TWI788298B - Curable composition, cured film, color filter, solid-state imaging device, ir sensor, method for producing cured film, method for producing color filter - Google Patents

Curable composition, cured film, color filter, solid-state imaging device, ir sensor, method for producing cured film, method for producing color filter Download PDF

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TWI788298B
TWI788298B TW106127429A TW106127429A TWI788298B TW I788298 B TWI788298 B TW I788298B TW 106127429 A TW106127429 A TW 106127429A TW 106127429 A TW106127429 A TW 106127429A TW I788298 B TWI788298 B TW I788298B
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curable composition
group
cured film
compound
metal
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TW106127429A
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TW201831527A (en
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伊藤純一
小川倫弘
金子祐士
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日商富士軟片股份有限公司
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    • 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
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/065—Polyamides; Polyesteramides; Polyimides
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures

Abstract

本發明的課題在於提供一種抑制在未曝光部產生殘渣，且可獲得具有優異的圖案形狀之硬化膜之硬化性組成物。並且，本發明的課題還在於提供一種硬化膜、彩色濾光片、固態攝影元件、紅外線感測器、硬化膜的製造方法及彩色濾光片的製造方法。本發明的硬化性組成物含有含金屬氮化物粒子、肟系聚合起始劑、聚合性化合物及酸酐。The subject of this invention is providing the curable composition which suppresses generation|occurrence|production of the residue in an unexposed part, and can obtain the cured film which has an excellent pattern shape. Furthermore, the subject of this invention is providing the manufacturing method of a cured film, a color filter, a solid-state imaging element, an infrared sensor, a cured film, and a color filter. The curable composition of the present invention contains metal nitride-containing particles, an oxime-based polymerization initiator, a polymerizable compound, and an acid anhydride.

Description

硬化性組成物、硬化膜、彩色濾光片、固態攝影元件、紅外線感測器、硬化膜的製造方法及彩色濾光片的製造方法Curable composition, cured film, color filter, solid-state imaging element, infrared sensor, method for producing cured film, and method for producing color filter

本發明係有關一種硬化性組成物、硬化膜、彩色濾光片、固態攝影元件、紅外線感測器、硬化膜的製造方法及彩色濾光片的製造方法。 The present invention relates to a curable composition, a cured film, a color filter, a solid-state photographic element, an infrared sensor, a method for manufacturing a cured film, and a method for manufacturing a color filter.

以往，已知有含有碳黑等遮光性粒子之硬化性組成物。 Conventionally, curable compositions containing light-shielding particles such as carbon black are known.

如上述之含有遮光性粒子之硬化性組成物用於各種用途，例如一直以來用於液晶顯示裝置及固態攝影元件等所含有之硬化膜的製造。 The above-mentioned curable composition containing light-shielding particles is used in various applications, for example, it has been conventionally used in the production of cured films contained in liquid crystal display devices and solid-state imaging devices.

更具體而言，用於液晶顯示裝置及固態攝影元件之彩色濾光片中，以遮蔽著色像素之間的光，提高對比度等目的，在玻璃基板上使用被稱作黑矩陣之硬化膜。 More specifically, in color filters used in liquid crystal display devices and solid-state imaging devices, a cured film called a black matrix is used on a glass substrate for the purpose of shielding light between colored pixels and improving contrast.

並且，固態攝影元件中，為了防止產生雜訊及提高畫質等而使用硬化膜。目前，在移動電話及PDA(Personal Digital Assistant(個人數字助理))等電子設備的便攜終端搭載有小型且薄型的固態攝像裝置。該種固態攝像裝置通常具備CCD(Charge Coupled Device(電荷耦合元件))圖像感測器及 CMOS(Complementary Metal-Oxide Semiconductor(互補型金屬氧化膜半導體))圖像感測器等固態攝影元件及用於在固態攝影元件上形成被攝體像之透鏡。 In addition, in solid-state imaging devices, a cured film is used for preventing noise, improving image quality, and the like. Currently, small and thin solid-state imaging devices are mounted on portable terminals of electronic equipment such as mobile phones and PDAs (Personal Digital Assistants). Such a solid-state imaging device generally includes a CCD (Charge Coupled Device (Charge Coupled Device)) image sensor and Solid-state imaging devices such as CMOS (Complementary Metal-Oxide Semiconductor) image sensors and lenses for forming subject images on solid-state imaging devices.

作為該種硬化性組成物，專利文獻1中記載有一種感光性黑色樹脂組成物，其含有遮光材料、鹼可溶性樹脂、光聚合起始劑、反應性單體及有機溶劑，其中，作為遮光材料，至少含有氮化鈦粒子，能夠形成具有規定的光學特性之塗膜。 As such a curable composition, Patent Document 1 describes a photosensitive black resin composition containing a light-shielding material, an alkali-soluble resin, a photopolymerization initiator, a reactive monomer, and an organic solvent. Among them, as the light-shielding material , containing at least titanium nitride particles, it is possible to form a coating film having predetermined optical characteristics.

[先前技術文獻] [Prior Art Literature] [專利文獻] [Patent Document]

[專利文獻1]：日本特開2010-97210號公報 [Patent Document 1]: Japanese Unexamined Patent Publication No. 2010-97210

本發明人等對利用專利文獻1中記載之感光性黑色樹脂組成物形成感光性黑色樹脂組成物層，對其進行曝光，之後進行顯影來獲得之圖案狀的膜進行了研究。發現上述膜雖然具有較高光學濃度(OD、optical density)，但在未曝光部易產生殘渣，且圖案形狀無法達到近來要求之水準。 The inventors of the present invention studied a patterned film obtained by forming a photosensitive black resin composition layer using the photosensitive black resin composition described in Patent Document 1, exposing it, and then developing it. It was found that although the above-mentioned film has a relatively high optical density (OD, optical density), it is easy to generate residue in the unexposed part, and the pattern shape cannot meet the level required recently.

故，本發明的課題在於提供一種抑制在未曝光部產生殘渣，且可獲得具有優異的圖案形狀之硬化膜(以下，還稱作“具有本發明的效果”。)之硬化性組成物。 Therefore, an object of the present invention is to provide a curable composition that suppresses residue generation in unexposed areas and can obtain a cured film having an excellent pattern shape (hereinafter also referred to as "having the effect of the present invention").

並且，本發明的課題還在於提供一種硬化膜、彩色濾光片、固態攝影元件、紅外線感測器、硬化膜的製造方法及彩色濾光片的製造方法。 Furthermore, the subject of this invention is providing the manufacturing method of a cured film, a color filter, a solid-state imaging element, an infrared sensor, a cured film, and a color filter.

本發明人等為了實現上述課題進行了深入研究，其結果發現藉由以下的結構，能夠實現上述課題。 The inventors of the present invention conducted intensive studies to achieve the above-mentioned problems, and as a result, found that the above-mentioned problems can be achieved by the following configuration.

[1]一種硬化性組成物，其含有含金屬氮化物粒子、肟系聚合起始劑、聚合性化合物及酸酐。 [1] A curable composition comprising metal nitride-containing particles, an oxime-based polymerization initiator, a polymerizable compound, and an acid anhydride.

[2]如[1]所述之硬化性組成物，其中，硬化性組成物中的酸酐的含量相對於肟系聚合起始劑的含量之含有質量比為0.005~0.5。 [2] The curable composition according to [1], wherein the mass ratio of the content of the acid anhydride to the content of the oxime-based polymerization initiator in the curable composition is 0.005 to 0.5.

[3]如[1]或[2]所述之硬化性組成物，其中，酸酐在1個分子中含有2個以上的酸酐基。 [3] The curable composition according to [1] or [2], wherein the acid anhydride contains two or more acid anhydride groups in one molecule.

[4]如[1]至[3]中任一項所述之硬化性組成物，其還含有聚合抑制劑。 [4] The curable composition according to any one of [1] to [3], which further contains a polymerization inhibitor.

[5]如[1]至[4]中任一項所述之硬化性組成物，其中，含金屬氮化物粒子含有氮化鈦。 [5] The curable composition according to any one of [1] to [4], wherein the metal nitride-containing particles contain titanium nitride.

[6]如[5]所述之硬化性組成物，其中，將CuKα射線設為X射線源時的來源於含金屬氮化物粒子的(200)面之峰的繞射角2θ為42.5°~42.8°。 [6] The curable composition according to [5], wherein the diffraction angle 2θ of the peak originating from the (200) plane of the metal nitride particles when CuKα rays are used as the X-ray source is 42.5° to 42.5°. 42.8°.

[7]如[1]至[6]中任一項所述之硬化性組成物，其還含有鹼可溶性樹脂。 [7] The curable composition according to any one of [1] to [6], further comprising an alkali-soluble resin.

[8]如[7]所述之硬化性組成物，其中，鹼可溶性樹脂含有選自包含聚醯亞胺前驅物及聚醯亞胺樹脂之群組之至少1種。 [8] The curable composition according to [7], wherein the alkali-soluble resin contains at least one selected from the group consisting of polyimide precursors and polyimide resins.

[9]如[1]至[8]中任一項所述之硬化性組成物，其中，硬化性組成物中的含金屬氮化物粒子的含量相對於硬化性組成物的總固體成分，為40質量%以上。 [9] The curable composition according to any one of [1] to [8], wherein the content of the metal nitride-containing particles in the curable composition is: More than 40% by mass.

[10]如[1]至[9]中任一項所述之硬化性組成物，其中，硬化性組成物中的肟系聚合起始劑的含量相對於含金屬氮化物粒子的含量之含有質量比為0.03~0.2。 [10] The curable composition according to any one of [1] to [9], wherein the content of the oxime-based polymerization initiator in the curable composition is equal to the content of the metal nitride-containing particles The mass ratio is 0.03~0.2.

[11]如[1]至[10]中任一項所述之硬化性組成物，其中，肟系聚合起始劑含有硝基。 [11] The curable composition according to any one of [1] to [10], wherein the oxime-based polymerization initiator contains a nitro group.

[12]如[1]至[11]中任一項所述之硬化性組成物，其還含有溶劑。 [12] The curable composition according to any one of [1] to [11], which further contains a solvent.

[13]一種硬化膜，其使[1]至[12]中任一項所述之硬化性組成物硬化來獲得。 [13] A cured film obtained by curing the curable composition according to any one of [1] to [12].

[14]一種彩色濾光片，其含有[13]所述之硬化膜。 [14] A color filter comprising the cured film described in [13].

[15]一種固態攝影元件，其含有[13]所述之硬化膜。 [15] A solid-state imaging device comprising the cured film described in [13].

[16]一種紅外線感測器，其含有[13]所述之硬化膜。 [16] An infrared sensor comprising the cured film described in [13].

[17]一種硬化膜的製造方法，其含有如下步驟：硬化性組成物層形成步驟，利用[1]至[12]中任一項所述之硬化性組成物來形成硬化性組成物層；曝光步驟，經由具備圖案狀開口部之光罩，對硬化性組成物層照射光化射線或放射線來進行曝光；及顯影步驟，對曝光後的硬化性組成物層進行顯影來形成硬化膜。 [17] A method for producing a cured film, comprising the step of forming a curable composition layer by using the curable composition described in any one of [1] to [12] to form a curable composition layer; In the exposure step, the curable composition layer is irradiated with actinic rays or radiation through a photomask having a patterned opening; and in the development step, the exposed curable composition layer is developed to form a cured film.

[18]一種彩色濾光片的製造方法，其含有[17]所述之硬化膜的製造方法。 [18] A method for producing a color filter, comprising the method for producing a cured film according to [17].

依本發明，能夠提供一種抑制在未曝光部產生殘渣，且可獲得具有優異的圖案形狀之硬化膜之硬化性組成物。 According to the present invention, it is possible to provide a curable composition capable of suppressing generation of residue in an unexposed portion and obtaining a cured film having an excellent pattern shape.

並且，依本發明，還能夠提供一種硬化膜、彩色濾光片、固態攝影元件、紅外線感測器、硬化膜的製造方法及彩色濾光片的製造方法。 Furthermore, according to the present invention, it is also possible to provide a cured film, a color filter, a solid-state imaging element, an infrared sensor, a method for manufacturing a cured film, and a method for manufacturing a color filter.

100:固態攝像裝置 100: solid-state imaging device

101、310:固態攝影元件 101, 310: Solid-state photography components

102:攝像部 102: Camera Department

103:蓋玻璃 103: cover glass

104:間隔物 104: spacer

105:層積基板 105:Laminated substrate

106:晶片基板 106: Wafer substrate

107:電路基板 107: Circuit substrate

108:電極墊 108: electrode pad

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

110:貫穿電極 110: penetrating electrode

111:透鏡層 111: Lens layer

112:透鏡材料 112: Lens material

113:支撐體 113: support body

114、115:遮光膜 114, 115: shading film

201:受光元件 201: Light receiving element

202、312:彩色濾光片 202, 312: color filter

203、315:微透鏡 203, 315: micro lens

204:基板 204: Substrate

205b:藍色像素 205b: blue pixel

205r:紅色像素 205r: red pixel

205g:綠色像素 205g: green pixel

205bm:黑矩陣 205bm: black matrix

206:p孔層 206:p hole layer

207:讀取柵極部 207: read the gate part

208:垂直轉移路徑 208: Vertical transfer path

209:元件分離區域 209: Component separation area

210:柵極絕緣膜 210: Gate insulating film

211:垂直轉移電極 211: vertical transfer electrode

212:遮光膜 212: shading film

213、214:絕緣膜 213, 214: insulating film

215、316:平坦化膜 215, 316: planarization film

300:紅外線感測器 300: infrared sensor

311:紅外線吸收濾波器 311: Infrared absorption filter

313:紅外線透射濾波器 313: Infrared transmission filter

314:樹脂膜 314: resin film

hν:入射光 hν: incident light

圖1係表示固態攝像裝置的結構例之概要剖面圖。 FIG. 1 is a schematic cross-sectional view showing a structural example of a solid-state imaging device.

圖2係放大表示圖1的攝像部之概要剖面圖。 Fig. 2 is an enlarged schematic cross-sectional view of the imaging unit in Fig. 1 .

圖3係表示紅外線感測器的結構例之概要剖面圖。 Fig. 3 is a schematic cross-sectional view showing a structural example of an infrared sensor.

以下，對本發明進行詳細說明。 Hereinafter, the present invention will be described in detail.

以下記載之構成要件的說明有時依據本發明的代表性實施態樣進行，但本發明並不限定於該種實施態樣。 The description of the constituent requirements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

另外，本說明書中，使用“~”表示之數值範圍表示含有記載於“~”的前後之數值作為下限值及上限值之範圍。 In addition, in this specification, the numerical range represented using "~" shows the range which includes the numerical value described before and after "~" as a lower limit and an upper limit.

並且，本說明書中的基團(原子團)的表述中，未記載取代及未取代之表述係與不含有取代基者一同還包含含有取代基者。例如，“烷基”不僅包含不含有取代基之烷基(未取代烷基)，還包含含有取代基之烷基(取代烷基)。 In addition, in the expression of the group (atomic group) in this specification, the expression which does not describe substitution and unsubstituted means the expression which contains a substituent as well as the expression which does not contain a substituent. For example, "alkyl" includes not only an alkyl group not having a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

並且，本說明書中，“光化射線”或“放射線”例如表示以水銀燈的明線光譜及準分子雷射為代表之遠紫外線、極紫外線(EUV：Extreme ultraviolet)、X射線以及電子束等。並且，本說明書中，光表示光化射線或放射線。關於本說明書中的“曝光”，除非另有指明，則不僅限於基於水銀燈、準分子雷射、遠紫外線、X射線及EUV光等之曝光，基於電子束及離子束等粒子束之描繪亦包含在曝光中。 In addition, in this specification, "actinic ray" or "radiation" means, for example, far ultraviolet rays, extreme ultraviolet rays (EUV: Extreme ultraviolet), X-rays, and electron beams represented by the bright-line spectrum of mercury lamps and excimer lasers. In addition, in this specification, light means actinic ray or radiation. Regarding "exposure" in this specification, unless otherwise specified, it is not limited to exposure based on mercury lamps, excimer lasers, far ultraviolet rays, X-rays, and EUV light, but also includes drawing based on particle beams such as electron beams and ion beams. in exposure.

並且，本說明書中，“(甲基)丙烯酸酯”表示丙烯酸酯及甲基丙烯酸酯。並且，本說明書中，“(甲基)丙烯酸”表示丙烯酸及甲基丙烯酸。並且，本說明書中，“(甲基)丙烯醯基”表示丙烯醯基及甲基丙烯醯基。並且，本說明書中，“(甲基)丙烯醯胺”表示丙烯醯胺及甲基丙烯醯胺。並且，本說明書中，“單體”與“單體(monomer)”的含義相同。單體與寡聚物及聚合物有所區別，指重量平均分子量為2,000以下的化合物。本說明書中，聚合性化合物係指含有聚合性基團之化合物，可以係單體，亦可以係聚合物。聚合性基團係指參與聚合反應之基團。 In addition, in this specification, "(meth)acrylate" means acrylate and methacrylate. In addition, in this specification, "(meth)acrylic acid" means acrylic acid and methacrylic acid. In addition, in this specification, a "(meth)acryl group" means an acryl group and a methacryl group. In addition, in this specification, "(meth)acrylamide" means acrylamide and methacrylamide. In addition, in this specification, "monomer" and "monomer" have the same meaning. Monomers are distinguished from oligomers and polymers, and refer to compounds with a weight average molecular weight of 2,000 or less. In this specification, a polymerizable compound refers to a compound containing a polymerizable group, which may be a monomer or a polymer. A polymerizable group refers to a group that participates in a polymerization reaction.

[硬化性組成物] [hardening composition]

本發明的實施形態之硬化性組成物含有含金屬氮化物粒子、肟系聚合起始劑、聚合性化合物及酸酐。上述硬化性組成物發揮本發明的效果之機理尚不明確，以下，說明推斷之機理。 A curable composition according to an embodiment of the present invention contains metal nitride-containing particles, an oxime-based polymerization initiator, a polymerizable compound, and an acid anhydride. The mechanism by which the above-mentioned curable composition exhibits the effect of the present invention is not clear, and the estimated mechanism will be described below.

另外，本發明並不限制在藉由以下機理獲得效果者，藉由以下機理以外的機理獲得本發明的效果時，亦作為包含於本發明的範圍者。 In addition, the present invention is not limited to those that obtain the effects by the following mechanisms, and those that obtain the effects of the present invention by mechanisms other than the following mechanisms are also included in the scope of the present invention.

近來，對用於彩色濾光片和/或固態攝影元件等之硬化膜，要求更高的遮光性。作為可獲得如上述的高遮光性的硬化膜之感光性組成物，已知有含有大量遮光性粒子者和/或含有含金屬氮化物粒子者。 Recently, higher light-shielding properties are required for cured films used for color filters and/or solid-state imaging elements. As a photosensitive composition which can obtain the above-mentioned highly light-shielding cured film, what contains many light-shielding particles and/or what contains a metal nitride particle is known.

關於含有大量遮光性粒子之感光性組成物，由於含有大量遮光性粒子，故所獲得之硬化膜示出高遮光性。但是，另一方面，本發明人等發現，如上述的感光性組成物在曝光時，光不易透射組成物中，故有時感光性組成物的硬化並不充分。 About the photosensitive composition containing many light-shielding particles, since it contains many light-shielding particles, the obtained cured film shows high light-shielding property. However, on the other hand, the inventors of the present invention have found that, when the photosensitive composition is exposed to light, light does not easily pass through the composition, so that the photosensitive composition may not be sufficiently hardened.

另一方面，含有肟系聚合起始劑之感光性組成物具有優異的硬化性。推測這是因為肟系聚合起始劑具有優異的靈敏度及優異的聚合效率。 On the other hand, a photosensitive composition containing an oxime-based polymerization initiator has excellent curability. This is presumably because the oxime-based polymerization initiator has excellent sensitivity and excellent polymerization efficiency.

但是，本發明人等新發現如專利文獻1中記載之感光性組成物那樣，併用含金屬氮化物粒子與肟系聚合起始劑時，有時無法獲得所希望的效果。本發明人等對上述現象進行了深入研究，其結果，推測係由於以下理由。 However, the inventors of the present invention have newly found that when metal-containing nitride particles and an oxime-based polymerization initiator are used in combination like the photosensitive composition described in Patent Document 1, desired effects may not be obtained. The inventors of the present invention have intensively studied the above-mentioned phenomenon, and as a result, it is presumed that it is due to the following reason.

本發明人等發現含金屬氮化物粒子的表面易變成鹼性。 The inventors of the present invention found that the surface of metal nitride-containing particles tends to become alkaline.

上述特性並不僅僅起因於含金屬氮化物粒子的特定的製造方法。但是，為了簡便，舉出特定的製造方法來進行說明。例如，作為含氮化鈦粒子的製造方法，已知有使四氯化鈦與氨氣在等離子體火焰中反應之方法(日本特開 平2-22110號公報)等。上述製造方法中，為了向鈦化合物導入氮而使用氨氣，藉此推斷為所製造之含氮化鈦粒子的表面易變成鹼性。 The above characteristics are not solely due to the specific production method of the metal nitride-containing particles. However, for the sake of simplicity, a specific production method will be mentioned and described. For example, as a method for producing titanium nitride-containing particles, a method of reacting titanium tetrachloride and ammonia gas in a plasma flame is known (Japanese Patent Laid-Open Ping 2-22110 Bulletin), etc. In the above production method, ammonia gas is used to introduce nitrogen into the titanium compound, and it is inferred that the surface of the produced titanium nitride-containing particles tends to become alkaline.

另一方面，本發明人等還發現肟系聚合起始劑具有易受到水解之性質。故，推斷併用含金屬氮化物粒子與肟系聚合起始劑時，藉由表面變成鹼性之含金屬氮化物粒子，有時會促進肟系聚合起始劑的水解。 On the other hand, the present inventors also found that oxime-based polymerization initiators are susceptible to hydrolysis. Therefore, it is inferred that when the metal nitride-containing particles and the oxime-based polymerization initiator are used together, the surface of the metal-containing nitride-containing particles whose surface becomes basic may promote the hydrolysis of the oxime-based polymerization initiator.

硬化性組成物含有大量的含金屬氮化物粒子時，上述趨勢較顯著。通常的感光性組成物中，含有大量的含金屬氮化物粒子時，利用上述感光性組成物，在基板上形成感光性組成物層並對其進行曝光時，有時圖案形狀會變差。 The above tendency is remarkable when the curable composition contains a large amount of metal nitride-containing particles. When a general photosensitive composition contains a large amount of metal nitride-containing particles, the pattern shape may deteriorate when a photosensitive composition layer is formed on a substrate using the photosensitive composition and exposed.

推斷這是因為，與靠近感光性組成物層的曝光面之區域(上層區域)相比，在其相反側的面(基板側的面，下層區域)上，所到達之光的量較少，不易硬化。推斷其原因在於，藉由大量的含金屬氮化物粒子，光更易被吸收。若對如上述的曝光後的感光性組成物層進行顯影，則與上層區域相比，下層區域的圖案變細。 It is presumed that this is because the amount of light reaching the surface on the opposite side (the surface on the substrate side, the lower layer region) is less than that of the region (upper layer region) close to the exposure surface of the photosensitive composition layer, Not easy to harden. The reason for this is presumed to be that light is more easily absorbed by a large number of metal-containing nitride particles. When the above-mentioned exposed photosensitive composition layer is developed, the pattern of the lower layer region becomes thinner than the upper layer region.

相對於此，本發明的實施形態之硬化性組成物將含有酸酐作為特徵之一。酸酐在硬化性組成物中，與成為肟系聚合起始劑的水解原因之水分子產生反應而產生酸。換言之，在上述硬化性組成物中，具有去除成為水解原因之水分子之功能。 On the other hand, the curable composition according to the embodiment of the present invention contains an acid anhydride as one of its characteristics. The acid anhydride reacts with water molecules that cause hydrolysis of the oxime-based polymerization initiator in the curable composition to generate an acid. In other words, the curable composition has a function of removing water molecules that cause hydrolysis.

故，上述硬化性組成物中，肟系聚合起始劑不易被水解，其結果，推斷利用上述硬化性組成物來獲得之硬化膜係具有優異的圖案形狀者。 Therefore, in the above-mentioned curable composition, the oxime-based polymerization initiator is not easily hydrolyzed, and as a result, it is presumed that the cured film obtained by the above-mentioned curable composition has an excellent pattern shape.

而且，推斷藉由酸酐去除水分子而產生之酸具有如下作用：在曝光時(在曝光之後進行加熱時尤為顯著。)向硬化性組成物層的上層區域移 動，之後的鹼顯影時促進顯影。 Furthermore, it is inferred that the acid generated by the removal of water molecules by the acid anhydride has an effect of moving to the upper layer region of the curable composition layer at the time of exposure (especially when heating is performed after exposure). to promote development during the subsequent alkali development.

亦即，推斷藉由硬化性組成物含有酸酐，藉此形成之硬化性組成物層的上層區域與下層區域相比，變得易被顯影，藉此所獲得之圖案形狀得到優化。這是基於上述硬化性組成物含有酸酐而獲得之意想不到之協同效果。 That is, it is presumed that when the curable composition contains an acid anhydride, the upper layer region of the curable composition layer formed thereby becomes easier to be developed than the lower layer region, thereby optimizing the pattern shape obtained. This is based on the unexpected synergistic effect obtained when the above curable composition contains an acid anhydride.

並且，依本發明人等的研究，還發現如下現象，亦即，藉由酸酐抑制肟系聚合起始劑的水解，尤其在未曝光部，抑制肟系聚合起始劑的分解引起之預料外的聚合反應。這是意想不到之效果。推斷本發明的實施形態之硬化性組成物藉由上述酐的作用，在未曝光部，顯影之後產生之殘渣的數量被抑制。 And, according to the research of the inventors of the present invention, it is also found that the hydrolysis of the oxime-based polymerization initiator is suppressed by the acid anhydride, especially in the unexposed part, the unexpected phenomenon caused by the suppression of the decomposition of the oxime-based polymerization initiator is also found. polymerization reaction. This is an unexpected effect. In the curable composition according to the embodiment of the present invention, the amount of residue generated after development in the unexposed portion is estimated to be suppressed by the action of the above-mentioned anhydride.

以下，對硬化性組成物所含有之各成分進行詳細說明。 Each component contained in the curable composition will be described in detail below.

[酸酐] [anhydride]

上述實施形態之硬化性組成物含有酸酐。作為酸酐，只要具有與水產生反應並捕獲，藉此從硬化性組成物中去除水之作用，則並無特別限制，能夠使用公知的酸酐。 The curable composition of the above-mentioned embodiment contains an acid anhydride. The acid anhydride is not particularly limited as long as it reacts with water and captures it to remove water from the curable composition, and known acid anhydrides can be used.

作為硬化性組成物中的酸酐的含量，並無特別限制，通常，相對於硬化性組成物的總固體成分，0.01~5質量%為較佳。 The content of the acid anhydride in the curable composition is not particularly limited, but usually, 0.01 to 5% by mass is preferable with respect to the total solid content of the curable composition.

酸酐可單獨使用1種，亦可併用2種以上。併用2種以上的酐時，合計含量在上述範圍內為較佳。 Acid anhydrides may be used alone or in combination of two or more. When two or more kinds of anhydrides are used in combination, the total content is preferably within the above range.

另外，本說明書中，酸酐表示在1個分子中含有1個以上的酸酐基之化合物。 In addition, in this specification, an acid anhydride means the compound which has one or more acid anhydride groups in 1 molecule.

並且，硬化性組成物中的酸酐的含量相對於後述之含金屬氮化物粒子的含量之含有質量比(酸酐的含量/含金屬氮化物粒子的含量，以下， 還簡稱為“酸酐/含金屬氮化物粒子”。)為1.0×10-5~1.0為較佳，0.0050~0.50為更佳。 In addition, the mass ratio of the content of acid anhydride in the curable composition to the content of metal nitride-containing particles described later (content of acid anhydride/content of metal nitride-containing particles, hereinafter also simply referred to as "acid anhydride/metal nitride-containing particles") Compound particles".) is preferably 1.0×10 -5 ~1.0, more preferably 0.0050~0.50.

若酸酐/含金屬氮化物粒子在0.0050~0.50的範圍內，則硬化性組成物具有更優異的本發明的效果。 When the acid anhydride/metal-containing nitride particle is in the range of 0.0050 to 0.50, the curable composition has a more excellent effect of the present invention.

作為酸酐所含有之酸酐基，並無特別限制，可舉出公知的酸酐基。作為酸酐基，例如，可舉出從相同種類的酸衍生之羧酸酐基、膦酸酐基及磺酸酐基等以及從不同的2種酸衍生之酸酐基。 It does not specifically limit as an acid anhydride group contained in an acid anhydride, Well-known acid anhydride groups are mentioned. As the acid anhydride group, for example, a carboxylic anhydride group, a phosphonic anhydride group, a sulfonic anhydride group, etc. derived from the same kind of acid, and an acid anhydride group derived from two different acids.

作為酸酐所含有之酸酐基的數量，並無特別限制，從硬化性組成物具有更優異的本發明的效果之角度考慮，在1個分子中含有2個以上為較佳。作為酸酐所含有之酸酐基的數量的上限值，並無特別限制，通常，4個以下為較佳。 The number of acid anhydride groups contained in the acid anhydride is not particularly limited, but it is preferable to contain two or more in one molecule from the viewpoint that the curable composition has more excellent effects of the present invention. The upper limit of the number of acid anhydride groups contained in the acid anhydride is not particularly limited, but generally, 4 or less are preferable.

作為酸酐，並無特別限制，例如，可舉出二硫酸、三氟甲烷磺酸酐、五氧化二氮、二磷酸、乙酸酐、琥珀酸酐、戊二酸酐、鄰苯二甲酸酐、馬來酸酐、2-磺基苯甲酸酐及對甲苯磺酸酐等。 The acid anhydride is not particularly limited, and examples include disulfuric acid, trifluoromethanesulfonic anhydride, dinitrogen pentoxide, diphosphoric acid, acetic anhydride, succinic anhydride, glutaric anhydride, phthalic anhydride, maleic anhydride, 2-sulfobenzoic anhydride and p-toluenesulfonic anhydride, etc.

