TW201806976A - Composition, film, cured film, optical sensor, and process for producing film - Google Patents

Composition, film, cured film, optical sensor, and process for producing film Download PDF

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TW201806976A
TW201806976A TW106110676A TW106110676A TW201806976A TW 201806976 A TW201806976 A TW 201806976A TW 106110676 A TW106110676 A TW 106110676A TW 106110676 A TW106110676 A TW 106110676A TW 201806976 A TW201806976 A TW 201806976A
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inorganic particles
group
composition
particles
film
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TW106110676A
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田口貴規
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富士軟片股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds

Abstract

Provided are: a composition which gives a film that, when having a thickness of 3.0 [mu]m, has a value of L* according to the CIE 1976 L*a*b* color system of 35 or greater and which has excellent liquid stability over time; a film; a cured film; an optical sensor; and a process for producing a film. The composition comprises inorganic particles and a resin, wherein the inorganic particles comprise at least one kind of inorganic particles selected from among hollow inorganic particles, solid inorganic particles, and porous inorganic particles, the inorganic substance contained in the inorganic particles having a refractive index of 1.65 or greater for light with a wavelength of 589 nm.

Description

組成物、膜、硬化膜、光學感測器及膜的製造方法Composition, film, cured film, optical sensor, and method for manufacturing film

本發明係關於一種組成物、膜、硬化膜、光學感測器及膜的製造方法。The invention relates to a composition, a film, a cured film, an optical sensor, and a method for manufacturing the film.

中空粒子及多孔質粒子能夠調整粒徑等，因此用於各種各樣的用途中（例如參閱專利文獻1～3）。 專利文獻1中記載有感光性組成物，其含有：聚合性烴單體及聚合性烴聚合物中的至少一種成分；孔隙率為30體積%以上且99體積%以下，且平均一次粒徑為0.1μm以上且20μm以下的中空粒子；及光聚合起始劑。 專利文獻2中記載有球狀多孔質氧化鈦奈米粒子的合成方法，其具備在超臨界流體中使異丙醇鈦和羧酸進行反應之製程，其中，超臨界流體為超臨界甲醇，羧酸為甲酸、乙酸、安息香酸、鄰苯二甲酸、反丁烯二酸或順丁烯二酸。 專利文獻3中記載有摻雜有Au原子之Au摻雜型球狀多孔質銳鈦礦型氧化鈦奈米粒子的合成方法，其具備：在甲醇中添加異丙醇鈦、四氯金酸四水合物或乙酸金、以及選自甲酸、乙酸、安息香酸及鄰苯二甲酸中之1種以上而製備甲醇溶液之製程；及在甲醇成為超臨界甲醇之溫度下加熱甲醇溶液之製程，加熱時的升溫速度為20℃/分鐘以下。 [先前技術文獻]Hollow particles and porous particles can be adjusted in particle size and the like, and are used for various applications (for example, see Patent Documents 1 to 3). Patent Document 1 describes a photosensitive composition containing at least one component of a polymerizable hydrocarbon monomer and a polymerizable hydrocarbon polymer; a porosity of 30% by volume to 99% by volume, and an average primary particle diameter of Hollow particles of 0.1 μm or more and 20 μm or less; and a photopolymerization initiator. Patent Document 2 describes a method for synthesizing spherical porous titanium oxide nano particles, which includes a process for reacting titanium isopropoxide and a carboxylic acid in a supercritical fluid, wherein the supercritical fluid is supercritical methanol and carboxylic acid. The acid is formic acid, acetic acid, benzoic acid, phthalic acid, fumaric acid or maleic acid. Patent Document 3 describes a method for synthesizing Au-doped spherical porous anatase-type titanium oxide nano particles doped with Au atoms, which comprises adding titanium isopropoxide and tetrachloroauric acid to methanol A process for preparing a methanol solution from hydrate or gold acetate, and one or more selected from formic acid, acetic acid, benzoic acid, and phthalic acid; and a process for heating a methanol solution at a temperature at which methanol becomes supercritical methanol, when heating The temperature rising rate is 20 ° C / minute or less. [Prior technical literature]

專利文獻1：日本特開2011-75786號公報 專利文獻2：國際公開WO2013-61621號 專利文獻3：日本特開2015-164881號公報Patent Document 1: Japanese Patent Application Laid-Open No. 2011-75786 Patent Document 2: International Publication No. WO2013-61621 Patent Document 3: Japanese Patent Application Laid-Open No. 2015-164881

使用了含有樹脂及粒子之組成物之膜，作為白色之膜能夠用於使用了半導體之光學感測器用途。使用了半導體之光學感測器用途的膜中，要求一種遮蔽膜，該膜為薄膜，同時具有能夠隱蔽光學感測器之遮蔽度。製成薄膜之情況下，亦從隱蔽光學感測器之觀點考慮，作為膜之白色度，CIE1976的L*a*b*色彩坐標系統中之L*需為35以上。因此，為了使遮蔽度變得適宜，要求係L*為35以上之膜。A film using a composition containing a resin and particles can be used as an optical sensor using a semiconductor as a white film. Among the films used for optical sensors using semiconductors, a shielding film is required. The film is a thin film and has a degree of shielding capable of concealing the optical sensor. In the case of a thin film, from the viewpoint of a hidden optical sensor, as the whiteness of the film, the L * in the L * a * b * color coordinate system of CIE1976 needs to be 35 or more. Therefore, in order to make the shielding degree suitable, a film having an L * of 35 or more is required.

並且，當使用含有粒子及樹脂之組成物來製造膜時，若組成物的溶液經時穩定性較低，則粒子等有可能沉降。尤其，在使用了半導體之光學感測器用途中，要求係粒子等不易沉降之組成物。In addition, when a film is produced using a composition containing particles and a resin, particles and the like may settle if the solution of the composition has low stability over time. In particular, in the application of an optical sensor using a semiconductor, a composition that is difficult to settle, such as particles, is required.

本發明所欲解決之課題為提供一種形成了厚度3.0μm的膜時之CIE1976（國際照明委員會；International Commission on Illumination）的L*a*b*色彩坐標系統中之L*為35以上且溶液經時穩定性優異之組成物。The problem to be solved by the present invention is to provide an L * a * b * color coordinate system of CIE1976 (International Commission on Illumination) when the thickness of a film of 3.0 μm is formed. Composition with excellent time stability.

在該種狀況下，本發明者進行了深入研究之結果，得知使用專利文獻1～3中所記載之中空粒子及多孔質粒子並使用含有粒子及樹脂之組成物之膜中，對於形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*及溶液經時穩定性中的至少一方，要求進一步進行改善。 本發明者發現藉由設為以下構成能夠解決上述課題，從而完成了本發明。本發明及本發明的較佳構成如下。Under these circumstances, as a result of intensive studies, the present inventors have found that the thickness of the film formed by using the hollow particles and porous particles described in Patent Documents 1 to 3 and using a composition containing particles and resins, At least one of L * in the L * a * b * color coordinate system of CIE1976 at the time of a 3.0 μm film and the stability of the solution over time requires further improvement. The inventors have found that the above-mentioned problems can be solved by having the following configuration, and have completed the present invention. The present invention and preferred configurations of the present invention are as follows.

[1]一種組成物，其含有無機粒子及樹脂， 無機粒子含有中空無機粒子、中實無機粒子及多孔質無機粒子中的至少1種， 無機粒子中所含之無機物對波長589nm的光之折射率為1.65以上。 [2]如[1]所述之組成物，其中組成物為硬化性組成物。 [3]如[1]或[2]所述之組成物，其中無機粒子含有中空無機粒子或多孔質無機粒子。 [4]如[1]至[3]中任一項所述之組成物，其中無機粒子含有金屬單體或金屬氧化物。 [5]如[1]至[4]中任一項所述之組成物，其中無機粒子為白色顏料。 [6]如[1]至[5]中任一項所述之組成物，其中無機粒子含有氧化鈦。 [7]如[1]至[6]中任一項所述之組成物，其中無機粒子的平均粒徑為100～1000nm。 [8]如[1]至[7]中任一項所述之組成物，其中無機粒子的含量相對於組成物的總固體成分為25～75質量%。 [9]如[1]至[8]中任一項所述之組成物，其中無機粒子中所含之無機物對波長589nm的光之折射率為1.8以上。 [10]如[1]至[9]中任一項所述之組成物，其中樹脂為鹼可溶性樹脂。 [11]如[1]至[10]中任一項所述之組成物，其中樹脂為聚矽氧烷系樹脂。 [12]如[1]至[11]中任一項所述之組成物，其中組成物還含有硬化性化合物及聚合起始劑中的至少一方。 [13]如[1]至[12]中任一項所述之組成物，其中組成物還含有自由基聚合性化合物及光聚合起始劑。 [14]如[1]至[13]中任一項所述之組成物，其中組成物還含有著色防止劑。 [15]如[1]至[14]中任一項所述之組成物，其中組成物還含有鏈轉移劑。 [16]如[1]至[15]中任一項所述之組成物，其中組成物還含有分散劑及分散助劑中的至少一方。 [17]一種膜，其係使用[1]至[16]中任一項所述之組成物而形成。 [18]一種膜，其含有無機粒子及樹脂， 無機粒子含有中空無機粒子、中實無機粒子及多孔質無機粒子中的至少1種， 無機粒子中所含之無機物對波長589nm的光之折射率為1.65以上。 [19]如[17]或[18]所述之膜，其中CIE1976的L*a*b*色彩坐標系統中之L*為35～75。 [20]如[17]至[19]中任一項所述之膜，其中當厚度為3.0μm時，波長400～700nm的範圍內之平均透射率為1%以上。 [21]如[17]至[20]中任一項所述之膜，其厚度為10μm以下。 [22]一種硬化膜，其係將[17]至[21]中任一項所述之膜進行硬化而得到。 [23]一種光學感測器，其具有[22]所述之硬化膜。 [24]一種膜的製造方法，其包括如下製程：將[1]至[16]中任一項所述之組成物經由具有圖案之遮罩進行曝光之製程；及 對經曝光之組成物進行顯影而形成圖案之製程。 [發明效果][1] A composition containing inorganic particles and a resin, the inorganic particles containing at least one of a hollow inorganic particle, a solid inorganic particle, and a porous inorganic particle, and a refracting of an inorganic substance contained in the inorganic particle to light having a wavelength of 589 nm The rate is above 1.65. [2] The composition according to [1], wherein the composition is a curable composition. [3] The composition according to [1] or [2], wherein the inorganic particles include hollow inorganic particles or porous inorganic particles. [4] The composition according to any one of [1] to [3], wherein the inorganic particles contain a metal monomer or a metal oxide. [5] The composition according to any one of [1] to [4], wherein the inorganic particles are white pigments. [6] The composition according to any one of [1] to [5], wherein the inorganic particles contain titanium oxide. [7] The composition according to any one of [1] to [6], wherein the average particle diameter of the inorganic particles is 100 to 1000 nm. [8] The composition according to any one of [1] to [7], wherein the content of the inorganic particles is 25 to 75% by mass based on the total solid content of the composition. [9] The composition according to any one of [1] to [8], wherein the refractive index of the inorganic substance contained in the inorganic particles with respect to light having a wavelength of 589 nm is 1.8 or more. [10] The composition according to any one of [1] to [9], wherein the resin is an alkali-soluble resin. [11] The composition according to any one of [1] to [10], wherein the resin is a polysiloxane resin. [12] The composition according to any one of [1] to [11], wherein the composition further contains at least one of a hardenable compound and a polymerization initiator. [13] The composition according to any one of [1] to [12], wherein the composition further contains a radical polymerizable compound and a photopolymerization initiator. [14] The composition according to any one of [1] to [13], wherein the composition further contains a coloring inhibitor. [15] The composition according to any one of [1] to [14], wherein the composition further contains a chain transfer agent. [16] The composition according to any one of [1] to [15], wherein the composition further contains at least one of a dispersant and a dispersing aid. [17] A film formed using the composition according to any one of [1] to [16]. [18] A film containing inorganic particles and resin, the inorganic particles containing at least one of hollow inorganic particles, solid inorganic particles, and porous inorganic particles, and the refractive index of an inorganic substance contained in the inorganic particles to light having a wavelength of 589 nm It is 1.65 or more. [19] The film according to [17] or [18], wherein L * in the L * a * b * color coordinate system of CIE1976 is 35 to 75. [20] The film according to any one of [17] to [19], wherein when the thickness is 3.0 μm, the average transmittance in a wavelength range of 400 to 700 nm is 1% or more. [21] The film according to any one of [17] to [20], which has a thickness of 10 μm or less. [22] A cured film obtained by curing the film according to any one of [17] to [21]. [23] An optical sensor having the cured film according to [22]. [24] A method for manufacturing a film, comprising the following processes: a process of exposing the composition according to any one of [1] to [16] through a mask having a pattern; and performing the exposed composition Process of developing to form a pattern. [Inventive effect]

依本發明，能夠提供一種形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*為35以上且溶液經時穩定性優異之組成物。 並且，依本發明，能夠提供一種膜、硬化膜、光學感測器及膜的製造方法。According to the present invention, it is possible to provide a composition having a L * a * b * color coordinate system of CIE1976 of 35 or more and excellent solution stability over time when a film having a thickness of 3.0 μm is formed. Furthermore, according to the present invention, it is possible to provide a film, a cured film, an optical sensor, and a method for manufacturing the film.

以下，對本發明的內容進行詳細說明。 以下所記載之構成要件的說明有時係基於本發明的代表性實施態樣而進行，但本發明並不限定於該種實施態樣。 本說明書中，用“～”表示之數值範圍係指將“～”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具有取代基之基團（原子團），並且還包含具有取代基之基團（原子團）。例如，“烷基”不僅包含不具有取代基之烷基（未經取代之烷基），還包含具有取代基之烷基（經取代之烷基）。 “（甲基）丙烯酸酯”表示丙烯酸酯及甲基丙烯酸酯，“（甲基）丙烯酸基”表示丙烯酸基及甲基丙烯酸基，“（甲基）丙烯醯基”表示丙烯醯基甲基丙烯醯基。 只要沒有特別指定，則“曝光”不僅包含使用了光之曝光，使用了電子束、離子束等粒子束之描畫亦包含於曝光中。並且，作為曝光中所使用之光，一般可以舉出水銀燈的明線光譜、以準分子雷射為代表之遠紫外線、極紫外線（EUV）、X射線、電子束等活性光線或放射線。 重量平均分子量及數量平均分子量被定義為藉由凝膠滲透層析術（GPC）測定之聚苯乙烯換算值。重量平均分子量（Mw）及數量平均分子量（Mn）例如能夠藉由使用HLC-8220（TOSOH CORPORATION製），並使用TSKgel Super AWM-H（TOSOH CORPORATION製，6.0mm（內徑）×15.0cm）作為管柱，使用10mmol/L溴化鋰NMP（N-吡咯啶酮）溶液作為洗提液（eluant）而求出。Hereinafter, the content of this invention is demonstrated in detail. The description of the constituent elements described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment. In the present specification, a numerical range indicated by "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value. In the description of the group (atomic group) in this specification, the unsubstituted and unsubstituted tags include a group (atomic group) having no substituent, and also include a group (atomic group) having a substituent. For example, "alkyl" includes not only alkyl groups (unsubstituted alkyl groups) without substituents, but also alkyl groups (substituted alkyl groups) with substituents. "(Meth) acrylate" means acrylate and methacrylate, "(meth) acrylate" means acrylic and methacrylate, and "(meth) acrylfluorenyl" means acrylmethylmethacryl醯 基. Unless otherwise specified, "exposure" includes not only exposure using light, but also drawing using particle beams such as electron beams and ion beams. In addition, as the light used in the exposure, generally, a bright line spectrum of a mercury lamp, active ultraviolet rays such as far ultraviolet rays, extreme ultraviolet rays (EUV), X-rays, and electron beams typified by excimer laser light, or radiation may be mentioned. The weight average molecular weight and number average molecular weight are defined as polystyrene conversion values measured by gel permeation chromatography (GPC). The weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION) and TSKgel Super AWM-H (manufactured by TOSOH CORPORATION, 6.0 mm (inner diameter) × 15.0 cm) can be used The column was determined using a 10 mmol / L lithium bromide NMP (N-pyrrolidone) solution as an eluant.

[組成物] 本發明的組成物含有無機粒子及樹脂， 無機粒子含有中空無機粒子、中實無機粒子及多孔質無機粒子中的至少1種， 無機粒子中所含之無機物對波長589nm的光之折射率為1.65以上。 藉由設為該種構成，能夠提供形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*為35以上且溶液經時穩定性優異之組成物。 藉由使用含有對波長589nm的光之折射率為1.65以上之無機物之無機粒子，隨著提高在粒子表面上之反射能而能夠提高白色度，容易將形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*控制為35以上。 中空無機粒子、中實無機粒子及多孔質無機粒子相比均勻組成的無機粒子，其體比重（（bulk specific gravity））（表觀密度）較小，因此能夠抑制含有折射率為1.65以上之無機物之無機粒子在組成物中之沉降，能夠提供溶液經時穩定性優異之組成物。 本說明書中，“中空粒子”係內部具有空洞之結構者，係指具有被外殼包圍之空洞之粒子。 中空無機粒子係中空粒子，係指含有無機物之粒子。 “中實粒子”係具有芯（亦稱為內核）和殼層（亦稱為外殻）之粒子，較佳地，係指構成粒子之殼層的密度大於構成粒子之芯的密度之粒子。 “中實無機粒子”係中實粒子，係指含有無機物之粒子。其中，中實無機粒子的芯可以是有機物，亦可以是無機物，但芯為有機物，殼為無機物為較佳。 “多孔質粒子”係指具有複數個空洞且為多孔質之粒子。多孔質粒子係一次粒子為具有複數個空洞之粒子為較佳。 “多孔質無機粒子”係多孔質粒子，係指含有無機物之粒子。 以下，對本發明的組成物的較佳態樣進行說明。[Composition] The composition of the present invention contains inorganic particles and resin, the inorganic particles contain at least one of hollow inorganic particles, solid inorganic particles, and porous inorganic particles, and the inorganic substances contained in the inorganic particles are related to light having a wavelength of 589 nm. The refractive index is 1.65 or more. With such a configuration, it is possible to provide a composition in which the L * a * b * color coordinate system of CIE1976 when forming a film having a thickness of 3.0 μm is 35 or more and the solution has excellent stability over time. By using inorganic particles containing an inorganic substance having a refractive index of 1.65 or more with respect to light having a wavelength of 589 nm, the whiteness can be improved by increasing the reflection energy on the surface of the particles, and the CIE1976 L when a film having a thickness of 3.0 μm is easily formed * a * b * L * control in color coordinate system is above 35. Hollow inorganic particles, solid inorganic particles, and porous inorganic particles have a smaller bulk specific gravity (apparent density) than inorganic particles having a uniform composition, and therefore can suppress the inclusion of inorganic substances having a refractive index of 1.65 or more. The sedimentation of the inorganic particles in the composition can provide a composition excellent in the stability of the solution over time. In this specification, "hollow particle" means a structure having a cavity inside, and means a particle having a cavity surrounded by a shell. Hollow inorganic particles are hollow particles, meaning particles containing inorganic substances. A "solid particle" is a particle having a core (also referred to as a core) and a shell (also referred to as an outer shell), and preferably refers to a particle having a density greater than that of the core constituting the particle. "Medium solid inorganic particles" are medium solid particles and refer to particles containing inorganic substances. Among them, the core of the solid inorganic particles may be an organic substance or an inorganic substance, but the core is an organic substance and the shell is preferably an inorganic substance. A "porous particle" refers to a porous particle having a plurality of voids. It is preferable that the primary particle of the porous plasmid particle is a particle having a plurality of voids. "Porous inorganic particles" are porous particles and refer to particles containing inorganic substances. Hereinafter, the preferable aspect of the composition of this invention is demonstrated.

＜特性＞ 本發明的組成物係硬化性組成物為較佳。“硬化性組成物”係指含有後述之硬化性化合物之組成物。硬化性組成物可以是光硬化性組成物，亦可以是熱硬化性組成物。 對本發明的組成物的特性的詳細內容進行說明。<Characteristics> The composition-based curable composition of the present invention is preferred. The "curable composition" refers to a composition containing a curable compound described later. The curable composition may be a photo-curable composition or a thermo-curable composition. The details of the characteristics of the composition of the present invention will be described.

＜＜L*＞＞ 本發明的組成物，當使用組成物來形成厚度3.0μm的膜時，CIE1976的L*a*b*色彩坐標系統中之L*為35以上，35～75為較佳。藉由將CIE1976的L*a*b*色彩坐標系統中之L*設為75以下，提高光的透射率，製成使用於驅動光學感測器而檢測受光量的變化所需之足夠量之光通過之遮蔽膜為較佳。當使用組成物來形成厚度3.0μm的膜時，CIE1976的L*a*b*色彩坐標系統中之L*的下限係50以上為更佳，60以上為特佳。另外，CIE1976的L*a*b*色彩坐標系統中之L*的值係利用後述之實施例中所記載之方法測定之值。<< L *> When the composition of the present invention is used to form a film having a thickness of 3.0 μm, the L * a * b * color coordinate system of CIE1976 is 35 or more, and 35 to 75 is preferred. . By setting the L * in the L * a * b * color coordinate system of CIE1976 to 75 or less, the light transmittance is increased, and a sufficient amount required for driving an optical sensor to detect a change in the amount of received light is produced. A shielding film through which light passes is preferred. When a composition is used to form a film having a thickness of 3.0 μm, the lower limit of L * in the L * a * b * color coordinate system of CIE1976 is more preferably 50 or more, and particularly preferably 60 or more. In addition, the value of L * in the L * a * b * color coordinate system of CIE1976 is a value measured by a method described in Examples described later.

＜＜a*及b*＞＞ 當使用組成物來形成厚度3.0μm的膜時，本發明的組成物的CIE1976的L*a*b*色彩坐標系統中之a*係-30～30為較佳，-20～20為更佳，-10～10為特佳。 當使用組成物來形成厚度3.0μm的膜時，本發明的組成物的CIE1976的L*a*b*色彩坐標系統中之b*係-35～30為較佳，-33～10為更佳，-30～0為特佳。<<< a * and b * >> When the composition is used to form a film with a thickness of 3.0 μm, the a * system in the L * a * b * color coordinate system of CIE1976 of the composition of the present invention is -30 to 30. Good, -20 to 20 is more preferred, and -10 to 10 is particularly preferred. When the composition is used to form a film having a thickness of 3.0 μm, the b * system in the L * a * b * color coordinate system of CIE1976 of the composition of the present invention is preferably -35 to 30, and more preferably -33 to 10 , -30 to 0 is particularly preferred.

＜＜固體成分沉降率＞＞ 本發明的組成物在室溫（25℃）下以3500rpm（每分鐘轉速：revolutions per minute）的條件離心分離47分鐘時之組成物的固體成分沉降率係10質量%以下為較佳，5質量%以下為更佳。作為降低組成物的固體成分沉降率之方法，可以舉出提高組成物的黏度之方法、降低組成物的固體成分濃度之方法、提高組成物中之固體成分（粒子為較佳）的分散性之方法、降低粒子的密度之方法、減小粒子的粒徑之方法等。只要沒有特別指定，則“固體成分”係指後述之“離心處理前的固體成分”。固體成分沉降率係將後述之“離心處理後的固體成分”與“離心處理前的固體成分”之差除以“離心處理前的固體成分”之值乘以100之百分率。<<< Solid content sedimentation rate> The composition of the present invention has a solid content sedimentation rate of 10 masses when the composition is centrifuged at 3500 rpm (revolutions per minute) for 47 minutes at room temperature (25 ° C). % Or less is preferable, and 5 mass% or less is more preferable. Examples of the method for reducing the solid content sedimentation rate of the composition include a method for increasing the viscosity of the composition, a method for reducing the solid content concentration of the composition, and a method for increasing the dispersibility of the solid content (preferably particles) in the composition. Method, method for reducing particle density, method for reducing particle size, and the like. Unless otherwise specified, "solid content" refers to "solid content before centrifugation" described later. The solid content sedimentation rate is a value obtained by multiplying the difference between the "solid content after centrifugation" and "solid content before centrifugation" described below by "the solid content before centrifugation" and multiplying by 100%.

＜＜固體成分濃度＞＞ 組成物的固體成分濃度係20～75質量%為較佳。上限係60質量%以下為更佳。下限係30質量%以上為更佳。藉由將組成物的固體成分濃度設在上述範圍，能夠提高組成物的黏度來有效地抑制粒子的沉降等，並能夠改良組成物的溶液經時穩定性。<<< Solid Content Concentration> The solid content concentration of the composition is preferably 20 to 75% by mass. The upper limit is more preferably 60% by mass or less. The lower limit is more preferably 30% by mass or more. By setting the solid content concentration of the composition in the above range, the viscosity of the composition can be increased to effectively suppress the sedimentation of particles, etc., and the stability of the solution of the composition over time can be improved.

＜組成物的組成＞ 以下，對組成物的組成進行詳細說明。<Composition of composition> Hereinafter, the composition of a composition is demonstrated in detail.

＜＜無機粒子＞＞ 本發明的組成物含有無機粒子，無機粒子含有中空無機粒子、中實無機粒子及多孔質無機粒子中的至少1種，無機粒子中所含之無機物對波長589nm的光之折射率為1.65以上。<< Inorganic particles >> The composition of the present invention contains inorganic particles, and the inorganic particles contain at least one of hollow inorganic particles, solid inorganic particles, and porous inorganic particles. The inorganic substances contained in the inorganic particles are related to light having a wavelength of 589 nm. The refractive index is 1.65 or more.

（平均粒徑） 從容易將形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*控制為35～75之觀點考慮，無機粒子的平均粒徑係100～1000nm為較佳。(Average particle diameter) From the viewpoint that it is easy to control L * in the L * a * b * color coordinate system of CIE1976 when the thickness of the film is 3.0 μm is 35 to 75, the average particle diameter of the inorganic particles is 100 to 1000 nm Is better.

無機粒子的平均粒徑係100～800nm為更佳，150～600nm為特佳。無機粒子在藉由透射型電子顯微鏡（TEM）拍攝而得到之圖像（以下，亦稱為“TEM圖像”。）中為圓狀粒子為較佳。無機粒子亦可以是具有長軸和短軸之粒子，而不是嚴密的圓狀粒子。具有長軸和短軸之粒子在TEM圖像中係棒狀粒子或橢圓狀粒子為較佳。本說明書中，“粒子的長軸”係指從粒子的TEM圖像觀測之粒子的最長的直徑。“粒子的短軸”係指從粒子的TEM圖像觀測之粒子的最短的直徑。關於粒子的長軸，例如能夠將平均長軸長度設為50～150nm，關於粒子的短軸，例如能夠將平均短軸長設為5～50nm。 本發明的組成物以30～60質量%的比例含有具有100～1000nm的平均粒徑之無機粒子為較佳，以35～50質量%的比例含有具有100～1000nm的平均粒徑之無機粒子為更佳。若具有100～1000nm的平均粒徑之無機粒子為30質量%以上，則容易將形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*控制為35～75，且容易提供溶液經時穩定性優異之組成物。The average particle diameter of the inorganic particles is more preferably 100 to 800 nm, and particularly preferably 150 to 600 nm. It is preferable that the inorganic particles are round particles in an image (hereinafter, also referred to as a "TEM image") obtained by photographing with a transmission electron microscope (TEM). The inorganic particles may also be particles having a long axis and a short axis, instead of strictly round particles. It is preferable that the particles having a long axis and a short axis are rod-like particles or oval-shaped particles in a TEM image. In this specification, the "major axis of a particle" means the longest diameter of a particle observed from a TEM image of the particle. The "minor axis of a particle" refers to the shortest diameter of a particle observed from a TEM image of the particle. The major axis of the particles can be, for example, an average major axis length of 50 to 150 nm, and the minor axis of the particles can be, for example, an average minor axis length of 5 to 50 nm. The composition of the present invention preferably contains inorganic particles having an average particle diameter of 100 to 1000 nm in a proportion of 30 to 60% by mass, and contains inorganic particles having an average particle diameter of 100 to 1000nm in a proportion of 35 to 50% by mass as Better. If the inorganic particles having an average particle diameter of 100 to 1000 nm are 30% by mass or more, it is easy to control L * in the L * a * b * color coordinate system of CIE1976 when forming a film having a thickness of 3.0 μm to 35 to 75, In addition, it is easy to provide a composition having excellent solution stability over time.

利用以下方法求出含有中空無機粒子、中實無機粒子及多孔質無機粒子中的至少1種之無機粒子的粒徑。 無機粒子的粒徑能够藉由利用透射型電子顯微鏡觀察粉體無機粒子並觀測無機粒子未凝聚之部分而求出。關於無機粒子的粒度分佈，使用透射型電子顯微鏡拍攝作為一次粒子的集合體之中空無機粒子、中實無機粒子或多孔質無機粒子之後，根據使用圖像處理裝置而得到之圖像測定粒度分佈。本發明中，關於中空無機粒子、中實無機粒子或多孔質無機粒子的平均粒徑，依據由粒度分佈計算出之個數基準的算術平均直徑而設為平均粒徑。關於粒度分佈，能夠使用Hitachi, Ltd.製電子顯微鏡（H-7000）作為透射型電子顯微鏡，並使用NIRECO CORPORATION製Luzex AP作為圖像處理裝置進行測定。The particle size of the inorganic particles containing at least one of hollow inorganic particles, solid inorganic particles, and porous inorganic particles was determined by the following method. The particle diameter of the inorganic particles can be determined by observing the powdery inorganic particles with a transmission electron microscope and observing the non-agglomerated portions of the inorganic particles. Regarding the particle size distribution of the inorganic particles, the transmission type electron microscope was used to photograph the hollow inorganic particles, solid inorganic particles, or porous inorganic particles as a collection of primary particles, and then the particle size distribution was measured based on an image obtained using an image processing device. In the present invention, the average particle diameter of the hollow inorganic particles, solid inorganic particles, or porous inorganic particles is set as the average particle diameter based on the arithmetic average diameter of the number basis calculated from the particle size distribution. The particle size distribution can be measured using an electron microscope (H-7000) manufactured by Hitachi, Ltd. as a transmission electron microscope and using Luzex AP manufactured by NIRECO CORPORATION as an image processing device.

（真比重） 無機粒子的真比重係1.0～6.0g/cm3 為較佳。下限係2.5g/cm3 以上為更佳，3.0g/cm3 以上為進一步較佳。上限係4.5g/cm3 以下為更佳。無機粒子的真比重越小於較佳範圍的上限值，在組成物中越不易產生粒子的沉降，能夠更有效地改善溶液經時穩定性、圖案形狀及缺陷。並且，真比重為2.5g/cm3 以上（較佳為3.0g/cm3 以上）的無機粒子在無機粒子總量中之比例係5質量%以上為較佳，10質量%以上為更佳。上限既能夠設為100質量%，亦能夠設為99質量%以下。(True Specific Gravity) The true specific gravity of the inorganic particles is preferably 1.0 to 6.0 g / cm 3 . The lower limit is more preferably 2.5 g / cm 3 or more, and more preferably 3.0 g / cm 3 or more. The upper limit is more preferably 4.5 g / cm 3 or less. The smaller the true specific gravity of the inorganic particles is, the lower the upper limit of the preferred range, the less likely it is that the particles will settle in the composition, and the solution's stability over time, pattern shape, and defects can be more effectively improved. In addition, the ratio of the inorganic particles having a true specific gravity of 2.5 g / cm 3 or more (preferably 3.0 g / cm 3 or more) to the total inorganic particles is preferably 5 mass% or more, and more preferably 10 mass% or more. The upper limit can be set to 100% by mass or 99% by mass or less.

（折射率） 本發明中，無機粒子中所含之無機物對波長589nm的光之折射率為1.65以上。 無機粒子中所含之無機物對波長589nm的光之折射率係1.8以上為較佳，1.8～2.8為更佳，1.90～2.80為特佳，2.10～2.75為更特佳，2.50～2.75為最佳。若無機粒子中所含之無機物對波長589nm的光之折射率為1.65以上，則能夠加大形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*，因此較佳。 無機粒子中所含之無機物的折射率能夠藉由以下的測定粒子的折射率之方法求出。 首先，使用已知折射率之分散劑和PGMEA，使粒子（無機粒子）分散而製作分散液。然後,將所製作出之分散液和已知折射率之樹脂以粒子在固體成分中的濃度成為10質量%、20質量%、30質量%、40質量%之方式混合，從而製作4種塗佈液。將該等塗佈液於Si晶片上以300nm製膜之後，使用橢圓偏光計（Lambda Ace RE-3300（商品名），Dainippon Screen Mfg. Co.,Ltd.）測定所得到之膜的折射率。然後，繪製粒子濃度和折射率並進行外插而導出粒子的折射率。 無機粒子中所含之無機物的折射率係藉由以下方法從組成物、膜或硬化膜中取出無機粒子之後利用上述方法進行測定。 當對從膜或硬化膜中取出之無機粒子中所含之無機物測定折射率時，作為從膜中取出無機粒子之方法，例如在膜或硬化膜（若為組成物，則進行塗佈而製成膜）上加入膜或硬化膜的10～30質量%的2～6mol/L的鹼性溶液，加熱回流12小時之後，進行過濾及清洗，藉此得到無機粒子成分。 並且，利用日本特開2001-233611號公報的＜0033＞～＜0034＞中所揭示之方法亦能夠進行測定。該公報的內容被併入本說明書中。(Refractive index) In the present invention, the refractive index of an inorganic substance contained in the inorganic particles with respect to light having a wavelength of 589 nm is 1.65 or more. The refractive index of the inorganic substance contained in the inorganic particles to light having a wavelength of 589 nm is preferably 1.8 or more, 1.8 to 2.8 is more preferred, 1.90 to 2.80 is particularly preferred, 2.10 to 2.75 is more particularly preferred, and 2.50 to 2.75 is most preferred . If the refractive index of an inorganic substance contained in the inorganic particles with respect to light having a wavelength of 589 nm is 1.65 or more, the L * a * b * color coordinate system of CIE1976 when forming a film having a thickness of 3.0 μm can be increased. good. The refractive index of the inorganic substance contained in the inorganic particles can be determined by the following method of measuring the refractive index of the particles. First, particles (inorganic particles) are dispersed using a dispersant and PGMEA with a known refractive index to prepare a dispersion. Then, the prepared dispersion liquid and a resin having a known refractive index were mixed so that the particle concentration in the solid content became 10% by mass, 20% by mass, 30% by mass, and 40% by mass, thereby preparing four kinds of coatings. liquid. After these coating solutions were formed on a Si wafer at 300 nm, the refractive index of the obtained film was measured using an ellipsometer (Lambda Ace RE-3300 (trade name), Dainippon Screen Mfg. Co., Ltd.). Then, the particle concentration and the refractive index are plotted and extrapolated to derive the refractive index of the particle. The refractive index of an inorganic substance contained in the inorganic particles is measured by the above method after the inorganic particles are taken out of the composition, film, or cured film by the following method. When measuring the refractive index of an inorganic substance contained in the inorganic particles taken out of the film or cured film, as a method of taking the inorganic particles out of the film, for example, the film or the cured film (if it is a composition, it is prepared by coating) A film or a hardened film is added with a 10-30% by mass 2-6 mol / L alkaline solution to the film, and the mixture is heated and refluxed for 12 hours, and then filtered and washed to obtain an inorganic particle component. In addition, measurement can also be performed using the methods disclosed in <0033> to <0034> of Japanese Patent Laid-Open No. 2001-233611. The contents of this bulletin are incorporated into this specification.

（種類） 無機粒子只要含有中空無機粒子、中實無機粒子及多孔質無機粒子中的至少1種，則並沒有特別限制。 作為無機粒子，可以舉出先前公知的各種無機粒子。與有機粒子相比，無機粒子中密度較大者較多，密度越大的粒子，在組成物中越不易產生沉降。含有中空無機粒子、中實無機粒子及多孔質無機粒子中的至少1種之無機粒子由於能夠抑制沉降，因此能夠提供溶液經時穩定性優異之組成物。 無機粒子係含有金屬之粒子為較佳。本發明的組成物係無機粒子含有金屬單體或金屬氧化物為更佳。(Type) The inorganic particles are not particularly limited as long as they contain at least one of hollow inorganic particles, solid inorganic particles, and porous inorganic particles. Examples of the inorganic particles include various conventionally known inorganic particles. Compared with organic particles, inorganic particles have a higher density, and particles with a higher density are less likely to cause sedimentation in the composition. The inorganic particles containing at least one of hollow inorganic particles, solid inorganic particles, and porous inorganic particles can suppress sedimentation, and thus can provide a composition having excellent stability over time of the solution. The inorganic particles are preferably particles containing a metal. The composition-based inorganic particles of the present invention preferably contain a metal monomer or a metal oxide.

作為無機粒子，可以舉出顏料、陶瓷材料、磁性體材料及其他粒子等，顏料為較佳。Examples of the inorganic particles include pigments, ceramic materials, magnetic materials, and other particles. Pigments are preferred.

無機粒子係白色顏料為較佳。藉由使用白色顏料作為無機粒子，使用組成物形成厚度3.0μm的膜時，容易將CIE1976的L*a*b*色彩坐標系統中之L*控制為較佳範圍。本發明中，白色顏料不僅包含純白色，還包含接近白色之亮灰色（例如灰白色、淡灰色等）顏料等。 白色顏料具有密度較大的傾向，在組成物中容易產生沉降。依本發明，若使用中空無機粒子、中實無機粒子或多孔質無機粒子的白色顏料，則能夠抑制白色顏料的沉降而提供溶液經時穩定性優異之組成物。 白色顏料例如可以舉出氧化鈦、鈦酸锶、鈦酸鋇、氧化鈰、氧化鋅、氧化鎂、氧化鋯、氧化鋁、硫酸鋇、二氧化矽、滑石、雲母、氫氧化鋁、矽酸鈣、矽酸鋁、硫化鋅等。白色顏料係具有鈦原子之粒子為較佳，氧化鈦為更佳。亦即，無機粒子含有氧化鈦為較佳。An inorganic particle-based white pigment is preferred. By using a white pigment as the inorganic particles and using the composition to form a film having a thickness of 3.0 μm, it is easy to control L * in the L * a * b * color coordinate system of CIE1976 to a preferable range. In the present invention, white pigments include not only pure white, but also bright gray (eg, off-white, light gray, etc.) pigments that are close to white. White pigments tend to have a high density, and sedimentation easily occurs in the composition. According to the present invention, if a white pigment of a hollow inorganic particle, a solid inorganic particle, or a porous inorganic particle is used, it is possible to provide a composition having excellent solution stability over time by suppressing the sedimentation of the white pigment. Examples of the white pigment include titanium oxide, strontium titanate, barium titanate, cerium oxide, zinc oxide, magnesium oxide, zirconia, aluminum oxide, barium sulfate, silicon dioxide, talc, mica, aluminum hydroxide, and calcium silicate , Aluminum silicate, zinc sulfide, etc. White pigments are more preferably particles having titanium atoms, and more preferably titanium oxide. That is, it is preferable that the inorganic particles contain titanium oxide.

無機粒子亦可以使用除白色顏料以外的無機粒子。作為除白色顏料以外的無機粒子的例子，可以舉出金剛石、氮化硼、氮化鋁、氧化鑭、氮化鈦等。As the inorganic particles, inorganic particles other than white pigments can also be used. Examples of the inorganic particles other than the white pigment include diamond, boron nitride, aluminum nitride, lanthanum oxide, and titanium nitride.

關於氧化鈦，二氧化鈦（TiO2 ）的純度係70%以上為較佳，80%以上為更佳，85%以上為進一步較佳。關於氧化鈦，Tin O2n-1 （n表示2～4的數。）所表示之低次氧化鈦、氮氧化鈦等的含量係30質量%以下為較佳，20質量%以下為更佳，15質量%以下為進一步較佳。Regarding titanium oxide, the purity of titanium dioxide (TiO 2 ) is preferably 70% or more, more preferably 80% or more, and more preferably 85% or more. Regarding titanium oxide, the content of low-order titanium oxide, titanium oxynitride, and the like represented by Ti n O 2n-1 (n represents a number of 2 to 4) is preferably 30% by mass or less, and more preferably 20% by mass or less. 15 mass% or less is more preferred.

氧化鈦既可以是金紅石型氧化鈦，亦可以是銳鈦礦型氧化鈦，但從著色性、溶液經時穩定性的觀點考慮，金紅石型氧化鈦為較佳。亦可以焼成銳鈦礦型氧化鈦而轉化為金紅石型。尤其將使用了金紅石型氧化鈦之組成物進行硬化而得到之硬化膜，即使加熱硬化膜，色差變化亦較少，具有良好的著色性。並且，氧化鈦的金紅石化率係95%以上為較佳，99%以上為更佳。 作為金紅石型氧化鈦，可以使用公知者。金紅石型氧化鈦的製造方法有硫酸法和氯化法這2種，本發明中，藉由任何一種製造方法製造者均可以較佳地進行使用。其中，硫酸法係指如下製造方法：將鈦鐵礦礦石或鈦渣作為原料，將其溶解於濃硫酸中，將鐵成分作為硫酸鐵而分離，並對溶液進行水解，藉此得到氫氧化物的沉澱物，將其在高溫下燒成而取出金紅石型氧化鈦。另一方面，氯化法係指如下製造方法：將合成金紅石或天然金紅石作為原料，將其在約1000℃的高溫下與氯氣和碳進行反應而合成四氯化鈦，並將其氧化而取出金紅石型氧化鈦。金紅石型氧化鈦係利用氯化法得到之金紅石型氧化鈦為較佳。The titanium oxide may be either a rutile-type titanium oxide or an anatase-type titanium oxide, but from the viewpoints of colorability and solution stability over time, a rutile-type titanium oxide is preferred. It can also be converted into anatase titanium oxide and converted into rutile. In particular, a cured film obtained by hardening a composition using rutile-type titanium oxide has less color variation even if it is cured by heating, and has good coloring properties. In addition, the rutile ratio of titanium oxide is preferably 95% or more, and more preferably 99% or more. As the rutile titanium oxide, a known one can be used. There are two methods for producing rutile titanium oxide, such as a sulfuric acid method and a chlorination method. In the present invention, a manufacturer can use either method by a suitable method. Here, the sulfuric acid method refers to a manufacturing method in which ilmenite ore or titanium slag is used as a raw material, which is dissolved in concentrated sulfuric acid, an iron component is separated as iron sulfate, and a solution is hydrolyzed to obtain a hydroxide. The rutile-type titanium oxide was taken out by firing the precipitate at a high temperature. On the other hand, the chlorination method refers to a production method in which synthetic rutile or natural rutile is used as a raw material, which is reacted with chlorine gas and carbon at a high temperature of about 1000 ° C. to synthesize titanium tetrachloride and oxidize The rutile titanium oxide was taken out. Rutile titanium oxide is preferably a rutile titanium oxide obtained by a chlorination method.

平均粒徑100～1000nm的氧化鈦粒子能夠將光散射而使光呈現白色，當使用組成物形成厚度3.0μm的膜時，容易將CIE1976的L*a*b*色彩坐標系統中之L*控制為35～75。氧化鈦粒子的平均粒徑的較佳範圍與無機粒子的平均粒徑的較佳範圍相同。Titanium oxide particles with an average particle diameter of 100 to 1000 nm can scatter light and make the light appear white. When the composition is used to form a 3.0 μm film, it is easy to control L * in the L * a * b * color coordinate system of CIE1976 It is 35 to 75. The preferable range of the average particle diameter of a titanium oxide particle is the same as the preferable range of the average particle diameter of an inorganic particle.

氧化鈦的pH（酸鹼度（power of hydrogen））係6～8為較佳。 氧化鈦的吸油量（g/100g）係10～60（g/100g）為較佳，10～40（g/100g）為更佳。 氧化鈦中，Fe2 O3 、Al2 O3 、SiO2 、Nb2 O5 、Na2 O的合計量係0.1質量%以下為較佳，0.05質量%以下為更佳，0.02質量%以下為進一步較佳，實質上不含該等為特佳。 對氧化鈦的形狀並沒有特別限制。例如可以舉出各向同性形狀（例如球狀、多面體狀等）、各向異性形狀（例如針狀、棒狀、板狀等）、不規則形狀等形狀。 氧化鈦的硬度（莫氏硬度）係5～8為較佳，7～7.5為更佳。 氧化鈦的真比重（密度）係1.0～6.0g/cm3 為較佳，3.9～4.5g/cm3 為更佳。 氧化鈦的體比重係0.1g/cm3 ～1.0g/cm3 為較佳。The pH (power of hydrogen) of titanium oxide is preferably 6 to 8. The oil absorption (g / 100g) of titanium oxide is preferably 10 to 60 (g / 100g), and more preferably 10 to 40 (g / 100g). Among titanium oxides, the total amount of Fe 2 O 3 , Al 2 O 3 , SiO 2 , Nb 2 O 5 , and Na 2 O is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and 0.02% by mass or less. It is further preferable, and it is particularly preferable not to substantially contain these. There is no particular limitation on the shape of the titanium oxide. Examples include shapes such as isotropic shapes (eg, spherical, polyhedral, etc.), anisotropic shapes (eg, needle-like, rod-like, plate-like, etc.), and irregular shapes. The hardness (Mohs hardness) of titanium oxide is preferably 5 to 8, and more preferably 7 to 7.5. The true specific gravity (density) of titanium oxide is preferably 1.0 to 6.0 g / cm 3, and more preferably 3.9 to 4.5 g / cm 3 . The bulk specific gravity of titanium oxide is preferably from 0.1 g / cm 3 to 1.0 g / cm 3 .

氧化鈦等無機粒子可以係藉由有機化合物等表面處理劑進行表面處理而得到者。表面處理中所使用之表面處理劑的例子可以舉出多元醇、氧化鋁、氫氧化鋁、二氧化矽（氧化矽）、含水二氧化矽、烷醇胺、硬脂酸、有機矽氧烷、氧化鋯、氫化二甲基矽油（hydrogen dimethicone）、矽烷偶合劑、鈦酸酯偶合劑等。其中，矽烷偶合劑為較佳。並且，氧化鈦等無機粒子利用選自包括Al（鋁）、Si（矽）、Zr及有機物之組群中之任意1個以上的表面處理劑進行處理而得到者為較佳，利用Al、Si及有機物的表面處理劑進行處理而得到者更佳，利用選自包括Al化合物及有機物之組群中之任意1個表面處理劑進行處理而得到者為特佳。由於氧化鈦等無機粒子的表面將被塗佈，因此能夠抑制氧化鈦等無機粒子的光催化活性，耐光性得到提高。表面處理既可以利用單獨1種表面處理劑來實施，亦可以將2種以上的表面處理劑組合來實施。並且，氧化鈦等無機粒子的表面由氧化鋁、二氧化矽、氧化鋯等氧化物塗覆亦較佳。藉此，耐光性及分散性得到進一步提高。Inorganic particles such as titanium oxide can be obtained by surface treatment with a surface treatment agent such as an organic compound. Examples of the surface treatment agent used in the surface treatment include polyhydric alcohol, alumina, aluminum hydroxide, silicon dioxide (silica), hydrous silicon dioxide, alkanolamine, stearic acid, organosiloxane, Zirconia, hydrogen dimethicone, silane coupling agent, titanate coupling agent, etc. Among them, a silane coupling agent is preferred. In addition, inorganic particles such as titanium oxide are preferably obtained by treating with any one or more surface treatment agents selected from the group consisting of Al (aluminum), Si (silicon), Zr, and organic matter. Al, Si are preferably used. It is more preferable to obtain the organic surface treatment agent, and it is particularly preferable to obtain the surface treatment agent selected from the group consisting of an Al compound and an organic material. Since the surface of the inorganic particles such as titanium oxide is coated, the photocatalytic activity of the inorganic particles such as titanium oxide can be suppressed, and the light resistance is improved. The surface treatment may be performed using a single surface treatment agent alone, or may be performed in combination of two or more surface treatment agents. It is also preferable that the surface of the inorganic particles such as titanium oxide is coated with an oxide such as alumina, silica, or zirconia. Thereby, light resistance and dispersibility are further improved.

氧化鈦等無機粒子由鹼性金屬氧化物或鹼性金屬氫氧化物塗覆亦較佳。作為鹼性金屬氧化物或鹼性金屬氫氧化物，可以舉出含有鎂、鋯、鈰、锶、銻、鋇或鈣等之金屬化合物。It is also preferable that inorganic particles such as titanium oxide are coated with an alkali metal oxide or an alkali metal hydroxide. Examples of the alkaline metal oxide or alkaline metal hydroxide include metal compounds containing magnesium, zirconium, cerium, strontium, antimony, barium, or calcium.

由鹼性金屬氧化物或鹼性金屬氫氧化物塗覆之無機粒子例如能夠以如下方式得到。 在水或以水為主成分之溶液中分散無機粒子而得到漿液。根據需要，藉由砂磨機或球磨機等粉碎無機粒子。接著，將漿液的pH設為中性或鹼性、根據情況設為酸性。然後，將成為塗覆材料的原料的水溶性鹽添加到漿液中來塗覆無機粒子的表面。然後，中和漿液，並回收無機粒子。所回收之無機粒子可以乾燥或乾式粉碎。The inorganic particles coated with an alkali metal oxide or an alkali metal hydroxide can be obtained, for example, as follows. Inorganic particles are dispersed in water or a solution containing water as a main component to obtain a slurry. If necessary, the inorganic particles are pulverized by a sand mill or a ball mill. Next, the pH of the slurry is set to be neutral or alkaline, and to be acidic as appropriate. Then, a water-soluble salt that becomes a raw material of the coating material is added to the slurry to coat the surface of the inorganic particles. Then, the slurry is neutralized, and inorganic particles are recovered. The recovered inorganic particles can be dried or dry-pulverized.

