORPORATION) ) 1 mass % of the composition), a curable resin layer is formed on the glass wafer on which the light-shielding film produced above is formed, the shape is transferred using a quartz mold having a lens shape, and the high-pressure mercury lamp is used to 400mJ/cm 2 A wafer-level lens array with a plurality of wafer-level lenses is produced by hardening the exposure amount. After cutting the produced wafer-level lens array, and using the obtained wafer-level lens to produce a lens module, a photographic element and a sensor substrate are mounted to produce an imaging unit (solid-state imaging device). The obtained wafer-level lens has no residue on the lens opening, has good transmittance, and has high uniformity on the coated surface and high light-shielding property of the light-shielding layer.

[實施例1-BL：具備黑矩陣之彩色濾光片的製作及評價] 〔黑矩陣的形成〕 利用旋塗法，將實施例1的硬化性組成物塗佈於玻璃晶片而得到了硬化性組成物層。接著，將玻璃晶片載置於加熱板上，並於120℃下加熱了2分鐘。加熱後的硬化性組成物層的厚度為2.0μm。 接著，使用i射線步進機，透過具有0.1mm的島狀（Island）圖案之光罩，以500mJ/cm2 的曝光量將硬化性組成物層進行了曝光。 接著，使用四甲基氫氧化銨0.3%水溶液，將曝光後的硬化性組成物層於23℃下進行60秒鐘浸置顯影而得到了硬化膜。接著，使用旋轉噴淋沖洗硬化膜，進一步利用純水清洗了硬化膜。藉由上述，得到了圖案狀的遮光膜（黑矩陣）。使用上述黑矩陣製作出彩色濾光片，其結果，具有良好的性能。[Example 1-BL: Preparation and Evaluation of Color Filter Equipped with Black Matrix] [Formation of Black Matrix] The curable composition of Example 1 was applied to a glass wafer by spin coating to obtain curable properties composition layer. Next, the glass wafer was placed on a hot plate and heated at 120° C. for 2 minutes. The thickness of the curable composition layer after heating was 2.0 μm. Next, using an i-ray stepper, the curable composition layer was exposed at an exposure amount of 500 mJ/cm 2 through a mask having an island pattern of 0.1 mm. Next, using the tetramethylammonium hydroxide 0.3% aqueous solution, the curable composition layer after exposure was immersed and developed at 23 degreeC for 60 second, and the cured film was obtained. Next, the cured film was rinsed using a rotary shower, and the cured film was further washed with pure water. As a result, a patterned light-shielding film (black matrix) was obtained. A color filter was produced using the above-mentioned black matrix, and as a result, it had good performance.

未使用界面活性劑，除此以外，進行與實施例1相同之操作而製作硬化性組成物並進行了評價，其結果，得到了與實施例1相同之結果。Except that the surfactant was not used, a curable composition was produced and evaluated in the same manner as in Example 1. As a result, the same results as in Example 1 were obtained.

未使用聚合抑制劑，除此以外，進行與實施例1相同之操作而製作硬化性組成物並進行了評價，其結果，除了經時穩定性成為B以外，得到了與實施例1相同之結果。A curable composition was prepared and evaluated in the same manner as in Example 1, except that no polymerization inhibitor was used. As a result, the same results as in Example 1 were obtained except that the stability over time was B. .

實施例1的硬化性組成物中，使用含金屬氮化物粒子P-1與著色劑（碳黑，商品名稱「color black S170」，Degussa公司製造，平均一次粒徑17nm，BET比表面積200m2 /g，藉由氣黑（gas black）方式製造出之碳黑）的混合物代替含金屬氮化物粒子P-1來製備出硬化性組成物。以硬化性組成物中之含金屬氮化物粒子P-1與著色劑的含有質量比（著色劑/含金屬氮化物粒子P-1）成為2/8之方式進行了製備。對上述硬化性組成物進行了評價，其結果，可知具有與實施例1相同之性能。In the curable composition of Example 1, metal-containing nitride particles P-1 and a coloring agent (carbon black, trade name "color black S170", manufactured by Degussa Corporation, average primary particle size 17 nm, BET specific surface area 200 m 2 / g, a curable composition is prepared by replacing the metal-containing nitride particles P-1 with a mixture of carbon black produced by a gas black method. It prepared so that the content mass ratio (coloring agent/metal-containing nitride particle P-1) of the metal-containing nitride particle P-1 in a curable composition and a coloring agent might become 2/8. As a result of evaluating the above-mentioned curable composition, it was found that it has the same performance as that of Example 1.

