TWI699614B - Composition, composition manufacturing method, cured film, color filter, light shielding film, solid-state imaging element, and image display device - Google Patents

Composition, composition manufacturing method, cured film, color filter, light shielding film, solid-state imaging element, and image display device Download PDF

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TWI699614B
TWI699614B TW106104991A TW106104991A TWI699614B TW I699614 B TWI699614 B TW I699614B TW 106104991 A TW106104991 A TW 106104991A TW 106104991 A TW106104991 A TW 106104991A TW I699614 B TWI699614 B TW I699614B
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久保田誠
浜田大輔
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日商富士軟片股份有限公司
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • 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

本發明提供一種能夠製作圖案形成性及電極的防腐性優 異之硬化膜之組成物，以及還提供組成物的製造方法、硬化膜、濾色器、遮光膜、固態攝影元件及圖像顯示裝置。組成物含有包含Fe原子之含氮化鈦粒子，上述含氮化鈦粒子中的上述Fe原子的含量超過0.001質量%且小於0.4質量%。硬化膜使用上述組成物來獲得，濾色器及遮光膜具有上述硬化膜。組成物的製造方法包含藉由熱等離子體法獲得含氮化鈦粒子之製程。 The present invention provides a pattern capable of making patterns and excellent electrode corrosion resistance The composition of the different cured film, as well as the manufacturing method of the composition, the cured film, the color filter, the light shielding film, the solid-state imaging element, and the image display device. The composition contains titanium nitride-containing particles containing Fe atoms, and the content of the Fe atoms in the titanium nitride-containing particles exceeds 0.001% by mass and less than 0.4% by mass. The cured film is obtained using the aforementioned composition, and the color filter and the light-shielding film have the aforementioned cured film. The manufacturing method of the composition includes a process of obtaining titanium nitride-containing particles by a thermal plasma method.

Description

組成物、組成物的製造方法、硬化膜、濾色器、遮光膜、 固態攝影元件及圖像顯示裝置 Composition, composition manufacturing method, cured film, color filter, shading film, Solid-state imaging element and image display device

本發明係一種組成物、組成物的製造方法、硬化膜、濾色器、遮光膜、固態攝影元件及圖像顯示裝置。 The present invention is a composition, a method for manufacturing the composition, a cured film, a color filter, a light shielding film, a solid-state imaging element, and an image display device.

一直以來周知有含有氮化鈦之組成物。含有氮化鈦之組成物用於各種用途，例如，用於製作設置於液晶顯示裝置及固態攝像裝置等之遮光膜。 There have been known compositions containing titanium nitride. The composition containing titanium nitride is used for various purposes, for example, for the production of light shielding films installed in liquid crystal display devices and solid-state imaging devices.

具體而言，用於液晶顯示裝置之濾色器中，為了遮蔽著色像素之間的光並提高對比度等，具備被稱作黑矩陣之遮光膜。 Specifically, a color filter used in a liquid crystal display device is provided with a light-shielding film called a black matrix in order to shield light between colored pixels and improve contrast.

並且，固態攝影元件中，亦為了防止產生噪聲、提高畫質等而設置有黑矩陣。目前，在移動電話及PDA(Personal Digital Assistant)等電子設備的便攜終端搭載有小型且薄型的攝像模組。該種攝像模組通常具備CCD(Charge Coupled Device)圖像感測器及CMOS(Complementary Metal-Oxide Semiconductor)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, the solid-state imaging element is also provided with a black matrix for the purpose of preventing noise generation and improving image quality. Currently, portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistant) are equipped with small and thin camera modules. This kind of camera module usually has solid-state imaging elements such as CCD (Charge Coupled Device) image sensor and CMOS (Complementary Metal-Oxide Semiconductor) image sensor, and is used to form a subject image on the solid-state imaging element. lens.

作為用於形成液晶顯示裝置用及固態攝影元件用黑矩陣的組成物，例如，專利文獻1中，公開有“一種樹脂黑矩陣用黑色樹脂組成物，其至少包含遮光材料、樹脂及溶劑，作為遮光材料至少含有氮化鈦粒子，其中，將CuKα射線作為X射線源時的前述氮化鈦粒子的源自(200)面之峰的衍 射角2θ為42.5°以上且42.8°以下。”(申請專利範圍第1項)。 As a composition for forming a black matrix for a liquid crystal display device and a solid-state imaging element, for example, Patent Document 1 discloses "a black resin composition for a resin black matrix, which contains at least a light-shielding material, a resin, and a solvent, as The light-shielding material contains at least titanium nitride particles, wherein the peak derived from the (200) plane of the aforementioned titanium nitride particles when CuKα rays are used as the X-ray source The firing angle 2θ is 42.5° or more and 42.8° or less. "(The first item in the scope of patent application).

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

[專利文獻1]：日本專利第5136139號公報 [Patent Document 1]: Japanese Patent No. 5136139

含有如上述的氮化鈦粒子(含氮化鈦粒子)之組成物有時為了在形成有電極圖案之基板上形成加工成圖案狀之硬化膜而使用。 The composition containing the above-mentioned titanium nitride particles (titanium nitride particles containing) may be used for forming a cured film processed into a pattern on a substrate on which an electrode pattern is formed.

因而，本發明人等在形成有電極圖案之基板上塗佈含有含氮化鈦粒子之組成物來製作了形成為圖案狀之硬化膜，其結果，得知依據含氮化鈦粒子的種類，有時產生電極圖案的劣化(腐蝕)，或無法獲得所希望的圖案(圖案形成性的下降)。 Therefore, the inventors of the present invention applied a composition containing titanium nitride particles to a substrate on which an electrode pattern was formed to produce a cured film formed in a pattern. As a result, it was found that depending on the type of titanium nitride particles, Deterioration (corrosion) of the electrode pattern may occur, or a desired pattern may not be obtained (decrease in pattern formability).

因而，本發明的目的為提供一種能夠製作圖案形成性及電極的防腐性優異之硬化膜之組成物。並且，本發明的目的為提供一種組成物的製造方法、硬化膜、濾色器、遮光膜、固態攝影元件及圖像顯示裝置。 Therefore, the object of the present invention is to provide a composition capable of producing a cured film excellent in pattern formation and electrode corrosion resistance. In addition, an object of the present invention is to provide a method of manufacturing a composition, a cured film, a color filter, a light-shielding film, a solid-state imaging element, and an image display device.

本發明人對上述課題進行了深入研究，其結果，發現藉由含氮化鈦粒子中的Fe原子的含量在規定範圍內，能夠製作圖案形成性及電極的防腐性優異之硬化膜，並完成了本發明。 The inventors of the present invention have conducted intensive research on the above-mentioned problems. As a result, they have found that by having the Fe atom content in the titanium nitride-containing particles within a predetermined range, a cured film with excellent pattern formation and electrode corrosion resistance can be produced, and completed The present invention.

亦即，本發明人發現藉由以下結構能夠解決上述課題。 That is, the inventors found that the above-mentioned problem can be solved by the following structure.

〔1〕一種組成物，其含有包含Fe原子之含氮化鈦粒子，上述含氮化鈦粒子中的上述Fe原子的含量超過0.001質量%且小於0.4質量%。 [1] A composition containing titanium nitride-containing particles containing Fe atoms, wherein the content of the Fe atoms in the titanium nitride-containing particles exceeds 0.001% by mass and less than 0.4% by mass.

〔2〕如上述〔1〕所述之組成物，其中，將CuKα射線作為X射線源時，上述含氮化鈦粒子的源自(200)面之峰的衍射角2θ超過42.6°且43.5°以下。 [2] The composition described in [1] above, wherein when CuKα rays are used as the X-ray source, the diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles exceeds 42.6° and 43.5° the following.

〔3〕如上述〔1〕或〔2〕所述之組成物，其中，上述含氮化鈦粒子還含有Si原子，上述含氮化鈦粒子中的上述Si原子的含量超過0.002質量%且小於0.3質量%。 [3] The composition according to [1] or [2] above, wherein the titanium nitride-containing particles further contain Si atoms, and the content of the Si atoms in the titanium nitride-containing particles exceeds 0.002 mass% and is less than 0.3% by mass.

〔4〕如上述〔1〕至〔3〕中任一項所述之組成物，其中，藉由以下粒子數測定方法求出之10μm以上尺寸的上述含氮化鈦粒子的數量為100個以下，粒子數測定方法：製備藉由丙二醇單甲醚乙酸酯將上述組成物稀釋為500倍之試料溶液，藉由流動式顆粒圖像分析儀測定上述試料溶液10ml中包含之10μm以上的尺寸的上述含氮化鈦粒子的數量。 [4] The composition according to any one of [1] to [3] above, wherein the number of the above-mentioned titanium nitride-containing particles having a size of 10 μm or more determined by the following particle number measurement method is 100 or less , Method of measuring the number of particles: Prepare a sample solution in which the above composition is diluted 500 times by propylene glycol monomethyl ether acetate, and measure the size of 10 μm or more contained in 10 ml of the sample solution by a flow-type particle image analyzer The number of the above-mentioned titanium nitride-containing particles.

〔5〕如上述〔1〕至〔4〕中任一項所述之組成物，其還含有2種以上的有機溶劑。 [5] The composition described in any one of [1] to [4] above, which further contains two or more organic solvents.

〔6〕如上述〔1〕至〔5〕中任一項所述之組成物，其還含有黏結樹脂。 [6] The composition according to any one of [1] to [5] above, which further contains a binding resin.

〔7〕如上述〔1〕至〔6〕中任一項所述之組成物，其還含有聚合性化合物。 [7] The composition as described in any one of [1] to [6] above, which further contains a polymerizable compound.

〔8〕如上述〔1〕至〔7〕中任一項所述之組成物，其還含有聚合起始劑。 [8] The composition according to any one of [1] to [7] above, which further contains a polymerization initiator.

〔9〕如上述〔1〕至〔8〕中任一項所述之組成物，其中，上述組成物中的固體含量為10~40質量%。 [9] The composition according to any one of [1] to [8] above, wherein the solid content in the composition is 10-40% by mass.

〔10〕如上述〔1〕至〔9〕中任一項所述之組成物，其中，上述含氮化鈦粒子的含量相對於上述組成物的總固體含量，為20~70質量%。 [10] The composition according to any one of [1] to [9] above, wherein the content of the titanium nitride-containing particles is 20 to 70% by mass relative to the total solid content of the composition.

〔11〕如上述〔1〕至〔10〕中任一項所述之組成物，其還含有水，上述水的含量相對於上述組成物總質量，為0.1~1質量%。 [11] The composition according to any one of [1] to [10] above, which further contains water, and the content of the water is 0.1 to 1% by mass relative to the total mass of the composition.

〔12〕如上述〔1〕至〔11〕中任一項所述之組成物，其還含有分散劑，上述分散劑具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組之至少1種結構。 [12] The composition according to any one of [1] to [11] above, which further contains a dispersant, and the dispersant is selected from the group consisting of polymethyl acrylate, polymethyl methacrylate and cyclic or At least one structure of the chain polyester group.

〔13〕如上述〔12〕所述之組成物，其中，上述分散劑相對於上述含氮化鈦粒子之含有比例以質量比計為0.05~0.30。 [13] The composition according to the above [12], wherein the content ratio of the dispersant to the titanium nitride-containing particles is 0.05 to 0.30 in terms of mass ratio.

〔14〕一種組成物的製造方法，其為上述〔1〕至〔13〕中任一項所述之組成物的製造方法，其包含藉由熱等離子體法獲得上述含氮化鈦粒子之製程。 [14] A method for producing a composition, which is the method for producing the composition described in any one of [1] to [13] above, comprising a process for obtaining the above-mentioned titanium nitride-containing particles by a thermal plasma method .

〔15〕一種硬化膜，其使用上述〔1〕至〔13〕中任一項所述之組成物來獲得。 [15] A cured film obtained by using the composition described in any one of [1] to [13] above.

〔16〕一種濾色器，其具有上述〔15〕所述之硬化膜。 [16] A color filter having the cured film described in [15] above.

〔17〕一種遮光膜，其具有上述〔15〕所述之硬化膜。 [17] A light-shielding film having the cured film described in [15] above.

〔18〕一種固態攝影元件，其具有上述〔15〕所述之硬化膜。 [18] A solid-state imaging element having the cured film described in [15] above.

〔19〕一種圖像顯示裝置，其具有上述〔15〕所述之硬化膜。 [19] An image display device having the cured film described in [15] above.

如以下所示，依本發明，能夠提供一種能夠製作圖案形成性及電 極的防腐性優異之硬化膜之組成物。並且，依本發明，能夠提供一種組成物的製造方法、硬化膜、濾色器、遮光膜、固態攝影元件及圖像顯示裝置。 As shown below, according to the present invention, it is possible to provide a pattern forming and electrical The composition of the hardened film with excellent corrosion resistance. Furthermore, according to the present invention, it is possible to provide a method of manufacturing a composition, a cured film, a color filter, a light shielding film, a solid-state imaging device, and an image display device.

以下，對本發明進行說明。 Hereinafter, the present invention will be explained.

本說明書中，使用“~”表示之數值範圍表示包含記載於“~”的前後之數值作為下限值及上限值之範圍。 In this manual, the numerical range indicated by "~" means the range that includes the numerical values before and after "~" as the lower limit and the upper limit.

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具有取代基者一同還包含具有取代基者。例如，“烷基”不僅包含不具有取代基之烷基(未取代烷基)，還包含具有取代基之烷基(取代烷基)。 In the expression of the group (atomic group) in the present specification, the expression that does not describe substitution and unsubstituted includes a substituent that does not have a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl), but also substituted alkyl (substituted alkyl).

本說明書中，“活性光線”或“放射線”例如表示水銀燈的明線光譜、準分子雷射為代表之遠紫外線、極紫外線(EUV光)、X射線及電子束等。並且，本發明中，光表示活性光線或放射線。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的明線光譜、準分子雷射為代表之遠紫外線、X射線、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 this specification, "active light" or "radiation" means, for example, the bright-ray spectrum of a mercury lamp, extreme ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams. In addition, in the present invention, light means active light or radiation. Regarding the "exposure" in this manual, unless otherwise specified, it is not limited to exposure based on the bright line spectrum of mercury lamps, extreme ultraviolet light represented by excimer lasers, X-rays, EUV light, etc., based on electron beams and ion beams, etc. The description of the particle beam is also included in the exposure.

本說明書中，“(甲基)丙烯酸酯”表示丙烯酸酯及甲基丙烯酸酯，“(甲基)丙烯酸”表示丙烯酸及甲基丙烯酸，“(甲基)丙烯醯基”表示丙烯醯基及甲基丙烯醯基，“(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。本發明中的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，聚合性化合物指具有聚合性基團之化合物，可以係單體，亦可以係聚合物。聚合性基團指參與聚合反應之基團。 In this specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic and methacrylic acid, and "(meth)acryloyl" means acryloyl and methyl Alkylacrylamide, "(meth)acrylamide" means acrylamide and methacrylamide. and, In this specification, "monomer" and "monomer" have the same meaning. In the present invention, 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 having a polymerizable group, and it may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.

〔組成物〕 〔Composition〕

本發明的組成物含有包含Fe原子之含氮化鈦粒子，上述含氮化鈦粒子中的上述Fe原子的含量超過0.001質量%且小於0.4質量%。 The composition of the present invention contains titanium nitride-containing particles containing Fe atoms, and the content of the Fe atoms in the titanium nitride-containing particles exceeds 0.001% by mass and less than 0.4% by mass.

依本發明的組成物，能夠製作圖案形成性及電極的防腐性優異之硬化膜。 According to the composition of the present invention, it is possible to produce a cured film excellent in pattern formation and electrode corrosion resistance.

本發明人等進行了深入研究，其結果，發現含氮化鈦粒子中的Fe原子的含量與圖案形成性及電極的防腐性相關。 The inventors of the present invention conducted intensive studies, and as a result, found that the content of Fe atoms in the titanium nitride-containing particles is related to the pattern formation properties and the corrosion resistance of the electrode.

含氮化鈦粒子中包含之Fe原子對電極及基板之黏附性優異，認為含氮化鈦粒子中的氮化鈦經由Fe原子附著於電極及基板。故，認為在顯影處理等硬化膜的圖案化之後，Fe原子殘留在電極及基板上，變得易去除氮化鈦。故，推斷為藉由將含氮化鈦粒子中的Fe原子的含量設為規定量以上，硬化膜的圖案形成性得到了提高。 The Fe atoms contained in the titanium nitride-containing particles have excellent adhesion to the electrode and the substrate, and it is considered that the titanium nitride in the titanium nitride-containing particles is attached to the electrode and the substrate via the Fe atoms. Therefore, it is considered that after patterning of the cured film such as development treatment, Fe atoms remain on the electrode and the substrate, and it becomes easy to remove the titanium nitride. Therefore, it is inferred that by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or more, the pattern formability of the cured film is improved.

另一方面，認為若含氮化鈦粒子中包含之Fe原子的含量過多，則殘留在電極及基板上之Fe原子的量增加，變成電極腐蝕的原因。故，推斷為藉由將含氮化鈦粒子中的Fe原子的含量設為規定量以下，成為電極的防腐性優異者。 On the other hand, it is considered that if the content of Fe atoms contained in the titanium nitride-containing particles is too large, the amount of Fe atoms remaining on the electrode and the substrate increases, which may cause corrosion of the electrode. Therefore, it is estimated that by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or less, the electrode has excellent corrosion resistance.

以下，對組成物中包含之成分及可包含之成分進行說明。 Hereinafter, the components included in the composition and the components that can be included are described.