氧化鈦等無機粒子具有酸性部位，且利用能夠與酸性部位反應之化合物進行表面處理為較佳。作為能夠與無機顏料的酸性部位反應之化合物，可以舉出三羥甲基丙烷、三羥甲基乙烷、雙-三羥甲基丙烷、乙氧基化三羥甲基丙烷或季戊四醇等多元醇、單乙醇胺、單丙醇胺、二乙醇胺、二丙醇胺、三乙醇胺或三丙醇胺等烷醇胺、氯矽烷或烷氧基矽烷等。 作為使無機粒子和能夠與無機粒子的酸性部位反應的化合物進行反應之方法，可以舉出（1）向流體能量粉碎機或衝擊粉碎機等乾式粉碎機中投入上述化合物和無機粒子並粉碎無機顏料之方法、（2）使用亨舍爾混合機或高速混合機等高速攪拌機攪拌上述化合物和經乾式粉碎之無機粒子並進行混合之方法、（3）向無機粒子的水性漿液中添加上述化合物並進行攪拌之方法等。Inorganic particles such as titanium oxide have acidic sites, and it is preferable to perform surface treatment with a compound capable of reacting with the acidic sites. Examples of compounds capable of reacting with acidic sites of inorganic pigments include polyhydric alcohols such as trimethylolpropane, trimethylolethane, bis-trimethylolpropane, ethoxylated trimethylolpropane, and pentaerythritol. , Alkanolamines such as monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, triethanolamine or tripropanolamine, chlorosilanes or alkoxysilanes. Examples of a method for reacting inorganic particles with a compound capable of reacting with an acidic part of the inorganic particles include (1) putting the above compound and inorganic particles into a dry pulverizer such as a fluid energy pulverizer or an impact pulverizer to pulverize the inorganic pigment Method, (2) using a high-speed stirrer such as a Henschel mixer or a high-speed mixer to stir and mix the above-mentioned compound and dry-pulverized inorganic particles, and (3) adding the above compound to an aqueous slurry of inorganic particles and performing Method of stirring, etc.

本發明的組成物中，無機粒子含有中空無機粒子、中實無機粒子及多孔質無機粒子中的至少1種。 本發明中，從塗佈適應性、缺陷、著色性的觀點考慮，無機粒子含有中空無機粒子或多孔質無機粒子為較佳。 無機粒子不僅可以使用僅包括單一無機物之者，亦可以使用與其他材料複合之粒子。例如，可以舉出內部具有空孔之中空無機粒子、內部具有其他材料之中實無機粒子、芯粒子上附著有複數個無機粒子之中實無機粒子、由包括聚合物粒子之芯粒子和包括無機奈米粒子之殼層構成之芯-殼複合粒子。 以下，對中空無機粒子、中實無機粒子及多孔質無機粒子的較佳態樣進行說明。In the composition of the present invention, the inorganic particles include at least one of hollow inorganic particles, solid inorganic particles, and porous inorganic particles. In the present invention, it is preferable that the inorganic particles contain hollow inorganic particles or porous inorganic particles from the viewpoints of coating adaptability, defects, and colorability. As the inorganic particles, not only a single inorganic substance can be used, but also particles compounded with other materials can be used. Examples include hollow inorganic particles with pores inside, solid inorganic particles with other materials inside, solid inorganic particles with a plurality of inorganic particles attached to the core particles, core particles including polymer particles, and inorganic particles including inorganic particles. Core-shell composite particles composed of a shell of nano particles. Hereinafter, the preferable aspect of a hollow inorganic particle, a solid inorganic particle, and a porous inorganic particle is demonstrated.

-中空無機粒子- 作為中空無機粒子並沒有特別限制。中空無機粒子既可以是一次粒子，亦可以是二次粒子。中空無機粒子係二次粒子為較佳。 作為中空無機粒子，可以舉出具有單一的中空部之單孔中空粒子、具有複數個中空部之多孔中空粒子。中空無機粒子係單孔中空粒子為較佳。 中空無機粒子的中空部的直徑並沒有特別限制。中空無機粒子的中空部的直徑係5～900nm為較佳，20～800nm為更佳，50～500nm為特佳。-Hollow inorganic particles- The hollow inorganic particles are not particularly limited. The hollow inorganic particles may be either primary particles or secondary particles. Hollow inorganic particle-based secondary particles are preferred. Examples of the hollow inorganic particles include single-hollow hollow particles having a single hollow portion, and porous hollow particles having a plurality of hollow portions. Hollow inorganic particles are preferably single-hole hollow particles. The diameter of the hollow portion of the hollow inorganic particles is not particularly limited. The diameter of the hollow portion of the hollow inorganic particles is preferably 5 to 900 nm, more preferably 20 to 800 nm, and particularly preferably 50 to 500 nm.

作為中空無機粒子的材料，亦即包圍中空無機粒子的中空部之材料，除了無機粒子中所含之無機物對波長589nm的光之折射率為1.65以上以外，並沒有特別限定，可以使用各種各樣的無機物。作為中空無機粒子的材料，可以舉出硫化鋅、硫酸鋇、碳酸鉛、氧化鉛、氧化銻、鈦酸鉀、鈦酸鋇、氧化鋅、氧化鋯、氧化鈰、氧化鑭及氧化鈦等。中空無機粒子的材料係氧化鈦為較佳。The material of the hollow inorganic particles, that is, the material that surrounds the hollow portion of the hollow inorganic particles, is not particularly limited except that the refractive index of the inorganic substance contained in the inorganic particles with respect to light having a wavelength of 589 nm is 1.65 or more. Of inorganic matter. Examples of the material of the hollow inorganic particles include zinc sulfide, barium sulfate, lead carbonate, lead oxide, antimony oxide, potassium titanate, barium titanate, zinc oxide, zirconia, cerium oxide, lanthanum oxide, and titanium oxide. The material of the hollow inorganic particles is preferably titanium oxide.

中空無機粒子的平均粒徑（較佳為平均二次粒徑）係100～1000nm為較佳，150～600nm為更佳，200～500nm為特佳。The average particle diameter (preferably the average secondary particle diameter) of the hollow inorganic particles is preferably 100 to 1000 nm, more preferably 150 to 600 nm, and particularly preferably 200 to 500 nm.

中空無機粒子的孔隙率係5～90體積%為較佳，10～80體積%為更佳，30～70體積%為特佳。 孔隙率係將中空無機粒子的整體體積設為100體積%時之中空無機粒子的中空部的總體積%。孔隙率能夠藉由使用中空無機粒子的折射率和由中空無機粒子的材料計算出之折射率的理論值進行計算而求出。另外，中空無機粒子的孔隙率例如亦能夠藉由切斷含有中空無機粒子之組成物的硬化物，觀察在切剖面上出現之複數個中空無機粒子和複數個中空無機粒子的中空部的形狀及大小，並計算中空無機粒子的總體積和中空無機粒子的中空部的總體積而求出。The porosity of the hollow inorganic particles is preferably 5 to 90% by volume, more preferably 10 to 80% by volume, and particularly preferably 30 to 70% by volume. The porosity is the total volume% of the hollow portion of the hollow inorganic particles when the entire volume of the hollow inorganic particles is 100% by volume. The porosity can be calculated by using the refractive index of the hollow inorganic particles and the theoretical value of the refractive index calculated from the material of the hollow inorganic particles. In addition, the porosity of the hollow inorganic particles can also be observed by cutting the hardened material of the composition containing the hollow inorganic particles, and observing the shape and the shape of the hollow portion of the plurality of hollow inorganic particles and the plurality of hollow inorganic particles appearing on the cut section. The size is calculated by calculating the total volume of the hollow inorganic particles and the total volume of the hollow portion of the hollow inorganic particles.

作為製備中空無機粒子之方法並沒有特別限制。 製備中空無機粒子之方法係溶劑熱法（solvothermal method）為較佳。中空無機粒子例如能夠藉由使用後述的多孔質無機粒子的製備方法中之溶劑熱法，將加熱至成為超臨界流體之溫度時之升溫速度控制為後述的範圍而進行合成。There is no particular limitation as a method for preparing the hollow inorganic particles. The method for preparing the hollow inorganic particles is preferably a solvothermal method. The hollow inorganic particles can be synthesized by, for example, using a solvothermal method in a method for producing a porous inorganic particle described later, and controlling the temperature increase rate when heated to a temperature at which the supercritical fluid is heated, to a range described later.

作為中空無機粒子，可以參閱日本特開2015-164881號公報的＜0013＞～＜0120＞的記載。該等公報的內容被併入本說明書中。As the hollow inorganic particles, reference can be made to the descriptions of <0013> to <0120> in Japanese Patent Application Laid-Open No. 2015-164881. The contents of these bulletins are incorporated into this specification.

-中實無機粒子- 作為中實無機粒子並沒有特別限制。中實無機粒子既可以是一次粒子，亦可以是二次粒子。中實無機粒子係二次粒子為較佳。 關於中實無機粒子，芯既可以是有機物，亦可以是無機物，從減小密度之觀點考慮，有機物為較佳。 作為中實無機粒子，例如可以舉出在芯中具有與殼層不同之無機粒子之中實無機粒子、在芯粒子上附著有複數個無機粒子之中實無機粒子、包括構成芯之聚合物粒子和構成殼層之無機粒子之芯-殼層的複合粒子。其中，芯-殼層的複合粒子、在芯粒子上附著有複數個無機粒子之中實無機粒子為較佳。-Solid inorganic particles- There are no particular restrictions on the solid inorganic particles. The solid inorganic particles can be either primary particles or secondary particles. Medium solid inorganic particle-based secondary particles are preferred. Regarding the solid inorganic particles, the core may be either an organic substance or an inorganic substance. From the viewpoint of reducing the density, an organic substance is preferred. Examples of the solid inorganic particles include solid inorganic particles having inorganic particles different from the shell in the core, solid inorganic particles having a plurality of inorganic particles attached to the core particles, and polymer particles including the core. And the core-shell composite particles of the inorganic particles constituting the shell. Among them, composite particles of a core-shell layer and solid inorganic particles in which a plurality of inorganic particles are attached to the core particles are preferred.

作為構成芯之聚合物粒子，平均粒徑1～500μm的聚合物粒子為較佳，平均粒徑3～300μm的聚合物粒子為更佳。 聚合物粒子係使含有交聯或非交聯的苯乙烯系、丙烯酸系、甲基丙烯酸系聚合物及該等的衍生物中的1種以上之單體進行聚合而得到之聚合物粒子為較佳。 並且，作為構成芯之聚合物粒子的另一較佳態樣，平均粒徑1～900nm的聚合物粒子為較佳，10～500nm的聚合物粒子為進一步較佳。As the polymer particles constituting the core, polymer particles having an average particle diameter of 1 to 500 μm are preferable, and polymer particles having an average particle diameter of 3 to 300 μm are more preferable. Polymer particles are polymer particles obtained by polymerizing one or more monomers including styrene-based, acrylic-based, methacrylic-based polymers, and derivatives thereof which are crosslinked or non-crosslinked. good. In addition, as another preferable aspect of the polymer particles constituting the core, polymer particles having an average particle diameter of 1 to 900 nm are preferable, and polymer particles of 10 to 500 nm are more preferable.

作為構成殼層之無機粒子，小於聚合物粒子為較佳，具有聚合物粒子的平均粒徑的1/5～1/100,000的平均粒徑為更佳。例如，能夠使用具有0.01～10μm的平均粒徑之無機粒子，較佳地，可使用具有0.02～2μm的平均粒徑之無機粒子。 作為無機粒子，例如能夠使用金剛石、氧化鈰（Ceria）、氧化鈦（Titania）、氮化硼、氮化鋁、二氧化鋯（Zilconia）。在該等之中，氧化鈰及氧化鈦為較佳，氧化鈦為更佳。The inorganic particles constituting the shell layer are preferably smaller than the polymer particles, and more preferably have an average particle diameter of 1/5 to 1 / 100,000 of the average particle diameter of the polymer particles. For example, inorganic particles having an average particle diameter of 0.01 to 10 μm can be used, and preferably, inorganic particles having an average particle diameter of 0.02 to 2 μm can be used. As the inorganic particles, for example, diamond, cerium oxide (Ceria), titanium oxide (Titania), boron nitride, aluminum nitride, and zirconia can be used. Among these, cerium oxide and titanium oxide are preferable, and titanium oxide is more preferable.

作為芯與殼層的組合，能夠任意組合上述聚合物粒子和無機粒子。As the combination of the core and the shell layer, the polymer particles and inorganic particles described above can be arbitrarily combined.

殼層的厚度能夠藉由調節液體或超臨界狀態的二氧化碳的溫度及壓力、無機奈米粒子的添加量而改變。殼層的厚度能夠藉由利用電子顯微鏡直接觀察中實無機粒子的剖面之方法、在加熱爐中使聚合物粒子燃燒並測定殘留物（無機粒子）的質量之方法等進行評價。The thickness of the shell layer can be changed by adjusting the temperature and pressure of carbon dioxide in liquid or supercritical state, and the amount of inorganic nano-particles added. The thickness of the shell layer can be evaluated by a method of directly observing the cross section of the solid inorganic particles with an electron microscope, a method of burning polymer particles in a heating furnace, and measuring the quality of the residue (inorganic particles).

中實無機粒子中之芯與殼層的折射率差係0.1～2.0為較佳，0.5～1.6為更佳，0.8～1.4為特佳。The difference in refractive index between the core and the shell in the solid inorganic particles is preferably 0.1 to 2.0, more preferably 0.5 to 1.6, and particularly preferably 0.8 to 1.4.

作為製備中實無機粒子之方法並沒有特別限制。 中實無機粒子係藉由溶劑熱法製造之粒子為較佳。例如，使構成芯之聚合物粒子和構成殼層之無機粒子與液體或超臨界狀態的二氧化碳接触而使聚合物粒子的表面軟化為較佳。在該製程中，不使用有機溶劑為較佳。該製程例如在耐壓容器內，在液體或超臨界狀態的二氧化碳存在之既定壓力（5～50MPa）及溫度（10～200℃）下進行為較佳。 在經軟化之聚合物表面固定無機奈米粒子而進行複合化之後，將溫度恢復至室溫為較佳。 接著，將壓力恢復至大氣壓，藉此除去二氧化碳而得到中實無機粒子為較佳。There is no particular limitation as a method for preparing solid inorganic particles. The solid inorganic particles are preferably particles produced by a solvothermal method. For example, it is preferable that the polymer particles constituting the core and the inorganic particles constituting the shell layer are brought into contact with liquid or supercritical carbon dioxide to soften the surface of the polymer particles. In this process, it is preferable not to use an organic solvent. This process is preferably performed, for example, in a pressure-resistant container under a predetermined pressure (5-50 MPa) and temperature (10-200 ° C) in the presence of liquid or supercritical carbon dioxide. After the inorganic nano particles are fixed on the surface of the softened polymer for recombination, the temperature is preferably returned to room temperature. Next, it is preferable to return the pressure to atmospheric pressure to remove carbon dioxide and obtain solid inorganic particles.

作為將構成芯之聚合物粒子和構成殼層之無機粒子進行複合化時之氣氛，在液體或超臨界狀態的二氧化碳中為較佳。用於維持液體狀態的二氧化碳之條件為三相點（-56.6℃、0.52MPa）以上的壓力與溫度的組合，在臨界點（31.1℃、7.4MPa）以上的壓力和溫度下，二氧化碳成為超臨界狀態。維持為溫度10～200℃且壓力5～50MPa的範圍為較佳。溫度20～50℃及壓力20～35MPa的組合為更佳。藉由利用液體或超臨界狀態的二氧化碳，將芯粒子表面藉由膨潤和/或加熱而進行可塑化，從而使芯粒子表面軟化為較佳。經軟化之芯粒子表面上容易附著無機粒子，進而藉由除去液體或超臨界狀態的二氧化碳，無機粒子固定於聚合物粒子的表面而形成殼層，從而容易成為中實無機粒子。The atmosphere when the polymer particles constituting the core and the inorganic particles constituting the shell layer are compounded is preferably carbon dioxide in a liquid or supercritical state. The conditions for maintaining carbon dioxide in a liquid state are a combination of pressure and temperature above the triple point (-56.6 ° C, 0.52MPa). At pressures and temperatures above the critical point (31.1 ° C, 7.4MPa), carbon dioxide becomes supercritical. status. It is preferable to maintain the temperature in the range of 10 to 200 ° C and the pressure in the range of 5 to 50 MPa. A combination of a temperature of 20 to 50 ° C and a pressure of 20 to 35 MPa is more preferred. By using liquid or supercritical carbon dioxide, the surface of the core particles is plasticized by swelling and / or heating, so that the surface of the core particles is preferably softened. It is easy to attach inorganic particles on the surface of the softened core particles, and then by removing carbon dioxide in a liquid or supercritical state, the inorganic particles are fixed on the surface of the polymer particles to form a shell layer, and thus easily become solid inorganic particles.

形成中實無機粒子之後，將溫度降低至室溫並停止攪拌，緩慢開放耐壓容器的排氣閥，將容器內的液體二氧化碳作為氣體緩慢從耐壓容器中排出為較佳。除去二氧化碳之後，打開耐壓容器，能夠取出中實無機粒子。After the solid inorganic particles are formed, it is preferable to lower the temperature to room temperature and stop stirring, slowly open the exhaust valve of the pressure-resistant container, and slowly discharge the liquid carbon dioxide in the container from the pressure-resistant container as a gas. After the carbon dioxide is removed, the pressure-resistant container is opened, and the solid inorganic particles can be taken out.

作為芯-殼層的複合粒子之中實無機粒子，例如可以參閱日本特開2015-47520號公報的0012～0042段的記載，其內容被併入本說明書中。As the solid-inorganic particles among the core-shell composite particles, for example, the descriptions in paragraphs 0012 to 0041 of Japanese Patent Application Laid-Open No. 2015-47520 can be referred to, and the contents are incorporated into this specification.

-多孔質無機粒子- 作為多孔質無機粒子並沒有特別限制。 多孔質無機粒子既可以是一次粒子，亦可以是二次粒子。多孔質無機粒子係形成有複數個一次粒子間的纏結而形成高次網絡從而成為密度高的二次粒子為較佳。並且，多孔質無機粒子係一次粒子間的纏結較少且孔隙較多的多孔質化之粒子為較佳。 “多孔質無機粒子”係在粒子表面具有能夠藉由使用了掃描型電子顯微鏡（SEM）之觀察而判別之孔徑10nm以上的細孔之多孔質無機粒子為較佳。並且，多孔質無機粒子具有複數個2nm以上且100nm以下的細孔為較佳，具有複數個10nm以上且50nm以下的細孔為更佳。 多孔質無機粒子的平均粒徑係50nm以上且1μm以下為較佳。藉由將多孔質無機粒子的平均粒徑設為該範圍，容易將CIE1976的L*a*b*色彩坐標系統中之L*設為較高。 為了顯示優異之穩定性、單分散性、較高的聚光特性、易再利用性等優異之特性，多孔質無機粒子係球狀為較佳。-Porous inorganic particles- The porous inorganic particles are not particularly limited. The porous inorganic particles may be primary particles or secondary particles. The porous inorganic particle system is preferably formed by entanglement between a plurality of primary particles to form a higher-order network and to form secondary particles with high density. In addition, porous inorganic particles are preferably porous particles having fewer entanglements between primary particles and having more pores. The "porous inorganic particle" is preferably a porous inorganic particle having a pore with a pore diameter of 10 nm or more that can be discriminated by observation using a scanning electron microscope (SEM) on the particle surface. The porous inorganic particles preferably have a plurality of pores of 2 nm to 100 nm, and more preferably a plurality of pores of 10 nm to 50 nm. The average particle diameter of the porous inorganic particles is preferably 50 nm or more and 1 μm or less. By setting the average particle diameter of the porous inorganic particles to this range, it is easy to set L * in the L * a * b * color coordinate system of CIE1976 to be high. In order to exhibit excellent characteristics such as excellent stability, monodispersity, high light-concentrating characteristics, and easy recyclability, the porous inorganic particles are preferably spherical.

在表面具有複數個細孔之粒子具有比表面積亦較大之傾向。藉此，粒子的比表面積可以說是表示粒子的多孔質化程度之一個指標，認為比表面積較高的粒子，係更為多孔質的粒子。更為多孔質的粒子由於粒子比重更小，因此能夠進一步抑制粒子的沉降。Particles having a plurality of pores on the surface tend to have a larger specific surface area. Accordingly, the specific surface area of the particles can be said to be an index indicating the degree of porosity of the particles, and the particles having a higher specific surface area are considered to be more porous particles. More porous particles have a smaller specific gravity of the particles, and thus can further suppress sedimentation of the particles.

作為多孔質無機粒子的材料，可以舉出硫化鋅、硫酸鋇、碳酸鉛、氧化鉛、氧化銻、鈦酸鉀、鈦酸鋇、氧化鋅、氧化鋯、氧化鈰及氧化鈦等。中空無機粒子的材料係氧化鈦為較佳。Examples of the material of the porous inorganic particles include zinc sulfide, barium sulfate, lead carbonate, lead oxide, antimony oxide, potassium titanate, barium titanate, zinc oxide, zirconia, cerium oxide, and titanium oxide. The material of the hollow inorganic particles is preferably titanium oxide.

作為多孔質無機粒子的製備方法並沒有特別限制。 作為多孔質無機粒子的製備方法，有水熱法、溶膠-凝膠法、自組裝（自組織化）法、溶劑熱法等。 作為多孔質無機粒子的製備方法，可以舉出一種氧化鈦粒子的製造方法，其具有將選自包括鈦醇鹽及鈦氯化物之組群中之化合物A進行水解並使其縮聚之製程，且具有在鹼性催化劑、水及抑制化合物A中至少一個的水解或縮聚反應之化合物B的存在下進行化合物A的水解之製程。The method for producing the porous inorganic particles is not particularly limited. As a method for preparing porous inorganic particles, there are a hydrothermal method, a sol-gel method, a self-assembly (self-organization) method, and a solvothermal method. Examples of the method for producing porous inorganic particles include a method for producing titanium oxide particles, which has a process of hydrolyzing and polycondensing Compound A selected from the group consisting of titanium alkoxide and titanium chloride, and The invention has a process for performing the hydrolysis of the compound A in the presence of a basic catalyst, water, and a compound B that inhibits at least one of the hydrolysis or polycondensation reaction of the compound A.

作為多孔質無機粒子的製備方法，溶劑熱法為較佳。 溶劑熱法為在超臨界流體中進行之製備方法。 “超臨界流體”係指臨界點以上的溫度及壓力下之物質的狀態，被稱為無法區分氣體與液體之狀態，具有氣體的擴散性和液體的溶解性。作為超臨界流體，可以較佳地使用超臨界甲醇。As a method for preparing the porous inorganic particles, a solvothermal method is preferred. The solvothermal method is a preparation method performed in a supercritical fluid. "Supercritical fluid" refers to the state of a substance at a temperature and pressure above the critical point. It is called a state where gas and liquid cannot be distinguished, and it has gas diffusibility and liquid solubility. As the supercritical fluid, supercritical methanol can be preferably used.

在超臨界流體中進行之溶劑熱法係具備以下兩個製程為較佳。 （製程A）在作為超臨界流體之溶劑（較佳為甲醇）中添加無機粒子和羧酸（較佳為選自甲酸、乙酸、安息香酸及鄰苯二甲酸中之1種以上）而製備溶液之製程 （製程B）在成為超臨界流體之溫度下對上述製程A中製備出之溶液進行加熱之製程It is preferable that the solvothermal method performed in a supercritical fluid has the following two processes. (Process A) Adding inorganic particles and carboxylic acid (preferably one or more selected from formic acid, acetic acid, benzoic acid and phthalic acid) to a solvent (preferably methanol) as a supercritical fluid to prepare a solution Process (Process B) Process of heating the solution prepared in Process A above at a temperature that becomes a supercritical fluid

作為上述羧酸相對於溶劑（較佳為甲醇）之濃度，0.05～5.0mol/L為較佳。The concentration of the carboxylic acid with respect to the solvent (preferably methanol) is preferably 0.05 to 5.0 mol / L.

藉由在超臨界流體中使無機粒子和上述羧酸進行反應，能夠在一次粒子彼此不分離之狀態下生成球狀的多孔質無機粒子。By reacting the inorganic particles and the carboxylic acid in a supercritical fluid, spherical porous inorganic particles can be produced without the primary particles being separated from each other.

反應溫度係200℃以上為較佳，300～400℃為更佳。當反應溫度為200℃以上時，藉由一次粒徑變大而孔徑變大，從而容易形成多孔質無機粒子。The reaction temperature is preferably 200 ° C or higher, and more preferably 300 to 400 ° C. When the reaction temperature is 200 ° C. or higher, the primary particle diameter becomes larger and the pore diameter becomes larger, thereby easily forming porous inorganic particles.

根據加熱至成為超臨界流體之溫度時之升溫速度（加熱速度）的大小，亦即根據是進行急劇加熱（急加熱）還是進行緩慢加熱（慢加熱），能夠控制無機粒子的形狀。 在製程B中，緩慢進行加熱為較佳。具體而言，將該加熱速度設為20℃/分鐘以下為較佳，設為0.1～10℃/分鐘為更佳。藉由將加熱速度設為上述數值範圍，容易得到中空無機粒子。 另一方面，若加熱速度超過20℃/分鐘，則容易得到多孔質無機粒子，設為200～1000℃/分鐘為更佳。 作為控制無機粒子的形狀之方法，可以參閱E. K. C. Pradeep, T. Habu, H. Tooriyama, M. Ohtani, K. Kobiro, J. Supercrit. Fluids 2015, 97, 217-223的記載。The shape of the inorganic particles can be controlled by the rate of heating (heating rate) when heated to the temperature at which it becomes a supercritical fluid, that is, whether it is subjected to rapid heating (rapid heating) or slow heating (slow heating). In the process B, heating is preferably performed slowly. Specifically, the heating rate is preferably 20 ° C./minute or less, and more preferably 0.1 to 10 ° C./minute. By setting the heating rate to the above-mentioned numerical range, hollow inorganic particles can be easily obtained. On the other hand, if the heating rate exceeds 20 ° C / min, porous inorganic particles are easily obtained, and more preferably 200 to 1000 ° C / min. As a method for controlling the shape of the inorganic particles, reference may be made to the records of E. K. C. Pradeep, T. Habu, H. Tooriyama, M. Ohtani, K. Kobiro, J. Supercrit. Fluids 2015, 97, 217-223.

達到加熱溫度之後之加熱時間至少為1秒鐘以上為較佳，1～10分鐘為更佳。The heating time after reaching the heating temperature is preferably at least 1 second, and more preferably 1 to 10 minutes.

作為多孔質無機粒子，可以參閱日本特開2015-199637號公報的＜0016＞～＜0049＞、日本特開2015-164881號公報的＜0013＞～＜0120＞的記載。該等公報的內容被併入本說明書中。As porous inorganic particles, the descriptions of <0016> to <0049> of JP-A-2015-199637, and <0013> to <0120> of JP-A-2015-164881 can be referred to. The contents of these bulletins are incorporated into this specification.

-其他形狀的無機粒子- 組成物還可以含有除中空無機粒子、中實無機粒子或多孔質無機粒子以外的其他形狀的無機粒子。 作為其他形狀的無機粒子，可以舉出不是中空無機粒子、中實無機粒子或多孔質無機粒子中的任何一種之具有50～300nm的平均一次粒徑之粒子，較佳為具有50～150nm的平均一次粒徑之粒子及平均長軸長度為50～150nm的粒子。 作為用作其他形狀的無機粒子之粒子，可以舉出顏料、陶瓷材料、磁性體材料及其他粒子等，顏料為較佳。-Inorganic Particles of Other Shapes-The composition may further include inorganic particles of other shapes than hollow inorganic particles, solid inorganic particles, or porous inorganic particles. Examples of the inorganic particles having other shapes include particles having an average primary particle diameter of 50 to 300 nm, which are not any of hollow inorganic particles, solid inorganic particles, or porous inorganic particles, and preferably have an average of 50 to 150 nm. Particles of primary particle size and particles having an average major axis length of 50 to 150 nm. Examples of particles used as inorganic particles of other shapes include pigments, ceramic materials, magnetic materials, and other particles. Pigments are preferred.

本發明的組成物中，其他形狀的無機粒子係白色顏料為較佳。藉由使用白色顏料作為其他形狀的無機粒子，當使用組成物形成厚度3.0μm的膜時，容易將CIE1976的L*a*b*色彩坐標系統中之L*控制在較佳範圍。本發明中，白色顏料不僅包含純白色，還包含接近白色之亮灰色（例如灰白色、淡灰色等）顏料等。 白色顏料具有密度較大的傾向，在組成物中容易產生沉降。若使用平均一次粒徑50～150nm的粒子及平均長軸長度為50～150nm的粒子中的至少一方作為其他形狀的無機粒子，則即使在使用白色顏料作為其他形狀的無機粒子的情況下，亦容易抑制白色顏料的沉降而提供溶液經時穩定性優異之組成物。 用作其他形狀的無機粒子之白色顏料例如可以舉出氧化鈦、鈦酸锶、鈦酸鋇、氧化鋅、氧化鎂、氧化鋯、氧化鋁、硫酸鋇、二氧化矽、滑石、雲母、氫氧化鋁、矽酸鈣、矽酸鋁、中空樹脂粒子、硫化鋅等。用作其他形狀的無機粒子之白色顏料係具有鈦原子之粒子為較佳，氧化鈦為更佳。In the composition of the present invention, an inorganic particle-based white pigment having another shape is preferred. By using white pigments as inorganic particles of other shapes, it is easy to control L * in the L * a * b * color coordinate system of CIE1976 in a better range when using the composition to form a film with a thickness of 3.0 μm. In the present invention, white pigments include not only pure white, but also bright gray (eg, off-white, light gray, etc.) pigments that are close to white. White pigments tend to have a high density, and sedimentation easily occurs in the composition. If at least one of particles having an average primary particle diameter of 50 to 150 nm and particles having an average major axis length of 50 to 150 nm is used as the inorganic particles of other shapes, even when a white pigment is used as the inorganic particles of other shapes, It is easy to suppress sedimentation of a white pigment and to provide a composition excellent in solution stability over time. Examples of white pigments used as inorganic particles of other shapes include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconia, aluminum oxide, barium sulfate, silicon dioxide, talc, mica, and hydroxide Aluminum, calcium silicate, aluminum silicate, hollow resin particles, zinc sulfide, etc. White pigments used as inorganic particles of other shapes are particles having titanium atoms, and titanium oxide is more preferable.

關於用作其他形狀的無機粒子之氧化鈦，二氧化鈦（TiO2 ）的純度係70%以上為較佳，80%以上為更佳，85%以上為進一步較佳。關於用作其他形狀的無機粒子之氧化鈦，Tin O2n-1 （n表示2～4的數。）所表示之低次氧化鈦、氧氮化鈦等的含量係30質量%以下為較佳，20質量%以下為更佳，15質量%以下為進一步較佳。Regarding titanium oxide used as inorganic particles of other shapes, the purity of titanium dioxide (TiO 2 ) is preferably 70% or more, more preferably 80% or more, and more preferably 85% or more. Regarding titanium oxide used as inorganic particles of other shapes, the content of low-order titanium oxide, titanium oxynitride, etc. represented by Ti n O 2n-1 (n represents a number of 2 to 4) is more than 30% by mass. 20% by mass or less is more preferable, and 15% by mass or less is more preferable.

用作其他形狀的無機粒子之氧化鈦既可以是金紅石型氧化鈦，亦可以是銳鈦礦型氧化鈦，從著色性、溶液經時穩定性的觀點考慮，金紅石型氧化鈦為較佳。尤其，將使用了金紅石型氧化鈦之組成物進行硬化而得到之硬化膜，即使加熱硬化膜，色差變化亦較少，具有良好的著色性。並且，氧化鈦的金紅石化率係95%以上為較佳，99%以上為更佳。 作為用作其他形狀的無機粒子之金紅石型氧化鈦，能夠使用公知者。用作其他形狀的無機粒子之金紅石型氧化鈦的製造方法有硫酸法和氯化法這2種，本發明中，藉由任何一種製造方法製造者均可以較佳地進行使用。其中，硫酸法係指如下製造方法：將鈦鐵礦礦石或鈦渣作為原料，將其溶解於濃硫酸中，將鐵成分以硫酸鐵形式分離，並對溶液進行水解，藉此得到氫氧化物的沉澱物，將其在高溫下燒成而取出金紅石型氧化鈦。另一方面，氯化法係指如下製造方法：將合成金紅石或天然金紅石作為原料，將其在約1000℃的高溫下與氯氣和碳進行反應而合成四氯化鈦，並將其氧化而取出金紅石型氧化鈦。用作其他形狀的無機粒子之金紅石型氧化鈦係利用氯化法得到之金紅石型氧化鈦為較佳。Titanium oxide used as inorganic particles of other shapes may be rutile-type titanium oxide or anatase-type titanium oxide. From the viewpoint of colorability and solution stability over time, rutile-type titanium oxide is preferred. . In particular, a cured film obtained by curing a composition using rutile-type titanium oxide has a small change in color difference even when the film is cured by heating, and has good coloring properties. In addition, the rutile ratio of titanium oxide is preferably 95% or more, and more preferably 99% or more. As the rutile-type titanium oxide used as inorganic particles of other shapes, a known one can be used. There are two methods for producing rutile titanium oxide used as inorganic particles of other shapes, such as a sulfuric acid method and a chlorination method. In the present invention, any one of the production methods can be suitably used by the manufacturer. Among them, the sulfuric acid method refers to a production method in which ilmenite ore or titanium slag is used as a raw material, which is dissolved in concentrated sulfuric acid, the iron component is separated as iron sulfate, and the solution is hydrolyzed to obtain a hydroxide. The rutile-type titanium oxide was taken out by firing the precipitate at a high temperature. On the other hand, the chlorination method refers to a production method in which synthetic rutile or natural rutile is used as a raw material, which is reacted with chlorine gas and carbon at a high temperature of about 1000 ° C. to synthesize titanium tetrachloride and oxidize The rutile titanium oxide was taken out. Rutile titanium oxide used as inorganic particles of other shapes is preferably rutile titanium oxide obtained by a chlorination method.

用作其他形狀的無機粒子之平均一次粒徑50～300nm的粒子、較佳為50～150nm的氧化鈦粒子及平均長軸長度為50～150nm的氧化鈦粒子能夠將光散射而使光呈現白色，當使用組成物形成厚度3.0μm的膜時，容易將CIE1976的L*a*b*色彩坐標系統中之L*控制為35～75。 用作其他形狀的無機粒子之平均一次粒徑50～150nm的氧化鈦粒子係平均一次粒徑為50～150nm為較佳，平均一次粒徑為60～140nm為較佳，80～130nm為更佳。平均一次粒徑50～150nm的粒子在拍攝粒子之透射型電子顯微鏡的照片中係圓狀粒子為較佳。平均一次粒徑50～150nm的粒子亦可以是具有前述長軸和短軸之粒子而不是嚴密的圓狀粒子。 用作其他形狀的無機粒子之平均長軸長度為50～150nm的粒子係平均長軸長度為60～140nm為較佳，80～130nm為更佳。 用作其他形狀的無機粒子之平均長軸長度為50～150nm的粒子係具有長軸和短軸之粒子為較佳。 用作其他形狀的無機粒子之平均長軸長度為50～150nm的粒子係平均短軸長為5～50nm為較佳，10～30nm為更佳，10～20nm為特佳。用作其他形狀的無機粒子之平均長軸長度為50～150nm的粒子係平均長軸長度為平均短軸長度的2～10倍為較佳，3～6倍為更佳，4～5倍為特佳。Particles having an average primary particle size of 50 to 300 nm, inorganic particles of other shapes, preferably titanium oxide particles of 50 to 150 nm, and titanium oxide particles having an average major axis length of 50 to 150 nm can scatter light and make the light appear white When the composition is used to form a film having a thickness of 3.0 μm, it is easy to control L * in the L * a * b * color coordinate system of CIE1976 to be 35 to 75. Titanium oxide particles having an average primary particle diameter of 50 to 150 nm used as inorganic particles of other shapes are preferably an average primary particle diameter of 50 to 150 nm, an average primary particle diameter of 60 to 140 nm is preferable, and 80 to 130 nm is more preferable. . The particles having an average primary particle diameter of 50 to 150 nm are preferably round particles in a transmission electron microscope photograph of the particles. The particles having an average primary particle diameter of 50 to 150 nm may be particles having the aforementioned long axis and short axis, instead of strictly round particles. A particle system having an average major axis length of 50 to 150 nm for inorganic particles having other shapes is preferably an average major axis length of 60 to 140 nm, and more preferably 80 to 130 nm. Particles having an average major axis length of 50 to 150 nm, which are used as inorganic particles of other shapes, are particles having a major axis and a minor axis. A particle system having an average major axis length of 50 to 150 nm for other shapes of inorganic particles is preferably an average minor axis length of 5 to 50 nm, more preferably 10 to 30 nm, and particularly preferably 10 to 20 nm. For particles of other shapes, the average major axis length of the particle system is 50 to 150 nm. The average major axis length is preferably 2 to 10 times the average minor axis length, more preferably 3 to 6 times, and 4 to 5 times. Extraordinary.

用作其他形狀的無機粒子之平均一次粒徑50～300nm的粒子、較佳為50～150nm的粒子及平均長軸長度為50～150nm的粒子對波長589nm的光之折射率係1.75～2.80為較佳，1.90～2.80為更佳，2.10～2.75為進一步較佳，2.50～2.75為特佳。若平均一次粒徑50～150nm的粒子及平均長軸長度為50～150nm的粒子對波長589nm的光之折射率為2.1以上，則能夠加大形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*，因此較佳。The refractive index of particles having an average primary particle diameter of 50 to 300 nm, particles having an average primary diameter of 50 to 150 nm, and particles having an average major axis length of 50 to 150 nm for light having a wavelength of 589 nm is 1.75 to 2.80 for other shapes of inorganic particles. Preferably, 1.90 to 2.80 are more preferred, 2.10 to 2.75 are further preferred, and 2.50 to 2.75 are particularly preferred. If the refractive index of particles having an average primary particle diameter of 50 to 150 nm and particles having an average major axis length of 50 to 150 nm for light having a wavelength of 589 nm is 2.1 or more, the L * a of CIE1976 when forming a film having a thickness of 3.0 μm can be increased. * b * L * in color coordinate system, so it is better.

關於用作其他形狀的無機粒子之氧化鈦的比表面積，藉由BET（Brunauer，Emmett，Teller）法測定之值係10～400m2 /g為較佳，10～200m2 /g為更佳，10～150m2 /g為進一步較佳，10～40m2 /g為特佳，10～20m2 /g為最佳。 作為其他形狀的無機粒子之氧化鈦的pH（酸鹼度）係6～8為較佳。 用作其他形狀的無機粒子之氧化鈦的吸油量（g/100g）係10～60（g/100g）為較佳，10～40（g/100g）為更佳。 關於用作其他形狀的無機粒子之氧化鈦，Fe2 O3 、Al2 O3 、SiO2 、Nb2 O5 、Na2 O的合計量係0.1質量%以下為較佳，0.05質量%以下為更佳，0.02質量%以下為進一步較佳，實質上不含該等為特佳。 用作其他形狀的無機粒子之氧化鈦的形狀並沒有特別限制。例如，可以舉出各向同性形狀（例如球狀、多面體狀等）、各向異性形狀（例如針狀、棒狀、板狀等）、不規則形狀等形狀。 用作其他形狀的無機粒子之氧化鈦的硬度（莫氏硬度）係5～8為較佳，7～7.5為更佳。 用作其他形狀的無機粒子之氧化鈦的真比重（密度）係1.0～6.0g/cm3 為較佳，3.9～4.5g/cm3 為更佳。 用作其他形狀的無機粒子之氧化鈦的體比重係0.1g/cm3 ～1.0g/cm3 為較佳，0.2g/cm3 ～0.4g/cm3 為更佳。Regarding the specific surface area of titanium oxide used as inorganic particles of other shapes, the value measured by the BET (Brunauer, Emmett, Teller) method is preferably 10 to 400 m 2 / g, and more preferably 10 to 200 m 2 / g. 10 to 150 m 2 / g is more preferable, 10 to 40 m 2 / g is particularly preferable, and 10 to 20 m 2 / g is most preferable. The pH (pH) of titanium oxide as inorganic particles of other shapes is preferably 6 to 8. The oil absorption (g / 100g) of titanium oxide used as inorganic particles of other shapes is preferably 10 to 60 (g / 100g), and more preferably 10 to 40 (g / 100g). Regarding titanium oxide used as inorganic particles of other shapes, the total amount of Fe 2 O 3 , Al 2 O 3 , SiO 2 , Nb 2 O 5 , and Na 2 O is preferably 0.1% by mass or less, and 0.05% by mass or less. More preferably, it is more preferably 0.02% by mass or less, and it is particularly preferable not to substantially contain these. The shape of titanium oxide used as the inorganic particles of other shapes is not particularly limited. For example, shapes such as an isotropic shape (for example, a spherical shape, a polyhedron shape, etc.), an anisotropic shape (for example, a needle shape, a rod shape, a plate shape, etc.), and an irregular shape are mentioned. The hardness (Mohs hardness) of titanium oxide used as inorganic particles of other shapes is preferably 5 to 8, and more preferably 7 to 7.5. The true specific gravity (density) of titanium oxide used as inorganic particles of other shapes is preferably 1.0 to 6.0 g / cm 3, and more preferably 3.9 to 4.5 g / cm 3 . The specific gravity of titanium oxide used as inorganic particles of other shapes is preferably 0.1 g / cm 3 to 1.0 g / cm 3, and more preferably 0.2 g / cm 3 to 0.4 g / cm 3 .

其他形狀的無機粒子可以較佳地使用市售者。作為用作其他形狀的無機粒子之氧化鈦的市售品，例如可以舉出ISHIHARA SANGYO KAISHA,LTD.製的商品名Tipaque R-550、R-580、R-630、R-670、R-680、R-780、R-780-2、R-820、R-830、R-850、R-855、R-930、R-980、CR-50、CR-50-2、CR-57、CR-58、CR-58-2、CR-60、CR-60-2、CR-63、CR-67、CR-Super70、CR-80、CR-85、CR-90、CR-90-2、CR-93、CR-95、CR-953、CR-97、PF-736、PF-737、PF-742、PF-690、PF-691、PF-711、PF-739、PF-740、PC-3、S-305、CR-EL、PT-301、PT-401M、PT-401L、PT-501A、PT-501R、UT771、TTO-51C、TTO-80A、TTO-S-2、A-220、MPT-136、MPT-140、MPT-141； SAKAI CHEMICAL INDUSTRY CO.,LTD.製的商品名R-3L、R-5N、R-7E、R-11P、R-21、R-25、R-32、R-42、R-44、R-45M、R-62N、R-310、R-650、SR-1、D-918、GTR-100、FTR-700、TCR-52、A-110、A-190、SA-1、SA-1L、STR-100A-LP、STR-100C-LP、TCA-123E； TAYCA CORPORATION製的商品名JR、JRNC、JR-301、JR-403、JR-405、JR-600A、JR-600E、JR-603、JR-605、JR-701、JR-800、JR-805、JR-806、JR-1000、MT-01、MT-05、MT-10EX、MT-100S、MT-100TV、MT-100Z、MT-100AQ、MT-100WP、MT-100SA、MT-100HD、MT-150EX、MT-150W、MT-300HD、MT-500B、MT-500SA、MT-500HD、MT-600B、MT-600SA、MT-700B、MT-700BS、MT-700HD、MT-700Z； Titan Kogyo, Ltd.製的商品名KR-310、KR-380、KR-380N、ST-485SA15； FUJI TITANIUM INDUSTRY CO.,LTD.製的商品名TR-600、TR-700、TR-750、TR-840、TR-900； SHIRAISHI CALCIUM KAISHA, LTD.製的商品名Brilliant1500等。並且，亦可以使用日本特開2015-67794號公報的0025～0027段中所記載之氧化鈦。 作為鈦酸锶的市售品，可以舉出SW-100（Titan Kogyo, Ltd.製）等。作為硫酸鋇的市售品，可以舉出BF-1L（SAKAI CHEMICAL INDUSTRY CO.,LTD.製）等。作為氧化鋅的市售品，可以舉出Zincox Super F-1（Hakusuitech Co.,Ltd.製）等。作為氧化鋯的市售品，可以舉出Z-NX（TAIYO KOKO CO.,LTD.製）等。 亦可以將氧化鈦的市售品進行分級處理之後，作為其他形狀的無機粒子而用於本發明的組成物中。例如，可以較佳地使用CR-90-2的分級處理品或MPT-141的分級處理品。Commercially available inorganic particles of other shapes can be preferably used. Examples of commercially available products of titanium oxide used as inorganic particles of other shapes include, for example, trade names Tipaque R-550, R-580, R-630, R-670, and R-680 manufactured by ISHIHARA SANGYO KAISHA, LTD. , R-780, R-780-2, R-820, R-830, R-850, R-855, R-930, R-980, CR-50, CR-50-2, CR-57, CR -58, CR-58-2, CR-60, CR-60-2, CR-63, CR-67, CR-Super70, CR-80, CR-85, CR-90, CR-90-2, CR -93, CR-95, CR-953, CR-97, PF-736, PF-737, PF-742, PF-690, PF-691, PF-711, PF-739, PF-740, PC-3 , S-305, CR-EL, PT-301, PT-401M, PT-401L, PT-501A, PT-501R, UT771, TTO-51C, TTO-80A, TTO-S-2, A-220, MPT -136, MPT-140, MPT-141; trade names R-3L, R-5N, R-7E, R-11P, R-21, R-25, R-32 manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD. , R-42, R-44, R-45M, R-62N, R-310, R-650, SR-1, D-918, GTR-100, FTR-700, TCR-52, A-110, A -190, SA-1, SA-1L, STR-100A-LP, STR-100C-LP, TCA-123E; Trade names JR, JRNC, JR-301, JR-403, JR-405, JR manufactured by TAYCA CORPORATION -600A, JR-600E, JR-603, JR-605, JR-701, JR-80 0, JR-805, JR-806, JR-1000, MT-01, MT-05, MT-10EX, MT-100S, MT-100TV, MT-100Z, MT-100AQ, MT-100WP, MT-100SA, MT-100HD, MT-150EX, MT-150W, MT-300HD, MT-500B, MT-500SA, MT-500HD, MT-600B, MT-600SA, MT-700B, MT-700BS, MT-700HD, MT- 700Z; trade names KR-310, KR-380, KR-380N, ST-485SA15 manufactured by Titan Kogyo, Ltd .; trade names TR-600, TR-700, TR-750 manufactured by FUJI TITANIUM INDUSTRY CO., LTD. , TR-840, TR-900; SHIRAISHI CALCIUM KAISHA, LTD. Trade name Brilliant1500 and so on. In addition, titanium oxide described in paragraphs 0025 to 0027 of Japanese Patent Application Laid-Open No. 2015-67794 may be used. As a commercial item of strontium titanate, SW-100 (made by Titan Kogyo, Ltd.) etc. are mentioned. Examples of commercially available products of barium sulfate include BF-1L (manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD.). Examples of commercially available products of zinc oxide include Zincox Super F-1 (manufactured by Hakusuitech Co., Ltd.). Examples of commercially available products of zirconia include Z-NX (manufactured by TAIYO KOKO CO., LTD.). A commercially available product of titanium oxide may be used in the composition of the present invention as an inorganic particle having another shape after being classified. For example, a graded processed product of CR-90-2 or a graded processed product of MPT-141 can be preferably used.

（無機粒子的製備方法） 作為無機粒子的製備方法並沒有特別限制，能夠使用公知的方法。 本發明中，無機粒子係藉由溶劑熱法製造出之粒子為較佳。 溶劑熱法係作為製備中空無機粒子、中實無機粒子及多孔質無機粒子之方法的例子而記載之方法為較佳。(Manufacturing method of inorganic particles) The manufacturing method of an inorganic particle is not specifically limited, A well-known method can be used. In the present invention, the inorganic particles are preferably particles produced by a solvothermal method. The solvothermal method is preferably described as an example of a method for producing hollow inorganic particles, solid inorganic particles, and porous inorganic particles.

（含量） 無機粒子的含量相對於組成物的總固體成分，係1質量%以上為較佳，3質量%以上為更佳，5質量%以上為特佳，25質量%以上為更特佳，35質量%以上為最佳。作為上限並沒有特別限制，但相對於組成物的總固體成分，係75質量%以下為更佳，60質量%以下為進一步較佳，55質量%以下為最佳。本發明的組成物可以僅含有1種無機粒子，亦可以含有2種以上。當本發明的組成物含有2種以上無機粒子時，其合計量在上述範圍內為較佳。 並且，中空無機粒子、中實無機粒子及多孔質無機粒子中的至少1種在無機粒子中之比例係50質量%以上為較佳，80質量%以上為更佳。上限既能夠設為100質量%，亦能夠設為99質量%以下。 並且，白色顏料在無機粒子中之比例係50質量%以上為較佳，80質量%以上為更佳。上限既可以設為100質量%，亦可以設為99質量%以下。從白色度、透射率、微影特性、耐光性的觀點考慮，99質量%以下為較佳，95質量%以下為進一步較佳。 並且，氧化鈦在無機粒子中之比例係50質量%以上為較佳，80質量%以上為更佳。上限既可以設為100質量%，亦可以設為99質量%以下。從白色度、透射率、微影特性、耐光性的觀點考慮，99質量%以下為較佳，95質量%以下為進一步較佳。 並且，真比重為1.0～6.0g/cm3 的粒子在無機粒子中之比例係50質量%以上為較佳，80質量%以上為更佳。上限既可以設為100質量%，亦可以設為99質量%以下。從白色度、透射率、微影特性、耐光性的觀點考慮，99質量%以下為較佳，95質量%以下為進一步較佳。(Content) The content of the inorganic particles is preferably 1% by mass or more, more preferably 3% by mass or more, particularly preferably 5% by mass or more, and more preferably 25% by mass or more. 35 mass% or more is the best. The upper limit is not particularly limited, but it is more preferably 75% by mass or less, more preferably 60% by mass or less, and most preferably 55% by mass or less with respect to the total solid content of the composition. The composition of the present invention may contain only one kind of inorganic particles, or may contain two or more kinds. When the composition of the present invention contains two or more kinds of inorganic particles, the total amount thereof is preferably within the above range. In addition, the proportion of at least one of the hollow inorganic particles, solid inorganic particles, and porous inorganic particles in the inorganic particles is preferably 50% by mass or more, and more preferably 80% by mass or more. The upper limit can be set to 100% by mass or 99% by mass or less. The proportion of the white pigment in the inorganic particles is preferably 50% by mass or more, and more preferably 80% by mass or more. The upper limit may be 100% by mass or 99% by mass or less. From the viewpoints of whiteness, transmittance, lithographic characteristics, and light resistance, 99% by mass or less is preferable, and 95% by mass or less is more preferable. The proportion of titanium oxide in the inorganic particles is preferably 50% by mass or more, and more preferably 80% by mass or more. The upper limit may be 100% by mass or 99% by mass or less. From the viewpoints of whiteness, transmittance, lithographic characteristics, and light resistance, 99% by mass or less is preferable, and 95% by mass or less is more preferable. In addition, the proportion of particles having a true specific gravity of 1.0 to 6.0 g / cm 3 in the inorganic particles is preferably 50% by mass or more, and more preferably 80% by mass or more. The upper limit may be 100% by mass or 99% by mass or less. From the viewpoints of whiteness, transmittance, lithographic characteristics, and light resistance, 99% by mass or less is preferable, and 95% by mass or less is more preferable.