作為酸酐，從硬化性組成物具有更優異的本發明的效果之角度考慮，以式(A1)表示之四羧酸二酐為較佳。 As an acid anhydride, tetracarboxylic dianhydride represented by formula (A1) is preferable from a viewpoint that a curable composition has the effect of this invention more excellently.

Figure 106127429-A0305-02-0011-1
Figure 106127429-A0305-02-0011-1

式(A1)中，R1表示4價的有機基。作為4價的有機基，並無特 別限制，可舉出可具有碳原子數1~40的取代基之脂肪族或芳香烴基。作為脂肪烴基，例如，可舉出以下述式表示之基等。 In formula (A1), R 1 represents a tetravalent organic group. The tetravalent organic group is not particularly limited, and examples thereof include aliphatic or aromatic hydrocarbon groups which may have a substituent having 1 to 40 carbon atoms. As an aliphatic hydrocarbon group, the group etc. which are represented by the following formula are mentioned, for example.

Figure 106127429-A0305-02-0012-2
Figure 106127429-A0305-02-0012-2

另外，上述式中，Ra表示氮原子或CRb，Rb表示氫原子或一價的有機基，n表示0或1以上的整數，存在複數個之Ra及Rb可分別相同，亦可不同，複數個Rb可相互鍵結而形成環。 In addition, in the above formula, R a represents a nitrogen atom or CR b , R b represents a hydrogen atom or a monovalent organic group, n represents an integer of 0 or more than 1, and there are plural R a and R b may be the same respectively, and also may be different, and a plurality of R b may be bonded to each other to form a ring.

作為芳香烴基，例如，可舉出以下述式表示之基等。 As an aromatic hydrocarbon group, the group represented by the following formula etc. are mentioned, for example.

Figure 106127429-A0305-02-0012-3
Figure 106127429-A0305-02-0012-3

作為以式(A1)表示之四羧酸二酐的具體例，例如，可舉出苯基-1,2,3,4-四羧酸二酐、meso-丁烷-1,2,3,4-四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、3-(羧甲基)-1,2,4-環戊烷三羧酸1,4：2,3-二酐、5-(2,5-二氧四氢呋喃基)-3-甲基-3-环己烯-1,2-二羧酸酐、4-(2,5-二氧四氫呋喃-3-基)-1,2,3,4-四氫萘-1,2-二羧酸酐、3,4,9,10-二萘嵌苯四羧酸二酐、1,2,5,6-萘四羧酸二酐、雙環[2,2,2]-辛-7-烯-2,3,5,6-四羧酸二酐、二 亞乙基三胺五乙酸二酐、2,6-二溴萘-1,4,5,8-四羧酸二酐、乙二胺四乙酸二酐、八氫-4a,8b：4b,8a-雙(亞甲基氧基亞甲基(methanooxymethano))聯伸苯基-9,11,12,14-四酮及1,2,3,4-四甲基-苯基-1,2,3,4-四羧酸二酐等，但不受限於該些。 Specific examples of tetracarboxylic dianhydride represented by formula (A1) include, for example, phenyl-1,2,3,4-tetracarboxylic dianhydride, meso-butane-1,2,3, 4-tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3-(carboxymethyl)- 1,2,4-Cyclopentanetricarboxylic acid 1,4: 2,3-dianhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2 -Dicarboxylic anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 3,4,9,10-di Rylene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic acid Dianhydride, two Ethylenetriaminepentaacetic dianhydride, 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, octahydro-4a,8b:4b,8a -bis(methyleneoxymethano)bisphenylene-9,11,12,14-tetraketone and 1,2,3,4-tetramethyl-phenyl-1,2, 3,4-tetracarboxylic dianhydride, etc., but not limited to these.

作為四羧酸二酐，從硬化性組成物具有更優異的本發明的效果之角度考慮，以下述式(A2)表示之化合物為更佳。 As a tetracarboxylic dianhydride, the compound represented by following formula (A2) is more preferable from a viewpoint that a curable composition has the effect of this invention more excellent.

Figure 106127429-A0305-02-0013-4
Figure 106127429-A0305-02-0013-4

式(A2)中，R2表示單鍵或2價的連結基。作為2價的連結基，並無特別限制，例如，可舉出以下述式表示之基及組合複數個以下述式表示之基之基團。 In formula (A2), R 2 represents a single bond or a divalent linking group. It does not specifically limit as a divalent linking group, For example, the group represented by the following formula and the group which combined several groups represented by the following formula are mentioned.

Figure 106127429-A0305-02-0013-5
Figure 106127429-A0305-02-0013-5

上述式中，Rb如已進行說明。其中，從硬化性組成物具有更優異 的本發明的效果之角度考慮，作為R2，單鍵、-O-或-C(=O)-為較佳。 In the above formula, R b is as explained above. Among them, a single bond, -O- or -C(=O)- is preferable as R 2 from the viewpoint that the curable composition has more excellent effects of the present invention.

作為以式(A2)表示之化合物的體例，例如，可舉出3,3’,4,4’-二苯甲酮四羧酸二酐、二苯基-3,3’,4,4’-四羧酸二酐、3,3’,4,4’-二苯基碸四羧酸二酐、4,4’-(乙炔-1,2-二基)二鄰苯二甲酸酐、4,4’-(六氟異丙叉基)二鄰苯二甲酸酐、4,4’-(4,4’-異亞丙基二苯氧基)二鄰苯二甲酸酐、3,4’-氧基二鄰苯二甲酸酐及4,4’-氧基二鄰苯二甲酸酐等，但並不受限於該些。 Examples of compounds represented by formula (A2) include 3,3',4,4'-benzophenone tetracarboxylic dianhydride, diphenyl-3,3',4,4' -tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 4,4'-(acetylene-1,2-diyl)diphthalic anhydride, 4 ,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 3,4' -oxydiphthalic anhydride, 4,4'-oxydiphthalic anhydride, etc., but are not limited to these.

作為酸酐的分子量，並無特別限制，從在曝光後的加熱步驟中，酸酐更加容易在硬化性組成物層的上層區域擴散，藉由之後的顯影，更加容易獲得具有更優異的圖案形狀之硬化膜之角度考慮，100~800為較佳，100~600為更佳。另外，本段落中，分子量表示能夠從結構式計算出之分子量。 The molecular weight of the acid anhydride is not particularly limited. In the heating step after exposure, the acid anhydride is more likely to diffuse in the upper region of the curable composition layer, and it is easier to obtain curing with a more excellent pattern shape by subsequent development. Considering the angle of the film, 100~800 is better, and 100~600 is more preferable. In addition, in this paragraph, molecular weight means the molecular weight which can be calculated from a structural formula.

[含金屬氮化物粒子] [Metal Nitride-Containing Particles]

上述硬化性組成物含有含金屬氮化物粒子。本說明書中，含金屬氮化物粒子表示含有金屬原子的氮化物之粒子。並且，含金屬氮化物粒子可含有金屬原子及氮原子以外的原子(例如，氧原子等)，其形態將進行後述。 The above curable composition contains metal nitride particles. In this specification, the metal-containing nitride particle means the particle|grains of the nitride containing a metal atom. In addition, the metal nitride-containing particles may contain metal atoms and atoms other than nitrogen atoms (for example, oxygen atoms, etc.), and the form thereof will be described later.

作為上述硬化性組成物中的含金屬氮化物粒子的含量，並無特別限制，相對於硬化性組成物的總固體成分，30質量%以上為較佳，從可獲得具有更優異的遮光性之硬化膜之角度考慮，40質量%以上為更佳。 The content of the metal nitride-containing particles in the curable composition is not particularly limited, but it is preferably 30% by mass or more with respect to the total solid content of the curable composition, in order to obtain more excellent light-shielding properties. From the viewpoint of the cured film, more than 40% by mass is more preferable.

另外，作為含金屬氮化物粒子的含量的上限值，並無特別限制，通常，70質量%以下為較佳。 In addition, the upper limit of the content of the metal nitride-containing particles is not particularly limited, but generally, 70% by mass or less is preferable.

並且，上述硬化性組成物中的後述之肟系聚合起始劑的含量相對於含金屬氮化物粒子的含量之含有質量比(以下，還稱作“肟系聚合起始劑/含金 屬氮化物粒子”。)並無特別限制，0.001~0.4為較佳，從可獲得具有更優異的本發明的效果之硬化性組成物之角度考慮，0.03~0.2為更佳。 In addition, the mass ratio of the content of the oxime-based polymerization initiator described later to the content of the metal nitride-containing particles in the curable composition (hereinafter also referred to as "oxime-based polymerization initiator/gold-containing Nitride particles.") is not particularly limited, but is preferably 0.001 to 0.4, and is more preferably 0.03 to 0.2 from the viewpoint of obtaining a curable composition having a more excellent effect of the present invention.

另外，含金屬氮化物粒子可單獨使用1種，亦可併用2種以上。併用2種以上的含金屬氮化物粒子時，合計含量在上述範圍內為較佳。 In addition, the metal-containing nitride particles may be used alone or in combination of two or more. When two or more types of metal nitride particles are used in combination, the total content is preferably within the above range.

如上所述，含金屬氮化物粒子含有金屬原子的氮化物。另外，本說明書中，簡單稱作“金屬原子”時，表示係含金屬氮化物粒子中包含之金屬原子，且作為氮化物而存在之金屬原子。 As described above, the metal nitride-containing particles contain nitrides of metal atoms. In addition, in this specification, when simply referring to a "metal atom", it means a metal atom contained in a metal-containing nitride particle, and a metal atom existing as a nitride.

作為金屬原子，並無特別限制，能夠使用公知的金屬原子。作為金屬原子，例如，可舉出過渡金屬，從可獲得能夠獲得具有更優異的遮光性之硬化膜之硬化性組成物之角度考慮，3~11族的過渡金屬為較佳，Ti、Sc、V、Cr、Mn、Fe、Co、Ni、Cu、Y、Zr、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Hf、Ta、W、Re或Pt為更佳，Ti、Sc、V、Cr、Co、Cu、Y、Zr、Mo、Tc、Ru、Rh、Pd、Hf、Ta、W、Re或Pt為進一步較佳，Ti、V、Cr、Y、Zr、Nb、Hf、Ta、W或Re尤為佳，Ti、V、Nb、Ta或Zr為最佳。 The metal atom is not particularly limited, and known metal atoms can be used. Examples of metal atoms include transition metals. From the standpoint of obtaining a curable composition capable of obtaining a cured film with more excellent light-shielding properties, transition metals of Groups 3 to 11 are preferred, and Ti, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Re or Pt are more preferred, Ti, Sc, V , Cr, Co, Cu, Y, Zr, Mo, Tc, Ru, Rh, Pd, Hf, Ta, W, Re or Pt are further preferred, Ti, V, Cr, Y, Zr, Nb, Hf, Ta , W or Re are particularly preferable, and Ti, V, Nb, Ta or Zr are most preferable.

作為含金屬氮化物粒子中的金屬原子的含量，並無特別限制，相對於含金屬氮化物粒子的總質量，50~80質量%為較佳。另外，含金屬氮化物粒子中的金屬原子的含量能夠藉由ICP(Inductively Coupled Plasma)發光分光分析法進行分析。 The content of metal atoms in the metal nitride particles is not particularly limited, but is preferably 50 to 80% by mass relative to the total mass of the metal nitride particles. In addition, the content of metal atoms in the metal nitride-containing particles can be analyzed by ICP (Inductively Coupled Plasma) emission spectrometry.

另外，金屬原子可單獨使用1種，亦可併用2種以上。併用2種以上的金屬原子時，合計含量在上述範圍內為較佳。 In addition, metal atoms may be used alone or in combination of two or more. When two or more metal atoms are used in combination, the total content is preferably within the above range.

含金屬氮化物粒子含有金屬原子的氮化物。合成金屬原子的氮化物時，有時會混入氧。 The metal nitride-containing particles contain nitrides of metal atoms. When synthesizing nitrides of metal atoms, oxygen may be mixed in.

金屬原子的氮化物中氧原子的含量相對於金屬原子的氮化物的總質量，0.001~40質量%為較佳，0.001~35質量%為更佳，0.001~30質量%為進一步較佳。氧原子的含量能夠利用惰性氣體熔融紅外線吸收法進行分析。 The content of oxygen atoms in the metal atom nitride is preferably 0.001 to 40% by mass, more preferably 0.001 to 35% by mass, and still more preferably 0.001 to 30% by mass, based on the total mass of the metal atom nitride. The content of oxygen atoms can be analyzed by an inert gas fusion infrared absorption method.

另外，關於金屬原子的氮化物，從使硬化性組成物硬化來獲得之硬化膜具有更優異的遮光性之角度考慮，實際上不含有氧原子為較佳。實際上不含有氧原子表示使用上述測定方法檢測不到氧原子。 Moreover, it is preferable that the nitride of a metal atom does not actually contain an oxygen atom from the viewpoint that the cured film obtained by hardening a curable composition has more excellent light-shielding property. The fact that oxygen atoms are not contained means that oxygen atoms cannot be detected by the above measurement method.

含金屬氮化物粒子含有氮化鈦為較佳。作為氮化鈦，並無特別限制，能夠使用公知的氮化鈦。 The metal nitride-containing particles preferably contain titanium nitride. The titanium nitride is not particularly limited, and known titanium nitride can be used.

作為氮化鈦，例如，可舉出含有TiN、TiO2、以TinO2n-1(1

Figure 106127429-A0305-02-0016-48
n
Figure 106127429-A0305-02-0016-47
20)表示之低次氧化鈦及以TiNxOy(0<x<2.0，0.1<y<2.0)表示之氧氮化鈦之態樣。 As titanium nitride, for example, TiN, TiO 2 , Ti n O 2n-1 (1
Figure 106127429-A0305-02-0016-48
no
Figure 106127429-A0305-02-0016-47
20) Low-order titanium oxide and titanium oxynitride represented by TiN x O y (0<x<2.0, 0.1<y<2.0).

上述氮化鈦中，將CuKα射線設為X射線源時的來源於(200)面之峰的繞射角2θ通常為42.5°~43.5°為較佳，從可獲得能夠獲得具有更優異的遮光性之硬化膜之硬化性組成物之角度考慮，42.5°~42.8°為更佳，42.5°~42.7°為進一步較佳。 Among the above-mentioned titanium nitrides, when the CuKα ray is used as the X-ray source, the diffraction angle 2θ of the peak originating from the (200) plane is usually 42.5° to 43.5°, and it is better to obtain a more excellent shading effect. From the viewpoint of the curable composition of the cured film, 42.5°~42.8° is more preferable, and 42.5°~42.7° is still more preferable.

將CuKα射線作為X射線源來測定含金屬氮化物粒子的X射線繞射光譜時，關於TiN，在2θ=42.5°附近觀測到來源於(200)面之峰，關於TiO，在2θ=43.4°附近觀測到來源於(200)面之峰。另一方面，雖然不是強度最強之峰，但關於銳鈦型TiO2，在2θ=48.1°附近觀測到來源於(200)面之峰，關於金紅石型TiO2，在2θ=39.2°附近觀測到來源於(200)面之峰。藉此，氮化鈦越含有大量氧原子，峰位置相對於42.5°越向高角度側位移。 When measuring the X-ray diffraction spectrum of metal nitride-containing particles using CuKα rays as the X-ray source, a peak originating from the (200) plane was observed around 2θ=42.5° for TiN, and a peak at 2θ=43.4° for TiO A peak originating from the (200) plane was observed nearby. On the other hand, although it is not the strongest peak, a peak originating from the (200) plane is observed around 2θ=48.1 ° for anatase TiO 2 , and is observed around 2θ=39.2° for rutile TiO 2 To the peak from (200) plane. Accordingly, the more oxygen atoms are contained in titanium nitride, the more the peak position shifts to the higher angle side with respect to 42.5°.

含金屬氮化物粒子的來源於(200)面之峰的繞射角2θ為42.5°以上43.5°以下為較佳，42.5°以上42.8°以下為更佳，42.5°以上42.7°以下為進一步較佳。 The diffraction angle 2θ of the peak derived from the (200) plane of the metal nitride-containing particles is preferably from 42.5° to 43.5°, more preferably from 42.5° to 42.8°, and still more preferably from 42.5° to 42.7° .

含金屬氮化物粒子含有氧化鈦TiO2時，作為強度最強之峰，在2θ=25.3°附近觀測到來源於銳鈦礦型TiO2(101)之峰，在2θ=27.4°附近觀測到來源於金紅石型TiO2(110)之峰。但是，TiO2為白色，會成為降低使硬化性組成物硬化來獲得之遮光膜的遮光性之主要原因，故降低至不會作為峰而被觀察之程度為較佳。 When metal nitride particles contain titanium oxide TiO 2 , as the strongest peak, a peak derived from anatase TiO 2 (101) is observed around 2θ=25.3°, and a peak derived from The peak of rutile TiO 2 (110). However, TiO 2 is white, and it is a factor that lowers the light-shielding properties of the light-shielding film obtained by curing the curable composition, so it is preferable to reduce it to such an extent that it is not observed as a peak.

能夠從藉由上述X射線繞射光譜的測定獲得之峰的半值幅求出構成含金屬氮化物粒子之微晶尺寸。微晶尺寸的計算能夠利用謝勒(Scherrer)公式進行。 The crystallite size constituting the metal-containing nitride particles can be determined from the half-value width of the peak obtained by the measurement of the X-ray diffraction spectrum described above. Calculation of the crystallite size can be performed using Scherrer's formula.

作為構成含金屬氮化物粒子之微晶尺寸，50nm以下為較佳，20nm以上為較佳，20~50nm為更佳。若微晶尺寸為20~50nm，利用硬化性組成物形成之遮光膜的紫外線(尤其i射線(365nm))透射率易變得更高，可獲得感光性更高之硬化性組成物。 The crystallite size constituting the metal-containing nitride particles is preferably 50 nm or less, more preferably 20 nm or more, and more preferably 20 to 50 nm. If the crystallite size is 20-50nm, the ultraviolet (especially i-ray (365nm)) transmittance of the light-shielding film formed by the curable composition is likely to become higher, and a curable composition with higher photosensitivity can be obtained.

對於含金屬氮化物粒子的比表面積，並無特別限制，能夠利用BET(Brunauer，Emmett，Teller)法求出。氮化鈦的比表面積為5~100m2/g為較佳，10~60m2/g為更佳。 The specific surface area of the metal nitride-containing particles is not particularly limited, and can be obtained by the BET (Brunauer, Emmett, Teller) method. The specific surface area of titanium nitride is preferably 5 to 100 m 2 /g, more preferably 10 to 60 m 2 /g.

並且，金屬氮化物可與其他金屬微粒進行複合化。 In addition, the metal nitride can be composited with other metal fine particles.

本說明書中，複合化係指，金屬氮化物與金屬微粒進行複合化或處於高度分散之狀態之粒子。其中，“進行複合化”表示，粒子由金屬氮化物與其他金屬的兩個成分構成，“高度分散之狀態”表示，金屬氮化物與其他金屬分別 個別地存在，且其他金屬的粒子未凝聚而均勻、相同地分散。 In this specification, "composite" refers to particles in which metal nitrides and metal fine particles are composited or in a highly dispersed state. Among them, "compounded" means that the particles are composed of two components of metal nitride and other metals, and "highly dispersed state" means that the metal nitride and other metals are separated It exists individually, and the particles of other metals are uniformly and uniformly dispersed without agglomeration.

作為金屬微粒的材料，並無特別限定，例如，可舉出選自銅、銀、金、鉑、釩、鎳、錫、鈷、銠、銥、釕、鋨、錳、鉬、鎢、鈮、鉭、鈣、鈦、鉍、銻及鉛、以及該些的合金之至少一種。其中，選自銅、銀、金、鉑、鈀、鎳、錫、鈷、銠及銥、以及該些的合金之至少1種為較佳，選自銅、銀、金、鉑及錫、以及該些的合金之至少一種為更佳。從耐濕性更優異的觀點考慮，銀為較佳。 The material of the fine metal particles is not particularly limited, and examples thereof include copper, silver, gold, platinum, vanadium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, At least one of tantalum, calcium, titanium, bismuth, antimony and lead, and alloys thereof. Among them, at least one selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and iridium, and their alloys is preferred, selected from copper, silver, gold, platinum and tin, and At least one of these alloys is more preferable. Silver is preferable from the viewpoint of being more excellent in moisture resistance.

作為含金屬氮化物粒子中的上述金屬微粒的含量，相對於含金屬氮化物粒子的總質量，5質量%以上50質量%以下為較佳，10質量%以上30質量%以下為更佳。 The content of the metal fine particles in the metal nitride-containing particles is preferably from 5 mass % to 50 mass %, more preferably from 10 mass % to 30 mass %, based on the total mass of the metal nitride-containing particles.

(含金屬氮化物粒子的製造方法) (Method for producing metal nitride-containing particles)

作為含金屬氮化物粒子的製造方法，並無特別限制，能夠使用公知的方法。作為含金屬氮化物粒子的製造方法，例如，可舉出氣相反應法。作為氣相反應法，可舉出電爐法及熱等離子體法等，從雜質的混入較少，粒徑易一致，並且，生產率較高之角度考慮，熱等離子法為較佳。 The method for producing the metal nitride-containing particles is not particularly limited, and known methods can be used. As a method for producing the metal nitride-containing particles, for example, a gas phase reaction method is mentioned. The gas phase reaction method includes an electric furnace method and a thermal plasma method, and the thermal plasma method is preferable in terms of less contamination of impurities, easier consistency of particle size, and higher productivity.

熱等離子法中，作為產生熱等離子體的方法，並無特別限制，可舉出直流電弧放電、多相電弧放電、高頻(RF)等離子體及混合式等離子體等，來自電極的雜質的混入較少之高頻等離子體為更佳。 In the thermal plasma method, the method of generating thermal plasma is not particularly limited, and examples include DC arc discharge, multiphase arc discharge, high-frequency (RF) plasma, and hybrid plasma. Less high frequency plasma is better.

作為基於熱等離子體法之金屬原子的氮化物之具體製造方法，並無特別限制，例如，作為氮化鈦的製造方法，可舉出：使四氯化鈦與氨氣在等離子體火焰中反應之方法(日本特開平2-22110號公報)；藉由高頻熱等離子體使鈦粉末蒸發，導入氮作為載體氣體，在冷卻過程中使其氮化來合成之方 法(日本特開昭61-11140號公報)；及向等離子體的周緣部吹入氨氣之方法(日本特開昭63-85007號)等。 The method for producing nitrides of metal atoms by the thermal plasma method is not particularly limited. For example, the method for producing titanium nitride includes reacting titanium tetrachloride and ammonia gas in a plasma flame. The method (Japanese Patent Laying-Open No. 2-22110); by high-frequency thermal plasma to evaporate titanium powder, introduce nitrogen as a carrier gas, and make it nitriding in the cooling process to synthesize method (Japanese Patent Application Laid-Open No. 61-11140); and a method of blowing ammonia gas into the peripheral portion of the plasma (Japanese Patent Application Publication No. 63-85007), etc.

其中，作為金屬原子的氮化物的製造方法，並非受限於上述者，只要可獲得具有所希望之物性之金屬原子的氮化物，則製造方法不受限。 However, the production method of the metal atom nitride is not limited to the above-mentioned ones, and the production method is not limited as long as the metal atom nitride having desired physical properties can be obtained.

用於含金屬氮化物粒子的製造之含有金屬原子之原料(以下，稱作“金屬原料”。)係高純度者為較佳。作為金屬原料的純度，並無特別限制，金屬原子的純度為99.99質量%以上為較佳，99.999質量%以上為更佳。 It is preferable that the raw material containing metal atoms (hereinafter referred to as "metal raw material") used in the production of metal nitride-containing particles be of high purity. The purity of the metal raw material is not particularly limited, but the purity of metal atoms is preferably at least 99.99% by mass, more preferably at least 99.999% by mass.

金屬原料有時會含有金屬原子以外的原子作為雜質(以下，稱作“雜質原子”。)。作為雜質原子，並無特別限制，可舉出Fe原子及Si原子等。 Metal raw materials may contain atoms other than metal atoms as impurities (hereinafter referred to as "impurity atoms"). The impurity atoms are not particularly limited, and examples thereof include Fe atoms, Si atoms, and the like.

金屬原料含有Si原子時，Si原子的含量相對於金屬原料的總質量，超過0.002質量%且小於0.3質量%為較佳，0.01~0.15質量%為更佳，0.02~0.1質量%為進一步較佳。若Si原子的含量超過0.002質量%，則硬化膜的圖案形成性更加提高。並且，認為若Si原子的含量小於0.3質量%，則所獲得之含金屬氮化物粒子的最表層的極性穩定，使含金屬氮化物粒子分散時，分散劑向含金屬氮化物粒子的吸附性得到優化，具有含金屬氮化物粒子的未分散物減少，藉此抑制產生顆粒之效果。 When the metal raw material contains Si atoms, the content of Si atoms is preferably more than 0.002% by mass and less than 0.3% by mass, more preferably 0.01 to 0.15% by mass, more preferably 0.02 to 0.1% by mass, based on the total mass of the metal raw material . When content of Si atom exceeds 0.002 mass %, the pattern formability of a cured film will improve more. And, think that if the content of Si atom is less than 0.3% by mass, the polarity of the outermost layer of the obtained metal-containing nitride particles is stable, and when the metal-containing nitride particles are dispersed, the adsorption of the dispersant to the metal-containing nitride particles is improved. Optimally, there is a reduction in undispersed matter containing metal nitride particles, thereby suppressing the effect of particle generation.

並且，含金屬氮化物粒子的製造中使用之金屬原料中的水分相對於金屬原料的總質量，小於1質量%為較佳，小於0.1質量%為更佳，實際上不包含為進一步較佳。 Furthermore, the moisture in the metal raw material used for the production of the metal nitride-containing particles is preferably less than 1% by mass, more preferably less than 0.1% by mass, and even more preferably not actually contained, relative to the total mass of the metal raw material.

其中，作為使含金屬氮化物粒子含有Fe原子之方法，並無特別限制，例如，可舉出在獲得金屬原料之階段導入Fe原子之方法等。更詳細 而言，藉由還原(Kroll)法等製造金屬原料時，作為反應容器，使用由不銹鋼(SUS)等含有Fe原子之材料構成者，或者作為破碎金屬原料時的沖壓機及粉碎機的材料使用含有Fe原子者，藉此能夠使Fe原子附著於鈦粒子的表面。 Among them, there are no particular limitations on the method of adding Fe atoms to the metal nitride-containing particles, and examples thereof include a method of introducing Fe atoms at the stage of obtaining the metal raw material. More detail Specifically, when producing metal raw materials by the reduction (Kroll) method, etc., as a reaction vessel, use a material that contains Fe atoms such as stainless steel (SUS), or use it as a material for a punch and a pulverizer when crushing metal raw materials When Fe atoms are contained, Fe atoms can be attached to the surface of the titanium particles.

並且，含金屬氮化物粒子的製造中使用熱等離子體法時，除了作為原料之金屬原子以外，添加Fe粒子、Fe氧化物等成分，並藉由熱等離子體法使該些氮化，藉此能夠使含金屬氮化物粒子含有Fe原子。 In addition, when a thermal plasma method is used in the production of metal nitride-containing particles, in addition to metal atoms as raw materials, components such as Fe particles and Fe oxides are added, and these are nitrided by a thermal plasma method, whereby Fe atoms can be contained in the metal nitride-containing particles.

另外，含金屬氮化物粒子中包含之Fe原子可以以離子、金屬化合物(亦包含錯合物)、金屬間化合物、合金、氧化物、複合氧化物、氮化物、氮氧化物、硫化物及硫氧化物等任意形態包含。並且，含金屬氮化物粒子中含有之Fe原子可作為晶格間位置的雜質而存在，亦可在晶界以非晶狀態作為雜質而存在。 In addition, the Fe atoms contained in the metal nitride-containing particles can be formed as ions, metal compounds (including complexes), intermetallic compounds, alloys, oxides, composite oxides, nitrides, nitrogen oxides, sulfides, and sulfur Arbitrary forms such as oxides are included. In addition, the Fe atoms contained in the metal nitride-containing particles may exist as impurities at inter-lattice positions, or may exist as impurities in an amorphous state at grain boundaries.

含金屬氮化物粒子中的Fe原子的含量相對於含金屬氮化物粒子的總質量，超過0.001質量%且小於0.4質量%為較佳。其中，0.01~0.2質量%為更佳，0.02~0.1質量%為進一步較佳。其中，含金屬氮化物粒子中的Fe原子的含量藉由ICP(Inductively Coupled Plasma；高頻電感耦合等離子體)發光分光分析法進行測定。 The content of Fe atoms in the metal nitride-containing particles is preferably more than 0.001% by mass and less than 0.4% by mass relative to the total mass of the metal nitride-containing particles. Among them, 0.01 to 0.2 mass % is more preferable, and 0.02 to 0.1 mass % is still more preferable. Wherein, the content of Fe atoms in the metal nitride-containing particles is measured by ICP (Inductively Coupled Plasma; high-frequency inductively coupled plasma) emission spectroscopic analysis.

含金屬氮化物粒子還含有Si原子(矽原子)為較佳。藉此，硬化膜的圖案形成性更加提高。作為藉由含有Si原子，圖案形成性更加提高之理由，認為與上述之Fe原子相同。 It is preferable that the metal nitride-containing particles further contain Si atoms (silicon atoms). Thereby, the pattern formability of a cured film improves further. The reason why the pattern formability is further improved by containing Si atoms is considered to be the same as the above-mentioned Fe atoms.

含金屬氮化物粒子中的Si原子的含量相對於含金屬氮化物粒子的總質量，超過0.002質量%且小於0.3質量%為較佳，0.01~0.15質量%為更佳， 0.02~0.1質量%為進一步較佳。含金屬氮化物粒子中的Si原子的含量藉由與上述之Fe原子相同的方法進行測定。 The content of Si atoms in the metal nitride-containing particles is preferably more than 0.002% by mass and less than 0.3% by mass, more preferably 0.01 to 0.15% by mass, relative to the total mass of the metal nitride-containing particles. 0.02 to 0.1% by mass is further more preferable. The content of Si atoms in the metal nitride-containing particles was measured by the same method as that of Fe atoms described above.