<含氮化鈦粒子> <Titanium Nitride Particles>

本發明的組成物含有包含Fe原子之含氮化鈦粒子。含氮化鈦粒子用作黑色顏料為較佳。 The composition of the present invention contains titanium nitride-containing particles containing Fe atoms. Titanium nitride-containing particles are preferably used as black pigments.

製造含氮化鈦粒子時，通常利用氣相反應法，具體而言，可舉出電爐法及熱等離子體法等。該些製法中，從雜質的混入較少之角度、粒徑易一致之角度及生產率較高之角度等理由考慮，熱等離子體法為較佳。 When producing titanium nitride-containing particles, a gas phase reaction method is generally used, and specifically, an electric furnace method, a thermal plasma method, and the like are mentioned. Among these production methods, the thermal plasma method is preferred from the viewpoint of less mixing of impurities, the viewpoint of easy particle size uniformity, and the viewpoint of higher productivity.

作為熱等離子體的產生方法，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，從來自電極的雜質的混入較少之高頻等離子體為較佳。作為基於熱等離子體法之含氮化鈦微粒的具體製造方法，例如，可舉出藉由高頻熱等離子體使鈦粉末蒸發，將氮作為載氣導入装置內，藉由冷卻過程，使鈦粉末氮化，從而合成含氮化鈦粒子之方法等。另外，熱等離子體法並不限定於上述。 The thermal plasma generation method includes direct current arc discharge, multiphase arc discharge, high-frequency (RF) plasma, and hybrid plasma. The high-frequency plasma with less impurities from the electrode is more good. As a specific manufacturing method of titanium nitride-containing particles based on the thermal plasma method, for example, the titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the device as a carrier gas, and the titanium Powder nitriding to synthesize titanium nitride particles. In addition, the thermal plasma method is not limited to the above.

作為本發明的組成物中包含之含氮化鈦粒子的製造方法，並無特別限定，可參閱國際公開第2010/147098號的段落<0037>~<0089>中記載之製造方法。例如，可如下製造，亦即，代替國際公開第2010/147098號的Ag粉末，使用後述之包含Fe之成分和/或包含Si之成分，將混合該成分與鈦粉末材料(鈦粒子)者作為原料，製造本發明的組成物中包含之含氮化鈦粒子。 The method of manufacturing the titanium nitride-containing particles contained in the composition of the present invention is not particularly limited, and the manufacturing method described in paragraphs <0037> to <0089> of International Publication No. 2010/147098 can be referred to. For example, it can be manufactured as follows, that is, instead of Ag powder of International Publication No. 2010/147098, a Fe-containing component and/or a Si-containing component described later is used, and the component is mixed with a titanium powder material (titanium particle) as The raw material is used to produce titanium nitride-containing particles contained in the composition of the present invention.

含氮化鈦粒子的製造中使用之鈦粉末材料(鈦粒子)係高純度者為較佳。鈦粉末材料並無特別限定，使用鈦元素的純度為99.99%以上者為較佳，使用99.999%以上者為更佳。 The titanium powder material (titanium particles) used in the production of the titanium nitride-containing particles is preferably of high purity. The titanium powder material is not particularly limited. It is better to use titanium with a purity of 99.99% or more, and it is more preferable to use 99.999% or more.

含氮化鈦粒子的製造中使用之鈦粉末材料(鈦粒子)有時含有鈦原子以外的原子。作為鈦粉末材料可包含之其他原子，例如，可舉出Fe原子及Si原子等。 Titanium powder materials (titanium particles) used in the production of titanium nitride-containing particles may contain atoms other than titanium atoms. Examples of other atoms that the titanium powder material may contain include Fe atoms and Si atoms.

鈦粉末材料含有Fe原子時，Fe原子的含量相對於鈦粉末材料的總質量，超過0.001質量%為較佳。藉此，硬化膜的圖案形成性更加優異。並且，鈦粉末材料含有Fe原子時，Fe原子的含量相對於鈦粉末材料的總量，小於0.4質量%為較佳。藉此，基於硬化膜之電極的防腐性更加優異(能夠更加抑制硬化膜腐蝕電極)。亦即，藉由含氮化鈦粒子的製造中使用之鈦粉末材料中包含之Fe原子在上述範圍內(超過0.001質量且小於0.4質量%)，能夠更顯著地獲得本發明的效果。 When the titanium powder material contains Fe atoms, the content of Fe atoms relative to the total mass of the titanium powder material is preferably more than 0.001% by mass. Thereby, the pattern formability of the cured film is more excellent. In addition, when the titanium powder material contains Fe atoms, the content of Fe atoms relative to the total amount of the titanium powder material is preferably less than 0.4% by mass. Thereby, the corrosion resistance of the electrode based on the cured film is more excellent (the electrode can be further suppressed from corrosion of the cured film). That is, when the Fe atoms contained in the titanium powder material used in the production of the titanium nitride-containing particles are within the above-mentioned range (more than 0.001 mass% and less than 0.4 mass %), the effects of the present invention can be more remarkably obtained.

鈦粉末材料含有Si原子時，Si原子的含量相對於鈦粉末材料總質量，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。藉由Si原子的含量超過0.002質量%，硬化膜的圖案形成性更加提高。並且認為，藉由Si原子的含量小於0.3質量%，所獲得之含氮化鈦粒子的最表層的極性穩定，使含氮化鈦粒子分散時的分散劑向含氮化鈦粒子的吸附性得到優化，含氮化鈦粒子的未分散物減少，藉此具有抑制產生顆粒之效果。亦即，藉由含氮化鈦粒子的製造中使用之鈦粉末材料中包含之Si原子在上述範圍內，能夠更加顯著地獲得本發明的效果。 When the titanium powder material contains Si atoms, the content of Si atoms relative to the total mass of the titanium powder material is preferably more than 0.002% by mass and less than 0.3% by mass, 0.01~0.15% by mass is more preferred, and 0.02~0.1% by mass is more preferred. good. When the content of Si atoms exceeds 0.002% by mass, the pattern formability of the cured film is further improved. It is also believed that by the Si atom content of less than 0.3% by mass, the polarity of the outermost layer of the obtained titanium nitride-containing particles is stabilized, and the adsorbability of the dispersant to the titanium nitride-containing particles when the titanium nitride-containing particles are dispersed is obtained. Optimized, the undispersed content of titanium nitride particles is reduced, thereby having the effect of suppressing particle generation. That is, when the Si atom contained in the titanium powder material used in the production of the titanium nitride-containing particles is within the above-mentioned range, the effect of the present invention can be more remarkably obtained.

並且，含氮化鈦粒子的製造中使用之鈦粉末材料(鈦粒子)中的水分相對於鈦粉末材料的總質量，小於1質量%為較佳，小於0.1質量%為更佳，實質上不包含為進一步較佳。藉由含氮化鈦粒子的製造中使用之鈦粉末材 料中的水分在上述範圍內，能夠更加顯著地獲得本發明的效果。 In addition, the moisture in the titanium powder material (titanium particles) used in the production of titanium nitride particles relative to the total mass of the titanium powder material is preferably less than 1% by mass, and more preferably less than 0.1% by mass. Inclusion is further preferred. With titanium powder material used in the production of titanium nitride particles If the moisture in the material is within the above range, the effect of the present invention can be obtained more significantly.

並且，藉由含氮化鈦粒子可利用熱等離子體法來獲得，可容易將CuKα射線作為X射線源時的源自(200)面之峰的衍射角2θ(詳細內容將進行後述)調整為超過42.6°且43.5°以下的範圍。 In addition, the titanium nitride-containing particles can be obtained by the thermal plasma method, and the diffraction angle 2θ of the peak derived from the (200) plane when CuKα rays are used as the X-ray source (details will be described later) can be easily adjusted to It exceeds the range of 42.6° and 43.5° or less.

其中，作為使含氮化鈦粒子含有Fe原子之方法，並無特別限定，例如，可舉出在獲得用作上述含氮化鈦粒子的原料之鈦粒子(鈦粉末)之階段導入Fe原子之方法等。更詳細而言，藉由還原(Kroll)法等製造鈦時，作為反應容器，使用由不鏽鋼(SUS)等含有Fe原子之材料構成者，或者作為破碎鈦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, the method for making the titanium nitride-containing particles contain Fe atoms is not particularly limited. For example, the method of introducing Fe atoms into the titanium particles (titanium powder) used as the raw material of the titanium nitride-containing particles is mentioned. Methods etc. In more detail, when titanium is produced by the reduction (Kroll) method, etc., it is used as a reaction vessel made of a material containing Fe atoms such as stainless steel (SUS), or used as a material for a punch and a pulverizer when titanium is crushed By containing Fe atoms, Fe atoms can be attached to the surface of titanium particles.

並且，含氮化鈦粒子的製造中利用熱等離子體法時，除了作為原料之鈦粒子以外，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，藉此能夠使含氮化鈦粒子含有Fe原子。 In addition, when the thermal plasma method is used in the production of titanium nitride-containing particles, in addition to the titanium particles as the raw material, components such as Fe particles and Fe oxide are added, and the thermal plasma method is used to nitrate these particles, thereby The titanium nitride-containing particles can contain Fe atoms.

另外，含氮化鈦粒子中包含之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、氧氮化物、硫化物及硫氧化物等任一形態包含。並且，含氮化鈦粒子中包含之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 titanium nitride-containing particles can be used as ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, sulfides, and sulfur. Any form such as oxide is included. In addition, the Fe atoms contained in the titanium nitride-containing particles may exist as impurities in inter-lattice positions, or may exist as impurities in an amorphous state at the grain boundaries.

含氮化鈦粒子中的Fe原子的含量相對於含氮化鈦粒子總質量，超過0.001質量%且小於0.4質量%。其中，0.01~0.2質量%為較佳，0.02~0.1質量%為更佳。藉由Fe原子的含量超過0.001質量%，硬化膜的圖案 形成性優異。藉由Fe原子的含量小於0.4質量%，基於硬化膜之電極的防腐性優異(能夠抑制硬化膜腐蝕電極)。 The content of Fe atoms in the titanium nitride-containing particles is more than 0.001% by mass and less than 0.4% by mass relative to the total mass of the titanium nitride-containing particles. Among them, 0.01 to 0.2% by mass is preferable, and 0.02 to 0.1% by mass is more preferable. With the Fe atom content exceeding 0.001% by mass, the pattern of the cured film Excellent formability. Since the Fe atom content is less than 0.4% by mass, the cured film-based electrode has excellent corrosion resistance (the cured film can inhibit corrosion of the electrode).

亦即，藉由含氮化鈦粒子中的Fe原子的含量在上述範圍內，可顯著地發揮本發明的效果(硬化膜的圖案形成性及電極的防腐性)。 That is, when the content of Fe atoms in the titanium nitride-containing particles is within the above range, the effects of the present invention (pattern forming properties of the cured film and corrosion resistance of the electrodes) can be significantly exhibited.

其中，含氮化鈦粒子中的Fe原子的含量藉由ICP(高頻電感耦合等離子體)發光分光分析法測定。 Among them, the content of Fe atoms in the titanium nitride-containing particles is measured by ICP (High Frequency Inductively Coupled Plasma) emission spectrometry.

含氮化鈦粒子還含有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，圖案形成性得到提高之理由，認為與上述之Fe原子相同。 The titanium nitride-containing particles preferably further contain Si atoms (silicon atoms). Thereby, the pattern formability of the cured film is further improved. The reason why the pattern formability is improved by containing Si atoms is considered to be the same as the aforementioned Fe atoms.

含氮化鈦粒子中的Si原子的含量相對於含氮化鈦粒子總質量，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。藉由Si原子的含量超過0.002質量%，硬化膜的圖案形成性更加提高。並且認為，藉由小於0.3質量%，含氮化鈦粒子的最表層的極性穩定，使含氮化鈦粒子分散時的分散劑向含氮化鈦粒子的吸附性得到優化，含氮化鈦粒子的未分散物減少，藉此具有抑制產生顆粒之效果。 The content of Si atoms in the titanium nitride-containing particles relative to the total mass of the titanium nitride-containing particles is preferably more than 0.002% by mass and less than 0.3% by mass, more preferably 0.01~0.15% by mass, and more preferably 0.02~0.1% by mass Better. When the content of Si atoms exceeds 0.002% by mass, the pattern formability of the cured film is further improved. It is also believed that by less than 0.3% by mass, the polarity of the outermost layer of the titanium nitride-containing particles is stabilized, and the adsorbability of the dispersant to the titanium nitride-containing particles when the titanium nitride-containing particles are dispersed is optimized. The undispersed matter is reduced, which has the effect of inhibiting the generation of particles.

含氮化鈦粒子中的Si原子的含量藉由與上述Fe原子相同的方法測定。 The content of Si atoms in the titanium nitride-containing particles is measured by the same method as the aforementioned Fe atoms.

作為使含氮化鈦粒子含有Si原子之方法，並無特別限定，例如，可舉出在獲得上述用作含氮化鈦粒子的原料之鈦粒子(鈦粉末)之階段導入Si原子之方法等。更詳細而言，藉由還原法等製造鈦時，作為反應容器，使用由含有Si原子之材料構成者，或者作為破碎鈦時的沖壓機及粉碎機的材料使用含有Si原子者，藉此能夠使Si原子附著於鈦粒子的表面。 The method for making the titanium nitride-containing particles contain Si atoms is not particularly limited. For example, a method of introducing Si atoms in the step of obtaining the above-mentioned titanium particles (titanium powder) used as the raw material of the titanium nitride-containing particles, etc. . In more detail, when titanium is produced by a reduction method or the like, a reaction vessel made of a material containing Si atoms is used, or a material containing Si atoms is used as a material for a punch and a crusher when titanium is crushed. The Si atoms are attached to the surface of the titanium particles.

並且，含氮化鈦粒子的製造中利用熱等離子體法時，除了作為原料之鈦粒子以外，添加Si粒子、Si氧化物等成分，並藉由熱等離子體法使該些氮化，藉此能夠使含氮化鈦粒子含有Si原子。 In addition, when the thermal plasma method is used in the production of titanium nitride-containing particles, in addition to the titanium particles as the raw material, components such as Si particles and Si oxide are added, and the thermal plasma method is used to nitrate these particles, thereby The titanium nitride-containing particles can contain Si atoms.

另外，含氮化鈦粒子中包含之Si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、氧氮化物、硫化物及硫氧化物等任一形態包含。並且，含氮化鈦粒子中包含之Si原子可以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 Si atoms contained in the titanium nitride-containing particles can be used as ions, metal compounds (including complexes), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, sulfides, and sulfur. Any form such as oxide is included. In addition, the Si atoms contained in the titanium nitride-containing particles may exist as impurities in inter-lattice positions, or may exist as impurities in an amorphous state at the grain boundaries.

含氮化鈦粒子中的鈦原子(Ti原子)的含量相對於含氮化鈦粒子的總質量，10~85質量%為較佳，15~75質量%為更佳，20~70質量%為進一步較佳。含氮化鈦粒子中的Ti原子的含量能夠藉由ICP發光分光分析法分析。 The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles relative to the total mass of the titanium nitride-containing particles is preferably 10 to 85% by mass, more preferably 15 to 75% by mass, and 20 to 70% by mass Further better. The content of Ti atoms in the titanium nitride-containing particles can be analyzed by ICP emission spectrometry.

含氮化鈦粒子中的氮原子(N原子)的含量相對於含氮化鈦粒子的總質量，3~60質量%為較佳，5~50質量%為更佳，10~40質量%為進一步較佳。氮原子的含量能夠藉由惰性氣體熔融熱導法分析。 The content of nitrogen atoms (N atoms) in the titanium nitride-containing particles relative to the total mass of the titanium nitride-containing particles is preferably 3-60% by mass, more preferably 5-50% by mass, and 10-40% by mass Further better. The content of nitrogen atoms can be analyzed by inert gas fusion thermal conductivity method.

含氮化鈦粒子作為主成分包含氮化鈦(TiN)，通常在其合成時混入氧之情況及粒徑較小之情況等時變得顯著，但亦可藉由粒子表面的氧化等，含有一部分氧原子。 Titanium nitride-containing particles contain titanium nitride (TiN) as the main component, which is usually noticeable when oxygen is mixed during synthesis and when the particle size is small. However, it may also be contained by oxidation of the particle surface. Part of the oxygen atom.

含氮化鈦粒子中的氧原子的含量相對於含氮化鈦粒子的總質量，1~40質量%為較佳，1~35質量%為更佳，5~30質量%為進一步較佳。氧原子的含量能夠藉由惰性氣體熔融紅外線吸收法分析。 The content of oxygen atoms in the titanium nitride-containing particles is preferably 1 to 40% by mass, more preferably 1 to 35% by mass, and more preferably 5 to 30% by mass relative to the total mass of the titanium nitride-containing particles. The content of oxygen atoms can be analyzed by inert gas melting infrared absorption method.

從分散穩定性及遮光性的觀點考慮，含氮化鈦粒子的比表面積為5m2/g以上100m2/g以下為較佳，10m2/g以上60m2/g以下為更佳。比表面積能夠藉由BET法求出。 From the viewpoint of dispersion stability and light-shielding properties, the specific surface area of the titanium nitride-containing particles is preferably 5 m 2 /g or more and 100 m 2 /g or less, and more preferably 10 m 2 /g or more and 60 m 2 /g or less. The specific surface area can be obtained by the BET method.

含氮化鈦粒子可以係包含氮化鈦粒子與金屬微粒之複合微粒。 The titanium nitride-containing particles may be composite particles comprising titanium nitride particles and metal particles.

複合微粒係指，氮化鈦粒子與金屬微粒複合化或處於高度分散之狀態之粒子。其中，“複合化”表示，粒子由氮化鈦與金屬的兩個成分構成，“高度分散之狀態”表示，氮化鈦粒子與金屬粒子分別個別地存在，且少量成分的粒子未凝聚而均勻、相同地分散。 Composite particles refer to particles in which titanium nitride particles and metal particles are compounded or in a highly dispersed state. Among them, "composite" means that the particles are composed of two components of titanium nitride and metal, and "highly dispersed state" means that titanium nitride particles and metal particles exist separately, and the particles of a small amount of components are not aggregated and uniform. , Disperse equally.