＜＜其他著色劑＞＞ 組成物還可以含有除無機粒子以外的其他著色劑。藉由含有其他著色劑，當使用組成物形成厚度3.0μm的膜時，容易將CIE1976的L*a*b*色彩坐標系統中之a*及b*控制為較佳範圍。作為其他著色劑，可以舉出彩色著色劑或黑色著色劑等。<< Other coloring agents >> The composition may contain other coloring agents other than inorganic particles. By containing other colorants, when the composition is used to form a film having a thickness of 3.0 μm, it is easy to control a * and b * in the L * a * b * color coordinate system of CIE1976 to a preferable range. Examples of the other coloring agents include a coloring agent and a black coloring agent.

（彩色著色劑） 組成物能夠含有彩色著色劑。本發明中，彩色著色劑係指除白色著色劑（包括白色顏料）及黑色著色劑以外的著色劑。 藉由含有彩色著色劑，例如能夠使由經時、加熱等引起之組成物的色調（CIE1976的L*a*b*色彩坐標系統中之L*、a*及b*）的目視評價的變動穩定。 彩色著色劑係在波長400nm以上且小於650nm的範圍具有極大吸收之著色劑為較佳。(Color colorant) The composition can contain a colorant. In the present invention, a coloring agent refers to a coloring agent other than a white coloring agent (including a white pigment) and a black coloring agent. By containing a coloring agent, for example, it is possible to change the visual evaluation of the hue (L *, a *, and b * in the L * a * b * color coordinate system of CIE1976) caused by aging, heating, and the like stable. The coloring agent is preferably a coloring agent having a great absorption in a wavelength range of 400 nm or more and less than 650 nm.

彩色著色劑既可以是彩色顏料，亦可以是染料。Color colorants can be either color pigments or dyes.

彩色顏料係有機顏料為較佳。作為有機顏料並沒有特別限定，能夠使用公知的彩色顏料。作為有機顏料，例如可以舉出以下者。但是，本發明並不限定於該等。 比色指數（C.I.）顏料黃（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等（以上為黄色顏料）； C.I.顏料橙（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等（以上為橙色顏料）； C.I.顏料紅（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等（以上為紅色顏料）； C.I.顏料綠（Pigment Green）7、10、36、37、58、59等（以上為綠色顏料）； C.I.顏料紫（Pigment Violet）1、19、23、27、32、37、42等（以上為紫色顏料）； C.I.顏料藍（Pigment Blue）1、2、15、15：1、15：2、15：3、15：4、15：6、16、22、60、64、66、79、80等（以上為藍色顏料）， 有機顏料可以單獨使用或者將2種以上組合使用。Color pigment-based organic pigments are preferred. The organic pigment is not particularly limited, and a known color pigment can be used. Examples of the organic pigment include the following. However, the present invention is not limited to these. Color index (CI) Pigment Yellow (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. (the above are yellow pigments); 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. (the above are orange pigments) ; CI Pigment Red (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. (the above are red Pigments); CI Pigment Green (Pigment Green) 7, 10, 36, 37, 58, 59, etc. (the above are green pigments); CI Pigment Violet (Pigment Violet) 1, 19, 23, 27, 32, 37, 42, etc. (The above is a purple pigment); CI Pigment Blue (Pigment Blue) 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc. (the above are blue pigments), organic pigments can be used alone or in combination of two or more.

作為染料並沒有特別限制，可以使用公知的染料。作為化學結構，可以使用吡唑偶氮系、苯胺基偶氮系、三苯基甲烷系、蒽醌系、蒽吡啶酮（Anthrapyridone）系、苯亞甲基系、氧雜菁（oxonol）系、吡唑并三唑偶氮系、吡啶酮偶氮系、花青系、噻吩嗪系、吡咯并吡唑次甲基偶氮（pyrrolo pyrazol azomethine）系、呫噸（xanthene）系、酞菁系、苯并吡喃系、靛藍系、吡咯甲川（pyrromethene）系等染料。並且，亦可以使用該等染料的多聚體。並且，亦可以使用日本特開2015-028144號公報、日本特開2015-34966號公報中所記載之染料。 並且，染料可以較佳地使用酸性染料及其衍生物。此外，亦可以有效地使用直接染料、鹼性染料、媒染染料、酸性媒染染料、冰染染料、分散染料、油溶染料、食品染料及該等的衍生物等。以下舉出酸性染料的具體例，但並不限定於該等。例如，可以舉出以下染料及該等染料的衍生物。The dye is not particularly limited, and a known dye can be used. As the chemical structure, a pyrazole azo system, an aniline azo system, a triphenylmethane system, an anthraquinone system, an anthrapyridone system, a benzylidene system, an oxonol system, Pyrazolotriazole azo, pyridone azo, cyanine, thiophenazine, pyrrolo pyrazol azomethine, xanthene, phthalocyanine, Dyes such as benzopyran, indigo, and pyrromethene. Furthermore, multimers of these dyes can also be used. In addition, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used. Further, as the dye, an acid dye and a derivative thereof can be preferably used. In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, ice dyes, disperse dyes, oil-soluble dyes, food dyes, and derivatives thereof can also be effectively used. Specific examples of the acid dye are given below, but are not limited thereto. For example, the following dyes and derivatives of these dyes are mentioned.

酸性茜素紫（Acid Alizarin violet）N； 酸性藍（Acid Blue）1、7、9、15、18、23、25、27、29、40～45、62、70、74、80、83、86、87、90、92、103、112、113、120、129、138、147、158、171、182、192、243、324:1； 酸性鉻紫（Acid Chrome violet）K； 酸性品紅（Acid Fuchsin）； 酸性綠（acid green）1、3、5、9、16、25、27、50； 酸性橙（Acid Orange）6、7、8、10、12、50、51、52、56、63、74、95； 酸性紅（Acid Red）1、4、8、14、17、18、26、27、29、31、34、35、37、42、44、50、51、52、57、66、73、80、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、183、198、211、215、216、217、249、252、257、260、266、274； 酸性紫（Acid Violet）6B、7、9、17、19； 酸性黃（Acid Yellow）1、3、7、9、11、17、23、25、29、34、36、42、54、72、73、76、79、98、99、111、112、114、116、184、243； 食品黃（Food Yellow）3。Acid Alizarin violet N; Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40 to 45, 62, 70, 74, 80, 83, 86 , 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; Acid Chrome violet K; Acid Magenta Fuchsin); acid green 1, 3, 5, 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63 , 74, 95; Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66 , 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215 , 216, 217, 249, 252, 257, 260, 266, 274; Acid Violet 6B, 7, 9, 17, 19; Acid Yellow 1, 3, 7, 9, 11, 17 , 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; Food yellow Yellow) 3.

並且，上述以外的偶氮系、呫噸系、酞菁系酸性染料亦較佳，還可以較佳地使用C.I.溶劑藍（Solvent Blue）44、38；C.I.溶劑橙（Solvent orange）45；玫瑰紅（Rhodamine）B、玫瑰紅110等酸性染料及該等染料的衍生物。In addition, azo-based, xanthene-based, and phthalocyanine-based acid dyes other than the above are also preferable. CI Solvent Blue 44 and 38, CI Solvent orange 45, and rose red can also be preferably used. (Rhodamine) B, rose red 110 and other acid dyes and derivatives of these dyes.

當本發明的組成物含有彩色著色劑時，彩色著色劑的含量在本發明的組成物的總固體成分中設為0.1～70質量%為較佳。下限係0.5質量%以上為更佳，1.0質量%以上為特佳。上限係60質量%以下為更佳，50質量%以下為特佳。當本發明的組成物含有2種以上彩色著色劑時，其合計量在上述範圍內為較佳。When the composition of the present invention contains a coloring agent, the content of the coloring agent is preferably 0.1 to 70% by mass in the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and particularly preferably 1.0% by mass or more. The upper limit is more preferably 60% by mass or less, and particularly preferably 50% by mass or less. When the composition of the present invention contains two or more kinds of coloring agents, the total amount thereof is preferably within the above range.

（黑色著色劑） 組成物能夠含有黑色著色劑。作為黑色著色劑，既可以是無機系黑色著色劑，亦可以是有機系黑色著色劑。(Black colorant) The composition can contain a black colorant. The black colorant may be an inorganic black colorant or an organic black colorant.

作為有機系黑色著色劑，例如可以舉出二苯并呋喃酮化合物、次甲基偶氮化合物、苝化合物、偶氮系化合物等，二苯并呋喃酮化合物、苝化合物為較佳。作為二苯并呋喃酮化合物，可以舉出日本特表2010-534726號公報、日本特表2012-515233號公報、日本特表2012-515234號公報等中所記載者，例如可以作為BASF公司製的“Irgaphor Black”而獲得。作為苝化合物，可以舉出C.I.顏料黑（Pigment Black）31、32等。作為次甲基偶氮化合物，可以舉出日本特開平1-170601號公報、日本特開平2-34664號公報等中所記載者，例如可以作為Dainichiseika公司製的“Chromofine Black A1103”而獲得。Examples of the organic black colorant include a dibenzofuranone compound, a methine azo compound, a fluorene compound, an azo-based compound, and the like. A dibenzofuranone compound and a fluorene compound are preferable. Examples of the dibenzofuranone compounds include those described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, Japanese Patent Application Publication No. 2012-515234, and the like, for example, as those manufactured by BASF Corporation. "Irgaphor Black". Examples of the fluorene compound include C.I. Pigment Black 31, 32, and the like. Examples of the methine azo compound include those described in Japanese Patent Application Laid-Open No. 1-170601, Japanese Patent Application Laid-Open No. 2-34664, and the like, and can be obtained, for example, as "Chromofine Black A1103" manufactured by Dainichiseika.

作為無機系黑色著色劑並沒有特別限定，可以使用公知者。例如可以舉出碳黑、鈦黑、石墨等，碳黑、鈦黑為較佳，鈦黑為更佳。鈦黑係指含有鈦原子之黑色粒子，低次氧化鈦和氮氧化鈦為較佳。以提高分散性、抑制凝聚性等目的，鈦黑可以根據需要修飾表面。例如可以利用氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鎂或氧化鋯塗覆鈦黑的表面。並且，亦可以進行基於日本特開2007-302836號公報所示之拒水性物質之處理。作為黑色顏料，具體而言，可以舉出C.I.顏料黑1、7、鈦黑顏料等。The inorganic black colorant is not particularly limited, and a known one can be used. Examples include carbon black, titanium black, and graphite. Carbon black and titanium black are more preferred, and titanium black is more preferred. Titanium black refers to black particles containing titanium atoms. Low titanium oxide and titanium oxynitride are preferred. For the purpose of improving dispersibility and suppressing cohesion, titanium black can modify the surface as required. For example, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide or zirconia. In addition, a treatment based on the water-repellent substance described in Japanese Patent Application Laid-Open No. 2007-302836 may be performed. Specific examples of the black pigment include C.I. Pigment Black 1, 7, and a titanium black pigment.

鈦黑的每個粒子的一次粒徑及平均一次粒徑均較小者較佳。具體而言，以平均一次粒徑計10nm～45nm範圍者為較佳。Titanium black has a smaller primary particle size and an average primary particle size. Specifically, the average primary particle diameter is preferably in a range of 10 nm to 45 nm.

鈦黑的比表面積並沒有特別限制，藉由BET（Brunauer，Emmett，Teller）法測定之值係5m2 /g以上且150m2 /g以下為較佳，20m2 /g以上且120m2 /g以下為更佳。作為鈦黑的市售品的例子，可以舉出鈦黑10S、12S、13R、13M、13M-C、13R、13R-N、13M-T（商品名稱：Mitsubishi Materials Corporation製）、Tilack D（商品名稱：AKO KASEI CO.,LTD.製）等。The specific surface area of titanium black is not particularly limited, the measurement value based by BET (Brunauer, Emmett, Teller) method 5m 2 / g or more and 150m 2 / g or less is preferred, and 120m 2 20m 2 / g or more / g The following is better. Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade names: manufactured by Mitsubishi Materials Corporation), Tilack D (commodity Name: made by AKO KASEI CO., LTD.).

鈦黑亦能夠用作分散物。例如，可以舉出含有鈦黑粒子和二氧化矽粒子，且分散物中的Si原子與Ti原子的含有比控制在0.20～0.50範圍之分散物等。關於上述分散物，可以參閱日本特開2012-169556號公報的0020～0105段的記載，其內容被併入本說明書中。Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silicon dioxide particles, and the content ratio of Si atoms to Ti atoms in the dispersion is controlled in the range of 0.20 to 0.50. Regarding the above-mentioned dispersion, the descriptions in paragraphs 0020 to 0105 of Japanese Patent Application Laid-Open No. 2012-169556 can be referred to, and the contents are incorporated into this specification.

＜＜樹脂＞＞ 本發明的組成物含有樹脂。樹脂例如以使顏料等粒子分散於組成物中之用途、黏結劑的用途配合。另外，將主要用於使粒子分散於組成物中之樹脂亦稱為分散劑。但是，如樹脂之類的用途為一例，亦可以以該種用途以外的目的使用。<< Resin> The composition of the present invention contains a resin. The resin is blended, for example, for use in dispersing particles such as pigments in a composition, or for use in a binder. In addition, a resin mainly used for dispersing particles in a composition is also referred to as a dispersant. However, an application such as a resin is an example, and it may also be used for purposes other than that application.

樹脂的重量平均分子量（Mw）係1000～200000為較佳，更佳為2000～100000。若在該等範圍，則從相容性和顯白的觀點考慮較佳。The weight average molecular weight (Mw) of the resin is preferably 1,000 to 200,000, and more preferably 2,000 to 100,000. If it is in these ranges, it is more preferable from the viewpoint of compatibility and whitening.

樹脂的含量相對於組成物的總固體成分係5～90質量%為較佳，更佳為10～60質量%。若在該等範圍，則從圖案形狀、耐熱性、L*的觀點考慮較佳。可以僅含有1種樹脂，亦可以含有2種以上。當含有2種以上時，其合計量在上述範圍內為較佳。The content of the resin is preferably 5 to 90% by mass based on the total solid content of the composition, and more preferably 10 to 60% by mass. If it is in these ranges, it is preferable from a viewpoint of pattern shape, heat resistance, and L *. It may contain only one kind of resin, or it may contain two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

（黏結劑） 本發明的組成物中含有黏結劑作為樹脂為較佳。藉由含有黏結劑，膜特性得到提高。黏結劑可以任意使用公知者。較佳地，為了能夠進行水顯影或弱鹼水顯影而選擇對水或弱鹼水為可溶性或膨潤性的樹脂。例如，若使用鹼可溶性的樹脂，則能夠進行鹼顯影。作為該種樹脂，可以舉出側鏈具有羧基之自由基聚合物，例如日本特開昭59-44615號公報、日本日本特公昭54-34327號公報、日本日本特公昭58-12577號公報、日本日本特公昭54-25957號公報、日本特開昭54-92723號公報、日本特開昭59-53836號公報、日本特開昭59-71048號公報中所記載之聚合物。亦即，可以舉出使具有羧基之單體均聚或共聚而得到之樹脂、使具有酸酐之單體均聚或共聚而將酸酐單元水解或半酯化或半醯胺化而得到之樹脂、利用不飽和單羧酸及酸酐將環氧樹脂改質而得到之環氧丙烯酸酯等。作為具有羧基之單體，可以舉出丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、順丁烯二酸、反丁烯二酸、4-羧基苯乙烯等，作為具有酸酐之單體，可以舉出順丁烯二酸酐等。並且，有側鏈具有羧基之酸性纖維素衍生物。並且，還可以舉出具有羥基之聚合物中加成環狀酸酐而得到之聚合物。黏結劑係可溶於鹼顯影液之樹脂亦較佳。本發明的組成物含有鹼可溶性樹脂為較佳。並且，作為黏結劑，亦可以使用環氧樹脂或三聚氰胺樹脂等作為熱硬化性化合物之樹脂。(Binder) It is preferable to include a binder as a resin in the composition of the present invention. By including a binder, the film characteristics are improved. The adhesive can be arbitrarily known. Preferably, a resin that is soluble or swellable to water or weak alkaline water is selected in order to enable water development or weak alkaline water development. For example, when an alkali-soluble resin is used, alkali development can be performed. Examples of the resin include a radical polymer having a carboxyl group in a side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Application No. 54-34327, Japanese Patent Application No. 58-12577, and Japan The polymers described in Japanese Patent Application Publication No. 54-25957, Japanese Patent Application Publication No. 54-92723, Japanese Patent Application Publication No. 59-53836, and Japanese Patent Application Publication No. 59-71048. That is, a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group, a resin obtained by homopolymerizing or copolymerizing a monomer having an acid anhydride and hydrolyzing or semi-esterifying or semi-esterifying an acid anhydride unit, An epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene, and the like. Examples include maleic anhydride. In addition, there are acidic cellulose derivatives having a carboxyl group in a side chain. In addition, a polymer obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group is also mentioned. The binder is also preferably a resin soluble in an alkali developer. The composition of the present invention preferably contains an alkali-soluble resin. In addition, as the binder, a resin such as an epoxy resin, a melamine resin, or the like as a thermosetting compound may be used.

鹼可溶性樹脂可以從具有至少1個促進鹼溶解之基團之聚合物中適當地選擇。The alkali-soluble resin can be appropriately selected from polymers having at least one group that promotes alkali dissolution.

鹼可溶性樹脂的數量平均分子量（Mn）係1000～20,000為較佳。 鹼可溶性樹脂的酸值係30～500mgKOH/g為較佳。下限係50mgKOH/g以上為更佳，70mgKOH/g以上為進一步較佳。上限係400mgKOH/g以下為更佳，200mgKOH/g以下為進一步較佳，150mgKOH/g以下為特佳，120mgKOH/g以下為最佳。The number-average molecular weight (Mn) of the alkali-soluble resin is preferably 1,000 to 20,000. The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, and more preferably 70 mg KOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, more preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.

從耐熱性的觀點考慮，鹼可溶性樹脂係聚羥基苯乙烯系樹脂、聚矽氧烷系樹脂、丙烯酸系樹脂、丙烯醯胺系樹脂、丙烯酸/丙烯醯胺共聚物樹脂為較佳，從控制顯影性之觀點考慮，係丙烯酸系樹脂、丙烯醯胺系樹脂、丙烯酸/丙烯醯胺共聚物樹脂為較佳。作為促進鹼溶解之基團（以下，亦稱為“酸基”），例如可以舉出羧基、磷酸基、磺基、酚性羥基等，羧基為較佳。酸基可以僅為1種，亦可以為2種以上。From the viewpoint of heat resistance, alkali-soluble resin-based polyhydroxystyrene resin, polysiloxane resin, acrylic resin, acrylamide resin, and acrylic / acrylamide copolymer resin are preferred. From the viewpoint of performance, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred. Examples of the group (hereinafter, also referred to as “acid group”) that promotes the dissolution of the base include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxyl group. A carboxyl group is preferred. There may be only one kind of acid group, or two or more kinds.

鹼可溶性樹脂例如能夠利用公知的自由基聚合法進行合成。利用自由基聚合法製造鹼可溶性樹脂時之溫度、壓力、自由基起始劑的種類及其量、溶劑的種類等聚合條件可以由本領域技術人員容易進行設定，亦能夠實験性地規定條件。The alkali-soluble resin can be synthesized, for example, by a known radical polymerization method. Polymerization conditions such as temperature, pressure, the type and amount of radical initiator, and the type of solvent when an alkali-soluble resin is produced by a radical polymerization method can be easily set by those skilled in the art, and conditions can be specified realistically.

鹼可溶性樹脂係在側鏈上具有羧基之聚合物為較佳，可以舉出甲基丙烯酸共聚物、丙烯酸共聚物、衣康酸共聚物、巴豆酸共聚物、順丁烯二酸共聚物、部分酯化順丁烯二酸共聚物、酚醛清漆型樹脂等鹼可溶性酚醛樹脂等、以及在側鏈上具有羧基之酸性纖維素衍生物、在具有羥基之聚合物中加成酸酐而得到者。尤其，（甲基）丙烯酸與能夠與其共聚之其他單體的共聚物適合作為鹼可溶性樹脂。作為能夠與（甲基）丙烯酸共聚之其他單體，可以舉出日本特開2015-34961號公報的0017～0019段中所記載之單體。例如，可以舉出（甲基）丙烯酸烷基酯、（甲基）丙烯酸芳基酯、乙烯基化合物等。 作為（甲基）丙烯酸烷基酯及（甲基）丙烯酸芳基酯，可以舉出（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸己酯、（甲基）丙烯酸辛酯、（甲基）丙烯酸苯酯、（甲基）丙烯酸苄酯、三（甲基）丙烯酸酯、（甲基）丙烯酸萘酯、（甲基）丙烯酸環己酯、甲基丙烯酸縮水甘油酯、甲基丙烯酸四氟糠酯等，作為乙烯基化合物，可以舉出苯乙烯、α-甲基苯乙烯、乙烯基甲苯、丙烯腈、乙酸乙烯酯、N-乙烯基吡咯啶酮、聚苯乙烯大分子單體、聚甲基丙烯酸甲酯大分子單體等，作為日本特開平10-300922號公報中所記載之N位取代之順丁烯二醯亞胺單體，可以舉出N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺等。另外，能夠與該等（甲基）丙烯酸共聚之其他單體可以僅為1種，亦可以為2種以上。The alkali-soluble resin is preferably a polymer having a carboxyl group on a side chain, and examples thereof include a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a portion thereof. It is obtained by esterifying a maleic acid copolymer, an alkali-soluble phenol resin such as a novolac resin, an acidic cellulose derivative having a carboxyl group on a side chain, and an acid anhydride added to a polymer having a hydroxyl group. In particular, a copolymer of (meth) acrylic acid and other monomers capable of being copolymerized therewith is suitable as the alkali-soluble resin. Examples of other monomers that can be copolymerized with (meth) acrylic acid include the monomers described in paragraphs 0017 to 0019 of Japanese Patent Application Laid-Open No. 2015-34961. Examples include alkyl (meth) acrylate, aryl (meth) acrylate, vinyl compounds, and the like. Examples of the alkyl (meth) acrylate and the aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) Butyl acrylate, isobutyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic acid Benzyl ester, tri (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrafluorofurfuryl methacrylate, etc., as vinyl compounds, may be Examples include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, polymethylmethacrylate macromonomer, etc. As the N-substituted cis-butylene diimide monomer described in Japanese Patent Application Laid-Open No. 10-300922, there can be mentioned N-phenyl-cis-butylene diimide and N-cyclohexyl-cis-butene Diammine and so on. In addition, the other monomers that can be copolymerized with the (meth) acrylic acid may be only one kind, or two or more kinds.

鹼可溶性樹脂可以較佳地使用包括（甲基）丙烯酸苄酯/（甲基）丙烯酸共聚物、（甲基）丙烯酸苄酯/（甲基）丙烯酸/（甲基）丙烯酸2-羥基乙酯共聚物、（甲基）丙烯酸苄酯/（甲基）丙烯酸/其他單體之多元共聚物。並且，亦可以較佳地使用將（甲基）丙烯酸2-羥基乙酯共聚而得到者、日本特開平7-140654號公報中所記載之（甲基）丙烯酸2-羥基丙酯/聚苯乙烯大分子單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物、丙烯酸2-羥基-3-苯氧基丙酯/聚甲基丙烯酸甲酯大分子單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物、甲基丙烯酸2-羥基乙酯/聚苯乙烯大分子單體/甲基丙烯酸甲酯/甲基丙烯酸共聚物、甲基丙烯酸2-羥基乙酯/聚苯乙烯大分子單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物等。並且，作為市售品，例如亦可以使用FF-426（FUJIKURA KASEI CO,LTD.製）等。As the alkali-soluble resin, benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / (meth) acrylic acid 2-hydroxyethyl copolymer can be preferably used. Polymer, benzyl (meth) acrylate / (meth) acrylic acid / other monomers. In addition, a copolymer obtained by copolymerizing 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate / polystyrene described in Japanese Patent Application Laid-Open No. 7-140654 can also be preferably used. Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid Copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic copolymer, 2-hydroxyethyl methacrylate / polystyrene macromer / formaldehyde Benzyl acrylate / methacrylic acid copolymer and the like. As a commercially available product, for example, FF-426 (manufactured by FUJIKURA KASEI CO, LTD.) Can be used.

並且，鹼可溶性樹脂可以使用具有聚合性基之鹼可溶性樹脂。依該態樣，具有所得到之膜的耐溶劑性提高之傾向。作為聚合性基，可以舉出（甲基）烯丙基、（甲基）丙烯醯基等。具有聚合性基之鹼可溶性樹脂中有用的是側鏈上具有聚合性基之鹼可溶性樹脂等。作為具有聚合性基之鹼可溶性樹脂，可以舉出Dianal NR系列（Mitsubishi Rayon Co.,Ltd.製）、Photomer6173（含有COOH之聚胺基甲酸酯丙烯酸寡聚物（polyurethane acrylic oligomer），Diamond Shamrock Co.,Ltd.製）、Viscote R-264、KS RESIST 106（均為OSAKA ORGANIC CHEMICAL INDUSTRY LTD.製）、CYCLOMER P系列（例如，ACA230AA）、PLACCEL CF200系列（均為Daicel Chemical Industries, Ltd.製）、Ebecryl3800（Dicel-UCB Company LTD.製）、ACRYCURE-RD-F8（NIPPON SHOKUBAI CO.,LTD.製）等。As the alkali-soluble resin, an alkali-soluble resin having a polymerizable group can be used. According to this aspect, the solvent resistance of the obtained film tends to be improved. Examples of the polymerizable group include a (meth) allyl group and a (meth) acrylfluorenyl group. Among alkali-soluble resins having a polymerizable group, alkali-soluble resins having a polymerizable group in a side chain are useful. Examples of the alkali-soluble resin having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer6173 (polyurethane acrylic oligomer containing COOH, Diamond Shamrock) Co., Ltd.), Viscote R-264, KS RESIST 106 (all manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (all manufactured by Daicel Chemical Industries, Ltd.) ), Ebecryl3800 (manufactured by Dicel-UCB Company LTD.), ACRYCURE-RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.), Etc.

鹼可溶性樹脂包含將含有下述式（ED1）所表示之化合物及下述式（ED2）所表示之化合物（以下，將該等化合物亦稱作“醚二聚體”。）中的至少一方之單體成分聚合而成之聚合物亦較佳。關於將含有醚二聚體之單體成分聚合而成之聚合物的詳細內容，可以參閱日本特開2015-34961號公報的0022～0031段，其內容被併入本說明書中。The alkali-soluble resin includes at least one of a compound represented by the following formula (ED1) and a compound represented by the following formula (ED2) (hereinafter, these compounds are also referred to as "ether dimers"). Polymers obtained by polymerizing monomer components are also preferred. For details of a polymer obtained by polymerizing a monomer component containing an ether dimer, refer to paragraphs 0022 to 0031 of Japanese Patent Application Laid-Open No. 2015-34961, the contents of which are incorporated herein.

[化學式1] [Chemical Formula 1]

式（ED1）中、R1 及R2 分別獨立地表示氫原子或可以具有取代基之碳數1～25的烴基。 [化學式2]式（ED2）中，R表示氫原子或碳數1～30的有機基。作為式（ED2）的具體例，可以參閱日本特開2010-168539號公報的記載。In the formula (ED1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. [Chemical Formula 2] In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), reference can be made to the description in Japanese Patent Application Laid-Open No. 2010-168539.

作為醚二聚體的具體例，例如可以參閱日本特開2013-29760號公報的0317段，其內容被併入本說明書中。醚二聚體可以僅為1種，亦可以為2種以上。As a specific example of the ether dimer, refer to, for example, paragraph 0317 of Japanese Patent Application Laid-Open No. 2013-29760, the content of which is incorporated into this specification. The ether dimer may be only one kind, or two or more kinds.

鹼可溶性樹脂可以含有源自下述式（X）所表示之化合物之結構單元。 [化學式3]式（X）中，R1 表示氫原子或甲基，R2 表示碳數2～10的伸烷基，R3 表示氫原子或可以含有苯環之碳數1～20的烷基。n表示1～15的整數。The alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X). [Chemical Formula 3] In the formula (X), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 10 carbon atoms, and R 3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer from 1 to 15.

上述式（X）中，R2 的伸烷基的碳數係2～3為較佳。並且，R3 的烷基的碳數為1～20，但更佳為1～10。作為R3 所表示之含有苯環之烷基，可以舉出苄基、2-苯基（異）丙基等。In the above formula (X), the carbon number of the alkylene group of R 2 is preferably from 2 to 3. The carbon number of the alkyl group of R 3 is 1 to 20, but more preferably 1 to 10. Examples of the benzene ring-containing alkyl group represented by R 3 include benzyl, 2-phenyl (iso) propyl, and the like.

作為鹼可溶性樹脂的具體例，例如可以舉出下述樹脂。並且，亦可以舉出日本特開2015-34961號公報的0037段中所記載之樹脂。在該等樹脂之中，從耐溶劑性的觀點考慮，下述C-2等具有聚合性基之鹼可溶性樹脂為較佳。 [化學式4] Specific examples of the alkali-soluble resin include the following resins. In addition, the resin described in paragraph 0037 of Japanese Patent Application Laid-Open No. 2015-34961 can also be cited. Among these resins, from the viewpoint of solvent resistance, alkali-soluble resins having a polymerizable group such as the following C-2 are preferred. [Chemical Formula 4]

鹼可溶性樹脂可以參閱日本特開2012-208494號公報的0558～0571段（對應之美國專利申請公開第2012/0235099號說明書的＜0685＞～＜0700＞）的記載，該等內容被併入本說明書中。另外，亦可以使用日本特開2012-32767號公報中所記載之0029～0063段中所記載之共聚物（B）及實施例中使用之鹼可溶性樹脂、日本特開2012-208474號公報的0088～0098段中所記載之黏結劑樹脂及實施例中使用之黏結劑樹脂、日本特開2012-137531號公報的0022～0032段中所記載之黏結劑樹脂及實施例中使用之黏結劑樹脂、日本特開2013-024934號公報的0132～0143段中所記載之黏結劑樹脂及實施例中使用之黏結劑樹脂、日本特開2011-242752號公報的0092～0098段及實施例中使用之黏結劑樹脂、日本特開2012-032770號公報的0030～0072段中所記載之黏結劑樹脂。該等內容被併入本說明書中。The alkali-soluble resin can be found in paragraphs 0558 to 0571 of Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to <0685> to <0700> of US Patent Application Publication No. 2012/0235099), which are incorporated herein In the manual. In addition, the copolymer (B) described in paragraphs 0029 to 0063 described in Japanese Patent Application Laid-Open No. 2012-32767 and the alkali-soluble resin used in the examples, 0088 of Japanese Patent Application No. 2012-208474 can also be used The binder resins described in paragraphs ~ 0098 and the binder resins used in the examples, the binder resins described in paragraphs 0022 to 0032 of JP 2012-137531 and the binder resins used in the examples, The binder resins described in paragraphs 0132 to 0143 of Japanese Patent Application Laid-Open No. 2013-024934 and the binder resins used in the examples, paragraphs 092 to 0098 of Japanese Patent Laid-Open No. 2011-242752 and the adhesives used in the examples Binder resin, binder resins described in paragraphs 0030 to 0072 of JP 2012-032770. Such content is incorporated into this specification.

作為黏結劑，可以使用對波長589nm的光之折射率為1.5以下之樹脂。 作為對波長589nm的光之折射率為1.5以下之樹脂，可以舉出氟系樹脂、或還作為上述鹼可溶性樹脂之聚矽氧烷系樹脂等。本發明中，樹脂係聚矽氧烷系樹脂為較佳，對波長589nm的光之折射率為1.5以下之聚矽氧烷系樹脂為更佳，對波長589nm的光之折射率為1.5以下之還作為鹼可溶性樹脂之聚矽氧烷系樹脂為特佳。 樹脂的折射率能夠藉由以下方法以未硬化的狀態進行測定。 具體的測定方法如下：在Si晶片上以300nm的厚度將僅包括成為測定對象之樹脂之膜進行製膜之後，使用橢圓偏光計（Lambda Ace RE-3300（商品名），Dainippon Screen Mfg. Co.,Ltd.）測定所得到之膜的折射率。As the binder, a resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm can be used. Examples of the resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm include a fluorine-based resin, and a polysiloxane-based resin that is also the above-mentioned alkali-soluble resin. In the present invention, a resin-based polysiloxane resin is preferable, and a polysiloxane resin having a refractive index of 1.5 or less for light having a wavelength of 589 nm is more preferable, and a refractive index of light having a wavelength of 589 nm is 1.5 or less. Polysiloxane resins which are also alkali-soluble resins are particularly preferred. The refractive index of the resin can be measured in an uncured state by the following method. The specific measurement method is as follows: After forming a film including only a resin to be measured on a Si wafer to a thickness of 300 nm, an ellipsometer (Lambda Ace RE-3300 (trade name), Dainippon Screen Mfg. Co. , Ltd.) The refractive index of the obtained film was measured.

-氟系樹脂- 作為氟系樹脂，只要在樹脂中含有氟原子，則並沒有特別限定。例如，將（a）具有源自通式（F1）所表示之單體之重複單元之高分子化合物用作氟系樹脂亦較佳。—Fluorine-Based Resin— The fluorine-based resin is not particularly limited as long as it contains fluorine atoms in the resin. For example, (a) a polymer compound having a repeating unit derived from a monomer represented by the general formula (F1) is preferably used as a fluorine-based resin.

[化學式5]通式（F1）中，Rf表示含有氟烷基或全氟烷基之取代基，n表示1或2，R1 表示氫原子或甲基。 Rf係氟原子的數為9以上的含有氟烷基或全氟烷基之取代基為較佳。作為氟原子的數為9以上的含有氟烷基或全氟烷基之取代基，具體而言，可以舉出如下（甲基）丙烯酸氟烷基酯。 CH2 =CRCO2 （CH2 ）m Cn F2n+1 （m表示1或2，n表示4～12的整數。並且，R表示氫原子或甲基。） CH2 =CRCO2 （CH2 ）m （CF2 ）n H （m表示1或2，n表示4～12的整數。並且，R表示氫原子或甲基。） 尤其，含有氟烷基或全氟烷基之取代基每一個的氟原子的數量為9～30者為較佳，更佳為13～25。[Chemical Formula 5] In the general formula (F1), Rf represents a fluoroalkyl group or a perfluoroalkyl-containing group of the substituent group, n represents 1 or 2, R 1 represents a hydrogen atom or a methyl group. Rf-based fluorine atom-containing substituents having a fluorine atom number of 9 or more are preferred. Specific examples of the fluoroalkyl group or perfluoroalkyl group-containing substituent having 9 or more fluorine atoms include the following fluoroalkyl (meth) acrylates. CH 2 = CRCO 2 (CH 2 ) m C n F 2n + 1 (m represents 1 or 2, n represents an integer from 4 to 12. And R represents a hydrogen atom or a methyl group.) CH 2 = CRCO 2 (CH 2 ) M (CF 2 ) n H (m represents 1 or 2, n represents an integer of 4 to 12. And R represents a hydrogen atom or a methyl group.) In particular, each of the substituents containing a fluoroalkyl group or a perfluoroalkyl group The number of fluorine atoms is preferably 9 to 30, and more preferably 13 to 25.

並且，將具有源自含有氟原子之不飽和單體之重複單元之高分子化合物用作氟系樹脂亦較佳。作為含有氟原子之不飽和單體，可以舉出具有聚氟烷基或聚氟醚基之自由基聚合性單體，作為全氟烷基，全氟甲基、全氟乙基、全氟丙基、全氟丁基、全氟己基、全氟辛基、全氟癸基、全氟十二烷基、全氟十四烷基為較佳。Further, it is also preferable to use a polymer compound having a repeating unit derived from an unsaturated monomer containing a fluorine atom as the fluorine-based resin. Examples of the fluorine atom-containing unsaturated monomer include a radically polymerizable monomer having a polyfluoroalkyl group or a polyfluoroether group. Examples of the perfluoroalkyl group include perfluoromethyl, perfluoroethyl, and perfluoropropyl. Base, perfluorobutyl, perfluorohexyl, perfluorooctyl, perfluorodecyl, perfluorododecyl, perfluorotetradecyl are preferred.

作為該種含有氟原子之不飽和單體，CH2 =C（CH3 ）COOCH2 （CF2 ）4 CF3 、CH2 =C（CH3 ）COOCH2 CH2 （CF2 ）6 CF3 、CH2 =CHCOO（CF2 ）6 CF3 、CH2 =CHCOOCH2 CH2 （CF2 ）7 CF3 、CH2 =CHCOOCH2 CH2 （CF2 ）5 CF（CF3 ）2 、CH2 =C（CH3 ）COOCH（OCOCH3 ）CH2 （CF2 ）6 CF（CF3 ）2 、CH2 =CHCOOCH2 CH（OH）CH2 （CF2 ）6 CF（CF3 ）2 、CH2 =CHCOOCH2 CH2 （CF2 ）8 CF3 、CH2 =C（CH3 ）COOCH2 CH2 NHCO（CF2 ）8 CF3 、CH2 =CHOCONHCO（CF2 ）7 CF（CF2 Cl）CF3 、CH2 =CHCOOCH2 CH2 N（C3 H7 ）SO2 （CF2 ）7 CF3 、CH2 =CHCOOCH2 CH2 CH2 CH2 （CF2 ）7 CF3 、CH2 =C（CH3 ）COOCH2 CH2 N（C2 H5 ）SO2 （CF2 ）7 CF3 、CH2 =CHCOOCH2 CH2 NHCO（CF2 ）7 CF3 、CH2 =CHCOO（CH2 ）3 （CF2 ）6 CF（CF3 ）2 、CH2 =CHCOOCH2 （CF2 ）10 H、CH2 =C（CH3 ）COOCH2 （CF2 ）10 CF2 Cl、CH2 =CHCONHCH2 CH2 OCOCF（CF3 ）OC3 F7 、CH2 =CHCONHCH2 CH2 OCOCF（CF3 ）（OC3 F6 ）2 OC3 F7 為較佳。 含有氟原子之不飽和單體亦可以單獨使用1種或者併用2種以上。作為含有氟原子之不飽和單體，亦可以使用市售品。例如，有Kyoeisha chemical Co.,Ltd.製、商品名LIGHT ESTER FM-108、LIGHT ESTER M-3F、LIGHT ESTER M-4F；NIPPON MEKTRON, LTD.製、商品名CHEMINOX FAAC、CHEMINOX FAMAC、CHEMINOX FAAC-M、CHEMINOX FAMAC-M、CHEMINOX PFAE、CHEMINOX PFOE等。As this kind of unsaturated monomer containing fluorine atom, CH 2 = C (CH 3 ) COOCH 2 (CF 2 ) 4 CF 3 , CH 2 = C (CH 3 ) COOCH 2 CH 2 (CF 2 ) 6 CF 3 , CH 2 = CHCOO (CF 2 ) 6 CF 3 , CH 2 = CHCOOCH 2 CH 2 (CF 2 ) 7 CF 3 , CH 2 = CHCOOCH 2 CH 2 (CF 2 ) 5 CF (CF 3 ) 2 , CH 2 = C (CH 3 ) COOCH (OCOCH 3 ) CH 2 (CF 2 ) 6 CF (CF 3 ) 2 , CH 2 = CHCOOCH 2 CH (OH) CH 2 (CF 2 ) 6 CF (CF 3 ) 2 , CH 2 = CHCOOCH 2 CH 2 (CF 2 ) 8 CF 3 , CH 2 = C (CH 3 ) COOCH 2 CH 2 NHCO (CF 2 ) 8 CF 3 , CH 2 = CHOCONHCO (CF 2 ) 7 CF (CF 2 Cl) CF 3 , CH 2 = CHCOOCH 2 CH 2 N (C 3 H 7 ) SO 2 (CF 2 ) 7 CF 3 , CH 2 = CHCOOCH 2 CH 2 CH 2 CH 2 (CF 2 ) 7 CF 3 , CH 2 = C (CH 3 ) COOCH 2 CH 2 N (C 2 H 5 ) SO 2 (CF 2 ) 7 CF 3 , CH 2 = CHCOOCH 2 CH 2 NHCO (CF 2 ) 7 CF 3 , CH 2 = CHCOO (CH 2 ) 3 (CF 2 ) 6 CF (CF 3 ) 2 , CH 2 = CHCOOCH 2 (CF 2 ) 10 H, CH 2 = C (CH 3 ) COOCH 2 (CF 2 ) 10 CF 2 Cl, CH 2 = CHCONHCH 2 CH 2 OCOCF (CF 3 ) OC 3 F 7 、 CH 2 = CHCONHCH 2 CH 2 OCOCF (CF 3 ) (OC 3 F 6 ) 2 OC 3 F 7 is preferred. The fluorine atom-containing unsaturated monomer may be used alone or in combination of two or more. As the fluorine atom-containing unsaturated monomer, a commercially available product may be used. For example, there are products manufactured by Kyoeisha chemical Co., Ltd. under the trade names LIGHT ESTER FM-108, LIGHT ESTER M-3F, and LIGHT ESTER M-4F; manufactured by NIPPON MEKTRON, LTD. And trade names CHEMINOX FAAC, CHEMINOX FAMAC, CHEMINOX FAAC- M, CHEMINOX FAMAC-M, CHEMINOX PFAE, CHEMINOX PFOE, etc.

並且，能夠將具有源自（a）通式（F1）所表示之單體之重複單元或源自含有氟原子之不飽和單體之重複單元、以及具有促進鹼溶解之基團之重複單元之高分子化合物用作氟系樹脂。促進鹼溶解之基團的較佳範圍與前述鹼可溶性樹脂所具有之促進鹼溶解之基團的較佳範圍相同。Further, it is possible to combine a repeating unit having a repeating unit derived from a monomer represented by (a) general formula (F1) or an unsaturated monomer containing a fluorine atom, and a repeating unit having a group that promotes alkali dissolution. A polymer compound is used as a fluorine-based resin. The preferable range of the group which promotes alkali dissolution is the same as the preferable range of the group which promotes alkali dissolution which the aforementioned alkali-soluble resin has.

作為氟系樹脂的例子，還可以參閱日本特開平2-804號公報的第6頁右下欄至第9頁右上欄中所記載之氟系界面活性劑，其內容被併入本說明書中。As an example of the fluorine-based resin, refer to the fluorine-based surfactants described in Japanese Patent Application Laid-Open Publication No. 2-804 on the lower right column on page 6 to the upper right column on page 9, and the contents are incorporated into this specification.

以下記載氟系樹脂的較佳具體例。Preferred specific examples of the fluorine-based resin are described below.

[化學式6] [Chemical Formula 6]

[化學式7] [Chemical Formula 7]

-聚矽氧烷系樹脂- 作為聚矽氧烷系樹脂並沒有特別限制。例如，作為聚矽氧烷系樹脂，可以使用將下述通式（1）所表示之化合物單獨水解縮合而得到之聚矽氧烷系樹脂、或下述通式（1）所表示之化合物和其他矽烷化合物藉由共水解縮合而得到之聚矽氧烷系樹脂。作為聚矽氧烷系樹脂，可以參閱日本特開2014-66988號公報的＜0014＞～＜0035＞的記載，其內容被併入本說明書中。 聚矽氧烷系樹脂中，從提高耐溶劑性之觀點考慮，將除了含有下述通式（1）所表示之化合物以外還含有下述通式（2）所表示之化合物之烷氧基矽烷化合物藉由共水解縮合而得到之聚矽氧烷系樹脂為較佳。 聚矽氧烷系樹脂中，從提高聚矽氧烷系樹脂的酸值並改善圖案形狀之觀點考慮，使用將除了含有下述通式（1）所表示之化合物以外還含有下述通式（3）所表示之化合物之烷氧基矽烷化合物藉由共水解縮合而得到之聚矽氧烷系樹脂為較佳。並且，將含有下述通式（3）所表示之化合物之烷氧基矽烷化合物藉由共水解縮合而得到之聚矽氧烷系樹脂亦能夠用作鹼可溶性樹脂。-Polysiloxane resin- The polysiloxane resin is not particularly limited. For example, as the polysiloxane resin, a polysiloxane resin obtained by separately hydrolyzing and condensing a compound represented by the following general formula (1), or a compound represented by the following general formula (1), and Polysiloxane resin obtained by co-hydrolysis condensation of other silane compounds. As a polysiloxane resin, the description of <0014>-<0035> of Unexamined-Japanese-Patent No. 2014-66988 can be referred, The content is incorporated into this specification. The polysiloxane resin contains an alkoxysilane containing a compound represented by the following general formula (2) in addition to a compound represented by the following general formula (1) from the viewpoint of improving solvent resistance. A polysiloxane resin obtained by co-hydrolyzing and condensing a compound is preferred. In the polysiloxane resin, from the viewpoint of increasing the acid value of the polysiloxane resin and improving the shape of the pattern, the polysiloxane resin is used in addition to the compound represented by the following general formula (1) to include the following general formula ( 3) A polysiloxane resin obtained by co-hydrolyzing and condensing an alkoxysilane compound of the compound represented by the compound is preferred. In addition, a polysiloxane resin obtained by co-hydrolyzing and condensing an alkoxysilane compound containing a compound represented by the following general formula (3) can also be used as an alkali-soluble resin.

通式（1） R1 2 Si（OR2 ）2 General formula (1) R 1 2 Si (OR 2 ) 2

通式（1）中之R1 分別獨立地表示烷基或苯基，R2 分別獨立地表示氫原子或烷基。 通式（1）中之R1 及R2 係碳數1～6的烷基為較佳，碳數1～4的烷基為更佳，碳數1～3的烷基為特佳，碳數1或2的烷基為更特佳，甲基為最佳。具體而言，可以舉出甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、己基、環己基等，其中，甲基或乙基為特佳。另外，當在同一分子內存在複數個R1 時，該等可以相同亦可以不同。在通式（1）中之R2 中亦相同。通式（1）中之R1 及R2 中之烷基可以是直鏈狀、分支狀及環狀中之任一種，直鏈狀為較佳。R 1 in the general formula (1) each independently represents an alkyl group or a phenyl group, and R 2 each independently represents a hydrogen atom or an alkyl group. R 1 and R 2 in the general formula (1) are more preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is particularly preferred. An alkyl group of 1 or 2 is more preferred, and a methyl group is most preferred. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, pentyl, hexyl, cyclohexyl and the like, among which methyl or ethyl The base is particularly good. In addition, when there are a plurality of R 1 in the same molecule, these may be the same or different. The same applies to R 2 in the general formula (1). The alkyl group in R 1 and R 2 in the general formula (1) may be any of linear, branched, and cyclic, and linear is preferred.

[化學式8] [Chemical Formula 8]

通式（2）中之R3 表示甲基或氫原子，R4 表示碳數1～4的伸烷基，R5 分別獨立地表示氫原子或碳數1～4的烷基，R6 分別獨立地表示碳數1～6的烷基，n表示1～3的整數。 通式（2）中之R4 係碳數1～3的伸烷基為較佳，碳數3的伸烷基為更佳。 通式（2）中之R6 及R5 的較佳範圍分別與通式（1）中之R1 及R2 的較佳範圍相同。 通式（2）中之n係2或3為較佳，3為更佳。In the general formula (2), R 3 represents a methyl group or a hydrogen atom, R 4 represents an alkylene group having 1 to 4 carbon atoms, R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 6 respectively It independently represents an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 3. R 4 in the general formula (2) is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 3 carbon atoms. The preferred ranges of R 6 and R 5 in the general formula (2) are the same as the preferred ranges of R 1 and R 2 in the general formula (1), respectively. In the general formula (2), n is 2 or 3, and 3 is more preferable.

[化學式9] [Chemical Formula 9]

通式（3）中之l表示0～2的整數，m表示0～3的整數，R7 表示碳數1～4的伸烷基，R8 分別獨立地表示氫原子或碳數1～4的烷基，R9 分別獨立地表示碳數1～6的烷基。 通式（3）中之l係1為更佳。 通式（3）中之m係2或3為較佳，3為更佳。 通式（3）中之R7 係碳數1～3的伸烷基為較佳，碳數3的伸烷基為更佳。 通式（3）中之R9 及R8 的較佳範圍分別與通式（1）中之R1 及R2 的較佳範圍相同。In the general formula (3), l represents an integer of 0 to 2, m represents an integer of 0 to 3, R 7 represents an alkylene group having 1 to 4 carbon atoms, and R 8 each independently represents a hydrogen atom or 1 to 4 carbon atoms. And R 9 each independently represent an alkyl group having 1 to 6 carbon atoms. In the general formula (3), l is 1 more preferably. In the general formula (3), m is 2 or 3, and 3 is more preferable. R 7 in the general formula (3) is more preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 3 carbon atoms. The preferred ranges of R 9 and R 8 in the general formula (3) are the same as the preferred ranges of R 1 and R 2 in the general formula (1), respectively.

作為通式（1）所表示之化合物，例如可以舉出二甲氧基二甲基矽烷、二乙氧基二甲基矽烷、二甲氧基二苯基矽烷、二乙氧基二苯基矽烷、二羥基二苯基矽烷、二甲氧基（甲基）（苯基）矽烷、二乙氧基（甲基）（苯基）矽烷、二甲氧基（甲基）（苯乙基）矽烷、二環戊基二甲氧基矽烷或環己基二甲氧基（甲基）矽烷、甲基三甲氧基矽烷、乙基三甲氧基矽烷、苯基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三乙氧基矽烷、苯基三乙氧基矽烷。 通式（1）所表示之化合物係二甲氧基二甲基矽烷、二甲氧基二苯基矽烷、苯基三甲氧基矽烷為較佳，二甲氧基二甲基矽烷為更佳。Examples of the compound represented by the general formula (1) include dimethoxydimethylsilane, diethoxydimethylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane , Dihydroxydiphenylsilane, dimethoxy (methyl) (phenyl) silane, diethoxy (methyl) (phenyl) silane, dimethoxy (methyl) (phenethyl) silane , Dicyclopentyldimethoxysilane or cyclohexyldimethoxy (methyl) silane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxy Silane, ethyltriethoxysilane, phenyltriethoxysilane. The compound represented by the general formula (1) is preferably dimethoxydimethylsilane, dimethoxydiphenylsilane, and phenyltrimethoxysilane, and more preferably dimethoxydimethylsilane.