並且，作為使含金屬氮化物粒子含有Si原子之方法，並無特別限定，與作為導入Fe原子之方法而已進行說明者相同。 In addition, the method of adding Si atoms to the metal-containing nitride particles is not particularly limited, and it is the same as that described as the method of introducing Fe atoms.

[肟系聚合起始劑] [Oxime-based polymerization initiator]

上述硬化性組成物含有肟系聚合起始劑。作為肟系聚合起始劑，並無特別限制，能夠使用公知的肟系聚合起始劑。 The aforementioned curable composition contains an oxime-based polymerization initiator. The oxime-based polymerization initiator is not particularly limited, and known oxime-based polymerization initiators can be used.

作為上述硬化性組成物中的肟系聚合起始劑的含量，並無特別限制，相對於硬化性組成物的總固體成分，通常，0.5~30質量%為較佳，從硬化性組成物具有更優異的本發明的效果之角度考慮，1~20質量%為更佳。 The content of the oxime-based polymerization initiator in the curable composition is not particularly limited, but generally, 0.5 to 30% by mass is preferably 0.5 to 30% by mass relative to the total solid content of the curable composition. From the standpoint of more excellent effects of the present invention, 1 to 20% by mass is more preferable.

並且，作為上述肟系聚合起始劑的含量，調整為已進行說明之酐/起始劑成為規定的範圍內為較佳。 In addition, it is preferable to adjust the content of the above-mentioned oxime-based polymerization initiator so that the anhydride/initiator described above falls within a predetermined range.

另外，肟系聚合起始劑可單獨使用1種，亦可併用2種以上。併用2種以上的肟系聚合起始劑時，合計含量在上述範圍內為較佳。 Moreover, an oxime type polymerization initiator may be used individually by 1 type, and may use 2 or more types together. When two or more oxime-based polymerization initiators are used in combination, the total content is preferably within the above range.

作為肟系聚合起始劑的具體例，例如，能夠使用日本特開2001-233842號公報記載的化合物、日本特開2000-80068號公報記載的化合物或日本特開2006-342166號公報記載的化合物。 As a specific example of an oxime-based polymerization initiator, for example, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, or a compound described in JP-A-2006-342166 can be used. .

作為肟系化合物，例如，可舉出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-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、以及2-乙氧基羰氧基亞胺基-1-苯基丙烷-1-酮等。 Examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetyloxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, Aminobutan-2-one, 2-acetyloxyiminopentan-3-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4 -tosyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

並且，亦可舉出J.C.S.Perkin II(1979年)pp.1653-1660、J.C.S.Perkin II (1979年)pp.156-162、Journal of Photopolymer Science and Technology(1995年)pp.202-232、日本特開2000-66385號公報記載之化合物、日本特開2000-80068號公報、日本特表2004-534797號公報及日本特開2006-342166號公報的各公報中記載之化合物等。 Also, J.C.S.Perkin II (1979) pp.1653-1660, J.C.S.Perkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, compounds described in JP 2000-66385, JP 2000-80068, JP 2004-534797 A and the compounds described in each of JP 2006-342166 A, etc.

市售品中，亦可適宜地使用IRGACURE OXE01(BASF公司製造)、IRGACURE OXE02(BASF公司製造)、IRGACURE OXE03(BASF公司製造)或IRGACURE OXE04(BASF公司製造)。並且，亦能夠使用TR-PBG-304(常州強力電子新材料有限公司製造)、ADEKA ARKLS NCI-831及ADEKA ARKLS NCI-930(ADEKA CORPORATION製造)、N-1919(含咔唑肟酯骨架光起始劑(ADEKA CORPORATION製造))及NCI-730(ADEKA CORPORATION製造)等。 Among commercially available products, IRGACURE OXE01 (manufactured by BASF), IRGACURE OXE02 (manufactured by BASF), IRGACURE OXE03 (manufactured by BASF), or IRGACURE OXE04 (manufactured by BASF) can also be used suitably. In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), N-1919 (a light generator containing a carbazole oxime ester skeleton) can also be used. Primer (manufactured by ADEKA CORPORATION)), NCI-730 (manufactured by ADEKA CORPORATION) and the like.

並且，作為上述記載以外的肟系聚合起始劑，亦可使用：咔唑N位上連結有肟之日本特表2009-519904號公報中記載之化合物；二苯甲酮部位上導入有雜取代基之美國專利第7626957號公報中記載之化合物；色素部位上導入有硝基之日本特開2010-15025號公報及美國專利公開2009-292039號記載的化合物；國際公開專利2009-131189號公報中記載之酮肟系化合物；同一分子內含有三嗪骨架與肟骨架之美國專利7556910號公報中記載之化合物；於405nm下具有最大吸收且相對於g射線光源具有良好的靈敏度之日本特開2009-221114號公報記載之化合物；等。 In addition, as oxime-based polymerization initiators other than those described above, compounds described in JP 2009-519904, in which an oxime is linked to the N-position of carbazole; The compound described in U.S. Patent No. 7,626,957; the compound described in Japanese Patent Application Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039 with a nitro group introduced into the pigment part; The ketoxime compound described; the compound described in US Patent No. 7,556,910 containing a triazine skeleton and an oxime skeleton in the same molecule; Japanese Patent Application Laid-Open 2009-2009- with maximum absorption at 405 nm and good sensitivity to g-ray light sources Compounds described in Bulletin No. 221114; etc.

較佳為，例如能夠參閱日本特開2013-29760號公報的段落0274~0275，該內容編入本說明書中。 Preferably, for example, paragraphs 0274 to 0275 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated in this specification.

具體而言，作為肟系聚合起始劑，以下述式(OX-1)表示之化合物為 較佳。另外，肟系聚合起始劑的N-O鍵可以係(E)體的肟系化合物，亦可以係(Z)體的肟系化合物，還可以係(E)體與(Z)體的混合物。 Specifically, as an oxime-based polymerization initiator, a compound represented by the following formula (OX-1) is better. In addition, the N—O bond of the oxime-based polymerization initiator can be an oxime-based compound of the (E) body, or an oxime-based compound of the (Z) body, or a mixture of the (E) body and (Z) body.

Figure 106127429-A0305-02-0023-6
Figure 106127429-A0305-02-0023-6

式(OX-1)中，R及B分別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。 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.

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。 In the formula (OX-1), as the monovalent substituent represented by R, a monovalent non-metal atomic group is preferable.

作為一價的非金屬原子團，可舉出烷基、芳基、醯基、烷氧基羰基、芳氧基羰基、雜環基、烷硫基羰基及芳硫基羰基等。並且，該些基團可以具有1個以上的取代基。並且，前述之取代基可以進一步被其他取代基取代。 Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, an acyl 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. Also, the aforementioned substituents may be further substituted with other substituents.

作為取代基，可舉出鹵素原子、芳氧基、烷氧基羰基或芳氧基羰基、醯氧基、醯基、烷基及芳基等。 Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

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。該等基團可具有1個以上的取代基。作為取代基，能夠例示前述之取代基。 In the formula (OX-1), as the one-valent substituent represented by B, an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group is preferable. These groups may have one or more substituents. As a substituent, the above-mentioned substituent can be illustrated.

式(OX-1)中，作為A所表示之二價的有機基，碳原子數1~12的伸烷基、環伸烷基或伸炔基為較佳。該些基團可以具有1個以上的取代基。作為取代基，能夠例示前述之取代基。 In the formula (OX-1), as the divalent organic group represented by A, an alkylene group, a cycloalkylene group, or an alkynylene group having 1 to 12 carbon atoms is preferable. These groups may have one or more substituents. As a substituent, the above-mentioned substituent can be illustrated.

作為光聚合起始劑，還能夠使用含有氟原子之肟系化合物。作為 含有氟原子之肟系化合物的具體例，可舉出：日本特開2010-262028號公報記載的化合物；日本特表2014-500852號公報記載的化合物24、36~40；日本特開2013-164471號公報記載的化合物(C-3)；等。該內容編入本說明書中。 As a photopolymerization initiator, an oxime compound containing a fluorine atom can also be used. as Specific examples of oxime-based compounds containing fluorine atoms include: compounds described in JP-A-2010-262028; compounds 24, 36-40 described in JP-A-2014-500852; JP-A-2013-164471 Compound (C-3) described in the Publication No.; This content is incorporated into this manual.

作為光聚合起始劑，還能夠使用以下述式(1)~(4)表示之化合物。 As a photoinitiator, the compound represented by following formula (1)-(4) can also be used.

Figure 106127429-A0305-02-0024-7
Figure 106127429-A0305-02-0024-7

Figure 106127429-A0305-02-0024-8
Figure 106127429-A0305-02-0024-8

式(1)中，R1及R2分別獨立地表示碳原子數1~20的烷基、碳原子數4~20的脂環式烴基、碳原子數6~30的芳基或碳原子數7~30的芳烷基，R1及R2為苯基時，苯基彼此可鍵結而形成茀基，R3及R4分別獨立地表示氫原子、碳原子數1~20的烷基、碳原子數6~30的芳基、碳原子數7~30的芳烷基或碳原子數4~20的雜環基，X表示單鍵(直接鍵結)或羰基。 In the formula ( 1 ), R and R independently represent an alkyl group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 4 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or a carbon number 7-30 aralkyl group, when R1 and R2 are phenyl groups, the phenyl groups can be bonded to each other to form a fenyl group, R3 and R4 independently represent a hydrogen atom, an alkyl group with 1-20 carbon atoms , an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 4 to 20 carbon atoms, and X represents a single bond (direct bond) or a carbonyl group.

式(2)中，R1、R2、R3及R4的含義與式(1)中的R1、R2、R3 及R4相同，R5表示-R6、-OR6、-SR6、-COR6、-CONR6R6、-NR6COR6、-OCOR6、-COOR6、-SCOR6、-OCSR6、-COSR6、-CSOR6、-CN、鹵原子或羥基，R6表示碳原子數1~20的烷基、碳原子數6~30的芳基、碳原子數7~30的芳烷基或碳原子數4~20的雜環基，X表示單鍵或羰基，a表示0~4的整數。 In formula (2), R 1 , R 2 , R 3 and R 4 have the same meanings as R 1 , R 2 , R 3 and R 4 in formula (1), and R 5 represents -R 6 , -OR 6 , -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6 , -CN, halogen atom or Hydroxyl, R 6 represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms or a heterocyclic group with 4 to 20 carbon atoms, and X represents a single Bond or carbonyl, a represents an integer of 0~4.

式(3)中，R1表示碳原子數1~20的烷基、碳原子數4~20的脂環式烴基、碳原子數6~30的芳基或碳原子數7~30的芳烷基，R3及R4分別獨立地表示氫原子、碳原子數1~20的烷基、碳原子數6~30的芳基、碳原子數7~30的芳烷基或碳原子數4~20的雜環基，X表示單鍵或羰基。 In formula (3), R 1 represents an alkyl group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 4 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or an arane with 7 to 30 carbon atoms R and R independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or an aralkyl group with 4 to 30 carbon atoms. 20 heterocyclic group, X represents a single bond or carbonyl.

式(4)中，R1、R3及R4的含義與式(3)中的R1、R3及R4相同，R5表示-R6、-OR6、-SR6、-COR6、-CONR6R6、-NR6COR6、-OCOR6、-COOR6、-SCOR6、-OCSR6、-COSR6、-CSOR6、-CN、鹵原子或羥基，R6表示碳原子數1~20的烷基、碳原子數6~30的芳基、碳原子數7~30的芳烷基或碳原子數4~20的雜環基，X表示單鍵或羰基，a表示0~4的整數。 In formula (4), R 1 , R 3 and R 4 have the same meanings as R 1 , R 3 and R 4 in formula (3), and R 5 represents -R 6 , -OR 6 , -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6 , -CN, halogen atom or hydroxyl, R 6 represents carbon An alkyl group with 1 to 20 atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 4 to 20 carbon atoms, X represents a single bond or a carbonyl group, and a represents An integer from 0 to 4.

上述式(1)及式(2)中，R1及R2分別獨立地為甲基、乙基、正丙基、異丙基、環己基或苯基為較佳。R3為甲基、乙基、苯基、甲苯基或二甲苯基為較佳。R4為碳原子數1~6的烷基或苯基為較佳。R5為甲基、乙基、苯基、甲苯基或萘基為較佳。X為單鍵為較佳。 In the above formula (1) and formula (2), it is preferable that R 1 and R 2 are independently methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl. R 3 is preferably methyl, ethyl, phenyl, tolyl or xylyl. R 4 is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R 5 is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a single bond.

並且，上述式(3)及(4)中，R1分別獨立地為甲基、乙基、正丙基、異丙基、環己基或苯基為較佳。R3為甲基、乙基、苯基、甲苯基或二甲苯基為較佳。R4為碳原子數1~6的烷基或苯基為較佳。R5為甲基、乙基、苯基、甲苯基或萘基為較佳。X為單鍵為較佳。 Furthermore, in the above formulas (3) and (4), R 1 is preferably methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl independently. R 3 is preferably methyl, ethyl, phenyl, tolyl or xylyl. R 4 is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R 5 is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a single bond.

作為以式(1)及式(2)表示之化合物的具體例，例如，可舉出日本特開2014-137466號公報的段落號0076~0079中記載之化合物。該內容編入本說明書中。 Specific examples of the compound represented by formula (1) and formula (2) include, for example, compounds described in paragraph numbers 0076 to 0079 of JP-A-2014-137466. This content is incorporated into this manual.

作為肟系聚合起始劑，從可獲得具有更優異的本發明的效果之硬化性組成物之角度考慮，含有硝基為較佳。 The oxime-based polymerization initiator preferably contains a nitro group from the viewpoint of obtaining a curable composition having a more excellent effect of the present invention.

作為肟系化合物所含有之硝基的數量，並無特別限制，1~4個為較佳，1個或2個為較佳。 The number of nitro groups contained in the oxime compound is not particularly limited, but 1 to 4 are preferred, and 1 or 2 are more preferred.

作為含有硝基之肟系聚合起始劑的具體例，例如，可舉出具有以下結構之NCI-831(商品名、ADEKA CORPORATION製造)等。 Specific examples of the nitro group-containing oxime-based polymerization initiator include NCI-831 (trade name, manufactured by ADEKA CORPORATION) having the following structure, for example.

Figure 106127429-A0305-02-0026-9
Figure 106127429-A0305-02-0026-9

以下，示出肟系聚合起始劑的具體例。 Specific examples of oxime-based polymerization initiators are shown below.

[化學式10]

Figure 106127429-A0305-02-0027-11
Figure 106127429-A0305-02-0028-12
 [chemical formula 10]
Figure 106127429-A0305-02-0027-11
Figure 106127429-A0305-02-0028-12

肟系聚合起始劑係於350~500nm的波長區域具有極大吸收波長者為較佳，於360~480nm的波長區域具有極大吸收波長者為更佳，365nm及405nm的吸光度較高者為進一步較佳。 Oxime-based polymerization initiators with maximum absorption wavelengths in the wavelength range of 350-500nm are preferred, those with maximum absorption wavelengths in the wavelength range of 360-480nm are better, and those with higher absorbance at 365nm and 405nm are further preferred. good.

從靈敏度的觀點考慮，肟系聚合起始劑化合物的365nm或405nm下的莫耳吸光系數為1,000~300,000為較佳，2,000~300,000為更佳，5,000~200,000為進一步較佳。 From the viewpoint of sensitivity, the molar absorption coefficient of the oxime-based polymerization initiator compound at 365 nm or 405 nm is preferably 1,000-300,000, more preferably 2,000-300,000, and still more preferably 5,000-200,000.

化合物的莫耳吸光系數能夠使用公知的方法，例如，利用紫外可見分光光度計(Varian公司製造Cary-5 spctrophotometer)，並利用乙酸乙酯溶劑，以0.01g/L的濃度進行測定為較佳。 The molar absorptivity of the compound can be measured using a known method, for example, using an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer, manufactured by Varian), and preferably measuring it at a concentration of 0.01 g/L using ethyl acetate solvent.

光聚合起始劑可使用2官能或3官能以上的化合物。作為該種化合物的具體例，可舉出日本特表2010-527339號公報、日本特表2011-524436號公報、國際公開第2015/004565號、日本特表2016-532675號公報的0417~0412段落、國際公開第2017/033680號的0039~0055段落中記載之肟化合物的二聚體、日本特表2013-522445號公報中記載之化合物(E)及(G)、以及國際公開第2016/034963號中記載之Cmpd1~7。 As the photopolymerization initiator, a bifunctional or trifunctional or higher compound can be used. Specific examples of such compounds include paragraphs 0417 to 0412 of JP 2010-527339, JP 2011-524436, International Publication No. 2015/004565, and JP 2016-532675. , dimers of oxime compounds described in paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E) and (G) described in JP 2013-522445, and International Publication No. 2016/034963 Cmpd1~7 recorded in No.

[聚合性化合物] [polymeric compound]

上述硬化性組成物含有聚合性化合物。本說明書中，聚合性化合物表示 具有聚合性基之化合物，表示與酐不同之化合物。 The above curable composition contains a polymerizable compound. In this specification, a polymeric compound means A compound having a polymerizable group means a compound different from an anhydride.

作為硬化性組成物中的聚合性化合物的含量，並無特別限制，相對於硬化性組成物的總固體成分，5~30質量%為較佳，10~25質量%為更佳。 The content of the polymerizable compound in the curable composition is not particularly limited, but is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, based on the total solid content of the curable composition.

聚合性化合物可單獨使用1種，亦可併用2種以上。併用2種以上的聚合性化合物時，合計含量在上述範圍內為較佳。 A polymeric compound may be used individually by 1 type, and may use 2 or more types together. When two or more polymerizable compounds are used in combination, the total content is preferably within the above range.

聚合性化合物係包含1個以上的含有乙烯性不飽和鍵之基團之化合物為較佳，含有2個以上之化合物為更佳，含有3個以上之化合物為進一步較佳，含有5個以上之化合物尤為佳。上限例如為15個以下為較佳。作為含有乙烯性不飽和鍵之基團，例如，可舉出乙烯基、(甲基)烯丙基及(甲基)丙烯醯基等。 The polymeric compound is preferably a compound containing one or more ethylenically unsaturated bond-containing groups, more preferably a compound containing two or more, further preferably a compound containing three or more, and a compound containing five or more compounds are particularly preferred. The upper limit is preferably, for example, 15 or less. As a group containing an ethylenically unsaturated bond, a vinyl group, (meth)allyl group, (meth)acryl group etc. are mentioned, for example.

作為聚合性化合物，例如，能夠使用日本特開2008-260927號公報的0050段落及日本特開2015-68893號公報的0040段落中記載之化合物，上述內容編入本說明書中。 As the polymerizable compound, for example, compounds described in Paragraph 0050 of JP-A-2008-260927 and Paragraph 0040 of JP-A-2015-68893 can be used, and the above contents are incorporated in the present specification.

聚合性化合物例如可以係單體、預聚物、低聚物及該些的混合物、以及該些的多聚體等化學形態的任一個。 The polymerizable compound may be in any chemical form such as a monomer, a prepolymer, an oligomer, a mixture of these, and a multimer of these, for example.

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。 It is preferable that the polymeric compound is a 3-15 functional (meth)acrylate compound, and a 3-6 functional (meth)acrylate compound is more preferable.

聚合性化合物係含有1個以上的包含乙烯性不飽和鍵之基團且在常壓下具有100℃以上的沸點之化合物亦較佳。例如，能夠參閱日本特開2013-29760號公報的段落0227、日本特開2008-292970號公報的段落0254~0257中記載之化合物，該內容編入本說明書中。 It is also preferable that the polymerizable compound is a compound containing one or more groups containing an ethylenically unsaturated bond and having a boiling point of 100° C. or higher under normal pressure. For example, the compounds described in paragraph 0227 of JP-A-2013-29760 and paragraphs 0254-0257 of JP-A-2008-292970 can be referred to, and the contents thereof are incorporated in this specification.

聚合性化合物還能夠使用雙季戊四醇三丙烯酸酯(作為市售品， KAYARAD D-330；Nippon Kayaku Co.,Ltd..製造)、雙季戊四醇四丙烯酸酯(作為市售品，KAYARAD D-320；Nippon Kayaku Co.,Ltd..製造)、雙季戊四醇五(甲基)丙烯酸酯(作為市售品，KAYARAD D-310；Nippon Kayaku Co.,Ltd..製造)、雙季戊四醇六(甲基)丙烯酸酯(作為市售品，KAYARAD DPHA；Nippon Kayaku Co.,Ltd..製造、A-DPH-12E；Shin-Nakamura Chemical Co.,Ltd製造)及該些(甲基)丙烯醯基經由乙二醇殘基、丙二醇殘基之結構(例如，由Sartomer company Inc.市售之SR454、SR499)為較佳。還能夠使用該些的低聚物類型。並且，還能夠使用NK酯A-TMMT(季戊四醇四丙烯酸酯、Shin-Nakamura Chemical Co.,Ltd製造)及KAYARAD RP-1040(Nippon Kayaku Co.,Ltd..製造)等。 The polymerizable compound can also use dipentaerythritol triacrylate (as a commercial item, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial item, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(methyl) Acrylate (commercially available, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available, KAYARAD DPHA; Nippon Kayaku Co., Ltd.. Manufactured, A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.) and the structure of these (meth)acryl groups via ethylene glycol residues, propylene glycol residues (for example, commercially available from Sartomer company Inc. SR454, SR499) are better. Oligomer types of these can also be used. Furthermore, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can also be used.

以下示出較佳聚合性化合物的態樣。 The aspects of preferable polymerizable compounds are shown below.

聚合性化合物可具有羧酸基、磺酸基及磷酸基等酸基。作為含有酸基之聚合性化合物，脂肪族聚羥基化合物與不飽和羧酸的酯為較佳，使非芳香族羧酸酐與脂肪族聚羥基化合物的未反應的羥基進行反應來使其具有酸基之聚合性化合物為更佳，該酯中，脂肪族聚羥基化合物為季戊四醇和/或雙季戊四醇者為進一步較佳。作為市售品，例如，可舉出TOAGOSEICO.,LTD.製造的ARONIX TO-2349、M-305、M-510及M-520等。 A polymeric compound may have acid groups, such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. As a polymeric compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and an acid group is formed by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. The polymeric compound is more preferable, and among the esters, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol is still more preferable. As a commercial item, ARONIX TO-2349, M-305, M-510, M-520 etc. by TOAGO SEI CO., LTD. are mentioned, for example.

作為含有酸基之聚合性化合物的較佳酸值，為0.1~40mgKOH/g，5~30mgKOH/g為更佳。若聚合性化合物的酸值為0.1mgKOH/g以上，則顯影溶解特性良好，若為40mgKOH/g以下，則在製造和/或操作上有利。而且，光聚合性能良好且硬化性優異。 The preferred acid value of the polymeric compound containing acid groups is 0.1-40 mgKOH/g, more preferably 5-30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the image development solubility property is favorable, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and/or handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

關於聚合性化合物，含有己內酯結構之化合物亦較佳。 As a polymerizable compound, a compound containing a caprolactone structure is also preferable.

作為含有己內酯結構之化合物，只要在分子內含有己內酯結構，則並無特別限制，例如，可舉出藉由使三羥甲基乙烷、二三羥甲基乙烷、三羥甲基丙烷、二三羥甲基丙烷、季戊四醇、雙季戊四醇、三季戊四醇、甘油、雙甘油、三羥甲基三聚氰胺等多元醇與(甲基)丙烯酸及ε-己內酯進行酯化來獲得之、ε-己內酯改性多官能(甲基)丙烯酸酯。其中，具有以下述式(Z-1)表示之己內酯結構之化合物為較佳。 The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule. It is obtained by esterifying polyhydric alcohols such as methyl propane, ditrimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, trimethylol melamine with (meth)acrylic acid and ε-caprolactone , ε-caprolactone modified multifunctional (meth)acrylate. Among them, a compound having a caprolactone structure represented by the following formula (Z-1) is preferable.

Figure 106127429-A0305-02-0031-13
Figure 106127429-A0305-02-0031-13

式(Z-1)中，6個R全部為以下述式(Z-2)表示之基團，或6個R中的1~5個為以下述式(Z-2)表示之基團，剩餘為以下述式(Z-3)表示之基團。 In formula (Z-1), all of the 6 Rs are groups represented by the following formula (Z-2), or 1 to 5 of the 6 Rs are groups represented by the following formula (Z-2), The remainder is a group represented by the following formula (Z-3).

Figure 106127429-A0305-02-0031-14
Figure 106127429-A0305-02-0031-14

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

Figure 106127429-A0305-02-0031-15
Figure 106127429-A0305-02-0031-15

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

含有己內酯結構之聚合性化合物例如由Nippon Kayaku CO.,LT D.作為KAYARAD DPCA系列而市售，可舉出DPCA-20(上述式(Z-1)~(Z-3)中，m=1，以式(Z-2)表示之基團的數=2，R1全部為氫原子之化合物)、DPCA-30(同式，m=1，以式(Z-2)表示之基團的數=3，R1全部為氫原子之化合物)、DPCA-60(同式，m=1，以式(Z-2)表示之基團的數=6，R1全部為氫原子之化合物)、DPCA-120(同式中，m=2，以式(Z-2)表示之基團的數=6，R1全部為氫原子之化合物)等。 Polymerizable compounds containing a caprolactone structure are commercially available from Nippon Kayaku CO., LT D. as KAYARAD DPCA series, for example, DPCA-20 (in the above formulas (Z-1) to (Z-3), m =1, the number of groups represented by formula (Z-2)=2, all R1 are compounds of hydrogen atoms), DPCA-30 (same formula, m=1, group represented by formula (Z-2) The number of groups = 3, all R 1 are hydrogen atoms), DPCA-60 (same formula, m = 1, the number of groups represented by formula (Z-2) = 6, all R 1 are hydrogen atoms compound), DPCA-120 (in the same formula, m=2, the number of groups represented by formula (Z-2)=6, and all R 1 are hydrogen atoms), etc.

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

Figure 106127429-A0305-02-0032-16
Figure 106127429-A0305-02-0032-16

式(Z-4)及(Z-5)中，E分別獨立地表示-((CH2)yCH2O)-或((CH2)yCH(CH3)O)-，y分別獨立地表示0~10的整數，X分別獨立地表示(甲基)丙烯醯基、氫原子或羧酸基。 In formulas (Z-4) and (Z-5), E each independently represents -((CH 2 ) y CH 2 O)- or ((CH 2 ) y CH(CH 3 )O)-, and y each independently represents an integer of 0 to 10, and X each independently represents a (meth)acryl group, a hydrogen atom or a carboxylic acid group.

式(Z-4)中，(甲基)丙烯醯基的合計為3個或4個，m分別獨立地表示0~10的整數，各m的合計為0~40的整數。 In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, m each independently represents an integer of 0-10, and the total number of each m is an integer of 0-40.

式(Z-5)中，(甲基)丙烯醯基的合計為5個或6個，n分別獨立地表示0~10的整數，各n的合計為0~60的整數。 In formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, n each independently represents an integer of 0-10, and the total number of each n is an integer of 0-60.

式(Z-4)中，m為0~6的整數為較佳，0~4的整數為更佳。 In formula (Z-4), m is preferably an integer of 0-6, more preferably an integer of 0-4.

並且，各m的合計為2~40的整數為較佳，2~16的整數為更佳，4~8的整數為進一步較佳。 In addition, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and still more preferably an integer of 4 to 8.

式(Z-5)中，n為0~6的整數為較佳，0~4的整數為更佳。 In formula (Z-5), n is preferably an integer of 0-6, more preferably an integer of 0-4.

並且，各n的合計為3~60的整數為較佳，3~24的整數為更佳，6~12的整數為進一步較佳。 In addition, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.

並且，式(Z-4)或式(Z-5)中的-((CH2)yCH2O)-或((CH2)yCH(CH3)O)-為氧原子側的末端與X鍵結之形態為較佳。 In addition, -((CH 2 ) y CH 2 O)- or ((CH 2 ) y CH(CH 3 )O)- in formula (Z-4) or formula (Z-5) is the terminal on the side of the oxygen atom The form of bonding with X is preferable.

以式(Z-4)或式(Z-5)表示之化合物可單獨使用1種，亦可併用2種以上。尤其，式(Z-5)中的6個X全部為丙烯醯基之態樣、式(Z-5)中的6個X全部為丙烯醯基之化合物與6個X中的至少1個為氫原子之化合物的混合物之態樣為較佳。藉由設為該種結構，能夠更加提高顯影性。 The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, the form in which all 6 Xs in the formula (Z-5) are acryloyl groups, the compound in which all 6 Xs in the formula (Z-5) are acryloyl groups, and at least one of the 6 Xs are A mixture of hydrogen atom compounds is preferred. Developability can be improved more by setting it as such a structure.

並且，作為以式(Z-4)或式(Z-5)表示之化合物在聚合性化合物中的總含量，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 formula (Z-4) or formula (Z-5) in the polymerizable compound is preferably at least 20% by mass, more preferably at least 50% by mass.

以式(Z-4)或式(Z-5)表示之化合物中，季戊四醇衍生物和/或雙季戊四醇衍生物為更佳。 Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferable.

並且，聚合性化合物可具有卡多骨架。 In addition, the polymerizable compound may have a cardo skeleton.

作為含有卡多骨架之聚合性化合物，具有9,9-二芳基芴骨架之聚合性化合物為較佳。 As the polymerizable compound containing a cardo skeleton, a polymerizable compound having a 9,9-diarylfluorene skeleton is preferable.

作為含有卡多骨架之聚合性化合物，並無限定，例如，可舉出Oncoat EX系列(NAGASE&CO.,LTD製造)及Ogsol(Osaka Gas Chemicals Co.,Ltd.製造)等。 It does not limit as a polymeric compound containing a cardo skeleton, For example, Oncoat EX series (manufactured by NAGASE & CO., LTD.) and Ogsol (manufactured by Osaka Gas Chemicals Co., Ltd.) etc. are mentioned.