作為金屬微粒，並無特別限定，例如可舉出選自銅、銀、金、鉑、鈀、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。從耐濕性更優異之觀點考慮，銀為較佳。 The metal particles are not particularly limited, and examples include those selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, and calcium. , Titanium, bismuth, antimony and lead, and at least one of these alloys. Among them, at least one selected from the group consisting of copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and iridium, and these alloys is preferred, and is preferably selected from copper, silver, gold, platinum and tin, and At least one of these alloys is more preferable. From the viewpoint of better moisture resistance, silver is preferred.

作為含氮化鈦粒子中的金屬微粒的含量，相對於含氮化鈦粒子的總質量，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。 As the content of the metal fine particles in the titanium nitride-containing particles, relative to the total mass of the titanium nitride-containing particles, 5% by mass or more and 50% by mass or less are preferable, and 10% by mass or more and 30% by mass or less are more preferable.

將CuKα射線作為X射線源時，含氮化鈦粒子的源自(200)面之峰的衍射角2θ超過42.6°且43.5°以下為較佳。利用含有具有該種特徵之含氮化鈦粒子之組成物來獲得之硬化膜(例如，黑矩陣等)能夠在將組成物中的含氮化鈦粒子的濃度保持為較低之狀態下實現較高OD值。其結果，硬化膜能夠確保高黏附性。 When CuKα rays are used as the X-ray source, it is preferable that the diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles exceeds 42.6° and 43.5° or less. The cured film (for example, black matrix, etc.) obtained by using a composition containing titanium nitride particles with such characteristics can achieve a relatively low concentration of the titanium nitride particles in the composition. High OD value. As a result, the cured film can ensure high adhesion.

將CuKα射線作為X射線源來測定鈦化合物的X射線衍射光譜時，作為強度最強之峰，關於TiN，源自(200)面之峰出現在2θ=42.5°附近，關於TiO，源自(200)面之峰出現在2θ=43.4°附近。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°附近觀測到源自(200)面之峰，關於金紅石型TiO2，在2θ=39.2°附近觀測到源自(200)面之峰。藉此，越是含有大量氧原子之晶體狀態，峰位置相對於42.5°越向高角度側位移。 When CuKα rays are used as X-ray sources to measure the X-ray diffraction spectrum of titanium compounds, as the strongest peak, for TiN, the peak derived from the (200) plane appears near 2θ=42.5°, and for TiO, it is derived from (200 The peak of the surface appears near 2θ=43.4°. On the other hand, although it is not the strongest peak, for anatase TiO 2 , a peak derived from the (200) plane is observed near 2θ=48.1°, and for rutile TiO 2 , it is observed near 2θ=39.2° To the peak from (200) face. Thereby, the more the crystal state contains a large amount of oxygen atoms, the more the peak position shifts to the higher angle side with respect to 42.5°.

從粒子的經時穩定性的觀點考慮，含氮化鈦粒子的源自(200)面之峰的衍射角2θ超過42.6°且小於43.5°為較佳，而且，從製造時的工藝餘量優異之觀點考慮，42.7°以上且小於43.5°為更佳，而且，從粒子性能的再現性優異之觀點考慮，42.7°以上且小於43.4°為進一步較佳。作為副成分含有氧化鈦TiO2時，作為強度最強之峰，源自銳鈦礦型TiO2(101)之峰出現在2θ=25.3°附近，源自金紅石型TiO2(110)之峰出現在2θ=27.4°附近。但是，TiO2為白色，會成為降低黑矩陣的遮光性之主要原因，因此降低至不會作為峰而被觀察之程度為較佳。 From the viewpoint of particle stability over time, the diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles is preferably more than 42.6° and less than 43.5°, and it is excellent in terms of process margin during manufacturing. From this viewpoint, 42.7° or more and less than 43.5° is more preferable, and from the viewpoint of excellent particle performance reproducibility, 42.7° or more and less than 43.4° is more preferable. When titanium oxide TiO 2 is contained as an auxiliary component, as the strongest peak, the peak derived from anatase TiO 2 (101) appears near 2θ=25.3°, and the peak derived from rutile TiO 2 (110) appears Now 2θ=27.4°. However, TiO 2 is white, which is the main cause of reducing the light-shielding property of the black matrix, so it is better to reduce it to the extent that it is not observed as a peak.

能夠藉由X射線衍射峰的半值幅求出構成含氮化鈦粒子之微晶尺寸，利用謝勒(Scherrer)公式進行計算。 The size of the crystallites constituting the titanium nitride-containing particles can be calculated from the half-value width of the X-ray diffraction peak, and calculated using Scherrer's formula.

作為微晶尺寸，20nm以上為較佳，20~50nm為更佳。藉由利用微晶尺寸為20nm以上的含氮化鈦粒子形成黑矩陣，硬化膜的透射光呈如其峰波長為475nm以下的藍色至藍紫色，能夠獲得兼具較高之遮光性與紫外線靈敏度之黑矩陣。藉由微晶尺寸為20nm以上，具有活性之粒子表面佔粒 子體積之比例變小，成為良好的平衡，成為含氮化鈦粒子的耐熱性和/或耐久性更優異者。 As the crystallite size, 20 nm or more is preferred, and 20-50 nm is more preferred. By using titanium nitride-containing particles with a crystallite size of 20nm or more to form a black matrix, the transmitted light of the cured film is blue to blue-violet with a peak wavelength of 475nm or less, which can achieve both high light shielding and ultraviolet sensitivity. The black matrix. With the crystallite size above 20nm, the surface of the active particles occupies the particles The ratio of the sub-volumes becomes small, and a good balance is achieved, and the heat resistance and/or durability of the titanium nitride-containing particles are more excellent.

含氮化鈦粒子的含量相對於組成物的總固體含量，20~70質量%為較佳，30~70質量%為更佳，40~70質量%為進一步較佳，45~70質量%尤為佳。藉由含氮化鈦粒子的含量為20質量%以上，遮光性得到提高。藉由含氮化鈦粒子的含量為70質量%以下，組成物的經時穩定性得到提高。 The content of titanium nitride-containing particles relative to the total solid content of the composition is preferably 20 to 70% by mass, more preferably 30 to 70% by mass, more preferably 40 to 70% by mass, and particularly preferably 45 to 70% by mass good. When the content of the titanium nitride-containing particles is 20% by mass or more, the light-shielding property is improved. When the content of the titanium nitride-containing particles is 70% by mass or less, the stability of the composition over time is improved.

另外，本說明書中，固體含量表示構成藉由組成物形成之硬化膜之成分，不包含溶劑。例如，後述之聚合性化合物為構成硬化膜之成分，即使係液體(液裝)，亦包含於固體含量中。 In addition, in this specification, the solid content means the components constituting the cured film formed by the composition, and does not include the solvent. For example, the polymerizable compound described later is a component constituting the cured film, and even if it is a liquid (liquid), it is included in the solid content.

組成物中的含氮化鈦粒子的粒徑D90為5~100nm為較佳，10~75nm為更佳，10~60nm為進一步較佳。組成物中的含氮化鈦粒子的粒徑利用Microtrac BEL Corp.製造的依據粒度分佈測定裝置Nanotrac UPA-150EX之装置進行測定。 The particle size D90 of the titanium nitride-containing particles in the composition is preferably 5 to 100 nm, more preferably 10 to 75 nm, and even more preferably 10 to 60 nm. The particle size of the titanium nitride-containing particles in the composition was measured with an apparatus based on the particle size distribution measuring apparatus Nanotrac UPA-150EX manufactured by Microtrac BEL Corp..

本發明的組成物中，藉由以下的粒子數測定方法求出之10μm以上的尺寸的含氮化鈦粒子的數量為100個以下為較佳，0~100個為更佳，0~20個為進一步較佳。藉此，組成物的過濾性得到提高。 In the composition of the present invention, the number of titanium nitride-containing particles with a size of 10 μm or more determined by the following particle number measurement method is preferably 100 or less, 0-100 is more preferably, 0-20 It is further preferred. Thereby, the filterability of the composition is improved.

粒子數測定方法：製備藉由丙二醇單甲醚乙酸酯將本發明的組成物稀釋為500之試料溶液。藉由流動式顆粒圖像分析儀測定試料溶液10ml中包含之10μm以上的尺寸的含氮化鈦粒子的數量。 Method for measuring the number of particles: Prepare a sample solution in which the composition of the present invention is diluted to 500 by propylene glycol monomethyl ether acetate. The number of titanium nitride-containing particles with a size of 10 μm or more contained in 10 ml of the sample solution was measured by a flow-type particle image analyzer.

含氮化鈦粒子的尺寸能夠使用流動式顆粒圖像分析儀(Flow Particle Image Analyzer)來測定。作為流動式顆粒圖像分析儀的具體例，可 舉出Sysmex Corporation製造流動式顆粒圖像分析儀FPIA？3000。FPIA？3000係利用成像流式細胞法測定粒子圖像，進行粒子分析之装置。 The size of the titanium nitride-containing particles can be measured using a flow particle image analyzer (Flow Particle Image Analyzer). As a specific example of a flow particle image analyzer, What is the flow-type particle image analyzer FPIA manufactured by Sysmex Corporation? 3000. FPIA? The 3000 series uses imaging flow cytometry to measure particle images and perform particle analysis.

關於含氮化鈦粒子的尺寸，使藉由有機溶劑或水等溶劑稀釋組成物之試料溶液通過流動式顆粒圖像分析儀的平面且扁平的透明流通槽(厚度約200μm)的流路(沿著流動方向擴展之流路)來進行測定。 Regarding the size of titanium nitride-containing particles, a sample solution of the composition diluted with a solvent such as an organic solvent or water is passed through the flow path (along the flat and flat transparent flow channel (thickness about 200 μm)) of the flow-type particle image analyzer. Measured along the flow path extending in the direction of flow).

流動式顆粒圖像分析儀中，為了形成沿與流通槽的厚度方向交叉之方向通過之光路，安裝成閃光燈與CCD相機相對於流通槽，位於相互相反側。閃光燈在試料溶液流過流路期間，以1/60秒間隔照射閃光燈光。其結果，流過流通槽之各個粒子作為在流通槽具有平行的一定範圍之2維圖像而被攝影。依各個粒子的2維圖像的面積，計算具有相同面積之圓的直徑作為本發明的“尺寸”。 In the flow-type particle image analyzer, in order to form an optical path passing in a direction crossing the thickness direction of the flow groove, the flash and the CCD camera are installed on the opposite sides of the flow groove. The flash lamp irradiates the flash lamp light at intervals of 1/60 second while the sample solution flows through the flow path. As a result, each particle flowing through the flow groove is photographed as a two-dimensional image having a certain range in parallel in the flow groove. Based on the area of the two-dimensional image of each particle, the diameter of a circle with the same area is calculated as the "size" of the present invention.

用於測定之試料藉由有機溶劑或水等溶劑稀釋組成物來製備為較佳。試料為以分散狀態含有含氮化鈦粒子之分散液為更佳。試料的製備方法為藉由有機溶劑或水等溶劑，以固體含量成為10~40質量%之方式稀釋包含含氮化鈦粒子之組成物為較佳，使含氮化鈦粒子以外的成分溶解於溶劑之後，使含氮化鈦粒子再分散為更佳。 The sample used for the measurement is preferably prepared by diluting the composition with a solvent such as an organic solvent or water. The sample is more preferably a dispersion liquid containing titanium nitride-containing particles in a dispersed state. The preparation method of the sample is preferably to dilute the composition containing titanium nitride particles with a solvent such as an organic solvent or water so that the solid content becomes 10-40% by mass, so that the components other than the titanium nitride particles are dissolved in After the solvent, it is better to redisperse the titanium nitride-containing particles.

試料為將已使含氮化鈦粒子再分散之分散液進一步稀釋為10~2000倍為進一步較佳。作為已使含氮化鈦粒子分散之分散液的狀態，藉由動態光散射法測定分散液之含氮化鈦粒子的平均粒徑(D90)為1μm以下之狀態為較佳。 As the sample, it is more preferable to further dilute the dispersion liquid in which the titanium nitride-containing particles have been redispersed to 10 to 2000 times. As the state of the dispersion liquid in which the titanium nitride-containing particles have been dispersed, it is preferable to measure the average particle size (D90) of the titanium nitride-containing particles in the dispersion liquid to be 1 μm or less by a dynamic light scattering method.

作為基於動態光散射法之測定装置，並無特別限定，可舉出 MicrotracBEL Corp.製造、產品名“Nanotrac UPA-150EX”等。 As a measuring device based on the dynamic light scattering method, there is no particular limitation, and examples include MicrotracBEL Corp., product name "Nanotrac UPA-150EX", etc.

<分散劑> <Dispersant>

本發明的組成物含有分散劑為較佳。分散劑有助於提高上述含氮化鈦粒子等顏料的分散性。本發明中，分散劑為與後述黏結樹脂不同之成分。 The composition of the present invention preferably contains a dispersant. The dispersant contributes to improving the dispersibility of the pigment such as the above-mentioned titanium nitride-containing particles. In the present invention, the dispersant is a component different from the binder resin described later.

作為分散劑，例如，可適當選擇公知的顏料分散劑來使用。其中，高分子化合物為較佳。 As the dispersant, for example, a known pigment dispersant 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, a polymer dispersant [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (formaldehyde) (Base) acrylic acid ester, (meth)acrylic acid copolymer, naphthalenesulfonate formalin condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine and pigment derivatives.

高分子化合物可依其結構，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.

高分子化合物吸附於作為含氮化鈦粒子的較佳態樣之黑色顏料及依需要併用之顏料等被分散體的表面，發揮防止被分散體的再凝聚之作用。故，具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、嵌段型高分子為較佳。 The polymer compound is adsorbed on the surface of the dispersed body such as a black pigment which is a preferred form of titanium nitride-containing particles and a pigment used in combination as needed to prevent the dispersed body from re-aggregating. Therefore, terminal-modified polymers, graft-type polymers, and block-type polymers having fixed sites on the surface of the pigment are preferred.

另一方面，藉由對含氮化鈦粒子的表面進行改質，還能夠促進高分子化合物對此的吸附性。 On the other hand, by modifying the surface of the titanium nitride-containing particles, the adsorbability of the polymer compound can also be promoted.

高分子化合物具有具備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。 The polymer compound preferably has a structural unit having a graft chain. In addition, in this specification, "structural unit" has the same meaning as "repeating unit".

具有該種具備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，故係黑色顏料等著色顏料的分散性及經時之後的分散穩定性優異者。並且，藉由存在接枝鏈，包含具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，在鹼顯影中不易生成殘渣。 The polymer compound with this kind of structural unit with graft chain has The affinity of the agent is excellent in the dispersibility of color pigments such as black pigments and the dispersion stability over time. In addition, by the presence of the graft chain, the polymer compound containing the structural unit having the graft chain has affinity with the polymerizable compound or other resins that can be used in combination. As a result, residues are less likely to be generated during alkali development.

若接枝鏈變長，則立體排斥效果提高而顏料等的分散性得到提高。另一方面，若接枝鏈過長，則向黑色顏料等著色顏料的吸附力下降，顏料等的分散性處於下降的趨勢。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。 If the graft chain becomes longer, the steric repulsion effect is improved and the dispersibility of the pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorption power to color pigments such as black pigments will decrease, and the dispersibility of the pigments and the like will tend 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 more preferably 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 (atoms bonded to the main chain from the group branched from the main chain) to the end of the group branched from the main chain.

接枝鏈具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 has a polymer structure. Examples of the polymer structure include poly(meth)acrylate structure (for example, poly(meth)acrylic acid structure), polyester structure, polyurethane structure, and poly(meth)acrylate structure. Urea structure, polyamide structure and polyether structure, etc.

為了提高接枝鏈與溶劑的相互作用性，並藉此提高分散性，接枝鏈係具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，具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 graft chain and the solvent and thereby improve the dispersibility, the graft chain has at least one selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylate structure. A graft chain is preferable, and a graft chain having at least any one of a polyester structure and a polyether structure is more preferable.

作為具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 having this kind of graft chain is not particularly limited, and a macromonomer having a reactive double bond group can be suitably used.

與高分子化合物所具有之具有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，可使用AA-6(商品名、TOAGOSEI 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.Company,Limited.製造)、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)及Blemmer PME-4000(商品名、NOF CORPORATION.製造)等為較佳。 Corresponding to the structural unit with graft chain possessed by polymer compounds, as a commercially available macromonomer suitable for synthesizing polymer compounds, AA-6 (trade name, TOAGOSEI CO., LTD..), AA-10 (trade name, TOAGOSEI CO., LTD..), AB-6 (trade name, TOAGOSEI CO., LTD..), AS-6 (trade name, 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, TOAGOSEI CO., LTD..), AY-707 (trade name, TOAGOSEI CO., LTD..), AY-714 (trade name, TOAGOSEI CO., LTD..), AK-5 (trade name, TOAGOSEI CO., LTD.), AK-30 (trade name, TOAGOSEI CO., LTD..), AK-32 (trade name, TOAGOSEI CO., LTD.), Blemmer PP-100 (trade name) , NOF CORPORATION.), Blemmer PP-500 (brand name, NOF CORPORATION.), Blemmer PP-800 (brand name, NOF CORPORATION.), Blemmer PP-1000 (brand name, NOF CORPORATION.), Blemmer 55-PET-800 (trade name, manufactured by NOF CORPORATION.), Blemmer PME-4000 (trade name, manufactured by NOF CORPORATION.), Blemmer PSE-400 (trade name, manufactured by NOF CORPORATION.), Blemmer PSE-1300 (trade name , NOF CORPORATION.), Blemmer 43PAPE-600B (trade name, NOF CORPORATION.), etc. Among them, AA-6 (trade name, manufactured by Toagosei. Company, Limited.), AA-10 (trade name, manufactured by TOAGOSEI CO., LTD..), AB-6 (trade name, TOAGOSEI CO., LTD.. Manufacturing), AS-6 (trade name, TOAGOSEI CO., LTD..), AN-6 (trade name, TOAGOSEI CO., LTD.. manufacturing), Blemmer PME-4000 (trade name, NOF CORPORATION.), etc. For better.