通式（1）所表示之化合物在供於共水解縮合之烷氧基矽烷化合物中所佔之比例係25～75莫耳%為較佳，35～75莫耳%為更佳，50～70莫耳%為特佳。並且，二甲氧基二苯基矽烷、二乙氧基二苯基矽烷及二羥基二苯基矽烷在供於共水解縮合之烷氧基矽烷化合物中所佔之比例係0～50莫耳%為較佳，0～45莫耳%為更佳，0～30莫耳%為特佳，0～10莫耳%為更特佳。The proportion of the compound represented by the general formula (1) in the alkoxysilane compound provided for co-hydrolysis condensation is preferably 25 to 75 mole%, more preferably 35 to 75 mole%, and 50 to 70. Mole% is particularly good. In addition, the proportion of dimethoxydiphenylsilane, diethoxydiphenylsilane, and dihydroxydiphenylsilane in the alkoxysilane compound for co-hydrolysis condensation is 0 to 50 mol% For the sake of preference, 0 to 45 mole% is more preferable, 0 to 30 mole% is particularly preferable, and 0 to 10 mole% is more particularly preferable.

作為通式（2）所表示之化合物，例如可以舉出3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-丙烯醯氧基丙基甲基二甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷或3-丙烯醯氧基丙基甲基二乙氧基矽烷。 通式（2）所表示之化合物係3-甲基丙烯醯氧基丙基三甲氧基矽烷為較佳。 通式（2）所表示之化合物在供於共水解縮合之烷氧基矽烷化合物中所佔之比例係10～45莫耳%為較佳，10～30莫耳%為更佳，15～20莫耳%為特佳。藉由使用通式（2）所表示之化合物作為供於共水解縮合之烷氧基矽烷化合物，能夠提高耐溶劑性。Examples of the compound represented by the general formula (2) include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-propenefluorene Oxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acrylic acid Propylmethyldimethoxysilane, 3-propenyloxypropyltriethoxysilane or 3-propenyloxypropylmethyldiethoxysilane. The compound represented by the general formula (2) is preferably 3-methacryloxypropyltrimethoxysilane. The proportion of the compound represented by the general formula (2) in the alkoxysilane compound provided for co-hydrolysis condensation is preferably 10 to 45 mole%, more preferably 10 to 30 mole%, and 15 to 20 Mole% is particularly good. By using a compound represented by the general formula (2) as an alkoxysilane compound for co-hydrolysis condensation, solvent resistance can be improved.

作為通式（3）所表示之化合物，例如可以舉出3-三甲氧基矽基丙基琥珀酸酐、3-三乙氧基矽基丙基琥珀酸酐、3-三甲氧基矽基乙基琥珀酸酐或3-三甲氧基矽基丁基琥珀酸酐、3-二乙氧基甲基矽基丙基琥珀酸酐、3-二甲氧基甲基矽基乙基琥珀酸酐或3-二甲氧基甲基矽基丁基琥珀酸酐。 通式（3）所表示之化合物係3-三甲氧基矽基丙基琥珀酸酐為較佳。 從提高聚矽氧烷系樹脂的酸值並改善圖案形狀之觀點考慮，通式（3）所表示之化合物在供於共水解縮合之烷氧基矽烷化合物中所佔之比例係1～30莫耳%為較佳，1～25莫耳%為更佳，從進一步抑制經過一個月後的濃度不均勻之觀點考慮，1～20莫耳%為特佳。Examples of the compound represented by the general formula (3) include 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, and 3-trimethoxysilylethyl succinic acid. Anhydride or 3-trimethoxysilylbutyl succinic anhydride, 3-diethoxymethylsilylpropylsuccinic anhydride, 3-dimethoxymethylsilylethylsuccinic anhydride, or 3-dimethoxy Methylsilylbutyl succinic anhydride. The compound represented by the general formula (3) is preferably 3-trimethoxysilylpropylsuccinic anhydride. From the viewpoint of increasing the acid value of the polysiloxane resin and improving the pattern shape, the proportion of the compound represented by the general formula (3) in the alkoxysilane compound used for the co-hydrolysis condensation is 1 to 30 moles. The ear% is more preferable, and 1 to 25 mole% is more preferable. From the viewpoint of further suppressing the concentration unevenness after one month, 1 to 20 mole% is particularly preferable.

供於共水解縮合之烷氧基矽烷化合物還含有通式（5）所表示之化合物為較佳。It is preferable that the alkoxysilane compound used for the co-hydrolysis condensation further contains a compound represented by the general formula (5).

通式（5） R12 Si（OR13 ）3 General formula (5) R 12 Si (OR 13 ) 3

通式（5）中之R12 表示具有環氧基之1價的有機基，R13 分別獨立地表示烷基。 通式（5）中之R12 所表示之具有環氧基之1價的有機基具有1～5個環氧基為較佳，具有1或2個為更佳，具有1個為特佳。通式（5）中之R12 所表示之具有環氧基之1價的有機基係經由連接基而在末端鍵結有環氧基之基團為較佳，經由伸烷基（較佳為碳數1～10，更佳為碳數1～6，特佳為碳數1～3）及氧原子中的至少一方而在末端鍵結有環氧基之基團為更佳。 通式（5）中之R13 的較佳範圍與通式（1）中之R2 的較佳範圍相同。R 12 in the general formula (5) represents a monovalent organic group having an epoxy group, and R 13 each independently represents an alkyl group. The monovalent organic group having an epoxy group represented by R 12 in the general formula (5) is preferably one to five epoxy groups, more preferably one or two, and particularly preferably one. The monovalent organic group having an epoxy group represented by R 12 in the general formula (5) is preferably a group having an epoxy group bonded to a terminal via a linking group, and an alkylene group (preferably The number of carbon atoms is from 1 to 10, more preferably from 1 to 6 carbon atoms, particularly preferably from 1 to 3 carbon atoms, and at least one of oxygen atoms, and a group having an epoxy group bonded to the terminal is more preferred. The preferred range of R 13 in the general formula (5) is the same as the preferred range of R 2 in the general formula (1).

作為通式（5）所表示之化合物，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-（3,4-環氧基環己基）丙基三甲氧基矽烷、3-（3,4-環氧基環己基）丙基三乙氧基矽烷。 通式（5）所表示之化合物係3-縮水甘油氧基丙基三甲氧基矽烷、3-（3,4-環氧基環己基）丙基三甲氧基矽烷為較佳。 通式（5）所表示之化合物在供於共水解縮合之烷氧基矽烷化合物中所佔之比例係10莫耳%以下為較佳，8莫耳%以下為更佳，5莫耳%以下為特佳。Examples of the compound represented by the general formula (5) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3- (3,4-cyclo Oxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane. The compound represented by the general formula (5) is preferably 3-glycidyloxypropyltrimethoxysilane and 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane. The proportion of the compound represented by the general formula (5) in the alkoxysilane compound provided for co-hydrolysis condensation is preferably 10 mol% or less, more preferably 8 mol% or less, and 5 mol% or less. Especially good.

供於共水解縮合之烷氧基矽烷化合物可以含有除通式（1）～（3）及（5）所表示之化合物以外的其他烷氧基矽烷化合物。作為除通式（1）～（3）及（5）所表示之化合物以外的其他烷氧基矽烷化合物，例如可以舉出苯乙基三甲氧基矽烷、萘基三甲氧基矽烷、苯乙基三乙氧基矽烷、萘基三乙氧基矽烷、四甲氧基矽烷或四乙氧基矽烷。 從抑制經過一個月後的濃度不均勻並改善耐溶劑性之觀點考慮，其他烷氧基矽烷化合物在供於共水解縮合之烷氧基矽烷化合物中所佔之比例係3莫耳%以下為較佳，2莫耳%以下為更佳，1莫耳%以下為特佳。The alkoxysilane compound used for the co-hydrolysis condensation may contain other alkoxysilane compounds other than the compounds represented by the general formulae (1) to (3) and (5). Examples of the other alkoxysilane compounds other than the compounds represented by the general formulae (1) to (3) and (5) include phenethyltrimethoxysilane, naphthyltrimethoxysilane, and phenethyl Triethoxysilane, naphthyltriethoxysilane, tetramethoxysilane, or tetraethoxysilane. From the viewpoint of suppressing uneven concentration after one month and improving solvent resistance, the proportion of other alkoxysilane compounds in the alkoxysilane compound used for co-hydrolysis condensation is 3 mol% or less. Good, less than 2 mole% is more preferable, and less than 1 mole% is particularly good.

本發明中，從容易將對波長589nm的光之折射率控制為1.5以下之觀點考慮，聚矽氧烷系樹脂的側鏈中20莫耳%以上（較佳為40莫耳%以上，更佳為50莫耳%以上，特佳為60莫耳%以上）係碳數1～4的烷基及碳數1～4的烷氧基中的至少一方為較佳。聚矽氧烷系樹脂的側鏈中20莫耳%以上（較佳為40莫耳%以上，更佳為50莫耳%以上，特佳為60莫耳%以上）係碳數1～3的烷基及碳數1～3的烷氧基中的至少一方為更佳，係碳數1或2的烷基及碳數1或2的烷氧基中的至少一方為特佳，係碳數1或2的烷基為更特佳。 從降低聚矽氧烷系樹脂的折射率之觀點考慮，在聚矽氧烷系樹脂的側鏈中含有苯基之側鏈係20莫耳%以下為較佳，10莫耳%以下為更佳，5莫耳%以下為特佳。In the present invention, from the viewpoint of easily controlling the refractive index of light having a wavelength of 589 nm to 1.5 or less, the side chain of the polysiloxane resin is 20 mol% or more (preferably 40 mol% or more, more preferably 50 mol% or more, particularly preferably 60 mol% or more) At least one of an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms is preferred. 20 mol% or more (preferably 40 mol% or more, more preferably 50 mol% or more, particularly preferably 60 mol% or more) in the side chain of the polysiloxane resin is a carbon number of 1 to 3 At least one of an alkyl group and an alkoxy group having 1 to 3 carbon atoms is more preferable. At least one of an alkyl group having 1 or 2 carbon atoms and an alkoxy group having 1 or 2 carbon atoms is particularly preferable. A 1 or 2 alkyl group is more preferred. From the viewpoint of reducing the refractive index of the polysiloxane resin, a side chain containing a phenyl group in the side chain of the polysiloxane resin is preferably 20 mol% or less, and more preferably 10 mol% or less. , 5 mole% or less is particularly preferred.

聚矽氧烷系樹脂藉由使烷氧基矽烷化合物進行共水解縮合亦即水解及部分縮合而得到。共水解縮合中能夠使用一般的方法。例如，可以使用向混合物中添加有機溶劑、水及根據需要添加催化劑，並在50～150℃下加熱攪拌0.5～100小時左右之方法。另外，加熱撹拌中，根據需要可以藉由蒸餾來餾去水解副產物（甲醇等醇）和縮合副產物（水）。The polysiloxane resin is obtained by subjecting an alkoxysilane compound to co-hydrolytic condensation, that is, hydrolysis and partial condensation. A common method can be used for co-hydrolytic condensation. For example, a method of adding an organic solvent, water and a catalyst as necessary to the mixture, and heating and stirring at 50 to 150 ° C. for about 0.5 to 100 hours can be used. In addition, during heating, the hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) can be distilled off by distillation if necessary.

作為聚矽氧烷系樹脂的較佳例，可以舉出藉由使作為下述表中所記載之烷氧基矽烷化合物之單體進行共水解縮合而得到之聚矽氧烷系樹脂。As a preferable example of a polysiloxane resin, the polysiloxane resin obtained by co-hydrolyzing and condensing the monomer which is an alkoxy silane compound shown in the following table | surface is mentioned.

下述表中，DMDS為二甲基二甲氧基矽烷的簡稱。MPTMS為3-甲基丙烯醯氧基丙基三甲氧基矽烷的簡稱。MPTES為3-甲基丙烯醯氧基丙基三乙氧基矽烷的簡稱。TMSPSAn為3-三甲氧基矽基丙基琥珀酸酐的簡稱。TESPSAn為3-三乙氧基矽基丙基琥珀酸酐的簡稱。GOPTS為3-縮水甘油氧基丙基三甲氧基矽烷的簡稱。GOPTES為3-縮水甘油氧基丙基三乙氧基矽烷的簡稱。TEOS為四乙氧基矽烷的簡稱。PTMS為苯基三甲氧基矽烷的簡稱。 [表1] [表2] In the following table, DMDS is an abbreviation of dimethyldimethoxysilane. MPTMS is an abbreviation for 3-methacryloxypropyltrimethoxysilane. MPTES is an abbreviation for 3-methacryloxypropyltriethoxysilane. TMSPSAn is an abbreviation for 3-trimethoxysilylpropylsuccinic anhydride. TESPSAn is short for 3-triethoxysilylpropylsuccinic anhydride. GOPTS is short for 3-glycidoxypropyltrimethoxysilane. GOPTES is short for 3-glycidoxypropyltriethoxysilane. TEOS is short for Tetraethoxysilane. PTMS is an abbreviation for phenyltrimethoxysilane. [Table 1] [Table 2]

（分散劑） 本發明的組成物可以含有分散劑作為樹脂。分散劑含有選自酸性樹脂、鹼性樹脂及兩性樹脂中之1種以上為較佳，選自酸性樹脂及兩性樹脂中之至少1種為更佳。依該態樣，粒子的分散性良好。(Dispersant) The composition of the present invention may contain a dispersant as a resin. The dispersant preferably contains at least one kind selected from an acidic resin, a basic resin, and an amphoteric resin, and more preferably at least one kind selected from an acidic resin and an amphoteric resin. In this aspect, the dispersibility of the particles is good.

本發明中，酸性樹脂係指具有酸基之樹脂，係指酸值為5mgKOH/g以上、胺值小於5mgKOH/g的樹脂。酸性樹脂不具有鹼性基為較佳。作為酸性樹脂所具有之酸基，例如可以舉出羧基、磷酸基、磺酸基、酚性羥基等，磷酸基、羧基為較佳。酸性樹脂的酸值係5～200mgKOH/g為較佳。酸值的下限係10mgKOH/g以上為更佳，20mgKOH/g以上為進一步較佳。酸值的上限係100mgKOH/g以下為更佳，60mgKOH/g以下為進一步較佳。並且，酸性樹脂的胺值係2mgKOH/g以下為較佳，1mgKOH/g以下為更佳。In the present invention, an acidic resin means a resin having an acid group, and means a resin having an acid value of 5 mgKOH / g or more and an amine value of less than 5 mgKOH / g. It is preferable that the acidic resin does not have a basic group. As an acid group which an acid resin has, a carboxyl group, a phosphate group, a sulfonic acid group, a phenolic hydroxyl group, etc. are mentioned, for example, A phosphate group and a carboxyl group are preferable. The acid value of the acid resin is preferably 5 to 200 mgKOH / g. The lower limit of the acid value is more preferably 10 mgKOH / g or more, and more preferably 20 mgKOH / g or more. The upper limit of the acid value is more preferably 100 mgKOH / g or less, and more preferably 60 mgKOH / g or less. The amine value of the acidic resin is preferably 2 mgKOH / g or less, and more preferably 1 mgKOH / g or less.

本發明中，鹼性樹脂係指具有鹼性基之樹脂，係指胺值為5mgKOH/g以上、酸值小於5mgKOH/g的樹脂。鹼性樹脂不具有酸基為較佳。作為鹼性樹脂所具有之鹼性基，胺基為較佳。鹼性樹脂的胺值係5～200mgKOH/g為較佳，5～150mgKOH/g為更佳，5～100mgKOH/g為進一步較佳。In the present invention, the basic resin means a resin having a basic group, and means a resin having an amine value of 5 mgKOH / g or more and an acid value of less than 5 mgKOH / g. It is preferable that the basic resin does not have an acid group. As the basic group possessed by the basic resin, an amine group is preferred. The amine value of the basic resin is preferably 5 to 200 mgKOH / g, more preferably 5 to 150 mgKOH / g, and still more preferably 5 to 100 mgKOH / g.

本發明中，兩性樹脂係指具有酸基和鹼性基之樹脂，係指酸值為5mgKOH/g以上、胺值為5mgKOH/g以上的樹脂。作為酸基，可以舉出前述者，羧基為較佳。作為鹼性基，胺基為較佳。 兩性樹脂的酸值係5～200mgKOH/g為較佳。下限係10mgKOH/g以上為更佳，20mgKOH/g以上為進一步較佳。上限係150mgKOH/g以下為更佳，100mgKOH/g以下為進一步較佳。胺值係5～200mgKOH/g為較佳。胺值的下限係10mgKOH/g以上為更佳，20mgKOH/g以上為進一步較佳。胺值的上限係150mgKOH/g以下為更佳，100mgKOH/g以下為進一步較佳。兩性樹脂的酸值與胺值的比率係酸值:胺值=1:4～4:1為較佳，1:3～3:1為更佳。In the present invention, an amphoteric resin means a resin having an acid group and a basic group, and means a resin having an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more. Examples of the acid group include the foregoing, and a carboxyl group is preferred. As the basic group, an amine group is preferred. The acid value of the amphoteric resin is preferably 5 to 200 mgKOH / g. The lower limit is more preferably 10 mgKOH / g or more, and more preferably 20 mgKOH / g or more. The upper limit is more preferably 150 mgKOH / g or less, and more preferably 100 mgKOH / g or less. The amine value is preferably 5 to 200 mgKOH / g. The lower limit of the amine value is more preferably 10 mgKOH / g or more, and more preferably 20 mgKOH / g or more. The upper limit of the amine value is more preferably 150 mgKOH / g or less, and more preferably 100 mgKOH / g or less. The ratio of the acid value to the amine value of the amphoteric resin is the acid value: amine value = 1: 4 to 4: 1 is more preferable, and 1: 3 to 3: 1 is more preferable.

作為分散劑，高分子分散劑〔例如，具有胺基（amine group）之樹脂（聚醯胺胺（polyamide amine）及其鹽等）、寡亞胺系樹脂、聚羧酸及其鹽、高分子量不飽和酸酯、改質聚胺基甲酸酯、改質聚酯、改質聚（甲基）丙烯酸酯、（甲基）丙烯酸系共聚物、萘磺酸福馬林缩聚物等〕。高分子分散劑根据其結構可以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、嵌段型高分子。As a dispersant, a polymer dispersant [for example, a resin having an amine group (polyamide amine and a salt thereof), an oligoimide resin, a polycarboxylic acid and a salt thereof, and a high molecular weight Unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, formalin naphthalenesulfonic acid, etc.]. Polymer dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers based on their structure.

分散劑具備具有對顏料之吸附能之部位為較佳（以下，統稱為“吸附部位”）。作為吸附部位，可以舉出具有至少1種選自包括酸基、脲基、胺基甲酸酯基、具有配位性氧原子之基團、具有鹼性氮原子之基團、雜環基、烷氧基羰基、烷基胺基羰基、羧基、磺醯胺基、烷氧基矽基、環氧基、异氰酸酯基及羥基之組群中之基團之1價的取代基等。吸附部位係酸系吸附部位為較佳。作為酸系吸附部位，可以舉出酸基等。其中，酸系吸附部位係含有磷原子之基團或羧基中的至少一方為較佳。作為含有磷原子之基團，可以舉出磷酸酯基、聚磷酸酯基、磷酸基等。關於吸附部位的詳細內容，可以參閱日本特開2015-34961號公報的0073～0080段，其內容被併入本說明書中。It is preferable that the dispersant has a site having an adsorption energy for the pigment (hereinafter, collectively referred to as “adsorption site”). Examples of the adsorption site include at least one member selected from the group consisting of an acid group, a urea group, a urethane group, a group having a cooperating oxygen atom, a group having a basic nitrogen atom, a heterocyclic group, Monovalent substituents of groups in the group of alkoxycarbonyl, alkylaminocarbonyl, carboxyl, sulfonamido, alkoxysilyl, epoxy, isocyanate, and hydroxyl groups, and the like. The adsorption site is preferably an acid-based adsorption site. Examples of the acid-based adsorption site include acid groups. Among them, the acid-based adsorption site is preferably at least one of a group containing a phosphorus atom or a carboxyl group. Examples of the group containing a phosphorus atom include a phosphate group, a polyphosphate group, and a phosphate group. For details of the adsorption site, refer to paragraphs 0073 to 080 of Japanese Patent Application Laid-Open No. 2015-34961, the contents of which are incorporated in this specification.

本發明中，樹脂（分散劑）係下述式（111）所表示之樹脂為較佳。In the present invention, the resin (dispersant) is preferably a resin represented by the following formula (111).

[化學式10] [Chemical Formula 10]

上述式（111）中，R1 表示（m+n）價的連接基，R2 表示單鍵或2價的連接基。A1 表示具有至少1種選自包括酸基、脲基、胺基甲酸酯基、具有配位性氧原子之基團、具有鹼性氮原子之基團、雜環基、烷氧基羰基、烷基胺基羰基、羧基、磺醯胺基、烷氧基矽基、環氧基、异氰酸酯基及羥基之組群中之基團之1價的取代基。n個A1 及R2 可以分別相同，亦可以不同。m表示8以下的正數，n表示1～9，m+n滿足3～10。P1 表示1價的聚合物鏈。m個P1 可以相同，亦可以不同。In the formula (111), R 1 represents a (m + n) -valent linking group, and R 2 represents a single bond or a divalent linking group. A 1 represents having at least one member selected from the group consisting of an acid group, a urea group, a urethane group, a group having a cooperating oxygen atom, a group having a basic nitrogen atom, a heterocyclic group, and an alkoxycarbonyl group. , A monovalent substituent of a group in the group of alkylaminocarbonyl, carboxyl, sulfonamido, alkoxysilyl, epoxy, isocyanate, and hydroxyl groups. The n A 1 and R 2 may be the same or different, respectively. m represents a positive number of 8 or less, n represents 1 to 9, and m + n satisfies 3 to 10. P 1 represents a monovalent polymer chain. The m P 1 may be the same or different.

式（111）所表示之樹脂所具有之取代基A1 能夠與顏料（例如，氧化鈦等無機粒子）相互作用，因此式（111）所表示之樹脂藉由具有n個（1～9個）取代基A1 而與顏料（例如，氧化鈦等無機粒子）牢固地相互作用，從而提高顏料在組成物中之分散性。並且，式（111）所表示之樹脂所具有之m個聚合物鏈P1 能夠作為立體排斥基發揮功能，藉由具有m個聚合物鏈P1 ，能夠發揮良好的立體排斥力而均勻地分散顏料（例如，氧化鈦等無機粒子）。The substituent A 1 in the resin represented by the formula (111) can interact with pigments (for example, inorganic particles such as titanium oxide). Therefore, the resin represented by the formula (111) has n (1 to 9) resins. The substituent A 1 strongly interacts with the pigment (for example, inorganic particles such as titanium oxide), thereby improving the dispersibility of the pigment in the composition. In addition, the m polymer chains P 1 possessed by the resin represented by the formula (111) can function as a steric repulsive group, and having m polymer chains P 1 can exhibit a good steric repulsive force and be uniformly dispersed. Pigments (for example, inorganic particles such as titanium oxide).

（m+n）價的連接基包括由1至100個碳原子、0個至10個氮原子、0個至50個氧原子、1個至200個氫原子及0個至20個硫原子構成之基團。作為R1 的具體例，可以舉出下述結構單元或2個以上的以下結構單元組合而構成之基團（亦可以形成環結構）。關於（m+n）價的連接基的詳細內容，可以參閱日本特開2007-277514號公報的0076～0084段，其內容被併入本說明書中。The (m + n) valence linking group consists of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. Of groups. Specific examples of R 1 include a group composed of the following structural units or a combination of two or more of the following structural units (which may also form a ring structure). For details of the (m + n) -valent linking group, refer to paragraphs 0076 to 0084 of Japanese Patent Application Laid-Open No. 2007-277514, the contents of which are incorporated into this specification.

[化學式11] [Chemical Formula 11]

式（111）中，P1 表示1價的聚合物鏈。1價的聚合物鏈係具有源自乙烯基化合物之重複單元之1價的聚合物鏈為較佳。關於聚合物鏈的詳細內容，可以參閱日本特開2007-277514號公報的0087～0098段，其內容被併入本說明書中。In Formula (111), P 1 represents a monovalent polymer chain. A monovalent polymer chain is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound. For details of the polymer chain, refer to paragraphs 0087 to 0098 of Japanese Patent Application Laid-Open No. 2007-277514, the contents of which are incorporated into this specification.

式（111）中，R2 表示單鍵或2價的連接基。作為2價的連接基，包括由1至100個碳原子、0個至10個氮原子、0個至50個氧原子、1個至200個氫原子及0個至20個硫原子構成之基團，可以未經取代，亦可以進一步具有取代基。作為2價的連接基的具體例，可以舉出下述結構單元或2個以上的以下結構單元組合而構成之基團。關於2價的連接基的詳細內容，可以參閱日本特開2007-277514號公報的0071～0075段，其內容被併入本說明書中。In formula (111), R 2 represents a single bond or a divalent linking group. The divalent linking group includes a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. The group may be unsubstituted or may further have a substituent. Specific examples of the divalent linking group include groups consisting of the following structural units or a combination of two or more of the following structural units. For details of the divalent linking group, refer to paragraphs 0071 to 0075 of Japanese Patent Application Laid-Open No. 2007-277514, the contents of which are incorporated into this specification.

[化學式12] [Chemical Formula 12]

式（111）中，關於A1 所表示之1價的取代基的詳細內容，可以參閱日本特開2007-277514號公報的0041～0070段，其內容被併入本說明書中。For details of the monovalent substituent represented by A 1 in formula (111), refer to paragraphs 0041 to 0070 of Japanese Patent Application Laid-Open No. 2007-277514, the contents of which are incorporated herein.

作為上述式（111）所表示之高分子化合物，可以參閱日本特開2007-277514號公報的0039段（對應之美國專利申請公開第2010/0233595號說明書的＜0053＞）的記載及日本特開2015-34961號公報的0081～0117段的記載，該等內容被併入本說明書中。As the polymer compound represented by the above formula (111), reference can be made to the description of paragraph 0039 of Japanese Patent Application Laid-Open No. 2007-277514 (corresponding to US Patent Application Publication No. 2010/0233595 <0053>) and Japanese Patent Application Laid-Open The descriptions in paragraphs 081 to 0117 of 2015-34961 are incorporated into this specification.

本發明中，樹脂（分散劑）亦可以使用含有下述式（11）～式（14）中的任一個所表示之重複單元之接枝共聚物。In the present invention, as the resin (dispersant), a graft copolymer containing a repeating unit represented by any one of the following formulae (11) to (14) may be used.

[化學式13] [Chemical Formula 13]

式（11）～式（14）中，W1 、W2 、W3 及W4 分別獨立地表示氧原子或NH，X1 、X2 、X3 、X4 及X5 分別獨立地表示氫原子或1價的基團，Y1 、Y2 、Y3 及Y4 分別獨立地表示2價的連接基，Z1 、Z2 、Z3 及Z4 分別獨立地表示1價的基團，R3 表示伸烷基，R4 表示氫原子或1價的基團，n、m、p及q分別獨立地表示1～500的整數，j及k分別獨立地表示2～8的整數。式（13）中，當p為2～500時，存在複數個之R3 可以相互相同亦可以不同，式（14）中，當q為2～500時，存在複數個之X5 及R4 可以相互相同亦可以不同。In the formulae (11) to (14), W 1 , W 2 , W 3, and W 4 each independently represent an oxygen atom or NH, and X 1 , X 2 , X 3 , X 4, and X 5 each independently represent hydrogen. An atom or a monovalent group, Y 1 , Y 2 , Y 3 and Y 4 each independently represent a divalent linking group, and Z 1 , Z 2 , Z 3 and Z 4 each independently represent a monovalent group, R 3 represents an alkylene group, R 4 represents a hydrogen atom or a monovalent group, n, m, p, and q each independently represent an integer of 1 to 500, and j and k each independently represent an integer of 2 to 8. In formula (13), when p is 2 to 500, a plurality of R 3 may be the same as or different from each other. In formula (14), when q is 2 to 500, a plurality of X 5 and R 4 are present. They may be the same as or different from each other.

W1 、W2 、W3 及W4 係氧原子為較佳。X1 、X2 、X3 、X4 及X5 係氫原子或碳數1～12的烷基為較佳，分別獨立地係氫原子或甲基為更佳，甲基為特佳。Y1 、Y2 、Y3 及Y4 分別獨立地表示2價的連接基，連接基在結構上並沒有特別限制。Z1 、Z2 、Z3 及Z4 所表示之1價的基團並沒有特別限定，具體而言，可以舉出烷基、羥基、烷氧基、芳氧基、雜芳氧基、烷基硫醚基、芳基硫醚基、雜芳基硫醚基及胺基等。在該等之中，作為Z1 、Z2 、Z3 及Z4 所表示之有機基，尤其從提高分散性之觀點考慮，具有立體排斥效果者為較佳，各自獨立地係碳數5～24的烷基或烷氧基為較佳，其中，各自獨立地係碳數5～24的分支狀烷基、碳數5～24的環狀烷基或碳數5～24的烷氧基為特佳。另外，烷氧基中所含之烷基可以是直鏈狀、支鏈狀、環狀中的任一種。W 1 , W 2 , W 3 and W 4 are more preferred oxygen atoms. X 1 , X 2 , X 3 , X 4 and X 5 are more preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, each independently being a hydrogen atom or a methyl group is more preferred, and a methyl group is particularly preferred. Y 1 , Y 2 , Y 3 and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure. The monovalent group represented by Z 1 , Z 2 , Z 3 and Z 4 is not particularly limited, and specific examples include alkyl, hydroxyl, alkoxy, aryloxy, heteroaryloxy, and alkane Sulfide group, aryl sulfide group, heteroaryl sulfide group and amine group. Among these, as the organic groups represented by Z 1 , Z 2 , Z 3, and Z 4 , especially from the viewpoint of improving dispersibility, those having a steric repulsive effect are preferred, and each independently has a carbon number of 5 to An alkyl group or alkoxy group of 24 is preferable. Among them, each is independently 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. Extraordinary. The alkyl group contained in the alkoxy group may be any of linear, branched, and cyclic groups.

從分散穩定性、顯影性的觀點考慮，式（11）及式（12）中之j及k係4～6的整數為較佳，5為最佳。From the viewpoint of dispersion stability and developability, j and k in the formulae (11) and (12) are preferably integers of 4 to 6, and 5 is the most preferable.

式（13）中，R3 係碳數1～10的伸烷基為較佳，碳數2或3的伸烷基為更佳。In formula (13), R 3 is more preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms.

式（14）中，作為R4 所表示之1價的基團，在結構上並沒有特別限定。作為R4 ，可以較佳地舉出氫原子、烷基、芳基及雜芳基，進一步較佳為氫原子或烷基。當R4 為烷基時，係碳數1～20的直鏈狀烷基、碳數3～20的分支狀烷基或碳數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的直鏈狀烷基為特佳。式（14）中，當q為2～500時，接枝共聚物中存在複數個之X5 及R4 可以相互相同亦可以不同。In the formula (14), the monovalent group represented by R 4 is not particularly limited in structure. Examples of R 4 include a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and a hydrogen atom or an alkyl group is more preferable. When R 4 is an alkyl group, a linear 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, and the carbon number is 1 to A linear alkyl group of 20 is more preferred, and a linear alkyl group of 1 to 6 carbons is particularly preferred. In formula (14), when q is 2 to 500, a plurality of X 5 and R 4 in the graft copolymer may be the same as or different from each other.

關於上述接枝共聚物，可以參閱日本特開2012-255128號公報的0025～0094段的記載，上述內容被併入本說明書中。作為上述接枝共聚物的具體例，例如可以舉出以下樹脂。並且，可以舉出日本特開2012-255128號公報的0072～0094段中所記載之樹脂，其內容被併入本說明書中。 [化學式14] Regarding the above-mentioned graft copolymer, the descriptions in paragraphs 0025 to 0094 of Japanese Patent Application Laid-Open No. 2012-255128 can be referred to, and the above contents are incorporated into this specification. Specific examples of the graft copolymer include the following resins. In addition, the resins described in paragraphs 0072 to 0094 of Japanese Patent Application Laid-Open No. 2012-255128 can be cited, and the contents thereof are incorporated into this specification. [Chemical Formula 14]

本發明中，樹脂（分散劑）係在主鏈及側鏈中的至少一方含有鹼性氮原子之寡亞胺系分散劑亦較佳。作為寡亞胺系分散劑，如下樹脂為較佳：具有包含具有pKa（power of Ka；Ka為酸解離常數）為14以下的官能基之部分結構X之重複單元、以及含有原子數40～10,000的寡聚物鏈或聚合物鏈Y之側鏈，且在主鏈及側鏈中的至少一方具有鹼性氮原子。該樹脂在氮原子和部分結構X中所包含之pKa為14以下的官能基這雙方中與顏料（例如，氧化鈦等無機粒子）相互作用，並且由於樹脂具有原子數40～10,000的寡聚物鏈或聚合物鏈Y，因此例如寡聚物鏈或聚合物鏈Y作為立體排斥基發揮功能，藉此能夠發揮良好的分散性而均勻地分散氧化鈦等無機粒子。並且，藉由寡聚物鏈或聚合物鏈Y和溶劑相互作用，能夠長期抑制氧化鈦等無機粒子的沉降。進而，藉由寡聚物鏈或聚合物鏈Y作為立體排斥基發揮功能，能夠防止顏料（例如，氧化鈦等無機粒子）的凝聚。因此，即使提高顏料（較佳為氧化鈦等無機粒子）的含量，亦能夠得到優異之分散性。In the present invention, a resin (dispersant) is also an oligoimide-based dispersant containing a basic nitrogen atom in at least one of the main chain and the side chain. As the oligoimide-based dispersant, a resin having a repeating unit including a partial structure X having a functional group having a pKa (power of Ka; Ka is an acid dissociation constant) of 14 or less, and a number of atoms of 40 to 10,000 is preferred. Oligomer chain or polymer chain Y has a side chain, and has a basic nitrogen atom in at least one of the main chain and the side chain. This resin interacts with pigments (for example, inorganic particles such as titanium oxide) in both the nitrogen atom and the functional group having a pKa of 14 or less in the structure X, and the resin has an oligomer having 40 to 10,000 atoms Chain or polymer chain Y, for example, the oligomer chain or polymer chain Y functions as a steric repulsive group, thereby being able to exhibit good dispersibility and uniformly disperse inorganic particles such as titanium oxide. In addition, by the interaction of the oligomer chain or the polymer chain Y with the solvent, it is possible to suppress the precipitation of inorganic particles such as titanium oxide for a long period of time. Furthermore, the oligomer chain or the polymer chain Y functions as a steric repulsive group, thereby preventing aggregation of pigments (for example, inorganic particles such as titanium oxide). Therefore, even if the content of the pigment (preferably inorganic particles such as titanium oxide) is increased, excellent dispersibility can be obtained.

在此，鹼性氮原子只要是呈鹼性之氮原子，則並沒有特別限制，但樹脂包含具有pKb（power of Kb；Kb為鹼解離常數）為14以下的氮原子之結構為較佳，包含具有pKb為10以下的氮原子之結構為更佳。本發明中，pKb（鹼強度）係指在水溫25℃下之pKb，係用於定量表示鹼的強度之指標之一。鹼強度pKb的含義與鹼性度常數的含義相同。鹼強度pKb與酸強度pKa具有pKb=14-pKa的關係。Here, the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom, but a resin containing a nitrogen atom having a pKb (power of Kb; Kb is an alkali dissociation constant) of 14 or less is preferred. A structure containing a nitrogen atom having a pKb of 10 or less is more preferred. In the present invention, pKb (base strength) refers to pKb at a water temperature of 25 ° C, and is one of the indicators for quantitatively indicating the strength of the base. The meaning of the base strength pKb is the same as that of the basicity constant. The relationship between the base strength pKb and the acid strength pKa is pKb = 14-pKa.

部分結構X中所包含之pKa為14以下的官能基並沒有特別限定，只要係物性滿足該條件者，則其結構等並沒有特別限定。pKa為12以下的官能基為特佳，pKa為11以下的官能基為最佳。具體而言，例如可以舉出羧基（pKa 3～5左右）、磺基（pKa -3～-2左右）、-COCH2 CO-基（pKa 8～10左右）、-COCH2 CN基（pKa 8～11左右）、-CONHCO-基、酚性羥基、-RF CH2 OH基或-（RF ）2 CHOH基（RF 表示全氟烷基。pKa 9～11左右）、磺醯胺基（pKa 9～11左右）等。具有pKa為14以下的官能基之部分結構X與具有氮原子之重複單元中之鹼性氮原子直接鍵結為較佳，但具有鹼性氮原子之重複單元的鹼性氮原子和部分結構X不僅可以以共價鍵的態樣連接，還可以以離子鍵結而形成鹽之態樣連接。The functional group having a pKa of 14 or less contained in the partial structure X is not particularly limited, and as long as the physical properties satisfy this condition, the structure and the like are not particularly limited. A functional group having a pKa of 12 or less is particularly preferred, and a functional group having a pKa of 11 or less is most preferred. Specific examples include a carboxyl group (about pKa 3 to 5), a sulfo group (about pKa -3 to -2), a -COCH 2 CO- group (about pKa 8 to 10), and a -COCH 2 CN group (pKa 8 to 11), -CONHCO- group, phenolic hydroxyl group, -R F CH 2 OH group or-(R F ) 2 CHOH group (R F represents perfluoroalkyl group. PKa 9 to 11), sulfonamide Group (pKa 9 ~ 11) and so on. It is preferred that a partial structure X having a functional group having a pKa of 14 or less be directly bonded to a basic nitrogen atom in a repeating unit having a nitrogen atom, but a basic nitrogen atom and a partial structure X having a repeating unit having a basic nitrogen atom. Not only can they be connected in the form of covalent bonds, but can also be connected in the form of salts by ionic bonding.

寡亞胺系分散劑係具有含有鹼性氮原子之重複單元且在側鏈上具有原子數40～10,000的寡聚物鏈或聚合物鏈Y之樹脂為較佳，該鹼性氮原子與具有pKa為14以下的官能基之部分結構X鍵結。 並且，寡亞胺系分散劑係（i）作為選自聚（低級伸烷基亞胺）系重複單元、聚烯丙胺系重複單元、聚二烯丙胺系重複單元、間二甲苯二胺-表氯醇縮聚物系重複單元及聚乙烯胺系重複單元中之至少1種之、具有鹼性氮原子之重複單元，係包含與鹼性氮原子鍵結且具有pKa為14以下的官能基之部分結構X之重複單元為較佳。寡亞胺系分散劑係（ii）在側鏈上具有原子數40～10,000的寡聚物鏈或聚合物鏈Y之樹脂亦較佳。另外，本發明中，聚（低級伸烷基亞胺）中之低級表示碳數為1～5，低級伸烷基亞胺表示碳數1～5的伸烷基亞胺。An oligoimide-based dispersant is preferably a resin having a repeating unit containing a basic nitrogen atom and having an oligomer chain or a polymer chain Y having 40 to 10,000 atoms in a side chain. The partial structure of the functional group having pKa of 14 or less is X-bonded. In addition, the oligoimide-based dispersant system (i) is selected from the group consisting of a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, and m-xylylenediamine. A repeating unit having at least one of a chlorohydrin polycondensate-based repeating unit and a polyvinylamine-based repeating unit having a basic nitrogen atom, which is a moiety containing a functional group bonded to a basic nitrogen atom and having a pKa of 14 or less Repeating units of structure X are preferred. The oligoimide-based dispersant (ii) is also preferably a resin having an oligomer chain or a polymer chain Y having 40 to 10,000 atoms in a side chain. In the present invention, the lower order in the poly (lower alkyleneimine) represents a carbon number of 1 to 5, and the lower alkyleneimine represents an alkyleneimine having 1 to 5 carbon atoms.

作為原子數40～10,000的寡聚物鏈或聚合物鏈Y，可以舉出能夠與樹脂的主鏈部連接之聚酯、聚醯胺、聚醯亞胺、聚（甲基）丙烯酸酯等公知的聚合物鏈。寡聚物鏈或聚合物鏈Y與樹脂之鍵結部位係寡聚物鏈或聚合物鏈Y的末端為較佳。Examples of the oligomer chain or polymer chain Y having 40 to 10,000 atoms include known polyesters, polyamides, polyimines, and poly (meth) acrylates which can be connected to the main chain portion of the resin. Polymer chain. It is preferable that the bonding site between the oligomer chain or the polymer chain Y and the resin is an end of the oligomer chain or the polymer chain Y.

寡聚物鏈或聚合物鏈Y與作為選自聚（低級伸烷基亞胺）系重複單元、聚烯丙胺系重複單元、聚二烯丙胺系重複單元、間二甲苯二胺-表氯醇缩聚物系重複單元及聚乙烯胺系重複單元中之至少1種之具有氮原子之重複單元的氮原子鍵結為較佳。作為選自聚（低級伸烷基亞胺）系重複單元、聚烯丙胺系重複單元、聚二烯丙胺系重複單元、間二甲苯二胺-表氯醇缩聚物系重複單元及聚乙烯胺系重複單元中之至少1種之含有氮原子之重複單元等的主鏈部與Y的鍵結方式為共價鍵、離子鍵或共價鍵及離子鍵的混合。主鏈部與Y的鍵結方式的比率為共價鍵:離子鍵=100:0～0:100，95:5～5:95為較佳。Y與含有氮原子之重複單元的氮原子進行醯胺鍵結、或作為羧酸鹽進行離子鍵結為較佳。The oligomer chain or polymer chain Y is selected from the group consisting of poly (lower alkyleneimine) repeating units, polyallylamine repeating units, polydiallylamine repeating units, m-xylylenediamine-epichlorohydrin It is preferable that a nitrogen atom of at least one of the polycondensate-based repeating unit and the polyvinylamine-based repeating unit has a repeating unit having a nitrogen atom. As the poly (lower alkyleneimine) -based repeating unit, polyallylamine-based repeating unit, polydiallylamine-based repeating unit, m-xylylenediamine-epichlorohydrin polycondensate-based repeating unit, and polyvinylamine-based At least one of the repeating units including a nitrogen atom-containing repeating unit and the main chain portion is bonded to Y by a covalent bond, an ionic bond, or a mixture of a covalent bond and an ionic bond. The ratio of the bonding mode of the main chain part to Y is a covalent bond: ionic bond = 100: 0 to 0: 100, and 95: 5 to 5:95 is preferable. It is preferable that Y is bonded to a nitrogen atom of a repeating unit containing a nitrogen atom, or to be ion-bonded as a carboxylate.

作為寡聚物鏈或聚合物鏈Y的原子數，從分散性、分散穩定性及顯影性的觀點考慮，50～5,000為較佳，60～3,000為更佳。並且，Y的數量平均分子量能夠藉由基於GPC法之聚苯乙烯換算值進行測定。Y的數量平均分子量係1,000～50,000為較佳，1,000～30,000為更佳。The number of atoms of the oligomer chain or polymer chain Y is preferably 50 to 5,000, and more preferably 60 to 3,000 from the viewpoint of dispersibility, dispersion stability, and developability. The number average molecular weight of Y can be measured by a polystyrene conversion value based on the GPC method. The number average molecular weight of Y is preferably 1,000 to 50,000, and more preferably 1,000 to 30,000.

寡亞胺系分散劑例如可以舉出含有式（I-1）所表示之重複單元和式（I-2）所表示之重複單元及式（I-2a）所表示之重複單元中的至少一方之樹脂等。Examples of the oligoimide-based dispersant include at least one of a repeating unit represented by formula (I-1), a repeating unit represented by formula (I-2), and a repeating unit represented by formula (I-2a). Of resin, etc.

[化學式15]R1 、R2 、R8 及R9 各自獨立地表示氫原子、鹵素原子或烷基（碳數1～6為較佳）。 a各自獨立地表示1～5的整數。*表示重複單元間的連接部。 L為單鍵、伸烷基（碳數1～6為較佳）、伸烯基（碳數2～6為較佳）、伸芳基（碳數6～24為較佳）、雜伸芳基（碳數1～6為較佳）、亞胺基（碳數0～6為較佳）、醚基、硫醚基、羰基、或該等的組合所涉及之連接基。其中，單鍵或-CR5 R6 -NR7 -（亞胺基成為X或Y側）為較佳。在此，R5 及R6 各自獨立地表示氫原子、鹵素原子、烷基（碳數1～6為較佳）。R7 為氫原子或碳數1～6的烷基。 La 係與CR8 CR9 和N一同形成環之結構部位，係與CR8 CR9 的碳原子一起形成碳數3～7的非芳香族雜環之結構部位為較佳。進一步較佳為與CR8 CR9 的碳原子及N（氮原子）一同形成5員～7員的非芳香族雜環之結構部位，更佳為形成5員的非芳香族雜環之結構部位，形成吡咯啶之結構部位為特佳。該結構部位可以進一步具有烷基等取代基。X表示具有pKa為14以下的官能基之基團。Y表示原子數40～10,000的寡聚物鏈或聚合物鏈。[Chemical Formula 15] R 1 , R 2 , R 8, and R 9 each independently represent a hydrogen atom, a halogen atom, or an alkyl group (carbon numbers of 1 to 6 are preferred). a each independently represents an integer of 1 to 5. * Indicates a connection portion between repeating units. L is a single bond, alkylene (carbon number 1 to 6 is preferred), alkylene (carbon number 2 to 6 is preferred), alkylene (carbon number 6 to 24 is preferred), hetero-arylene A linking group involving a group (carbon number 1 to 6 is preferred), an imino group (carbon number 0 to 6 is preferred), an ether group, a thioether group, a carbonyl group, or a combination thereof. Among them, a single bond or -CR 5 R 6 -NR 7- (imide group becomes the X or Y side) is preferred. Here, R 5 and R 6 each independently represent a hydrogen atom, a halogen atom, and an alkyl group (carbon numbers of 1 to 6 are preferred). R 7 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. La is a structural site that forms a ring together with CR 8 CR 9 and N, and a structural site that forms a non-aromatic heterocyclic ring having 3 to 7 carbon atoms with CR 8 CR 9 carbon atoms. It is more preferable to form a 5-member to 7-member non-aromatic heterocyclic structure site together with the carbon atom and N (nitrogen atom) of CR 8 CR 9 and more preferred to form a 5-member non-aromatic heterocyclic structure site. The structural site forming pyrrolidine is particularly preferred. The structural site may further have a substituent such as an alkyl group. X represents a group having a functional group having a pKa of 14 or less. Y represents an oligomer chain or a polymer chain having 40 to 10,000 atoms.

上述分散劑（寡亞胺系分散劑）還可以具有選自式（I-3）、式（I-4）及式（I-5）所表示之重複單元中之1種以上作為共聚成分。藉由上述分散劑含有該種重複單元，能夠進一步提高粒子的分散性。 [化學式16] The dispersant (oligoimide-based dispersant) may further have, as a copolymerization component, one or more kinds selected from the repeating units represented by formula (I-3), formula (I-4), and formula (I-5). When the dispersant contains such a repeating unit, the dispersibility of the particles can be further improved. [Chemical Formula 16]

R1 、R2 、R8 、R9 、L、La、a及*的含義與式（I-1）、（I-2）、（I-2a）中之定義相同。Ya表示具有陰離子基之原子數40～10,000的寡聚物鏈或聚合物鏈。R 1 , R 2 , R 8 , R 9 , L, La, a, and * have the same meanings as defined in the formulae (I-1), (I-2), and (I-2a). Ya represents an oligomer chain or a polymer chain having an anionic group of 40 to 10,000 atoms.

關於寡亞胺系分散劑，可以參閱日本特開2015-34961號公報的0118～0190段的記載，上述內容被併入本說明書中。作為寡亞胺系分散劑的具體例，例如能夠使用下述樹脂、或日本特開2015-34961號公報的0169～0190段中所記載之樹脂。 [化學式17] Regarding the oligoimide-based dispersant, the descriptions in paragraphs 0118 to 0190 of Japanese Patent Application Laid-Open No. 2015-34961 can be referred to, and the above contents are incorporated into this specification. As specific examples of the oligoimide-based dispersant, for example, the following resins or the resins described in paragraphs 0169 to 0190 of JP-A-2015-34961 can be used. [Chemical Formula 17]

分散劑亦可以作為市售品而獲得，作為該等的具體例，可以舉出BYK Chemie公司製“Disperbyk-101（聚醯胺胺磷酸鹽）、107（羧酸酯）、110、180（含有酸基之共聚物）、130（聚醯胺）、161、162、163、164、165、166、170（高分子共聚物）”、BYK Chemie公司製“BYK-P104、P105（高分子量不飽和聚羧酸）”、EFKA公司製“EFKA4047、4050、4010、4165（聚胺基甲酸酯系）、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“Ajisuper PB821、PB822”、KYOEISHA CHEMICAL Co.,Ltd.製“FLOWLEN TG-710（胺基甲酸酯寡聚物）”、KYOEISHA CHEMICAL Co.,Ltd.製“Polyflow No.50E、No.300（丙烯酸系共聚物）”、Kusumoto Chemicals, Ltd.製“Disparlon KS-860、873SN、874、#2150（脂肪族多價羧酸）、#7004（聚醚酯）、DA-703-50、DA-705、DA-725”、Kao Corporation製“Demor RN、N（萘磺酸福馬林缩聚物）、MS、C、SN-B（芳香族磺酸福馬林缩聚物）”、Kao Corporation製“Homogenol L-18（高分子聚羧酸）”、Kao Corporation製“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“Solsperse 5000（酞菁衍生物）、22000（偶氮顏料衍生物）、13240（聚酯胺）、3000、17000、27000（末端部具有功能部之高分子）、24000、26000、28000、32000、36000、38500（接枝型高分子）、41000、46000”、NIKKO CHEMICAL CO.,LTD.製“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）”等。 並且，在分散劑中，具有含有磷原子之基團（例如磷酸基等）作為酸系吸附部位之分散劑、包含式（11）～式（14）中任一個所表示之重複單元之接枝共聚物及寡亞胺系分散劑為較佳。從圖案形狀的觀點考慮，具有含有磷原子之基團作為酸系吸附部位之分散劑及包含式（11）～式（14）中任一個所表示之重複單元之接枝共聚物為更佳。 並且，從分散穩定性的觀點考慮，係在酸系吸附部位以外，還具有聚酯結構、較佳為對ε-己內酯、δ-戊內酯進行開環聚合而成之聚酯結構作為立體排斥基之分散劑為較佳。 作為具有含有磷原子之基團作為酸系吸附部位之分散劑的市售品，可以舉出Japan Lubrizol Corporation製“Solsperse 26000、36000（具有聚酯系結構）、41000（具有聚醚系結構）”。能夠較佳地使用該等。在具有含有磷原子之基團作為酸系吸附部位之分散劑的市售品中，Japan Lubrizol Corporation製Solsperse 36000為較佳。 分散劑能夠單獨使用1種或者將2種以上組合使用。 分散劑可以使用用作黏結劑之樹脂。並且，分散劑亦可以使用對波長589nm的光之折射率為1.5以下之樹脂。Dispersants can also be obtained as commercially available products. Specific examples of these include "Disperbyk-101 (polyamidophosphate), 107 (carboxylate), 110, 180 (containing Acid-based copolymers), 130 (polyamidamine), 161, 162, 163, 164, 165, 166, 170 (polymer copolymers) ", BYK-P104, P105 (high molecular weight unsaturated) made by BYK Chemie Polycarboxylic acid) "," EFKA4047, 4050, 4010, 4165 (polyurethane), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (manufactured by EFKA) Polyester amidamine), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajinomoto Fine-Techno Co., Inc. "Ajisuper PB821, PB822", "FLOWLEN TG-710 (urethane oligomer)" by KYOEISHA CHEMICAL Co., Ltd., "Polyflow No. 50E, No. 300 by KYOEISHA CHEMICAL Co., Ltd." (Acrylic Copolymer) "," Disparlon KS-860, 873SN, 874, # 2150 (made by Kusumoto Chemicals, Ltd., Aliphatic polyvalent carboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 "," Demor RN, N (formalin naphthalenesulfonate polycondensate), manufactured by Kao Corporation, MS , C, SN-B (Aromatic Sulfonic Formalin Polycondensate) "," Homogenol L-18 (Polymer Polycarboxylic Acid) "manufactured by Kao Corporation," Emulgen 920, 930, 935, 985 (Polyoxygen) manufactured by Kao Corporation Ethylene Nonyl Phenyl Ether) "," Acetamin 86 (Stearylamine Acetate) "," Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester) manufactured by Japan Lubrizol Corporation Amine), 3000, 17000, 27000 (polymers with functional parts at the ends), 24000, 26000, 28000, 32000, 36000, 38500 (graft polymers), 41000, 46000 ", NIKKO CHEMICAL CO., LTD. "Nikkol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)" and the like. Further, the dispersant has a dispersant containing a phosphorus atom-containing group (for example, a phosphate group) as an acid-based adsorption site, and a graft comprising a repeating unit represented by any one of formulas (11) to (14) Copolymers and oligoimide-based dispersants are preferred. From the viewpoint of pattern shape, a graft copolymer having a group containing a phosphorus atom as a dispersant for an acid-based adsorption site and a repeating unit represented by any one of formulas (11) to (14) is more preferable. In addition, from the viewpoint of dispersion stability, it is a polyester structure having a polyester structure in addition to the acidic adsorption site, and preferably a ring-opening polymerization of ε-caprolactone and δ-valerolactone. A dispersant having a steric repulsion group is preferred. Examples of commercially available dispersants having a group containing a phosphorus atom as an acid-based adsorption site include "Solsperse 26000, 36000 (having a polyester-based structure), and 41000 (having a polyether-based structure)" manufactured by Japan Lubrizol Corporation. . These can be used better. Among commercially available dispersants having a group containing a phosphorus atom as an acid-based adsorption site, Solsperse 36000 manufactured by Japan Lubrizol Corporation is more preferred. The dispersant can be used alone or in combination of two or more. As the dispersant, a resin used as a binder can be used. In addition, as the dispersant, a resin having a refractive index of 1.5 or less with respect to light having a wavelength of 589 nm may be used.