[任意成分] [optional ingredient]

上述硬化性組成物可含有上述以外的任意成分。作為任意成分，例如，可舉出脫水劑、聚合抑制劑、鹼可溶性樹脂、分散劑、溶劑、矽烷偶聯劑、紫外線吸收劑、界面活性劑、黏附性改良劑及著色劑等。另外，著色劑表示含金屬氮化物粒子以外的著色劑。以下，對各成分進行詳細說明。 The above-mentioned curable composition may contain optional components other than those mentioned above. Examples of optional components include dehydrating agents, polymerization inhibitors, alkali-soluble resins, dispersants, solvents, silane coupling agents, ultraviolet absorbers, surfactants, adhesion improvers, and colorants. In addition, the coloring agent means a coloring agent other than the metal nitride-containing particle. Each component will be described in detail below.

<脫水劑> <Dehydrating agent>

上述硬化性組成物可含有脫水劑。本說明書中，脫水劑表示與酸酐不同之化合物。 The above curable composition may contain a dehydrating agent. In this specification, a dehydrating agent means a compound different from an acid anhydride.

作為脫水劑，並無特別限制，能夠使用公知的脫水劑。其中，作為脫水劑，原酸酯化合物為更佳。作為原酸酯化合物，並無特別限制，例如，可舉出日本特表第2012-524759號公報的0039段落及0040段落中記載的化合物。 The dehydrating agent is not particularly limited, and known dehydrating agents can be used. Among them, an orthoester compound is more preferable as a dehydrating agent. It does not specifically limit as an orthoester compound, For example, the compound described in paragraph 0039 and 0040 of JP-A-2012-524759 is mentioned.

作為硬化性組成物中的脫水劑的含量，並無特別限制，通常，相對於硬化性組成物中的總固體成分，0.01~5質量%為較佳。 The content of the dehydrating agent in the curable composition is not particularly limited, but usually, 0.01 to 5% by mass is preferable with respect to the total solid content in the curable composition.

<聚合抑制劑> <polymerization inhibitor>

上述硬化性組成物含有聚合抑制劑為較佳。含有聚合抑制劑之硬化性組成物具有更優異的保存穩定性，且更加抑制在未曝光部產生殘渣。另外，本說明書中，硬化性組成物的保存穩定性表示能夠藉由實施例中記載之方法評價之保存穩定性。 It is preferable that the above curable composition contains a polymerization inhibitor. A curable composition containing a polymerization inhibitor has more excellent storage stability, and further suppresses residue generation in unexposed areas. In addition, in this specification, the storage stability of a curable composition means the storage stability which can be evaluated by the method described in an Example.

作為聚合抑制劑，並無特別限制，能夠使用公知的聚合抑制劑。 The polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used.

作為硬化性組成物中的聚合抑制劑的含量，並無特別限制，通常，相對於硬化性組成物的總固體成分，0.1~5質量%為較佳。 The content of the polymerization inhibitor in the curable composition is not particularly limited, but usually, 0.1 to 5% by mass is preferable with respect to the total solid content of the curable composition.

另外，聚合抑制劑可單獨使用1種，亦可併用2種以上。併用2種以 上的聚合抑制劑時，合計含量在上述範圍內為較佳。 Moreover, a polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together. and use 2 kinds of When using the above polymerization inhibitors, the total content is preferably within the above range.

作為聚合抑制劑，並無特別限制，能夠使用用作聚合抑制劑之公知的化合物。作為用作聚合抑制劑之化合物，例如，可舉出酚系化合物、醌系化合物、受阻胺系化合物、吩噻嗪系化合物及硝基苯系化合物等。 The polymerization inhibitor is not particularly limited, and known compounds used as polymerization inhibitors can be used. Examples of compounds used as polymerization inhibitors include phenolic compounds, quinone-based compounds, hindered amine-based compounds, phenothiazine-based compounds, and nitrobenzene-based compounds.

作為上述酚系化合物，例如，可舉出苯酚、4-甲氧基苯酚、氫醌、2-叔丁基氫醌、鄰苯二酚、4-叔丁基鄰苯二酚、2,6-二-叔丁基苯酚、2,6-二-叔丁基4-甲基苯酚、2,6-二-叔丁基4-乙基苯酚、4-羥基甲基-2,6-二-叔丁基苯酚、新戊四醇四(3,5-二-叔丁基4-羥基苯基丙酸乙酯)、4-甲氧基-1-萘酚及1,4-二羥基萘等。 Examples of the phenolic compounds include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butylcatechol, 2,6- Di-tert-butylphenol, 2,6-di-tert-butyl 4-methylphenol, 2,6-di-tert-butyl 4-ethylphenol, 4-hydroxymethyl-2,6-di-tert Butylphenol, neopentylthritol tetrakis (3,5-di-tert-butyl ethyl 4-hydroxyphenylpropionate), 4-methoxy-1-naphthol and 1,4-dihydroxynaphthalene, etc.

作為酚系化合物，以式(IH-1)表示之酚系化合物為較佳。 As the phenolic compound, a phenolic compound represented by formula (IH-1) is preferable.

Figure 106127429-A0305-02-0035-17
Figure 106127429-A0305-02-0035-17

式(IH-1)中，R1~R5分別獨立地表示氫原子、烷基、烯基、羥基、胺基、芳基、烷氧基、羧基、烷氧羰基或醯基。R1~R5可分別連結而形成環。 In formula (IH-1), R 1 to R 5 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a hydroxyl group, an amino group, an aryl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group or an acyl group. R 1 to R 5 may be linked to each other to form a ring.

作為式(IH-1)中的R1~R5，氫原子、碳原子數1~5的烷基(例如，甲基及乙基等)、碳原子數1~5的烷氧基(例如，甲氧基及乙氧基等)、碳原子數2~4的烯基(例如，乙烯基等)或苯基為較佳。 As R 1 to R 5 in formula (IH-1), a hydrogen atom, an alkyl group with 1 to 5 carbon atoms (for example, methyl and ethyl, etc.), an alkoxy group with 1 to 5 carbon atoms (such as , methoxy, ethoxy, etc.), alkenyl groups having 2 to 4 carbon atoms (for example, vinyl, etc.) or phenyl groups are preferred.

其中，R1及R5分別獨立地為氫原子或叔丁基為更佳，R2及R4為氫原 子為更佳，R3為氫原子、碳原子數1~5的烷基或碳原子數1~5的烷氧基為更佳。 Among them, R 1 and R 5 are independently hydrogen atom or tert-butyl group, more preferably R 2 and R 4 are hydrogen atom, R 3 is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms or a carbon An alkoxy group having 1 to 5 atoms is more preferable.

作為上述醌系化合物，例如，可舉出1,4-苯醌、1,2-苯醌及1,4-萘醌等。 As said quinone compound, 1,4-benzoquinone, 1,2-benzoquinone, 1,4-naphthoquinone, etc. are mentioned, for example.

作為受阻胺系化合物，例如，可舉出以下述式(IH-2)表示之聚合抑制劑。 As a hindered amine compound, the polymerization inhibitor represented by following formula (IH-2) is mentioned, for example.

Figure 106127429-A0305-02-0036-18
Figure 106127429-A0305-02-0036-18

式(IH-2)中的R6表示氫原子、羥基、胺基、烷氧基、烷氧羰基或醯基。其中，氫原子或羥基為較佳，羥基為更佳。 R 6 in the formula (IH-2) represents a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, an alkoxycarbonyl group or an acyl group. Among them, a hydrogen atom or a hydroxyl group is preferred, and a hydroxyl group is more preferred.

並且，式(IH-2)中的R7~R10分別獨立地表示氫原子或烷基。作為R7~R10所表示之烷基，碳原子數1~5的烷基為較佳，甲基或乙基為更佳。 In addition, R 7 to R 10 in the formula (IH-2) each independently represent a hydrogen atom or an alkyl group. The alkyl group represented by R 7 to R 10 is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group.

<鹼可溶性樹脂> <Alkali-soluble resin>

硬化性組成物含有鹼可溶性樹脂為較佳。本說明書中，鹼可溶性樹脂表示含有促進鹼可溶性之基(鹼可溶性基)之樹脂。 The curable composition preferably contains an alkali-soluble resin. In this specification, an alkali-soluble resin means resin containing the group (alkali-soluble group) which promotes alkali solubility.

作為硬化性組成物中的鹼可溶性樹脂的含量，並無特別限制，通常，相對於硬化性組成物的總固體成分，0.1~40質量%為較佳，從硬化性組成物具有更優異的本發明的效果之角度考慮，1~20質量%為更佳。 The content of the alkali-soluble resin in the curable composition is not particularly limited, but generally, 0.1 to 40% by mass relative to the total solid content of the curable composition is preferred, since the curable composition has more excellent properties. From the viewpoint of the effect of the invention, 1 to 20% by mass is more preferable.

鹼可溶性樹脂可單獨使用1種，亦可併用2種以上。併用2種以上的 鹼可溶性樹脂時，合計含量在上述範圍內為較佳。 Alkali-soluble resin may be used individually by 1 type, and may use 2 or more types together. and use two or more In the case of an alkali-soluble resin, the total content is preferably within the above range.

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

作為鹼可溶性樹脂的具體例，可舉出不飽和羧酸與乙烯性不飽和化合物的共聚物。 As a specific example of alkali-soluble resin, the copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is mentioned.

作為不飽和羧酸，並無特別限制，可舉出：(甲基)丙烯酸、巴豆酸及醋酸乙烯酯等單羧酸類；衣康酸、馬來酸及反丁烯二酸等二羧酸或其酸酐；鄰苯二甲酸單(2-(甲基)丙烯醯氧基乙酯)等多元羧酸單酯類；等。 The unsaturated carboxylic acid is not particularly limited, and examples thereof include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and vinyl acetate; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid; Its acid anhydride; polycarboxylic acid monoesters such as phthalic acid mono(2-(meth)acryloxyethyl ester); etc.

作為能夠共聚之乙烯性不飽和化合物，可舉出(甲基)丙烯酸甲酯等。並且，還能夠使用日本特開2010-97210號公報的0027段落及日本特開2015-68893號公報的0036~0037段落中記載之化合物，上述內容編入本說明書中。 Methyl (meth)acrylate etc. are mentioned as a copolymerizable ethylenically unsaturated compound. Furthermore, the compounds described in paragraph 0027 of JP-A-2010-97210 and paragraphs 0036-0037 of JP-A-2015-68893 can also be used, and the above contents are incorporated in the present specification.

並且，亦可組合能夠共聚之乙烯性不飽和化合物且在側鏈含有乙烯性不飽和基之化合物來使用。作為乙烯性不飽和基，(甲基)丙烯酸基為較佳。例如亦可如下獲得在側鏈具有乙烯性不飽和基之丙烯酸樹脂，亦即，使含有縮水基或脂環式環氧基之乙烯性不飽和化合物與含有羧酸基之丙烯酸樹脂的羧酸基加成反應。 In addition, a copolymerizable ethylenically unsaturated compound and a compound having an ethylenically unsaturated group in a side chain can also be used in combination. As the ethylenically unsaturated group, a (meth)acrylic group is preferable. For example, an acrylic resin having an ethylenically unsaturated group in a side chain can also be obtained by combining an ethylenically unsaturated compound containing a shrinkage group or an alicyclic epoxy group with a carboxylic acid group of an acrylic resin containing a carboxylic acid group. Addition reaction.

作為鹼可溶性樹脂，例如，能夠使用：日本特開昭59-44615號、日本特公昭54-34327號、日本特公昭58-12577號、日本特公昭54-25957號、日本特開昭54-92723號、日本特開昭59-53836號及日本特開昭59-71 048號中記載之在側鏈含有羧酸基之自由基聚合物；歐洲專利第993966號、歐洲專利第1204000號及日本特開2001-318463號等各公報中記載之含有鹼可溶性基之縮醛改性聚乙烯醇系黏結樹脂；聚乙烯吡咯烷酮；聚環氧乙烷；醇溶性尼龍及2,2-雙-(4-羥苯基)-丙烷與環氧氯丙烷的反應物亦即聚醚等；國際公開第2008/123097號中記載之聚醯亞胺樹脂；等。 As the alkali-soluble resin, for example, JP-A-59-44615, JP-A-54-34327, JP-A-58-12577, JP-A-54-25957, JP-A-54-92723 No., Japanese Patent Application No. 59-53836 and Japanese Patent Application No. 59-71 Radical polymers containing carboxylic acid groups in the side chains described in No. 048; acetals containing alkali-soluble groups described in European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463 Modified polyvinyl alcohol-based binder resin; polyvinylpyrrolidone; polyethylene oxide; alcohol-soluble nylon and the reactant of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin, that is, polyether etc.; the polyimide resin described in International Publication No. 2008/123097; etc.

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

作為鹼可溶性樹脂，還能夠使用聚醯亞胺前驅物。聚醯亞胺前驅物通常係使含有酸酐基之化合物與二胺化合物在40~100℃下進行加成聚合反應來獲得之樹脂，表示與上述酸酐不同之化合物。 As the alkali-soluble resin, a polyimide precursor can also be used. The polyimide precursor is usually a resin obtained by performing an addition polymerization reaction between a compound containing an acid anhydride group and a diamine compound at 40 to 100°C, and represents a compound different from the above-mentioned acid anhydride.

作為聚醯亞胺前驅物，例如，可舉出含有以式(1)表示之重複單元之樹脂。作為聚醯亞胺前驅物的結構，例如，可舉出含有以下述式(2)表示之醯胺酸結構與醯胺酸結構進行局部醯亞胺閉環而成之以下述式(3)表示和/或進行全部醯亞胺閉環之以下述式(4)表示之醯亞胺結構者。 As a polyimide precursor, the resin containing the repeating unit represented by formula (1), for example is mentioned. As the structure of the polyimide precursor, for example, include the amide acid structure represented by the following formula (2) and the amide acid structure with partial imide ring closure, represented by the following formula (3) and /or one having an imide structure represented by the following formula (4) in which all imide rings are closed.

Figure 106127429-A0305-02-0038-19
Figure 106127429-A0305-02-0038-19

Figure 106127429-A0305-02-0038-20
Figure 106127429-A0305-02-0038-20

Figure 106127429-A0305-02-0039-21
Figure 106127429-A0305-02-0039-21

Figure 106127429-A0305-02-0039-22
Figure 106127429-A0305-02-0039-22

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

作為上述聚醯亞胺前驅物的具體例，例如，可舉出日本特開2008-106250號公報的0011~0031段落中記載之化合物、日本特開2016-122101號公報的0022~0039段落中記載之化合物及日本特開2016-68401號公報的0061~0092段落中記載之化合物等，上述內容編入本說明書中。 Specific examples of the aforementioned polyimide precursor include, for example, the compounds described in paragraphs 0011 to 0031 of JP-A-2008-106250 and the compounds described in paragraphs 0022-0039 of JP-A-2016-122101. and the compounds described in paragraphs 0061 to 0092 of JP-A-2016-68401, etc., the above contents are incorporated into this specification.

關於鹼可溶性樹脂，從利用硬化性組成物來獲得之圖案狀的硬化膜的圖案形狀更優異的角度考慮，含有選自包含聚醯亞胺前驅物及聚醯亞胺樹脂之群組之至少1種為較佳。 The alkali-soluble resin contains at least 1 selected from the group consisting of polyimide precursors and polyimide resins from the viewpoint that the pattern shape of the patterned cured film obtained by the curable composition is more excellent. species is better.

作為含有鹼可溶性基之聚醯亞胺樹脂，並無特別限制，能夠利用公知的含有鹼可溶性基之聚醯亞胺樹脂。作為上述聚醯亞胺樹脂，例如，可舉出日本特開2014-137523號公報的0050段落中記載之樹脂、日本特開2015-187676號公報的0058段落中記載之樹脂及日本特開2014-106326號公報的0012~0013段落中記載之樹脂等，上述內容編入本說明書中。 The alkali-soluble group-containing polyimide resin is not particularly limited, and known alkali-soluble group-containing polyimide resins can be used. Examples of the above-mentioned polyimide resins include the resins described in paragraph 0050 of JP-A-2014-137523, the resins described in paragraph 0058 of JP-A-2015-187676, and the resins described in JP-A-2014-187676. The resins and the like described in paragraphs 0012 to 0013 of Publication No. 106326 are incorporated in this specification.

<分散劑> <Dispersant>

上述硬化性組成物含有分散劑為較佳。本說明書中，分散劑表示與後述之鹼可溶性樹脂不同之成分。 It is preferable that the above curable composition contains a dispersant. In this specification, a dispersant means a component different from the alkali-soluble resin mentioned later.

作為硬化性組成物中的分散劑的含量，並無特別限制，通常，相對於硬化性組成物的總固體成分，5~30質量%為較佳。 The content of the dispersant in the curable composition is not particularly limited, but usually, 5 to 30% by mass is preferable with respect to the total solid content of the curable composition.

分散劑可單獨使用1種，亦可併用2種以上。併用2種以上的分散劑時，合計含量在上述範圍內為較佳。 A dispersant may be used individually by 1 type, and may use 2 or more types together. When using two or more types of dispersants in combination, the total content is preferably within the above range.

作為分散劑，例如，能夠適當選擇公知的分散劑來使用。其中，高分子化合物為較佳。 As the dispersant, for example, known dispersants can be appropriately selected and used. Among them, polymer compounds are preferred.

作為分散劑，可舉出高分子分散劑[例如，聚醯胺胺及其鹽、聚羧酸及其鹽、高分子量不飽和酸酯、改性聚氨酯、改性聚酯、改性聚(甲基)丙烯酸酯、(甲基)丙烯酸系共聚物、萘磺酸福爾馬林縮合物]、聚氧乙烯烷基磷酸酯、聚氧乙烯烷基胺及顏料衍生物等。 As the dispersant, high molecular dispersant [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated ester, modified polyurethane, modified polyester, modified poly(formyl base) acrylate, (meth)acrylic acid copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine and pigment derivatives, etc.

高分子化合物依其結構，能夠進一步分類為直鏈狀高分子、末端改質型高分子、接枝型高分子及嵌段型高分子。 Polymer compounds can be further classified into linear polymers, end-modified polymers, grafted polymers, and block polymers according to their structures.

(高分子化合物) (polymer compound)

高分子化合物吸附於含金屬氮化物粒子的表面，發揮防止被分散體的再凝聚之作用。故，含有針對顏料表面的固定部位之末端改質型高分子、接枝型高分子及嵌段型高分子為較佳。 The polymer compound is adsorbed on the surface of the metal nitride-containing particles to prevent re-agglomeration of the dispersed body. Therefore, terminal-modified polymers, grafted polymers, and block-type polymers containing fixed sites on the surface of the pigment are preferred.

高分子化合物包含含有接枝鏈之結構單元為較佳。另外，本說明書中，“結構單元”的含義與“重複單元”相同。 It is preferable that the polymer compound includes a structural unit containing a graft chain. In addition, in this specification, a "structural unit" has the same meaning as a "repeating unit".

包含含有該種接枝鏈之結構單元之高分子化合物，藉由接枝鏈具有與 溶劑的親和性，故含金屬氮化物粒子等的分散性及經時之後的分散穩定性(經時穩定性)優異。並且，藉由存在接枝鏈，包含含有接枝鏈之結構單元之高分子化合物與聚合性化合物或其他能夠併用之樹脂等具有親和性。其結果，鹼顯影中不易生成殘渣。 A polymer compound comprising a structural unit containing such a grafted chain, which has the same properties as the grafted chain Because of its affinity for solvents, it is excellent in dispersibility of metal nitride-containing particles and the like, and dispersion stability over time (temporal stability). Furthermore, due to the presence of the graft chain, the polymer compound including the structural unit containing the graft chain has affinity with a polymerizable compound or other resins that can be used in combination. As a result, residues are less likely to be generated during alkali image development.

若接枝鏈變長，則立體排斥效果提高而含金屬氮化物粒子等的分散性得到提高。另一方面，若接枝鏈過長，則向含金屬氮化物粒子等的吸附力下降，含金屬氮化物粒子等的分散性呈下降的趨勢。故，接枝鏈為氫原子以外的原子數為40~10000者為較佳，氫原子以外的原子數為50~2000者為更佳，氫原子以外的原子數為60~500者為進一步較佳。 When the graft chain becomes longer, the steric repulsion effect increases and the dispersibility of the metal nitride-containing particles and the like improves. On the other hand, if the graft chain is too long, the adsorption force to the metal nitride-containing particles and the like decreases, and the dispersibility of the metal nitride-containing particles and the like tends to decrease. Therefore, the graft chain is preferably 40 to 10,000 atoms other than hydrogen atoms, more preferably 50 to 2,000 atoms other than hydrogen atoms, and 60 to 500 atoms other than hydrogen atoms. good.

其中，接枝鏈表示共聚物的主鏈的根部(從主鏈支化之基團中與主鏈鍵結之原子)至從主鏈支化之基團的末端。 Here, the graft chain means the root of the main chain of the copolymer (the atom bonded to the main chain in the group branched from the main chain) to the terminal of the group branched from the main chain.

接枝鏈含有聚合物結構為較佳，作為該種聚合物結構，例如可舉出聚(甲基)丙烯酸酯結構(例如，聚(甲基)丙烯酸結構)、聚酯結構、聚氨酯結構、聚脲結構、聚醯胺結構及聚醚結構等。 It is preferable that the graft chain contains a polymer structure. As such a polymer structure, for example, a poly(meth)acrylate structure (for example, a poly(meth)acrylic acid structure), a polyester structure, a polyurethane structure, a poly Urea structure, polyamide structure and polyether structure, etc.

為了提高接枝鏈與溶劑的相互作用性，並藉此提高黑色顏料等的分散性，接枝鏈係含有選自包含聚酯結構、聚醚結構及聚(甲基)丙烯酸酯結構之組之至少1種之接枝鏈為較佳，含有聚酯結構及聚醚結構的至少任一個之接枝鏈為更佳。 In order to improve the interaction between the grafted chain and the solvent, and thereby improve the dispersibility of black pigments, etc., the grafted chain contains a compound selected from the group consisting of polyester structure, polyether structure and poly(meth)acrylate structure. A graft chain of at least one type is preferable, and a graft chain containing at least one of a polyester structure and a polyether structure is more preferable.

作為含有該種接枝鏈之巨單體，並無特別限定，能夠適當使用具有反應性雙鍵性基之巨單體。 The macromonomer containing such a graft chain is not particularly limited, and a macromonomer having a reactive double bond group can be suitably used.

與高分子化合物所含有之包含接枝鏈之結構單元對應，作為適合用於合成高分子化合物之市售的巨單體，可舉出AA-6(商品名、TOAGOS EI CO.,LTD.)、AA-10(商品名、TOAGOSEI CO.,LTD.製造)、AB-6(商品名、TOAGOSEI CO.,LTD.製造)、AS-6(商品名、TOAGOSEI CO.,LTD.)、AN-6(商品名、TOAGOSEI CO.,LTD.製造)、AW-6(商品名、TOAGOSEI CO.,LTD.製造)、AA-714(商品名、TOAGOSEI CO.,LTD.製造)、AY-707(商品名、TOAGOSEI CO.,LTD.製造)、AY-714(商品名、TOAGOSEI CO.,LTD.製造)、AK-5(商品名、TOAGOSEI CO.,LTD.製造)、AK-30(商品名、TOAGOSEI CO.,LTD.製造)、AK-32(商品名、TOAGOSEI CO.,LTD.製造)、Blemmer PP-100(商品名、NOF CORPORATION.製造)、Blemmer PP-500(商品名、NOF CORPORATION.製造)、Blemmer PP-800(商品名、NOF CORPORATION.製造)、Blemmer PP-1000(商品名、NOF CORPORATION.製造)、Blemmer 55-PET-800(商品名、NOF CORPORATION.製造)、Blemmer PME-4000(商品名、NOF CORPORATION.製造)、Blemmer PSE-400(商品名、NOF CORPORATION.製造)、Blemmer PSE-1300(商品名、NOF CORPORATION.製造)、Blemmer 43PAPE-600B(商品名、NOF CORPORATION.製造)等。其中，使用AA-6(商品名、TOAGOSEI CO.,LTD.製造)、AA-10(商品名、TOAGOSEI CO.,LTD.)、AB-6(商品名、TOAGOSEI CO.,LTD.製造)、AS-6(商品名、TOAGOSEI CO.,LTD.)、AN-6(商品名、TOAGOSEI CO.,LTD.製造)及Blemmer PME-4000(商品名、NOF CORPORATION.製造)等為較佳。 AA-6 (trade name, TOAGOS EI CO., LTD.), AA-10 (trade name, manufactured by TOAGOSEI CO., LTD.), AB-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AS-6 (trade name, manufactured by TOAGOSEI CO. , LTD.), AN-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AW-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AA-714 (trade name, manufactured by TOAGOSEI CO., LTD. Manufactured), AY-707 (trade name, manufactured by TOAGOSEI CO., LTD.), AY-714 (trade name, manufactured by TOAGOSEI CO., LTD.), AK-5 (trade name, manufactured by TOAGOSEI CO., LTD.) , AK-30 (trade name, manufactured by TOAGOSEI CO., LTD.), AK-32 (trade name, manufactured by TOAGOSEI CO., LTD.), Blemmer PP-100 (trade name, manufactured by NOF CORPORATION.), Blemmer PP- 500 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-800 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-1000 (trade name, manufactured by NOF CORPORATION.), Blemmer 55-PET-800 (trade name, manufactured by NOF CORPORATION.) CORPORATION.), Blemmer PME-4000 (trade name, NOF CORPORATION.), Blemmer PSE-400 (trade name, NOF CORPORATION.), Blemmer PSE-1300 (trade name, NOF CORPORATION.), Blemmer 43PAPE- 600B (trade name, manufactured by NOF CORPORATION.) and the like. Among them, AA-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AA-10 (trade name, manufactured by TOAGOSEI CO., LTD.), AB-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AS-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AN-6 (trade name, manufactured by TOAGOSEI CO., LTD.), Blemmer PME-4000 (trade name, manufactured by NOF CORPORATION.) and the like are preferable.

上述分散劑含有選自包含聚丙烯酸甲酯、聚甲基丙烯酸甲酯及環狀或鏈狀的聚酯之群組之至少1種結構為較佳。上述分散劑含有選自包含聚丙烯酸甲酯、聚甲基丙烯酸甲酯及鏈狀的聚酯之群組之至少1種結構為 更佳。上述分散劑含有選自包含聚丙烯酸甲酯結構、聚甲基丙烯酸甲酯結構、聚己內酯結構及聚戊內酯結構之群組之至少1種結構為進一步較佳。分散劑可以在1個分散劑中單獨含有上述結構，亦可以在1個分散劑中含有複數個該種結構。 It is preferable that the above-mentioned dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. The above-mentioned dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate and chain-like polyester: better. It is still more preferable that the above-mentioned dispersant contains at least one structure selected from the group consisting of polymethyl acrylate structure, polymethyl methacrylate structure, polycaprolactone structure and polyvalerolactone structure. A dispersant may contain the above-mentioned structure alone in one dispersant, or may contain plural such structures in one dispersant.

其中，聚己內酯結構係指作為重複單元含有對ε-己內酯進行開環之結構者。聚戊內酯結構係指作為重複單元含有對δ-戊內酯進行開環之結構者。 Here, the polycaprolactone structure means what contains the structure which ring-opens ε-caprolactone as a repeating unit. The polyvalerolactone structure refers to a structure containing ring-opening of δ-valerolactone as a repeating unit.

作為上述分散劑的具體例，例如，能夠使用日本特開2015-34983號公報的0035~0096段落中記載之化合物、日本特開2012-255148號公報的0025~0105段落中記載之化合物、日本特開2013-249417號公報的0127~0129段落的化合物、日本特開2010-106268號公報的0037~0115段落(所對應之US2011/0124824的段落0075~0133欄)中記載之化合物、包含含有日本特開2011-153283號公報的0028~0084段落(所對應之US2011/0279759的段落0075~0133欄)的酸性基經由連結基鍵結而成之側鏈結構之構成成分之化合物、日本特開2016-109763號公報的0033~0049段落中記載之化合物，上述內容編入本說明書中。 As specific examples of the above-mentioned dispersant, for example, compounds described in paragraphs 0035 to 0096 of JP 2015-34983 , compounds described in paragraphs 0025 to 0105 of JP 2012-255148 , JP 2012-255148 , Compounds disclosed in paragraphs 0127 to 0129 of Publication No. 2013-249417, compounds described in paragraphs 0037 to 0115 of Japanese Patent Application Publication No. 2010-106268 (corresponding to paragraphs 0075 to 0133 of US2011/0124824), including those containing JP Paragraphs 0028 to 0084 of Publication No. 2011-153283 (corresponding to paragraphs 0075 to 0133 of US2011/0279759), a compound that is a constituent of a side chain structure in which the acidic group is bonded via a linking group, JP 2016- For the compounds described in paragraphs 0033 to 0049 of Publication No. 109763, the above content is incorporated in this specification.

<溶劑> <solvent>

上述硬化性組成物含有溶劑為較佳。硬化性組成物含有溶劑時，作為溶劑的含量，並無特別限制，調整為硬化性組成物的總固體成分成為5~40質量%為較佳。 It is preferable that the above curable composition contains a solvent. When the curable composition contains a solvent, the content of the solvent is not particularly limited, but it is preferably adjusted so that the total solid content of the curable composition is 5 to 40% by mass.

溶劑可單獨使用1種，亦可併用2種以上。併用2種以上的溶劑時，調整為硬化性組成物的總固體成分成為上述範圍內為較佳。 A solvent may be used individually by 1 type, and may use 2 or more types together. When two or more solvents are used in combination, it is preferable to adjust the total solid content of the curable composition to fall within the above-mentioned range.

作為溶劑的種類，並無特別限制，能夠使用公知的溶劑。作為溶 劑，例如，可舉出水或有機溶劑。 The type of solvent is not particularly limited, and known solvents can be used. as a solvent As an agent, for example, water or an organic solvent can be mentioned.