本發明的分散劑具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組之至少1種結構為較佳。本發明的分散劑為選自 包含聚丙烯酸甲酯、聚甲基丙烯酸甲酯及鏈狀的聚酯之組之至少1種為更佳。本發明的分散劑為選自包含聚丙烯酸甲酯、聚甲基丙烯酸甲酯、聚己內酯及聚戊內酯之組之至少1種為進一步較佳。分散劑可以係在1個分散劑中單獨具有上述結構者，亦可以係在1個分散劑中具有複數個該些結構者。 The dispersant of the present invention preferably has at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. The dispersant of the present invention is selected from It is more preferable to include at least one of the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyester. The dispersant of the present invention is more preferably at least one selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, polycaprolactone, and polyvalerolactone. The dispersant may be one having the above-mentioned structure alone in one dispersing agent, or one having a plurality of these structures in one dispersing agent.

其中，聚己內酯結構係指作為重複單元具有對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具有對δ-戊內酯進行開環之結構者。 Here, the polycaprolactone structure refers to a structure having a ring-opening structure for ε-caprolactone as a repeating unit. The polyvalerolactone structure refers to a repeating unit having a structure in which δ-valerolactone is ring-opened.

作為具有聚己內酯結構之分散劑的具體例，可舉出下述式(1)及下述式(2)中的j及k為5者。並且，作為具有聚戊內酯結構之分散劑的具體例，可舉出下述式(1)及下述式(2)中的j及k為4者。 As a specific example of the dispersing agent which has a polycaprolactone structure, j and k in the following formula (1) and following formula (2) are mentioned. In addition, as a specific example of the dispersant having a polyvalerolactone structure, one in which j and k in the following formula (1) and the following formula (2) are 4 can be given.

作為具有聚丙烯酸甲酯結構之分散劑的具體例，可舉出下述式(4)中的X5為氫原子，且R4為甲基者。並且，作為具有聚甲基丙烯酸甲酯結構之分散劑的具體例，可舉出下述式(4)中的X5為甲基，且R4為甲基者。 As a specific example of the dispersant having a polymethyl acrylate structure, X 5 in the following formula (4) is a hydrogen atom, and R 4 is a methyl group. In addition, as a specific example of the dispersant having a polymethyl methacrylate structure, X 5 in the following formula (4) is a methyl group and R 4 is a methyl group.

高分子化合物作為具有接枝鏈之結構單元，包含以下述式(1)~式(4)的任一個表示之結構單元為較佳，包含以下述式(1A)、下述式(2A)、下述式(3A)、下述式(3B)及下述(4)的任一個表示之結構單元為更佳。 As a structural unit having a graft chain, the polymer compound preferably includes a structural unit represented by any one of the following formulas (1) to (4), including the following formula (1A), the following formula (2A), The structural unit represented by any one of the following formula (3A), the following formula (3B), and the following (4) is more preferable.

Figure 106104991-A0305-02-0020-1
Figure 106104991-A0305-02-0020-1

式(1)~式(4)中，W1、W2、W3及W4分別獨立地表示氧原子或NH。W1、W2、W3及W4為氧原子為較佳。 In formula (1) to formula (4), W 1 , W 2 , W 3 and W 4 each independently represent an oxygen atom or NH. W 1 , W 2 , W 3 and W 4 are preferably oxygen atoms.

式(1)~式(4)中，X1、X2、X3、X4及X5分別獨立地表示氫原子或1價的有機基團。作為X1、X2、X3、X4及X5，從合成方面的限制的觀點考慮，分別獨立地為氫原子或碳原子數(碳素原子數)1~12的烷基為較佳，分別獨立地為氫原子或甲基為更佳，甲基為進一步較佳。 In formula (1) to formula (4), X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a monovalent organic group. As X 1 , X 2 , X 3 , X 4 and X 5 , from the viewpoint of synthesis restriction, each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms) is preferred , Each independently being a hydrogen atom or a methyl group is more preferred, and a methyl group is even more preferred.

式(1)~式(4)中，Y1、Y2、Y3及Y4分別獨立地表示2價的連結基，連結基的結構方面並無特別的限制。作為以Y1、Y2、Y3及Y4表示之2價的連結基，具體而言，可舉出下述(Y-1)~(Y-21)的連結基等為例。下述所示之結構中，A、B分別表示與式(1)~式(4)中的左末端基、右末端基的鍵結部位。下述中示出之結構中，從合成的簡便性考慮，(Y-2)或(Y-13)為更佳。 In formulas (1) to (4), Y 1 , Y 2 , Y 3 and Y 4 each independently represent a divalent linking group, and there is no particular restriction on the structure of the linking group. As the divalent linking group represented by Y 1 , Y 2 , Y 3 and Y 4 , specifically, the linking group of the following (Y-1) to (Y-21) and the like can be given as examples. In the structure shown below, A and B respectively represent the bonding site with the left end group and the right end group in formula (1) to formula (4). Among the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.

Figure 106104991-A0305-02-0021-2
Figure 106104991-A0305-02-0021-2

式(1)~式(4)中，Z1、Z2、Z3及Z4分別獨立地表示1價的有機基團。有機基團的結構並無特別限定，具體而言，可舉出烷基、羥基、烷氧基、芳氧基、雜芳氧基、烷硫醚基、芳硫醚基、雜芳硫醚基及胺基等。該些中，作為以Z1、Z2、Z3及Z4表示之有機基團，尤其從分散性提高的觀點考慮，具有立體排斥效果者為較佳，分別獨立地為碳原子數5至24的烷基或烷氧基為較佳，其中，分別獨立地為碳原子數5至24的分支烷基、碳原子數5至24的環狀烷基或碳原子數5至24的烷氧基尤為佳。另外，烷氧基中包含之烷基可以係直鏈狀、支鏈狀及環狀的任一個。 In formulas (1) to (4), Z 1 , Z 2 , Z 3 and Z 4 each independently represent a monovalent organic group. The structure of the organic group is not particularly limited. Specifically, it includes an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl sulfide group, an arylene sulfide group, and a heteroarylene sulfide group. And amino groups, etc. Among these, as the organic groups represented by Z 1 , Z 2 , Z 3 and Z 4 , especially from the viewpoint of improving dispersibility, those having a stereorepulsive effect are preferred, and each independently has a carbon number of 5 to The alkyl group or alkoxy group of 24 is preferred, wherein each independently is a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms. Kie is better. In addition, the alkyl group contained in the alkoxy group may be any of linear, branched, and cyclic.

式(1)~式(4)中，n、m、p及q分別獨立地為1至500的整數。 In formula (1) to formula (4), n, m, p, and q are each independently an integer from 1 to 500.

並且，式(1)及式(2)中，j及k分別獨立地表示2~8的整數。從組成物的分散穩定性及顯影性的觀點考慮，式(1)及式(2)中的j及k為4~6的整數為較佳，5最為佳。 In addition, in formula (1) and formula (2), j and k each independently represent an integer of 2-8. From the viewpoint of dispersion stability and developability of the composition, it is preferable that j and k in formula (1) and formula (2) be an integer of 4 to 6, and 5 is most preferable.

式(3)中，R3表示分支或者直鏈的伸烷基，碳原子數1~10的伸烷基為較佳，碳原子數2或3的伸烷基為更佳。p為2~500時，存在複數個之R3可相互相同亦可互不相同。 In the formula (3), R 3 represents a branched or linear alkylene group, and an alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 2 or 3 carbon atoms is more preferred. When p is 2 to 500, there are a plurality of R 3 which may be the same or different from each other.

式(4)中，R4表示氫原子或1價的有機基團，作為該1價的有機基團，結構上並無特別限定。作為R4，可較佳地舉出氫原子、烷基、芳基及雜芳基，氫原子或烷基為更佳。R4為烷基時，作為烷基，碳原子數1~20的直鏈狀烷基、碳原子數3~20的分支狀烷基或碳原子數5~20的環狀烷基為較佳，碳原子數1~20的直鏈狀烷基為更佳，碳原子數1~6的直鏈狀烷基 為進一步較佳。式(4)中，q為2~500時，接枝共聚物中存在複數個之X5及R4可相互相同亦可互不相同。 In formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. As R 4 , preferably a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group are mentioned, and a hydrogen atom or an alkyl group is more preferable. When R 4 is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. , A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is more preferable. In the formula (4), when q is 2 to 500, multiple X 5 and R 4 in the graft copolymer may be the same or different from each other.

並且，高分子化合物可具有2種以上的不同結構且具有接枝鏈之結構單元。亦即，高分子化合物的分子中可以包含結構互不相同之以式(1)~式(4)表示之結構單元，並且，式(1)~式(4)中，n、m、p及q分別表示2以上的整數時，式(1)及式(2)中，可在側鏈中包含j及k互不相同之結構，式(3)及式(4)中，分子內存在複數個之R3、R4及X5可相互相同亦可互不相同。 In addition, the polymer compound may have two or more different structures and a structural unit of a graft chain. That is, the molecules of the polymer compound may contain structural units represented by formulas (1) to (4) that are different in structure, and in formulas (1) to (4), n, m, p, and When q represents an integer of 2 or more, in formulas (1) and (2), structures with different j and k can be included in the side chain. In formulas (3) and (4), there are plural numbers in the molecule R 3 , R 4 and X 5 may be the same or different from each other.

作為以式(1)表示之結構單元，從組成物的分散穩定性及顯影性的觀點考慮，以下述式(1A)表示之結構單元為更佳。 As the structural unit represented by the formula (1), from the viewpoint of dispersion stability and developability of the composition, a structural unit represented by the following formula (1A) is more preferable.

並且，作為以式(2)表示之結構單元，從組成物的分散穩定性及顯影性的觀點考慮，以下述式(2A)表示之結構單元為更佳。 In addition, as the structural unit represented by the formula (2), from the viewpoint of dispersion stability and developability of the composition, a structural unit represented by the following formula (2A) is more preferable.

Figure 106104991-A0305-02-0023-3
Figure 106104991-A0305-02-0023-3

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

並且，作為以式(3)表示之結構單元，從組成物的分散穩定性及 顯影性的觀點考慮，以下述式(3A)或式(3B)表示之結構單元為更佳。 And, as a structural unit represented by formula (3), from the dispersion stability of the composition and From the viewpoint of developability, a structural unit represented by the following formula (3A) or formula (3B) is more preferable.

Figure 106104991-A0305-02-0024-4
Figure 106104991-A0305-02-0024-4

式(3A)或(3B)中，X3、Y3、Z3及p的含義與式(3)中的X3、Y3、Z3及p相同，較佳範圍亦相同。 Formula (3A) or (3B) in, 3, Y 3, Z 3 and same p X 3, Y 3, Z 3 and p are defined for the formula X (3) is, preferred ranges are also the same.

高分子化合物作為具有接枝鏈之結構單元，具有以式(1A)表示之結構單元為更佳。 As the structural unit having a graft chain, the polymer compound preferably has a structural unit represented by formula (1A).

高分子化合物中，具有接枝鏈之結構單元(例如，以上述式(1)~式(4)表示之結構單元)以質量換算，相對於高分子化合物的總質量，以2~90%的範圍包含為較佳，以5~30%的範圍包含為更佳。若在該範圍內包含具有接枝鏈之結構單元，則黑色顏料的分散性較高，形成硬化膜時的顯影性良好。 In polymer compounds, structural units with graft chains (for example, structural units represented by the above formula (1) to formula (4)) are converted by mass, and relative to the total mass of the polymer compound, 2~90% It is better to include in the range, and more preferably to include in the range of 5 to 30%. If the structural unit having a graft chain is included in this range, the dispersibility of the black pigment is high, and the developability when forming a cured film is good.

並且，高分子化合物具有與具有接枝鏈之結構單元不同(亦即，並不相當於具有接枝鏈之結構單元)之疏水性結構單元為較佳。其中，本發明中，疏水性結構單元係不具有酸基(例如，羧酸基、磺酸基、磷酸基、酚性羥基等)之結構單元。 In addition, it is preferable that the polymer compound has a hydrophobic structural unit that is different from the structural unit having a grafted chain (that is, it is not equivalent to a structural unit having a grafted chain). Among them, in the present invention, the hydrophobic structural unit system does not have a structural unit having an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).

疏水性結構單元係源自(對應)ClogP值為1.2以上的化合物(單體)之結構單元為較佳，係源自ClogP值為1.2~8的化合物之結構單元為更佳。藉此，能夠更可靠地顯現本發明的效果。 The hydrophobic structural unit is preferably derived from (corresponding to) a structural unit of a compound (monomer) having a ClogP value of 1.2 or more, and more preferably a structural unit derived from a compound having a ClogP value of 1.2 to 8. Thereby, the effect of the present invention can be more reliably expressed.

ClogP值係藉由能夠從Daylight Chemical Information System，Inc，獲得之程序“CLOGP”計算之值。該程序提供藉由Hansch，Leo的fragmentapproach(參閱下述文獻)計算出之“計算logP”的值。Fragmentapproach依據化合物的化學結構，將化學結構分割為部分結構(片段)，合計分配於該片段之logP貢獻量，藉此推算化合物的logP值。其詳細內容記載於以下文獻中。本發明中，使用藉由程序CLOGP v4.82計算出之ClogP值。 The ClogP value is the value calculated by the program "CLOGP" that can be obtained from Daylight Chemical Information System, Inc. This program provides the value of "calculated logP" calculated by Hansch, Leo's fragment approach (refer to the following literature). Fragmentapproach divides the chemical structure into partial structures (fragments) according to the chemical structure of the compound, and sums up the logP contribution allocated to the fragments to calculate the logP value of the compound. The details are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.

A. J. Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, P. G. Sammnens,J. B. Taylor and C. A. Ramsden, Eds., p.295, Pergamon Press, 1990 C. Hansch & A. J. Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A.J. Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993. AJ Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, PG Sammnens, JB Taylor and CA Ramsden, Eds., p. 295, Pergamon Press, 1990 C. Hansch & AJ Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. AJ Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.

logP表示分配係數P(Partition Coefficient)的常用對數，係以定量的數值表示某一有機化合物在油(通常為1-辛醇)與水的2相系的平衡中如何分配之物性值，由以下式表示。 logP represents the common logarithm of the partition coefficient P (Partition Coefficient), which is a quantitative value that represents the physical property value of how a certain organic compound is distributed in the balance of the two-phase system of oil (usually 1-octanol) and water, as follows式 expression.

logP=log(Coil/Cwater) logP=log(Coil/Cwater)

式中，Coil表示油相中的化合物的莫耳濃度，Cwater表示水相中的化合物的莫耳濃度。 In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the water phase.

若logP的值夾著0而正向(plus)增大，則表示油溶性增加，若絕對值負向(minus)增大，則表示水溶性增加，與有機化合物的水溶性有負相關，作為估計有機化合物的親疏水性之參數而廣泛利用。 If the value of logP sandwiches 0 and increases in the positive direction (plus), it means that the oil solubility increases. If the absolute value increases in the negative direction (minus), it means that the water solubility increases, which has a negative correlation with the water solubility of organic compounds. It is widely used to estimate the hydrophilic and hydrophobic parameters of organic compounds.

高分子化合物作為疏水性結構單元，具有選自源自以下述通式(i) ~(iii)表示之單體的結構單元之1種以上的結構單元為較佳。 As the hydrophobic structural unit, the polymer compound has the following general formula (i) One or more structural units among the structural units of the monomer represented by ~(iii) are preferred.

Figure 106104991-A0305-02-0026-5
Figure 106104991-A0305-02-0026-5

上述式(i)~(iii)中，R1、R2及R3分別獨立地表示氫原子、鹵原子(例如，氟、氯、溴等)或碳原子數為1~6的烷基(例如，甲基、乙基、丙基等)。 In the above formulas (i) to (iii), R 1 , R 2 and R 3 each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.) or an alkyl group having 1 to 6 carbon atoms ( For example, methyl, ethyl, propyl, etc.).

R1、R2及R3係氫原子或碳原子數為1~3的烷基為較佳，氫原子或甲基為更佳。R2及R3係氫原子尤為佳。 R 1 , R 2 and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R 2 and R 3 are particularly preferably hydrogen atoms.

X表示氧原子(-O-)或亞胺基(-NH-)，氧原子為較佳。 X represents an oxygen atom (-O-) or an imino group (-NH-), and an oxygen atom is preferred.

L係單鍵或2價的連結基。作為2價的連結基，可舉出2價的脂肪族基(例如，亞烷基、取代亞烷基、亞烯基、取代亞烯基、亞炔基、取代亞炔基)、2價的芳香族基(例如，伸芳基、取代伸芳基)、2價的雜環基、氧原子(-O-)、硫原子(-S-)、亞胺基(-NH-)、取代亞胺基(-NR31-，其中，R31為脂肪族基、芳香族基或雜環基)、羰基(-CO-)及該些的組合等。 L is a single bond or a divalent linking group. Examples of the divalent linking group include divalent aliphatic groups (for example, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, and substituted alkynylene), divalent Aromatic groups (for example, aryl group, substituted aryl group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted aryl group An amino group (-NR 31 -, where R 31 is an aliphatic group, an aromatic group, or a heterocyclic group), a carbonyl group (-CO-), a combination of these, and the like.