本發明的組成物中，作為分散助劑，可以含有具有酸基和交聯性基之分散助劑。作為較佳的酸基，可以舉出磺酸基、磷酸基、膦酸基及羧酸基，磷酸基為更佳。作為交聯性基，可以舉出含有乙烯性不飽和鍵之基團、環氧基及巰基等，含有乙烯性不飽和鍵之基團為更佳。作為含有乙烯性不飽和鍵之基團，還包括在聚合性化合物的說明中舉出之可加成聚合之伸乙基。 作為分散助劑的市售品，可以舉出LIGHT ESTER P-1M、LIGHT ESTER P-2M、LIGHT ESTER HO-MS、LIGHT ESTER HO-HH（以上為KYOEISHA CHEMICAL Co.,Ltd.製）Phosmer M、Phosmer PE、Phosmer MH、Phosmer CL、Phosmer PP（以上為Uni-Chemical Corporation製）、TBAS-Q、TBAS-R（以上為MRC Unitec Co.,Ltd.製）等。The composition of the present invention may contain a dispersing assistant having an acid group and a crosslinkable group as a dispersing assistant. As a preferable acid group, a sulfonic acid group, a phosphate group, a phosphonic acid group, and a carboxylic acid group are mentioned, More preferably, a phosphate group is used. Examples of the crosslinkable group include a group containing an ethylenically unsaturated bond, an epoxy group, and a mercapto group. A group containing an ethylenically unsaturated bond is more preferred. Examples of the group containing an ethylenically unsaturated bond include an ethylenic group that can be additionally polymerized as described in the description of the polymerizable compound. Examples of commercially available dispersion aids include LIGHT ESTER P-1M, LIGHT ESTER P-2M, LIGHT ESTER HO-MS, and LIGHT ESTER HO-HH (the above are manufactured by KYOEISHA CHEMICAL Co., Ltd.) Phosmer M, Phosmer PE, Phosmer MH, Phosmer CL, Phosmer PP (above manufactured by Uni-Chemical Corporation), TBAS-Q, TBAS-R (above manufactured by MRC Unitec Co., Ltd.), etc.

從圖案形狀及黏附性的觀點考慮，分散劑的含量相對於組成物的總固體成分係1～80質量%為較佳。上限係70質量%以下為較佳，60質量%以下為進一步較佳。下限係1.5質量%以上為較佳，2質量%以上為進一步較佳。 並且，分散劑的含量相對於顏料100質量份係1～100質量份為較佳。上限係80質量份以下為較佳，60質量份以下為進一步較佳。下限係2.5質量份以上為較佳，5質量份以上為進一步較佳。 並且，分散劑的含量相對於無機顏料100質量份係1～100質量份為較佳。上限係80質量份以下為較佳，60質量份以下為進一步較佳。下限係2.5質量份以上為較佳，5質量份以上為進一步較佳。 並且，分散劑的含量相對於氧化鈦100質量份係1～100質量份為較佳。上限係80質量份以下為較佳，60質量份以下為進一步較佳。下限係2.5質量份以上為較佳，5質量份以上為進一步較佳。From the viewpoint of pattern shape and adhesion, the content of the dispersant is preferably 1 to 80% by mass based on the total solid content of the composition. The upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less. The lower limit is preferably 1.5% by mass or more, and more preferably 2% by mass or more. The content of the dispersant is preferably 1 to 100 parts by mass based on 100 parts by mass of the pigment. The upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, and more preferably 5 parts by mass or more. The content of the dispersant is preferably 1 to 100 parts by mass based on 100 parts by mass of the inorganic pigment. The upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, and more preferably 5 parts by mass or more. The content of the dispersant is preferably 1 to 100 parts by mass based on 100 parts by mass of titanium oxide. The upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, and more preferably 5 parts by mass or more.

＜＜溶劑＞＞ 本發明的組成物含有溶劑為較佳。溶劑能夠使用各種有機溶劑而構成。作為有機溶劑，可以舉出丙酮、甲乙酮、環己烷、乙酸乙酯、二氯乙烷、四氫呋喃、甲苯、乙二醇單甲醚、乙二醇單乙醚、乙二醇二甲醚、丙二醇單甲醚、丙二醇單乙醚、乙醯丙酮、環己酮、二丙酮醇、乙二醇單甲醚乙酸酯、乙二醇乙醚乙酸酯、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、二乙二醇單乙醚、二乙二醇二甲醚、二乙二醇二乙醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、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、乳酸甲酯、乳酸乙酯等。該等有機溶劑可以單獨使用或者混合使用。<< Solvent> The composition of the present invention preferably contains a solvent. The solvent can be configured using various organic solvents. Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, and propylene glycol monoamine. Methyl ether, propylene glycol monoethyl ether, acetone acetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether 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, dimethylmethylene, γ-butyrolactone, Methyl lactate, ethyl lactate, etc. These organic solvents can be used alone or in combination.

溶劑使用金屬含量較少的溶劑為較佳。溶劑的金屬含量例如係10質量ppb（十億分點：parts per billion）以下為較佳。根據需要亦可以使用質量ppt（十億分點）水準的高純度溶劑。該種高純度溶劑例如能夠從Toyo Gosei Co.,Ltd.獲得（化學工業日報、2015年11月13日）。 作為從溶劑中除去金屬等雜質之方法，例如可以舉出蒸餾（分子蒸餾或薄膜蒸餾等）或使用了過濾器之濾過。作為過濾中所使用之過濾器的過濾器孔徑（細孔尺寸），10nm以下為較佳，5nm以下為更佳，3nm以下為進一步較佳。作為過濾器，聚四氟乙烯製、聚乙烯製或尼龍製的過濾器為較佳。 溶劑中可以含有異構體（相同原子數且不同結構的化合物）。並且，異構體可以僅含有1種，亦可以含有複數種。As the solvent, a solvent having a small metal content is preferably used. The metal content of the solvent is preferably 10 mass ppb (parts per billion) or less. High-purity solvents with mass ppt (billion points) can be used as required. Such a high-purity solvent can be obtained from Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015). Examples of a method for removing impurities such as metals from a solvent include distillation (molecular distillation, thin film distillation, and the like) or filtration using a filter. The filter pore size (pore size) of the filter used in the filtration is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferred. The solvent may contain isomers (compounds having the same number of atoms and different structures). In addition, the isomers may contain only one kind or plural kinds.

溶劑的含量係組成物的固體成分濃度成為25～70質量%之量為較佳，組成物的固體成分濃度成為30～60質量%之量為更佳。The content of the solvent is preferably an amount in which the solid content concentration of the composition is 25 to 70% by mass, and more preferably an amount in which the solid content concentration of the composition is 30 to 60% by mass.

＜＜硬化性化合物＞＞ 本發明的組成物含有硬化性化合物為較佳。 作為硬化性化合物，能夠使用可藉由自由基、酸或熱進行交聯（包括聚合及縮合）之化合物。本發明中所使用之硬化性化合物例如可以舉出具有含有乙烯性不飽和鍵之基團之化合物、具有環氧基之化合物、具有羥甲基之化合物等，具有含有乙烯性不飽和鍵之基團之化合物為較佳。作為含有乙烯性不飽和鍵之基團，可以舉出乙烯基、（甲基）丙烯酸基、（甲基）丙烯醯基等。 本發明中，硬化性化合物係自由基聚合性化合物為較佳。作為自由基聚合性化合物，可以舉出具有含有乙烯性不飽和鍵之基團之化合物等。本發明的組成物可以含有後述之具有環氧基之化合物作為硬化性化合物。以下，當沒有特別指定而稱為聚合性化合物時，係指自由基聚合性化合物。<<< Sclerosing Compound> The composition of the present invention preferably contains a sclerosing compound. As the curable compound, a compound that can be crosslinked (including polymerization and condensation) by radical, acid, or heat can be used. Examples of the curable compound used in the present invention include a compound having a group containing an ethylenically unsaturated bond, a compound having an epoxy group, a compound having a methylol group, and the like, and a group having an ethylenically unsaturated bond. A group of compounds is preferred. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) acrylic group, and a (meth) acrylfluorenyl group. In the present invention, a curable compound is preferably a radical polymerizable compound. Examples of the radical polymerizable compound include compounds having a group containing an ethylenically unsaturated bond. The composition of this invention may contain the compound which has an epoxy group mentioned later as a curable compound. Hereinafter, when it is referred to as a polymerizable compound without specific designation, it means a radical polymerizable compound.

硬化性化合物的含量相對於組成物的總固體成分係1～70質量%為較佳。下限係3質量%以上為較佳，5質量%以上為更佳。上限係60質量%以下為較佳，50質量%以下為更佳。若在該等範圍，則從圖案形狀、耐熱性、L*的觀點考慮較佳。組成物中所使用之硬化性化合物可以僅為1種，亦可以為2種以上。當為2種以上時，合計量在上述範圍內為較佳。The content of the curable compound is preferably 1 to 70% by mass based on the total solid content of the composition. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less. If it is in these ranges, it is preferable from a viewpoint of pattern shape, heat resistance, and L *. The curable compound used in the composition may be only one kind, or two or more kinds. When there are two or more kinds, it is preferable that the total amount is within the above range.

當使用聚合性化合物作為硬化性化合物時，聚合性化合物的含量相對於組成物的總固體成分係1～70質量%為較佳。下限係3質量%以上為較佳，5質量%以上為更佳。上限係60質量%以下為較佳，50質量%以下為更佳。組成物中所使用之聚合性化合物可以僅含有1種，亦可以含有2種以上。當含有2種以上的聚合性化合物時，合計量在上述範圍內為較佳。 並且，聚合性化合物的含量相對於硬化性化合物的總質量係10～100質量%為較佳，30～100質量%為更佳。When a polymerizable compound is used as the curable compound, the content of the polymerizable compound is preferably 1 to 70% by mass based on the total solid content of the composition. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less. The polymerizable compound used in the composition may contain only one kind, or may contain two or more kinds. When two or more kinds of polymerizable compounds are contained, the total amount is preferably within the above range. The content of the polymerizable compound is preferably 10 to 100% by mass, and more preferably 30 to 100% by mass based on the total mass of the curable compound.

（聚合性化合物） 作為聚合性化合物，具有至少1個含有乙烯性不飽和鍵之基團之化合物為較佳，具有至少1個、較佳為2個以上含有末端乙烯性不飽和鍵之基團之化合物為更佳。並且，聚合性化合物係具有6個以上含有乙烯性不飽和鍵之基團之化合物、或具有3～4個含有乙烯性不飽和鍵之基團之化合物為較佳，具有3～4個含有乙烯性不飽和鍵之基團之化合物為更佳。含有乙烯性不飽和鍵之基團係（甲基）丙烯醯基、（甲基）丙烯醯氧基為較佳。並且，聚合性化合物係自由基聚合性化合物為較佳。(Polymerizable compound) As the polymerizable compound, a compound having at least one group containing an ethylenically unsaturated bond is preferred, and at least one, and preferably two or more groups containing a terminal ethylenically unsaturated bond Compounds are more preferred. In addition, the polymerizable compound is preferably a compound having 6 or more ethylenically unsaturated bond-containing groups, or a compound having 3 to 4 ethylenically unsaturated bond-containing groups, and 3 to 4 containing ethylene Compounds having a group of unsaturated bonds are more preferred. The (meth) acrylfluorenyl group and (meth) acrylfluorenyl group which are ethylenically unsaturated bonds are preferable. In addition, a polymerizable compound is preferably a radical polymerizable compound.

聚合性化合物可以係單體、聚合物中的任一形態，但單體為較佳。單體類型的聚合性化合物的分子量係100～3000為較佳。上限係2000以下為較佳，1500以下為進一步較佳。下限係150以上為較佳，250以上為進一步較佳。The polymerizable compound may be in any form of a monomer and a polymer, but a monomer is preferred. The molecular weight of the polymerizable compound of the monomer type is preferably 100 to 3000. The upper limit is preferably below 2,000, and more preferably below 1500. The lower limit is preferably 150 or more, and more preferably 250 or more.

聚合性化合物係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，從圖案形狀的觀點考慮，3～4官能的（甲基）丙烯酸酯化合物為進一步較佳。依該態樣，能夠改善所得到之膜的耐溶劑性、及與基材之黏附性、圖案形狀。並且，聚合性化合物係6官能以上的（甲基）丙烯酸酯化合物亦較佳。The polymerizable compound is preferably a 3 to 15-functional (meth) acrylate compound, and a 3 to 6-functional (meth) acrylate compound is more preferred. From the viewpoint of pattern shape, a 3 to 4-functional (meth) acrylate (Meth) acrylate compounds are further preferred. According to this aspect, the solvent resistance of the obtained film, the adhesion to the substrate, and the pattern shape can be improved. Further, the polymerizable compound is preferably a (meth) acrylate compound having 6 or more functions.

聚合性化合物係具有至少1個可加成聚合之伸乙基且在常壓下具有100℃以上的沸點之、具有含有乙烯性不飽和鍵之基團之化合物亦較佳。作為其例子，可以舉出聚乙二醇單（甲基）丙烯酸酯、聚丙二醇單（甲基）丙烯酸酯、（甲基）丙烯酸苯氧基乙酯等單官能的丙烯酸酯或甲基丙烯酸酯；聚乙二醇二（甲基）丙烯酸酯、三羥甲基乙烷三（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、己二醇（甲基）丙烯酸酯、三羥甲基丙烷三（丙烯醯氧基丙基）醚、三（丙烯醯氧基乙基）异氰脲酸酯及該等的混合物，季戊四醇四（甲基）丙烯酸酯為較佳。The polymerizable compound is also a compound having at least one addition-polymerizable ethylene group and having a boiling point of 100 ° C. or higher under normal pressure, and having a group containing an ethylenically unsaturated bond. Examples thereof include monofunctional acrylates or methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate. ; Polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylates, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tris (acryloxypropyl) ) Ether, tris (propenyloxyethyl) isocyanurate and mixtures thereof, pentaerythritol tetra (meth) acrylate is preferred.

聚合性化合物亦能夠較佳地使用下述式（MO-1）～（MO-5）所表示之聚合性化合物。As the polymerizable compound, a polymerizable compound represented by the following formulae (MO-1) to (MO-5) can be preferably used.

[化學式18] [Chemical Formula 18]

上述式（MO-1）～（MO-5）中，n為0～14的整數，m為1～8的整數。在同一分子內存在複數個之R、T可以分別相同，亦可以不同。式中，當T為氧伸烷基時，碳原子側的末端與R鍵結。 上述式（MO-1）～（MO-5）所表示之聚合性化合物各自中，複數個R中的至少1個表示-OC（=O）CH=CH2 或-OC（=O）C（CH3 ）=CH2 所表示之基團。 作為上述式（MO-1）～（MO-5）所表示之聚合性化合物的具體例，可以舉出日本特開2007-269779號公報的0248～0251段中所記載之化合物。 並且，日本特開平10-62986號公報中所記載之在多官能醇中加成環氧乙烷或環氧丙烷之後進行（甲基）丙烯酸酯化而得到之化合物亦可以用作聚合性化合物。In the formulae (MO-1) to (MO-5), n is an integer of 0 to 14 and m is an integer of 1 to 8. A plurality of R and T in the same molecule may be the same or different. In the formula, when T is an oxyalkylene group, a terminal on the carbon atom side is bonded to R. In each of the polymerizable compounds represented by the formulae (MO-1) to (MO-5), at least one of the plurality of R represents -OC (= O) CH = CH 2 or -OC (= O) C ( CH 3 ) = a group represented by CH 2 . Specific examples of the polymerizable compound represented by the formulae (MO-1) to (MO-5) include compounds described in paragraphs 0248 to 0251 of Japanese Patent Application Laid-Open No. 2007-269779. In addition, the compound described in Japanese Patent Application Laid-Open No. 10-62986 can be used as a polymerizable compound by adding (meth) acrylate to a polyfunctional alcohol after addition of ethylene oxide or propylene oxide.

聚合性化合物係季戊四醇四丙烯酸酯（作為市售品為NK Ester A-TMMT；Shin-Nakamura Chemical Co.,Ltd.製）、二季戊四醇三丙烯酸酯（作為市售品為KAYARAD D-330；Nippon Kayaku Co.,Ltd.製）、二季戊四醇四丙烯酸酯（作為市售品為KAYARAD D-320；Nippon Kayaku Co.,Ltd.製）二季戊四醇五（甲基）丙烯酸酯（作為市售品為KAYARAD D-310；Nippon Kayaku Co.,Ltd.製）、二季戊四醇六（甲基）丙烯酸酯（作為市售品為KAYARAD DPHA；Nippon Kayaku Co.,Ltd.製）為較佳，從圖案形狀的觀點考慮，季戊四醇四丙烯酸酯為更佳。Polymerizable compounds are pentaerythritol tetraacrylate (commercially available as NK Ester A-TMMT; manufactured by Shin-Nakamura Chemical Co., Ltd.), and dipentaerythritol triacrylate (commercially available as KAYARAD D-330; Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.) dipentaerythritol penta (meth) acrylate (KAYARAD D as a commercial product) -310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) is preferred, and from the viewpoint of pattern shape Pentaerythritol tetraacrylate is more preferred.

聚合性化合物可以具有羧基、磺基、磷酸基等酸基。具有酸基之聚合性化合物係利用將多官能醇的一部分羥基進行（甲基）丙烯酸酯化並使酸酐與剩餘之羥基進行加成反應而製成羧基等的方法而得到。作為具有酸基之聚合性化合物，可以舉出脂肪族聚羥基化合物與不飽和羧酸的酯等。具有酸基之聚合性化合物係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導入了酸基之酯化合物為較佳。在該酯化合物中，脂肪族聚羥基化合物為季戊四醇或二季戊四醇之化合物為特佳。作為市售品，例如TOAGOSEI CO.,LTD.製的多元酸改質丙烯酸寡聚物可以舉出ARONIX系列的M-305、M-510、M-520等。具有酸基之聚合性化合物的酸值係0.1～40mgKOH/g為較佳。下限係5mgKOH/g以上為較佳。上限係30mgKOH/g以下為較佳。The polymerizable compound may have an acid group such as a carboxyl group, a sulfo group, or a phosphate group. The polymerizable compound having an acid group is obtained by a method in which a part of the hydroxyl groups of the polyfunctional alcohol is (meth) acrylated, and an acid anhydride is added to the remaining hydroxyl group to form a carboxyl group. Examples of the polymerizable compound having an acid group include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. The polymerizable compound having an acid group is preferably an ester compound into which an acid group is introduced by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. Among the ester compounds, compounds in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol are particularly preferred. As a commercially available product, for example, polyacid modified acrylic oligomers manufactured by TOAGOSEI CO., LTD. Include ARONIX series M-305, M-510, M-520, and the like. The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g. The lower limit is preferably 5 mgKOH / g or more. The upper limit is preferably 30 mgKOH / g or less.

並且，關於聚合性化合物，具有己內酯結構之聚合性化合物亦係較佳態樣。作為具有己內酯結構之聚合性化合物，只要在分子內具有己內酯結構，則並沒有特別限定。例如可以舉出藉由將三羥甲基乙烷、雙-三羥甲基乙烷、三羥甲基丙烷、雙-三羥甲基丙烷、季戊四醇、二季戊四醇、三季戊四醇、甘油、二甘油、三羥甲基三聚氰胺等多元醇與（甲基）丙烯酸及ε-己內酯進行酯化而得到之ε-己內酯改質多官能（甲基）丙烯酸酯。具有己內酯結構之聚合性化合物係下述式（Z-1）所表示之化合物為較佳。In addition, as for the polymerizable compound, a polymerizable compound having a caprolactone structure is also preferable. The polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. Examples include trimethylolethane, bis-trimethylolethane, trimethylolpropane, bis-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, Polyol such as trimethylolmelamine and (meth) acrylic acid and ε-caprolactone are esterified to obtain ε-caprolactone modified polyfunctional (meth) acrylate. The polymerizable compound having a caprolactone structure is preferably a compound represented by the following formula (Z-1).

[化學式19] [Chemical Formula 19]

式（Z-1）中，6個R全部為式（Z-2）所表示之基團、或者6個R中1～5個係式（Z-2）所表示之基團，且剩餘係式（Z-3）所表示之基團。In formula (Z-1), all 6 Rs are groups represented by formula (Z-2), or 1 to 5 of 6 R are groups represented by formula (Z-2), and the rest are A group represented by formula (Z-3).

[化學式20]式（Z-2）中，R1 表示氫原子或甲基，m表示1或2的整數，“*”表示鍵結鍵。[Chemical Formula 20] In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents an integer of 1 or 2, and "*" represents a bonding bond.

[化學式21]式（Z-3）中，R1 表示氫原子或甲基，“*”表示鍵結鍵。[Chemical Formula 21] In the formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and "*" represents a bonding bond.

具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KAYARAD DPCA-20（上述式（Z-2）中，m=1、式（Z-2）所表示之基團的數量=2、R1 全部為氫原子之化合物）、DPCA-30（該式（Z-2）中，m=1、式（Z-2）所表示之基團的數量=3、R1 全部為氫原子之化合物）、DPCA-60（該式（Z-2）中，m=1、式（Z-2）所表示之基團的數量=6、R1 全部為氫原子之化合物）、DPCA-120（該式（Z-2）中，m=2、式（Z-2）所表示之基團的數量=6、R1 全部為氫原子之化合物）等。A polymerizable compound having a caprolactone structure is marketed, for example, by the Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series. Examples include KAYARAD DPCA-20 (in the above formula (Z-2), m = 1, the number of groups represented by the formula (Z-2) = 2, compounds in which all of R 1 are hydrogen atoms), DPCA-30 (In the formula (Z-2), m = 1, the number of groups represented by the formula (Z-2) = 3, all compounds in which R 1 is a hydrogen atom), DPCA-60 (the formula (Z-2 ), M = 1, the number of groups represented by formula (Z-2) = 6, compounds in which R 1 is all a hydrogen atom), DPCA-120 (in the formula (Z-2), m = 2 The number of groups represented by the formula (Z-2) = 6, a compound in which all of R 1 is a hydrogen atom) and the like.

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

[化學式22] [Chemical Formula 22]

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 formulae (Z-4) and (Z-5), E each independently represents-((CH 2 ) y CH 2 O)-or-((CH 2 ) y CH (CH 3 ) O)-, y each Each independently represents an integer of 0 to 10, and X each independently represents a (meth) acrylfluorenyl group, a hydrogen atom, or a carboxyl group. In formula (Z-4), the total number of (meth) acrylfluorenyl groups is three or four, m each independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. In the formula (Z-5), the total number of (meth) acrylfluorenyl groups is five or six, 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係0～6的整數為較佳，0～4的整數為更佳。 並且，各m的合計係2～40的整數為較佳，2～16的整數為更佳，4～8的整數為特佳。 式（Z-5）中，n係0～6的整數為較佳，0～4的整數為更佳。 並且，各n的合計係3～60的整數為較佳，3～24的整數為更佳，6～12的整數為特佳。 並且，式（Z-4）或式（Z-5）中的-（（CH2 ）y CH2 O）-或-（（CH2 ）y CH（CH3 ）O）-係氧原子側的末端與X鍵結之形態為較佳。In formula (Z-4), m is preferably an integer of 0 to 6, and an integer of 0 to 4 is more preferred. In addition, the total of each m is preferably an integer of 2 to 40, an integer of 2 to 16 is more preferable, and an integer of 4 to 8 is particularly preferable. In the formula (Z-5), n is an integer of 0 to 6 is more preferable, and an integer of 0 to 4 is more preferable. In addition, the total of each n is preferably an integer of 3 to 60, an integer of 3 to 24 is more preferable, and an integer of 6 to 12 is particularly preferable. In addition,-((CH 2 ) y CH 2 O)-or-((CH 2 ) y CH (CH 3 ) O)-in the formula (Z-4) or (Z-5) is an oxygen atom side The morphology of the terminal and X bond is preferred.

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。尤其係式（Z-5）中6個X全部為丙烯醯基之形態為較佳。The compound represented by the formula (Z-4) or the formula (Z-5) may be used singly or in combination of two or more kinds. In particular, the form in which all six X's in the formula (Z-5) are acrylfluorenyl is preferred.

並且，作為式（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，係20質量%以上為較佳，50質量%以上為更佳。In addition, 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, and more preferably 50% by mass or more.

式（Z-4）或式（Z-5）所表示之化合物能夠藉由公知的方法進行合成。例如，能夠藉由如下製程來合成式（Z-4）或式（Z-5）所表示之化合物：使環氧乙烷或環氧丙烷藉由開環加成反應而將開環骨架鍵結於季戊四醇或二季戊四醇之製程；及例如使（甲基）丙烯醯氯與開環骨架的末端羥基進行反應而導入（甲基）丙烯醯基之製程。The compound represented by the formula (Z-4) or the formula (Z-5) can be synthesized by a known method. For example, the compound represented by formula (Z-4) or formula (Z-5) can be synthesized by the following process: Ethylene oxide or propylene oxide is bonded to the ring-opening skeleton through a ring-opening addition reaction. In a process of pentaerythritol or dipentaerythritol; and, for example, a process of introducing (meth) acrylfluorenyl group by reacting (meth) acrylfluorene chloride with a terminal hydroxyl group of a ring-opening skeleton.

在式（Z-4）或式（Z-5）所表示之化合物中，季戊四醇衍生物或二季戊四醇衍生物為更佳。 具體而言，可以舉出下述式（a）～（f）所表示之化合物（以下，亦稱作“例示化合物（a）～（f）”。），其中，例示化合物（a）、（b）、（e）、（f）為較佳。Among the compounds represented by formula (Z-4) or formula (Z-5), a pentaerythritol derivative or a dipentaerythritol derivative is more preferable. Specific examples include compounds represented by the following formulae (a) to (f) (hereinafter, also referred to as "exemplary compounds (a) to (f)"). Among them, exemplary compounds (a), ( b), (e), (f) are preferred.

[化學式23] [Chemical Formula 23]

[化學式24] [Chemical Formula 24]

作為式（Z-4）、（Z-5）所表示之聚合性化合物的市售品，例如可以舉出Sartomer公司製的具有4個伸乙氧基之4官能丙烯酸酯之SR-494、Nippon Kayaku Co.,Ltd.製的具有6個伸戊氧基之6官能丙烯酸酯之DPCA-60、具有3個異伸丁氧基之3官能丙烯酸酯之TPA-330等。Examples of commercially available polymerizable compounds represented by the formulae (Z-4) and (Z-5) include SR-494 and Nippon, a tetrafunctional acrylate having four ethoxy groups, manufactured by Sartomer Corporation. Kayaku Co., Ltd.'s DPCA-60, a 6-functional acrylate having 6 pentyloxy groups, TPA-330, a trifunctional acrylate having 3 isobutoxy groups, and the like.

作為聚合性化合物，如日本特公昭48-41708號公報、日本特開昭51-37193號公報、日本特公平2-32293號公報、日本特公平2-16765號公報中所記載之胺基甲酸酯丙烯酸酯類、或日本特公昭58-49860號公報、日本特公昭56-17654號公報、日本特公昭62-39417號公報、日本特公昭62-39418號公報中所記載之具有環氧乙烷系骨架之胺基甲酸酯化合物類亦較佳。並且，日本特開昭63-277653號公報、日本特開昭63-260909號公報、日本特開平1-105238號公報中所記載之在分子內具有胺基結構或硫化物（sulfide）結構之加成聚合性化合物類亦較佳。 作為聚合性化合物的市售品，可以舉出胺基甲酸酯寡聚物UAS-10、UAB-140（Sanyo Kokusaku Pulp Co.,Ltd.製）、U-4HA、U-6LPA、UA-32P、U-10HA、U-10PA、UA-122P、UA-1100H、UA-7200（Shin-Nakamura Chemical Co.,Ltd.製）、DPHA-40H（Nippon Kayaku Co.,Ltd.製）、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600（KYOEISHA CHEMICAL Co.,Ltd.製）、UA-9050、UA-9048（BASF公司製）等。Examples of the polymerizable compound include the aminoformic acids described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Ester acrylates, or those disclosed in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 Also preferred are carbamate compounds based on a skeleton. In addition, Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 1-105238 describe the addition of an amine structure or a sulfide structure in the molecule Polymerizable compounds are also preferred. Examples of commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), U-4HA, U-6LPA, and UA-32P , U-10HA, U-10PA, UA-122P, UA-1100H, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H , UA-306T, UA-306I, AH-600, T-600, AI-600 (made by KYOEISHA CHEMICAL Co., Ltd.), UA-9050, UA-9048 (made by BASF), etc.

並且，作為聚合性化合物，在分子內具有Si原子之聚合性化合物亦係較佳的態樣。作為在分子內具有Si原子之聚合性化合物的市售品，可以舉出含有矽氧烷鍵之多官能丙烯酸酯之EBECRYL1360（DAICEL-ALLNEX LTD.製）、含有Si原子之多官能乙烯基化合物之VINYL TRIISOPROPENOXY SILANE（AZMAX Corp.製）等。In addition, as the polymerizable compound, a polymerizable compound having a Si atom in the molecule is also in a preferable aspect. Examples of commercially available polymerizable compounds having a Si atom in the molecule include EBECRYL 1360 (manufactured by DAICEL-ALLNEX LTD.) Containing a polyfunctional acrylate containing a siloxane bond, and polyfunctional vinyl compounds containing a Si atom. VINYL TRIISOPROPENOXY SILANE (manufactured by AZMAX Corp.).

對於該等聚合性化合物，其結構、單獨使用或併用、添加量等使用方法的詳細內容可以根據組成物的最終性能設計任意地進行設定。例如，從靈敏度的觀點考慮，每1分子的不飽和基含量較多的結構為較佳，在多數情況下，2官能以上為較佳。並且，從提高硬化膜的強度之觀點考慮，3官能以上的化合物為較佳，進而，藉由將官能數及聚合性基（例如丙烯酸酯、甲基丙烯酸酯、苯乙烯系化合物、乙烯醚系化合物）中的至少一方不同之化合物併用來調節靈敏度和強度雙方之方法亦有效。另外， 將作為3官能以上的化合物之環氧乙烷鏈長不同之聚合性化合物併用亦較佳。依該態樣，能夠調節組成物的顯影性，可得到優異之圖案形成。並且，對於與組成物中所含之其他成分（例如，光聚合起始劑、樹脂等）之相容性及分散性中的至少一方，聚合性化合物的選擇及使用方法中的至少一方亦係重要的因素，例如藉由使用低純度化合物或併用2種以上，能夠提高相容性等。The details of the use of the polymerizable compound such as its structure, single use or combination, and addition amount can be arbitrarily set according to the final performance design of the composition. For example, from the viewpoint of sensitivity, a structure having a large amount of unsaturated groups per molecule is preferred, and in most cases, a bifunctional or higher functionality is preferred. In addition, from the viewpoint of improving the strength of the cured film, a tri- or more functional compound is preferable, and further, the functional number and the polymerizable group (for example, acrylate, methacrylate, styrene-based compound, vinyl ether-based A method in which at least one of the compounds is different and used to adjust both sensitivity and intensity is also effective. It is also preferable to use a polymerizable compound having a different ethylene oxide chain length as a trifunctional or higher compound. According to this aspect, the developability of the composition can be adjusted, and excellent pattern formation can be obtained. In addition, for at least one of compatibility and dispersibility with other components (for example, photopolymerization initiator, resin, etc.) contained in the composition, at least one of the selection and use method of the polymerizable compound is also Important factors include, for example, the use of a low-purity compound or the use of two or more kinds in combination to improve compatibility.

（具有環氧基之化合物） 本發明的組成物中亦可以使用具有環氧基之化合物作為硬化性化合物。依該態樣，能夠提高所得到之膜的耐溶劑性。作為具有環氧基之化合物，可以舉出單官能或多官能縮水甘油醚化合物、或多官能脂肪族縮水甘油醚化合物等。並且，亦可以使用（甲基）丙烯酸縮水甘油酯或烯丙基縮水甘油醚等將環氧基作為縮水甘油基的一部分而具有之化合物、或具有脂環式環氧基之化合物。(A compound having an epoxy group) A compound having an epoxy group may be used as the curable compound in the composition of the present invention. According to this aspect, the solvent resistance of the obtained film can be improved. Examples of the compound having an epoxy group include a monofunctional or polyfunctional glycidyl ether compound, or a polyfunctional aliphatic glycidyl ether compound. In addition, a compound having an epoxy group as a part of a glycidyl group such as glycidyl (meth) acrylate or allyl glycidyl ether, or a compound having an alicyclic epoxy group may be used.

作為具有環氧基之化合物，可以舉出在1個分子中具有1個以上環氧基之化合物。在1分子中具有1～100個環氧基為較佳。上限例如既可以設為10個以下，亦可以設為5個以下。下限係2個以上為較佳。Examples of the compound having an epoxy group include compounds having one or more epoxy groups in one molecule. It is preferable to have 1 to 100 epoxy groups in one molecule. The upper limit may be, for example, 10 or less, or 5 or less. The lower limit is preferably two or more.

具有環氧基之化合物中，環氧基當量（=具有環氧基之化合物的分子量/環氧基的數）係500g/當量以下為較佳，100～400g/當量為更佳，100～300g/當量為進一步較佳。In the compound having an epoxy group, the epoxy group equivalent (= molecular weight of the compound having an epoxy group / number of epoxy groups) is preferably 500 g / equivalent or less, more preferably 100 to 400 g / equivalent, 100 to 300 g / Equivalent is further preferred.

具有環氧基之化合物可以係低分子化合物（例如，分子量小於1000）、高分子化合物（macromolecule）（例如，分子量為1000以上，聚合物時重量平均分子量為1000以上）中的任一種。具有環氧基之化合物的重量平均分子量係200～100000為較佳，500～50000為更佳。重量平均分子量的上限係10000以下為較佳，5000以下為更佳，3000以下為進一步較佳。 從耐溶劑性的觀點考慮，具有環氧基之化合物係脂肪族環氧樹脂為較佳。The compound having an epoxy group may be any of a low-molecular compound (for example, a molecular weight of less than 1,000) and a macromolecule (for example, a molecular weight of 1,000 or more and a weight average molecular weight of 1,000 or more when the polymer is used). The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, and more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less. From the viewpoint of solvent resistance, a compound-based aliphatic epoxy resin having an epoxy group is preferred.

具有環氧基之化合物亦能夠使用日本特開2013-011869號公報的0034～0036段、日本特開2014-043556號公報的0147～0156段、日本特開2014-089408號公報的0085～0092段中所記載之化合物。該等內容被併入本說明書中。關於市售品，例如作為雙酚A型環氧樹脂，為jER825、jER827、jER828、jER834、jER1001、jER1002、jER1003、jER1055、jER1007、jER1009、jER1010（以上為Mitsubishi Chemical Corporation製）、EPICLON860、EPICLON1050、EPICLON1051、EPICLON1055（以上為DIC CORPORATION製）等，作為雙酚F型環氧樹脂，為jER806、jER807、jER4004、jER4005、jER4007、jER4010（以上為Mitsubishi Chemical Corporation製）、EPICLON830、EPICLON835（以上為DIC CORPORATION製）、LCE-21、RE-602S（以上為Nippon Kayaku Co.,Ltd.製）等，作為苯酚酚醛清漆型環氧樹脂，為jER152、jER154、jER157S70、jER157S65（以上為Mitsubishi Chemical Corporation製）、EPICLON N-740、EPICLON N-770、EPICLON N-775（以上為DIC CORPORATION製）等，作為甲酚酚醛清漆型環氧樹脂，為EPICLON N-660、EPICLON N-665、EPICLON N-670、EPICLON N-673、EPICLON N-680、EPICLON N-690、EPICLON N-695（以上為DIC CORPORATION製）、EOCN-1020（Nippon Kayaku Co.,Ltd.製）等，作為脂肪族環氧樹脂，為ADEKA RESIN EP-4080S、ADEKA RESIN EP-4085S、ADEKA RESIN EP-4088S（以上為ADEKA CORPORATION製）、CELLOXIDE 2021P、CELLOXIDE 2081、CELLOXIDE 2083、CELLOXIDE 2085、EHPE3150、EPOLEAD PB 3600、EPOLEAD PB 4700（以上為Daicel Chemical Industries, Ltd.製）、Denacol EX-212L、EX-214L、EX-216L、EX-321L、EX-850L（以上為Nagase Chemtex Corporation等。此外，可以舉出ADEKA RESIN EP-4000S、ADEKA RESIN EP-4003S、ADEKA RESIN EP-4010S、ADEKA RESIN EP-4011S（以上為ADEKA CORPORATION製）、NC-2000、NC-3000、NC-7300、XD-1000、EPPN-501、EPPN-502（以上為ADEKA CORPORATION製）、jER1031S（Mitsubishi Chemical Corporation製）等。Compounds having an epoxy group can also use paragraphs 0034 to 0036 of JP 2013-011869, paragraphs 0147 to 0156 of JP 2014-043556, and paragraphs 0085 to 0092 of JP 2014-089408. Compounds described in. Such content is incorporated into this specification. For commercial products, for example, as bisphenol A epoxy resins, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (the above are manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (above manufactured by DIC Corporation), etc., as the bisphenol F-type epoxy resin, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (the above are manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (the above are DIC CORPORATION) Manufactured), LCE-21, RE-602S (above manufactured by Nippon Kayaku Co., Ltd.), etc., as the phenol novolac epoxy resin, jER152, jER154, jER157S70, jER157S65 (above manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above manufactured by DIC Corporation), etc., as cresol novolac epoxy resins, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above manufactured by DIC Corporation), EOCN-1020 (Nippon Kayak u Co., Ltd.), etc., as the aliphatic epoxy resin, ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (the above is made by ADEKA CORPORATION), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (above manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above Nagase Chemtex Corporation and others. In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (the above are made by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD- 1000, EPPN-501, EPPN-502 (the above are manufactured by ADEKA CORPORATION), jER1031S (made by Mitsubishi Chemical Corporation), and the like.

具有環氧基之化合物亦可以使用日本特開2009-265518號公報的0045段等中所記載之化合物，該等內容被併入本說明書中。As the compound having an epoxy group, the compounds described in paragraph 0045 and the like of Japanese Patent Application Laid-Open No. 2009-265518 can also be used, and the contents are incorporated into this specification.

＜＜聚合起始劑＞＞ 本發明的組成物含有聚合起始劑為較佳。 從耐溶劑性、著色性的觀點考慮，聚合起始劑的含量相對於組成物的總固體成分係0.1～50質量%為較佳，更佳為0.5～30質量%，進一步較佳為1～20質量%。組成物可以僅含有1種聚合起始劑，亦可以含有2種以上。當含有2種以上時，其合計量在上述範圍內為較佳。 作為聚合起始劑，光聚合起始劑或熱聚合起始劑為較佳，光聚合起始劑為較佳。作為熱聚合起始劑並沒有特別限制，可以使用公知的化合物。<< Polymerization initiator >> The composition of the present invention preferably contains a polymerization initiator. From the viewpoints of solvent resistance and coloring property, the content of the polymerization initiator is preferably 0.1 to 50% by mass based on the total solid content of the composition, more preferably 0.5 to 30% by mass, and still more preferably 1 to 20% by mass. The composition may contain only one type of polymerization initiator, or may contain two or more types. When two or more kinds are contained, the total amount is preferably within the above range. As the polymerization initiator, a photopolymerization initiator or a thermal polymerization initiator is preferred, and a photopolymerization initiator is preferred. The thermal polymerization initiator is not particularly limited, and a known compound can be used.

（光聚合起始劑） 本發明的組成物可以含有光聚合起始劑。尤其，當組成物含有聚合性化合物時，含有光聚合起始劑為較佳。作為光聚合起始劑並沒有特別限制，可以從公知的光聚合起始劑中適當地選擇。例如，對從紫外線區域至可見區域的光線具有感光性者為較佳。作為光聚合起始劑，係光自由基聚合起始劑為較佳。並且，光聚合起始劑含有至少1種在約300nm～800nm（330nm～500nm為更佳。）範圍內具有至少約50莫耳的吸光係數之化合物為較佳。(Photopolymerization initiator) The composition of this invention may contain a photopolymerization initiator. In particular, when the composition contains a polymerizable compound, it is preferable to include a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have sensitivity to light from the ultraviolet region to the visible region. As the photopolymerization initiator, a photoradical polymerization initiator is preferred. In addition, the photopolymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 moles in a range of about 300 nm to 800 nm (more preferably, 330 nm to 500 nm.).

作為光聚合起始劑，例如可以舉出鹵化烴衍生物（例如，具有三嗪骨架者、具有噁二唑骨架者等）、醯基氧化膦等醯基膦化合物、六芳基雙咪唑、肟衍生物等肟化合物、有機過氧化物、硫化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮化合物、羥基苯乙酮等。作為具有三嗪骨架之鹵化烴化合物，例如可以舉出若林等著、Bull.Chem.Soc.Japan，42，2924（1969）中所記載之化合物、英國專利1388492號說明書中所記載之化合物、日本特開昭53-133428號公報中所記載之化合物、德國專利3337024號說明書中所記載之化合物、F.C.Schaefer等著、J.Org.Chem.;29，1527（1964）中所記載之化合物、日本特開昭62-58241號公報中所記載之化合物、日本特開平5-281728號公報中所記載之化合物、日本特開平5-34920號公報中所記載之化合物、美國專利第4212976號說明書中所記載之化合物等。Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and those having an oxadiazole skeleton), fluorenyl phosphine compounds such as fluorenylphosphine oxide, hexaarylbisimidazole, and oxime Derivatives such as oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like. Examples of the halogenated hydrocarbon compound having a triazine skeleton include a compound described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1384492, and Japan Compounds described in JP 53-133428, compounds described in German Patent No. 3370024, FC Schaefer et al., Compounds described in J. Org. Chem .; 29, 1527 (1964), Japan Compounds described in Japanese Patent Application Laid-Open No. 62-58241, compounds described in Japanese Patent Application Laid-Open No. 5-281728, compounds described in Japanese Patent Application Laid-Open No. 5-34920, and US Patent No. 4212976 Documented compounds, etc.

並且，從曝光靈敏度的觀點考慮，係選自包括三鹵甲基三嗪化合物、苄基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三烯丙基咪唑二聚體、鎓化合物、苯并噻唑化合物、二苯甲酮化合物、苯乙酮化合物及其衍生物、環戊二烯-苯-鐵錯合物及其鹽、鹵甲基噁二唑化合物、3-芳基取代之香豆素化合物之組群中之化合物為較佳。From the viewpoint of exposure sensitivity, it is selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, fluorenylphosphine compounds, and phosphine oxides. Compounds, metallocene compounds, oxime compounds, triallyl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron Compounds and their salts, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds are preferred.

作為光聚合起始劑，亦可以較佳地使用羥基苯乙酮化合物、胺基苯乙酮化合物及醯基膦化合物。更具體而言，例如亦可以使用日本特開平10-291969號公報中所記載之胺基苯乙酮系起始劑、日本專利第4225898號公報中所記載之醯基膦系起始劑。作為羥基苯乙酮系起始劑，可以使用IRGACURE 184、DAROCUR 1173、IRGACURE 500、IRGACURE 2959、IRGACURE 127（商品名稱：均為BASF公司製）。作為胺基苯乙酮系起始劑，可以使用市售品之IRGACURE 907、IRGACURE 369及IRGACURE 379、IRGACURE 379EG（商品名稱：均為BASF公司製）。胺基苯乙酮系起始劑亦可以使用吸收波長與365nm或405nm等長波光源匹配之日本特開2009-191179號公報中所記載之化合物。 作為醯基膦系起始劑，可以使用市售品之IRGACURE 819或IRGACURE TPO（商品名稱：均為BASF公司製）。 從著色性的觀點考慮，肟化合物、胺基苯乙酮系起始劑或醯基膦系起始劑為較佳，從著色性及黏附性的觀點考慮，具有硝基之肟化合物或醯基膦系起始劑為更佳。As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a fluorenylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and a fluorenylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used. As the hydroxyacetophenone-based initiator, IRGACURE 184, DAROCUR 1173, IRGACURE 500, IRGACURE 2959, and IRGACURE 127 (trade names: all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, commercially available IRGACURE 907, IRGACURE 369, IRGACURE 379, and IRGACURE 379EG (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 whose absorption wavelength matches a long-wave light source such as 365 nm or 405 nm can also be used. As the fluorenylphosphine-based initiator, commercially available IRGACURE 819 or IRGACURE TPO (trade name: all manufactured by BASF) can be used. From the viewpoint of colorability, oxime compounds, aminoacetophenone-based initiators, or fluorenylphosphine-based initiators are preferred. From the viewpoint of colorability and adhesion, oxime compounds or fluorenyl groups having a nitro group A phosphine-based initiator is more preferred.

光聚合起始劑亦可以較佳地使用肟化合物。作為肟化合物，肟酯化合物為更佳。作為肟化合物的具體例，可以使用日本特開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、日本特開2006-342166號公報中所記載之化合物、日本特開2016-21012號公報中所記載之化合物。As the photopolymerization initiator, an oxime compound can also be preferably used. As the oxime compound, an oxime ester compound is more preferable. As specific examples of the oxime compound, a compound described in JP 2001-233842, a compound described in JP 2000-80068, and a compound described in JP 2006-342166 can be used. Compounds described in Japanese Patent Application Laid-Open No. 2016-21012.

本發明中，作為可以較佳地使用之肟化合物，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。並且，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、日本特開2006-342166號公報的各公報中所記載之化合物等。市售品中，亦可以較佳地使用IRGACURE OXE01、IRGACURE OXE02、IRGACURE-OXE03、IRGACURE-OXE04（以上為BASF公司製）。並且，還能夠使用TR-PBG-304（CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO.,LTD.製）、ADEKA ARKLS NCI-930（ADEKA CORPORATION製）、ADEKA OPTOMER N-1919（ADEKA CORPORATION製，日本特開2012-14052號公報中所記載之光聚合起始劑2）。In the present invention, as the oxime compound that can be preferably used, for example, 3-benzyloxyiminobutane-2-one and 3-ethoxyiminobutane-2-one 3-propanyloxyiminobutane-2-one, 2-ethoxyloxyiminopentane-3-one, 2-ethoxyloxyimino-1-phenylpropane-1 -Ketone, 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxy Carbooxyimino-1-phenylpropane-1-one and the like. In addition, JCSPerkin II (1979) pp. 1653-1660, JCSPerkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) ) Pp.202-232, compounds described in Japanese Patent Laid-Open No. 2000-66385, Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2004-534797, and Japanese Patent Laid-Open No. 2006-342166 Compounds described in Among commercially available products, IRGACURE OXE01, IRGACURE OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (the above are manufactured by BASF) can also be preferably used. In addition, TR-PBG-304 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Laid-Open 2012- Photopolymerization initiator 2) described in Japanese Patent No. 14052.

並且，作為除上述以外的肟化合物，可以使用在咔唑N位上連接有肟之日本特表2009-519904號公報中所記載之化合物、在二苯甲酮部位導入有雜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號中所記載之化合物、國際公開WO2009/131189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具有極大吸收且對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、日本特開2014-137466號公報的0076～0079段中所記載之化合物等。 較佳地，例如可以參閱日本特開2013-29760號公報的0274～0275段，其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。肟化合物可以是肟的N-O鍵為（E）體的肟化合物，亦可以是肟的N-O鍵為（Z）體的肟化合物，亦可以是（E）體與（Z）體的混合物。In addition, as the oxime compound other than the above, a compound described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N-position of carbazole, and a U.S. patent having a heterosubstituent introduced into a benzophenone moiety can be used. The compound described in Japanese Patent No. 7626957, the compound described in Japanese Patent Application Laid-Open No. 2010-15025 and the US Patent Publication No. 2009-292039, in which a nitro group is introduced into a pigment part, and the International Patent Publication No. WO2009 / 131189 A ketoxime compound, a compound described in U.S. Patent No. 7,565,910 containing a triazine skeleton and an oxime skeleton in the same molecule, Japanese Patent Application Laid-Open No. 2009-221114, which has a maximum absorption at 405 nm and a good sensitivity to a g-ray light source Compounds described in the gazette, compounds described in paragraphs 0076 to 079 of JP-A-2014-137466, and the like. Preferably, for example, refer to paragraphs 0274 to 0275 of Japanese Patent Application Laid-Open No. 2013-29760, the contents of which are incorporated in this specification. Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferred. The oxime compound may be an oxime compound in which the N-O bond of the oxime is the (E) form, or an oxime compound in which the N-O bond of the oxime is the (Z) form, or a mixture of the (E) form and the (Z) form.