作為有機溶劑，例如，可舉出丙酮、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***、乙二醇二甲醚、丙二醇單甲醚、丙二醇單***、乙醯丙酮、環己酮、環戊酮、二丙酮醇、乙二醇單甲醚乙酸酯、乙二醇***乙酸酯、乙二醇單異丙醚、乙二醇單丁醚乙酸酯、3-甲氧基丙醇、甲氧基甲氧基乙醇、二乙二醇單甲醚、二乙二醇單***、二乙二醇二甲醚、二乙二醇二乙基醚、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、3-甲氧基乙酸丙酯、N，N-二甲基甲醯胺、二甲基亞碸、γ-丁內酯、乙酸丁酯、乳酸甲酯及乳酸乙酯等，但並不限制於該些。 Examples of organic solvents include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether , Ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, butyl acetate, methyl lactate, ethyl lactate, etc., but not limited thereto.

<矽烷偶聯劑> <Silane coupling agent>

硬化性組成物可含有矽烷偶聯劑。 The curable composition may contain a silane coupling agent.

矽烷偶聯劑係在分子中含有水解性基團及其以外的官能基團之化合物。另外，烷氧基等水解性基團與矽原子鍵結。 Silane coupling agents are compounds that contain hydrolyzable groups and other functional groups in their molecules. In addition, a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.

水解性基團係指，與矽原子直接鍵結，並且可藉由水解反應和/或縮合反應生成矽氧烷鍵之取代基。作為水解性基團，例如，可舉出鹵原子、烷氧基、醯氧基及烯氧基。水解性基團含有碳原子時，其碳原子數為6以下為較佳，4以下為更佳。碳原子數4以下的烷氧基或碳原子數4以下的烯氧基為較佳。 The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through a hydrolysis reaction and/or a condensation reaction. As a hydrolyzable group, a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group are mentioned, for example. When the hydrolyzable group contains carbon atoms, the number of carbon atoms is preferably 6 or less, more preferably 4 or less. An alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.

並且，在基板上形成硬化膜時，為了提高基板與硬化膜之間的黏附性，矽烷偶聯劑不包含氟原子及矽原子(其中，水解性基團所鍵結之矽原子除外)為較佳，不包含氟原子、矽原子(其中，水解性基團所鍵結之矽原子除外)、被矽原子取代之伸烷基、碳原子數8以上的直鏈烷基及碳原子數3以上的 支鏈烷基為更佳。 In addition, when forming a cured film on the substrate, in order to improve the adhesion between the substrate and the cured film, it is preferable that the silane coupling agent does not contain fluorine atoms and silicon atoms (except for silicon atoms bonded by hydrolyzable groups). Preferably, it does not contain fluorine atoms, silicon atoms (except for silicon atoms bonded by hydrolyzable groups), alkylene groups substituted by silicon atoms, straight-chain alkyl groups with 8 or more carbon atoms, and 3 or more carbon atoms of Branched alkyl groups are more preferred.

上述硬化性組成物中的矽烷偶聯劑的含量相對於硬化性組成物中的總固體成分，0.1~10質量%為較佳，0.5~8質量%為更佳，1.0~6質量%為進一步較佳。 The content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, further preferably 1.0 to 6% by mass relative to the total solid content of the curable composition. better.

上述硬化性組成物可單獨含有1種矽烷偶聯劑，亦可含有2種以上。硬化性組成物含有2種以上的矽烷偶聯劑時，其合計在上述範圍內即可。 The said curable composition may contain 1 type of silane coupling agent independently, and may contain 2 or more types. When the curable composition contains two or more types of silane coupling agents, the total of them may be within the above-mentioned range.

<紫外線吸收劑> <Ultraviolet absorber>

硬化性組成物可含有紫外線吸收劑。藉此，能夠將硬化膜的圖案形狀設為更優異(精細)者。 The curable composition may contain an ultraviolet absorber. Thereby, the pattern shape of a cured film can be made into a more excellent (finer) one.

作為紫外線吸收劑，能夠使用水楊酸鹽系、二苯甲酮系、苯并***系、取代丙烯腈系及三嗪系的紫外線吸收劑。作為該些的具體例，能夠使用日本特開2012-068418號公報的段落0137~0142(所對應之US2012/0068292的段落0251~0254)的化合物，能夠援用該些內容，將其編入本說明書中。 As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. As specific examples of these, the compounds of paragraphs 0137 to 0142 of JP-A-2012-068418 (paragraphs 0251 to 0254 of the corresponding US2012/0068292) can be used, and these contents can be cited and incorporated in this specification. .

此外，二乙基胺基-苯基磺醯基系紫外線吸收劑(DAITOCHEMICALCO.,LTD.製造、商品名：UV-503)等亦可較佳地使用。 In addition, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by DAITOCHEMICAL CO., LTD., trade name: UV-503) and the like can also be preferably used.

作為紫外線吸收劑，可舉出日本特開2012-32556號公報的段落0134~0148中例示之化合物。 Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP-A-2012-32556.

紫外線吸收劑的含量相對於硬化性組成物的總固體成分，0.001~15質量%為較佳，0.01~10質量%為更佳，0.1~5質量%為進一步較佳。 The content of the ultraviolet absorber is preferably from 0.001 to 15% by mass, more preferably from 0.01 to 10% by mass, and still more preferably from 0.1 to 5% by mass, based on the total solid content of the curable composition.

<界面活性劑> <Surfactant>

硬化性組成物可含有界面活性劑。界面活性劑有助於提高硬化性組成物的塗佈性。 The curable composition may contain a surfactant. The surfactant contributes to the improvement of the coatability of the curable composition.

上述硬化性組成物含有界面活性劑時，作為界面活性劑的含量，相對於硬化性組成物的總固體成分，0.001~2.0質量%為較佳。 When the above curable composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass relative to the total solid content of the curable composition.

界面活性劑可單獨使用1種，亦可併用2種以上。併用2種以上的界面活性劑時，合計量在上述範圍內為較佳。 Surfactants may be used alone or in combination of two or more. When two or more surfactants are used in combination, the total amount is preferably within the above range.

作為界面活性劑，例如，可舉出氟系界面活性劑、非離子系界面活性劑、陽離子系界面活性劑、陰離子系界面活性劑及矽酮系界面活性劑等。 As a surfactant, a fluorine-type surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a silicone-type surfactant, etc. are mentioned, for example.

例如，藉由硬化性組成物含有氟系界面活性劑，硬化性組成物的液特性(尤其，流動性)更加提高。亦即，使用含有氟系界面活性劑之硬化性組成物形成膜時，藉由降低被塗佈面與塗佈液之間的界面張力，向被塗佈面的潤濕性得到改善，向被塗佈面的塗佈性得到提高。故，即使是以少量的液量形成數μm左右的薄膜時，亦容易形成厚度不均較小之膜，在這一點上較有效。 For example, when the curable composition contains a fluorine-based surfactant, the liquid properties (in particular, fluidity) of the curable composition are further improved. That is, when a curable composition containing a fluorine-based surfactant is used to form a film, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid, and the wettability to the coated surface is improved. The coatability of the coated surface is improved. Therefore, even when a thin film of about several μm is formed with a small amount of liquid, it is more effective in that it is easy to form a film with less unevenness in thickness.

氟系界面活性劑中的氟含有率為3~40質量%為較佳，5~30質量%為更佳，7~25質量%為進一步較佳。氟含有率在該範圍內之氟系界面活性劑在塗佈膜的厚度的均勻和/或省液性方面較有效，且硬化性組成物中的溶解性亦良好。 The fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, and still more preferably from 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in uniformity of coating film thickness and/or liquid-saving properties, and also has good solubility in curable compositions.

作為氟系界面活性劑，例如，可舉出MEGAFACE F171、MEGAFACE F172、MEGAFACE F173、MEGAFACE F176、MEGAFACE F177、MEGAFACE F141、MEGAFACE F142、MEGAFACE F143、MEGAFACE F144、MEGAFACE R30、MEGAFACE F437、MEGAFACE F475、MEGAFACE F479、MEGAFACE F482、MEGAFACE F554、MEGAFACE F780(以上，DICCORPORATION製造)、Fluorado FC430、Fluorado FC431、F luorado FC171(以上，3MJapanLimited製造)、Surflon S-382、Surflon SC-101、Surflon SC-103、Surflon SC-104、Surflon SC-105、Surflon SC1068、Surflon SC-381、Surflon SC-383、Surflon S393、Surflon KH-40(以上，ASAHIGLASSCO.,LTD.製造)、PF636、PF656、PF6320、PF6520、PF7002(OMNOVASOLUTIONSINC.製造)等。 Examples of fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479 , MEGAFACE F482, MEGAFACE F554, MEGAFACE F780 (above, manufactured by DICCORPORATION), Fluorado FC430, Fluorado FC431, F luorado FC171 (above, manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, manufactured by ASAHIGLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVASOLUTION SINC.) and the like.

作為氟系界面活性劑，還能夠使用嵌段聚合物，作為具體例，例如，可舉出日本特開2011-89090號公報中記載之化合物。 A block polymer can also be used as a fluorine-type surfactant, and as a specific example, the compound described in Unexamined-Japanese-Patent No. 2011-89090 is mentioned, for example.

<黏附性改良劑> <Adhesion Improver>

硬化性組成物可含有矽烷偶聯劑作為黏附性改良劑。作為矽烷偶聯劑，例如，可舉出3-縮水甘油醚丙基三甲氧基矽烷、3-縮水甘油醚丙基三乙氧基矽烷、3-縮水甘油醚丙基甲基二甲氧基矽烷、3-縮水甘油醚丙基甲基二乙氧基矽烷、乙烯基三甲氧基矽烷及乙烯基三乙氧基矽烷等。 The curable composition may contain a silane coupling agent as an adhesion improving agent. Examples of the silane coupling agent include 3-glycidyl ether propyl trimethoxysilane, 3-glycidyl ether propyl triethoxy silane, 3-glycidyl ether propyl methyl dimethoxy silane , 3-glycidyl ether propylmethyldiethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane, etc.

作為黏附性改良劑的含量，並無特別限制，相對於硬化性組成物的總固體成分，0.02~20質量%為較佳。 The content of the adhesion improving agent is not particularly limited, but is preferably 0.02 to 20% by mass relative to the total solid content of the curable composition.

<著色劑> <Colorant>

硬化性組成物可含有著色劑。本說明書中，著色劑表示與含金屬氮化物粒子不同之著色劑。 The curable composition may contain a colorant. In the present specification, the coloring agent means a coloring agent different from the metal nitride-containing particles.

作為硬化性組成物中的著色劑的含量，並無特別限制，通常，30~60質量%為較佳。 The content of the coloring agent in the curable composition is not particularly limited, but generally, 30 to 60% by mass is preferable.

作為著色劑，能夠使用各種公知的顏料(著色顏料)及染料(著色染料)。 As the colorant, various known pigments (coloring pigments) and dyes (coloring dyes) can be used.

含有著色劑時，其含量能夠依據硬化來獲得之遮光膜的光學特性來確 定。並且，其他著色劑可單獨使用1種，亦可併用2種以上。 When a colorant is contained, its content can be determined according to the optical properties of the light-shielding film obtained by curing. Certainly. Moreover, other coloring agents may be used individually by 1 type, and may use 2 or more types together.

作為著色劑，例如，能夠使用日本特開2014-42375的段落0027~0200、日本特開2008-260927號公報的0031段落及日本特開2015-68893號公報的0015~0025段落中記載之著色劑，上述內容編入本說明書中。 As the colorant, for example, the colorants described in paragraphs 0027 to 0200 of JP 2014-42375, 0031 of JP 2008-260927, and 0015 to 0025 of JP 2015-68893 can be used. , the above content is compiled into this manual.

作為著色劑，還能夠使用具有紅外線吸收性之顏料。 As a colorant, an infrared absorbing pigment can also be used.

作為具有紅外線吸收性之顏料，鎢化合物及金屬硼化物等為較佳，其中，從紅外區域的波長中的遮光性優異的角度考慮，鎢化合物為更佳。尤其，從與基於曝光之硬化效率相關之肟系聚合起始劑的光吸收波長區域與可見光線區域的透光性優異的觀點考慮，鎢化合物為較佳。 As the infrared absorbing pigment, tungsten compounds, metal borides, and the like are preferable, and among them, tungsten compounds are more preferable from the viewpoint of excellent light-shielding properties at wavelengths in the infrared region. In particular, a tungsten compound is preferable from the viewpoint of the oxime-based polymerization initiator having excellent light-absorbing wavelength range and visible light transmittance related to curing efficiency by exposure.

該些顏料可併用2種以上，並且，亦可與後述之染料併用。可舉出為了調整色調及為了提高所希望的波長區域的遮光性，例如向黑色或具有紅外線遮光性之顏料混合紅色、綠色、黄色、橙色、紫色及藍色等彩色顏料或者後述之染料之態樣。向黑色或具有紅外線遮光性之顏料混合紅色顏料或者染料、或紫色顏料或者染料為較佳，向黑色或具有紅外線遮光性之顏料混合紅色顏料為更佳。 These pigments may use 2 or more types together, and may use together with the dye mentioned later. Examples include mixing color pigments such as red, green, yellow, orange, purple, and blue, or dyes described later, with black or infrared-shielding pigments to adjust the color tone and improve the light-shielding properties in the desired wavelength region. Sample. It is preferable to mix a red pigment or dye, or a purple pigment or dye with a black or an infrared-shielding pigment, and it is more preferable to mix a red pigment with a black or an infrared-shielding pigment.

而且，亦可添加後述之近紅外線吸收劑、紅外線吸收劑。 Furthermore, a near-infrared absorber and an infrared absorber described later may also be added.

‧有機顏料 ‧Organic Pigments

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

(染料) (dye)

作為染料，例如能夠使用日本特開昭64-90403號公報、日本特開昭64-91102號公報、日本特開平1-94301號公報、日本特開平6-11614號公報、特登2592207號、美國專利4808501號說明書、美國專利5667920號說明書、美國專利505950號說明書、美國專利5667920號說明書、日本特開平 5-333207號公報、日本特開平6-35183號公報、日本特開平6-51115號公報、日本特開平6-194828號公報等中公開之色素。若作為化學結構予以區分，則能夠使用吡唑偶氮化合物、吡咯亞甲基化合物、苯胺偶氮化合物、三苯甲烷化合物、蒽醌化合物、亞苄基化合物、氧雜菁(Oxonol)化合物、吡唑並***偶氮化合物、吡啶酮偶氮化合物、花青化合物、啡噻嗪化合物、吡咯並吡唑甲亞胺化合物等。並且，作為染料，還可使用色素多聚體。作為色素多聚體，可舉出日本特開2011-213925號公報、日本特開2013-041097號公報中記載之化合物。並且，可使用分子內具有聚合性之聚合性染料，作為市售品，例如，可舉出Wako Pure Chemical Industries,Ltd.製RDW系列。 As the dye, for example, JP-A-64-90403, JP-A-64-91102, JP-1-94301, JP-6-11614, Teden 2592207, U.S. Patent No. 4,808,501, U.S. Patent No. 5,667,920, U.S. Patent No. 505,950, U.S. Patent No. 5,667,920, Japanese Patent Laid-Open Pigments disclosed in JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. If classified as chemical structures, pyrazole azo compounds, pyrromethene compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazole compounds, Azolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenthiazine compounds, pyrrolopyrazole carboximine compounds, and the like. Furthermore, as a dye, a pigment multimer can also be used. Examples of the dye multimer include compounds described in JP-A-2011-213925 and JP-A-2013-041097. In addition, polymerizable dyes having polymerizability in the molecule can be used, and examples of commercially available products include RDW series manufactured by Wako Pure Chemical Industries, Ltd.

(紅外線吸收劑) (infrared absorber)

上述著色劑可還含有紅外線吸收劑。 The above-mentioned colorant may further contain an infrared absorber.

紅外線吸收劑表示在紅外區域(波長650~1300nm為較佳)的波長區域具有吸收之化合物。紅外線吸收劑為在波長675~900nm的波長區域具有極大吸收波長之化合物為較佳。 Infrared absorber refers to a compound that absorbs in the wavelength region of the infrared region (preferably a wavelength of 650-1300nm). The infrared absorber is preferably a compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm.

作為具有該種分光特性之著色劑，例如，可舉出吡咯并吡咯化合物、銅化合物、花青化合物、酞菁化合物、亞銨鎓(Iminium)化合物、硫醇錯合物系化合物、過渡金屬氧化物系化合物、方酸菁化合物、萘酞菁化合物、夸特銳烯(Quaterrylene)化合物、二硫醇金屬錯合物系化合物、克酮鎓化合物等。 Examples of coloring agents having such spectroscopic properties include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxidation Phosphate-based compounds, squaraine compounds, naphthalocyanine compounds, quaterrylene compounds, dithiol metal complex-based compounds, crotonium compounds, and the like.

酞菁化合物、萘酞菁化合物、亞銨鎓化合物、花青化合物、方酸菁化合物及克酮鎓化合物可使用日本特開2010-111750號公報的段落0010~0081中公開的化合物，該內容編入本說明書中。花青化合物例如能夠參閱“功能 性色素、大河原信/松崗賢/北尾悌次郎/平嶋恆亮編著、Kodansha Scientific Ltd.”，該內容編入本申請說明書中。 As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and crotonium compound, compounds disclosed in paragraphs 0010 to 0081 of JP-A-2010-111750 can be used. in this manual. Cyanine compounds can be referred to for example in "Functional Sexual Pigment, Ogawara Nobu/Matsuoka Ken/Kitao Teijiro/Hirashima Tsuneaki Edited, Kodansha Scientific Ltd.", the content is incorporated into this application specification.

作為具有上述分光特性之著色劑，還能夠使用日本特開平07-164729號公報的段落0004~0016中公開的化合物和/或日本特開2002-146254號公報的段落0027~0062中公開的化合物、日本特開2011-164583號公報的段落0034~0067中公開的包含含有Cu和/或P之氧化物的微晶且數平均凝聚粒徑為5~200nm之近紅外線吸收粒子。 As a coloring agent having the above-mentioned spectroscopic properties, compounds disclosed in paragraphs 0004 to 0016 of JP 07-164729 A and/or compounds disclosed in paragraphs 0027 to 0062 of JP 2002-146254 A, Near-infrared absorbing particles comprising microcrystals containing oxides of Cu and/or P disclosed in paragraphs 0034 to 0067 of Japanese Unexamined Patent Publication No. 2011-164583 and having a number average aggregated particle diameter of 5 to 200 nm.

作為在波長675~900nm的波長區域具有極大吸收波長之化合物，選自包含花青化合物、吡咯并吡咯化合物、方酸菁化合物、酞菁化合物及萘酞菁化合物之群組之至少1種為較佳。 As a compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm, at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds is preferred. good.

並且，紅外線吸收劑係在25℃的水中溶解1質量%以上之化合物為較佳，在25℃的水中溶解10質量%以上之化合物為更佳。藉由使用該種化合物，耐溶劑性得到優化。 In addition, it is preferable that the infrared absorber dissolves 1% by mass or more of the compound in water at 25°C, and more preferably dissolves 10% by mass or more of the compound in water at 25°C. By using this compound, solvent resistance is optimized.

吡咯并吡咯化合物能夠參閱日本特開2010-222557號公報的段落番號0049~0062，該內容編入本說明書中。花青化合物及方酸菁化合物能夠參閱國際公開第2014/088063號的段落番號0022~0063、國際公開第2014/030628號的段落番號0053~0118、日本特開2014-59550號公報的段落番號0028~0074、國際公開第2012/169447號的段落番號0013~0091、日本特開2015-176046號公報的段落番號0019~0033、日本特開2014-63144號公報的段落番號0053~0099、日本特開2014-52431號公報的段落番號0085~0150、日本特開2014-44301號公報的段落番號0076~0124、日本特開2012-8532號公報的段落番號0045~0078、日本特開2015-172102號公 報的段落番號0027~0067、日本特開2015-172004號公報的段落番號0029~0067、日本特開2015-40895號公報的段落番號0029~0085、日本特開2014-126642號公報的段落番號0022~0036、日本特開2014-148567號公報的段落番號0011~0017、日本特開2015-157893號公報的段落番號0010~0025、日本特開2014-095007號公報的段落番號0013~0026、日本特開2014-80487號公報的段落番號0013~0047及日本特開2013-227403號公報的段落番號0007~0028等，該內容編入本說明書中。 The pyrrolopyrrole compound can refer to paragraph number 0049-0062 of Unexamined-Japanese-Patent No. 2010-222557, The content is incorporated in this specification. Cyanine compounds and squaraine compounds can refer to paragraph numbers 0022-0063 of International Publication No. 2014/088063, paragraph numbers 0053-0118 of International Publication No. 2014/030628, and paragraphs of JP-A-2014-59550 Serial number 0028~0074, paragraph number 0013~0091 of International Publication No. 2012/169447, paragraph number 0019~0033 of Japanese Patent Application Laid-Open No. 2015-176046, paragraph number 0053 of Japanese Patent Application Publication No. 2014-63144 ~0099, paragraph numbers 0085~0150 of JP 2014-52431, paragraph numbers 0076~0124 of JP 2014-44301, paragraph numbers 0045~0078 of JP 2012-8532 , Japanese Patent Laid-Open No. 2015-172102 Paragraph numbers 0027~0067 of the newspaper, paragraph numbers 0029~0067 of the Japanese Patent Application Publication No. 2015-172004, paragraph numbers 0029~0085 of the Japanese Patent Application Publication No. 2015-40895, and paragraph numbers of the Japanese Patent Application Publication No. 2014-126642 Paragraph numbers 0022~0036, paragraph numbers 0011~0017 of Japanese Patent Application Publication No. 2014-148567, paragraph numbers 0010~0025 of Japanese Patent Application Publication No. 2015-157893, paragraph numbers of Japanese Patent Application Publication No. 2014-095007 Nos. 0013 to 0026, paragraph numbers 0013 to 0047 of JP-A No. 2014-80487, and paragraph numbers 0007-0028 of JP-A No. 2013-227403 are included in this specification.

紅外線吸收劑係選自包含以下述式1~3表示之化合物之群組之至少1種為較佳。 The infrared absorber is preferably at least one selected from the group consisting of compounds represented by the following formulas 1 to 3.

Figure 106127429-A0305-02-0052-23
Figure 106127429-A0305-02-0052-23

式1中，A1及A2分別獨立地表示芳基、雜芳基或以下述式1-A表示之基。 In Formula 1, A 1 and A 2 each independently represent an aryl group, a heteroaryl group, or a group represented by the following Formula 1-A.

Figure 106127429-A0305-02-0052-24
Figure 106127429-A0305-02-0052-24

式1-A、Z1A表示形成含氮雜環之非金屬原子團，R2A表示烷基、烯基或芳烷基，d表示0或1，波浪線表示連結鍵。 Formula 1-A, Z 1A represents a non-metallic atomic group forming a nitrogen-containing heterocycle, R 2A represents an alkyl, alkenyl or aralkyl group, d represents 0 or 1, and the wavy line represents a connecting bond.

Figure 106127429-A0305-02-0053-25
Figure 106127429-A0305-02-0053-25

式2中，R1a及R1b分別獨立地表示烷基、芳基或雜芳基，R2~R5分別獨立地表示氫原子或取代基，R2與R3、R4與R5可分別鍵結而形成環，R6、及R7分別獨立地表示氫原子、烷基、芳基、雜芳基、-BRARB或金屬原子，RA及RB分別獨立地表示氫原子或取代基，R6可與R1a或R3共價鍵結或配位鍵結，R7可與R1b或R5共價鍵結或配位鍵結。 In Formula 2, R 1a and R 1b independently represent an alkyl group, an aryl group or a heteroaryl group, R 2 ~ R 5 independently represent a hydrogen atom or a substituent, R 2 and R 3 , R 4 and R 5 can be Each is bonded to form a ring, R 6 and R 7 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group , -BR A R B or a metal atom, and RA and R B each independently represent a hydrogen atom or a substituent, R6 may be covalently or coordinately bonded to R1a or R3 , and R7 may be covalently or coordinately bonded to R1b or R5 .

Figure 106127429-A0305-02-0053-26
Figure 106127429-A0305-02-0053-26

式3中，Z1及Z2分別獨立地為形成可以縮環之5員或6員的含氮雜環之非金屬原子團，R101及R102分別獨立地表示烷基、烯基、炔基、芳烷基或芳基， L1表示包含奇數個次甲基之次甲基鏈，a及b分別獨立地為0或1，a為0時，碳原子與氮原子以雙鍵鍵結，b為0時，碳原子與氮原子以單鍵鍵結，式中以Cy表示之部位為陽離子部時，X1表示陰離子，c表示為了維持電荷的平衡而所需之數，式中以Cy表示之部位為陰離子部時，X1表示陽離子，c表示為了維持電荷的平衡而所需之數，式中以Cy表示之部位的電荷在分子內被中和時，c為0。 In Formula 3, Z 1 and Z 2 are each independently a non-metallic atomic group that forms a 5-membered or 6-membered nitrogen-containing heterocyclic ring that can be condensed, and R 101 and R 102 independently represent an alkyl group, an alkenyl group, or an alkynyl group , aralkyl group or aryl group, L 1 represents a methine chain containing an odd number of methine groups, a and b are independently 0 or 1, and when a is 0, a carbon atom and a nitrogen atom are bonded with a double bond, When b is 0, the carbon atom and the nitrogen atom are bonded with a single bond. When the part represented by Cy in the formula is a cationic part, X1 represents an anion, and c represents the number required to maintain the balance of charges. In the formula, Cy When the part represented is an anion part, X1 represents a cation, c represents the number required to maintain the balance of charges, and when the charge of the part represented by Cy in the formula is neutralized in the molecule, c is 0.

(顏料衍生物) (pigment derivatives)

硬化性組成物可含有顏料衍生物。顏料衍生物係具有藉由酸性基、鹼性基或鄰苯二甲酸亞胺甲基取代有機顏料的一部分之結構之化合物為較佳。作為顏料衍生物，從著色劑A的分散性及分散穩定性的觀點考慮，具有酸性基或鹼性基之顏料衍生物為較佳。顏料衍生物具有鹼性基尤為佳。並且，上述樹脂(分散劑)與顏料衍生物的組合係分散劑為酸性分散劑且顏料衍生物具有鹼性基之組合為較佳。 The curable composition may contain pigment derivatives. The pigment derivative is preferably a compound having a structure in which a part of the organic pigment is substituted with an acidic group, a basic group, or a phthalimide methyl group. As the pigment derivative, those having an acidic group or a basic group are preferable from the viewpoint of the dispersibility and dispersion stability of the colorant A. It is especially preferred that the pigment derivative has a basic group. Furthermore, the above-mentioned combination of the resin (dispersant) and the pigment derivative is preferably a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group.

作為用於構成顏料衍生物之有機顏料，可舉出二氧代吡咯并吡咯系顏料、偶氮系顏料、酞菁系顏料、蒽醌系顏料、喹吖啶酮系顏料、二噁嗪系顏料、紫環酮系顏料、苝系顏料、硫靛系顏料、異吲哚啉系顏料、異吲哚啉酮系顏料、喹酞酮系顏料、士林系顏料、金屬絡合物系顏料等。 Examples of organic pigments used to constitute pigment derivatives include dioxopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, and dioxazine pigments. , peroxide pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, shihlin pigments, metal complex pigments, etc.

並且，作為顏料衍生物所具有之酸性基，磺酸基、羧酸基及其鹽為較佳，羧酸基及磺酸基為進一步較佳，磺酸基尤為佳。作為顏料衍生物所具有之鹼性基，胺基為較佳，三級胺基尤為佳。 Furthermore, as the acidic group possessed by the pigment derivative, a sulfonic acid group, a carboxylic acid group and their salts are preferred, a carboxylic acid group and a sulfonic acid group are further preferred, and a sulfonic acid group is particularly preferred. As the basic group of the pigment derivative, an amine group is preferable, and a tertiary amine group is particularly preferable.

從所獲得之硬化膜具有更優異的遮光性之角度考慮，上述硬化性組成物在400~1100nm的波長區域中的每1.5μm的膜厚的光學濃度(OD：Optical Dnsity)為2.5以上為較佳，3.0以上為更佳。另外，上限值並無特別限制，通常，5.0以下為較佳。利用具有上述特性之硬化性組成物來形成之硬化膜能夠較佳地用作遮光膜(黑矩陣)。 From the viewpoint that the obtained cured film has more excellent light-shielding properties, the optical density (OD: Optical Density) of the above-mentioned curable composition per 1.5 μm film thickness in the wavelength range of 400 to 1100 nm is relatively 2.5 or more. Good, more than 3.0 is better. In addition, the upper limit is not particularly limited, but generally, it is preferably 5.0 or less. A cured film formed using a curable composition having the above characteristics can be preferably used as a light-shielding film (black matrix).

另外，本說明書中，光學濃度表示藉由實施例中記載之方法測定之光學濃度。並且，本說明書中，400~1100nm的波長區域中的每1.5μm的膜厚的光學濃度為2.5以上表示，在波長400~1100nm的整個區域，每1.5μm的膜厚的光學濃度為2.5以上。 In addition, in this specification, an optical density shows the optical density measured by the method described in an Example. In addition, in this specification, the optical density per film thickness of 1.5 μm in the wavelength region of 400 to 1100 nm is 2.5 or more, and the optical density per film thickness of 1.5 μm in the entire wavelength range of 400 to 1100 nm is 2.5 or more.

[硬化性組成物的製造方法] [Manufacturing method of curable composition]

硬化性組成物能夠藉由公知的混合方法(例如，利用攪拌機、均質器、高壓乳化裝置、濕式粉碎機或濕式分散機之混合方法)混合上述各種成分來製備。 The curable composition can be prepared by mixing the above-mentioned various components by a known mixing method (for example, a mixing method using a mixer, a homogenizer, a high-pressure emulsification device, a wet pulverizer, or a wet disperser).