2價的脂肪族基可具有環狀結構或分支結構。脂肪族基的碳原子數為1~20為較佳，1~15為更佳，1~10為進一步較佳。脂肪族基可以係 不飽和脂肪族基，亦可以係飽和脂肪族基，但飽和脂肪族基為較佳。並且，脂肪族基可具有取代基。取代基的例子可舉出鹵原子、芳香族基及雜環基等。 The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. Aliphatic groups can be The unsaturated aliphatic group may also be a saturated aliphatic group, but a saturated aliphatic group is preferred. In addition, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups, heterocyclic groups, and the like.

2價的芳香族基的碳原子數為6~20為較佳，6~15為更佳，6~10為進一步較佳。並且，芳香族基可具有取代基。取代基的例子可舉出鹵原子、脂肪族基、芳香族基及雜環基等。 The number of carbon atoms of the divalent aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. In addition, the aromatic group may have a substituent. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups, and heterocyclic groups.

2價的雜環基作為雜環具有5員環或6員環為較佳。雜環上可縮合有其他雜環、脂肪族環或芳香族環。並且，雜環基可具有取代基。作為取代基的例子，可舉出鹵原子、羥基、氧代基(=O)、硫代基(=S)、亞胺基(=NH)、取代亞胺基(=N-R32，其中，R32為脂肪族基、芳香族基或雜環基)、脂肪族基、芳香族基或雜環基。 The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as the heterocyclic ring. The heterocyclic ring may be condensed with other heterocyclic rings, aliphatic rings or aromatic rings. In addition, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thio groups (=S), imino groups (=NH), and substituted imino groups (=NR 32 , where R 32 is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group or a heterocyclic group.

L係單鍵、亞烷基或包含氧化烯結構之2價的連結基為較佳。氧化烯結構係氧乙烯結構或氧丙烯結構為更佳。並且，L可包含重複包含2個以上的氧化烯結構之聚氧化烯結構。作為聚氧化烯結構，聚氧乙烯結構或聚氧丙烯結構為較佳。聚氧乙烯結構以-(OCH2CH2)n-表示，n為2以上的整數為較佳，2~10的整數為更佳。 L-based single bonds, alkylene groups, or divalent linking groups containing an oxyalkylene structure are preferred. The alkylene oxide structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L may include a polyoxyalkylene structure repeatedly including two or more alkylene oxide structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by -(OCH 2 CH 2 )n-, and n is preferably an integer of 2 or more, and more preferably an integer of 2-10.

作為Z，可舉出脂肪族基(例如，烷基、取代烷基、不飽和烷基及取代不飽和烷基)、芳香族基(例如，芳基、取代芳基、伸芳基、取代伸芳基)、雜環基或該些的組合。該些基團中可包含氧原子(-O-)、硫原子(-S-)、亞胺基(-NH-)、取代亞胺基(-NR31-、其中，R31為脂肪族基、芳香族基或雜環基)、羰基(-CO-)。 As Z, aliphatic groups (for example, alkyl, substituted alkyl, unsaturated alkyl, and substituted unsaturated alkyl), aromatic groups (for example, aryl, substituted aryl, arylene, substituted alkyl) Aryl), heterocyclic group or a combination of these. These groups may contain oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino group (-NR 31 -, wherein R 31 is an aliphatic group , Aromatic group or heterocyclic group), carbonyl group (-CO-).

脂肪族基可具有環狀結構或分支結構。脂肪族基的碳原子數為1 ~20為較佳，1~15為更佳，1~10為進一步較佳。脂肪族基中還包含環集合烴基、交聯環式烴基，作為環集合烴基的例子，包含雙環己基、全氫萘基、聯苯基、4-環己基苯基等。作為交聯環式烴環，例如，可舉出：蒎烷(pinane)、莰烷(bornane)、降蒎烷(norpinane)、降莰烷(norbornane)、雙環辛烷環(雙環[2.2.2]辛烷環、雙環[3.2.1]辛烷環等)等2環式烴環；高佈雷烷(homobledane)、金剛烷、三環[5.2.1.02，6]癸烷、三環[4.3.1.12，5]十一烷環等3環式烴環；四環[4.4.0.12，5.17，10]十二烷、全氫-1，4-亞甲基-5，8-亞甲基萘環等4環式烴環等。並且，交聯環式烴環中還包含稠環式烴環，例如，全氫萘(十氫萘)、全氫蒽、全氫菲、全氫苊、全氫芴、全氫茚、全氫葩環等縮合有複數個5~8員環烷烴環之稠環。 The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. The aliphatic group also includes a ring assembly hydrocarbyl group and a cross-linked cyclic hydrocarbyl group. Examples of the ring assembly hydrocarbyl group include bicyclohexyl, perhydronaphthyl, biphenyl, 4-cyclohexylphenyl, and the like. As the crosslinked cyclic hydrocarbon ring, for example, pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo[2.2.2 ] Octane ring, bicyclic [3.2.1] octane ring, etc.) and other 2-cyclic hydrocarbon rings; homobredane (homobledane), adamantane, tricyclic [5.2.1.0 2, 6 ] decane, tricyclic [4.3 .1.1 2,5 cyclic hydrocarbon ring 3] undecane ring; tetracyclo [4.4.0.1 2,5 .1 7,10] dodecane, perhydro-1,4--5,8 -4-cyclic hydrocarbon rings such as methylene naphthalene ring, etc. In addition, the cross-linked cyclic hydrocarbon ring also includes a fused-ring hydrocarbon ring, for example, perhydronaphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydro The condensed ring is a condensed ring consisting of multiple 5- to 8-membered cycloalkane rings.

與不飽和脂肪族基相比，脂肪族基係飽和脂肪族基為較佳。並且，脂肪族基可具有取代基。取代基的例子可舉出鹵原子、芳香族基及雜環基。其中，脂肪族基作為取代基不具有酸基。 Compared with unsaturated aliphatic groups, aliphatic groups are preferably saturated aliphatic groups. In addition, the aliphatic group may have a substituent. Examples of the substituent include halogen atoms, aromatic groups and heterocyclic groups. Among them, the aliphatic group does not have an acid group as a substituent.

芳香族基的碳原子數為6~20為較佳，6~15為更佳，6~10為進一步較佳。並且，芳香族基可具有取代基。取代基的例子可舉出鹵原子、脂肪族基、芳香族基及雜環基。其中，芳香族基作為取代基不具有酸基。 The number of carbon atoms of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. In addition, the aromatic group may have a substituent. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups, and heterocyclic groups. Among them, the aromatic group does not have an acid group as a substituent.

雜環基作為雜環具有5員環或6員環為較佳。雜環上可縮合有其他雜環、脂肪族環或芳香族環。並且，雜環基可具有取代基。作為取代基的例子，可舉出鹵原子、羥基、氧代基(=O)、硫代基(=S)、亞胺基(=NH)、取代亞胺基(=N-R32，其中，R32為脂肪族基、芳香族基或雜環基)、脂肪族基、芳香族基及雜環基。其中，雜環基作為取代基不具有酸基。 The heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocyclic ring may be condensed with other heterocyclic rings, aliphatic rings or aromatic rings. In addition, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thio groups (=S), imino groups (=NH), and substituted imino groups (=NR 32 , where R 32 is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group. Among them, the heterocyclic group does not have an acid group as a substituent.

上述式(iii)中，R4、R5及R6分別獨立地表示氫原子、鹵原子(例如，氟、氯、溴等)、碳原子數為1~6的烷基(例如，甲基、乙基、丙基等)、Z或-L-Z。其中，L及Z的含義與上述中的L及Z相同。作為R4、R5及R6，氫原子或碳原子數為1~3的烷基為較佳，氫原子為更佳。 In the above formula (iii), R 4 , R 5 and R 6 each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 6 carbon atoms (for example, methyl , Ethyl, propyl, etc.), Z or -LZ. However, the meanings of L and Z are the same as those of L and Z in the above. As R 4 , R 5 and R 6 , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred, and a hydrogen atom is more preferred.

本發明中，作為以上述通式(i)表示之單體，R1、R2及R3為氫原子或甲基、L為單鍵或亞烷基或者包含氧化烯結構之2價的連結基、X為氧原子或亞胺基、Z為脂肪族基、雜環基或芳香族基之化合物為較佳。 In the present invention, as a monomer represented by the above general formula (i), R 1 , R 2 and R 3 are hydrogen atoms or methyl groups, and L is a single bond or an alkylene group, or a divalent link including an alkylene oxide structure The compound wherein X is an oxygen atom or imino group, and Z is an aliphatic group, heterocyclic group or aromatic group is preferred.

並且，作為以上述通式(ii)表示之單體，R1為氫原子或甲基、L為亞烷基、Z為脂肪族基、雜環基或芳香族基之化合物為較佳。並且，作為以上述通式(iii)表示之單體，R4、R5及R6為氫原子或甲基、Z為脂肪族基、雜環基或芳香族基之化合物為較佳。 In addition, as the monomer represented by the above general formula (ii), a compound in which R 1 is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable. In addition, as the monomer represented by the above general formula (iii), compounds in which R 4 , R 5 and R 6 are hydrogen atoms or methyl groups, and Z is an aliphatic group, heterocyclic group or aromatic group are preferred.

作為以式(i)~(iii)表示之代表性化合物的例子，可舉出選自丙烯酸酯類、甲基丙烯酸酯類及苯乙烯類等之自由基聚合性化合物。 Examples of representative compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic esters, methacrylic esters, and styrenes.

另外，作為以式(i)~(iii)表示之代表性化合物的例子，能夠參閱日本特開2013-249417號公報的段落0089~0093中記載之化合物，該些內容引入本說明書中。 In addition, as examples of representative compounds represented by formulas (i) to (iii), reference can be made to the compounds described in paragraphs 0089 to 0093 of JP 2013-249417 A, and these contents are incorporated in this specification.

高分子化合物中，疏水性結構單元以質量換算，相對於高分子化合物的總質量，以10~90%的範圍包含為較佳，以20~80%的範圍包含為更佳。含量在上述範圍中可實現充分的圖案形成。 In the polymer compound, the hydrophobic structural unit is calculated by mass, and relative to the total mass of the polymer compound, it is preferably contained in the range of 10 to 90%, and more preferably contained in the range of 20 to 80%. The content in the above range can achieve sufficient pattern formation.

高分子化合物能夠導入可與黑色顏料等著色顏料形成相互作用之官能基。其中，高分子化合物還包含具有可與黑色顏料等著色顏料形成相 互作用之官能基之結構單元為較佳。 The polymer compound can introduce functional groups that can interact with color pigments such as black pigments. Among them, the polymer compound also contains a phase that can form with black pigments and other color pigments. The structural unit of the functional group that interacts is preferred.

作為可與該黑色顏料等著色顏料形成相互作用之官能基，例如，可舉出酸基、鹼性基、配位性基及具有反應性之官能基等。 As a functional group which can form an interaction with color pigments, such as this black pigment, an acid group, a basic group, a coordination group, a functional group which has a reactivity, etc. are mentioned, for example.

高分子化合物具有酸基、鹼性基、配位性基或具有反應性之官能基時，分別含有具有酸基之結構單元、具有鹼性基之結構單元、具有配位性基之結構單元或包含具有反應性之結構單元為較佳。 When a polymer compound has an acid group, a basic group, a coordination group or a reactive functional group, it contains a structural unit with an acid group, a structural unit with a basic group, a structural unit with a coordination group, or It is preferable to include a reactive structural unit.

尤其，高分子化合物進一步具有羧酸基等鹼可溶性基作為酸基，藉此能夠對高分子化合物賦予用於基於鹼顯影之圖案形成的顯影性。 In particular, the polymer compound further has an alkali-soluble group such as a carboxylic acid group as an acid group, whereby the polymer compound can be provided with developability for pattern formation by alkali development.

亦即，藉由向高分子化合物導入鹼可溶性基，本發明的組成物中，作為有助於黑色顏料等著色顏料的分散之分散劑的高分子化合物具有鹼可溶性。含有該種高分子化合物之組成物成為曝光部的遮光性優異者，且未曝光部的鹼顯影性得到提高。 That is, by introducing an alkali-soluble group into the polymer compound, in the composition of the present invention, the polymer compound as a dispersant that contributes to the dispersion of color pigments such as black pigments has alkali solubility. The composition containing this kind of polymer compound is excellent in the light-shielding property of the exposed part, and the alkali developability of an unexposed part is improved.

並且，藉由高分子化合物具有含有酸基之結構單元，高分子化合物變得易與溶劑整合且塗佈性亦提高之趨勢。 In addition, since the polymer compound has a structural unit containing an acid group, the polymer compound becomes easy to integrate with the solvent and the coatability is also improved.

推測這是因為，具有酸基之結構單元中的酸基易與黑色顏料等著色顏料相互作用，高分子化合物使黑色顏料等著色顏料穩定地分散，並且使黑色顏料等著色顏料分散之高分子化合物的黏度變低，高分子化合物本身亦容易穩定地分散。 It is presumed that this is because the acid group in the structural unit with the acid group easily interacts with color pigments such as black pigments, and the polymer compound stabilizes the dispersion of color pigments such as black pigments, and the polymer compound that disperses color pigments such as black pigments The viscosity becomes lower, and the polymer compound itself is easily dispersed stably.

其中，具有作為酸基的鹼可溶性基之結構單元可以係與上述之具有接枝鏈之結構單元相同的結構單元，亦可以係不同的結構單元，但具有作為酸基的鹼可溶性基之結構單元係與上述之疏水性結構單元不同的結構單 元(亦即，並不相當於上述疏水性結構單元)。 Among them, the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the above-mentioned structural unit having a graft chain, or a different structural unit, but a structural unit having an alkali-soluble group as an acid group It is a structural unit different from the above hydrophobic structural unit Yuan (that is, it does not correspond to the aforementioned hydrophobic structural unit).

作為可與黑色顏料等著色顏料形成相互作用之官能基亦即酸基，例如有羧酸基、磺酸基、磷酸基或酚性羥基等，羧酸基、磺酸基及磷酸基中的至少1種為較佳，針對黑色顏料等著色顏料的吸附力良好且著色顏料的分散性較高之角度考慮，羧酸基尤為佳。 As a functional group that can interact with color pigments such as black pigments, that is, acid groups, for example, there are carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, or phenolic hydroxyl groups. At least One is preferred, and the carboxylic acid group is particularly preferred from the viewpoint of good absorption of black pigments and other colored pigments and high dispersibility of the colored pigments.

亦即，高分子化合物還具有含有羧酸基、磺酸基及磷酸基中的至少1種之結構單元為較佳。 That is, it is preferable that the polymer compound further has a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

高分子化合物可具有1種或2種以上的具有酸基之結構單元。 The polymer compound may have one type or two or more types of structural units having acid groups.

高分子化合物可含有具有酸基之結構單元，亦可不含有，但含有時，具有酸基之結構單元的含量以質量換算，相對於高分子化合物的總質量，5~80%為較佳，從抑制基於鹼顯影之圖像強度的損傷之觀點考慮，10~60%為更佳。 The polymer compound may or may not contain the structural unit with acid group, but when it contains, the content of the structural unit with acid group is calculated by mass. Relative to the total mass of the polymer compound, 5~80% is preferred. From the viewpoint of suppressing damage to the image strength based on alkali development, 10-60% is more preferable.

作為可與黑色顏料等著色顏料形成相互作用之官能基亦即鹼性基，例如有第1級胺基、第2級胺基、第3級胺基、包含N原子之雜環及醯胺基等，從針對黑色顏料等著色顏料的吸附力良好且著色顏料的分散性較高之角度考慮，第3級胺基為較佳。高分子化合物能夠具有1種或2種以上的該些鹼性基。 Functional groups that can interact with color pigments such as black pigments, that is, basic groups, include, for example, first-level amino groups, second-level amino groups, third-level amino groups, heterocycles containing N atoms, and amide groups For example, from the viewpoint of good adsorption force for color pigments such as black pigments and high dispersibility of the color pigments, a tertiary amino group is preferred. The polymer compound can have one kind or two or more kinds of these basic groups.

高分子化合物可含有具有鹼性基之結構單元，亦可不含有，含有時，具有鹼性基之結構單元的含量以質量換算，相對於高分子化合物的總質量，0.01%以上且50%以下為較佳，從抑制阻礙顯影性之觀點考慮，0.01%以上且30%以下為更佳。 The polymer compound may or may not contain a structural unit with a basic group. When it is contained, the content of the structural unit with a basic group is calculated by mass. Relative to the total mass of the polymer compound, 0.01% to 50% is Preferably, from the viewpoint of suppressing the inhibition of developability, 0.01% or more and 30% or less are more preferable.

作為可與黑色顏料等著色顏料形成相互作用之官能基亦即配位性基及具有反應性之官能基，例如可舉出乙醯乙醯氧基、三烷氧基甲矽烷基、異氰酸酯基、酸酐及醯氯等。從針對黑色顏料等著色顏料吸附力良好且著色顏料的分散性較高之角度考慮，乙醯乙醯氧基為較佳。高分子化合物可具有1種或2種以上的該些基團。 As the functional group that can interact with color pigments such as black pigments, that is, coordination groups and reactive functional groups, for example, acetylacetoxy, trialkoxysilyl, isocyanate, Acid anhydride and chlorinated acid etc. From the viewpoints of good adsorption force for black pigments and other colored pigments and high dispersibility of the colored pigments, the acetylacetoxy group is preferred. The polymer compound may have one kind or two or more kinds of these groups.