實施例1的硬化性組成物中，使用含金屬氮化物粒子P-1與著色劑（顏料黃150，Hangzhou Star-up Pigment Co.,Ltd.製造，商品名稱6150顏料黃5GN）的混合物代替含金屬氮化物粒子P-1來製備出硬化性組成物。以硬化性組成物中之含金屬氮化物粒子P-1與著色劑的含有質量比（著色劑/含金屬氮化物粒子P-1）成為2/8之方式進行了製備。對上述硬化性組成物進行了評價，其結果，可知具有與實施例1相同之性能，此外，可知進而可得到深黑色的遮光膜。根據該結果可知，即使與著色劑（有機顏料或彩色染料）併用，亦可得到本發明的效果。In the curable composition of Example 1, a mixture of metal nitride particles P-1 and a colorant (Pigment Yellow 150, manufactured by Hangzhou Star-up Pigment Co., Ltd., trade name 6150 Pigment Yellow 5GN) was used instead of The metal nitride particle P-1 was used to prepare a curable composition. It prepared so that the content mass ratio (coloring agent/metal-containing nitride particle P-1) of the metal-containing nitride particle P-1 in a curable composition and a coloring agent might become 2/8. As a result of evaluating the above-mentioned curable composition, it was found that it has the same performance as that of Example 1, and further, it was found that a dark black light-shielding film can be obtained. From this result, even if it uses together with a coloring agent (organic pigment or a color dye), it turns out that the effect of this invention can be acquired.

100‧‧‧固體攝像裝置101‧‧‧固體攝影元件102‧‧‧攝像部103‧‧‧蓋玻璃104‧‧‧間隔件105‧‧‧積層基板106‧‧‧芯片基板107‧‧‧電路基板108‧‧‧電極焊盤109‧‧‧外部連接端子110‧‧‧貫穿電極111‧‧‧透鏡層112‧‧‧透鏡材料113‧‧‧支撐體114、115‧‧‧硬化膜201‧‧‧受光元件202‧‧‧彩色濾光片203‧‧‧微透鏡204‧‧‧基板205b‧‧‧藍色像素205r‧‧‧紅色像素205g‧‧‧綠色像素205bm‧‧‧黑矩陣206‧‧‧p阱層207‧‧‧讀出閘極部208‧‧‧垂直傳輸路徑209‧‧‧元件分離區域210‧‧‧閘極絕緣膜211‧‧‧垂直傳輸電極212‧‧‧硬化膜213、214‧‧‧絕緣膜215‧‧‧平坦化膜300‧‧‧紅外線感測器310‧‧‧固體攝影元件311‧‧‧紅外線吸收濾光片312‧‧‧彩色濾光片313‧‧‧紅外線透射濾光片314‧‧‧樹脂膜315‧‧‧微透鏡316‧‧‧平坦化膜hν‧‧‧入射光100‧‧‧Solid-state imaging device 101‧‧‧Solid-state imaging element 102‧‧‧Imaging section 103‧‧‧Cover glass 104‧‧‧Spacer 105‧‧‧Multilayer substrate 106‧‧‧Chip substrate 107‧‧‧Circuit board 108‧‧‧Electrode pad 109‧‧‧External connection terminal 110‧‧‧Through electrode 111‧‧‧Lens layer 112‧‧‧Lens material 113‧‧‧Support body 114, 115‧‧‧Curing film 201‧‧‧ Light-receiving element 202‧‧‧Color filter 203‧‧‧Micro lens 204‧‧‧Substrate 205b‧‧‧Blue pixel 205r‧‧‧Red pixel 205g‧‧‧Green pixel 205bm‧‧‧Black matrix 206‧‧‧ p-well layer 207‧‧‧read gate portion 208‧‧‧vertical transfer path 209‧‧‧element isolation region 210‧‧‧gate insulating film 211‧‧‧vertical transfer electrode 212‧‧‧hardened film 213, 214 ‧‧‧Insulating film 215‧‧‧Planarizing film 300‧‧‧Infrared sensor 310‧‧‧Solid state imaging element 311‧‧‧Infrared absorption filter 312‧‧‧Color filter 313‧‧‧Infrared transmission Filter 314‧‧‧Resin film 315‧‧‧Micro lens 316‧‧‧Flattening film hν‧‧‧Incoming light

圖1是表示固體攝像裝置的構成例之概略剖面圖。 圖2是放大表示圖1的攝像部之概略剖面圖。 圖3是表示紅外線感測器的構成例之概略剖面圖。FIG. 1 is a schematic cross-sectional view showing a configuration example of a solid-state imaging device. FIG. 2 is an enlarged schematic cross-sectional view showing the imaging unit of FIG. 1 . FIG. 3 is a schematic cross-sectional view showing a configuration example of an infrared sensor.