[化學式25] [Chemical Formula 25]

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、芳硫基羰基等。並且，該等基團可以具有1個以上的取代基。並且，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、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。該等基團可以具有1個以上的取代基，作為取代基，可以例示出前述取代基。 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、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，可以例示出前述取代基。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-metal atomic group is preferred. Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, a fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. In addition, these groups may have one or more substituents. The substituent may be further substituted with another substituent. Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a fluorenyl group, a fluorenyl group, an alkyl group, and an aryl group. In the formula (OX-1), as the monovalent substituent represented by B, an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group is preferred. These groups may have one or more substituents, and examples of the substituent include the aforementioned substituents. In the formula (OX-1), as the divalent organic group represented by A, an alkylene group, a cycloalkylene group, and an alkynyl group having 1 to 12 carbon atoms are preferred. These groups may have one or more substituents, and examples of the substituent include the aforementioned substituents.

本發明中，作為光聚合起始劑，亦可以使用具有茀環之肟化合物。作為具有茀環之肟化合物的具體例，可以舉出日本特開2014-137466號公報中所記載之化合物。其內容被併入本說明書中。In the present invention, as the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include compounds described in Japanese Patent Application Laid-Open No. 2014-137466. Its content is incorporated into this specification.

本發明中，作為光聚合起始劑，亦可以使用具有氟原子之肟化合物。作為具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。其內容被併入本說明書中。In the present invention, as the photopolymerization initiator, an oxime compound having a fluorine atom may be used. Specific examples of the oxime compound having a fluorine atom include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, compounds 24, 36-40 of Japanese Patent Application No. 2014-500852, and Japanese Patent Laid-Open Compound (C-3) and the like described in Gazette 2013-164471. Its content is incorporated into this specification.

本發明中，作為光聚合起始劑，可以使用具有硝基之肟化合物。具有硝基之肟化合物設為二聚體亦較佳。作為具有硝基之肟化合物的具體例，可以舉出日本特開2013-114249號公報的0031～0047段、日本特開2014-137466號公報的0008～0012、0070～0079段中所記載之化合物、日本專利4223071號公報的0007～0025段中所記載之化合物、ADEKA ARKLS NCI-831（ADEKA CORPORATION製）。In the present invention, as the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferred that the oxime compound having a nitro group is a dimer. Specific examples of the nitro-containing oxime compound include the compounds described in paragraphs 0131 to 0047 of Japanese Patent Application Laid-Open No. 2013-114249 and paragraphs 0008 to 0012, 0070 to 0007 of Japanese Patent Laid-Open No. 2014-137466. Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4222071, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

作為光聚合起始劑，亦能夠使用具有苯并呋喃骨架之肟化合物。作為具體例，可以舉出國際公開WO2015/036910號公報中所記載之OE-01～OE-75。As the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. WO2015 / 036910.

以下示出本發明中可以較佳地使用之肟化合物的具體例，但本發明並不限定於該等。Specific examples of the oxime compound that can be preferably used in the present invention are shown below, but the present invention is not limited to these.

[化學式26][化學式27] [Chemical Formula 26] [Chemical Formula 27]

肟化合物係在350nm～500nm的波長區域具有極大吸收波長之化合物為較佳，在360nm～480nm的波長區域具有吸收波長之化合物為更佳，365nm及405nm的吸光度較高的化合物為特佳。The oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, a compound having an absorption wavelength in a wavelength region of 360 nm to 480 nm is more preferable, and a compound having higher absorbance at 365 nm and 405 nm is particularly preferable.

從靈敏度的觀點考慮，肟化合物在365nm或405nm下之莫耳吸光係數係1,000～300,000為較佳，2,000～300,000為更佳，5,000～200,000為特佳。化合物的莫耳吸光係數的測定中可以使用公知的方法，具體而言，例如藉由紫外可見分光光度計（Varian公司製，Cary-5分光光度計（spectrophotometer）），使用乙酸乙酯以0.01g/L的濃度進行測定為較佳。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 particularly preferably 5,000 to 200,000. A known method can be used for the measurement of the Mohr absorption coefficient of the compound, and specifically, for example, a UV-visible spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian Corporation), and 0.01 g of ethyl acetate can be used. The concentration of / L is preferably measured.

本發明中，將2種以上光聚合起始劑併用亦較佳。例如，將在甲醇中之365nm的吸光係數為1.0×103 mL/gcm以上的光聚合起始劑和在甲醇中之365nm的吸光係數為1.0×102 mL/gcm以下且254nm的吸光係數為1.0×103 mL/gcm以上的光聚合起始劑併用亦較佳。作為具體例，可以舉出胺基苯乙酮化合物和肟化合物的併用。依該態樣，即使在低溫條件下，亦能够製造硬化性優異之膜。例如，在圖案形成製程中，在顯影製程前及顯影製程後這2個階段對組成物進行曝光，藉此能夠藉由最初的曝光使組成物適度硬化，並藉由接下來的曝光使組成物整體幾乎硬化。因此，即使在低溫條件下，亦能夠提高組成物的硬化性。In the present invention, it is also preferable to use two or more photopolymerization initiators in combination. For example, a photopolymerization initiator having an absorption coefficient of 365 nm in methanol of 1.0 × 10 3 mL / gcm or more and an absorption coefficient of 365 nm in methanol of 1.0 × 10 2 mL / gcm or less and an absorption coefficient of 254 nm A photopolymerization initiator of 1.0 × 10 3 mL / gcm or more is preferably used in combination. As a specific example, a combined use of an aminoacetophenone compound and an oxime compound can be mentioned. According to this aspect, a film excellent in hardenability can be produced even under low temperature conditions. For example, in the pattern forming process, the composition is exposed at two stages before the development process and after the development process, so that the composition can be appropriately hardened by the initial exposure, and the composition can be made by the subsequent exposure. The whole is almost hardened. Therefore, the hardenability of the composition can be improved even under low temperature conditions.

＜＜著色防止劑＞＞ 本發明的組成物含有著色防止劑為較佳。 本說明書中所記載之著色防止劑亦可以用作抗氧化劑，抗氧化劑亦可以用作著色防止劑。 作為著色防止劑，可以舉出酚化合物、亞磷酸酯化合物、硫醚化合物等，分子量500以上的酚化合物、分子量500以上的亞磷酸酯化合物或分子量500以上的硫醚化合物為更佳。並且，著色防止劑係酚化合物為較佳，分子量500以上的酚化合物為更佳。<<< Coloring inhibitor> It is preferable that the composition of this invention contains a coloring inhibitor. The coloring preventive agent described in this specification can also be used as an antioxidant, and an antioxidant can also be used as a coloring preventive agent. Examples of the coloring inhibitor include a phenol compound, a phosphite compound, and a thioether compound. A phenol compound having a molecular weight of 500 or more, a phosphite compound having a molecular weight of 500 or more, or a sulfide compound having a molecular weight of 500 or more are more preferable. In addition, a coloring preventive phenol compound is more preferable, and a phenol compound having a molecular weight of 500 or more is more preferable.

作為酚化合物，可以使用作為酚系著色防止劑而已知之任意的酚化合物。作為較佳的酚化合物，可以舉出受阻酚化合物。在與酚性羥基相鄰之部位（邻位）具有取代基之化合物為特佳。作為前述取代基，碳數1～22的經取代或未經取代之烷基為較佳，甲基、乙基、丙醯基、異丙醯基、丁基、異丁基、第三丁基、戊基、異戊基、第三戊基、己基、辛基、異辛基、2-乙基己基為更佳。並且，在同一分子內具有酚基和亞磷酸酯基之化合物亦較佳。As the phenol compound, any phenol compound known as a phenol-based coloring inhibitor can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. A compound having a substituent at a position adjacent to a phenolic hydroxyl group (ortho position) is particularly preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred, and methyl, ethyl, propionyl, isopropylmethyl, butyl, isobutyl, and third butyl , Pentyl, isopentyl, tertiary pentyl, hexyl, octyl, isooctyl, 2-ethylhexyl are more preferred. In addition, a compound having a phenol group and a phosphite group in the same molecule is also preferable.

作為含有酚系羥基之化合物類，尤其可以較佳地使用多取代之酚系化合物。 多取代之酚系化合物中，從由穩定地生成苯氧基自由基所引起之對所捕獲之過氧化自由基的反應性考慮，有取代位置及結構不同之3種：下述式（A）受阻型（hindered type）、式（B）半受阻型（semi-hindered type）及式（C）少受阻型（less-hindered type）。 [化學式28]顯現著色防止功能之結構部分亦即上述式（A）～（C）中，R為取代基，可以舉出氫原子、鹵素原子、可以具有取代基之胺基、可以具有取代基之烷基、可以具有取代基之芳基、可以具有取代基之烷氧基、可以具有取代基之芳氧基、可以具有取代基之烷基胺基、可以具有取代基之芳基胺基、可以具有取代基之烷基磺醯基、可以具有取代基之芳基磺醯基等。其中，可以具有取代基之胺基、可以具有取代基之烷基、可以具有取代基之芳基、可以具有取代基之烷氧基、可以具有取代基之芳氧基、可以具有取代基之烷基胺基、可以具有取代基之芳基胺基為較佳。As the compounds containing a phenolic hydroxyl group, a polysubstituted phenolic compound is particularly preferably used. Among the polysubstituted phenolic compounds, there are three kinds of different substitution positions and structures in consideration of the reactivity to the captured peroxide radicals caused by the stable generation of phenoxy radicals: the following formula (A) Hindered type, formula (B) semi-hindered type, and formula (C) less-hindered type. [Chemical Formula 28] In the above-mentioned formulae (A) to (C), the structural part which exhibits the function of preventing coloring is R as a substituent, and examples thereof include a hydrogen atom, a halogen atom, an amine group which may have a substituent, an alkyl group which may have a substituent, An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamine group which may have a substituent, and a substituent which may have a substituent An alkylsulfonyl group, an arylsulfonyl group which may have a substituent, and the like. Among them, an amine group which may have a substituent, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, and an alkane which may have a substituent An aminoamino group or an arylamino group which may have a substituent is more preferable.

進一步較佳的形態係上述式（A）～（C）所表示之顯現著色防止功能之結構在同一分子內存在複數個之複合系著色防止劑，具體而言，係上述式（A）～（C）所表示之顯現著色防止功能之結構在同一分子內存在2～4個之化合物為較佳。在該等之中，從著色性的觀點考慮，式（B）半受阻型為更佳。 作為含有酚系羥基之化合物，例如可以舉出選自包括對甲氧基苯酚、二-第三丁基-對甲酚、五倍子酚、第三丁基鄰苯二酚、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）、酚醛樹脂類及甲酚樹脂類之組群中之化合物等。 可作為市售品而獲得之代表例，作為（A）有Sumilizer BHT（Sumitomo Chemical Co.,Ltd.製）、Irganox 1010、1222（BASF公司製）、Adekastab AO-20、AO-50、AO-60（ADEKA製）等。作為（B）有Sumilizer BBM-S（Sumitomo Chemical Co.,Ltd.製）、Irganox 245（BASF公司製）、Adekastab AO-80（ADEKA製）等。作為（C）有Adekastab AO-30、AO-40（ADEKA製）等。A further preferable aspect is a compound-type coloring inhibitor having a structure exhibiting a coloring prevention function represented by the above formulae (A) to (C) in the same molecule, and more specifically, it is the formulae (A) to ( C) It is preferable that there are 2 to 4 compounds having a structure exhibiting a coloring prevention function in the same molecule. Among these, from the viewpoint of colorability, the semi-obstructed formula (B) is more preferable. Examples of the compound containing a phenolic hydroxyl group include a compound selected from the group consisting of p-methoxyphenol, di-third-butyl-p-cresol, gallophenol, third butylcatechol, 4,4-thio Group of bis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4-methyl-6-third butylphenol), phenol resins and cresol resins Compounds in the group. Representative examples available as commercially available products include (A) Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.), Irganox 1010, 1222 (manufactured by BASF), Adekastab AO-20, AO-50, AO- 60 (made by ADEKA), etc. (B) includes Sumilizer BBM-S (manufactured by Sumitomo Chemical Co., Ltd.), Irganox 245 (manufactured by BASF), Adekastab AO-80 (manufactured by ADEKA), and the like. Examples of (C) include Adekastab AO-30 and AO-40 (made by ADEKA).

作為亞磷酸酯化合物，可以舉出選自包括三[2-[[2,4,8,10-四（1,1-二甲基乙基）二苯并[d,f][1,3,2]二氧雜膦雜環庚二烯（dioxaphosphepin）-6-基]氧基]乙基]胺、三[2-[（4,6,9,11-四-第三丁基二苯并[d,f][1,3,2]二氧雜膦雜環庚二烯-2-基）氧基]乙基]胺及亞磷酸乙基雙（2,4-二-第三丁基-6-甲基苯基）之組群中之至少1種化合物。 能夠作為市售品而獲得之亞磷酸酯化合物的代表例可以舉出Adekastab PEP-36A（ADEKA CORPORATION製）。Examples of the phosphite compounds include tris [2-[[2,4,8,10-tetra (1,1-dimethylethyl) dibenzo [d, f] [1,3 , 2] dioxaphosphepin-6-yl] oxy] ethyl] amine, tri [2-[(4,6,9,11-tetra-tert-butyldiphenyl Benzene [d, f] [1,3,2] dioxaphosphacycloheptadien-2-yl) oxy] ethyl] amine and ethylbis (2,4-di-tert-butyl) phosphite At least one compound in the group 6-methylphenyl). As a typical example of a phosphite compound which can be obtained as a commercial item, Adekastab PEP-36A (made by ADEKA CORPORATION) is mentioned.

作為硫醚化合物，例如係硫代二丙酸二月桂基酯、硫代二丙酸二二肉豆蔻基酯、硫代二丙酸二硬脂基酯等硫代二丙酸二烷基酯類及季戊四醇四（β-烷基硫代丙酸）酯類；季戊四醇四（3-月桂基硫代丙酸酯）、3,3’-硫代二丙烯酸二月桂基酯、3,3’-硫代二丙酸二肉豆蔻基酯、3,3’-硫代二丙酸二硬脂基酯等；四[亞甲基-3-（月桂基硫代）丙酸酯]甲烷、雙（甲基-4-[3-正烷基（C12/C14）硫代丙醯氧基]5-第三丁基苯基）硫醚、3,3’-硫代二丙酸雙（十三烷基）酯、3,3’-硫代二丙酸二月桂基酯、3,3’-硫代二丙酸二肉豆蔻基酯、3,3’-硫代二丙酸二硬脂基酯、硫代二丙酸月桂基酯/硬脂基酯、4,4’-硫代雙（6-第三丁基-間甲酚）、2,2’-硫代雙（6-第三丁基-對甲酚）、二硬脂基二硫醚為較佳。 能夠作為市售品而獲得之硫醚化合物的代表例可以舉出Adekastab AO-412S（CAS：29598-76-3、ADEKA CORPORATION製）、Adekastab AO-503（CAS：10595-72-9、ADEKA CORPORATION製）、KEMINOX PLS（CAS：29598-76-3、CHEMIPRO KASEI CO.,LTD.製）。Examples of the thioether compounds include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate. And pentaerythritol tetra (β-alkylthiopropionate) esters; pentaerythritol tetra (3-laurylthiopropionate), 3,3'-thiodiacrylate dilauryl ester, 3,3'-thio Dimyristyl dipropionate, distearyl 3,3'-thiodipropionate, etc .; tetra [methylene-3- (laurylthio) propionate] methane, bis (methyl 4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-third-butylphenyl) sulfide, 3,3'-thiodipropionate bis (tridecyl) ) Ester, 3,3'-thiodipropionate dilauryl ester, 3,3'-thiodipropionate dimyristyl ester, 3,3'-thiodipropionate distearyl ester, Lauryl thiodipropionate / stearyl, 4,4'-thiobis (6-third butyl-m-cresol), 2,2'-thiobis (6-third butyl) -P-cresol) and distearyl disulfide are preferred. Typical examples of sulfide compounds that can be obtained as commercially available products include Adekastab AO-412S (CAS: 29598-76-3, manufactured by ADEKA CORPORATION), Adekastab AO-503 (CAS: 10595-72-9, ADEKA CORPORATION) System), KEMINOX PLS (CAS: 29598-76-3, manufactured by CHEMIPRO KASEI CO., LTD.).

著色防止劑能夠作為市售品容易獲得，除了能夠作為市售品而獲得之上述代表例以外，可以舉出Adekastab AO-50F、Adekastab AO-60G、Adekastab AO-330（ADEKA CORPORATION）等。The coloring inhibitor can be easily obtained as a commercially available product. In addition to the above-mentioned representative examples that can be obtained as a commercially available product, Adekastab AO-50F, Adekastab AO-60G, Adekastab AO-330 (ADEKA CORPORATION), and the like can be mentioned.

從著色性及耐溶劑性的觀點考慮，著色防止劑的含量相對於組成物的總固體成分係0.01～20質量%為較佳，0.1～15質量%為更佳，0.3～5質量%為特佳。著色防止劑可以僅為1種，亦可以為2種以上。當為2種以上時，合計量在上述範圍內為較佳。From the viewpoint of colorability and solvent resistance, the content of the coloring preventive agent is preferably 0.01 to 20% by mass based on the total solid content of the composition, more preferably 0.1 to 15% by mass, and 0.3 to 5% by mass. good. The coloring preventive agent may be only one kind, or two or more kinds. When there are two or more kinds, it is preferable that the total amount is within the above range.

＜＜紫外線吸收劑＞＞ 本發明的組成物可以含有紫外線吸收劑。紫外線吸收劑係共軛二烯系化合物為較佳，下述式（I）所表示之化合物為更佳。 [化學式29] <<< ultraviolet absorber> The composition of this invention may contain an ultraviolet absorber. The ultraviolet absorber-based conjugated diene-based compound is more preferable, and the compound represented by the following formula (I) is more preferable. [Chemical Formula 29]

式（I）中，R1 及R2 各自獨立地表示氫原子、碳原子數1～20的烷基或碳原子數6～20的芳基，R1 與R2 可以分別相同亦可以不同，但不同時表示氫原子。 R1 及R2 可以與R1 及R2 所鍵結之氮原子一同形成環狀胺基。作為環狀胺基，例如可以舉出哌啶基、嗎啉基、吡咯啶基、六氫氮呯（hexahydro azepino）基、哌嗪基等。 R1 及R2 各自獨立地係碳原子數1～20的烷基為較佳，碳原子數1～10的烷基為更佳，碳原子數1～5的烷基為進一步較佳。 R3 及R4 表示拉電子基團。在此，拉電子基團係哈米特（Hammett）取代基常數σp 值（以下，簡稱為“σp 值”。）為0.20以上且1.0以下的拉電子基團。較佳係σp 值為0.30以上且0.8以下的拉電子基團。R3 及R4 可以相互鍵結而形成環。R3 及R4 係醯基、胺甲醯基、烷氧基羰基、芳氧基羰基、氰基、硝基、烷基磺醯基、芳基磺醯基、磺醯氧基、胺磺醯基為較佳，醯基、胺甲醯基、烷氧基羰基、芳氧基羰基、氰基、烷基磺醯基、芳基磺醯基、磺醯氧基、胺磺醯基為更佳。 上述R1 、R2 、R3 及R4 中的至少1個可以係從經由連接基而與乙烯基鍵結之單體衍生之聚合物的形態。亦可以係與其他單體之共聚物。In formula (I), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 1 and R 2 may be the same or different, However, it does not mean a hydrogen atom at the same time. R 1 and R 2 may form a cyclic amine group together with the nitrogen atom bonded to R 1 and R 2 . Examples of the cyclic amino group include piperidinyl, morpholinyl, pyrrolidinyl, hexahydroazepino, and piperazinyl. R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 5 carbon atoms is more preferable. R 3 and R 4 represent an electron-withdrawing group. Here, the electron-withdrawing group is a Hammett substituent constant σ p value (hereinafter, simply referred to as “σ p- value”) which is an electron-withdrawing group of 0.20 or more and 1.0 or less. An electron-withdrawing group having a σ p value of 0.30 or more and 0.8 or less is preferred. R 3 and R 4 may be bonded to each other to form a ring. R 3 and R 4 are fluorenyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, nitro, alkylsulfonyl, arylsulfonyl, sulfonyloxy, aminesulfonyl Is preferred, fluorenyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, alkylsulfonyl, arylsulfonyl, sulfonyloxy, and aminesulfonyl . At least one of R 1 , R 2 , R 3, and R 4 may be in the form of a polymer derived from a monomer that is bonded to a vinyl group through a linking group. It can also be a copolymer with other monomers.

式（I）所表示之紫外線吸收劑的取代基的說明可以參閱WO2009/123109號公報的0024～0033段（對應之美國專利申請公開第2011/0039195號說明書的＜0040＞～＜0059＞）的記載，該等內容被併入本說明書中。式（I）所表示之化合物的較佳的具體例可以參閱WO2009/123109號公報的0034～0037段（對應之美國專利申請公開第2011/0039195號說明書的＜0060＞）的例示化合物（1）～（14）的記載，該等內容被併入本說明書中。 作為式（I）所表示之紫外線吸收劑的具體例，可以舉出下述化合物（後述之實施例中使用之紫外線吸收劑J-1）。 [化學式30] The description of the substituents of the ultraviolet absorbent represented by formula (I) can be found in paragraphs 0024 to 0033 of the WO2009 / 123109 publication (corresponding to <0040> to <0059> of the specification of US Patent Application Publication No. 2011/0039195). Recorded, these contents are incorporated into this specification. Preferred specific examples of the compound represented by the formula (I) can be referred to the exemplified compound (1) of paragraphs 0034 to 0037 of the WO2009 / 123109 publication (corresponding to the US Patent Application Publication No. 2011/0039195 specification <0060>). The contents of ～ (14) are incorporated into this specification. Specific examples of the ultraviolet absorbent represented by the formula (I) include the following compounds (ultraviolet absorbent J-1 used in Examples described later). [Chemical Formula 30]

從圖案形狀及耐溶劑性的觀點考慮，紫外線吸收劑的含量相對於組成物的總固體成分，係0.1～10質量%為較佳，0.1～7質量%為更佳，0.1～5質量%為特佳，0.1～3質量%為更特佳。並且，本發明中，紫外線吸收劑可以僅為1種，亦可以為2種以上。當為2種以上時，合計量在上述範圍內為較佳。From the viewpoint of pattern shape and solvent resistance, the content of the ultraviolet absorber is preferably 0.1 to 10% by mass, more preferably 0.1 to 7% by mass, and 0.1 to 5% by mass relative to the total solid content of the composition. Particularly preferred is 0.1 to 3% by mass. In addition, in the present invention, the ultraviolet absorber may be only one kind, or two or more kinds. When there are two or more kinds, it is preferable that the total amount is within the above range.

紫外線吸收劑亦能夠使用Uvinul A（BASF公司製）。並且，紫外線吸收劑能夠使用胺基二烯化合物、水楊酸酯（salicylate）化合物、二苯甲酮化合物、苯并三唑化合物、丙烯腈化合物、三嗪化合物等紫外線吸收劑，作為具體例，可以舉出日本特開2013-68814號中所記載之化合物。作為苯并三唑化合物，可以使用MIYOSHI OIL & FAT CO.,LTD.製的MYUA系列（化學工業日報、2016年2月1日）。As the ultraviolet absorber, Uvinul A (manufactured by BASF) can also be used. In addition, as the ultraviolet absorber, ultraviolet absorbers such as amine diene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, and triazine compounds can be used as specific examples. Examples thereof include compounds described in Japanese Patent Application Laid-Open No. 2013-68814. As the benzotriazole compound, a MYUA series (Chemical Industry Daily, February 1, 2016) manufactured by MIYOSHI OIL & FAT CO., LTD. Can be used.

＜＜黏附劑＞＞ 本發明的組成物還含有黏附劑為較佳。作為黏附劑並沒有特別限制，可以使用公知的黏附劑。作為黏附劑，例如可以舉出矽烷偶合劑。依該態樣，能夠改善膜與基材之黏附性。 本發明中，矽烷偶合劑係指具有水解性基和其以外的官能基之矽烷化合物。並且，水解性基係指與矽原子直接連接且能夠藉由水解反應及縮合反應中的至少一方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、醯氧基等，烷氧基為較佳。亦即，矽烷偶合劑係具有烷氧基矽基之化合物為較佳。並且，除水解性基以外的官能基具有在與樹脂之間相互作用或形成鍵而顯示親和性之基團為較佳。例如可以舉出（甲基）丙烯醯基、苯基、巰基、環氧基、氧雜環丁基，（甲基）丙烯醯基及環氧基為較佳。亦即，矽烷偶合劑係具有烷氧基矽基和（甲基）丙烯醯基及環氧基中的至少一方之化合物為較佳。 烷氧基矽基中之烷氧基的碳數係1～5為較佳，1～3為更佳，1或2為特佳。在同一分子內具有2個以上烷氧基矽基為較佳，具有2～3個為進一步較佳。<<< Adhesive> The composition of the present invention preferably further contains an adhesive. The adhesive is not particularly limited, and a known adhesive can be used. Examples of the adhesive include a silane coupling agent. According to this aspect, the adhesion between the film and the substrate can be improved. In the present invention, the silane coupling agent refers to a silane compound having a hydrolyzable group and a functional group other than the silane compound. In addition, the hydrolyzable group refers to a substituent directly connected to a silicon atom and capable of generating a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and a fluorenyl group. An alkoxy group is preferred. That is, a silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, it is preferable that the functional group other than the hydrolyzable group has a group that exhibits affinity by interacting with or forming a bond with the resin. Examples include (meth) acrylfluorenyl, phenyl, mercapto, epoxy, and oxetanyl, and (meth) acrylfluorenyl and epoxy are preferred. That is, the silane coupling agent is preferably a compound having at least one of an alkoxysilyl group, a (meth) acrylfluorenyl group, and an epoxy group. The carbon number of the alkoxy group in the alkoxysilyl group is preferably from 1 to 5, more preferably from 1 to 3, and particularly preferably from 1 or 2. It is more preferable to have two or more alkoxysilyl groups in the same molecule, and it is more preferable to have two to three alkoxysilyl groups.

作為矽烷偶合劑的具體例，例如可以舉出3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、苯基三甲氧基矽烷、甲基三甲氧基矽烷、二甲基二甲氧基矽烷、甲基三乙氧基矽烷、二甲基二乙氧基矽烷、苯基三乙氧基矽烷、正丙基三甲氧基矽烷、正丙基三乙氧基矽烷、己基三甲氧基矽烷、己基三乙氧基矽烷、辛基三乙氧基矽烷、癸基三甲氧基矽烷、1,6-雙（三甲氧基矽基）己烷、三氟丙基三甲氧基矽烷、六甲基二矽氮烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-（3,4-環氧基環己基）乙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、N-2-（胺基甲基乙基）-3-胺基丙基甲基二甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-三乙氧基矽基-N-（1,3-二甲基-亞丁基）丙胺、N-苯基-3-胺基丙基三甲氧基矽烷、N-（乙烯基苄基）-2-胺基乙基-3-胺基丙基三甲氧基矽烷的鹽酸鹽、三-（三甲氧基矽基丙基）异氰脲酸酯、3-脲丙基三乙氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、雙（三乙氧基矽基丙基）四硫化物、3-异氰酸酯丙基三乙氧基矽烷等。並且，可以使用上述以外的烷氧基寡聚物。並且，亦可以使用下述化合物。 [化學式31] Specific examples of the silane coupling agent include, for example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropylpropane Trimethoxysilane, 3-propenyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, phenyltrimethoxysilane, methyl Trimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyl Triethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, Trifluoropropyltrimethoxysilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethyl Oxysilane, 3-glycidyloxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methylpropylene Methoxypropylmethyldiethoxysilane, N-2- (aminomethylethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- Triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2- Aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tri- (trimethoxysilylpropyl) isocyanurate, 3-ureapropyltriethoxysilane, 3- Mercaptopropylmethyldimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, etc. In addition, an alkoxy oligomer other than the above can be used. The following compounds can also be used. [Chemical Formula 31]

作為市售品，可以舉出Shin-Etsu Silicone Co.,Ltd.製的KBM-13、KBM-22、KBM-103、KBE-13、KBE-22、KBE-103、KBM-3033、KBE-3033、KBM-3063、KBM-3066、KBM-3086、KBE-3063、KBE-3083、KBM-3103、KBM-3066、KBM-7103、SZ-31、KPN-3504、KBM-1003、KBE-1003、KBM-303、KBM-402、KBM-403、KBE-402、KBE-403、KBM-1403、KBM-502、KBM-503、KBE-502、KBE-503、KBM-5103、KBM-602、KBM-603、KBM-903、KBE-903、KBE-9103、KBM-573、KBM-575、KBM-9659、KBE-585、KBM-802、KBM-803、KBE-846、KBE-9007、X-40-1053、X-41-1059A、X-41-1056、X-41-1805、X-41-1818、X-41-1810、X-40-2651、X-40-2655A、KR-513、KC-89S、KR-500、KR-516、KR-517、X-40-9296、X-40-9225、X-40-9246、X-40-9250、KR-401N、X-40-9227、X-40-9247、KR-510、KR-9218、KR-213、X-40-2308、X-40-9238等。並且，矽烷偶合劑可以舉出日本特開2009-288703號公報的0018～0036段中所記載之化合物、日本特開2009-242604號公報的0056～0066段中所記載之化合物，該等內容被併入本說明書中。 並且，具有烷氧基矽基之化合物亦能夠使用在側鏈上具有烷氧基矽基之聚合物。 作為矽烷偶合劑，還能夠參閱並使用日本特開2009-288703號公報的＜0011＞～＜0037＞中所記載之特定矽烷化合物，其內容被併入本說明書中。Examples of commercially available products include KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, and KBE-3033 manufactured by Shin-Etsu Silicone Co., Ltd. , KBM-3063, KBM-3066, KBM-3086, KBE-3063, KBE-3083, KBM-3103, KBM-3066, KBM-7103, SZ-31, KPN-3504, KBM-1003, KBE-1003, KBM -303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603 , KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, KBE-9007, X-40-1053 , X-41-1059A, X-41-1056, X-41-1805, X-41-1818, X-41-1810, X-40-2651, X-40-2655A, KR-513, KC-89S , KR-500, KR-516, KR-517, X-40-9296, X-40-9225, X-40-9246, X-40-9250, KR-401N, X-40-9227, X-40 -9247, KR-510, KR-9218, KR-213, X-40-2308, X-40-9238, etc. In addition, the silane coupling agent may include compounds described in paragraphs 0018 to 0036 of JP 2009-288703 and compounds described in paragraphs 0056 to 0066 of JP 2009-242604. Incorporated into this manual. Moreover, the compound which has a silicon alkoxy group can also use the polymer which has a silicon alkoxy group in a side chain. As the silane coupling agent, specific silane compounds described in <0011> to <0037> of Japanese Patent Application Laid-Open No. 2009-288703 can also be referred to and used, and the contents thereof are incorporated into this specification.

黏附劑的含量相對於組成物的總固體成分係0.01～10質量%為較佳，0.1～7質量%為更佳，1～5質量%為特佳。若在該等範圍，則從黏附性和缺陷的觀點考慮較佳。並且，本發明中，組成物所含有之黏附劑可以僅為1種，亦可以為2種以上。當為2種以上時，合計量在上述範圍內為較佳。The content of the adhesive is preferably 0.01 to 10% by mass based on the total solid content of the composition, more preferably 0.1 to 7% by mass, and particularly preferably 1 to 5% by mass. If it is within these ranges, it is more preferable from the viewpoint of adhesion and defects. In addition, in the present invention, the adhesive contained in the composition may be only one kind, or two or more kinds. When there are two or more kinds, it is preferable that the total amount is within the above range.

＜＜鏈轉移劑＞＞ 本發明的組成物含有鏈轉移劑為較佳。依該態樣，能夠藉由圖案形成時的曝光來促進膜表面（圖案表面）的硬化。因此，能夠抑制曝光時的膜厚度的減少等，容易形成矩形性及黏附性更優異之圖案。<< chain transfer agent >> The composition of the present invention preferably contains a chain transfer agent. According to this aspect, the film surface (pattern surface) can be hardened by exposure during pattern formation. Therefore, it is possible to suppress a reduction in film thickness and the like during exposure, and it is easy to form a pattern having more excellent rectangularity and adhesion.

作為鏈轉移劑，可以舉出N,N-二烷基胺基苯甲酸烷基酯、或硫醇化合物等，硫醇化合物為較佳。硫醇化合物係在分子內具有2個以上（較佳為2～8個，更佳為3～6個）巰基之化合物為較佳。作為硫醇化合物的具體例，可以舉出2-巰基苯并噻唑、2-巰基苯并噁唑、2-巰基苯并咪唑、N-苯基巰基苯并咪唑、1,3,5-三（3-巰基丁氧基乙基）-1,3,5-三嗪-2,4,6（1H,3H,5H）-三酮等具有雜環之硫醇化合物、季戊四醇四（3-巰基丁酸酯）、1,4-雙（3-巰基丁醯氧基）丁烷等脂肪族系硫醇化合物等。 並且，作為鏈轉移劑的市售品，可以舉出PEMP（SC Organic Chemical Co.,Ltd.製，硫醇化合物）、Sanceler M（SANSHIN CHEMICAL INDUSTRY CO.,LTD.製，硫醇化合物）、Karenz MT BD1（SHOWA DENKO K.K.製，硫醇化合物）等。 並且，使用下述化合物亦較佳。 [化學式32] Examples of the chain transfer agent include N, N-dialkylaminobenzoic acid alkyl ester, or a thiol compound. A thiol compound is preferred. The thiol compound is preferably a compound having two or more (preferably 2 to 8 and more preferably 3 to 6) mercapto groups in the molecule. Specific examples of the thiol compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenylmercaptobenzimidazole, 1,3,5-tris ( 3-Mercaptobutoxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and other heterocyclic thiol compounds, pentaerythritol tetrakis (3-mercaptobutane Esters), aliphatic thiol compounds such as 1,4-bis (3-mercaptobutyryloxy) butane, and the like. Examples of commercially available chain transfer agents include PEMP (thiol compound manufactured by SC Organic Chemical Co., Ltd.), Sanceler M (thiol compound manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.), And Karenz MT BD1 (made by SHOWA DENKO KK, thiol compound), etc. In addition, it is preferable to use the following compounds. [Chemical Formula 32]

鏈轉移劑的含量相對於組成物的總固體成分，係0.2～5.0質量%為較佳，0.4～3.0質量%為更佳。 鏈轉移劑的含量相對於聚合性化合物的100質量份，係1～40質量份為較佳，2～20質量份為更佳。 鏈轉移劑可以僅為1種，亦可以為2種以上。當為2種以上時，合計量在上述範圍內為較佳。The content of the chain transfer agent is preferably 0.2 to 5.0% by mass, and more preferably 0.4 to 3.0% by mass based on the total solid content of the composition. The content of the chain transfer agent is preferably 1 to 40 parts by mass, and more preferably 2 to 20 parts by mass based on 100 parts by mass of the polymerizable compound. The chain transfer agent may be only one kind, or two or more kinds. When there are two or more kinds, it is preferable that the total amount is within the above range.

＜＜增感劑＞＞ 本發明的組成物可以以提高光聚合起始劑的自由基產生效率和感光波長的長波長化為目的而含有增感劑。作為增感劑，係藉由電子移動機構或能量移動機構使光聚合起始劑增感者為較佳。增感劑可以舉出在300nm～450nm的波長區域具有吸收波長者。具體而言，可以參閱日本特開2010-106268號公報的0231～0253段（對應之美國專利申請公開第2011/0124824號說明書的＜0256＞～＜0273＞）的說明，該等內容被併入本說明書中。<<< Sensitizer> The composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the photopolymerization initiator and increasing the wavelength of the photosensitive wavelength. As the sensitizer, a photopolymerization initiator is preferably sensitized by an electronic moving mechanism or an energy moving mechanism. Examples of the sensitizer include those having an absorption wavelength in a wavelength range of 300 nm to 450 nm. Specifically, reference can be made to the descriptions of paragraphs 0231 to 0253 of Japanese Patent Application Laid-Open No. 2010-106268 (corresponding to US Patent Application Publication No. 2011/0124824, <0256> to <0273>), and these contents are incorporated into In this manual.

增感劑的含量相對於組成物的總固體成分，係0.1～20質量%為較佳，0.5～15質量%為更佳。增感劑可以僅為1種，亦可以為2種以上。當為2種以上時，合計量在上述範圍內為較佳。The content of the sensitizer is preferably 0.1 to 20% by mass, and more preferably 0.5 to 15% by mass with respect to the total solid content of the composition. The sensitizer may be only one kind, or two or more kinds. When there are two or more kinds, it is preferable that the total amount is within the above range.

＜＜共增感劑＞＞ 本發明的組成物還含有共增感劑亦較佳。共增感劑具有進一步提高光聚合起始劑或增感劑對活性放射線之靈敏度或者抑制氧引起之聚合性化合物的聚合阻礙等作用。作為共增感劑，具體而言，可以參閱日本特開2010-106268號公報的0254～0257段（對應之美國專利申請公開第2011/0124824號說明書的＜0277＞～＜0279＞）的說明，該等內容被併入本說明書中。<< Co-Sensitizer >> The composition of the present invention also preferably contains a co-sensitizer. Co-sensitizers have the effect of further improving the sensitivity of photopolymerization initiators or sensitizers to active radiation or inhibiting the polymerization barrier of polymerizable compounds caused by oxygen. As the co-sensitizer, specifically, please refer to the descriptions of paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2010-106268 (corresponding to US Patent Application Publication No. 2011/0124824, <0277> to <0279>), Such content is incorporated into this specification.

從提高聚合成長速度和硬化速度之觀點考慮，共增感劑的含量相對於組成物的總固體成分，係0.1～30質量%為較佳，1～25質量%為更佳，1.5～20質量%為進一步較佳。共增感劑可以僅為1種，亦可以為2種以上。當為2種以上時，合計量在上述範圍內為較佳。From the viewpoint of increasing the polymerization growth rate and the hardening rate, the content of the co-sensitizer is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and 1.5 to 20% by mass relative to the total solid content of the composition. % Is further preferred. The co-sensitizer may be only one kind, or two or more kinds. When there are two or more kinds, it is preferable that the total amount is within the above range.

＜＜聚合抑制劑＞＞ 為了在製造或保存組成物時阻止聚合性化合物等的不必要的聚合，本發明的組成物中添加聚合抑制劑為較佳。 作為聚合抑制劑，可以舉出以下化合物類： 含有酚系羥基之化合物類（較佳為選自包括氫醌、對甲氧基苯酚、二-第三丁基-對甲酚、五倍子酚、第三丁基鄰苯二酚、苯醌、4,4-硫代雙（3-甲基-6-第三丁基苯酚）、2,2’-亞甲基雙（4-甲基-6-第三丁基苯酚）、2,6-二-第三丁基-4-甲基苯酚（BHT）、酚醛樹脂類及甲酚樹脂類之組群中之化合物）； N-氧化物類（較佳為選自包括5,5-二甲基-1-二氫吡咯N-氧化物、4-甲基嗎啉N-氧化物、吡啶N-氧化物、4-硝基吡啶N-氧化物、3-羥基吡啶N-氧化物、吡啶甲酸N-氧化物、菸鹼酸N-氧化物及異菸鹼酸N-氧化物之組群中之化合物）； 哌啶1-氧基自由基（free radical）化合物類（較佳為選自包括哌啶1-氧基自由基、2,2,6,6-四甲基哌啶1-氧基自由基、4-氧代-2,2,6,6-四甲基哌啶1-氧基自由基、4-羥基-2,2,6,6-四甲基哌啶1-氧基自由基、4-乙醯胺-2,2,6,6-四甲基哌啶1-氧基自由基、4-順丁烯二醯亞胺-2,2,6,6-四甲基哌啶1-氧基自由基及4-膦醯氧基-2,2,6,6-四甲基哌啶1-氧基自由基之組群中之化合物）； 吡咯啶1-氧基自由基化合物類（較佳為3-carboxy proxyl free radical（3-羧基-2,2,5,5-四甲基吡咯啶1-氧基自由基））； N-亞硝基苯基羥基胺類（較佳為選自包括N-亞硝基苯基羥基胺第一鈰鹽及N-亞硝基苯基羥基胺鋁鹽之化合物組群中之化合物）； 重氮化合物類（較佳為選自包括4-重氮苯基二甲胺的硫酸氫鹽、4-重氮二苯胺的四氟硼酸鹽及3-甲氧基-4-重氮二苯胺的六氟磷酸鹽之組群中之化合物）； 陽離子染料類； 含硫醚基化合物類； 含硝基化合物類；及 FeCl3 、CuCl2 等過渡金屬化合物類。 並且，在該等化合物類中，聚合抑制劑亦可以為在同一分子內存在複數個酚骨架或含磷骨架等顯現聚合抑制功能之結構之複合系化合物。例如，還可以較佳地使用日本特開平10-46035號公報中所記載之化合物等。<<< Polymerization Inhibitor> In order to prevent unnecessary polymerization of a polymerizable compound and the like during production or storage of the composition, it is preferable to add a polymerization inhibitor to the composition of the present invention. Examples of the polymerization inhibitor include compounds containing phenolic hydroxyl groups (preferably selected from the group consisting of hydroquinone, p-methoxyphenol, di-third-butyl-p-cresol, gallophenol, Tributylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4-methyl-6- Tertiary butyl phenol), 2,6-di-tertiary butyl-4-methylphenol (BHT), phenolic resins, and compounds in the group of cresol resins); N-oxides (compared to Preferably selected from the group consisting of 5,5-dimethyl-1-dihydropyrrole N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, Compounds in the group of 3-hydroxypyridine N-oxide, picolinic acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide); piperidine 1-oxyl radical (free radical) compounds (preferably selected from the group consisting of piperidine 1-oxy radical, 2,2,6,6-tetramethylpiperidine 1-oxy radical, 4-oxo-2,2,6 , 6-tetramethylpiperidine 1-oxy radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy radical, 4-acetamidamine-2,2,6 , 6- Methylpiperidine 1-oxy radical, 4-cis-butene diamidine-2,2,6,6-tetramethylpiperidine 1-oxy radical and 4-phosphinofluorenoxy-2, Compounds in the group of 2,6,6-tetramethylpiperidine 1-oxy radicals); pyrrolidine 1-oxy radical compounds (preferably 3-carboxy proxyl free radical (3-carboxy- 2,2,5,5-tetramethylpyrrolidine 1-oxy radical)); N-nitrosophenylhydroxylamines (preferably selected from the group consisting of N-nitrosophenylhydroxylamines) Compounds in the group of compounds of cerium salt and aluminum salt of N-nitrosophenylhydroxylamine); diazonium compounds (preferably selected from the group consisting of 4-diazophenyldimethylamine hydrogen sulfate, 4- Compounds in the group of tetrafluoroborate of diazodiphenylamine and hexafluorophosphate of 3-methoxy-4-diazodiphenylamine); cationic dyes; thioether-based compounds; nitro-containing compounds And transition metal compounds such as FeCl 3 and CuCl 2 . In addition, among these compounds, the polymerization inhibitor may be a composite compound having a structure exhibiting a polymerization inhibitory function such as a plurality of phenol skeletons or phosphorus-containing skeletons in the same molecule. For example, compounds described in Japanese Patent Application Laid-Open No. 10-46035 can also be preferably used.

作為聚合抑制劑的具體例，可以舉出日本特開2015-34961號公報的0211～0223段中所記載之化合物，其內容被併入本說明書中。Specific examples of the polymerization inhibitor include compounds described in paragraphs 0211 to 0223 of Japanese Patent Application Laid-Open No. 2015-34961, the contents of which are incorporated herein.

聚合抑制劑的含量相對於光聚合起始劑100質量份，係0.01質量份～10質量份為較佳，0.01～8質量份為更佳，0.01～5質量份為最佳。藉由設為上述範圍，可充分抑制非圖像部中之硬化反應及促進圖像部中之硬化反應，圖案形狀及靈敏度變得良好。聚合抑制劑可以僅為1種，亦可以為2種以上。當為2種以上時，合計量在上述範圍內為較佳。The content of the polymerization inhibitor relative to 100 parts by mass of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 8 parts by mass, and most preferably 0.01 to 5 parts by mass. By setting it as the said range, the hardening reaction in a non-image part can be fully suppressed and the hardening reaction in an image part can be promoted, and a pattern shape and sensitivity become favorable. The polymerization inhibitor may be only one kind, or two or more kinds. When there are two or more kinds, it is preferable that the total amount is within the above range.

＜＜界面活性劑＞＞ 從進一步提高塗佈適應性之觀點考慮，本發明的組成物可以含有各種界面活性劑。作為界面活性劑，可以使用氟系界面活性劑、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、矽酮系界面活性劑等各種界面活性劑。<<< Surfactant> The composition of the present invention may contain various surfactants from the viewpoint of further improving coating suitability. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

藉由在上述組成物中含有氟系界面活性劑，製備成塗佈液時的液體特性（尤其流動性）進一步得到提高，能夠進一步改善塗佈厚度的均勻性和省液性。亦即，當使用適用了含有氟系界面活性劑的組成物之塗佈液形成膜時，被塗佈面與塗佈液的界面張力下降而改善對被塗佈面之潤濕性，對被塗佈面之塗佈適應性得到提高。因此，能夠更適當地形成厚度不均勻較小的均勻厚度的膜。By containing a fluorine-based surfactant in the composition, the liquid characteristics (especially fluidity) when the coating liquid is prepared are further improved, and the uniformity of coating thickness and the liquid-saving property can be further improved. That is, when a coating liquid using a composition containing a fluorine-based surfactant is used to form a film, the interfacial tension between the coated surface and the coating liquid is reduced, and the wettability to the coated surface is improved. The coating adaptability of the coated surface is improved. Therefore, it is possible to more appropriately form a film having a uniform thickness with small thickness unevenness.

氟系界面活性劑中的氟含有率係3～40質量%為較佳，更佳為5～30質量%，特佳為7～25質量%。氟含有率在該範圍內之氟系界面活性劑在塗佈膜的厚度均勻性及省液性的觀點上有效，且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 particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective from the viewpoints of thickness uniformity and liquid-saving properties of the coating film, and also has good solubility in the composition.

作為氟系界面活性劑，具體而言，可以舉出日本特開2014-41318號公報的0060～0064段（對應之國際公開WO2014/17669號小冊子的0060～0064段）等中所記載之界面活性劑、日本特開2011-132503號公報的0117～0132段中所記載之界面活性劑，該等內容被併入本說明書中。作為氟系界面活性劑的市售品，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）、Fluorad FC430、Fluorad FC431、Fluorad FC171（以上為Sumitomo 3M Limited製）、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）、PolyFox PF636、PF656、PF6320、PF6520、PF7002（OMNOVA Solutions Inc.製）等。Specific examples of the fluorine-based surfactant include the interfacial activities described in paragraphs 0060 to 0064 of Japanese Patent Laid-Open No. 2014-41318 (corresponding paragraphs 0060 to 0064 of International Publication WO2014 / 17669 pamphlet) and the like. Agents, surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 2011-132503, which are incorporated into this specification. Examples of commercially available 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, and Megafac F475. , Megafac F479, Megafac F482, Megafac F554, Megafac F780 (above manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above 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.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.) and the like.

並且，關於氟系界面活性劑，亦能夠較佳地使用丙烯酸系化合物，該丙烯酸系化合物係在具有含有氟原子之官能基之分子結構中加熱時，含有氟原子之官能基的部分被切斷而氟原子發生揮發。作為該種氟系界面活性劑，可以舉出DIC CORPORATION製的Megafac DS系列（化學工業日報、2016年2月22日）（日經產業新聞、2016年2月23日），例如Megafac DS-21，能夠使用該等。In addition, as the fluorine-based surfactant, an acrylic compound can also be preferably used. When the acrylic compound is heated in a molecular structure having a functional group containing a fluorine atom, the functional group containing a fluorine atom is cut off. The fluorine atom is volatilized. Examples of such fluorine-based surfactants include Megafac DS series (Chemical Industry Daily, February 22, 2016) manufactured by DIC Corporation (Nikkei Industry News, February 23, 2016), such as Megafac DS-21 To be able to use these.

氟系界面活性劑還可以使用嵌段聚合物。例如可以舉出日本特開2011-89090號公報中所記載之化合物。氟系界面活性劑還可以較佳地使用含氟高分子化合物，該含氟高分子化合物含有：源自具有氟原子之（甲基）丙烯酸酯化合物之重複單元；及源自具有2個以上（較佳為5個以上）伸烷氧基（較佳為伸乙氧基、伸丙氧基）之（甲基）丙烯酸酯化合物之重複單元。作為本發明中所使用之氟系界面活性劑，還例示出下述化合物。 [化學式33]上述化合物的重量平均分子量較佳為3,000～50,000，例如為14,000。As the fluorine-based surfactant, a block polymer may be used. Examples thereof include compounds described in Japanese Patent Application Laid-Open No. 2011-89090. As the fluorine-based surfactant, a fluorine-containing polymer compound can also be preferably used. The fluorine-containing polymer compound contains: a repeating unit derived from a (meth) acrylate compound having a fluorine atom; and a derivative derived from a compound having two or more ( It is preferably 5 or more) repeating units of a (meth) acrylate compound of an alkoxy group (preferably an ethoxy group and a propyleneoxy group). The following compounds are exemplified as the fluorine-based surfactant used in the present invention. [Chemical Formula 33] The weight average molecular weight of the compound is preferably 3,000 to 50,000, and is, for example, 14,000.

並且，氟系界面活性劑還能夠使用在側鏈上具有含有乙烯性不飽和鍵之基團之含氟聚合物。作為具體例，可以舉出日本特開2010-164965號公報的0050～0090段及0289～0295段中所記載之化合物，例如DIC CORPORATION製的Megafac RS-101、RS-102、RS-718K、RS-72-K等。氟系界面活性劑還能夠使用日本特開2015-117327號公報的0015～0158段中所記載之化合物。As the fluorine-based surfactant, a fluorine-containing polymer having a group containing an ethylenically unsaturated bond in a side chain can also be used. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Laid-Open No. 2010-164965, such as Megafac RS-101, RS-102, RS-718K, and RS manufactured by DIC Corporation. -72-K and so on. As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Laid-Open No. 2015-117327 can also be used.