高分子化合物可含有具有配位性基之結構單元或具有反應性之官能基，亦可不含有，但含有時，該些結構單元的含量以質量換算，相對於高分子化合物的總質量，10%以上且80%以下為較佳，從抑制阻礙顯影性之觀點考慮，20%以上且60%以下為更佳。 The polymer compound may contain structural units with coordinating groups or reactive functional groups, or not, but when it contains, the content of these structural units is converted by mass, relative to the total mass of the polymer compound, 10% The above and 80% or less are preferable, and from the viewpoint of suppressing the hindrance of developability, 20% or more and 60% or less are more preferable.

本發明中的高分子化合物除了接枝鏈以外還具有可與黑色顏料等著色顏料形成相互作用之官能基時，含有如上述之各種可與黑色顏料等著色顏料形成相互作用之官能基即可，並不特別限定該些官能基如何被導入，但高分子化合物具有選自源自以下述通式(iv)~(vi)表示之單體的結構單元之1種以上的結構單元為較佳。 When the polymer compound in the present invention has, in addition to the graft chain, a functional group that can interact with color pigments such as black pigments, it may contain various functional groups that can interact with color pigments such as black pigments as described above. It is not particularly limited how these functional groups are introduced, but the polymer compound preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulas (iv) to (vi).

Figure 106104991-A0305-02-0032-6
Figure 106104991-A0305-02-0032-6

通式(iv)~通式(vi)中，R11、R12及R13分別獨立地表示氫原子、鹵原子(例如，氟原子、氯原子、溴原子等)或碳原子數為1~6的烷基(例如，甲基、乙基、丙基等)。 In general formula (iv) to general formula (vi), R 11 , R 12 and R 13 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or the number of carbon atoms is 1~ 6 alkyl groups (for example, methyl, ethyl, propyl, etc.).

通式(iv)~通式(vi)中，R11、R12及R13分別獨立地為氫原子或碳原子數為1~3的烷基為較佳，分別獨立地為氫原子或甲基為更佳。通式(iv)中，R12及R13分別為氫原子尤為佳。 In general formula (iv) to general formula (vi), R 11 , R 12 and R 13 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently is a hydrogen atom or methyl The base is better. In the general formula (iv), R 12 and R 13 are each a hydrogen atom.

通式(iv)中的X1表示氧原子(-O-)或亞胺基(-NH-)，氧原子為較佳。 X 1 in the general formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), and an oxygen atom is preferred.

並且，通式(v)中的Y表示次甲基或氮原子。 In addition, Y in the general formula (v) represents a methine group or a nitrogen atom.

並且，通式(iv)~通式(v)中的L1表示單鍵或2價的連結基。作為2價的連結基的例子，可舉出2價的脂肪族基(例如，亞烷基、取代亞烷基、亞烯基、取代亞烯基、亞炔基及取代亞炔基)、2價的芳香族基(例如，伸芳基及取代伸芳基)、2價的雜環基、氧原子(-O-)、硫原子(-S-)、亞胺基(-NH-)、取代亞胺鍵(-NR31’-，其中，R31’為脂肪族基、芳香族基或雜環基)、羰鍵(-CO-)及該些的組合等。 In addition, L 1 in general formula (iv) to general formula (v) represents a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic groups (for example, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, and substituted alkynylene), 2 Valence aromatic groups (for example, arylene and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH-), substituted imine bond (-NR 31 '-, wherein, R 31' is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), and the like, and combinations of the these.

2價的脂肪族基可具有環狀結構或分支結構。脂肪族基的碳原子數為1~20為較佳，1~15為更佳，1~10為進一步較佳。與不飽和脂肪族基相比，脂肪族基為飽和脂肪族基為較佳。並且，脂肪族基可具有取代基。作為取代基的例子，可舉出鹵原子、羥基、芳香族基及雜環基。 The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. Compared with an unsaturated aliphatic group, the aliphatic group is preferably a saturated aliphatic group. In addition, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, aromatic groups, and heterocyclic groups.

2價的芳香族基的碳原子數為6~20為較佳，6~15為更佳，6~10為最佳。並且，芳香族基可具有取代基。取代基的例子可舉出鹵原子、 羥基、脂肪族基、芳香族基及雜環基。 The number of carbon atoms of the divalent aromatic group is preferably 6-20, more preferably 6-15, and most preferably 6-10. In addition, the aromatic group may have a substituent. Examples of substituents include halogen atoms, Hydroxy, aliphatic, aromatic and heterocyclic groups.

2價的雜環基作為雜環具有5員環或6員環為較佳。雜環中可縮合有其他雜環、脂肪族環或芳香族環中的1個以上。並且，雜環基可具有取代基。作為取代基的例子，可舉出鹵原子、羥基、氧代基(=O)、硫代基(=S)、亞胺基(=NH)、取代亞胺基(=N-R32，其中，R32為脂肪族基、芳香族基或雜環基)、脂肪族基、芳香族基及雜環基。 The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as the heterocyclic ring. One or more of other heterocyclic rings, aliphatic rings, or aromatic rings may be condensed in the heterocyclic ring. In addition, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thio groups (=S), imino groups (=NH), and substituted imino groups (=NR 32 , where R 32 is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

L1係單鍵、亞烷基或包含氧化烯結構之2價的連結基為較佳。氧化烯結構係氧乙烯結構或氧丙烯結構為更佳。並且，L1可包含重複包含2個以上的氧化烯結構之聚氧化烯結構。作為聚氧化烯結構，聚氧乙烯結構或聚氧丙烯結構為較佳。聚氧乙烯結構以-(OCH2CH2)n-表示，n為2以上的整數為較佳，2~10的整數為更佳。 L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The alkylene oxide structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L 1 may include a polyoxyalkylene structure repeatedly including two or more alkylene oxide structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by -(OCH 2 CH 2 )n-, and n is preferably an integer of 2 or more, and more preferably an integer of 2-10.

通式(iv)~通式(vi)中，Z1表示接枝鏈以外可與黑色顏料等著色顏料形成相互作用之官能基，羧酸基及第三級胺基為較佳，羧酸基為更佳。 In general formula (iv) ~ general formula (vi), Z 1 represents a functional group other than the graft chain that can interact with color pigments such as black pigments. Carboxylic acid groups and tertiary amine groups are preferred. Carboxylic acid groups For better.

通式(vi)中，R14、R15及R16分別獨立地表示氫原子、鹵原子(例如，氟、氯、溴等)、碳原子數為1~6的烷基(例如，甲基、乙基及丙基等)、-Z1或-L1-Z1。其中，L1及Z1的含義與上述中的L1及Z1相同，較佳例亦相同。作為R14、R15及R16，分別獨立地為氫原子、或碳原子數為1~3的烷基為較佳，氫原子為更佳。 In the general formula (vi), R 14 , R 15 and R 16 each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 6 carbon atoms (for example, methyl , ethyl and propyl, etc.), - Z 1 or -L 1 -Z 1. Wherein, L 1 and Z 1 meaning the same as the above L 1 and Z 1, preferred embodiments are also the same. As R 14 , R 15 and R 16 , each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred, and a hydrogen atom is more preferred.

本發明中，作為以通式(iv)表示之單體，R11、R12及R13分別獨立地為氫原子或甲基、L1為亞烷基或包含氧化烯結構之2價的連結基、X1為氧原子或亞胺基、Z1為羧酸基之化合物為較佳。 In the present invention, as a monomer represented by the general formula (iv), R 11 , R 12 and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or a divalent link including an alkylene oxide structure The compound wherein X 1 is an oxygen atom or imino group, and Z 1 is a carboxylic acid group is preferred.

並且，作為以通式(v)表示之單體，R11為氫原子或甲基、L1為亞烷基、Z1為羧酸基、Y為次甲基之化合物為較佳。 In addition, as the monomer represented by the general formula (v), a compound in which R 11 is a hydrogen atom or a methyl group, L 1 is an alkylene group, Z 1 is a carboxylic acid group, and Y is a methine group is preferable.

而且，作為以通式(vi)表示之單體，R14、R15及R16分別獨立地為氫原子或甲基、L1為單鍵或亞烷基、Z為羧酸基之化合物為較佳。 Moreover, as a monomer represented by the general formula (vi), compounds in which R 14 , R 15 and R 16 are each independently a hydrogen atom or a methyl group, L 1 is a single bond or an alkylene group, and Z is a carboxylic acid group are Better.

以下，示出以通式(iv)~通式(vi)表示之單體(化合物)的代表例。 Hereinafter, representative examples of monomers (compounds) represented by general formula (iv) to general formula (vi) are shown.

作為單體的例子，可舉出甲基丙烯酸、巴豆酸、異巴豆酸、分子內具有加成聚合性雙鍵及羥基之化合物(例如，甲基丙烯酸2-羥乙基)與琥珀酸酐的反應物、分子內具有加成聚合性雙鍵及羥基之化合物與鄰苯二甲酸酐的反應物、分子內具有加成聚合性雙鍵及羥基之化合物與四羥基鄰苯二甲酸酐的反應物、分子內具有加成聚合性雙鍵及羥基之化合物與偏苯三酸酐的反應物、分子內具有加成聚合性雙鍵及羥基之化合物與均苯四甲酸酐的反應物、丙烯酸、丙烯酸二聚物、丙烯酸寡聚物、馬來酸、伊康酸、反丁烯二酸、4-乙烯基安息香酸、乙烯基苯酚及4-羥基苯甲基丙烯醯等。 Examples of monomers include the reaction of methacrylic acid, crotonic acid, isocrotonic acid, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride The reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and phthalic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride, The reactant of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a reactant of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid Oligomers, maleic acid, itaconic acid, fumaric acid, 4-vinyl benzoic acid, vinyl phenol and 4-hydroxybenzyl acryl, etc.

從與黑色顏料等著色顏料的相互作用、分散穩定性及向顯影液的浸透性的觀點考慮，具有可與黑色顏料等著色顏料形成相互作用之官能基之結構單元的含量相對於高分子化合物的總質量，0.05質量%~90質量%為較佳，1.0質量%~80質量%為更佳，10質量%~70質量%為進一步較佳。 From the viewpoints of interaction with black pigments and other color pigments, dispersion stability, and permeability to developing solutions, the content of structural units having functional groups that can interact with color pigments such as black pigments is relative to that of polymer compounds. The total mass is preferably 0.05% to 90% by mass, more preferably 1.0% to 80% by mass, and more preferably 10% to 70% by mass.

而且，為了提高圖像強度等各種性能，高分子化合物可在無損本發明的效果之前提下，進一步含有與具有接枝鏈之結構單元、疏水性結構單元及具有可與黑色顏料等著色顏料形成相互作用之官能基之結構單元不同 之、具有各種功能之其他結構單元(例如，具有與用於分散物之分散介質具有親和性之官能基等之結構單元)。 Moreover, in order to improve various properties such as image strength, the polymer compound can further contain a structural unit having a graft chain, a hydrophobic structural unit, and a color pigment that can be formed with black pigments without impairing the effect of the present invention. Different structural units of interacting functional groups Other structural units with various functions (for example, structural units with functional groups that have affinity with the dispersion medium used for the dispersion).

作為該種其他結構單元，例如可舉出源自選自丙烯腈類及甲基丙烯腈類等之自由基聚合性化合物的結構單元。 Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles.

高分子化合物能夠使用1種或者2種以上的該些其他結構單元，其含量以質量換算，相對於高分子化合物的總質量，0%以上且80%以下為較佳，10%以上且60%以下尤為佳。含量在上述範圍內可維持充分的圖案形成性。 The polymer compound can use one or more of these other structural units, and the content is calculated by mass. Relative to the total mass of the polymer compound, 0% or more and 80% or less is preferred, 10% or more and 60% The following is particularly good. The content can maintain sufficient pattern formability within the above range.

高分子化合物的酸值為0mgKOH/g以上且160mgKOH/g以下的範圍為較佳，10mgKOH/g以上且140mgKOH/g以下的範圍為更佳，20mgKOH/g以上且120mgKOH/g以下的範圍進一步較佳。 The acid value of the polymer compound is preferably in the range from 0 mgKOH/g to 160 mgKOH/g, more preferably in the range from 10 mgKOH/g to 140 mgKOH/g, and more preferably in the range from 20 mgKOH/g to 120 mgKOH/g. good.

若高分子化合物的酸值為160mgKOH/g以下，則更有效地抑制形成硬化膜時的顯影中的圖案剥離。並且，若高分子化合物的酸值為10mgKOH/g以上，則鹼顯影性更加良好。並且，若高分子化合物的酸值為20mgKOH/g以上，則能夠更加抑制黑色顏料等著色顏料的沉澱，能夠使粗大粒子數更少，能夠更加提高組成物的經時穩定性。 If the acid value of the polymer compound is 160 mgKOH/g or less, it is more effective to suppress pattern peeling during development when the cured film is formed. In addition, when the acid value of the polymer compound is 10 mgKOH/g or more, the alkali developability is more favorable. In addition, if the acid value of the polymer compound is 20 mgKOH/g or more, the precipitation of color pigments such as black pigments can be more suppressed, the number of coarse particles can be reduced, and the temporal stability of the composition can be further improved.

本發明中，高分子化合物的酸值例如能夠由高分子化合物中的酸基的平均含量計算。並且，能夠藉由改變含有高分子化合物的構成成份亦即酸基之結構單元的含量來獲得具有所希望的酸值之樹脂。 In the present invention, the acid value of the polymer compound can be calculated from the average content of acid groups in the polymer compound, for example. In addition, it is possible to obtain a resin having a desired acid value by changing the content of the structural unit of the acid group that is the constituent component of the polymer compound.

形成硬化膜時，從顯影時的圖案剥離的抑制和顯影性的觀點考慮，本發明中的高分子化合物的重量平均分子量作為基於GPC(凝膠滲透層析法)法之聚苯乙烯換算值，4,000以上且300,000以下為較佳，5,000以上且 200,000以下為更佳，6,000以上且100,000以下進一步較佳，10,000以上且50,000以下尤為佳。 When forming a cured film, from the viewpoints of suppression of pattern peeling during development and developability, the weight average molecular weight of the polymer compound in the present invention is taken as a polystyrene conversion value based on the GPC (gel permeation chromatography) method. 4,000 or more and 300,000 or less are preferable, 5,000 or more and It is more preferably 200,000 or less, more preferably 6,000 or more and 100,000 or less, and particularly preferably 10,000 or more and 50,000 or less.

GPC法基於如下方法，亦即，利用HLC-8020GPC(TOSOH CORPORATION.製造)，作為管柱使用TSKgel SuperHZM-H、TSKgel SuperHZ4000、TSKgel SuperHZ2000(TOSOH CORPORATION製造、4.6mmID×15cm)，作為溶離液使用THF(四氫呋喃)。 The GPC method is based on the following method: HLC-8020GPC (manufactured by TOSOH CORPORATION), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6mmID×15cm) as the column, and THF as the eluting solution (Tetrahydrofuran).

高分子化合物能夠依公知的方法合成，作為合成高分子化合物時使用之溶劑，例如可舉出二氯乙烷、環己酮、甲乙酮、丙酮、甲醇、乙醇、丙醇、丁醇、乙二醇單甲醚、乙二醇單***、2-甲氧基乙基乙酸酯、1-甲氧基-2-丙醇、1-甲氧基-2-乙酸丙酯、N，N-二甲基甲醯胺、N，N-二甲基乙醯胺、二甲基亞碸、甲苯、乙酸乙酯、乳酸甲酯及乳酸乙酯等。該些溶劑可單獨使用亦可混合2種以上來使用。 The polymer compound can be synthesized according to a known method. As a solvent used when synthesizing polymer compounds, for example, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethyl Methyl methamide, N,N-dimethyl acetamide, dimethyl sulfide, toluene, ethyl acetate, methyl lactate, ethyl lactate, etc. These solvents may be used alone or in mixture of two or more kinds.