製備硬化性組成物時，可總括配合各成分，亦可在將各成分分別溶解或分散於溶劑之後依次配合。並且，配合時的投入順序及作業條件並無特別限制。 When preparing a curable composition, each component may be compounded collectively, or may be compounded sequentially after dissolving or dispersing each component in a solvent. In addition, there are no particular restrictions on the input order and working conditions at the time of compounding.

為了去除異物和/或減少缺陷等，用過濾器過濾硬化性組成物為較佳。作為過濾器，只要係過濾用，則能夠無特別限制地使用。例如，可舉出基於如下之過濾器：PTFE(聚四氟乙烯)等氟樹脂；尼龍等聚醯胺系樹脂；聚乙烯、聚丙烯(PP)等聚烯烴系樹脂(包括高密度、超高分子量)；等。其中，作為過濾器的材料，聚丙烯(包括高密度聚丙烯)或尼龍為較佳。 In order to remove foreign matter and/or reduce defects, it is preferable to filter the curable composition with a filter. As the filter, any filter can be used without particular limitation as long as it is for filtration. For example, filters based on fluorine resins such as PTFE (polytetrafluoroethylene); polyamide resins such as nylon; polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high molecular weight); etc. Among them, as the filter material, polypropylene (including high-density polypropylene) or nylon is preferable.

過濾器的孔徑為0.1~7.0μm為較佳，0.2~2.5μm為更佳，0.2~1.5μm 為進一步較佳，0.3~0.7μm尤為佳。藉由設為該範圍，能夠抑制顏料的過濾堵塞，並且能夠可靠地去除顏料中包含之雜質及凝聚物等微細的異物。 The pore size of the filter is preferably 0.1~7.0μm, more preferably 0.2~2.5μm, 0.2~1.5μm More preferably, 0.3-0.7 μm is particularly preferred. By setting it as this range, filter clogging of a pigment can be suppressed, and fine foreign matter, such as the impurity contained in a pigment, and an aggregate, can be reliably removed.

使用過濾器時，可組合不同過濾器。此時，藉由第1過濾器的過濾可以係1次，亦可以係2次以上。組合不同過濾器來進行2次以上的過濾時，第2次之後的孔徑與第1次過濾的孔徑相比，相同或更大為較佳。並且，亦可組合在上述範圍內不同之孔徑的第1過濾器。此處的孔徑能夠參閱過濾器製造商的公稱值。作為市售的過濾器，例如，能夠從由NIHON PALL LTD.、AdvantecToyo Kaisha,Ltd.、Nihon Entegris K.K.(原Mykrolis Corpration)或KITZ MICROFILTER CORPORATION等提供之各種過濾器中選擇。 When using filters, different filters can be combined. At this time, the filtration by the first filter may be performed once, or may be performed twice or more. When performing two or more filtrations in combination with different filters, it is preferable that the pore diameter after the second filtration be the same or larger than the pore diameter of the first filtration. In addition, first filters having different pore diameters within the above-mentioned range may be combined. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, it is possible to select from various filters provided by NIHON PALL LTD., Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (formerly Mykrolis Corporation), KITZ MICROFILTER CORPORATION, and the like.

第2過濾器能夠使用由與上述第1過濾器相同的材料等形成者。第2過濾器的孔徑為0.2~10.0μm程度為較佳，0.2~7.0μm為更佳，0.3~6.0μm為進一步較佳。 As the second filter, one formed of the same material as that of the above-mentioned first filter can be used. The pore diameter of the second filter is preferably about 0.2 to 10.0 μm, more preferably 0.2 to 7.0 μm, and still more preferably 0.3 to 6.0 μm.

硬化性組成物不含有金屬、包含鹵之金屬鹽、酸及鹼等雜質為較佳。作為該些材料中包含之雜質的含量，1ppm以下為較佳，1ppb以下為更佳，100ppt以下為進一步較佳，10ppt以下尤為佳，實際上不含有(測定裝置的檢測極限以下)為最佳。 It is preferable that the curable composition does not contain impurities such as metals, metal salts including halogens, acids, and alkalis. The content of impurities contained in these materials is preferably not more than 1 ppm, more preferably not more than 1 ppb, more preferably not more than 100 ppt, particularly preferably not more than 10 ppt, and most preferably not containing (below the detection limit of the measuring device) .

另外，上述雜質能夠藉由電感耦合等離子體質量分析裝置(Analytical systems Inc.製造、Agilent 7500cs型)進行測定。 In addition, the above-mentioned impurities can be measured with an inductively coupled plasma mass spectrometer (manufactured by Analytical Systems Inc., Agilent 7500cs model).

[硬化膜及其製造方法] [Cured film and its manufacturing method]

能夠藉由硬化性組成物形成硬化膜。 A cured film can be formed with a curable composition.

硬化膜的厚度並無特別限制，0.2~25μm為較佳。 The thickness of the cured film is not particularly limited, but is preferably 0.2-25 μm.

上述厚度為平均厚度，係測定硬化膜的任意的5點以上的厚度並對該 些進行算術平均之值。 The above-mentioned thickness is an average thickness, which is measured at any 5 or more points of the cured film and These are the values of the arithmetic mean.

硬化膜的製造方法並無特別限制，可舉出將上述硬化性組成物塗佈於基板上來形成塗膜，對塗膜實施硬化處理來製造硬化膜之方法。 The method for producing the cured film is not particularly limited, and examples thereof include a method in which a cured film is produced by applying the curable composition above to a substrate to form a coating film, and then subjecting the coating film to a curing treatment.

硬化處理的方法並無特別限制，可舉出光硬化處理或熱硬化處理，從圖案形成較容易之角度考慮，光硬化處理(尤其，基於光化射線或放射線的照射之硬化處理)為較佳。 The method of hardening treatment is not particularly limited, and photohardening treatment or thermosetting treatment can be mentioned. From the viewpoint of easier pattern formation, photohardening treatment (especially, hardening treatment based on irradiation of actinic rays or radiation) is preferred. .

本發明的實施形態之硬化膜係使利用上述硬化性組成物形成之硬化性組成物層硬化來獲得之硬化膜。 The cured film according to the embodiment of the present invention is a cured film obtained by curing the curable composition layer formed from the curable composition described above.

作為硬化膜的製造方法，並無特別限制，具有以下的步驟為較佳。 Although it does not specifically limit as a manufacturing method of a cured film, It is preferable to have the following steps.

‧硬化性組成物層形成步驟 ‧Formation step of curable composition layer

‧曝光步驟 ‧Exposure steps

‧顯影步驟 ‧Development step

以下，對各步驟進行說明。 Each step will be described below.

<硬化性組成物層形成步驟> <Formation Step of Curable Composition Layer>

硬化性組成物層形成步驟係利用上述硬化性組成物形成硬化性組成物層之步驟。作為利用硬化性組成物形成硬化性組成物層之步驟，例如，可舉出在基板上塗佈硬化性組成物來形成硬化性組成物層之步驟。 The step of forming a curable composition layer is a step of forming a curable composition layer using the above curable composition. As a step of forming a curable composition layer using a curable composition, for example, a step of applying a curable composition on a substrate to form a curable composition layer can be mentioned.

基板的種類並無特別限制，用作固態攝影元件時，例如，可舉出矽基板，用作彩色濾光片(包含固態攝影元件用彩色濾光片)時，可舉出玻璃基板等。 The type of the substrate is not particularly limited, and when used as a solid-state imaging device, for example, a silicon substrate is used, and when used as a color filter (including a color filter for a solid-state imaging device), a glass substrate is used.

作為向基板上塗佈硬化性組成物之方法，能夠適用旋塗法、狹縫塗佈、噴墨法、噴射塗佈、旋轉塗佈、流延塗佈、輥塗佈及網板印刷法等各種塗佈方法。 As a method of coating a curable composition on a substrate, spin coating, slit coating, inkjet method, jet coating, spin coating, cast coating, roll coating, screen printing, etc. can be applied. Various coating methods.

塗佈於基板上之硬化性組成物通常在70~150℃下乾燥1~4分鐘，從而形成硬化性組成物層。 The curable composition coated on the substrate is usually dried at 70-150° C. for 1-4 minutes to form a curable composition layer.

<曝光步驟> <Exposure step>

曝光步驟係經由具備圖案狀開口部之光罩，對在硬化性組成物層形成步驟中形成之硬化性組成物層照射光化射線或放射線來進行曝光之步驟。 The exposing step is a step of exposing the curable composition layer formed in the curable composition layer forming step by irradiating actinic rays or radiation through a photomask having patterned openings.

曝光藉由放射線的照射進行為較佳，作為曝光時能夠使用之放射線，可舉出g射線、h射線及i射線等紫外線，作為光源可舉出高壓水銀燈。照射強度為5~1500mJ/cm2為較佳，10~1000mJ/cm2為更佳。 Exposure is preferably performed by irradiation with radiation. Examples of radiation that can be used for exposure include ultraviolet rays such as g-rays, h-rays, and i-rays, and examples of light sources include high-pressure mercury lamps. The irradiation intensity is preferably 5~1500mJ/cm 2 , more preferably 10~1000mJ/cm 2 .

<顯影步驟> <Development step>

接著曝光步驟進行顯影處理(顯影步驟)，使曝光步驟中的光未照射部分溶出於顯影液。藉此，僅殘留已光硬化之部分。 Following the exposure step, a development treatment (development step) is performed to dissolve the portion not irradiated with light in the exposure step in a developing solution. Thereby, only the photohardened part remains.

作為顯影液，可使用鹼顯影液。此時，使用有機鹼顯影液為較佳。作為顯影溫度，通常，20~30℃為較佳，顯影時間為20~90秒為較佳。 As a developing solution, an alkali developing solution can be used. At this time, it is better to use an organic alkali developer. Usually, 20-30 degreeC is preferable as image development temperature, and 20-90 second is preferable for image development time.

作為鹼水溶液(鹼顯影液)，例如，作為無機系顯影液，可舉出將氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、矽酸鈉及偏矽酸鈉等鹼性化合物，溶解成濃度為0.001~10質量%，較佳地為0.005~0.5質量%之鹼水溶液。 As an alkaline aqueous solution (alkaline developing solution), for example, as an inorganic developing solution, alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate are dissolved. Aqueous alkali solution with a concentration of 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass.

並且，作為有機鹼顯影液，可舉出將氨水、乙胺、二乙胺、二甲基乙醇胺、氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化芐基三甲基銨、膽鹼、吡咯、哌啶及1,8-二氮雜雙環-[5,4,0]-7-十一碳烯等鹼性化合物，溶解成濃度為0.001~10質量%，較佳地為0.005~0.5質量%之鹼水溶液。 In addition, examples of organic alkali developing solutions include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrahydroxide Basic compounds such as butylammonium, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo-[5,4,0]-7-undecene, dissolved Aqueous alkali solution with a concentration of 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass.

鹼水溶液中，例如，能夠添加適量的甲醇、乙醇等水溶性有機溶劑和/ 或界面活性劑等。另外，使用包含該種鹼水溶液之顯影液時，通常在顯影後以純水清洗(沖洗)遮光膜。 In the alkaline aqueous solution, for example, water-soluble organic solvents such as methanol, ethanol and/or an appropriate amount can be added or surfactants, etc. In addition, when using a developing solution containing such an aqueous alkali solution, the light-shielding film is usually washed (rinsed) with pure water after development.

另外，硬化膜的製造方法可含有其他步驟。 In addition, the manufacturing method of a cured film may contain another process.

作為其他步驟，並無特別限制，能夠需要適當選擇。 There are no particular limitations on other steps, and appropriate selection may be required.

作為其他步驟，例如，可舉出基材的表面處理步驟、前加熱步驟(預烘烤步驟)、後加熱步驟(後烘烤步驟)等。 As other steps, for example, a surface treatment step of a base material, a pre-heating step (pre-baking step), a post-heating step (post-baking step), and the like can be mentioned.

上述前加熱步驟及後加熱步驟之加熱溫度為80~300℃為較佳。 The heating temperature of the above-mentioned pre-heating step and post-heating step is preferably 80-300°C.

上限為220℃以下為更佳。下限為90℃以上為較佳。 The upper limit is more preferably 220°C or less. The lower limit is preferably 90°C or higher.

前加熱步驟及後加熱步驟之加熱時間為30~300秒為較佳。 The heating time of the pre-heating step and the post-heating step is preferably 30 to 300 seconds.

[固態攝像裝置及固態攝影元件] [Solid-state imaging device and solid-state imaging element]

本發明的實施形態之固態攝像裝置及固態攝影元件含有上述硬化膜。作為固態攝影元件含有硬化膜之態樣，並無特別限制，例如，可舉出如下結構者：在基板上具有構成固態攝影元件(CCD圖像感測器、CMOS圖像感測器等)的受光區之複數個包含光電二極體及多晶矽等之受光元件，在支撐體的受光元件形成面側(例如，受光部以外的部分和/或顏色調整用像素等)或該形成面的相反側具備本發明的硬化膜。 A solid-state imaging device and a solid-state imaging element according to an embodiment of the present invention include the above-mentioned cured film. There are no particular limitations on the aspect in which the solid-state imaging element includes a cured film. For example, one with a structure that constitutes a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) is provided on a substrate. A plurality of light-receiving elements in the light-receiving region, including photodiodes and polysilicon, are located on the side of the support where the light-receiving elements are formed (for example, parts other than the light-receiving part and/or pixels for color adjustment, etc.) or on the opposite side of the formation surface The cured film of this invention is provided.

固態攝像裝置含有上述固態攝影元件。 A solid-state imaging device includes the above-mentioned solid-state imaging element.

參閱圖1~圖2，對固態攝像裝置及固態攝影元件的結構例進行說明。另外，圖1~圖2中，為了使各部明確，無視彼此的厚度和/或寬度的比例，放大顯示一部分。 Referring to FIGS. 1 to 2 , configuration examples of the solid-state imaging device and the solid-state imaging element will be described. In addition, in FIGS. 1 to 2 , in order to clarify each part, a part is enlarged and displayed regardless of the ratio of mutual thickness and/or width.

如圖1所示，固態攝像裝置100具備：矩形狀的固態攝影元件101；及透明的蓋玻璃103，其保持於固態攝影元件101的上方，密封該固態攝影元 件101。而且，該蓋玻璃103上，經由間隔物104重疊設置有透鏡層111。透鏡層111由支撐體113及透鏡材料112構成。透鏡層111可以係支撐體113與透鏡材料112一體成型之結構。若雜散光入射於透鏡層111的周緣區域，則由於光的擴散，藉由透鏡材料112的聚光的效果減弱，到達攝像部102之光減少。並且，還產生雜散光引起之雜訊。故，該透鏡層111的周緣區域設置有遮光膜114來進行遮光。本發明的實施形態之硬化膜還能夠用作上述遮光膜114。 As shown in FIG. 1 , a solid-state imaging device 100 includes: a rectangular solid-state imaging element 101; and a transparent cover glass 103 held on top of the solid-state imaging element 101 to seal the solid-state imaging element piece 101. Furthermore, a lens layer 111 is superimposed on the cover glass 103 via a spacer 104 . The lens layer 111 is composed of a support body 113 and a lens material 112 . The lens layer 111 can be a structure in which the support body 113 and the lens material 112 are integrally formed. When stray light is incident on the peripheral region of the lens layer 111 , due to the diffusion of light, the effect of light collection by the lens material 112 is weakened, and the light reaching the imaging unit 102 decreases. In addition, noise caused by stray light is also generated. Therefore, the peripheral region of the lens layer 111 is provided with a light-shielding film 114 for light-shielding. The cured film according to the embodiment of the present invention can also be used as the above-mentioned light-shielding film 114 .

固態攝影元件101對成像於成為其受光面之攝像部102之光學圖像進行光電轉換來作為圖像信號而輸出。該固態攝影元件101具備層積有2張基板之層積基板105。層積基板105包含相同尺寸的矩形狀的晶片基板106及電路基板107，在晶片基板106的背面層積有電路基板107。 The solid-state imaging device 101 performs photoelectric conversion of an optical image formed on the imaging unit 102 serving as its light-receiving surface, and outputs it as an image signal. The solid-state imaging device 101 includes a laminated substrate 105 in which two substrates are laminated. The laminate substrate 105 includes a rectangular chip substrate 106 and a circuit substrate 107 of the same size, and the circuit substrate 107 is laminated on the back surface of the chip substrate 106 .

作為用作晶片基板106之基板的材料，並無特別限制，能夠利用公知的材料。 The material used as the substrate of the wafer substrate 106 is not particularly limited, and known materials can be used.

在晶片基板106的表面中央部設置有攝像部102。並且，若攝像部102的周緣區域入射有雜散光，則從該周緣區域內的電路產生暗電流(雜訊)，故，該周緣區域設置有遮光膜115來進行遮光。本發明的實施形態之硬化膜還能夠用作遮光膜115。 The imaging unit 102 is provided at the center of the surface of the wafer substrate 106 . Furthermore, if stray light enters the peripheral region of the imaging unit 102, dark current (noise) will be generated from circuits in the peripheral region, so the peripheral region is provided with a light-shielding film 115 for light-shielding. The cured film according to the embodiment of the present invention can also be used as the light shielding film 115 .

在晶片基板106的表面緣部設置有複數個電極墊108。電極墊108經由設置於晶片基板106的表面之未圖示的信號線(鍵合線亦可)，與攝像部102電性連接。 A plurality of electrode pads 108 are provided on the edge of the surface of the wafer substrate 106 . The electrode pads 108 are electrically connected to the imaging unit 102 via unillustrated signal wires (bonding wires are also acceptable) provided on the surface of the chip substrate 106 .

在電路基板107的背面，在各電極墊108的大致下方位置分別設置有外部連接端子109。各外部連接端子109經由垂直地貫穿層積基板105 之貫穿電極110，分別與電極墊108連接。並且，各外部連接端子109經由未圖示的配線，與控制固態攝影元件101的驅動之控制電路及對從固態攝影元件101輸出之攝像信號實施圖像處理之圖像處理電路等連接。 On the back surface of the circuit board 107 , external connection terminals 109 are respectively provided at substantially lower positions of the electrode pads 108 . Each external connection terminal 109 vertically penetrates through the laminated substrate 105 The penetrating electrodes 110 are respectively connected to the electrode pads 108 . In addition, each external connection terminal 109 is connected to a control circuit for controlling driving of the solid-state imaging device 101 , an image processing circuit for performing image processing on an imaging signal output from the solid-state imaging device 101 , and the like via unshown wiring.

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

作為基板204的材料，能夠使用與前述晶片基板106相同的材料。在基板204的表層形成有p孔層206。在該p孔層206內，以正方格子狀排列形成有包含n型層且藉由光電轉換生成信號電荷並蓄積之受光元件201。 As the material of the substrate 204, the same material as that of the aforementioned wafer substrate 106 can be used. A p-hole layer 206 is formed on the surface layer of the substrate 204 . In the p-hole layer 206, light-receiving elements 201 including an n-type layer and generating and accumulating signal charges by photoelectric conversion are formed in a square grid arrangement.

在受光元件201的一側，經由p孔層206的表層的讀取柵極部207，形成有包含n型層之垂直轉移路徑208。並且，在受光元件201的另一側，經由包含p型層之元件分離區域209，形成有屬於相鄰像素之垂直轉移路徑208。讀取柵極部207係用於將蓄積在受光元件201之信號電荷讀取至垂直轉移路徑208之信道區域。 On one side of the light-receiving element 201 , a vertical transfer path 208 including an n-type layer is formed via the reading gate portion 207 on the surface layer of the p-hole layer 206 . Furthermore, on the other side of the light receiving element 201, a vertical transfer path 208 belonging to adjacent pixels is formed through an element isolation region 209 including a p-type layer. The read gate portion 207 is used to read the signal charge accumulated in the light receiving element 201 to the channel region of the vertical transfer path 208 .

在基板204的表面上，形成有包含ONO(Oxide-Nitride-Oxide)膜之柵極絕緣膜210。在該柵極絕緣膜210上，以覆蓋垂直轉移路徑208、讀取柵極部207及元件分離區域209的大致正上方之方式，形成有包含多晶矽或非晶矽之垂直轉移電極211。垂直轉移電極211作為驅動垂直轉移路徑208來進行電荷轉移之驅動電極及驅動讀取柵極部207來使其讀取信號電荷之讀取電極而發揮作用。信號電荷從垂直轉移路徑208依次轉移至未圖示的水平轉移路徑及輸出部(浮動擴散放大器)之後，作為電壓信號來輸 出。 On the surface of the substrate 204, a gate insulating film 210 including an ONO (Oxide-Nitride-Oxide) film is formed. On the gate insulating film 210 , a vertical transfer electrode 211 made of polysilicon or amorphous silicon is formed so as to cover substantially directly above the vertical transfer path 208 , the reading gate portion 207 and the element isolation region 209 . The vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to perform charge transfer, and a read electrode that drives the read gate portion 207 to read signal charges. The signal charge is sequentially transferred from the vertical transfer path 208 to a not-shown horizontal transfer path and an output unit (floating diffusion amplifier), and then output as a voltage signal. out.

在垂直轉移電極211上，以覆蓋其表面之方式形成有遮光膜212。遮光膜212在受光元件201的正上方位置具有開口部，對除此以外的區域進行遮光。本發明的實施形態之硬化膜還能夠用作遮光膜212。 A light-shielding film 212 is formed on the vertical transfer electrode 211 so as to cover the surface. The light-shielding film 212 has an opening at a position directly above the light-receiving element 201 , and shields other regions from light. The cured film according to the embodiment of the present invention can also be used as the light-shielding film 212 .

在遮光膜212上，設置有包含如下之透明的中間層：包含BPSG(borophospho silicate glass)之絕緣膜213、包含P-SiN之絕緣膜(鈍化膜)214、包含透明樹脂等之平坦化膜215。彩色濾光片202形成於中間層上。 On the light-shielding film 212, there is provided a transparent intermediate layer including an insulating film 213 including BPSG (borophospho silicate glass), an insulating film (passivation film) 214 including P-SiN, and a planarizing film 215 including transparent resin, etc. . The color filter 202 is formed on the intermediate layer.

[黑矩陣] [Black Matrix]

黑矩陣含有本發明的實施形態之硬化膜。黑矩陣有時包含於彩色濾光片、固態攝影元件及液晶顯示裝置。 A black matrix contains the cured film which concerns on embodiment of this invention. Black matrices are sometimes included in color filters, solid-state imaging devices, and liquid crystal display devices.

作為黑矩陣，可舉出：上述中已說明者；設置於液晶顯示裝置等顯示裝置的周緣部之黑色邊緣；紅、藍及綠的像素之間的格子狀和/或條紋狀的黑色部分；用於TFT(thin film transistor)遮光的點狀和/或線狀的黑色圖案等。對於該黑矩陣的定義，例如，菅野泰平著、“液晶顯示器製造裝置用語辭典”、第2版、NIKKAN KOGYO SHIMBUN,LTD.、1996年、p.64中有記載。 Examples of the black matrix include: those described above; black borders provided on the periphery of display devices such as liquid crystal display devices; grid-like and/or stripe-like black parts between red, blue, and green pixels; Dot-shaped and/or linear black patterns for TFT (thin film transistor) light-shielding, etc. The definition of the black matrix is described in, for example, Yahei Kanno, "A Dictionary of Liquid Crystal Display Manufacturing Apparatus Terms", 2nd Edition, NIKKAN KOGYO SHIMBUN, LTD., 1996, p.64.

由於黑矩陣提高顯示對比度，並且在使用薄膜晶體管(TFT)之有源矩陣驅動方式的液晶顯示裝置之情況下，防止光的電流洩露引起之畫質下降，故具有較高遮光性(光學濃度OD為3以上)為較佳。 Because the black matrix improves the display contrast, and in the case of a liquid crystal display device using an active matrix drive method of a thin film transistor (TFT), it prevents the image quality from being reduced due to the current leakage of light, so it has a high light-shielding property (optical density OD 3 or more) is preferred.

作為黑矩陣的製造方法，並無特別限制，能夠藉由與上述硬化膜的製造方法相同的方法製造。具體而言，能夠在基板塗佈硬化性組成物來形成硬化性組成物層，進行曝光及顯影來製造圖案狀的硬化膜(黑矩陣)。另外，作為用作黑矩陣之硬化膜的膜厚，0.1~4.0μm為較佳。 It does not specifically limit as a manufacturing method of a black matrix, It can manufacture by the method similar to the manufacturing method of the said cured film. Specifically, a curable composition can be applied on a substrate to form a curable composition layer, followed by exposure and development to produce a patterned cured film (black matrix). Moreover, as a film thickness of the cured film used as a black matrix, 0.1-4.0 micrometers are preferable.

作為上述基板的材料，並無特別限制，相對於可見光(波長：400~800nm)，具有80%以上的透射率為較佳。作為該種材料，具體而言，例如可舉出：鈉鈣玻璃、無鹼玻璃、石英玻璃及硼矽酸玻璃等玻璃；聚酯系樹脂及聚烯烴矽樹脂等塑膠；等，從耐化學藥品性及耐熱性的觀點，無鹼玻璃或石英玻璃等為較佳。 The material of the substrate is not particularly limited, and preferably has a transmittance of 80% or higher with respect to visible light (wavelength: 400-800 nm). As such materials, concretely, for example, glass such as soda-lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resin and polyolefin silicone resin; etc., from chemical resistance From the standpoint of properties and heat resistance, non-alkali glass, quartz glass, etc. are preferable.

[彩色濾光片] [color filter]

本發明的實施形態之彩色濾光片含有硬化膜。 The color filter according to the embodiment of the present invention includes a cured film.

作為彩色濾光片含有硬化膜之形態，並無特別限制，可舉出具備基板及上述黑矩陣之彩色濾光片。亦即，能夠例示具備形成於形成為基板狀之上述黑矩陣的開口部之紅色、綠色及藍色的著色像素之彩色濾光片。 Although it does not specifically limit as a form which a color filter contains a cured film, The color filter provided with the board|substrate and the said black matrix is mentioned. That is, the color filter provided with the red, green, and blue colored pixel formed in the opening part of the said black matrix formed in the board|substrate shape can be illustrated.

含有黑矩陣(硬化膜)之彩色濾光片例如能夠藉由以下方法製造。 A color filter including a black matrix (cured film) can be manufactured by the following method, for example.

首先，在形成為基板狀之圖案狀的黑矩陣的開口部，形成含有與彩色濾光片的各著色像素對應之顏料之樹脂組成物的塗膜(樹脂組成物層)。另外，作為各顏色用樹脂組成物，並無特別限制，能夠使用公知的樹脂組成物，但本發明的實施形態之硬化性組成物中，使用將含金屬氮化物粒子替換為與各像素對應之著色劑者為較佳。 First, a coating film (resin composition layer) of a resin composition containing a pigment corresponding to each colored pixel of the color filter is formed on the openings of the patterned black matrix formed in the form of a substrate. In addition, the resin composition for each color is not particularly limited, and a known resin composition can be used, but in the curable composition according to the embodiment of the present invention, a metal nitride particle corresponding to each pixel is used instead of a metal nitride particle. Colorants are preferred.

接著，經由具有與黑矩陣的開口部對應之圖案之光罩對樹脂組成物層進行曝光。接著，藉由顯影處理去除未曝光部之後，進行烘烤，藉此能夠在黑矩陣的開口部形成著色像素。例如利用含有紅色、綠色及藍色顏料之各顏色用樹脂組成物進行一系列操作，藉此能夠製造具有紅色、綠色及藍色像素之彩色濾光片。 Next, the resin composition layer is exposed through a photomask having a pattern corresponding to the openings of the black matrix. Next, after removing the unexposed part by developing process, baking is performed, and the colored pixel can be formed in the opening part of a black matrix by this. For example, a color filter having red, green, and blue pixels can be produced by performing a series of operations using resin compositions for respective colors containing red, green, and blue pigments.

[液晶顯示裝置] [Liquid crystal display device]

本發明的實施形態之液晶顯示裝置含有硬化膜。作為液晶顯示裝置含有硬化膜之態樣，並無特別限制，可舉出已說明之包含含有黑矩陣(硬化膜)之彩色濾光片之形態。 The liquid crystal display device of embodiment of this invention contains a cured film. The form in which the liquid crystal display device includes the cured film is not particularly limited, and the form in which the color filter including the black matrix (cured film) described above is included.

作為本實施形態之液晶顯示裝置，例如，可舉出具備對置配置之一對基板及封入該些基板之間之液晶化合物之態樣。作為上述基板，如作為黑矩陣用基板已進行說明之內容。 As the liquid crystal display device of this embodiment, for example, an aspect including a pair of substrates arranged to face each other and a liquid crystal compound sealed between these substrates can be mentioned. As said board|substrate, what was already demonstrated as a board|substrate for black matrices is used.

作為上述液晶顯示裝置的具體態樣，例如，可舉出從使用者側依次含有偏光板/基板/彩色濾光片/透明電極層/取向膜/液晶層/取向膜/透明電極層/TFT(ThinFilmTransistor)元件/基板/偏光板/背光單元之層積體。 As a specific aspect of the above-mentioned liquid crystal display device, for example, a polarizing plate/substrate/color filter/transparent electrode layer/alignment film/liquid crystal layer/alignment film/transparent electrode layer/TFT ( ThinFilmTransistor) element/substrate/polarizer/backlight unit laminate.

另外，作為本發明的實施形態之液晶顯示裝置，並不限制在上述，例如可舉出記載於“電子顯示裝置(佐佐木 昭夫著、Kogyo Chosakai Publishing Co.,Ltd.1990年發行)”、“顯示裝置(伊吹 順章著、產業圖書(株)平成元年發行)”等之液晶顯示裝置。並且，例如可舉出記載於“第二代液晶顯示器技術(內田 龍男編輯、Kogyo Chosakai Publishing Co.,Ltd.1994年發行)”之液晶顯示裝置。 In addition, the liquid crystal display device as an embodiment of the present invention is not limited to the above, and examples thereof include "Electronic Display Devices (written by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd., 1990)", "Display Device (written by Junsho Ibuki, published by Sangyo Book Co., Ltd. in the first year of Heisei)" and other liquid crystal display devices. Also, for example, a liquid crystal display device described in "Second Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd., 1994)" can be mentioned.