100:固體攝像裝置 100: Solid state camera

101:固體攝影元件 101: Solid-state photographic elements

102:攝像部 102: Camera Department

103:蓋玻璃 103: Cover glass

104:間隔件 104: Spacer

105:積層基板 105: Laminated substrate

106:芯片基板 106: Chip substrate

107:電路基板 107: circuit substrate

108:電極焊盤 108: Electrode pad

109:外部連接端子 109: External connection terminal

110:貫穿電極 110: Through the electrode

111:透鏡層 111: Lens layer

112:透鏡材料 112: Lens Material

113:支撐體 113: Support body

114、115:硬化膜 114, 115: Hardened film

Claims (22)

一種含金屬氮化物粒子，其含有3~11族的過渡金屬的氮化物，前述含金屬氮化物粒子的平均一次粒徑為200nm以下，前述含金屬氮化物粒子含有氮原子和原子T，前述原子T不是氧原子、氯原子及氮原子中的任意一者，並選自包括硼原子、碳原子、氟原子、磷原子、硫原子、鍺原子、硒原子、溴原子、碲原子、碘原子及砈原子之組群中之任意一種原子，當將藉由X射線光電子光譜分析檢測之前述含金屬氮化物粒子的表面上之前述原子T的質量基準的含量設為TE，並且將藉由X射線螢光分析檢測之前述含金屬氮化物粒子中之前述原子T的質量基準的含量設為TX時，滿足下述式(1)所表示之關係，所述含金屬氮化物粒子中之所述原子T的含量相對於所述含金屬氮化物粒子的總質量為0.05~40質量%；所述含金屬氮化物粒子中的過渡金屬原子的含量相對於所述含金屬氮化物粒子的總質量為10質量%~99質量%；以及所述含金屬氮化物粒子中的所述氮原子的含量相對於所述含金屬氮化物粒子的總質量為0.1質量%~80質量%，另外，TE和TX的單位為質量%，式(1) TE/TX<2.0。 A metal-containing nitride particle containing a nitride of a transition metal of Groups 3 to 11, wherein the average primary particle diameter of the metal-containing nitride particle is 200 nm or less, the metal-containing nitride particle contains nitrogen atoms and atoms T, and the atomic T is not any one of oxygen atom, chlorine atom and nitrogen atom, and is selected from the group consisting of boron atom, carbon atom, fluorine atom, phosphorus atom, sulfur atom, germanium atom, selenium atom, bromine atom, tellurium atom, iodine atom and Any one of the atoms in the group of slug atoms, when the mass-based content of the aforementioned atom T on the surface of the aforementioned metal-containing nitride particle detected by X-ray photoelectron spectroscopic analysis is set as T E , and by X-ray photoelectron spectroscopy When the mass-based content of the atoms T in the metal-containing nitride particles detected by radiofluorescence analysis is set as T X , the relationship represented by the following formula (1) is satisfied, and the content in the metal-containing nitride particles is The content of the atomic T is 0.05 to 40 mass % relative to the total mass of the metal-containing nitride particles; the content of transition metal atoms in the metal-containing nitride particles is relative to the total mass of the metal-containing nitride particles. 10 mass% to 99 mass%; and the nitrogen atom content of said metal-containing nitride particles with respect to the total mass of the metal-containing nitride particles is 0.1 mass% to 80 mass%, further, T E The units of and T X are mass %, and the formula (1) T E /T X <2.0. 如申請專利範圍第1項所述之含金屬氮化物粒子，其進一步含有氧原子。 The metal-containing nitride particle as described in claim 1 further contains an oxygen atom. 如申請專利範圍第2項所述之含金屬氮化物粒子，其中 前述氮原子的含量相對於前述氮化物所含有之過渡金屬原子的含量之含有原子數比X、前述氧原子的含量相對於前述氮化物所含有之過渡金屬原子的含量之含有原子數比Y、及前述原子T的含量相對於前述氮化物所含有之過渡金屬原子的含量之含有原子數比Z分別超過0且小於2，其中前述X、前述Y及前述Z之和超過0.4且小於1.6。 The metal-containing nitride particles as described in item 2 of the claimed scope, wherein The atomic ratio X of the content of the nitrogen atoms to the content of the transition metal atoms contained in the nitride, the atomic ratio Y of the content of the oxygen atoms to the content of the transition metal atoms contained in the nitride, The atomic number ratio Z of the content of the atoms T to the content of the transition metal atoms contained in the nitride is more than 0 and less than 2, and the sum of the X, the Y and the Z is more than 0.4 and less than 1.6. 