作為可在本發明中使用之高分子化合物的具體例，可舉出Kusumoto Chemicals,Ltd.製造“DA-7301”、BYK Chemie公司製造“Disperbyk-101(聚醯胺胺磷酸鹽)、107(羧酸酯)、110(包含酸基之共聚物)、111(磷酸系分散劑)、130(聚醯胺)、161、162、163、164、165、166、170、190(高分子共聚物)”、“BYK-P104、P105(高分子量不飽和聚羧酸)”、EFKA公司製造“EFKA4047、4050~4010~4165(聚氨酯系)、EFKA4330~4340(嵌段共聚物)、4400~4402(改性聚丙烯酸酯)、5010(聚醯胺酯)、5765(高分子量聚羧酸鹽)、6220(脂肪酸聚酯)、6745(酞菁衍生物)、6750(偶氮顏料衍生物)”、Ajinomoto Fine-Techno Co.,Inc.製造“AJISPER PB821、 PB822、PB880、PB881”、KYOEISHA CHEMICAL Co.,LTD製造“Floren TG-710(氨酯低聚物)”、“Polyflow No.50E、No.300(丙烯酸系共聚物)”、Kusumoto Chemicals,Ltd.製造“Disparlon KS-860、873SN、874、# 2150(脂肪族多元羧酸)、# 7004(聚醚酯)、DA-703-50、DA-705、DA-725”、Kao Corporation製造“DEMOL RN、N(萘磺酸福爾馬林縮聚物)、MS、C、SN-B(芳香族磺酸福爾馬林縮聚物)”、“Homogenol L-18(高分子聚羧酸)”、“EMULGEN 920、930、935、985(聚氧乙烯壬基苯基醚)”、“ACETAMIN 86(硬脂胺醋酸鹽)”、The Lubrinzol corporatin製造“SOLSPERSE 5000(酞菁衍生物)、22000(偶氮顏料衍生物)、13240(聚酯胺)、3000、12000、17000、20000、27000(在末端部具有功能部之高分子)、24000、28000、32000、38500(接枝共聚物)”、Nikko Chemicals Co.,Ltd.製造“Nikkor T106(聚氧乙烯山梨醇單油酸酯)、MYS-IEX(聚氧乙烯單硬脂酸酯)”、Kawaken Fine Chemicals Co.,Ltd.製造Hinoakuto T-8000E等、Shin-Etsu Chemical Co.,Ltd.製造聚有機基團矽氧烷聚合物KP341、Yusho Co Ltd製造“W001：陽離子系表面活性劑”、聚氧乙烯月桂基醚、聚氧乙烯硬脂醚、聚氧乙烯油烯醚、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、脫水山梨醇脂肪酸酯等非離子系表面活性劑、“W004、W005、W017”等陰離子系表面活性劑、MORISHITA & CO.,LTD.製造“EFKA-46、EFKA-47、EFKA-47EA、EFKA聚合物100、EFKA聚合物400、EFKA聚合物401、EFKA聚合物450”、SAN NOPCO LIMITED製造“Disperse Aid 6、Disperse Aid 8、Disperse Aid 15、Disperse Aid 9100”等高分子分散劑、ADEKA CORPORATION製造“Adeka Pluronic L31、F38、L42、L44、L61、L64、F68、L72、P95、F77、P84、F87、P94、L101、P103、F108、L121、P-123”及Sanyo Chemical Industries,Ltd.製造“Ionet(商品名)S-20”等。並且，還可使用Acrylicbase FFS-6752、Acrylicbase FFS-187、Acrycure-RD-F8及Cyclomer P。 Specific examples of polymer compounds that can be used in the present invention include "DA-7301" manufactured by Kusumoto Chemicals, Ltd., "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylate) manufactured by BYK Chemie Acid ester), 110 (copolymer containing acid group), 111 (phosphate-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer) ", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", "EFKA4047, 4050-4010-4165 (polyurethane series), EFKA4330-4340 (block copolymer), 4400-4402 (modified Polyacrylate), 5010 (polyamide ester), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)", Ajinomoto Fine-Techno Co., Inc. manufactured "AJISPER PB821, PB822, PB880, PB881", "Floren TG-710 (urethane oligomer)" manufactured by KYOEISHA CHEMICAL Co., LTD, "Polyflow No.50E, No.300 (acrylic copolymer)", Kusumoto Chemicals, Ltd. Manufacturing "Disparlon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA-703-50, DA-705, DA-725", Kao Corporation "DEMOL RN , N (formalin naphthalenesulfonate condensation polymer), MS, C, SN-B (aromatic sulfonate formalin condensation polymer)", "Homogenol L-18 (polymer polycarboxylic acid)", " EMULGEN 920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether)", "ACETAMIN 86 (stearyl amine acetate)", The Lubrinzol corporatin "SOLSPERSE 5000 (phthalocyanine derivatives), 22000 (azo Pigment derivatives), 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymers with functional parts at the end), 24000, 28000, 32000, 38500 (graft copolymer)", Nikko Chemicals "Nikkor T106 (polyoxyethylene sorbitol monooleate), MYS-IEX (polyoxyethylene monostearate)" manufactured by Co., Ltd., Hinoakuto T-8000E manufactured by Kawaken Fine Chemicals Co., Ltd., etc. , Shin-Etsu Chemical Co., Ltd. manufactured polyorganosiloxane polymer KP341, Yusho Co Ltd manufactured "W001: cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester Plasma nonionic surfactants, anionic surfactants such as "W004, W005, W017", MORISHITA & CO., LTD. "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymerization Product 400, EFKA polymer 401, EFKA polymer 450", "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100" manufactured by SAN NOPCO LIMITED ”And other polymer dispersants, ADEKA Corporation manufactures "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" and Sanyo Chemical Industries, Ltd. Manufactured "Ionet (trade name) S-20" etc. In addition, Acrylicbase FFS-6752, Acrylicbase FFS-187, Acrycure-RD-F8 and Cyclomer P can also be used.

並且，作為兩性樹脂的市售品，例如可舉出BYK Additives&Instruments製造的DISPERBYK-130、DISPERBYK-140、DISPERBYK-142、DISPERBYK-145、DISPERBYK-180、DISPERBYK-187、DISPERBYK-191、DISPERBYK-2001、DISPERBYK-2010、DISPERBYK-2012、DISPERBYK-2025、BYK-9076、Ajinomoto Fine-Techno Co.,Inc.製造的AJISPER PB821、AJISPER PB822及AJISPER PB881等。 In addition, as commercial products of amphoteric resins, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, manufactured by BYK Additives & Instruments, DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, AJISPER PB821, AJISPER PB822 and AJISPER PB881 manufactured by Ajinomoto Fine-Techno Co., Inc. etc.

該些高分子化合物可單獨使用，亦可組合2種以上來使用。 These polymer compounds may be used alone or in combination of two or more kinds.

另外，作為高分子化合物的具體例的例子，能夠參閱日本特開2013-249417號公報的段落0127~0129中記載之高分子化合物，該些內容引入本說明書中。 In addition, as an example of a specific example of a polymer compound, the polymer compound described in paragraphs 0127 to 0129 of JP 2013-249417 A can be referred to, and these contents are incorporated in this specification.

並且，作為分散劑，除了上述之高分子化合物以外，還能夠使用日本特開2010-106268號公報的段落0037~0115(對應之US2011/0124824的段落0075~0133欄)的接枝共聚物，該些內容可援用並引入本說明書中。 In addition, as the dispersant, in addition to the above-mentioned polymer compounds, the graft copolymers of paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 of US2011/0124824) of JP 2010-106268 A can also be used. These contents can be cited and introduced into this manual.

並且，上述以外，還能夠使用日本特開2011-153283號公報的段落0028~0084(對應之US2011/0279759的段落0075~0133欄)的包含具有酸性基經由連結基鍵結而成之側鏈結構之構成成份之高分子化合物，該些內容 可援用並引入本說明書中。 In addition to the above, paragraphs 0028~0084 of JP 2011-153283 A (corresponding to paragraphs 0075~0133 of US2011/0279759) containing side chain structures having acidic groups bonded via linking groups can also be used. The polymer compound of the constituent components, the content Can be cited and incorporated into this specification.

組成物含有分散劑時，分散劑的含量相對於組成物的總固體含量，0.1~50質量%為較佳，0.5~30質量%為更佳。 When the composition contains a dispersant, the content of the dispersant relative to the total solid content of the composition is preferably 0.1-50% by mass, and more preferably 0.5-30% by mass.

分散劑可單獨使用1種，亦可併用2種以上。併用2種以上時，合計量成為上述範圍為較佳。 A dispersant may be used individually by 1 type, and may use 2 or more types together. When two or more types are used in combination, the total amount is preferably in the above range.

本發明的組成物中，相對於上述含氮化鈦粒子之上述分散劑的含有比例((組成物中的分散劑的含量(質量%))/(組成物中的含氮化鈦粒子的含量(質量%))。以下，還稱作“D/P”。)為0.05~0.30為較佳，0.10~0.30為更佳，0.12~0.30為進一步較佳。藉由含有比例(D/P)在上述範圍內，組成物的經時穩定性變得良好。 In the composition of the present invention, the content ratio of the dispersant relative to the titanium nitride-containing particles ((the content of the dispersant in the composition (mass%))/(the content of the titanium nitride-containing particles in the composition (Mass %)). Hereinafter, it is also referred to as "D/P".) It is preferably 0.05 to 0.30, more preferably 0.10 to 0.30, and still more preferably 0.12 to 0.30. When the content ratio (D/P) is within the above range, the stability of the composition over time becomes good.

本發明的組成物中，相對於上述Fe原子的含量之上述分散劑的含有比例〔(組成物中的分散劑的含量(質量%))/(組成物中的Fe原子的含量(質量%))〕的下限值為0.8以上為較佳，1.0以上為更佳，1.5以上為進一步較佳。上限值為270以下為較佳，150以下為更佳，50以下為進一步較佳。 In the composition of the present invention, the content ratio of the dispersant relative to the content of the Fe atoms [(the content of the dispersant in the composition (mass%))/(the content of the Fe atoms in the composition (mass%) The lower limit of )] is preferably 0.8 or more, more preferably 1.0 or more, and more preferably 1.5 or more. The upper limit is preferably 270 or less, more preferably 150 or less, and even more preferably 50 or less.

另外，能夠如下計算組成物中的Fe原子的含量(質量%)，亦即，如上述那樣求出之含氮化鈦粒子中的Fe原子的含量(質量%)乘以組成物中包含之含氮化鈦粒子的含量(質量%)。 In addition, the Fe atom content (mass %) in the composition can be calculated as follows, that is, the Fe atom content (mass %) in the titanium nitride-containing particles obtained as described above is multiplied by the content contained in the composition. The content of titanium nitride particles (mass%).

藉由相對於Fe原子的含量之分散劑的含有比例在上述範圍內，可顯著獲得所希望的效果。尤其，藉由上述含有比例在1.5~50的範圍內，可更加顯著獲得所希望的效果。作為其理由，認為組成物中的Fe原子與分散劑相 互作用，藉此對圖案形成性(硬化性及顯影性)帶來影響。 When the content ratio of the dispersant with respect to the content of Fe atoms is within the above range, the desired effect can be remarkably obtained. In particular, when the aforementioned content ratio is in the range of 1.5-50, the desired effect can be more remarkably obtained. As the reason, it is believed that the Fe atoms in the composition and the dispersant phase The interaction affects the pattern formation (hardenability and developability).

本發明的組成物中，相對於上述Fe原子的含量之上述聚合性化合物的含有比例〔(組成物中的聚合性化合物的含量(質量%))/(組成物中的Fe原子的含量(質量%))〕的下限值為0.7以上為較佳，0.85以上為更佳，1.0以上為進一步較佳。上限值為50以下為較佳，11以下為更佳，7.0以下為進一步較佳。 In the composition of the present invention, the content ratio of the polymerizable compound relative to the content of the Fe atom [(the content of the polymerizable compound in the composition (mass %))/(the content of the Fe atoms in the composition (mass %))] is preferably 0.7 or more, more preferably 0.85 or more, and even more preferably 1.0 or more. The upper limit is preferably 50 or less, more preferably 11 or less, and even more preferably 7.0 or less.

另外，能夠如上述那樣進行組成物中的Fe原子的含量(質量%)的計算。 In addition, the calculation of the content (mass %) of Fe atoms in the composition can be performed as described above.

藉由相對於Fe原子的含量之聚合性化合物的含有比例在上述範圍內，可顯著獲得所希望的效果。尤其，藉由上述含有比例在1.0~7.0的範圍內，可更加顯著獲得所希望的效果。作為其理由，認為組成物中的Fe原子與聚合性化合物相互作用，藉此對圖案形成性(硬化性及顯影性)帶來影響。 When the content ratio of the polymerizable compound with respect to the content of Fe atoms is within the above range, the desired effect can be remarkably obtained. In particular, when the aforementioned content ratio is in the range of 1.0 to 7.0, the desired effect can be more remarkably obtained. As the reason, it is thought that the Fe atoms in the composition interact with the polymerizable compound, thereby affecting the patterning properties (curability and developability).

<黏結樹脂> <Binder Resin>

本發明的組成物含有黏結樹脂為較佳。 The composition of the present invention preferably contains a binder resin.

作為黏結樹脂，使用線狀有機聚合物為較佳。作為該種線狀有機聚合物，能夠任意地使用公知者。為了實現水顯影或弱鹼性水顯影，選擇對水或弱鹼性水為可溶性或膨潤性之線狀有機聚合物為更佳。其中，作為黏結樹脂，鹼可溶性樹脂(具有促進鹼可溶性之基團之樹脂)尤為佳。 As the binder resin, linear organic polymers are preferably used. As such linear organic polymers, known ones can be used arbitrarily. In order to realize water development or weak alkaline water development, it is better to select linear organic polymers that are soluble or swellable to water or weak alkaline water. Among them, as the binder resin, alkali-soluble resins (resins having groups that promote alkali solubility) are particularly preferred.

作為黏結樹脂，可從線狀有機聚合物且分子(較佳地為以(甲基)丙烯酸系共聚物或苯乙烯系共聚物為主鏈之分子)中具有至少1個促進鹼可溶性之基團之鹼可溶性樹脂中適當選擇。從耐熱性的觀點考慮，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)丙烯醯胺系樹脂、(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系樹脂為較佳，從顯影性控制的觀點考慮，(甲基)丙烯酸樹脂、(甲基)丙烯醯胺系樹脂、(甲基)丙烯酸/(甲基)丙烯醯胺共聚物樹脂及聚醯亞胺系樹脂為較佳。 As a binding resin, it can be a linear organic polymer and a molecule (preferably a molecule with a (meth)acrylic copolymer or a styrene copolymer as the main chain) having at least one group that promotes alkali solubility The alkali-soluble resin is appropriately selected. From the viewpoint of heat resistance, polyhydroxystyrene Resins, polysiloxane resins, (meth)acrylic resins, (meth)acrylamide resins, (meth)acrylic acid/(meth)acrylamide copolymer resins, epoxy resins, and poly The imine-based resin is preferred. From the viewpoint of developability control, (meth)acrylic resin, (meth)acrylamide resin, (meth)acrylic acid/(meth)acrylamide copolymer resin And polyimide resins are preferred.

作為促進鹼可溶性之基團(以下，還稱作酸基)，例如，可舉出羧基、磷酸基、磺酸基及酚性羥基等。其中，可溶於有機溶劑且能夠藉由弱鹼性水溶液顯影者為較佳，作為更佳者，可舉出具有源自(甲基)丙烯酸的結構單元之鹼可溶性樹脂。該些酸基可以係僅為1種，亦可以係2種以上。 Examples of groups that promote alkali solubility (hereinafter, also referred to as acid groups) include carboxyl groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups. Among them, those that are soluble in organic solvents and can be developed with a weakly alkaline aqueous solution are preferred, and more preferred are alkali-soluble resins having structural units derived from (meth)acrylic acid. These acid groups may be only one type or two or more types.

作為黏結樹脂，例如，可舉出在側鏈具有羧酸基之自由基聚合物、例如日本特開昭59-44615號、日本特公昭54-34327號、日本特公昭58-12577號、日本特公昭54-25957號、日本特開昭54-92723號、日本特開昭59-53836號及日本特開昭59-71048號中記載者，亦即，具有羧基之單體單獨或使其共聚之樹脂、具有酸酐之單體單獨或使其共聚並且對酸酐單元進行水解或半酯化或半醯胺化之樹脂及藉由不飽和單羧酸及酸酐對環氧樹脂進行改性之環氧丙烯酸酯等。作為具有羧基之單體的例子，可舉出丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、馬來酸、富马酸及4-羧基苯乙烯等，作為具有酸酐之單體的例子，可舉出馬來酸酐等。並且，亦可舉出同樣在側鏈具有羧酸基之酸性纖維素衍生物為例。此外，對具有羥基之聚合物加成環狀酸酐者等較有用。 As the binder resin, for example, a radical polymer having a carboxylic acid group in the side chain, for example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Those described in KK 54-25957, JP 54-92723, JP 59-53836, and JP 59-71048, that is, monomers having carboxyl groups alone or by copolymerization Resins, monomers with acid anhydrides alone or by copolymerization and hydrolyzed or semi-esterified or semi-aminated resins with acid anhydride units, and epoxy acrylics modified with epoxy resins by unsaturated monocarboxylic acids and acid anhydrides Ester etc. Examples of monomers having carboxyl groups include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene, and the like. Examples of monomers having acid anhydride include Examples include maleic anhydride. In addition, an acidic cellulose derivative having a carboxylic acid group in the side chain can also be cited as an example. In addition, it is more useful to add cyclic anhydrides to polymers with hydroxyl groups.

並且，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具有酸基之縮醛改性聚乙烯醇系黏結樹脂的膜強度及顯影性的平衡優異，為較佳。 In addition, European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Publication 2001- The acetal-modified polyvinyl alcohol-based binder resin having an acid group described in each publication such as No. 318463 has an excellent balance of film strength and developability, which is preferable.

而且，作為水溶性線狀有機聚合物，聚乙烯吡咯烷酮或聚環氧乙烷等較有用。並且，為了提高硬化皮膜的強度，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亦有用。 Furthermore, as a water-soluble linear organic polymer, polyvinylpyrrolidone or polyethylene oxide is useful. In addition, in order to increase the strength of the cured film, polyethers, which are alcohol-soluble nylon and 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin, which are reaction products, are also useful.

並且，國際公開第2008/123097號中記載之聚醯亞胺樹脂亦有用。 In addition, the polyimide resin described in International Publication No. 2008/123097 is also useful.

尤其，該些中，〔苄基(甲基)丙烯酸酯/(甲基)丙烯酸/依據需要為其他加成聚合性乙烯單體〕共聚物及〔(甲基)丙烯酸烯丙酯/(甲基)丙烯酸/依據需要為其他加成聚合性乙烯單體〕共聚物的膜強度、靈敏度及顯影性的平衡優異，為較佳。 In particular, among these, [benzyl (meth)acrylate/(meth)acrylic acid/other addition polymerizable vinyl monomers as necessary] copolymer and [(meth)allyl acrylate/(meth) )Acrylic acid/other addition polymerizable vinyl monomers as needed] The copolymer has excellent film strength, sensitivity, and developability, and is preferable.

作為市售品，例如，可舉出Acrylicbase FF-187、FF-426(FUJIKURA KASEI CO.,LTD.製造)、Acrycure-RD-F8(NIPPON SHOKUBAI CO.,LTD.)及DAICEL-ALLNEX LTD.製造Cyclomer P(ACA)230AA等。 As commercially available products, for example, Acrylicbase FF-187, FF-426 (manufactured by FUJIKURA KASEI CO., LTD.), Acrycure-RD-F8 (NIPPON SHOKUBAI CO., LTD.), and DAICEL-ALLNEX LTD. Cyclomer P (ACA) 230AA and so on.