[紅外線感測器] [Infrared sensor]

本發明的實施形態之紅外線感測器含有上述硬化膜。 An infrared sensor according to an embodiment of the present invention includes the above-mentioned cured film.

用圖3，對上述實施態樣之紅外線感測器進行說明。圖3所示之紅外線感測器300中，符號310係固態攝影元件。 The infrared sensor of the above embodiment will be described with reference to FIG. 3 . In the infrared sensor 300 shown in FIG. 3 , symbol 310 is a solid-state imaging element.

設置於固態攝影元件310上之攝像區域組合紅外線吸收濾波器311與本發明的實施形態之彩色濾光片312而構成。 The imaging region provided on the solid-state imaging device 310 is composed of an infrared absorption filter 311 and a color filter 312 according to an embodiment of the present invention.

紅外線吸收濾波器311係使可見光線區域的光(例如，波長400~700nm 的光)透射，並遮蔽紅外區域的光(例如，波長800~1300nm的光，波長900~1200nm的光為較佳，波長900~1000nm的光為更佳)之膜，能夠使用作為著色劑含有紅外線吸收劑(作為紅外線吸收劑的態樣，如已進行說明。)之使用本發明的實施形態之硬化膜。 Infrared absorption filter 311 is to make light in the visible light region (for example, wavelength 400~700nm The film that transmits and shields light in the infrared region (for example, light with a wavelength of 800~1300nm, light with a wavelength of 900~1200nm is better, and light with a wavelength of 900~1000nm is better), can be used as a colorant containing Infrared ray absorbing agent (As an aspect of an infrared ray absorbing agent, it has already been described.) Use the cured film of embodiment of this invention.

彩色濾光片312係形成有對可見光線區域的特定波長的光進行透射或吸收之像素之彩色濾光片，例如，使用形成有紅色(R)、綠色(G)、藍色(B)的像素之彩色濾光片等，其態樣如已進行說明。紅外線透射濾波器313與固態攝影元件310之間配置有能夠使透射紅外線透射濾波器313之波長的光透射之樹脂膜314(例如，透明樹脂膜等)。 The color filter 312 is a color filter formed with pixels that transmit or absorb light of a specific wavelength in the visible ray range, for example, red (R), green (G), and blue (B) pixels are used. The color filter of the pixel and the like are as described above. Between the infrared transmission filter 313 and the solid-state imaging device 310 is arranged a resin film 314 (for example, a transparent resin film, etc.) capable of transmitting light of a wavelength passing through the infrared transmission filter 313 .

紅外線透射濾波器313係具有可見光線遮蔽性且使特定波長的紅外線透射之濾波器，能夠使用含有吸收可見光線區域的光之著色劑(例如，苝化合物和/或二苯并呋喃化合物等)及紅外線吸收劑(例如，吡咯并吡咯化合物、酞菁化合物、萘酞菁化合物及聚次甲基化合物等)之本發明的實施形態之硬化膜。紅外線透射濾波器313例如遮光波長400~830nm的光並使波長900~1300nm的光透射為較佳。 The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength, and can use a colorant that absorbs light in the visible light region (for example, a perylene compound and/or a dibenzofuran compound, etc.) and The cured film of embodiment of this invention which uses an infrared absorber (for example, a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, a polymethine compound, etc.). It is preferable that the infrared transmission filter 313 blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1300 nm, for example.

在彩色濾光片312及紅外線透射濾波器313的入射光hν側配置有微透鏡315。以覆蓋微透鏡315之方式形成有平坦化膜316。 A microlens 315 is disposed on the incident light hν side of the color filter 312 and the infrared transmission filter 313 . A planarizing film 316 is formed to cover the microlens 315 .

圖3所示之實施形態中，配置有樹脂膜314，但亦可代替樹脂膜314形成紅外線透射濾波器313。亦即，可在固態攝影元件310上形成紅外線透射濾波器313。 In the embodiment shown in FIG. 3 , the resin film 314 is disposed, but the infrared transmission filter 313 may be formed instead of the resin film 314 . That is, the infrared transmission filter 313 can be formed on the solid-state imaging device 310 .

並且，圖3所示之實施形態中，彩色濾光片312的膜厚與紅外線透射濾波器313的膜厚相同，但兩者的膜厚亦可不同。 Moreover, in the embodiment shown in FIG. 3, the film thickness of the color filter 312 and the film thickness of the infrared transmission filter 313 are the same, but the film thickness of both may differ.

並且，圖3所示之實施形態中，彩色濾光片312設置於比紅外線吸收濾波器311更靠入射光hν側，但亦可替換紅外線吸收濾波器311與彩色濾光片312的順序，將紅外線吸收濾波器311設置於比彩色濾光片312更靠入射光hν側。 In addition, in the embodiment shown in FIG. 3, the color filter 312 is provided on the incident light hν side of the infrared absorption filter 311, but the order of the infrared absorption filter 311 and the color filter 312 may be replaced, and the The infrared absorption filter 311 is provided on the incident light hν side with respect to the color filter 312 .

並且，圖3所示之實施形態中，相鄰層積有紅外線吸收濾波器311與彩色濾光片312，但兩個濾波器並不一定要相鄰，兩者之間可設置有其他層。 Furthermore, in the embodiment shown in FIG. 3 , the infrared absorption filter 311 and the color filter 312 are laminated adjacent to each other, but the two filters do not have to be adjacent to each other, and other layers may be provided between them.

依該紅外線感測器，能夠同時讀入圖像資訊，故能夠進行識別檢測動作之對象之運動感測等。而且，由於能夠獲取距離資訊，故還能夠進行包含3D資訊之圖像的攝影等。 According to the infrared sensor, image information can be read in at the same time, so it is possible to perform motion sensing, etc., to identify and detect objects that are moving. Furthermore, since the distance information can be acquired, it is also possible to photograph an image including 3D information.

接著，對適用上述紅外線感測器之固態攝像裝置進行說明。 Next, a solid-state imaging device to which the above-mentioned infrared sensor is applied will be described.

上述固態攝像裝置含有透鏡光學系統、固態攝影元件及紅外發光二極體等。另外，對於固態攝像裝置的各結構，能夠參閱日本特開2011-233983號公報的段落0032~0036，該內容編入本申請說明書中。 The solid-state imaging device includes a lens optical system, a solid-state imaging element, an infrared light-emitting diode, and the like. In addition, for each configuration of the solid-state imaging device, paragraphs 0032 to 0036 of JP-A-2011-233983 can be referred to, and the contents thereof are incorporated in the specification of the present application.

並且，上述硬化膜適於個人計算機、平板電腦、移動電話、智能手機及數位相機等便攜式設備；多功能打印機及掃描儀等OA(Office Aut omation(辦公室自動化))設備；監視攝影機、條碼讀取器、自動存提款機(ATM：automated teller machine)、高速相機及使用人臉圖像認證之具有本人認證功能之設備等產業用設備；車載用相機設備；內窺鏡、膠囊內窺鏡及導管等醫療用相機設備；生物體感測器、生物感測器(Biosensor)、軍事偵查用相機、立體地圖用相機、氣象及海洋觀測相機、陸地資源偵查相機、以及宇宙的天文及深空目標用勘探相機等航天設備等中使用之光學濾波器及模組的遮光構件及遮光膜，進一步適於防反射構件以及防反射膜。 In addition, the above-mentioned cured film is suitable for portable devices such as personal computers, tablet computers, mobile phones, smart phones, and digital cameras; OA (Office Automation) equipment such as multi-function printers and scanners; surveillance cameras, barcode reading devices, etc. Industrial equipment such as automatic deposit and withdrawal machines (ATM: automated teller machine), high-speed cameras, and equipment with identity authentication functions using face image authentication; vehicle-mounted camera equipment; endoscopes, capsule endoscopes, and Catheters and other medical camera equipment; biosensors, biosensors (Biosensor), cameras for military reconnaissance, cameras for three-dimensional maps, cameras for meteorological and oceanographic observation, cameras for terrestrial resources reconnaissance, and astronomical and deep space targets in the universe The light-shielding member and light-shielding film of an optical filter and module used in aerospace equipment such as a survey camera are further suitable for an anti-reflection member and an anti-reflection film.

上述硬化膜還能夠使用於微型LED(Light Emitting Diode(發光二極體))及微型OLED(Organic Light Emitting Diode(有機發光二極體))等用途。上述硬化膜除了微型LED及微型OLED中使用之光學濾波器及光學薄膜以外，還適於賦予遮光功能或防反射功能之構件。 The said cured film can also be used for uses, such as a micro LED (Light Emitting Diode (light emitting diode)) and a micro OLED (Organic Light Emitting Diode (organic light emitting diode)). The above-mentioned cured film is suitable for members imparting a light-shielding function or an anti-reflection function in addition to optical filters and optical films used in micro LEDs and micro OLEDs.

作為微型LED及微型OLED的例子，可舉出日本特表2015-500562號及日本特表2014-533890中記載者。 Examples of micro LEDs and micro OLEDs include those described in JP 2015-500562 and JP 2014-533890.

上述硬化膜適合作為量子點顯示器中使用之光學濾波器及光學薄膜。並且，上述硬化膜適合作為賦予遮光功能及防反射功能之構件。 The above-mentioned cured film is suitable as an optical filter and an optical film used in a quantum dot display. Moreover, the said cured film is suitable as a member which provides a light-shielding function and an antireflection function.

作為量子點顯示器的例子，可舉出美國專利申請公開第2013/0335677號、美國專利申請公開第2014/0036536號、美國專利申請公開第2014/0036203號及美國專利申請公開第2014/0035960號中記載者。 Examples of quantum dot displays include U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, and U.S. Patent Application Publication No. 2014/0035960. Recorder.

[實施例] [Example]

以下，依據實施例對本發明進行更詳細說明。以下實施例所示之材料、使用量、比例、處理內容及處理步驟等，只要不脫離本發明的宗旨，則能夠進行適當變更。故，本發明的範圍不應藉由以下所示之實施例限定地解釋。另外，關於%及份，除非另有指明，則表示質量基準。 Hereinafter, the present invention will be described in more detail based on examples. Materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the Examples shown below. In addition, about % and a part, unless otherwise indicated, it shows a mass standard.

[含金屬氮化物粒子的製作] [Production of Metal Nitride Particles]

藉由以下的方法，分別製作了含金屬氮化物粒子。 Metal-containing nitride particles were prepared by the following methods, respectively.

[含氮化鈦粒子TiN-1的製作] [Production of TiN-1 containing titanium nitride particles]

利用表1中記載之各成分製作了含氮化鈦粒子TiN-1。 Titanium nitride-containing particles TiN-1 were prepared using the components described in Table 1.

首先，將表1中記載之Ti粒子在Ar氣中進行等離子體處理，藉此獲得了Ti奈米粒子。將上述Ti奈米粒子在Ar氣體氣氛下，在O2濃度50ppm 以下、30℃的條件下靜置了24小時之後，在以O2濃度成為100ppm之方式向Ar氣體氣氛導入O2氣體之狀態下，將Ti奈米粒子在30℃下靜置24小時(將以上內容稱作“Ti粒子的前處理”。)。 First, Ti nanoparticles described in Table 1 were subjected to plasma treatment in Ar gas to obtain Ti nanoparticles. The above-mentioned Ti nanoparticles were left to stand at 30°C for 24 hours in an Ar gas atmosphere with an O 2 concentration of 50 ppm or less, and then O 2 gas was introduced into the Ar gas atmosphere so that the O 2 concentration became 100 ppm. , the Ti nanoparticles were left to stand at 30° C. for 24 hours (the above is referred to as “pretreatment of Ti particles”).

之後，利用Hosokawa Micron Corporation製造的TTSP分離器，以產率成為10%之條件下，對所獲得之Ti奈米粒子進行分級，從而獲得了Ti粒子粉末。對於所獲得之粉末的一次粒徑，藉由TEM(Transmission Electron Microscope)觀察，求出100個粒子的粒徑，進一步藉由該些的算術平均求出，其結果為120nm。 Thereafter, the obtained Ti nanoparticles were classified using a TTSP separator manufactured by Hosokawa Micron Corporation under the condition that the yield became 10%, thereby obtaining Ti particle powder. The primary particle diameter of the obtained powder was observed with a TEM (Transmission Electron Microscope), and the particle diameters of 100 particles were obtained. Further, the arithmetic mean of these was obtained, and the result was 120 nm.

利用依據國際公開第2010/147098號的圖1中記載的黑色複合微粒製造裝置之裝置製造了含氮化鈦粒子TiN-1。 Titanium nitride-containing particles TiN-1 were produced using an apparatus based on the apparatus for producing black composite fine particles described in FIG. 1 of International Publication No. 2010/147098.

具體而言，黑色複合微粒製造裝置中，對等離子體焰炬的高頻振蕩用線圈施加約4MHz及約80kVA的高頻電壓，從等離子氣體供給源，作為等離子氣體供給氬氣50L/min及氮50L/min的混合氣體，在等離子體焰炬內產生氬-氮熱等離子火焰。並且，從材料供給裝置的噴霧氣體供給源供給了10L/min的載體氣體(Ar氣)。 Specifically, in the production apparatus of black composite particles, a high-frequency voltage of about 4 MHz and about 80 kVA is applied to the high-frequency oscillation coil of the plasma torch, and argon gas 50 L/min and nitrogen gas are supplied as plasma gas from the plasma gas supply source. A mixed gas of 50L/min produces an argon-nitrogen thermal plasma flame in the plasma torch. Furthermore, 10 L/min of carrier gas (Ar gas) was supplied from the spray gas supply source of the material supply apparatus.

並且，以成為表1中記載之組成之方式，混合如上述那樣來獲得之Ti奈米粒子及表1中記載之添加粒子，與作為載體氣體之Ar氣一同供給至等離子體焰炬內的熱等離子體火焰中，使所供給之粒子在熱等離子體火焰中蒸發，使其以氣相狀態高度分散。 Then, the Ti nanoparticles obtained as described above and the additive particles described in Table 1 were mixed so as to have the composition described in Table 1, and were supplied to the heat in the plasma torch together with Ar gas as a carrier gas. In the plasma flame, the supplied particles are vaporized in the thermal plasma flame, and highly dispersed in a gas phase state.

並且，作為藉由氣體供給裝置供給至腔室內之氣體，使用了氮氣。作為此時的腔室內的氮氣的流速設為5m/sec，氮氣的供給量設為1000L/min。並且，將旋風分離器內的壓力設為50kPa，並且，將從腔室向旋風分離器供給 各原料之速度設為10m/s(平均值)。 In addition, nitrogen gas was used as the gas supplied into the chamber by the gas supply device. The flow velocity of the nitrogen gas in the chamber at this time was set to 5 m/sec, and the supply rate of the nitrogen gas was set to 1000 L/min. And, the pressure in the cyclone separator is set to 50kPa, and from the chamber to the cyclone separator The velocity of each raw material was set at 10 m/s (average value).

如此獲得了含氮化鈦粒子TiN-1。 TiN-1 containing titanium nitride particles was thus obtained.

對所獲得之含氮化鈦粒子TiN-1，藉由ICP(Inductively Coupled Plasma)發光分光分析法，測定了鈦(Ti)原子、鐵(Fe)原子及矽(Si)原子的含量。將結果示於表1。另外，ICP發光分光分析法中，利用了Seiko Instruments Inc.製造的ICP發光分光分析裝置“SPS3000”(商品名)。 The content of titanium (Ti) atoms, iron (Fe) atoms and silicon (Si) atoms in the obtained titanium nitride-containing particles TiN-1 was measured by ICP (Inductively Coupled Plasma) emission spectrometry. The results are shown in Table 1. In addition, in the ICP emission spectrometry, an ICP emission spectrometry apparatus "SPS3000" (trade name) manufactured by Seiko Instruments Inc. was used.

並且，利用HORIBA,Ltd.製造的氧.氮分析裝置“EMGA-620W/C”(商品名)測定並藉由惰性氣體熔融熱導法計算出了氮原子的含量。將結果示於表1。 In addition, the content of nitrogen atoms was measured by an oxygen-nitrogen analyzer "EMGA-620W/C" (trade name) manufactured by HORIBA, Ltd. and calculated by the inert gas fusion thermal conductivity method. The results are shown in Table 1.

另外，對後述之含氮化鈦粒子TiN-2~TiN-4，亦藉由與含氮化鈦粒子TiN-1相同的方法，測定了Ti原子、Fe原子、矽原子及氮原子的含量。將結果示於表1。 In addition, for titanium nitride-containing particles TiN-2 to TiN-4 described later, the contents of Ti atoms, Fe atoms, silicon atoms, and nitrogen atoms were measured by the same method as that of titanium nitride-containing particles TiN-1. The results are shown in Table 1.

關於含氮化鈦粒子TiN-1的X射線繞射，將粉末試料裝入於鋁製標準試料保持器，藉由廣角X射線繞射法(Rigaku Corporation製造、商品名“RU-200R”)進行測定。作為測定條件，X射線源設為CuKα射線，輸出設為50kV/200mA，狹縫系統設為1°-1°-0.15mm-0.45mm，測定步長(2θ)設為0.02°，掃描速度設為2°/分鐘。 Regarding the X-ray diffraction of TiN-1 containing titanium nitride particles, the powder sample was placed in an aluminum standard sample holder, and it was carried out by a wide-angle X-ray diffraction method (manufactured by Rigaku Corporation, trade name "RU-200R") Determination. As measurement conditions, the X-ray source is set to CuKα ray, the output is set to 50kV/200mA, the slit system is set to 1°-1°-0.15mm-0.45mm, the measurement step (2θ) is set to 0.02°, and the scanning speed is set to 2°/min.

並且，測定了在繞射角2θ(42.6°)附近觀察到之來源於TiN(200)面之峰的繞射角2θ。而且，藉由該來源於(200)面之峰的半值幅，利用謝勒公式，求出了構成粒子之微晶尺寸。 Furthermore, the diffraction angle 2θ of the peak originating from the TiN (200) plane observed near the diffraction angle 2θ (42.6°) was measured. Then, the crystallite size of the constituting particles was obtained using the Scherrer formula from the half-value width of the peak derived from the (200) plane.

另外，對以下的含氮化鈦粒子TiN-2~TiN-4，亦藉由與含氮化鈦粒子TiN-1相同的方法，測定了繞射角2θ、微晶尺寸。將結果示於表1。另外， 關於任意含氮化鈦粒子，亦均完全沒有觀察到TiO2引起之X射線繞射峰。 In addition, for the following titanium nitride-containing particles TiN-2 to TiN-4, the diffraction angle 2θ and the crystallite size were measured by the same method as that of the titanium nitride-containing particle TiN-1. The results are shown in Table 1. In addition, no X-ray diffraction peak due to TiO 2 was observed in any of the titanium nitride-containing particles.

[含氮化鈦粒子TiN-2~TiN-4的製作] [Production of titanium nitride-containing particles TiN-2~TiN-4]

將原料及組成設為如表1所示，除此以外，以與含氮化鈦粒子TiN-1相同的方法製造了含氮化鈦粒子TiN-2~TiN-4。 Except that the raw materials and compositions were as shown in Table 1, titanium nitride-containing particles TiN-2 to TiN-4 were produced in the same manner as titanium nitride-containing particles TiN-1.

Figure 106127429-A0305-02-0071-27
Figure 106127429-A0305-02-0071-27

另外，表中，“wt%”表示質量%。並且，表中，“TiN粒子”表示含氮化鈦粒子。 In addition, in the table|surface, "wt%" shows mass %. In addition, in the table, "TiN particles" means titanium nitride-containing particles.

[含金屬氮化物粒子分散液1~11的製作] [Preparation of Metal Nitride-Containing Particle Dispersion Liquids 1~11]

將含金屬氮化物粒子、分散劑及有機溶劑，以分別成為表2所示之組成之方式，藉由攪拌機(IKA公司製造EUROSTAR)混合15分鐘來獲得了混合液。接著，對所獲得之混合液，使用SHINMARU ENTERPRISES CORPORATION製造的NPM-Pilot，在下述條件下進行分散處理，從而獲得了含金屬氮化物粒子分散液。 The metal nitride-containing particles, the dispersant, and the organic solvent were mixed with a stirrer (Eurostar manufactured by IKA Corporation) for 15 minutes so as to have the compositions shown in Table 2, respectively, to obtain a liquid mixture. Next, the obtained mixed solution was subjected to dispersion treatment under the following conditions using NPM-Pilot manufactured by SHINMARU ENTERPRISES CORPORATION, thereby obtaining a metal nitride-containing particle dispersion.

<分散條件> <Dispersion condition>

‧珠徑：φ0.05mm、(NIKKATO CORPORATION製造氧化鋯珠、YTZ) ‧Bead diameter: φ0.05mm, (zirconia beads manufactured by NIKKATO CORPORATION, YTZ)

‧珠填充率：65體積% ‧Bead filling rate: 65% by volume

‧研磨圓周速度：10m/sec ‧Grinding peripheral speed: 10m/sec

‧分離器圓周速度：13m/s ‧Circumferential speed of separator: 13m/s

‧進行分散處理之混合液量：15kg ‧Amount of mixed liquid for dispersion treatment: 15kg

‧循環流量(泵供給量)：90kg/hour ‧Circulation flow (pump supply): 90kg/hour

‧處理液溫度：19~21℃ ‧Treatment liquid temperature: 19~21℃

‧冷卻水：水 ‧Cooling water: water

‧處理時間：22小時左右 ‧Processing time: about 22 hours

Figure 106127429-A0305-02-0073-28
Figure 106127429-A0305-02-0073-28

另外，表2中的各簡稱表示以下成分。 In addition, each abbreviation in Table 2 represents the following components.

(含金屬氮化物粒子) (containing metal nitride particles)

‧ZrN：含氮化鋯粒子、JAPAN NEW METALS CO.,LTD.製造、商品名“ZrN-01” ‧ZrN: Zirconium nitride-containing particles, manufactured by JAPAN NEW METALS CO.,LTD., trade name "ZrN-01"

‧VN：含氮化釩粒子、JAPAN NEW METALS CO.,LTD.製造、商品名“VN-O” ‧VN: Vanadium nitride-containing particles, manufactured by JAPAN NEW METALS CO.,LTD., trade name "VN-O"

‧NbN：含氮化鈮粒子、JAPAN NEW METALS CO.,LTD.製造、商品名“NbN-O‧ ‧NbN: Niobium nitride-containing particles, manufactured by JAPAN NEW METALS CO.,LTD., trade name "NbN-O‧

(分散劑) (Dispersant)

‧分散劑1：BYK ADDITIVES & INSTRUMENTS製、商品名“BYK-111” ‧Dispersant 1: BYK ADDITIVES & INSTRUMENTS, trade name "BYK-111"

‧分散劑2：藉由下述式表示之分散劑 ‧Dispersant 2: Dispersant represented by the following formula

[化學式25]

Figure 106127429-A0305-02-0074-34
[chemical formula 25]
Figure 106127429-A0305-02-0074-34

另外，“Mw‧表示重量平均分子量。 In addition, "Mw‧ means weight average molecular weight.

‧分散劑3：藉由下述式表示之分散劑 ‧Dispersant 3: a dispersant represented by the following formula

Figure 106127429-A0305-02-0074-35
Figure 106127429-A0305-02-0074-35

‧分散劑4：藉由下述式表示之分散劑(重量平均分子量：240000) ‧Dispersant 4: a dispersant represented by the following formula (weight average molecular weight: 240000)

Figure 106127429-A0305-02-0074-36
Figure 106127429-A0305-02-0074-36

(溶劑) (solvent)

‧PGMEA：丙二醇1-單甲醚2-乙酸酯 ‧PGMEA: Propylene glycol 1-monomethyl ether 2-acetate

[實施例1~26及比較例1~5：硬化性組成物的製備] [Examples 1-26 and Comparative Examples 1-5: Preparation of curable composition]

接著，以成為表3中記載的組成之方式，向上述含金屬氮化物粒子分散液混合其他成分，從而獲得了各硬化性組成物。另外，表3中的各成分的含量均表示質量%。 Next, other components were mixed into the metal nitride-containing particle dispersion liquid so as to have the composition described in Table 3, thereby obtaining each curable composition. In addition, the content of each component in Table 3 shows mass %.

另外，以各硬化性組成物的最終固體成分成為30質量%之方式，用有機溶劑進行了調整。另外，固體成分調整用溶劑使用了PGMEA(propyleneglycol monomethyl ether acetate)。 Moreover, it adjusted with the organic solvent so that the final solid content of each curable composition might become 30 mass %. In addition, PGMEA (propyleneglycol monomethyl ether acetate) was used as the solvent for solid content adjustment.

另外，表3中的各編號表示以下成分。 In addition, each number in Table 3 represents the following components.

(酸酐) (anhydride)

‧酸酐1：馬來酸酐 ‧Anhydride 1: Maleic anhydride

‧酸酐2：鄰苯二甲酸酐 ‧Anhydride 2: Phthalic anhydride

‧酸酐3：3,3’,4,4’-聯苯四羧酸二酐(4,4’-雙鄰苯二甲酸酐)(1個分子中含有2個酸酐基。) ‧Anhydride 3: 3,3’,4,4’-biphenyltetracarboxylic dianhydride (4,4’-diphthalic anhydride) (one molecule contains two acid anhydride groups.)

Figure 106127429-A0305-02-0075-37
Figure 106127429-A0305-02-0075-37

‧酸酐4：4,4’-氧基二鄰苯二甲酸酐(1個分子中含有2個酸酐基。) ‧Anhydride 4: 4,4’-oxydiphthalic anhydride (two anhydride groups in one molecule.)

Figure 106127429-A0305-02-0075-39
Figure 106127429-A0305-02-0075-39

‧酸酐5：3,4’-羰基二鄰苯二甲酸酐(1個分子中含有2個酸酐基。) ‧Anhydride 5: 3,4’-carbonyl diphthalic anhydride (one molecule contains two acid anhydride groups.)

[化學式30]

Figure 106127429-A0305-02-0076-40
[chemical formula 30]
Figure 106127429-A0305-02-0076-40

(鹼可溶性樹脂) (alkali soluble resin)

‧鹼可溶性樹脂1：甲基丙烯酸苄酯/丙烯酸共聚物[組成比：甲基丙烯酸苄酯/丙烯酸共聚物=80/20(質量%)、Mw：25000] ‧Alkali-soluble resin 1: benzyl methacrylate/acrylic acid copolymer [composition ratio: benzyl methacrylate/acrylic acid copolymer=80/20 (mass %), Mw: 25000]

‧鹼可溶性樹脂2：藉由以下方法合成之聚醯亞胺前驅物(聚醯胺酸) ‧Alkali-soluble resin 2: polyimide precursor (polyamic acid) synthesized by the following method

上述聚醯亞胺前驅物(聚醯胺酸)藉由以下方法合成。首先，將4,4’-二氨基苯醯替苯胺(0.475莫耳當量)、3,3’-二氨基二苯碸(0.475莫耳當量)及二(3-氨基丙基)-四甲基二環己烷(0.05莫耳當量)，與N-甲基-2-吡咯烷酮1700g一同放入反應容器，從而獲得了混合物。向上述混合物添加3,3’,4,4’-聯苯四羧酸二酐(0.98莫耳當量)，使其在70℃下反應3小時，從而獲得了反應液。向上述反應液添加鄰苯二甲酸酐(0.04莫耳當量)，進一步使其在70℃下反應1小時，從而獲得了聚醯胺酸A-1(聚合物濃度17重量%、醯亞胺閉環率13%、重複單元的分子量532)溶液。其中，聚醯胺酸A-1的重複單元的分子量係依據下述要領計算出者。 The above-mentioned polyimide precursor (polyamic acid) is synthesized by the following method. First, 4,4'-diaminobenzoyl aniline (0.475 molar equivalents), 3,3'-diaminodiphenylphenidine (0.475 molar equivalents) and bis(3-aminopropyl)-tetramethyl Dicyclohexane (0.05 molar equivalent) and 1700 g of N-methyl-2-pyrrolidone were put into a reaction vessel to obtain a mixture. 3,3',4,4'-biphenyltetracarboxylic dianhydride (0.98 molar equivalent) was added to the above mixture, and it was made to react at 70 degreeC for 3 hours, and the reaction liquid was obtained. Phthalic anhydride (0.04 molar equivalents) was added to the above reaction solution, and it was further reacted at 70° C. for 1 hour to obtain polyamic acid A-1 (polymer concentration 17% by weight, imide ring-closed The ratio is 13%, the molecular weight of the repeating unit is 532) solution. However, the molecular weight of the repeating unit of polyamide acid A-1 is calculated according to the following procedure.

重複單元的分子量=2×(227×0.475+248×0.475+249×0.05+294×0.98)/(0.475+0.475+0.05+0.98)=532 Molecular weight of repeat unit = 2×(227×0.475+248×0.475+249×0.05+294×0.98)/(0.475+0.475+0.05+0.98)=532

並且，使聚醯胺酸A-1進行醯亞胺化來獲得之聚醯亞胺樹脂的重複單 元的分子量M1成為496，聚醯亞胺樹脂的重複單元中包含之亞氨基和/或亞氨基羰基的莫耳數n1為0.475莫耳。 In addition, the repeating unit of polyimide resin obtained by imidizing polyamic acid A-1 The molecular weight M1 of the unit was 496, and the molar number n1 of the imino group and/or iminocarbonyl contained in the repeating unit of the polyimide resin was 0.475 mole.