作為非離子系界面活性劑，可以舉出甘油、三羥甲基丙烷、三羥甲基乙烷及該等的乙氧基化物及丙氧基化物（例如，甘油丙氧基化物、甘油乙氧基化物等）、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、Pluronic L10、L31、L61、L62、10R5、17R2、25R2（BASF公司製）、Tetronic 304、701、704、901、904、150R1（BASF公司製）、Solsperse 20000（Japan Lubrizol Corporation製）、NCW-101、NCW-1001、NCW-1002（Wako Pure Chemical Industries, Ltd.製）、PIONIN D-6112、D-6112-W、D-6315（Takemoto Oil & Fat Co.,Ltd.製）、OLFIN E1010、Surfynol 104、400、440（Nissin Chemical Co.,Ltd.製）等。Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate). Base compounds, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol di Lauric acid ester, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901 , 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112- W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), and the like.

作為陽離子系界面活性劑，可以舉出有機矽氧烷聚合物KP341（Shin-Etsu Chemical Co.,Ltd.製）、（甲基）丙烯酸系（共）聚合物Polyflow No.75、No.90、No.95（KYOEISHA CHEMICAL Co.,Ltd.製）、W001（Yusho Co.,Ltd.製）等。Examples of the cationic surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic (co) polymer Polyflow No. 75, No. 90, No. 95 (manufactured by KYOEISHA CHEMICAL Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

作為陰離子系界面活性劑，可以舉出W004、W005、W017（Yusho Co.,Ltd.製）、Sundet BL（Sanyo Chemical Industries, Ltd.製）等。Examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.), Sundet BL (manufactured by Sanyo Chemical Industries, Ltd.), and the like.

作為矽酮系界面活性劑，例如可以舉出Toray Silicone DC3PA、Toray Silicone SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone SH8400（以上為Dow Corning Toray Co.,Ltd.製）、TSF-4440、TSF-4300、TSF-4445、TSF-4460、TSF-4452（以上為Momentive Performance Materials Inc.製）、KP341、KF6001、KF6002（以上為Shin-Etsu Silicone Co.,Ltd.製）、BYK307、BYK323、BYK330（以上為BYK-Chemie Corporation製）等。Examples of the silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (The above is Dow Corning Toray Co. ., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (the above are Shin-Etsu Silicone Co ., Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK-Chemie Corporation), and the like.

界面活性劑可以僅使用1種，亦可以將2種以上組合。 界面活性劑的含量相對於組成物的總固體成分係0.001～2.0質量%為較佳，0.005～1.0質量%為更佳。The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.001 to 2.0% by mass based on the total solid content of the composition, and more preferably 0.005 to 1.0% by mass.

＜＜其他添加劑＞＞ 為了改善膜或硬化膜的物性，可以對組成物加入可塑劑或感脂化劑等公知的添加劑。作為可塑劑，例如可以舉出鄰苯二甲酸二辛酯、鄰苯二甲酸雙十二烷基酯、三乙二醇二辛酸酯、二甲基二醇鄰苯二甲酸酯、磷酸三甲苯酯、己二酸二辛酯、癸二酸二丁酯、甘油三乙醯酯等。可塑劑的含量相對於聚合性化合物和樹脂的合計量係10質量%以下為較佳。<< Other additives >> In order to improve the physical properties of a film or a cured film, a known additive such as a plasticizer or a lipophilic agent may be added to the composition. Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, and triphosphate Tolyl ester, dioctyl adipate, dibutyl sebacate, triethylglyceride and the like. The content of the plasticizer is preferably 10% by mass or less based on the total amount of the polymerizable compound and the resin.

＜組成物的製備方法＞ 上述組成物能夠將前述成分混合而進行製備。 在製備組成物時，可以將各成分統括配合，亦可以在溶劑中逐次配合各成分而使其溶解或分散。並且，配合時的投入順序和作業條件不受特別限制。 並且，作為使顏料分散之程序，可以舉出使用壓縮、壓榨、衝擊、剪斷、氣蝕等作為用於顏料的分散中之機械力之程序。作為該等程序的具體例，可以舉出珠磨機（beads mill）、混砂機（sand mill）、輥軋機（roll mill）、高速葉輪、磨砂機（sand grinder）、流動噴射混合機（flow jet mixer）、高壓濕式微粒化、超音波分散等。並且，可以較佳地使用“分散技術大全，JOHOKIKO CO.,LTD.發行，2005年7月15日”或“以懸浮（固/液分散系）為中心之分散技術與工業應用的實際 綜合資料集，Keiei Kaihatsu Center Publishing Department發行，1978年10月10日”中所記載之程序及分散機。<Method for preparing composition> The composition can be prepared by mixing the aforementioned components. In the preparation of the composition, each component may be mixed together, or each component may be sequentially mixed in a solvent to dissolve or disperse them. In addition, the input sequence and working conditions at the time of cooperation are not particularly limited. In addition, examples of the procedure for dispersing the pigment include a procedure using compression, pressing, impact, shearing, cavitation, etc. as the mechanical force for dispersing the pigment. Specific examples of such procedures include a beads mill, a sand mill, a roll mill, a high-speed impeller, a sand grinder, and a flow jet mixer. jet mixer), high-pressure wet micronization, and ultrasonic dispersion. Moreover, it is better to use "Encyclopedia of Dispersion Technology, issued by JOHOKIKO CO., LTD., July 15, 2005" or "Practical comprehensive information on dispersion technology and industrial applications centered on suspension (solid / liquid dispersion system). Episode, published by Keeii Kaihatsu Center Publishing Department, October 10, 1978. "

當製備組成物時，以去除異物和減少缺陷等為目的，利用過濾器過濾為較佳。作為過濾器，只要是一直以來用於過濾用途等者，就可以無特別限定地進行使用。例如，可以舉出使用了聚四氟乙烯（PTFE）等氟系樹脂、尼龍（例如尼龍-6、尼龍-6,6）等聚醯胺系樹脂、聚乙烯、聚丙烯（PP）等聚烯烴樹脂（包括高密度、超高分子量之者）等之過濾器。在該等材料之中，聚丙烯（包括高密度聚丙烯）及尼龍為較佳。 過濾器的孔徑為0.01～7.0μm左右是適當的，較佳為0.01～3.0μm左右，進一步較佳為0.05～0.5μm左右。藉由設為該範圍，能夠製備微細的異物可靠地被除去之組成物，能夠在後製程中形成均勻及平滑的組成物層。並且，使用纖維狀的過濾器亦較佳。作為纖維狀的過濾器，例如可以舉出聚丙烯纖維、尼龍纖維、玻璃纖維等，具體而言，能夠使用ROKI TECHNO CO.,LTD.製的SBP型系列（SBP008等）、TPR型系列（TPR002、TPR005等）、SHPX型系列（SHPX003等）的過濾器濾筒。When preparing a composition, it is preferable to filter with a filter for the purpose of removing foreign matter and reducing defects. The filter can be used without particular limitation as long as it has been conventionally used for filtering purposes and the like. Examples include fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), polyolefins such as polyethylene, and polypropylene (PP). Filters for resins (including those with high density and ultra high molecular weight). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred. The pore diameter of the filter is preferably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. By setting it as this range, the composition which the fine foreign material is reliably removed can be prepared, and a uniform and smooth composition layer can be formed in a post process. It is also preferable to use a fibrous filter. Examples of the fibrous filter include polypropylene fiber, nylon fiber, and glass fiber. Specifically, SBP series (SBP008, etc.) and TPR series (TPR002, manufactured by ROKI TECHNO CO., LTD.) Can be used. , TPR005, etc.), SHPX series (SHPX003, etc.) filter cartridges.

在使用過濾器時，亦可以組合不同之過濾器。此時，利用第1過濾器之過濾可以僅進行1次，亦可以進行2次以上。 並且，第1過濾器可以係將在上述範圍內不同孔徑的過濾器組合而成之者。此處的孔徑可以參閱過濾器製造商的標稱值。作為市售的過濾器，例如可以從由日本PALL Corporation（DFA4201NXEY等）、Advantec Toyo Kaisha, Ltd.、Nihon Entegris K.K.（原Nihon Mykrolis K.K.）或KITZ MICROFILTER CORPORATION等提供之各種過濾器中進行選擇。 第2過濾器可以使用由與上述第1過濾器相同的材料等形成者。 例如，可以僅在分散液中進行利用第1過濾器之過濾，在混合其他成分之後進行利用第2過濾器之過濾。When using filters, different filters can also be combined. In this case, the filtration using the first filter may be performed only once, or may be performed twice or more. The first filter may be a combination of filters having different pore diameters within the above range. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, various filters provided by PALL Corporation (DFA4201NXEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (formerly Nihon Mykrolis K.K.), or KITZ MICROFILTER CORPORATION can be selected. The second filter may be formed from the same material as the first filter. For example, filtration using the first filter may be performed only in the dispersion, and filtration using the second filter may be performed after mixing the other components.

[膜] 本發明的膜的第1態樣係使用本發明的組成物而形成之膜。 本發明的膜的第2態樣係一種膜，其含有無機粒子及樹脂，無機粒子含有中空無機粒子、中實無機粒子及多孔質無機粒子中的至少1種，無機粒子中所含之無機物對波長589nm的光之折射率為1.65以上。[Film] The first aspect of the film of the present invention is a film formed using the composition of the present invention. A second aspect of the film of the present invention is a film containing inorganic particles and a resin, the inorganic particles containing at least one of hollow inorganic particles, solid inorganic particles, and porous inorganic particles, and an inorganic substance pair contained in the inorganic particles. The refractive index of light having a wavelength of 589 nm is 1.65 or more.

＜L*＞ 本發明的膜在CIE1976的L*a*b*色彩坐標系統中之L*係35以上為較佳，35～75為更佳。膜在CIE1976的L*a*b*色彩坐標系統中之L*的下限係50以上為更佳，60以上為特佳。<L *> The film of the present invention has a L * of 35 or more in the L * a * b * color coordinate system of CIE1976, and more preferably 35 to 75. The lower limit of the L * of the film in the L * a * b * color coordinate system of CIE1976 is more preferably 50 or more, and more preferably 60 or more.

＜a*及b*＞ 依本發明的膜，CIE1976的L*a*b*色彩坐標系統中之a*係-30～30為較佳，-20～20為更佳，-10～10為特佳。 依本發明的膜，CIE1976的L*a*b*色彩坐標系統中之b*係-35～30為較佳，-33～10為更佳，-30～0為特佳。<A * and b *> According to the film of the present invention, the a * system in the L * a * b * color coordinate system of CIE1976 is preferably -30-30, more preferably -20-20, and -10-10 Extraordinary. According to the film of the present invention, b * of -35 to 30 in the L * a * b * color coordinate system of CIE1976 is more preferred, -33 to 10 is more preferred, and -30 to 0 is particularly preferred.

＜厚度＞ 本發明的膜的厚度係10μm以下為較佳，3μm以下為更佳，1μm以下為特佳。厚度的下限值係0.5μm以上為較佳。<Thickness> The thickness of the film of the present invention is preferably 10 μm or less, more preferably 3 μm or less, and particularly preferably 1 μm or less. The lower limit of the thickness is preferably 0.5 μm or more.

＜平均透射率＞ 本發明的膜在厚度3.0μm時在波長400～700nm範圍內之平均透射率係1%以上為較佳，10%以上為更佳，30%以上為特佳。波長400～700nm範圍內之平均透射率的上限值係50%以下為較佳。<Average transmittance> When the thickness of the film of the present invention is 3.0 μm, the average transmittance in the wavelength range of 400 to 700 nm is preferably 1% or more, more preferably 10% or more, and particularly preferably 30% or more. The upper limit of the average transmittance in the wavelength range of 400 to 700 nm is preferably 50% or less.

＜用途＞ 本發明的膜能夠組裝於固體攝像元件等各種感測器和圖像顯示裝置（例如，液晶顯示裝置和有機電致發光（有機EL）顯示裝置等）中進行使用。並且，亦能夠用作調整光學構件的外觀之用途的材料。 本發明的膜例如亦可以組裝於各種感測器和圖像顯示裝置等中，用作將光適當遮擋或透射之構件和散射光之構件。並且，還可以用於發光二極體（LED）反射用途、有機EL光散射層用途、導電材料、絕緣材料、太陽能電池用材料等。<Application> The film of the present invention can be used by being assembled in various sensors such as solid-state imaging elements and image display devices (for example, liquid crystal display devices and organic electroluminescence (organic EL) display devices). Moreover, it can be used as a material for the purpose of adjusting the external appearance of an optical member. The film of the present invention can be incorporated in various sensors, image display devices, and the like, for example, and can be used as a member that appropriately blocks or transmits light and a member that scatters light. It can also be used for light-emitting diode (LED) reflection applications, organic EL light scattering layer applications, conductive materials, insulating materials, and materials for solar cells.

[硬化膜] 本發明的硬化膜係將本發明的膜進行硬化而得到之硬化膜。硬化膜係從本發明的膜中溶劑被除去者為較佳。並且，硬化膜係將本發明的膜中之聚合性化合物進行聚合後硬化而得到者為較佳。 硬化膜在CIE1976的L*a*b*色彩坐標系統中之L*係35～75為較佳。硬化膜的L*的上限係70以下為較佳。硬化膜的L*的下限係40以上為較佳，50以上為更佳。[Cure Film] The cured film of the present invention is a cured film obtained by curing the film of the present invention. The cured film is preferably one in which the solvent is removed from the film of the present invention. In addition, the cured film is preferably obtained by polymerizing the polymerizable compound in the film of the present invention and curing it. The L * of the hardened film in the L * a * b * color coordinate system of CIE1976 is 35-75. The upper limit of L * of the cured film is preferably 70 or less. The lower limit of L * of the cured film is preferably 40 or more, and more preferably 50 or more.

[光學感測器] 本發明的光學感測器係具有本發明的硬化膜之光學感測器。作為光學感測器，可以舉出固體攝像元件等。[Optical Sensor] The optical sensor of the present invention is an optical sensor having a cured film of the present invention. Examples of the optical sensor include a solid-state imaging device and the like.

[膜的製造方法] 本發明的膜的製造方法包括如下製程：將本發明的組成物經由具有圖案之遮罩進行曝光之製程；及對經曝光之組成物進行顯影而形成圖案之製程。[Manufacturing Method of Film] The manufacturing method of the film of the present invention includes the following processes: a process of exposing the composition of the present invention through a mask having a pattern; and a process of developing the exposed composition to form a pattern.

在將本發明的組成物經由具有圖案之遮罩進行曝光之製程之前，經將本發明的組成物適用於基材等而形成膜之製程、對膜進行乾燥之製程為較佳。關於膜的厚度、層疊結構等，可以根據目的適當地選擇。Prior to the process of exposing the composition of the present invention through a mask with a pattern, the process of forming the film by applying the composition of the present invention to a substrate or the like and the process of drying the film are preferred. The thickness of the film, the laminated structure, and the like can be appropriately selected according to the purpose.

作為形成膜之製程中組成物的適用方法，可以使用公知的方法。例如可以舉出滴加法（滴鑄：drop cast）；狹縫塗佈法；噴霧法；輥塗法；旋轉塗佈法（旋塗）；流延塗佈法；狹縫及旋塗法；預濕法（prewet method）（例如，日本特開2009-145395號公報中所記載之方法）；噴墨（例如按需（on demand）方式、壓電方式、熱（thermal）方式）、噴嘴噴射等噴出系印刷、柔版印刷、網版印刷、凹版印刷、逆轉偏移印刷、金屬遮罩印刷法等各種印刷法；使用金屬模具等之轉印法；奈米壓印法等。作為使用了噴墨之適用方法，只要能夠噴出組成物，則並沒有特別限定，例如可以舉出“能夠擴展使用之噴墨-從專利角度來看之無限可能性-，2005年2月發行，Sumitomo Bakelite Techno-research”所示之專利公報中所記載之方法（尤其是第115頁～第133頁）和日本特開2003-262716、日本特開2003-185831、日本特開2003-261827、日本特開2012-126830、日本特開2006-169325等中將噴出之組成物替換成本發明的組成物之方法。從塗佈適應性的觀點考慮，利用旋塗法之塗佈以300～6000rpm的範圍旋塗為較佳，以400～3000rpm的範圍旋塗為進一步較佳。並且，旋塗時之基材溫度係10～100℃為較佳，20～70℃為更佳。若在上述範圍，則容易製造塗佈均勻性優異之膜。As a suitable method for the composition in the process of forming a film, a known method can be used. Examples include a drop casting method; a slit coating method; a spray coating method; a roll coating method; a spin coating method (spin coating); a cast coating method; a slit and spin coating method; Prewet method (for example, the method described in Japanese Patent Application Laid-Open No. 2009-145395); inkjet (for example, on-demand method, piezoelectric method, thermal method), nozzle ejection, etc. Various printing methods such as jet printing, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc .; transfer methods using metal molds, etc .; nano-imprinting. As an applicable method using inkjet, there is no particular limitation as long as the composition can be ejected. For example, "Inkjet that can be used widely-unlimited possibilities from a patent point of view", issued in February 2005, "Sumitomo Bakelite Techno-research", the method described in the patent gazette (especially pages 115 to 133) and Japanese Patent Application Laid-Open No. 2003-262716, Japanese Patent Application No. 2003-185831, Japanese Patent Application No. 2003-261827, Japan The method of replacing the sprayed composition with the composition of the invention in JP 2012-126830 and JP 2006-169325. From the viewpoint of coating adaptability, it is more preferable to apply spin coating in a range of 300 to 6000 rpm, and more preferably to apply spin coating in a range of 400 to 3000 rpm. The substrate temperature during spin coating is preferably 10 to 100 ° C, and more preferably 20 to 70 ° C. If it is in the said range, it will be easy to manufacture the film excellent in coating uniformity.

在滴加法（滴鑄）的情況下，為了以既定的厚度得到均勻的膜，在基材上形成以光阻劑作為隔壁之組成物的滴加區域為較佳。藉由控制組成物的滴加量及固體成分濃度、滴加區域的面積，能夠得到所希望之厚度的膜。作為乾燥後的膜的厚度並沒有特別限制，可以根據目的適當地選擇。In the case of the dropwise addition method (drip casting), in order to obtain a uniform film with a predetermined thickness, it is preferable to form a dropwise addition region of a composition having a photoresist as a partition on a substrate. By controlling the dropping amount of the composition, the solid content concentration, and the area of the dropping area, a film having a desired thickness can be obtained. The thickness of the film after drying is not particularly limited, and can be appropriately selected depending on the purpose.

作為基材並沒有特別限定，可以根據用途適當地選擇。例如，可以舉出液晶顯示裝置等中所使用之無鹼玻璃、鈉玻璃、Pyrex（登錄商標）玻璃、石英玻璃、及在該等之上附著有透明導電膜之基材、固體攝像元件等中所使用之光電轉換元件基材、矽基材等、互補性金屬氧化物半導體（CMOS）等。 並且，為了改善與上部層之黏附性、防止物質的擴散或者將表面平坦化，在該等基材上可以根據需要設置底塗層。底塗層為了提高黏附性而設置於（較佳為塗佈於）基材上為較佳。The base material is not particularly limited, and can be appropriately selected depending on the application. Examples include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used in liquid crystal display devices and the like, and substrates with a transparent conductive film attached to them, and solid-state imaging elements. Used photoelectric conversion element substrate, silicon substrate, etc., complementary metal oxide semiconductor (CMOS), etc. In addition, in order to improve the adhesion to the upper layer, prevent the diffusion of substances, or flatten the surface, an undercoat layer may be provided on these substrates as needed. The undercoat layer is preferably provided (preferably applied) on a substrate in order to improve adhesion.

在乾燥膜之製程中，依各成分及溶劑的種類、或使用比例等改變乾燥條件為較佳。乾燥條件例如係60～150℃的溫度、30秒鐘～15分鐘為較佳。In the process of drying the film, it is better to change the drying conditions depending on the type of each component and solvent, or the ratio of use. The drying conditions are, for example, a temperature of 60 to 150 ° C., and preferably 30 seconds to 15 minutes.

作為將本發明的組成物經由具有圖案之遮罩進行曝光之製程和對經曝光之組成物進行顯影而形成圖案之製程，例如可以舉出包括如下製程之方法等：將本發明的組成物適用於基材上而形成膜狀的組成物層之製程；將組成物層曝光成圖案形狀之製程；顯影去除未曝光部而形成圖案之製程。作為形成圖案之製程，既可以利用光微影法形成圖案，亦可以利用乾式蝕刻法形成圖案。As a process for exposing the composition of the present invention through a mask having a pattern and developing the exposed composition to form a pattern, for example, a method including the following processes can be cited: the composition of the present invention is applied A process of forming a film-like composition layer on a substrate; a process of exposing the composition layer into a pattern shape; a process of developing and removing unexposed portions to form a pattern. As a process for forming a pattern, a pattern can be formed by a photolithography method or a dry etching method.

在曝光製程中，將形成於基材上之膜曝光成圖案形狀為較佳。例如，使用步進機等曝光裝置，對基材上的膜經由具有既定的遮罩圖案之遮罩進行曝光，由此能夠進行圖案曝光。藉此，能夠將曝光部分進行硬化。 作為能夠在曝光時使用之放射線（光），可以較佳地使用g射線、i射線等紫外線（特佳為i射線）。照射量（曝光量）例如係0.03～2.5J/cm2 為較佳，0.05～1.0J/cm2 為更佳。 關於曝光時之氧濃度，可以適當地選擇，除了在大氣下進行以外，例如可以在氧濃度為19體積%以下的低氧氣氛下（例如，15體積%以下，進一步為5體積%以下，尤其為實質上無氧）下進行曝光，亦可以在氧濃度超過21體積%之高氧氣氛下（例如，22體積%以上，進一步為30體積%以上，尤其為50體積%以上）下進行曝光。並且，曝光照度可以適當地設定，通常可以從1000W/m2 ～100000W/m2 （例如，5000W/m2 以上，進一步為15000W/m2 以上，尤其為35000W/m2 以上）的範圍選擇。亦可以將氧濃度和曝光照度的條件適當地進行組合，例如能夠設為氧濃度10體積%且照度10000W/m2 、氧濃度35體積%且照度20000W/m2 等。In the exposure process, it is preferable to expose the film formed on the substrate into a pattern shape. For example, pattern exposure can be performed by exposing a film on a substrate through a mask having a predetermined mask pattern using an exposure device such as a stepper. This makes it possible to harden the exposed portion. As radiation (light) that can be used at the time of exposure, ultraviolet rays such as g-rays and i-rays (i-rays are particularly preferred) can be preferably used. The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J / cm 2, and more preferably 0.05 to 1.0 J / cm 2 . The oxygen concentration at the time of exposure can be appropriately selected, and in addition to being performed in the atmosphere, it can be, for example, a low-oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume or less, and further 5% by volume or less, especially Exposure is performed under substantially oxygen-free conditions, and exposure may also be performed in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume or more, further 30% by volume or more, and especially 50% by volume or more). And, exposure illuminance can be set appropriately, usually from 1000W / m 2 ~ 100000W / m 2 ( e.g., 5000W / m 2 or more, and further 15000W / m 2 or more, in particular 35000W / m 2 or more) of the range selection. The conditions of the oxygen concentration and the exposure illuminance may be appropriately combined, and for example, the oxygen concentration may be 10% by volume and the illuminance is 10,000 W / m 2 , the oxygen concentration is 35% by volume and the illuminance is 20,000 W / m 2 .

接著，顯影去除未曝光部而形成圖案為較佳。未曝光部的顯影去除能夠使用顯影液來進行。藉此，曝光製程中之未曝光部的組成物層溶出於顯影液中，只有光硬化之部分殘留。作為顯影液，不會對基底的電路等產生損傷之鹼顯影液為較佳。作為顯影液，可以使用本說明書中所記載之溶劑進行顯影。顯影液的溫度例如係20～30℃為較佳。顯影時間係20～180秒鐘為較佳，20～90秒鐘為更佳。Next, it is preferable to form a pattern by removing unexposed portions by development. The development and removal of the unexposed portion can be performed using a developing solution. As a result, the composition layer of the unexposed portion in the exposure process is dissolved in the developing solution, and only the light-hardened portion remains. As the developing solution, an alkali developing solution that does not damage the circuit or the like of the substrate is preferred. As a developing solution, the solvent described in this specification can be used for development. The temperature of the developing solution is preferably, for example, 20 to 30 ° C. The development time is preferably 20 to 180 seconds, and more preferably 20 to 90 seconds.

作為鹼顯影液中所使用之鹼劑，例如可以舉出氨水、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、1,8-二氮雜雙環[5,4,0]-7-十一碳烯、二甲基雙（2-羥基乙基）氫氧化銨等有機鹼性化合物。將該等鹼劑以濃度成為0.001～10質量%、較佳為0.01～1質量%之方式用純水稀釋而成之鹼性水溶液較佳地用作顯影液。 並且，顯影液中亦可以使用無機鹼。作為無機鹼，例如係氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、矽酸鈉、偏矽酸鈉等為較佳。 並且，顯影液中亦可以使用界面活性劑。作為界面活性劑的例子，可以舉出在上述組成物中說明之界面活性劑，非離子系界面活性劑為較佳。 另外，當使用該種包括鹼性水溶液之顯影液時，一般在顯影後用純水清洗（沖洗）為較佳。Examples of the alkaline agent used in the alkaline developer include ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, dimethyl Organic basic compounds such as bis (2-hydroxyethyl) ammonium hydroxide. An alkaline aqueous solution obtained by diluting these alkaline agents with pure water in a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is preferably used as a developing solution. In addition, an inorganic base may be used in the developing solution. Examples of the inorganic base include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. A surfactant may be used in the developer. Examples of the surfactant include the surfactants described in the above composition, and nonionic surfactants are preferred. In addition, when such a developing solution including an alkaline aqueous solution is used, it is generally preferable to wash (rinse) with pure water after development.

膜的製造方法亦可以包含其他製程。作為其他製程並沒有特別限制，可以根據目的適當地選擇。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。顯影後還可以進行加熱及曝光中的至少一方。依該態樣，能夠進一步進行膜的硬化而製造更牢固硬化之膜。The manufacturing method of the film may also include other processes. The other processes are not particularly limited, and may be appropriately selected according to the purpose. For example, a surface treatment process, a pre-heating process (pre-baking process), a post-heating process (post-baking process), etc. of a base material are mentioned. After development, at least one of heating and exposure may be performed. According to this aspect, it is possible to further harden the film to produce a more hardened film.

預加熱製程及後加熱製程中之加熱溫度係80～200℃為較佳。上限係150℃以下為較佳。下限係90℃以上為更佳。並且，預加熱製程及後加熱製程中之加熱時間係30～240秒鐘為更佳。上限係180秒鐘以下為更佳。下限係60秒鐘以上為更佳。The heating temperature in the pre-heating process and the post-heating process is preferably 80 to 200 ° C. The upper limit is preferably 150 ° C or lower. The lower limit is more preferably above 90 ° C. The heating time in the pre-heating process and the post-heating process is preferably 30 to 240 seconds. The upper limit is more preferably 180 seconds or less. The lower limit is more preferably 60 seconds or more.

作為加熱處理的方法，可以舉出加熱所形成之上述膜的整個面之方法。藉由加熱處理，圖案的膜強度得到提高。加熱溫度係100～260℃為較佳。下限係120℃以上為更佳，160℃以上為特佳。上限係240℃以下為更佳，220℃以下為特佳。若加熱溫度在上述範圍，則容易得到強度優異之膜。加熱時間係1～180分鐘為較佳。下限係3分鐘以上為更佳。上限係120分鐘以下為更佳。作為加熱裝置並沒有特別限制，可以從公知的裝置中根據目的適當地選擇，例如可以舉出乾燥烘箱、加熱板、紅外線加熱器等。 [實施例]As a method of heat processing, the method of heating the whole surface of the said film formed is mentioned. By the heat treatment, the film strength of the pattern is improved. The heating temperature is preferably 100 to 260 ° C. The lower limit is more preferably above 120 ° C, and particularly preferably above 160 ° C. The upper limit is more preferably 240 ° C or lower, and particularly preferably 220 ° C or lower. When the heating temperature is in the above range, a film having excellent strength is easily obtained. The heating time is preferably 1 to 180 minutes. The lower limit is more preferably 3 minutes or more. The upper limit is more preferably 120 minutes or less. The heating device is not particularly limited, and may be appropriately selected from known devices according to the purpose, and examples thereof include a drying oven, a heating plate, and an infrared heater. [Example]

以下，利用實施例對本發明進行具體說明，但本發明並不限定於該等實施例。另外，只要沒有特別指定，“份”及“%”為質量基準。 黏度係使用E型黏度計（TOKI SANGYO CO.,LTD.製RE85L）進行了測定。測定係使用1°34’×R24的錐型旋轉計（corn roter）在將轉速設為5rpm之條件下進行。在該條件下無法測定時，適當地變更轉速後進行了測定。Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "part" and "%" are quality standards. The viscosity was measured using an E-type viscometer (RE85L manufactured by TOKI SANGYO CO., LTD.). The measurement was performed using a 1 ° 34 '× R24 corn roter with a rotation speed of 5 rpm. When measurement was not possible under these conditions, the measurement was performed after changing the rotation speed appropriately.

＜重量平均分子量的測定＞ 樹脂的重量平均分子量利用以下方法進行了測定。 管柱的種類：將TOSOH TSKgel Super HZM-H、TOSOH TSKgel Super HZ4000及TOSOH TSKgel Super HZ2000連接而成之管柱 展開溶劑：四氫呋喃 管柱溫度：40℃ 流量（樣品注入量）：1.0μL（樣品濃度：0.1質量%） 裝置名稱：TOSOH CORPORATION製HLC-8220 GPC檢測器：RI（折射率）檢測器 校準曲線基礎樹脂（base resin）：聚苯乙烯<Measurement of weight average molecular weight> The weight average molecular weight of the resin was measured by the following method. Type of column: column developed by connecting TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 Solvent: tetrahydrofuran column temperature: 40 ° C flow rate (sample injection volume): 1.0 μL (sample concentration : 0.1% by mass) Device name: HLC-8220 GPC detector manufactured by TOSOH CORPORATION: RI (refractive index) detector calibration curve Base resin: polystyrene

＜酸值的測定方法＞ 酸值係表示中和每1g固體成分的酸性成分所需之氫氧化鉀的質量者。將試樣溶解於四氫呋喃/水=9/1（質量比）混合溶劑中而製備測定樣品，並使用電位差滴定裝置（商品名：AT-510，KYOTO ELECTRONICS MANUFACTURING CO.,LTD.製），利用25℃的0.1mol/L氫氧化鈉水溶液中和滴定了測定樣品。將滴定pH曲線的拐點設為滴定終點，利用下式計算出酸值。 A=56.11×Vs×0.5×f/w A：酸值（mgKOH/g） Vs：滴定所需之0.1mol/L氫氧化鈉水溶液的使用量（mL） f：0.1mol/L氫氧化鈉水溶液的滴定量（titer） w：測定樣品質量（g）（固體成分換算）<Method for measuring acid value> The acid value indicates a mass of potassium hydroxide required to neutralize an acid component per 1 g of a solid content. The sample was dissolved in a tetrahydrofuran / water = 9/1 (mass ratio) mixed solvent to prepare a measurement sample, and a potential difference titration device (trade name: AT-510, manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD.) Was used. The measurement sample was neutralized and titrated with a 0.1 mol / L sodium hydroxide aqueous solution at ℃. The inflection point of the titration pH curve was set as the end point of the titration, and the acid value was calculated by the following formula. A = 56.11 × Vs × 0.5 × f / w A: Acid value (mgKOH / g) Vs: Amount of 0.1mol / L sodium hydroxide aqueous solution required for titration (mL) f: 0.1mol / L sodium hydroxide aqueous solution Titer w: determination of sample mass (g) (solid content conversion)

＜胺值的測定＞ 胺值係以與每1g固體成分的鹼性成分當量的氫氧化鉀（KOH）的質量表示者。將試樣溶解於乙酸中而製備測定樣品，並使用電位差滴定裝置（商品名：AT-510，KYOTO ELECTRONICS MANUFACTURING CO.,LTD.製），利用25℃的0.1mol/L過氯酸/乙酸溶液中和滴定了測定樣品。將滴定pH曲線的拐點設為滴定終點，利用下式計算出胺值。 B=56.11×Vs×0.1×f/w B：胺值（mgKOH/g） Vs：滴定所需之0.1mol/L過氯酸/乙酸溶液的使用量（mL） f：0.1mol/L過氯酸/乙酸溶液的滴定量 w：測定樣品的質量（g）（固體成分換算）<Measurement of Amine Value> The amine value is expressed by the mass of potassium hydroxide (KOH) equivalent to an alkaline component per 1 g of a solid component. The sample was dissolved in acetic acid to prepare a measurement sample, and a potentiometric titration device (trade name: AT-510, manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD.) Was used, and a 0.1 mol / L perchloric acid / acetic acid solution at 25 ° C was used. The measurement sample was neutralized and titrated. The inflection point of the titration pH curve was set as the end point of the titration, and the amine value was calculated by the following formula. B = 56.11 × Vs × 0.1 × f / w B: Amine value (mgKOH / g) Vs: 0.1mol / L perchloric acid / acetic acid solution used in titration (mL) f: 0.1mol / L perchloride Titration of acid / acetic acid solution w: Measure the mass (g) of the sample (in terms of solid content)

＜無機粒子的平均粒徑的測定＞ 對於比較顏料1～3，利用以下方法測定了粉體無機粒子的平均一次粒徑。將比較顏料1～3示於表4。 藉由利用透射型電子顯微鏡（TEM）觀察粉體無機粒子，並觀測無機粒子未凝聚之一次粒子而求出了一次粒徑。關於無機粒子的粒度分佈，拍攝作為一次粒子之粉體無機粒子的TEM圖像之後，使用圖像處理裝置，由TEM圖像測定了粒度分佈。關於無機粒子的平均一次粒徑，依由粒度分佈計算出之個數基準的算術平均直徑而設為平均一次粒徑。作為透射型電子顯微鏡，使用了Hitachi, Ltd.製電子顯微鏡（H-7000），作為圖像處理裝置，使用了NIRECO CORPORATION製Luzex AP。 對於中空無機粒子A-5及比較顏料4、中實無機粒子A-2～A-4、以及多孔質無機粒子A-1，利用以下方法測定了粉體無機粒子的平均粒徑。 藉由利用透射型電子顯微鏡（TEM）觀察粉體無機粒子，並觀測無機粒子未凝聚之部分而求出了粒徑。本發明中，關於中空無機粒子、中實無機粒子及多孔質無機粒子的粒度分佈，拍攝作為一次粒子的集合體之中空無機粒子、中實無機粒子及多孔質無機粒子的TEM圖像之後，使用圖像處理裝置，由TEM圖像測定了粒度分佈。本發明中，關於中空無機粒子、中實無機粒子及多孔質無機粒子的平均粒徑，依由粒度分佈計算出之個數基準的算術平均直徑而設為平均粒徑。使用Hitachi, Ltd.製電子顯微鏡（H-7000）作為透射型電子顯微鏡，並使用NIRECO CORPORATION製Luzex AP作為圖像處理裝置來測定了粒度分佈。<Measurement of Average Particle Size of Inorganic Particles> For Comparative Pigments 1 to 3, the average primary particle diameter of powder inorganic particles was measured by the following method. Comparative pigments 1 to 3 are shown in Table 4. The primary particle diameter was determined by observing the powder inorganic particles with a transmission electron microscope (TEM) and observing the primary particles in which the inorganic particles were not aggregated. Regarding the particle size distribution of the inorganic particles, after taking a TEM image of the powdered inorganic particles as primary particles, the particle size distribution was measured from the TEM image using an image processing device. The average primary particle diameter of the inorganic particles is set as the average primary particle diameter based on the arithmetic average diameter of the number basis calculated from the particle size distribution. As a transmission electron microscope, an electron microscope (H-7000) manufactured by Hitachi, Ltd. was used, and as an image processing apparatus, Luzex AP manufactured by NIRECO CORPORATION was used. With respect to the hollow inorganic particles A-5 and the comparative pigment 4, the solid inorganic particles A-2 to A-4, and the porous inorganic particles A-1, the average particle diameter of the powder inorganic particles was measured by the following method. The particle diameter was determined by observing the powder inorganic particles with a transmission electron microscope (TEM) and observing the non-agglomerated portion of the inorganic particles. In the present invention, regarding the particle size distribution of the hollow inorganic particles, the solid inorganic particles, and the porous inorganic particles, a TEM image of the hollow inorganic particles, the solid inorganic particles, and the porous inorganic particles, which are aggregates of primary particles, is used and then used. An image processing apparatus measures a particle size distribution from a TEM image. In the present invention, the average particle diameter of the hollow inorganic particles, solid inorganic particles, and porous inorganic particles is set as the average particle diameter based on the arithmetic average diameter of the number basis calculated from the particle size distribution. The particle size distribution was measured using an electron microscope (H-7000) manufactured by Hitachi, Ltd. as a transmission electron microscope, and Luzex AP manufactured by NIRECO CORPORATION as an image processing apparatus.

[實施例1～27、比較例1～4] ＜分散液的製造＞ 使用循環型分散裝置（珠磨機，KOTOBUKI KOGYOU.CO.,LTD.製ULTRA APEX MILL），在下述分散條件下對下述所示之組成的混合液進行分散處理而製造出分散液。 ＜＜混合液的組成＞＞ 下述表中所記載之粒子：30質量份 下述表中所記載之分散劑：下述表中所記載之量 下述表中所記載之分散助劑：下述表中所記載之量 丙二醇-1-單甲醚-2-乙酸酯（PGMEA）：下述表中所記載之量 ＜＜分散條件＞＞ 珠徑：直徑0.2mm珠子 填充率：65體積% 圓周速度：6m/秒 泵供給量：10.8kg/小時 冷卻水：自來水 珠磨機環狀通路內容積：0.15L 分散處理之混合液量：0.65kg[Examples 1 to 27, Comparative Examples 1 to 4] <Production of Dispersion Liquid> A circulation type dispersing device (bead mill, KOTOBUKI KOGYOU.CO., LTD., ULTRA APEX MILL) was used, and the dispersion conditions were as follows. The mixed liquid having the composition shown above is subjected to a dispersion treatment to produce a dispersed liquid. <<< Composition of the mixed liquid >> The particles described in the following table: 30 parts by mass of the dispersant described in the following table: the amount described in the following table: the dispersing aid described in the following table: below The amount of propylene glycol-1-monomethylether-2-acetate (PGMEA) described in the table: The amount described in the following table <<< dispersion conditions >> Bead diameter: 0.2mm diameter Bead filling rate: 65 volumes % Circumferential speed: 6m / s Pump supply: 10.8kg / hour Cooling water: Water ring mill ring passage Internal volume: 0.15L Mixing liquid for dispersing treatment: 0.65kg

在分散開始後，以30分鐘間隔測定了粒子的平均粒徑。粒子的平均粒徑隨著分散時間的經過而減小，但其變化量逐漸減少。在粒度分佈中之d50（積算值50%）的變化量消失之時點，結束了分散。 將所得到之分散液1～15的組成示於下述表。After the start of the dispersion, the average particle diameter of the particles was measured at 30-minute intervals. The average particle size of the particles decreases with the passage of the dispersion time, but the amount of change gradually decreases. When the amount of change in d50 (50% of the accumulated value) in the particle size distribution disappeared, the dispersion was ended. The compositions of the obtained dispersion liquids 1 to 15 are shown in the following table.

[表3] [table 3]

（粒子） 作為A-1～A-5及比較顏料1～4，使用了以下粒子。(Particles) As A-1 to A-5 and Comparative Pigments 1 to 4, the following particles were used.

-A-1：多孔質氧化鈦粒子（多孔質無機粒子）的製備- 在乙醇（EtOH）溶液中添加正丁醇鈦（TBOT）（多孔質無機粒子）而得到了溶液。在所得到之溶液中添加抑制TBOT的水解或縮聚反應之乙醯乙酸乙酯（EAcAc）（β-酮酯化合物）之後，在室溫下攪拌約2小時而製作出溶液a。在溶液a中添加乙醇與1質量%氨水（NH3 水溶液）的混合液，並攪拌約6小時，藉此得到了含有多孔質氧化鈦粒子之溶液。各原料的莫耳比設為TBOT:EtOH:EAcAc:NH3 水溶液=1:100:1:4.5。使用離心分離機使多孔質氧化鈦粒子沉降，然後利用乙醇進行清洗之後，得到了多孔質氧化鈦粒子A-1。 藉由使用掃描型電子顯微鏡（Hitachi High-Technologies Corporation製，型號S-4800）之觀察，確認到得到了表面具有複數個孔徑10nm～100nm的細孔之結構的多孔質氧化鈦粒子。多孔質氧化鈦粒子A-1的平均粒徑為約750nm。多孔質氧化鈦粒子A-1的折射率為2.7。-A-1: Preparation of porous titanium oxide particles (porous inorganic particles)-A solution was obtained by adding titanium n-butoxide (TBOT) (porous inorganic particles) to an ethanol (EtOH) solution. To the obtained solution was added ethyl acetate (EAcAc) (β-ketoester compound), which inhibits the hydrolysis or polycondensation reaction of TBOT, and then stirred at room temperature for about 2 hours to prepare a solution a. A solution of ethanol and a 1% by mass aqueous ammonia (NH 3 aqueous solution) was added to the solution a and stirred for about 6 hours, thereby obtaining a solution containing porous titanium oxide particles. The molar ratio of each raw material is TBOT: EtOH: EAcAc: NH 3 aqueous solution = 1: 100: 1: 4.5. The porous titanium oxide particles were sedimented using a centrifugal separator, and then washed with ethanol to obtain porous titanium oxide particles A-1. By observation with a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, model S-4800), it was confirmed that porous titanium oxide particles having a structure having a plurality of pores having a pore diameter of 10 to 100 nm on the surface were obtained. The average particle diameter of the porous titanium oxide particles A-1 was about 750 nm. The refractive index of the porous titanium oxide particles A-1 was 2.7.

-A-2：中實氧化鈰粒子（中實無機粒子）的製備- 使用作為形成殼層之無機奈米粒子之氧化鈰粒子（TAIYO KOKO CO.,LTD.製，產品名：SERIKO CH-501，平均一次粒徑：0.6μm）和作為成為芯之聚合物粒子之非交聯聚苯乙烯粒子（Sekisui Plastics Co.,Ltd.製，產品名：DuoMaster S-20，平均一次粒徑：300μm）製備出複合粒子。 將氧化鈰粒子0.05g及非交聯聚苯乙烯粒子1.0g稱取到樣品管中，輕輕振蕩混勻樣品管。 在樣品管中放入經特氟隆（登錄商標）塗覆之磁力攪拌子，並固定於耐壓容器（Taiatsu Techno Corporation製）後進行密閉。使用注射泵（TELEDYNE ISCO INC.製，產品名：260D）加壓至8MPa，並將液化之二氧化碳加入到耐壓容器中使其充満。將耐壓容器浸漬於水浴中，利用磁力攪拌器，一邊以300rpm旋轉攪拌子，一邊將溫度上升至50℃。升溫後，將壓力調整為34MPa，進而攪拌6小時。 然後，將溫度下降至室溫（約20℃），停止攪拌。接著，經約2分鐘將液化之二氧化碳逐漸從耐壓容器內除去。藉此，在耐壓容器中得到了複合粒子（中實氧化鈰粒子A-2）。 中實氧化鈰粒子A-2的芯的折射率為1.6，殼層的折射率為2.2，芯與殼層的折射率差為0.6。-A-2: Preparation of solid cerium oxide particles (solid solid inorganic particles)-Use of cerium oxide particles (made by TAIYO KOKO CO., LTD., Inorganic nano particles forming a shell), product name: SERIKO CH-501 , Average primary particle diameter: 0.6 μm) and non-crosslinked polystyrene particles (made by Sekisui Plastics Co., Ltd., product name: DuoMaster S-20, average primary particle diameter: 300 μm) as polymer particles serving as a core. Composite particles were prepared. Weigh 0.05g of cerium oxide particles and 1.0g of non-crosslinked polystyrene particles into a sample tube, and gently shake and mix the sample tube. A Teflon (registered trademark) -coated magnetic stir bar was placed in a sample tube, fixed in a pressure-resistant container (manufactured by Taiatsu Techno Corporation), and sealed. A syringe pump (product name: TELEDYNE ISCO INC., Product name: 260D) was used to pressurize it to 8 MPa, and liquefied carbon dioxide was added to a pressure-resistant container to fill it. The pressure-resistant container was immersed in a water bath, and the temperature was raised to 50 ° C. while the stirrer was rotated at 300 rpm using a magnetic stirrer. After raising the temperature, the pressure was adjusted to 34 MPa, and the mixture was further stirred for 6 hours. Then, the temperature was lowered to room temperature (about 20 ° C), and stirring was stopped. Then, the liquefied carbon dioxide was gradually removed from the pressure-resistant container over about 2 minutes. Thereby, composite particles (neutral cerium oxide particles A-2) were obtained in a pressure-resistant container. The core of the solid cerium oxide particle A-2 has a refractive index of 1.6, the refractive index of the shell layer is 2.2, and the refractive index difference between the core and the shell layer is 0.6.

-A-3：中實氧化鈦粒子（中實無機粒子）的製備- 使用作為形成殼層之無機奈米粒子之氧化鈦粒子（Aldrich公司製，金紅石型，平均一次粒徑：28nm）和作為成為芯之聚合物粒子之非交聯聚苯乙烯粒子（Sekisui Plastics Co.,Ltd.製，產品名：DuoMaster S-20，平均一次粒徑：300μm）製備出複合粒子。 將氧化鈦粒子0.05g及非交聯聚苯乙烯粒子1.0g稱取至樣品管中，並輕輕振蕩混勻樣品管。 在樣品管中放入經特氟隆（登錄商標）塗覆之磁力攪拌子，並固定於耐壓容器（Taiatsu Techno Corporation製）後進行密閉。使用注射泵，加壓至8MPa，並將液化之二氧化碳加入耐壓容器中使其充満。將耐壓容器浸漬於水浴中，利用磁力攪拌器，一邊以300rpm旋轉攪拌子，一邊將溫度上升至50℃。升溫後，將壓力調整為20MPa，進而攪拌6小時。 然後，將溫度下降至室溫（約20℃），停止攪拌。接著，經約2分鐘將液化之二氧化碳緩慢從耐壓容器內除去。藉此，在耐壓容器中得到了複合粒子（中實氧化鈦粒子A-3）。 中實氧化鈦粒子A-3的芯的折射率為1.6，殼層的折射率為2.7，芯與殼層的折射率差為1.1。-A-3: Preparation of solid solid titanium oxide particles (solid solid inorganic particles)-Titanium oxide particles (made by Aldrich, rutile type, average primary particle size: 28 nm) as inorganic nano particles forming a shell layer, and Non-crosslinked polystyrene particles (manufactured by Sekisui Plastics Co., Ltd., product name: DuoMaster S-20, average primary particle size: 300 μm) as polymer particles serving as a core were prepared as composite particles. Weigh 0.05g of titanium oxide particles and 1.0g of non-crosslinked polystyrene particles into a sample tube, and gently shake and mix the sample tube. A Teflon (registered trademark) -coated magnetic stir bar was placed in a sample tube, fixed in a pressure-resistant container (manufactured by Taiatsu Techno Corporation), and sealed. Using a syringe pump, pressurize to 8 MPa, and add the liquefied carbon dioxide to a pressure-resistant container to fill it. The pressure-resistant container was immersed in a water bath, and the temperature was raised to 50 ° C. while the stirrer was rotated at 300 rpm using a magnetic stirrer. After raising the temperature, the pressure was adjusted to 20 MPa, and the mixture was further stirred for 6 hours. Then, the temperature was lowered to room temperature (about 20 ° C), and stirring was stopped. Then, the liquefied carbon dioxide was slowly removed from the pressure-resistant container over about 2 minutes. Thereby, composite particles (neutral titanium oxide particles A-3) were obtained in a pressure-resistant container. The core of the solid titanium oxide particles A-3 has a refractive index of 1.6, the refractive index of the shell layer is 2.7, and the refractive index difference between the core and the shell layer is 1.1.

-A-4：多孔質氧化鈦粒子（多孔質無機粒子）的製備- 將異丙醇鈦（0.1mmol）及鄰苯二甲酸（0.5mmol）與10mL的甲醇混合，並攪拌一晩。將所得到之混合物3.5mL移到SUS316反應管中，以升溫速度800℃/分鐘升溫至300℃，藉此將甲醇設為超臨界狀態，並使混合物反應了10分鐘。接著，離心分離生成物之後，使用甲醇清洗，並進行了乾燥。藉此，得到了白色中實球狀多孔質銳鈦礦型氧化鈦奈米粒子（多孔質氧化鈦粒子A-4）。 藉由使用掃描型電子顯微鏡（Hitachi High-Technologies Corporation製，型號S-4800）之觀察，確認到得到表面具有複數個孔徑2nm～50nm的細孔之結構的多孔質氧化鈦粒子。多孔質氧化鈦粒子A-4的平均粒徑為800nm。多孔質氧化鈦粒子A-4的折射率為2.6。-A-4: Preparation of porous titanium oxide particles (porous inorganic particles)-Titanium isopropoxide (0.1 mmol) and phthalic acid (0.5 mmol) were mixed with 10 mL of methanol and stirred for a while. 3.5 mL of the obtained mixture was transferred to a SUS316 reaction tube, and the temperature was raised to 300 ° C. at a heating rate of 800 ° C./minute, thereby setting the methanol to a supercritical state, and reacting the mixture for 10 minutes. Next, the product was centrifuged, washed with methanol, and dried. Thus, white solid spherical porous anatase titanium oxide nano particles (porous titanium oxide particles A-4) were obtained. By observation with a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, model S-4800), it was confirmed that porous titanium oxide particles having a structure having a plurality of pores having a pore diameter of 2 to 50 nm on the surface were obtained. The average particle diameter of the porous titanium oxide particles A-4 was 800 nm. The refractive index of the porous titanium oxide particles A-4 was 2.6.