如申請專利範圍第3項所述之含金屬氮化物粒子，其中所述X為超過0.3且小於1.3，所述Y為超過0.03且小於0.25，且所述T為超過0.03且0.5以下。 The metal-containing nitride particle according to claim 3, wherein the X is more than 0.3 and less than 1.3, the Y is more than 0.03 and less than 0.25, and the T is more than 0.03 and 0.5 or less. 如申請專利範圍第1項至第3項中任一項所述之含金屬氮化物粒子，其中當由下述式(2)表示在波長400~1200nm下之前述含金屬氮化物粒子的複介電常數ε時，ε’的最小值小於0，式(2) ε=ε’+ε”j另外，上述式(2)中，ε’表示複介電常數ε的實數部，ε”表示複介電常數ε的虛數部，j表示虛數單位。 The metal-containing nitride particle according to any one of the first to third claims of the claimed scope, wherein the compound of the metal-containing nitride particle at a wavelength of 400 to 1200 nm is represented by the following formula (2). When the permittivity ε, the minimum value of ε' is less than 0, Equation (2) ε=ε'+ε"j In addition, in the above equation (2), ε' represents the real part of the complex permittivity ε, and ε” represents the complex permittivity ε. The imaginary part of the dielectric constant ε, and j represents an imaginary unit. 如申請專利範圍第1項至第3項中任一項所述之含金屬氮化物粒子，其中前述過渡金屬為Sc、V、Cr、Mn、Fe、Co、Ni、Cu、Y、Zr、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Hf、Ta、W、Re、Os、Ir或Pt。 The metal-containing nitride particle according to any one of items 1 to 3 of the claimed scope, wherein the transition metal is Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb , Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir or Pt. 如申請專利範圍第1項至第3項中任一項所述之含金屬氮化物粒子，其中前述原子T選自13~16族元素。 The metal-containing nitride particle according to any one of items 1 to 3 of the claimed scope, wherein the aforementioned atom T is selected from elements of Groups 13-16. 如申請專利範圍第1項至第3項中任一項所述之含金屬氮化物粒子，其中前述原子T是選自包括硼原子、碳原子、硫原子及磷原子之組群中之任意一種原子。 The metal-containing nitride particle according to any one of items 1 to 3 of the claimed scope, wherein the aforementioned atom T is any one selected from the group consisting of boron atom, carbon atom, sulfur atom and phosphorus atom atom. 如申請專利範圍第1項至第3項中任一項所述之含金屬氮化物粒子，其中前述原子T是選自包括硼原子、硫原子及磷原子之組群中之任意一種原子。 The metal-containing nitride particle according to any one of items 1 to 3 of the claimed scope, wherein the aforementioned atom T is any atom selected from the group consisting of boron atom, sulfur atom and phosphorus atom. 一種分散組成物，其含有如申請專利範圍第1項至第9項中任一項所述之含金屬氮化物粒子和樹脂。 A dispersion composition comprising the metal-containing nitride particles described in any one of items 1 to 9 of the patent application scope and a resin. 一種硬化性組成物，其含有如申請專利範圍第10項所述之分散組成物、聚合性化合物及聚合起始劑。 A curable composition comprising the dispersing composition, a polymerizable compound and a polymerization initiator as described in claim 10 of the scope of application. 一種硬化性組成物，其含有如申請專利範圍第1項至第9項中任一項所述之含金屬氮化物粒子、樹脂、聚合性化合物及聚合起始劑。 A curable composition comprising the metal-containing nitride particles described in any one of the first to ninth claims, a resin, a polymerizable compound, and a polymerization initiator. 如申請專利範圍第11或12項所述之硬化性組成物，其進一步含有溶劑。 The curable composition according to claim 11 or 12, which further contains a solvent. 一種硬化膜，其是將如申請專利範圍第11項至第13項中任一項所述之硬化性組成物進行硬化而得到。 A cured film obtained by curing the curable composition described in any one of Claims 11 to 13. 一種彩色濾光片，其含有如申請專利範圍第14項所述之硬化膜。 A color filter comprising the hardened film as described in item 14 of the patent application scope. 一種固體攝影元件，其含有如申請專利範圍第14項所述之硬化膜。 