(聚合性化合物) (polymeric compound)

藉由下述式表示之聚合性化合物 A polymeric compound represented by the following formula

Figure 106127429-A0305-02-0077-42
Figure 106127429-A0305-02-0077-42

(肟系聚合起始劑) (Oxime-based polymerization initiator)

‧肟系聚合起始劑1：IRGACURE OXE-02(BASF公司製造) ‧Oxime-based polymerization initiator 1: IRGACURE OXE-02 (manufactured by BASF)

‧肟系聚合起始劑2：ADEKA ARKLS NCI-831(ADEKA CORPORA TION製造、含有硝基。) ‧Oxime-based polymerization initiator 2: ADEKA ARKLS NCI-831 (ADEKA CORPORA TION is manufactured and contains nitro. )

(聚合抑制劑) (polymerization inhibitor)

‧聚合抑制劑：4-甲氧基苯酚 ‧Polymerization inhibitor: 4-methoxyphenol

(界面活性劑) (surfactant)

‧界面活性劑1：藉由下述式表示之界面活性劑(重量平均分子量(Mw)=15311) ‧Surfactant 1: Surfactant represented by the following formula (weight average molecular weight (Mw)=15311)

其中，下述式中，式中(A)及(B)所表示的結構單元分別為62莫耳%、38莫耳%。以式(B)表示之結構單元中，a、b、c分別滿足a+c=14、b=17的關係。 Among them, in the following formula, the structural units represented by (A) and (B) in the formula are 62 mole % and 38 mole %, respectively. In the structural unit represented by formula (B), a, b, and c respectively satisfy the relationship of a+c=14, b=17.

Figure 106127429-A0305-02-0078-43
Figure 106127429-A0305-02-0078-43

‧界面活性劑2：“LC95l”、Kusumoto Chemicals,Ltd.製造 ‧Surfactant 2: "LC95l", manufactured by Kusumoto Chemicals, Ltd.

[評價] [evaluate]

藉由以下方法對上述各硬化性組成物進行了評價。 The respective curable compositions described above were evaluated by the following methods.

[光學濃度(OD：Optical densicty)的測定] [Measurement of optical density (OD: Optical density)]

以乾燥後的膜厚成為1.5μm之方式，將上述硬化性組成物塗佈於玻璃基板上，從而獲得了硬化性組成物層。將所獲得之硬化性組成物層，以將玻璃基板朝下之方式載置於加熱板上，在100℃下加熱2分鐘，使其乾燥。 The above-mentioned curable composition was applied on a glass substrate so that the film thickness after drying became 1.5 μm, thereby obtaining a curable composition layer. The obtained curable composition layer was placed on a hot plate with the glass substrate facing down, heated at 100° C. for 2 minutes, and dried.

對乾燥後的硬化性組成物層，以500mJ/cm2的照射量進行曝光，從而獲得了硬化膜。 The dried curable composition layer was exposed at an irradiation dose of 500 mJ/cm 2 to obtain a cured film.

對上述硬化膜，利用V-7200F(JASCO Corporation製造)，測定了波長380~1100nm中的光學濃度(OD)。將結果示於表3(表3(其1)~表3(其3))。 The optical density (OD) in wavelength 380-1100nm was measured about the said cured film using V-7200F (made by JASCO Corporation). The results are shown in Table 3 (Table 3 (Part 1) to Table 3 (Part 3)).

另外，所獲得之OD係波長400~1100nm中的最小OD。亦即，上述硬化膜(膜厚：1.5μm)在波長400~1100nm的整個區域，具有表3(表3(其1)~表3(其3))所示之OD以上的OD。 In addition, the obtained OD is the minimum OD in the wavelength range of 400-1100nm. That is, the above-mentioned cured film (film thickness: 1.5 μm) has an OD greater than or equal to the OD shown in Table 3 (Table 3 (Part 1) to Table 3 (Part 3)) over the entire wavelength range of 400 to 1100 nm.

[保存穩定性的評價] [evaluation of storage stability]

<1.硬化性組成物的曝光靈敏度(初始)> <1. Exposure sensitivity of curable composition (initial)>

利用旋轉塗佈將剛製備之後的各硬化性組成物塗佈於玻璃基板上，進行乾燥來形成了膜厚1.0μm的硬化性組成物層。關於旋轉塗佈的條件，首先，以轉速300rpm(rotation per minute)旋轉塗佈5秒，接著以800rpm旋轉塗佈20秒。並且，乾燥條件設為100℃下進行80秒。 Each curable composition immediately after preparation was applied on a glass substrate by spin coating, and dried to form a curable composition layer with a film thickness of 1.0 μm. Regarding the spin coating conditions, first, spin coating was performed at a rotation speed of 300 rpm (rotation per minute) for 5 seconds, and then at 800 rpm for 20 seconds. In addition, drying conditions were performed at 100° C. for 80 seconds.

對藉由上述來獲得之塗膜，利用i射線步進曝光裝置FPA-3000i5+(Canon Co.,Ltd.製造)，通過具有1μm的線與空間之圖案遮罩，以10~1600mJ/cm2的曝光量照射了波長365nm的光。接著，使用60%CD-2000(FUJIFILMElectronicMaterialsCo.,Ltd.製造)顯影液，在25℃、60秒的條件下，對曝光之後的硬化性組成物層進行顯影，從而獲得了圖案狀的硬化膜。之後，用流水將圖案狀的硬化膜沖洗20秒之後，進行空氣乾燥。 For the coating film obtained above, use the i-ray stepper FPA-3000i5+ (manufactured by Canon Co., Ltd.) to pass through a pattern mask with 1 μm line and space at 10~1600mJ/cm 2 The exposure dose was irradiated with light having a wavelength of 365 nm. Next, the exposed curable composition layer was developed using 60% CD-2000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) developing solution at 25° C. for 60 seconds to obtain a patterned cured film. After that, the patterned cured film was rinsed with running water for 20 seconds, and then air-dried.

上述曝光步驟中，將照射有光之區域的顯影之後的圖案線寬成為1.0μm以上之最小的曝光量作為曝光靈敏度，將該曝光靈敏度作為初始曝光靈敏度。 In the above exposure step, the minimum exposure amount at which the pattern line width after development of the region irradiated with light becomes 1.0 μm or more is defined as the exposure sensitivity, and the exposure sensitivity is defined as the initial exposure sensitivity.

<2.硬化性組成物的曝光靈敏度(經時後：45℃下經過30天之後)> <2. Exposure sensitivity of curable composition (after time: after 30 days at 45°C)>

將剛製備之後的硬化性組成物封入密封容器，保持在器內溫度設定為45℃之恆溫器(EYELA/LTI-700)內，經過30天之後取出。利用所取出之硬化性組成物，進行與利用剛製備之後的硬化性組成物進行之試驗相同的試驗，求出了曝光靈敏度。將此作為經時後的曝光靈敏度。 The curable composition immediately after preparation was sealed in a sealed container and kept in a thermostat (EYELA/LTI-700) with an internal temperature set at 45°C, and was taken out after 30 days. Using the curable composition taken out, the same test as the test using the curable composition immediately after preparation was performed to obtain the exposure sensitivity. Let this be the exposure sensitivity after time lapse.

<評價> <Evaluation>

從初始曝光靈敏度與經時後的曝光靈敏度，計算出藉由以下的式求出 之曝光靈敏度的變動率(%)。上述變動率(%)的值越小，表示保存穩定性越優異。 Calculated from the initial exposure sensitivity and the exposure sensitivity after time, by the following formula The change rate (%) of the exposure sensitivity. The smaller the value of the above-mentioned rate of change (%), the better the storage stability.

(式)變動率=(經時後的曝光靈敏度-初始曝光靈敏度)/初始曝光靈敏度×100 (Formula) Rate of Change = (Exposure Sensitivity Over Time - Initial Exposure Sensitivity)/Initial Exposure Sensitivity×100

[未曝光部殘渣的評價] [Evaluation of unexposed portion residue]

上述<1.硬化性組成物的曝光靈敏度(初始)>的試驗中，將以顯影後的圖案線寬成為1.0μm以上之最小曝光量獲得之硬化膜，按每個玻璃基板，藉由220℃的烘箱加熱1小時。加熱硬化膜之後，藉由SEM(Scanning Electron Microscope、倍率：20000倍)觀察玻璃基板上的曝光步驟中未照射光之區域(未曝光部)中存在之殘渣的數量，藉此評價了未曝光部殘渣。依據以下基準進行評價，將結果示於表3(表3(其1)~表3(其3))。另外，實際使用上，評價“3”以上為較佳，4及5評價為具有優異的性能。 In the above test of <1. Exposure sensitivity of curable composition (initial)>, the cured film obtained with the minimum exposure amount at which the pattern line width after development becomes 1.0 μm or more was heated at 220°C for each glass substrate. in the oven for 1 hour. After heating the cured film, the number of residues present in the area (unexposed area) that was not irradiated with light during the exposure step on the glass substrate was observed by SEM (Scanning Electron Microscope, magnification: 20,000 times), and the unexposed area was evaluated. residue. Evaluation was performed based on the following criteria, and the results are shown in Table 3 (Table 3 (No. 1) to Table 3 (No. 3)). In addition, in actual use, an evaluation of "3" or higher is preferable, and evaluations of 4 and 5 have excellent performance.

-評價基準- -Evaluation criteria-

5：形成有圖案，未曝光部中完全觀察不到殘渣。 5: A pattern is formed, and residues are not observed at all in the unexposed part.

4：形成有圖案，在未曝光部1.0μm四邊觀察到1~3個殘渣。 4: A pattern is formed, and 1 to 3 residues are observed on the 1.0 μm four sides of the unexposed portion.

3：形成有圖案，在未曝光部1.0μm四邊觀察到4~10個殘渣。 3: A pattern is formed, and 4 to 10 residues are observed on the 1.0 μm four sides of the unexposed portion.

2：形成有圖案，在未曝光部1.0μm四邊觀察到11個以上的殘渣。 2: A pattern is formed, and 11 or more residues are observed on four sides of 1.0 μm in an unexposed portion.

1：由於顯影不良，未形成圖案。 1: No pattern was formed due to poor development.

[圖案邊緣形狀的評價] [Evaluation of Pattern Edge Shape]

藉由以下方法，評價了利用各硬化性組成物形成之圖案狀硬化膜的圖案邊緣形狀。 The pattern edge shape of the patterned cured film formed by each curable composition was evaluated by the following method.

<硬化性組成物層形成步驟> <Formation Step of Curable Composition Layer>

在矽晶圓上，以乾燥後的膜厚成為1.5μm之方式，形成了硬化性組成物層。利用旋轉塗佈進行了硬化性組成物層的形成。以成為上述膜厚之方式，調整了旋轉塗佈的轉速。將塗佈後的硬化性組成物層，以將矽晶圓朝下之方式載置於加熱板上來進行了乾燥。加熱板的表面溫度設為100℃，乾燥時間設為120秒。 On the silicon wafer, a curable composition layer was formed so that the film thickness after drying became 1.5 μm. Formation of the curable composition layer was performed by spin coating. The rotation speed of spin coating was adjusted so that the said film thickness might become. The coated curable composition layer was placed on a hot plate with the silicon wafer facing down, and dried. The surface temperature of the hot plate was set to 100° C., and the drying time was set to 120 seconds.

<曝光步驟> <Exposure step>

在以下條件下對所獲得之硬化性組成物層進行了曝光。 The obtained curable composition layer was exposed under the following conditions.

曝光利用i射線步進機(商品名“FPA-3000iS+”、Canon Co.,Ltd.製造)進行。對硬化性組成物層，經由具有線形20μm(寬度20μm、長度4mm)之遮罩，以400mJ/cm2的曝光量(照射時間0.5秒)進行了照射(曝光)。 Exposure was performed with an i-ray stepper (trade name "FPA-3000iS+", manufactured by Canon Co., Ltd.). The curable composition layer was irradiated (exposed) with an exposure amount of 400 mJ/cm 2 (irradiation time 0.5 seconds) through a mask having a linear shape of 20 μm (width 20 μm, length 4 mm).

<加熱步驟> <Heating step>

接著，將曝光後的硬化性組成物層，以將矽晶圓朝下之方式載置於加熱板上來進行了乾燥。加熱板的表面溫度設為100℃，乾燥時間設為120秒。乾燥後的硬化性組成物層的膜厚為1.5μm。 Next, the exposed curable composition layer was placed on a hot plate with the silicon wafer facing down, and dried. The surface temperature of the hot plate was set to 100° C., and the drying time was set to 120 seconds. The film thickness of the curable composition layer after drying was 1.5 μm.

<顯影步驟> <Development step>

藉由以下條件對乾燥後的硬化性組成物層進行顯影，從而獲得了圖案狀硬化膜。 The dried curable composition layer was developed under the following conditions to obtain a patterned cured film.

對乾燥後的硬化性組成物層，利用四甲基氫氧化銨(TMAH)0.3質量%水溶液，反覆進行5次在23℃下60秒的旋覆浸沒顯影，從而獲得了圖案狀硬化膜。之後，利用噴淋沖洗對圖案狀硬化膜進行沖洗，進一步用純水進行了清洗。 The dried curable composition layer was subjected to spin-on immersion development at 23° C. for 60 seconds five times using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), thereby obtaining a patterned cured film. Then, the patterned cured film was rinsed by shower rinse, and it washed with pure water further.

<後烘烤步驟> <Post-baking step>

利用潔淨烘箱CLH-21CDH(Koyo Thermo Systems Co.,Ltd.製造)，在220℃下將上述中獲得之圖案狀硬化膜加熱300秒。 The patterned cured film obtained above was heated at 220°C for 300 seconds in a clean oven CLH-21CDH (manufactured by Koyo Thermo Systems Co., Ltd.).

而且，將加熱後的圖案狀硬化膜載置於表面溫度220℃的加熱板，並加熱300秒。 And the patterned cured film after heating was mounted on the hot plate of surface temperature 220 degreeC, and it heated for 300 second.

<評價> <Evaluation>

用掃描型電子顯微鏡拍攝上述圖案狀硬化膜，測定了20μm圖案剖面的邊緣部分(短邊)與玻璃基板所呈之角(以下，簡單稱作“邊緣角度”。)。藉由以下基準評價圖案邊緣的形狀，將結果示於表3(表3(其1)~表3(其3))。另外，實際使用上，評價“3”以上為較佳。 The patterned cured film was photographed with a scanning electron microscope, and the angle (hereinafter simply referred to as "edge angle") formed by the edge portion (short side) of the 20 μm pattern cross section and the glass substrate was measured. The shape of the edge of the pattern was evaluated according to the following criteria, and the results are shown in Table 3 (Table 3 (Part 1) to Table 3 (Part 3)). In addition, in actual use, evaluation "3" or higher is preferable.

-評價基準- -Evaluation criteria-

5：邊緣角度超過85°且90°以下。 5: The edge angle exceeds 85° and is 90° or less.

4：邊緣角度超過80°且85°以下。 4: The edge angle exceeds 80° and is 85° or less.

3：邊緣角度超過75°且80°以下。 3: The edge angle exceeds 75° and is 80° or less.

2：邊緣角度超過70°且75°以下。 2: The edge angle exceeds 70° and is 75° or less.

1：邊緣角度為70°以下。 1: The edge angle is 70° or less.

Figure 106127429-A0305-02-0083-29
Figure 106127429-A0305-02-0083-29

Figure 106127429-A0305-02-0084-30
Figure 106127429-A0305-02-0084-30

Figure 106127429-A0305-02-0085-31
Figure 106127429-A0305-02-0085-31

從表3所示之結果，含有含金屬氮化物粒子、肟系聚合起始劑、聚合性化合物及酸酐之實施例1~26的硬化性組成物具有本發明的效果。另一方面，比較例的硬化性組成物不具有本發明的效果。 From the results shown in Table 3, the curable compositions of Examples 1 to 26 containing metal nitride particles, an oxime-based polymerization initiator, a polymerizable compound, and an acid anhydride have the effect of the present invention. On the other hand, the curable composition of the comparative example did not have the effect of the present invention.

並且，得知硬化性組成物中的酸酐的含量相對於肟系聚合起始劑的含量之含有質量比為0.005~0.5之實施例2的硬化性組成物與實施例4、實施 例24及實施例25的硬化性組成物相比，可獲得具有更優異的圖案形狀之硬化膜。 In addition, it was found that the curable composition of Example 2 in which the content of the acid anhydride in the curable composition is contained in a mass ratio of 0.005 to 0.5 with respect to the content of the oxime-based polymerization initiator is the same as that of Example 4 and the implementation. Compared with the curable compositions of Example 24 and Example 25, a cured film having a more excellent pattern shape was obtained.

並且，酸酐在1個分子中含有2個以上的酸酐基之實施例2的硬化性組成物與實施例8及9的硬化性組成物相比，可獲得具有更優異的圖案形狀之硬化膜，並且，更加抑制在未曝光部中產生殘渣。 In addition, the curable composition of Example 2 in which the acid anhydride contains two or more acid anhydride groups in one molecule can obtain a cured film having a more excellent pattern shape than the curable compositions of Examples 8 and 9. In addition, generation of residue in unexposed portions is further suppressed.

並且，含有聚合抑制劑之實施例5的硬化性組成物與實施例2的硬化性組成物相比，具有更優異的保存穩定性，且更加抑制在未曝光部產生殘渣。 Furthermore, the curable composition of Example 5 containing a polymerization inhibitor has more excellent storage stability than the curable composition of Example 2, and further suppresses the generation of residue in unexposed areas.

並且，含金屬氮化物粒子含有氮化鈦之實施例2的硬化性組成物與實施例15~17的硬化性組成物相比，可獲得具有更優異的圖案形狀之硬化膜，且更加抑制未曝光部中產生殘渣。 In addition, the curable composition of Example 2 in which the metal nitride-containing particles contain titanium nitride can obtain a cured film with a more excellent pattern shape than the curable compositions of Examples 15 to 17, and can further suppress failure. Residue is generated in the exposed part.

並且，含金屬氮化物粒子含有氮化鈦，且在規定條件下測定之來源於粒子的(200)面之峰的繞射角2θ為42.5°~42.8°之實施例2的硬化性組成物與實施例19及實施例20的硬化性組成物相比，硬化膜具有更優異的遮光性(較高之OD值)。 In addition, the metal nitride-containing particles contain titanium nitride, and the diffraction angle 2θ of the peak derived from the (200) plane of the particles measured under predetermined conditions is 42.5° to 42.8°. The curable composition of Example 2 and Compared with the curable compositions of Example 19 and Example 20, the cured film has better light-shielding properties (higher OD value).

並且，硬化性組成物中的含金屬氮化物粒子的含量為40質量%以上之實施例13的硬化性組成物與實施例14的硬化性組成物相比，所獲得之硬化膜具有更優異的遮光性。 In addition, the cured composition of Example 13 in which the content of the metal nitride-containing particles in the curable composition is 40% by mass or more has a cured film that is more excellent than the cured composition of Example 14. Shading.

並且，肟系聚合起始劑含有硝基之實施例12的硬化性組成物與實施例2的硬化性組成物相比，獲得了具有更優異的圖案形狀之硬化膜。 Furthermore, the curable composition of Example 12 in which the oxime-based polymerization initiator contained a nitro group obtained a cured film having a more excellent pattern shape than the curable composition of Example 2.

[含金屬氮化物粒子分散液12及13的製作] [Preparation of Metal Nitride-Containing Particle Dispersion Liquids 12 and 13]

代替含氮化鈦粒子TiN-1，使用了含氮化鈦粒子TiN-1與碳黑的混合物(含有質量比(含氮化鈦粒子TiN-1/碳黑)為35/5)，除此以外，藉由與含 金屬氮化物粒子分散液1的製作方法相同的方法，製作了含金屬氮化物粒子分散液12。 Instead of titanium nitride-containing particles TiN-1, a mixture of titanium nitride-containing particles TiN-1 and carbon black (containing a mass ratio (titanium nitride-containing particles TiN-1/carbon black) of 35/5) was used, and in addition Besides, by including The metal nitride-containing particle dispersion 12 was prepared in the same manner as the preparation method of the metal nitride particle dispersion 1 .

並且，代替含氮化鈦粒子TiN-1，使用了含氮化鈦粒子TiN-1與有機顏料(Irgaphor Black S0100CF、BASF公司製造)的混合物(含有質量比(含氮化鈦粒子TiN-1/有機顏料)為35/5)，除此以外，藉由與含金屬氮化物粒子分散液1的製作方法相同的方法，製作了含金屬氮化物粒子分散液13。 And, instead of titanium nitride-containing particles TiN-1, a mixture (containing mass ratio (titanium nitride-containing particles TiN-1/ Organic pigment) was 35/5), and the metal nitride-containing particle dispersion 13 was prepared by the same method as the preparation method of the metal nitride-containing particle dispersion 1.

[實施例2-12、2-13：硬化性組成物的製作] [Example 2-12, 2-13: Production of curable composition]

代替含金屬氮化物粒子分散液1，分別使用了含金屬氮化物粒子分散液12及13，除此以外，藉由與實施例2相同的方法製作硬化性組成物2-12及2-13，進行了與上述相同的評價，其結果，獲得了與實施例2相同的結果。 Instead of the metal nitride-containing particle dispersion 1, except that the metal nitride-containing particle dispersions 12 and 13 were used, respectively, curable compositions 2-12 and 2-13 were produced by the same method as in Example 2, The same evaluation as above was performed, and as a result, the same result as in Example 2 was obtained.

代替IRGACURE OXE-02(BASF公司製造)，使用了以下述式表示之PI-03，除此以外，藉由與實施例5相同的方法，製作硬化性組成物，進行了評價，其結果，圖案邊緣形狀成為5，除此以外，獲得了與實施例5相同的結果。 Instead of IRGACURE OXE-02 (manufactured by BASF), except that PI-03 represented by the following formula was used, by the same method as Example 5, a curable composition was produced and evaluated. As a result, the pattern The same result as in Example 5 was obtained except that the edge shape was 5.

‧PI-03(以下述式表示之化合物，相當於肟系聚合起始劑。) ‧PI-03 (The compound represented by the following formula corresponds to an oxime-based polymerization initiator.)

Figure 106127429-A0305-02-0087-44
Figure 106127429-A0305-02-0087-44

代替IRGACURE OXE-02(BASF公司製造)，使用了以下述式 表示之PI-04，除此以外，藉由與實施例5相同的方法，製作硬化性組成物並進行了評價，其結果，保存穩定性成為1，且圖案邊緣形狀成為5，除此以外，獲得了相同的結果。 Instead of IRGACURE OXE-02 (manufactured by BASF Corporation), the following formula was used PI-04 shown, except that, by the same method as in Example 5, a curable composition was produced and evaluated. As a result, the storage stability was 1, and the pattern edge shape was 5. In addition, The same result was obtained.

‧PI-04(WO2015/036910中以OE74表示之化合物，相當於肟系聚合起始劑。) ‧PI-04 (the compound represented by OE74 in WO2015/036910, which is equivalent to an oxime-based polymerization initiator.)

Figure 106127429-A0305-02-0088-45
Figure 106127429-A0305-02-0088-45

未使用界面活性劑，除此以外，藉由與實施例5相同的方法，製作硬化性組成物並進行了評價，其結果，獲得了與實施例5相同的結果。 A curable composition was produced and evaluated by the same method as in Example 5 except that no surfactant was used. As a result, the same results as in Example 5 were obtained.

100‧‧‧固態攝像裝置 100‧‧‧Solid state imaging device

101‧‧‧固態攝影元件 101‧‧‧Solid-state imaging device

102‧‧‧攝像部 102‧‧‧Photography Department

103‧‧‧蓋玻璃 103‧‧‧Cover glass

104‧‧‧間隔物 104‧‧‧Spacer

105‧‧‧層積基板 105‧‧‧Laminated substrate

106‧‧‧晶片基板 106‧‧‧chip substrate

107‧‧‧電路基板 107‧‧‧circuit board

108‧‧‧電極墊 108‧‧‧electrode pad

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

110‧‧‧貫穿電極 110‧‧‧through electrode

111‧‧‧透鏡層 111‧‧‧lens layer

112‧‧‧透鏡材料 112‧‧‧Lens material

113‧‧‧支撐體 113‧‧‧Support

114、115‧‧‧遮光膜 114, 115‧‧‧shading film

Claims (22)

一種硬化性組成物，其含有含金屬氮化物粒子、肟系聚合起始劑、聚合性化合物及酸酐，前述酸酐為以式(A2)表示之四羧酸二酐，
Figure 106127429-A0305-02-0091-32
 式(A2)中，R2表示單鍵或2價的連結基。 A curable composition comprising metal nitride particles, an oxime-based polymerization initiator, a polymerizable compound, and an acid anhydride, wherein the acid anhydride is tetracarboxylic dianhydride represented by formula (A2),
Figure 106127429-A0305-02-0091-32
 In formula (A2), R 2 represents a single bond or a divalent linking group. 如申請專利範圍第1項所述之硬化性組成物，其中前述硬化性組成物中的前述酸酐的含量相對於前述肟系聚合起始劑的含量之含有質量比為0.005~0.5。 The curable composition described in claim 1, wherein the mass ratio of the content of the acid anhydride in the curable composition to the content of the oxime-based polymerization initiator is 0.005-0.5. 如申請專利範圍第1或2項所述之硬化性組成物，其中前述酸酐在1個分子中含有2個以上的酸酐基。 The curable composition as described in claim 1 or 2, wherein the acid anhydride contains two or more acid anhydride groups in one molecule. 如申請專利範圍第1項所述之硬化性組成物，其還含有聚合抑制劑。 The curable composition described in claim 1, which further contains a polymerization inhibitor. 如申請專利範圍第1項所述之硬化性組成物，其中前述含金屬氮化物粒子含有氮化鈦。 The curable composition as described in claim 1, wherein the metal nitride-containing particles contain titanium nitride. 如申請專利範圍第5項所述之硬化性組成物，其中將CuKα射線設為X射線源時的來源於前述含金屬氮化物粒子的(200)面之峰的繞射角2θ為42.5°~42.8°。 The hardenable composition as described in claim 5, wherein the diffraction angle 2θ of the peak originating from the (200) plane of the metal-containing nitride particles when CuKα rays are used as the X-ray source is 42.5°~ 42.8°. 如申請專利範圍第1項所述之硬化性組成物，其還含有鹼可溶性樹脂。 The curable composition described in claim 1, which further contains an alkali-soluble resin. 如申請專利範圍第7項所述之硬化性組成物，其中前述鹼可溶性樹脂含有選自包含聚醯亞胺前驅物及聚醯亞胺樹脂之群組之至少1種。 The curable composition according to claim 7, wherein the alkali-soluble resin contains at least one selected from the group consisting of polyimide precursors and polyimide resins. 如申請專利範圍第1項所述之硬化性組成物，其中前述硬化性組成物中的前述含金屬氮化物粒子的含量相對於前述硬化性組成物的總固體成分，為40質量%以上。 The curable composition according to claim 1, wherein the content of the metal nitride particles in the curable composition is 40% by mass or more relative to the total solid content of the curable composition. 如申請專利範圍第1項所述之硬化性組成物，其中前述硬化性組成物中的前述肟系聚合起始劑的含量相對於前述含金屬氮化物粒子的含量之含有質量比為0.03~0.2。 The curable composition as described in claim 1, wherein the mass ratio of the content of the oxime-based polymerization initiator in the curable composition to the content of the metal-containing nitride particles is 0.03 to 0.2 . 如申請專利範圍第1項所述之硬化性組成物，其中前述肟系聚合起始劑含有硝基。 The curable composition as described in claim 1, wherein the oxime-based polymerization initiator contains a nitro group. 如申請專利範圍第1項所述之硬化性組成物，其還含有溶劑。 The curable composition as described in Claim 1, which further contains a solvent. 如申請專利範圍第1項所述之硬化性組成物，其中前述含金屬氮化物粒子中包含之金屬原子為Ti、V、Nb、Ta或Zr，且前述金屬原子為Ti時，前述含金屬氮化物粒子更包括超過0.002質量%且小於0.3質量%的Si原子。 The hardenable composition as described in Claim 1 of the patent application, wherein the metal atom contained in the metal-containing nitride particles is Ti, V, Nb, Ta or Zr, and when the metal atom is Ti, the metal nitrogen-containing The compound particles further include more than 0.002% by mass and less than 0.3% by mass of Si atoms. 如申請專利範圍第1或2項所述之硬化性組成物，其中前述酸酐在1個分子中含有2個以上且4個以下的酸酐基。 The curable composition according to claim 1 or 2, wherein the acid anhydride contains 2 or more and 4 or less acid anhydride groups in one molecule. 如申請專利範圍第1項所述之硬化性組成物，其中前述聚合性化合物為包含含有乙烯性不飽和鍵之基團之化合物。 The curable composition as described in claim 1, wherein the aforementioned polymerizable compound is a compound containing a group containing an ethylenically unsaturated bond. 如申請專利範圍第15項所述之硬化性組成物，其中前述包含含有乙烯性不飽和鍵之基團之化合物為包含(甲基)丙烯醯基之化合物。 The curable composition as described in claim 15, wherein the aforementioned compound containing a group containing an ethylenically unsaturated bond is a compound containing a (meth)acryl group. 一種硬化膜，其使申請專利範圍第1至16中任一項所述之硬化性組成物硬化來獲得。 A cured film obtained by curing the curable composition described in any one of claims 1 to 16. 一種彩色濾光片，其含有申請專利範圍第17項所述之硬化膜。 A color filter comprising the hardened film described in claim 17 of the patent application. 一種固態攝影元件，其含有申請專利範圍第17項所述之硬化膜。 A solid-state imaging element, which includes the cured film described in item 17 of the scope of application. 一種紅外線感測器，其含有申請專利範圍第17項所述之硬化膜。 An infrared sensor comprising the hardened film described in item 17 of the scope of the patent application. 一種硬化膜的製造方法，其含有如下步驟：硬化性組成物層形成步驟，利用申請專利範圍第1至16中任一項所述之硬化性組成物來形成硬化性組成物層；曝光步驟，經由具備圖案狀開口部之光罩，對前述硬化性組成物層照射光化射線或放射線來進行曝光；及顯影步驟，對前述曝光後的前述硬化性組成物層進行顯影來形成硬化膜。 A method for producing a cured film, comprising the following steps: a step of forming a curable composition layer, using the curable composition described in any one of claims 1 to 16 to form a curable composition layer; an exposure step, Exposure is performed by irradiating the curable composition layer with actinic rays or radiation through a photomask having patterned openings; and a developing step of developing the exposed curable composition layer to form a cured film. 一種彩色濾光片的製造方法，其含有申請專利範圍第21項所述之硬化膜的製造方法。 A method for manufacturing a color filter, which includes the method for manufacturing a cured film described in claim 21 of the patent application.
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