-A-5：中空氧化鈦粒子（中空無機粒子）的製備- 將異丙醇鈦（0.1mmol）及鄰苯二甲酸（0.5mmol）與10mL的甲醇混合，並攪拌一晩。將所得到之混合物3.5mL移到SUS316反應管中，以升溫速度6.0℃/分鐘升溫至300℃，藉此將甲醇設為超臨界狀態，並使混合物反應了10分鐘。接著，離心分離生成物之後，使用甲醇清洗，並進行了乾燥。藉此，得到了白色中空球狀多孔質銳鈦礦型氧化鈦奈米粒子（中空氧化鈦粒子A-5）。 中空氧化鈦粒子A-5的平均粒徑為700nm。中空氧化鈦粒子A-5的折射率為2.6。-A-5: Preparation of hollow titanium oxide particles (hollow inorganic particles)-Titanium isopropoxide (0.1 mmol) and phthalic acid (0.5 mmol) were mixed with 10 mL of methanol and stirred for a while. 3.5 mL of the obtained mixture was transferred to a SUS316 reaction tube, and the temperature was raised to 300 ° C. at a temperature increase rate of 6.0 ° C./minute, thereby setting methanol to a supercritical state, and reacting the mixture for 10 minutes. Next, the product was centrifuged, washed with methanol, and dried. Thereby, white hollow spherical porous anatase titanium oxide nano particles (hollow titanium oxide particles A-5) were obtained. The average particle diameter of the hollow titanium oxide particles A-5 was 700 nm. The refractive index of the hollow titanium oxide particles A-5 was 2.6.

[表4] [Table 4]

-比較顏料4：中空樹脂粒子的製備- 將甲基丙烯酸甲酯40質量份、三羥甲基丙烷三丙烯酸酯10質量份、作為聚合起始劑之偶氮雙異丁腈0.25質量份、作為（W/O）型乳化劑之去水山梨醇單油酸酯0.5質量份混合並進行攪拌而得到了單體溶液。 接著，在離子交換水中添加氯化鈉以使其成為1質量%的濃度，藉此調整滲透壓，製備出氯化鈉水溶液50質量份。 在所得到之單體溶液中加入所得到之氯化鈉水溶液，使用攪拌分散裝置緩慢攪拌混合液，以得到微米級（micron size）的（W/O）型（油中水型）的乳液。將含有1質量%濃度的聚乙烯醇（分散劑）及0.02質量%濃度的亞硝酸鈉（水溶性聚合抑制劑）之水溶液300質量份加入到所得到之（W/O）型乳液中，使用攪拌分散裝置進行攪拌，得到了（W/O/W）型（水相中存在油相，該油相中再含有水相之狀態）複合乳液懸浮液。 準備具備攪拌機、夾套、回流冷卻機及溫度計之聚合器，接著將聚合器內減壓而除氧之後，進行氮置換而將聚合器內設為氮氣氣氛。在聚合器內一次性投入所得到之（W/O/W）型複合乳液懸浮液，在室溫下攪拌了既定時間。由於聚合器中的（W/O）型乳化劑的量較少，因此內含微小的水滴之油滴的狀態不穩定，隨著時間的經過，該等緩慢結合而成為一體，得到了（W/O/W）型複合乳液懸浮液。所得到之（W/O/W）型複合乳液懸浮液使用光學顯微鏡確認到油滴中內含有單一大小的水滴。接著，將聚合器升溫至60℃，並聚合了4小時。然後，熟化1小時，並將聚合器冷卻至室溫，得到了懸浮體。使用脫水裝置，對所得到之懸浮體進行脫水，接著進行真空乾燥，藉此得到了使用了（甲基）丙烯酸化合物之單孔的中空樹脂粒子（比較顏料4）。 比較顏料4的中空樹脂粒子的平均粒徑為1.0μm。比較顏料4的中空樹脂粒子的折射率為1.5。-Comparative pigment 4: Preparation of hollow resin particles-40 parts by mass of methyl methacrylate, 10 parts by mass of trimethylolpropane triacrylate, 0.25 parts by mass of azobisisobutyronitrile as a polymerization initiator, and 0.5 mass parts of sorbitan monooleate (W / O) type emulsifier was mixed and stirred to obtain a monomer solution. Next, sodium chloride was added to the ion-exchanged water so as to have a concentration of 1% by mass, thereby adjusting the osmotic pressure to prepare 50 parts by mass of an aqueous sodium chloride solution. The obtained sodium chloride aqueous solution was added to the obtained monomer solution, and the mixed solution was slowly stirred using a stirring dispersing device to obtain a micron size (W / O) type (water-in-oil) emulsion. 300 parts by mass of an aqueous solution containing 1% by mass of polyvinyl alcohol (dispersant) and 0.02% by mass of sodium nitrite (water-soluble polymerization inhibitor) was added to the obtained (W / O) type emulsion and used The stirring and dispersing device was stirred to obtain a (W / O / W) type (a state in which an oil phase exists in the water phase and the oil phase further contains a water phase) composite emulsion suspension. A polymerizer including a stirrer, a jacket, a reflux cooler, and a thermometer was prepared, and then the inside of the polymerizer was depressurized to remove oxygen, and then replaced with nitrogen to set the inside of the polymerizer to a nitrogen atmosphere. The obtained (W / O / W) type composite emulsion suspension was put into the polymerizer at one time, and stirred at room temperature for a predetermined time. Because the amount of (W / O) emulsifier in the polymerizer is small, the state of the oil droplets containing tiny water droplets is unstable. With the passage of time, these slowly combine to become one. / O / W) type composite emulsion suspension. The obtained (W / O / W) type composite emulsion suspension was confirmed to contain a single-sized water droplet in the oil droplet using an optical microscope. Next, the polymerizer was heated to 60 ° C. and polymerized for 4 hours. Then, it was aged for 1 hour, and the polymerizer was cooled to room temperature to obtain a suspension. The obtained suspension was dehydrated using a dehydration device, followed by vacuum drying, thereby obtaining single-hole hollow resin particles (comparative pigment 4) using a (meth) acrylic compound. The average particle diameter of the hollow resin particles of Comparative Pigment 4 was 1.0 μm. The refractive index of the hollow resin particles of the comparative pigment 4 was 1.5.

-無機粒子的折射率- 利用以下方法測定了粒子的折射率。 使已知折射率之分散劑和PGMEA分散而製作分散液，將已知折射率之樹脂和分散液以固體成分中的粒子的濃度分別成為10質量%、20質量%、30質量%、40質量%之方式混合，從而製作出4種塗佈液。將該等塗佈液於Si晶片上以300nm的膜厚進行製膜之後，使用橢圓偏光計（Lambda Ace RE-3300（商品名），Dainippon Screen Mfg. Co.,Ltd.）測定了所得到之膜的折射率。然後，標繪粒子濃度和折射率並進行外插而導出粒子的折射率。—Refractive Index of Inorganic Particles— The refractive index of the particles was measured by the following method. A dispersant having a known refractive index and PGMEA are dispersed to prepare a dispersion liquid, and the concentration of the particles in the solid content of the resin and the dispersion having a known refractive index is 10% by mass, 20% by mass, 30% by mass, and 40% by mass %, And 4 kinds of coating liquids were produced. These coating solutions were formed on a Si wafer with a film thickness of 300 nm, and then the obtained solution was measured using an elliptical polarimeter (Lambda Ace RE-3300 (trade name), Dainippon Screen Mfg. Co., Ltd.). The refractive index of the film. Then, the particle concentration and the refractive index are plotted and extrapolated to derive the refractive index of the particle.

（分散劑） H-1：Solsperse 36000 Japan Lubrizol Corporation製 H-2：Solsperse 41000 Japan Lubrizol Corporation製 H-3：下述結構的樹脂（酸值=51.7mgKOH/g、Mw=13000） H-4：下述結構的樹脂（酸值=32mgKOH/g、胺值=45mgKOH/g、Mw=15000） （H-3）及（H-4）所表示之各重複單元中併記之數值表示各重複單元的含量〔質量比〕。側鏈的重複部位中併記之數值表示重複部位的重複數量。 [化學式34] (Dispersant) H-1: Solsperse 36000 Japan Lubrizol Corporation H-2: Solsperse 41000 Japan Lubrizol Corporation H-3: Resin of the following structure (acid value = 51.7mgKOH / g, Mw = 13000) H-4: Resins of the following structure (acid value = 32mgKOH / g, amine value = 45mgKOH / g, Mw = 15000) The values in each repeating unit represented by (H-3) and (H-4) indicate the Content [mass ratio]. The numerical value in the repeating portion of the side chain indicates the repeating number of the repeating portion. [Chemical Formula 34]

（分散助劑） X-1：LIGHT ESTER P-1M，KYOEISHA CHEMICAL Co.,Ltd製(Dispersion Aid) X-1: LIGHT ESTER P-1M, manufactured by KYOEISHA CHEMICAL Co., Ltd

＜組成物的製備＞ 將表5所示之各成分混合而製備出實施例1～27及比較例1～4的各組成物。<Preparation of composition> Each component shown in Table 5 was mixed, and each composition of Examples 1-27 and Comparative Examples 1-4 was prepared.

[表5] [table 5]

＜＜原料＞＞ 以下示出表5所示之各成分的詳細內容。<<< raw material >> The detail of each component shown in Table 5 is shown below.

（分散液） 分散液1～15：上述分散液1～15。(Dispersion) Dispersions 1 to 15: The dispersions 1 to 15 described above.

（鹼可溶性樹脂） C-1：下述結構的樹脂（酸值113mgKOH/g、Mw=33000） C-2：下述結構的樹脂（酸值32mgKOH/g、Mw=14000） （C-1）及（C-2）所表示之各重複單元中併記之數值表示各重複單元的含量〔質量比〕。 [化學式35] (Alkali-soluble resin) C-1: Resin of the following structure (acid value 113mgKOH / g, Mw = 33000) C-2: Resin of the following structure (acid value 32mgKOH / g, Mw = 14000) (C-1) The numerical value in each repeating unit represented by (C-2) represents the content [mass ratio] of each repeating unit. [Chemical Formula 35]

（聚合性化合物） D-1：KAYARAD DPHA（Nippon Kayaku Co.,Ltd.製） D-2：NK ESTER A-TMMT（Shin-Nakamura Chemical Co, Ltd.製）(Polymerizable compound) D-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) D-2: NK ESTER A-TMMT (manufactured by Shin-Nakamura Chemical Co, Ltd.)

（光聚合起始劑） E-1：IRGACURE OXE01（BASF公司製） E-2：IRGACURE 379（BASF公司製） E-3：IRGACURE TPO（BASF公司製） E-4：IRGACURE 819（BASF公司製） E-5：ADEKA ARKLS NCI-831（ADEKA CORPORATION製）(Photopolymerization initiator) E-1: IRGACURE OXE01 (manufactured by BASF) E-2: IRGACURE 379 (manufactured by BASF) E-3: IRGACURE TPO (manufactured by BASF) E-4: IRGACURE 819 (manufactured by BASF) E-5: ADEKA ARKLS NCI-831 (made by ADEKA CORPORATION)

（溶劑） PGMEA：丙二醇單甲醚乙酸酯 PGME：丙二醇單甲醚(Solvent) PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

（著色防止劑） F-1：Adekastab PEP-36A（ADEKA CORPORATION製，下述結構，CAS（Chemical Abstracts Service）登錄號：80693-00-1） F-2：Adekastab AO-50（ADEKA CORPORATION製，下述結構，CAS登錄號：2082-79-3） F-3:Adekastab AO-80（ADEKA CORPORATION製，下述結構，CAS登錄號：90498-90-1） F-4：Adekastab AO-412S（ADEKA CORPORATION製，下述結構，CAS登錄號：29598-76-3） [化學式36] (Coloring inhibitor) F-1: Adekastab PEP-36A (manufactured by ADEKA CORPORATION, the following structure, CAS (Chemical Abstracts Service) registration number: 80693-00-1) F-2: Adekastab AO-50 (manufactured by ADEKA CORPORATION, The following structure, CAS registration number: 2082-79-3) F-3: Adekastab AO-80 (manufactured by ADEKA CORPORATION, the following structure, CAS registration number: 90498-90-1) F-4: Adekastab AO-412S ( Made by ADEKA CORPORATION, the following structure, CAS registration number: 29598-76-3) [Chemical Formula 36]

（具有環氧基之化合物） G-1：EHPE3150（Daicel Chemical Industries, Ltd.製） G-2：EPICLON N-695（DIC CORPORATION製）(Compound having an epoxy group) G-1: EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.) G-2: EPICLON N-695 (manufactured by DIC Corporation)

（紫外線吸收劑） J-1：日本特開2009-217221號公報的化合物III，下述結構。 [化學式37] (Ultraviolet absorbent) J-1: Compound III of Japanese Patent Application Laid-Open No. 2009-217221, which has the following structure. [Chemical Formula 37]

（黏附劑） I-1：日本特開2009-288703號公報中所記載之化合物C，下述結構。 [化學式38] (Adhesive) I-1: Compound C described in Japanese Patent Application Laid-Open No. 2009-288703, and has the following structure. [Chemical Formula 38]

[評價] ＜L*＞ 使用旋塗機，將上述中所得到之各組成物以乾燥後的膜厚成為3.0μm之方式塗佈於帶有底塗層（FUJIFILM Electronic Materials Co.,Ltd.製CT-4000L；厚度0.1μm）之8英寸（1英寸為2.54cm）玻璃晶片上，並使用110℃的加熱板進行了120秒鐘加熱處理（預烘烤）而形成了塗佈膜。 接著，使用i射線步進機曝光裝置FPA-3000i5+（Canon Co.,Ltd.製），以曝光量成為1000mJ/cm2 的方式經由具有2cm×2cm的圖案之遮罩照射365nm的波長的光而對塗佈膜進行了曝光。 然後，將形成有曝光後的塗佈膜之玻璃晶片載置於旋轉噴淋顯影機（spin shower developing device）（DW-30型，Chemitronics Co.,Ltd.製）的水平旋轉台上，並使用四甲基氫氧化銨（TMAH）0.3質量%水溶液，在23℃下進行了60秒鐘浸沒顯影。如此，在玻璃晶片上形成了白色圖案。 將形成有白色圖案之玻璃晶片以真空吸盤方式固定於水平旋轉台，藉由旋轉裝置，一邊以轉速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。接著，對玻璃晶片進行噴霧乾燥。 L*係在膜中所含之溶劑成為1質量%以下之狀態下進行了測定。 使用分光測光器，使用D65光源，將觀測視野設為2°，白色基準使用X-rite528（商品名，X-rite Inc.製）所附帶之校正基準板的白色片痕（white patch）進行設定，測定了所得到之白色圖案的CIE1976的L*a*b*色彩坐標系統中之L*值。作為分光測光器，使用了X-rite528（商品名，X-rite Inc.製）。 按以下基準，對其結果進行了評價。若為A、B或C的評價，則判斷為實用上沒有問題。A或B的評價為較佳，A的評價為更佳。將所得到之結果記載於下述表。 A：形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*為60以上且75以下。 B：形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*為50以上且小於60。 C：形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*為35以上且小於50。 D：形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*為30以上且小於35。 E：形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*小於30。[Evaluation] <L *> Using a spin coater, each composition obtained in the above was applied to an undercoat layer (manufactured by FUJIFILM Electronic Materials Co., Ltd.) so that the film thickness after drying became 3.0 μm. CT-4000L; thickness 0.1 μm) on an 8-inch (1 inch 2.54 cm) glass wafer, and heat-treated (pre-baked) for 120 seconds using a 110 ° C hot plate to form a coating film. Next, using an i-ray stepper exposure device FPA-3000i5 + (manufactured by Canon Co., Ltd.), light with a wavelength of 365 nm was irradiated through a mask having a pattern of 2 cm × 2 cm so that the exposure amount became 1000 mJ / cm 2 . The coating film was exposed. Then, the glass wafer on which the exposed coating film was formed was placed on a horizontal rotary table of a spin shower developing device (DW-30 type, manufactured by Chemitronics Co., Ltd.) and used. Tetramethylammonium hydroxide (TMAH) 0.3% by mass aqueous solution was immersed and developed at 23 ° C for 60 seconds. In this way, a white pattern is formed on the glass wafer. The glass wafer on which the white pattern was formed was fixed to a horizontal rotary table by a vacuum chuck, and the rotary device was rotated at a speed of 50 rpm, while pure water was sprayed from a spray nozzle from above the center of rotation, and rinsed. deal with. Next, the glass wafer is spray-dried. L * was measured in a state where the solvent contained in the film was 1% by mass or less. Use a spectrophotometer, use a D65 light source, set the observation field of view to 2 °, and set the white reference using the white patch of the calibration reference plate included with X-rite528 (trade name, manufactured by X-rite Inc.) The L * value in the L * a * b * color coordinate system of CIE1976 of the obtained white pattern was measured. As a spectrophotometer, X-rite528 (trade name, manufactured by X-rite Inc.) was used. The results were evaluated based on the following criteria. In the case of evaluation of A, B, or C, it is determined that there is no practical problem. The evaluation of A or B is better, and the evaluation of A is better. The obtained results are described in the following table. A: The L * a * b * color coordinate system of CIE1976 when forming a film having a thickness of 3.0 μm is 60 or more and 75 or less. B: L * a * b * color coordinate system of CIE1976 when forming a film having a thickness of 3.0 μm is 50 or more and less than 60. C: The L * a * b * color coordinate system of CIE1976 when forming a film having a thickness of 3.0 μm is 35 or more and less than 50. D: The L * a * b * color coordinate system of CIE1976 when forming a film having a thickness of 3.0 μm is 30 or more and less than 35. E: L * a * b * color coordinate system of CIE1976 when forming a film having a thickness of 3.0 μm is less than 30.

＜塗佈適應性＞ 使用Micasa Corporation.製旋塗機MS-B100，將上述中所得到之各組成物以乾燥後的厚度成為3.0μm的方式塗佈於帶有底塗層（FUJIFILM Electronic Materials Co.,Ltd.製CT-4000L；厚度0.1μm）之4英寸矽晶片上。接著，使用110℃的加熱板，對矽晶片進行了120秒鐘加熱處理（預烘烤）。對於加熱處理後的矽晶片，在螢光燈下及鈉光源下藉由目視觀察了塗佈面的條紋狀的不均勻。根據觀察到之條紋狀的不均勻的數量，基於以下基準評價了塗佈適正。 A：在螢光燈下及鈉光源下，塗佈面上均完全沒有條紋狀的不均勻。 B：僅在鈉光源下，觀察到1～5個條紋狀的不均勻。 C：僅在鈉光源下，觀察到6～10個條紋狀的不均勻。 D：在螢光燈下，觀察到1～5個以上條紋狀的不均勻。 E：在螢光燈下，觀察到6個以上條紋狀的不均勻。 若為A～C的評價，則判斷為實用上沒有問題。A或B的評價為較佳，A的評價為更佳。將所得到之結果記載於下述表。<Applicability> Using a spin coater MS-B100 made by Micasa Corporation, each composition obtained in the above was applied to an undercoat layer (FUJIFILM Electronic Materials Co., Ltd.) so that the thickness after drying became 3.0 μm. , Ltd. CT-4000L; thickness: 0.1 μm) on a 4-inch silicon wafer. Next, the silicon wafer was heat-treated (pre-baked) for 120 seconds using a 110 ° C. hot plate. The silicon wafer after the heat treatment was visually observed under a fluorescent lamp and a sodium light source to show a striped unevenness on the coated surface. Based on the number of observed streak-like unevenness, the coating suitability was evaluated based on the following criteria. A: Under the fluorescent lamp and the sodium light source, there is no streak-like unevenness on the coated surface at all. B: Only under the sodium light source, 1 to 5 streaks were observed. C: Only 6 to 10 streaks were observed under the sodium light source. D: 1 to 5 or more streaks are observed under a fluorescent lamp. E: Six or more streaks were observed under fluorescent light. In the evaluation of A to C, it was determined that there was no practical problem. The evaluation of A or B is better, and the evaluation of A is better. The obtained results are described in the following table.

＜溶液經時穩定性＞ 使用烘箱，將上述中所得到之各組成物在160℃、1小時的條件下乾燥揮發成分。測定乾燥前後的質量，由減量求出揮發量，計算各組成物的乾燥前的質量與揮發量之差而計算出“離心處理前的固體成分”。 並且，將所得到之各組成物在室溫、47分鐘、3500rpm的條件下進行離心處理，對所得到之上清液藉由與上述相同的方法計算出“離心處理後的固體成分”。 將“離心處理後的固體成分”與“離心處理前的固體成分”之差除以“離心處理前的固體成分”，以百分率計算出固體成分沉降率。根據固體成分沉降率，基於下述基準評價了溶液經時穩定性。 若為A～C的評價，則判斷為實用上沒有問題。A或B的評價為較佳，A的評價為更佳。將所得到之結果記載於下述表。 A：固體成分沉降率在2質量%以下的範圍者。 B：固體成分沉降率在超過2質量%且5質量%以下的範圍者。 C：固體成分沉降率在超過5質量%且10質量%以下的範圍者。 D：固體成分沉降率在超過10質量%且15質量%以下的範圍者。 E：固體成分沉降率超過15質量%者。<Solid time-dependent stability> Using an oven, each composition obtained in the above was dried under conditions of 160 ° C and 1 hour. The mass before and after drying was measured, the volatilization amount was calculated from the reduction, and the difference between the mass before drying and the volatilization amount of each composition was calculated to calculate the "solid content before centrifugation". Then, each of the obtained compositions was subjected to a centrifugal treatment under the conditions of room temperature, 47 minutes, and 3500 rpm, and the obtained supernatant was subjected to the same method as described above to calculate the "solid content after centrifugation". The difference between the "solid content after centrifugation" and the "solid content before centrifugation" was divided by the "solid content before centrifugation", and the solid content sedimentation rate was calculated as a percentage. Based on the solid content sedimentation rate, the stability of the solution over time was evaluated based on the following criteria. In the evaluation of A to C, it was determined that there was no practical problem. The evaluation of A or B is better, and the evaluation of A is better. The obtained results are described in the following table. A: A solid content sedimentation rate is in the range of 2 mass% or less. B: The solid content sedimentation rate is in the range of more than 2% by mass and not more than 5% by mass. C: A solid content sedimentation rate is in the range of more than 5 mass% to 10 mass%. D: A solid content sedimentation rate is in a range of more than 10% by mass to 15% by mass. E: The solid content sedimentation rate exceeds 15% by mass.

＜耐溶劑性＞ 使用旋塗機，將上述中所得到之各組成物以乾燥後的厚度成為3.0μm的方式塗佈於帶有底塗層（FUJIFILM Electronic Materials Co.,Ltd.製CT-4000L；厚度0.1μm）之8英寸玻璃晶片上，並使用110℃的加熱板進行120秒鐘加熱處理（預烘烤）而形成了塗佈膜。 接著，使用i射線步進機曝光裝置FPA-3000i5+（Canon Co.,Ltd.製），以曝光量成為1000mJ/cm2 的方式經由具有2cm×2cm的圖案之遮罩照射365nm的波長的光而對塗佈膜進行了曝光。 然後，將形成有曝光後的塗佈膜之玻璃晶片載置於旋轉噴淋顯影機（DW-30型，Chemitronics Co.,Ltd.製）的水平旋轉台上，並使用四甲基氫氧化銨（TMAH）0.3質量%水溶液，在23℃下浸沒顯影了60秒鐘。如此，在玻璃晶片上形成了白色圖案。 將形成有白色圖案之玻璃晶片以真空吸盤方式固定於水平旋轉台，藉由旋轉裝置，一邊以轉速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。接著，對玻璃晶片進行噴霧乾燥。然後，使用230℃的加熱板對玻璃晶片進行了5分鐘加熱處理（後烘烤）。 使用MCPD-3000（Otsuka Electronics Co.,Ltd.製），測定了所得到之白色圖案和將白色圖案在N-甲基-2-吡咯啶酮中浸漬5分鐘之後的白色圖案在波長400～700nm下之透射率。以百分率表示各波長下之透射率之差除以白色圖案的透射率而得到之值，將其設為分光變動（ΔT%）。對於該分光變動，將分光變動最大的波長下之變動設為ΔTmax，作為耐溶劑性的評價。變動越小，耐溶劑性越良好，為更佳。A、B、C或D的評價為較佳，A、B或C的評價為更佳，A或B的評價為特佳，A的評價為更特佳。將所得到之結果記載於下述表。 A：ΔTmax＜0.5%。 B：0.5%≤ΔTmax＜1.0%。 C：1.0%≤ΔTmax＜3.0%。 D：3.0%≤ΔTmax＜5.0%。 E：ΔTmax≥5.0%。<Solvent resistance> Using a spin coater, each composition obtained in the above was applied to an undercoat layer (manufactured by FUJIFILM Electronic Materials Co., Ltd.) with a thickness of 3.0 μm after drying. ; A thickness of 0.1 μm) on an 8-inch glass wafer, and a heat treatment (pre-baking) was performed for 120 seconds using a 110 ° C. hot plate to form a coating film. Next, using an i-ray stepper exposure device FPA-3000i5 + (manufactured by Canon Co., Ltd.), light with a wavelength of 365 nm was irradiated through a mask having a pattern of 2 cm × 2 cm so that the exposure amount became 1000 mJ / cm 2 . The coating film was exposed. Then, the glass wafer on which the coating film after exposure was formed was placed on a horizontal rotary table of a rotary shower developing machine (model DW-30, manufactured by Chemitronics Co., Ltd.), and tetramethylammonium hydroxide was used. (TMAH) 0.3 mass% aqueous solution, immersed and developed at 23 ° C for 60 seconds. In this way, a white pattern is formed on the glass wafer. The glass wafer on which the white pattern was formed was fixed to a horizontal rotary table by a vacuum chuck, and the rotary device was rotated at a speed of 50 rpm, while pure water was sprayed from a spray nozzle from above the center of rotation, and rinsed. deal with. Next, the glass wafer is spray-dried. Then, the glass wafer was heat-treated (post-baking) for 5 minutes using a 230 ° C. hot plate. Using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.), the obtained white pattern and the white pattern after immersing the white pattern in N-methyl-2-pyrrolidone for 5 minutes were measured at a wavelength of 400 to 700 nm. Transmittance. The value obtained by dividing the difference in transmittance at each wavelength by the transmittance of the white pattern is expressed as a percentage, and it is set as the spectral change (ΔT%). With respect to this spectral variation, the variation at the wavelength at which the spectral variation was the largest was set as ΔTmax as an evaluation of the solvent resistance. The smaller the variation, the better the solvent resistance and the better. The evaluation of A, B, C, or D is better, the evaluation of A, B, or C is better, the evaluation of A or B is particularly good, and the evaluation of A is more particularly good. The obtained results are described in the following table. A: ΔTmax <0.5%. B: 0.5% ≤ΔTmax <1.0%. C: 1.0% ≤ΔTmax <3.0%. D: 3.0% ≤ΔTmax <5.0%. E: ΔTmax≥5.0%.

＜圖案形狀＞ 使用旋塗法，將上述中所得到之各組成物以塗佈後的厚度成為3.0μm的方式塗佈於帶有底塗層（FUJIFILM Electronic Materials Co.,Ltd.製CT-4000L；厚度0.1μm）之8英寸矽晶片上。然後，使用100℃的加熱板，將矽晶片加熱2分鐘而得到了組成物層。 接著，對於所得到之組成物層，使用i射線步進機曝光裝置FPA-3000i5+（Canon Co.,Ltd.製），將20μm見方的島狀圖案經由遮罩進行曝光（曝光量50～1700mJ/cm2 ）。 接著，使用顯影裝置（Tokyo Electron Limited.製Act8），對曝光後的組成物層進行了顯影。顯影液使用四甲基氫氧化銨（TMAH）0.3質量%水溶液，噴淋顯影在23℃下進行了60秒鐘。然後，藉由使用了純水之旋轉噴淋進行沖洗，得到了圖案。使用掃描型電子顯微鏡（SEM）（S-4800H，Hitachi High-Technologies Corporation製）觀察（倍率：5000倍）所得到之圖案，基於下述評價基準評價了形狀。 A、B、C或D的評價為較佳，A、B或C的評價為更佳，A或B的評價為特佳，A的評價為更特佳。將所得到之結果記載於下述表。 A：如圖1的（a）圖案的一邊為直線狀。 B：如圖1的（b）圖案的角部稍呈圓狀。 C：如圖1的（c）圖案的一邊稍呈圓狀。 D：如圖1的（d）圖案呈圓狀。 E：如圖1的（e）圖案較圓。<Pattern shape> Using a spin coating method, each composition obtained in the above was applied to an undercoat layer (CT-4000L, manufactured by FUJIFILM Electronic Materials Co., Ltd.) so that the thickness after coating became 3.0 μm. ; Thickness of 0.1 μm) on an 8-inch silicon wafer. Then, the silicon wafer was heated for 2 minutes using a 100 ° C hot plate to obtain a composition layer. Next, with respect to the obtained composition layer, an i-ray stepper exposure device FPA-3000i5 + (manufactured by Canon Co., Ltd.) was used to expose an island-like pattern of 20 μm square through a mask (exposure amount 50 to 1700 mJ / cm 2 ). Next, the developed composition layer was developed using a developing device (Act8 manufactured by Tokyo Electron Limited.). As the developing solution, a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used, and spray development was performed at 23 ° C. for 60 seconds. Then, the pattern was obtained by rinsing with a spin shower using pure water. The obtained pattern was observed (magnification: 5000 times) using a scanning electron microscope (SEM) (S-4800H, manufactured by Hitachi High-Technologies Corporation), and the shape was evaluated based on the following evaluation criteria. The evaluation of A, B, C, or D is better, the evaluation of A, B, or C is better, the evaluation of A or B is particularly good, and the evaluation of A is more particularly good. The obtained results are described in the following table. A: One side of the pattern is linear as shown in (a) of FIG. 1. B: The corners of the pattern shown in FIG. 1 (b) are slightly rounded. C: One side of the pattern is slightly rounded as shown in (c) of FIG. 1. D: The pattern is circular as shown in (d) of FIG. 1. E: The pattern shown in (e) of Figure 1 is round.

＜黏附性＞ 在圖案形狀的評價中製作出之圖案中，將圖案尺寸為20μm的圖案組群藉由光學顯微鏡（Olympus Corporation製）進行觀察，並評價了黏附性。計算相對於所有島圖案之圖案的剝落或缺損的產生比例，基於下述評價基準進行了黏附性的評價。 A、B、C或D的評價為較佳，A、B或C的評價為更佳，A或B的評價為特佳，A的評價為更特佳。將所得到之結果記載於下述表。 A：圖案無剝落或缺損。 B：被觀察之圖案的剝落或缺損超過0%且小於5%。 C：被觀察之圖案的剝落或缺損為5%以上且小於10%。 D：被觀察之圖案的剝落或缺損為10%以上且小於30%。 E：被觀察之圖案的剝落或缺損為30%以上。<Adhesiveness> Among the patterns produced in the evaluation of the pattern shape, a pattern group having a pattern size of 20 μm was observed with an optical microscope (manufactured by Olympus Corporation), and the adhesion was evaluated. The occurrence ratio of peeling or defect with respect to the pattern of all island patterns was calculated, and the adhesiveness was evaluated based on the following evaluation criteria. The evaluation of A, B, C, or D is better, the evaluation of A, B, or C is better, the evaluation of A or B is particularly good, and the evaluation of A is more particularly good. The obtained results are described in the following table. A: No peeling or defect of the pattern. B: The peeling or defect of the observed pattern is more than 0% and less than 5%. C: The peeling or defect of the observed pattern is 5% or more and less than 10%. D: The peeling or defect of the observed pattern is 10% or more and less than 30%. E: The peeling or defect of the observed pattern is 30% or more.

＜著色性＞ 使用分光測光器（X-rite528（商品名，X-rite Inc.製））測定了以與耐溶劑性的評價相同的方法製作出之圖案的分光L*、a*、b*。使用D65光源，將觀察視野設為2°，使用X-rite528（商品名，X-rite Inc.製）所附帶之校正基準板的白色片痕設定白色基準來進行分光的測定。將形成有圖案之玻璃晶片置於被黑色抗蝕劑塗覆之台（黑色台）上進行了測定。關於黑色台的黑色抗蝕劑層，OD（光學密度：Optical Density）在400nm下為3.5（透射率0.03%），在550nm下為3.2（透射率0.06），在700nm下為2.5（透射率0.32%），在400nm～700nm的範圍內之平均反射率為7%。黑色台的OD係利用Otsuka Electronics Co.,Ltd.製“MCPD-3000”進行測定，平均反射率係利用Konica Minolta, Inc.製“SPECTROPHOTOMETER CM-2600”進行測定。 接著，利用265℃的加熱板，將製作出之圖案加熱15分鐘，並測定了加熱後的圖案的分光。計算出CIE1976的L*a*b*色彩坐標系統中之加熱前後的圖案的色差ΔE*ab。色差ΔE*ab藉由下式進行計算。 ΔE* ab=〔（ΔL* ）2 +（Δa* ）2 +（Δb* ）2 〕1/2 利用色差ΔE*ab，基於下述評價基準評價了著色性。 A：色差ΔE*ab為0以上且小於0.5。 B：色差ΔE*ab為0.5以上且小於1.0。 C：色差ΔE*ab為1.0以上且小於2.0。 D：色差ΔE*ab為2.0以上且小於3.0。 E：色差ΔE*ab為3.0以上。 A、B、C或D的評價為較佳，A、B或C的評價為更佳，A或B的評價為特佳，A的評價為更特佳。將所得到之結果記載於下述表。<Colorability> Using a spectrophotometer (X-rite528 (trade name, manufactured by X-rite Inc.)), the spectroscopic L *, a *, b * of the pattern produced by the same method as the evaluation of the solvent resistance were measured. . A D65 light source was used, the observation field of view was set to 2 °, and the spectroscopic measurement was performed by using a white reference mark of a calibration reference plate attached to X-rite528 (trade name, manufactured by X-rite Inc.) to set a white reference. The patterned glass wafer was measured on a black resist-coated table (black table). Regarding the black resist layer of the black stage, the OD (optical density: Optical Density) is 3.5 (transmittance 0.03%) at 400 nm, 3.2 (transmittance 0.06) at 550 nm, and 2.5 (transmittance 0.32) at 700 nm. %), And the average reflectance in the range of 400nm to 700nm is 7%. The OD of the black station was measured using "MCPD-3000" manufactured by Otsuka Electronics Co., Ltd., and the average reflectance was measured using "SPECTROPHOTOMETER CM-2600" manufactured by Konica Minolta, Inc. Next, the pattern produced was heated for 15 minutes using a 265 ° C. hot plate, and the spectrophotometry of the pattern after heating was measured. The color difference ΔE * ab of the pattern before and after heating in the L * a * b * color coordinate system of CIE1976 was calculated. The color difference ΔE * ab is calculated by the following formula. ΔE * ab = [(ΔL * ) 2 + (Δa * ) 2 + (Δb * ) 2 ] 1/2 The colorability was evaluated based on the following evaluation criteria using the color difference ΔE * ab. A: The color difference ΔE * ab is 0 or more and less than 0.5. B: The color difference ΔE * ab is 0.5 or more and less than 1.0. C: The color difference ΔE * ab is 1.0 or more and less than 2.0. D: The color difference ΔE * ab is 2.0 or more and less than 3.0. E: The color difference ΔE * ab is 3.0 or more. The evaluation of A, B, C, or D is better, the evaluation of A, B, or C is better, the evaluation of A or B is particularly good, and the evaluation of A is more particularly good. The obtained results are described in the following table.

＜缺陷＞ 使用旋塗機，將上述中所得到之各組成物以乾燥後的厚度成為3.0μm之方式塗佈於帶有底塗層（FUJIFILM Electronic Materials Co.,Ltd.製CT-4000L；厚度0.1μm）之8英寸矽晶片上。然後，使用110℃的加熱板，對矽晶片進行120秒鐘加熱處理（預烘烤）而形成了組成物層。 接著，使用缺陷評價裝置ComPLUS（Applied Materials, Inc.製），計數所形成之組成物層中的具有5.0μm以上大小之異物。 在剛製備組成物層之後、以及剛製備組成物層之後在室溫（23℃）下經過1個月之後，進行組成物層中的異物的計數，計算異物增加率，並基於下述評價基準評價了缺陷。 異物增加率利用（在室溫下經過1個月後的異物數量/剛製備後的異物數量）進行計算。A、B、C或D的評價為較佳，A、B或C的評價為更佳，A或B的評價為特佳，A的評價為更特佳。將所得到之結果記載於下述表。 A：小於1.1。 B：1.1以上且小於1.3。 C：1.3以上且小於1.5。 D：1.5以上且小於3.0。 E：3.0以上。<Defects> Using a spin coater, apply each composition obtained above to a thickness of 3.0 μm after drying on an undercoat layer (CT-4000L, manufactured by FUJIFILM Electronic Materials Co., Ltd .; thickness) 0.1 μm) on an 8-inch silicon wafer. Then, the silicon wafer was heat-treated (pre-baked) for 120 seconds using a 110 ° C. hot plate to form a composition layer. Next, using a defect evaluation device ComPLUS (manufactured by Applied Materials, Inc.), foreign matter having a size of 5.0 μm or more in the composition layer formed was counted. Immediately after the composition layer was prepared and immediately after the composition layer was prepared at room temperature (23 ° C.), the number of foreign substances in the composition layer was counted, the foreign substance increase rate was calculated, and based on the following evaluation criteria Defects were evaluated. The foreign substance increase rate was calculated using (the number of foreign substances after 1 month at room temperature / the number of foreign substances immediately after preparation). The evaluation of A, B, C, or D is better, the evaluation of A, B, or C is better, the evaluation of A or B is particularly good, and the evaluation of A is more particularly good. The obtained results are described in the following table. A: Less than 1.1. B: 1.1 or more and less than 1.3. C: 1.3 or more and less than 1.5. D: 1.5 or more and less than 3.0. E: 3.0 or more.

[表6] [TABLE 6]

可知各實施例的組成物，在形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*為35以上，且溶液經時穩定性優異。 相對於此，可知使用了均勻的無機粒子之比較例1及2的組成物，其溶液經時穩定性較差。 使用了無機粒子中所含之無機物對波長589nm的光之折射率小於1.65之無機粒子之比較例3的組成物，在形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*小於35，溶液經時穩定性亦較差。 可知使用了中空有機粒子之比較例4的組成物，在形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*小於35，溶液經時穩定性亦較差。It can be seen that the composition of each example has a L * a * b * color coordinate system of CIE1976 of 35 or more when a film having a thickness of 3.0 μm is formed, and the solution has excellent stability over time. In contrast, it was found that the compositions of Comparative Examples 1 and 2 using uniform inorganic particles had poor solution stability over time. The composition of Comparative Example 3 using the composition of Comparative Example 3 in which the refractive index of inorganic substances contained in inorganic particles with respect to light having a wavelength of 589 nm is less than 1.65, and the film thickness of CIE1976 when forming a 3.0 μm film The L * in it is less than 35, and the stability of the solution over time is also poor. It was found that the composition of Comparative Example 4 using hollow organic particles had a L * a * b * color coordinate system of CIE1976 of less than 35 when forming a film having a thickness of 3.0 μm, and the solution had poor stability over time.

[實施例101] 上述實施例1中，將鹼可溶性樹脂由C-1變更為下述C-3，除此以外，使用完全相同的方法進行了評價。評價結果與實施例1相同。 C-3：表2所示之具體例54的聚矽氧烷系樹脂（Mw=10000） 聚矽氧烷系樹脂C-3係參考WO2014/126013號公報的＜0117＞的合成例11及＜0107＞的合成例1，按照以下步驟進行了合成。該公報的內容被併入本說明書中。 將下述組成所示之各成分加入到茄形燒瓶中，一邊在室溫下攪拌一邊經30分鐘向其中滴加將2g的磷酸溶於54g的水中而得到之水溶液。然後，在40℃下將溶液攪拌30分鐘之後，接著在70℃下攪拌30分鐘，最後在110℃下攪拌3小時後，結束反應。利用蒸發器，從反應後的溶液中除去溶劑而得到了聚矽氧烷系樹脂C-3。 -組成- 二甲氧基二甲基矽烷：84質量份（70莫耳%） 3-丙烯醯氧基丙基三甲氧基矽烷：47質量份（20莫耳%） 3-三甲氧基矽基丙基琥珀酸酐：13質量份（5莫耳%） 3-縮水甘油氧基丙基三甲氧基矽烷：14質量份（5莫耳%） PGMEA：102質量份[Example 101] In Example 1 described above, the alkali-soluble resin was changed from C-1 to the following C-3, and the evaluation was performed using the exact same method. The evaluation results were the same as in Example 1. C-3: Polysiloxane resin (Mw = 10000) of specific example 54 shown in Table 2 Polysiloxane resin C-3 refers to Synthesis Example 11 and <0117> of WO2014 / 126013 Synthesis Example 1 of 0107> was synthesized by the following procedure. The contents of this bulletin are incorporated into this specification. Each component shown in the following composition was put into an eggplant-shaped flask, and an aqueous solution obtained by dissolving 2 g of phosphoric acid in 54 g of water was added dropwise thereto over 30 minutes while stirring at room temperature. Then, the solution was stirred at 40 ° C for 30 minutes, then at 70 ° C for 30 minutes, and finally stirred at 110 ° C for 3 hours, and then the reaction was terminated. The solvent was removed from the solution after the reaction using an evaporator to obtain a polysiloxane resin C-3. -Composition- Dimethoxydimethylsilane: 84 parts by mass (70 mole%) 3-propenyloxypropyltrimethoxysilane: 47 parts by mass (20 mole%) 3-trimethoxysilyl Propyl succinic anhydride: 13 parts by mass (5 mol%) 3-glycidoxypropyltrimethoxysilane: 14 parts by mass (5 mol%) PGMEA: 102 parts by mass

＜平均透射率＞ 對於評價了耐溶劑性之各實施例的厚度3.0μm的白色圖案（膜），使用Otsuka Electronics Co.,Ltd.製MCPD-3000，以5nm間距測定波長400～700nm的範圍內之透射率，將其平均值設為平均透射率。 其結果，可知各實施例的膜在厚度3.0μm時在波長400～700nm的範圍內之平均透射率為1～45%。<Average Transmittance> For a 3.0-m-thick white pattern (film) in each Example evaluated for solvent resistance, MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. was used to measure a wavelength in the range of 400 to 700 nm at 5 nm intervals. The average transmittance is the average transmittance. As a result, it was found that the average transmittance of the film of each example in the range of the wavelength of 400 to 700 nm at a thickness of 3.0 μm was 1 to 45%.

＜顯影液的影響＞ 即使代替圖案形狀的評價中所使用之顯影液而利用本說明書中所記載之溶劑進行顯影，亦能夠得到同樣的圖案。<Effect of developing solution> The same pattern can be obtained even if it develops using the solvent described in this specification instead of the developing solution used for evaluation of a pattern shape.

藉由在各實施例的組成物中添加本說明書中所記載之界面活性劑，塗佈適應性得到提高，得到了厚度不均勻較小的均勻的膜。 即使在各實施例的組成物中添加本說明書中所記載之彩色著色劑，亦能夠得到同樣的效果。 藉由在各實施例的組成物中還添加本說明書中所記載之鏈轉移劑，得到了黏附性優異之膜。 即使在本說明書中所記載之範圍內變更各實施例的分散液、粒子、鹼可溶性樹脂、聚合性化合物、光聚合起始劑、溶劑、著色防止劑、具有環氧基之化合物、紫外線吸收劑、黏附劑的量（質量份），亦能夠得到同樣的效果。 [產業上的可利用性]By adding the surfactant described in this specification to the composition of each Example, the coating adaptability is improved, and a uniform film with small thickness unevenness is obtained. Even if the coloring agent described in this specification is added to the composition of each Example, the same effect can be acquired. By adding the chain transfer agent described in the present specification to the composition of each example, a film having excellent adhesion was obtained. The dispersions, particles, alkali-soluble resins, polymerizable compounds, photopolymerization initiators, solvents, coloration inhibitors, compounds having epoxy groups, and ultraviolet absorbers of the examples were changed within the scope described in this specification. The same effect can be obtained with the amount (parts by mass) of the adhesive. [Industrial availability]

由本發明的組成物形成之膜係在形成厚度3.0μm的膜時之CIE1976的L*a*b*色彩坐標系統中之L*為35以上且溶液經時穩定性優異之膜。該種膜在進行硬化而作為硬化膜利用於固體攝像元件等各種光學感測器時，能夠發揮良好的光學感測器功能，產業上的可利用性較高。The film formed from the composition of the present invention is a film whose L * in the L * a * b * color coordinate system of CIE1976 when the film having a thickness of 3.0 μm is formed is 35 or more and the solution has excellent stability over time. When this kind of film is cured and used as a cured film in various optical sensors such as solid-state imaging elements, it can exhibit a good optical sensor function and has high industrial applicability.

無no

圖1係表示圖案形狀的評價基準之圖。FIG. 1 is a diagram showing evaluation criteria of a pattern shape.

Claims (24)

一種組成物，其含有無機粒子及樹脂， 前述無機粒子含有中空無機粒子、中實無機粒子及多孔質無機粒子中的至少1種， 前述無機粒子中所含之無機物對波長589nm的光之折射率為1.65以上。A composition containing inorganic particles and a resin, wherein the inorganic particles include at least one of hollow inorganic particles, solid inorganic particles, and porous inorganic particles, and a refractive index of an inorganic substance contained in the inorganic particles with respect to light having a wavelength of 589 nm It is 1.65 or more. 如申請專利範圍第1項所述之組成物，其中前述組成物為硬化性組成物。The composition according to item 1 of the scope of patent application, wherein the aforementioned composition is a hardenable composition. 如申請專利範圍第1項所述之組成物，其中前述無機粒子含有中空無機粒子或多孔質無機粒子。The composition according to item 1 of the scope of patent application, wherein the inorganic particles include hollow inorganic particles or porous inorganic particles. 如申請專利範圍第1項所述之組成物，其中前述無機粒子含有金屬單體或金屬氧化物。The composition according to item 1 of the patent application range, wherein the inorganic particles contain a metal monomer or a metal oxide. 如申請專利範圍第1項所述之組成物，其中前述無機粒子為白色顏料。The composition according to item 1 of the scope of patent application, wherein the aforementioned inorganic particles are white pigments. 如申請專利範圍第1項所述之組成物，其中前述無機粒子含有氧化鈦。The composition according to item 1 of the scope of patent application, wherein the inorganic particles contain titanium oxide. 如申請專利範圍第1項所述之組成物，其中前述無機粒子的平均粒徑為100～1000nm。The composition according to item 1 of the scope of patent application, wherein the average particle diameter of the inorganic particles is 100 to 1000 nm. 如申請專利範圍第1項所述之組成物，其中前述無機粒子的含量相對於前述組成物的總固體成分為25～75質量%。The composition according to item 1 of the scope of patent application, wherein the content of the inorganic particles is 25 to 75% by mass relative to the total solid content of the composition. 如申請專利範圍第1項所述之組成物，其中前述無機粒子中所含之無機物對波長589nm的光之折射率為1.8以上。The composition according to item 1 of the scope of patent application, wherein the refractive index of the inorganic substance contained in the aforementioned inorganic particles with respect to light having a wavelength of 589 nm is 1.8 or more. 如申請專利範圍第1項至第9項中任一項所述之組成物，其中前述樹脂為鹼可溶性樹脂。The composition according to any one of claims 1 to 9 of the scope of patent application, wherein the resin is an alkali-soluble resin. 如申請專利範圍第1項至第9項中任一項所述之組成物，其中前述樹脂為聚矽氧烷系樹脂。The composition according to any one of claims 1 to 9 of the scope of patent application, wherein the resin is a polysiloxane resin. 如申請專利範圍第1項至第9項中任一項所述之組成物，其中前述組成物還含有硬化性化合物及聚合起始劑中的至少一方。The composition according to any one of claims 1 to 9, in which the aforementioned composition further contains at least one of a hardenable compound and a polymerization initiator. 如申請專利範圍第1項至第9項中任一項所述之組成物，其中前述組成物還含有自由基聚合性化合物及光聚合起始劑。The composition according to any one of claims 1 to 9 in the scope of the patent application, wherein the composition further contains a radical polymerizable compound and a photopolymerization initiator. 如申請專利範圍第1項至第9項中任一項所述之組成物，其中前述組成物還含有著色防止劑。The composition according to any one of claims 1 to 9 of the scope of patent application, wherein the composition further contains a coloring inhibitor. 如申請專利範圍第1項至第9項中任一項所述之組成物，其中前述組成物還含有鏈轉移劑。The composition according to any one of claims 1 to 9 of the scope of patent application, wherein the aforementioned composition further contains a chain transfer agent. 如申請專利範圍第1項至第9項中任一項所述之組成物，其中前述組成物還含有分散劑及分散助劑中的至少一方。The composition according to any one of claims 1 to 9 of the scope of patent application, wherein the composition further contains at least one of a dispersant and a dispersing aid. 一種膜，其係使用申請專利範圍第1項至第16項中任一項所述之組成物而形成。A film formed by using the composition described in any one of claims 1 to 16 of the scope of patent application. 一種膜，其含有無機粒子及樹脂， 前述無機粒子含有中空無機粒子、中實無機粒子及多孔質無機粒子中的至少1種， 前述無機粒子中所含之無機物對波長589nm的光之折射率為1.65以上。A film containing inorganic particles and a resin, wherein the inorganic particles include at least one of hollow inorganic particles, solid inorganic particles, and porous inorganic particles, and a refractive index of an inorganic substance contained in the inorganic particles with respect to light having a wavelength of 589 nm is 1.65 or more. 如申請專利範圍第17項或第18項所述之膜，其中CIE1976的L*a*b*色彩坐標系統中之L*為35～75。The film as described in the 17th or 18th in the scope of patent application, wherein the L * in the L * a * b * color coordinate system of CIE1976 is 35 to 75. 如申請專利範圍第17項或第18項所述之膜，其中當厚度為3.0μm時，波長400～700nm的範圍內之平均透射率為1%以上。The film according to item 17 or item 18 of the scope of patent application, wherein when the thickness is 3.0 μm, the average transmittance in the range of wavelength 400 to 700 nm is 1% or more. 如申請專利範圍第17項或第18項所述之膜，其厚度為10μm以下。The film according to item 17 or item 18 of the scope of patent application has a thickness of 10 μm or less. 一種硬化膜，其係將申請專利範圍第17項至第21項中任一項所述之膜進行硬化而得到。A hardened film obtained by hardening the film described in any one of the 17th to 21st patent applications. 一種光學感測器，其具有申請專利範圍第22項所述之硬化膜。An optical sensor having a hardened film as described in claim 22 of the scope of patent application. 一種膜的製造方法，其包括如下製程： 將申請專利範圍第1項至第16項中任一項所述之組成物經由具有圖案之遮罩進行曝光之製程；及 對經曝光之前述組成物進行顯影而形成圖案之製程。A method for manufacturing a film, including the following processes: a process of exposing the composition described in any one of the scope of claims 1 to 16 through a mask with a pattern; and the exposed composition A process of developing to form a pattern.
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TWI826562B (en) * 2019-10-30 2023-12-21 台灣太陽油墨股份有限公司 Photosensitive resin compositions, their cured products, dry films and printed wiring boards using them

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