A solid-state photographic element comprising the cured film described in claim 14 of the scope of the application. 一種固體攝像裝置，其含有如申請專利範圍第14項所述之硬化膜。 A solid-state imaging device including the cured film described in claim 14 of the scope of the application. 一種紅外線感測器，其含有如申請專利範圍第14項所述之硬化膜。 An infrared sensor comprising the cured film as described in item 14 of the patent application scope. 一種含金屬氮化物粒子的製造方法，其是如申請專利範圍第1項至第9項中任一項所述之含金屬氮化物粒子的製造方法，包含以下製程：原材料準備製程，準備含有氮原子之原材料A及含有過渡金屬原子及原子T之原材料B、或者準備含有氮原子之原材料A、含有過渡金屬原子之原材料C及含有原子T之原材料D；將2種以上的原材料以氣相狀態進行混合而得到混合物之製程；以及使氣相狀態的前述混合物凝縮而得到含金屬氮化物粒子之製程。 A method for producing metal-containing nitride particles, which is the method for producing metal-containing nitride particles as described in any one of items 1 to 9 of the patent application scope, comprising the following processes: a raw material preparation process, preparing a nitrogen-containing particle Atomic raw materials A and raw materials B containing transition metal atoms and atoms T, or prepare raw materials A containing nitrogen atoms, raw materials C containing transition metal atoms, and raw materials D containing atoms T; two or more raw materials are prepared in the gas phase A process of mixing to obtain a mixture; and a process of condensing the aforementioned mixture in a gas phase to obtain metal-containing nitride particles. 一種分散組成物的製造方法，其是如申請專利範圍第10項所述之分散組成物的製造方法，包含以下製程：原材料準備製程，準備含有氮原子之原材料A及含有過渡金屬原子及原子T之原材料B、或者準備含有氮原子之原材料A、含有過渡金屬原子之原材料C及含有原子T之原材料D； 將2種以上的原材料以氣相狀態進行混合而得到混合物之製程；使氣相狀態的前述混合物凝縮而得到含金屬氮化物粒子之製程；以及混合前述含金屬氮化物粒子及前述樹脂而得到分散組成物之製程。 A method for producing a dispersed composition, which is the method for producing a dispersed composition as described in item 10 of the scope of the application, comprising the following processes: a raw material preparation process, preparing a raw material A containing nitrogen atoms and a transition metal atom and an atom T Raw material B, or prepare raw material A containing nitrogen atom, raw material C containing transition metal atom and raw material D containing atom T; A process of mixing two or more raw materials in a gas phase to obtain a mixture; a process of condensing the mixture in a gas phase to obtain metal-containing nitride particles; and mixing the metal-containing nitride particles and the resin to obtain dispersion Process of composition. 一種硬化性組成物的製造方法，其是含有分散組成物、聚合性化合物及聚合起始劑之硬化性組成物的製造方法，包含如申請專利範圍第20項所述之分散組成物的製造方法。 A method for producing a curable composition, which is a method for producing a curable composition containing a dispersion composition, a polymerizable compound and a polymerization initiator, including the method for producing a dispersion composition described in claim 20 of the scope of the application . 一種硬化膜的製造方法，其包含以下製程：硬化性組成物層形成製程，使用如申請專利範圍第11項至第13項中任一項所述之硬化性組成物而形成硬化性組成物層；曝光製程，經由具備圖案狀的開口部之光罩，向前述硬化性組成物層照射光化射線或放射線而進行曝光；以及顯影製程，對前述曝光後的前述硬化性組成物層進行顯影而形成硬化膜。 A method for manufacturing a cured film, comprising the following process: a process for forming a curable composition layer, and a curable composition layer is formed by using the curable composition described in any one of the 11th to 13th items of the patent application scope ; Exposure process, through a mask with patterned openings, to the above-mentioned curable composition layer by irradiating actinic rays or radiation to expose; A hardened film is formed.
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