黏結樹脂的製造中，例如，能夠適用基於公知的自由基聚合法之方法。本領域技術人員能夠輕鬆設定藉由自由基聚合法製造鹼可溶性樹脂時的溫度、壓力、自由基起始劑的種類及其量以及溶劑的種類等聚合條件。 In the production of the binder resin, for example, a method based on a known radical polymerization method can be applied. Those skilled in the art can easily set polymerization conditions such as the temperature, pressure, the type and amount of the radical initiator, and the type of solvent when the alkali-soluble resin is produced by the radical polymerization method.

並且，作為黏結樹脂，使用包含具有接枝鏈之結構單元及具有酸基(鹼可溶性基)之結構單元之聚合物亦較佳。 Furthermore, as the binding resin, it is also preferable to use a polymer containing a structural unit having a graft chain and a structural unit having an acid group (alkali-soluble group).

具有接枝鏈之結構單元的定義與上述之分散劑所具有之具有接枝鏈之結構單元相同，並且較佳範圍亦相同。 The definition of the structural unit having a grafted chain is the same as the structural unit having a grafted chain of the above-mentioned dispersant, and the preferred range is also the same.

作為酸基，例如有羧酸基、磺酸基、磷酸基或酚性羥基等，羧酸基、磺 酸基及磷酸基中的至少1種為較佳，羧酸基為更佳。 The acid group includes, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group or a phenolic hydroxyl group. At least one of an acid group and a phosphoric acid group is preferable, and a carboxylic acid group is more preferable.

作為具有酸基之結構單元，具有選自源自以下述通式(vii)~通式(ix)表示之單量體之結構單元之1種以上結構單元為較佳。 As the structural unit having an acid group, it is preferable to have one or more structural units selected from structural units derived from the monomers represented by the following general formula (vii) to general formula (ix).

Figure 106104991-A0305-02-0044-7
Figure 106104991-A0305-02-0044-7

通式(vii)~通式(ix)中，R21、R22及R23分別獨立地表示氫原子、鹵原子(例如，氟原子、氯原子、溴原子等)或碳原子數為1~6的烷基(例如，甲基、乙基、丙基等)。 In general formula (vii) to general formula (ix), R 21 , R 22 and R 23 each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or the number of carbon atoms is 1~ 6 alkyl groups (for example, methyl, ethyl, propyl, etc.).

通式(vii)~通式(ix)中、R21、R22及R23分別獨立地為氫原子或碳原子數為1~3的烷基，分別獨立地為氫原子或甲基為更佳。通式(vii)中，R21及R23分別為氫原子尤為佳。 In general formula (vii) ~ general formula (ix), R 21 , R 22 and R 23 are each independently a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, and each independently is a hydrogen atom or a methyl group. good. In the general formula (vii), R 21 and R 23 are each a hydrogen atom.

通式(vii)中的X2表示氧原子(-O-)或亞胺基(-NH-)，氧原子為較佳。 X 2 in the general formula (vii) represents an oxygen atom (-O-) or an imino group (-NH-), and an oxygen atom is preferred.

並且，通式(viii)中的Y表示次甲基或氮原子。 In addition, Y in the general formula (viii) represents a methine group or a nitrogen atom.

並且，通式(vii)~通式(ix)中的L2表示單鍵或2價的連結基。 作為2價的連結基的例子，可舉出2價的脂肪族基(例如，亞烷基、取代亞烷基、亞烯基、取代亞烯基、亞炔基及取代亞炔基)、2價的芳香族基(例如，伸芳基及取代伸芳基)、2價的雜環基、氧原子(-O-)、硫原子(-S-)、亞胺基(-NH-)、取代亞胺鍵(-NR41’-，其中，R41’為脂肪族基、芳香族基或雜環基)、羰鍵(-CO-)及該些的組合等。 In addition, L 2 in general formula (vii) to general formula (ix) represents a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic groups (for example, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, and substituted alkynylene), 2 Valence aromatic groups (for example, arylene and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH-), substituted imine bond (-NR 41 '-, wherein, R 41' is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), and the plurality of combinations.

2價的脂肪族基可具有環狀結構或分支結構。脂肪族基的碳原子數為1~20為較佳，1~15為更佳，1~10為進一步較佳。關於脂肪族基，與不飽和脂肪族基相比，飽和脂肪族基為更佳。並且，脂肪族基可具有取代基。作為取代基的例子，可舉出鹵原子、羥基、芳香族基及雜環基。 The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. Regarding the aliphatic group, the saturated aliphatic group is more preferable than the unsaturated aliphatic group. In addition, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, aromatic groups, and heterocyclic groups.

2價的芳香族基的碳原子數為6~20為較佳，6~15為進一步較佳，6~10為最佳。並且，芳香族基可具有取代基。取代基的例子可舉出鹵原子、羥基、脂肪族基、芳香族基及雜環基。 The number of carbon atoms of the divalent aromatic group is preferably 6-20, more preferably 6-15, and most preferably 6-10. In addition, the aromatic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, aliphatic groups, aromatic groups, and heterocyclic groups.

2價的雜環基作為雜環具有5員環或6員環為較佳。雜環上可縮合有其他雜環、脂肪族環或芳香族環中的1個以上。並且，雜環基可具有取代基。作為取代基的例子，可舉出鹵原子、羥基、氧代基(=O)、硫代基(=S)、亞胺基(=NH)、取代亞胺基(=N-R42，其中，R42為脂肪族基、芳香族基或雜環基)、脂肪族基、芳香族基及雜環基。 The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as the heterocyclic ring. One or more of other heterocyclic rings, aliphatic rings, or aromatic rings may be condensed on the heterocyclic ring. In addition, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thio groups (=S), imino groups (=NH), and substituted imino groups (=NR 42 , where R 42 is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

L2係單鍵、亞烷基或包含氧化烯結構之2價的連結基為較佳。氧化烯結構係氧乙烯結構或氧丙烯結構為更佳。並且，L2可包含重複包含2個以上的氧化烯結構之聚氧化烯結構。作為聚氧化烯結構，聚氧乙烯結構或聚氧丙烯結構為較佳。聚氧乙烯結構以-(OCH2CH2)n-表示，n為2以上的整 數為較佳，2~10的整數為更佳。 L 2 is preferably a single bond, an alkylene group, or a divalent linking group containing an oxyalkylene structure. The alkylene oxide structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L 2 may include a polyoxyalkylene structure repeatedly including two or more alkylene oxide structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by -(OCH 2 CH 2 )n-, and n is preferably an integer of 2 or more, and more preferably an integer of 2-10.

通式(vii)~通式(ix)中，Z2為酸基，羧酸基為較佳。 In general formula (vii) to general formula (ix), Z 2 is an acid group, and a carboxylic acid group is preferred.

通式(ix)中，R24、R25及R26分別獨立地表示氫原子、鹵原子(例如，氟、氯、溴等)、碳原子數為1~6的烷基(例如，甲基、乙基、丙基等)、-Z2或L2-Z2。其中，L2及Z2的含義與上述中的L2及Z2相同，較佳例子亦相同。作為R24、R25及R26，分別獨立地為氫原子或碳原子數為1~3的烷基為較佳，氫原子為更佳。 In the general formula (ix), R 24 , R 25 and R 26 each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 6 carbon atoms (for example, methyl , ethyl, propyl, etc.), - Z 2 or L 2 -Z 2. Wherein, L 2, and the meaning is the same as Z 2 in the above-described L 2 and Z 2, preferred examples are also the same. As R 24 , R 25 and R 26 , each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred, and a hydrogen atom is more preferred.

本發明中，作為以通式(vii)表示之單量體，R21、R22及R23分別獨立地為氫原子或甲基、L2為亞烷基或包含氧化烯結構之2價的連結基、X2為氧原子或亞胺基、Z2為羧酸基之化合物為較佳。 In the present invention, as a monomer represented by the general formula (vii), R 21 , R 22 and R 23 are each independently a hydrogen atom or a methyl group, and L 2 is an alkylene group or a divalent one containing an alkylene oxide structure The linking group, X 2 is an oxygen atom or an imino group, and Z 2 is a compound in which a carboxylic acid group is preferred.

並且，作為以通式(vii)表示之單量體，R21為氫原子或甲基、L2為亞烷基、Z2為羧酸基、Y為次甲基之化合物為較佳。 In addition, as a monomer represented by the general formula (vii), a compound in which R 21 is a hydrogen atom or a methyl group, L 2 is an alkylene group, Z 2 is a carboxylic acid group, and Y is a methine group is preferable.

而且，作為以通式(ix)表示之單量體，R24、R25及R26分別獨立地為氫原子或甲基、Z2為羧酸基之化合物為較佳。 Furthermore, as a monomer represented by the general formula (ix), compounds in which R 24 , R 25 and R 26 are each independently a hydrogen atom or a methyl group, and Z 2 is a carboxylic acid group are preferred.

上述黏結樹脂能夠藉由與上述之包含具有接枝鏈之結構單元之分散劑相同之方法合成，並且，其較佳酸值、重量平均分子量亦相同。 The above-mentioned binding resin can be synthesized by the same method as the above-mentioned dispersant containing a structural unit having a grafted chain, and its preferred acid value and weight average molecular weight are also the same.

上述黏結樹脂可具有1種或2種以上具有酸基之結構單元。 The above-mentioned bonding resin may have one or more structural units having acid groups.

具有酸基之結構單元的含量以質量換算計，相對於上述黏結樹脂的總質量，5~95%為較佳，從抑制基於鹼顯影之圖像強度的損傷之觀點考慮，10~90%為更佳。 The content of the structural unit having acid groups is calculated by mass conversion. Relative to the total mass of the above-mentioned binder resin, 5-95% is preferred. From the viewpoint of suppressing damage to the image strength due to alkali development, 10~90% is Better.

本發明的組成物中的黏結樹脂的含量相對於組成物的總固體含 量，0.1~30質量%為較佳，0.3~25質量%為更佳。 The content of the binder resin in the composition of the present invention is relative to the total solid content of the composition The amount is preferably 0.1-30% by mass, more preferably 0.3-25% by mass.

黏結樹脂可單獨使用1種，亦可併用2種以上。併用2種以上時，合計量成為上述範圍為較佳。 The binding resin may be used singly or in combination of two or more. When two or more types are used in combination, the total amount is preferably in the above range.

<聚合性化合物> <Polymerizable compound>

本發明的組成物含有聚合性化合物為較佳。 The composition of the present invention preferably contains a polymerizable compound.

聚合性化合物係包含1個以上的具有烯屬不飽和鍵之基團之化合物為較佳，具有2個以上之化合物為更佳，具有3個以上為進一步較佳，具有5個以上尤為佳。上限例如為15個以下。作為具有烯屬不飽和鍵之基團，例如，可舉出乙烯基、(甲基)烯丙基及(甲基)丙烯醯基等。 The polymerizable compound is preferably a compound containing at least one ethylenically unsaturated bond-containing group, more preferably a compound having two or more, more preferably three or more, and particularly preferably five or more. The upper limit is, for example, 15 or less. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group.

聚合性化合物例如可以係單體、預聚物及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。單體為較佳。 The polymerizable compound may be any of chemical forms such as monomers, prepolymers, oligomers, mixtures of these, and polymers of these, for example. Monomers are preferred.

聚合性化合物的分子量為100~3000為較佳，250~1500為更佳。 The molecular weight of the polymerizable compound is preferably 100 to 3000, more preferably 250 to 1500.

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。 The polymerizable compound is preferably a 3 to 15 functional (meth)acrylate compound, and a 3 to 6 functional (meth)acrylate compound is more preferable.

作為單體、預聚物的例子，可舉出不飽和羧酸(例如，丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、異巴豆酸、馬來酸等)和其酯類、醯胺類、以及該些的多聚體，不飽和羧酸與脂肪族多元醇化合物的酯、及不飽和羧酸與脂肪族多元胺化合物的醯胺類、以及該些的多聚體為較佳。並且，亦可適當地使用具有羥基、胺基、巰基等親核性取代基之不飽和羧酸酯或者醯胺類與單官能或多官能異氰酸酯類或者環氧類的加成反應物、或上述不飽和羧酸酯或者醯胺類與單官能或多官能的羧酸的脫水縮合反應物等。並且，具有異氰酸 酯基、環氧基等親電子性取代基之不飽和羧酸酯或者醯胺類與單官能或多官能的醇類、胺類、硫醇類的反應物、具有鹵素基或甲苯磺醯基等分離性取代基之不飽和羧酸酯或者醯胺類與單官能或多官能的醇類、胺類、硫醇類的反應物亦較佳。並且，還可代替上述不飽和羧酸，使用不飽和膦酸、苯乙烯等苯乙烯衍生物及被取代為乙烯基醚、烯丙基醚等之化合物組。 Examples of monomers and prepolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides And these polymers, esters of unsaturated carboxylic acids and aliphatic polyol compounds, amides of unsaturated carboxylic acids and aliphatic polyamine compounds, and these polymers are preferred. In addition, addition reactants of unsaturated carboxylic acid esters having nucleophilic substituents such as hydroxyl groups, amino groups, and mercapto groups, or addition reactants of amides with monofunctional or polyfunctional isocyanates or epoxy groups, or the above Dehydration condensation reaction products of unsaturated carboxylic acid esters or amides and monofunctional or polyfunctional carboxylic acids, etc. And has isocyanic acid Unsaturated carboxylic acid esters with electrophilic substituents such as ester groups and epoxy groups or reactants of amides and monofunctional or polyfunctional alcohols, amines, and mercaptans, with halogen groups or toluene groups A reaction product of unsaturated carboxylic acid esters or amides having dissociative substituents and monofunctional or polyfunctional alcohols, amines, and thiols is also preferred. In addition, in place of the above-mentioned unsaturated carboxylic acids, styrene derivatives such as unsaturated phosphonic acid and styrene, and compound groups substituted with vinyl ethers, allyl ethers, and the like may be used.

作為該些的具體化合物，本發明中亦能夠適當使用日本特開2009-288705號公報的段落〔0095〕~〔0108〕中記載之化合物。 As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP 2009-288705 A can also be suitably used in the present invention.

本發明中，作為聚合性化合物，包含1個以上的具有烯屬不飽和鍵之基團、且常壓下具有100℃以上的沸點之化合物亦較佳。作為其例子，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。 In the present invention, as the polymerizable compound, a compound containing one or more groups having an ethylenically unsaturated bond and having a boiling point of 100°C or higher under normal pressure is also preferable. As an example, for example, the compounds described in paragraph 0227 of JP 2013-29760 A and paragraphs 0254 to 0257 of JP 2008-292970 A can be referred to, and this content is 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。 As the polymerizable compound, dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as a commercial product) For sale, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and these (meth)acrylic acid residues via ethylene glycol residues and propylene glycol residues The base structure (for example, SR454 and SR499 commercially available from Sartomer company Inc.) is preferred. These oligomer types can also be used. In addition, 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.

以下示出較佳聚合性化合物的態様。 The state of the preferable polymerizable compound is shown below.

聚合性化合物可具有羧基、磺酸基及磷酸基等酸基。作為具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TOAGOSEI CO.,LTD.製造的ARONIX TO-2349、M-305、M-510及M-520等。 The polymerizable compound may have acid groups such as carboxyl groups, sulfonic acid groups, and phosphoric acid groups. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred. The non-aromatic carboxylic acid anhydride is reacted with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to give it an acid group The polymerizable compound is more preferable, and among the esters, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. Examples of commercially available products include ARONIX TO-2349, M-305, M-510, and M-520 manufactured by TOAGOSEI CO., LTD.

作為具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，則在製造和操作上有利。而且，光聚合性能良好且硬化性優異。 The preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, and more preferably 5 to 30 mgKOH/g. If the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development dissolution characteristic is good, and if it is 40 mgKOH/g or less, it is advantageous in terms of production and handling. Moreover, it has good photopolymerization performance and excellent curability.

關於聚合性化合物，具有己內酯結構之化合物亦為較佳態様。 Regarding the polymerizable compound, a compound having a caprolactone structure is also preferred.

作為具有己內酯結構之化合物，只要在分子內具有己內酯結構，則並無特別限定，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，具有以下述通式(Z-1)表示之己內酯結構之化合物為較佳。 The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, it can be exemplified by using trimethylolethane, ditrimethylolethane, and trimethylolethane. Methylpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine and other polyols are esterified with (meth)acrylic acid and ε-caprolactone , Ε-caprolactone modified multifunctional (meth)acrylate. Among them, compounds having a caprolactone structure represented by the following general formula (Z-1) are preferred.

[化學式8]

Figure 106104991-A0305-02-0050-8
[Chemical formula 8]
Figure 106104991-A0305-02-0050-8

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

Figure 106104991-A0305-02-0050-9
Figure 106104991-A0305-02-0050-9

通式(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 the general formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents the number of 1 or 2, and "*" represents a bonding bond.

Figure 106104991-A0305-02-0050-10
Figure 106104991-A0305-02-0050-10

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

具有己內酯結構之聚合性化合物例如由Nippon Kayaku Co.,Ltd.作為KAYARAD DPCA系列而市售，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 having a caprolactone structure, for example, are commercially available as KAYARAD DPCA series by Nippon Kayaku Co., Ltd., DPCA-20 (in the above formulas (Z-1)~(Z-3), m=1, with the number of groups represented by the formula (Z-2) = 2, R 1 all hydrogen atoms is), the number of groups represented by the DPCA-30 (the same formula, m = 1, the formula (Z-2) = 3. Compounds with all R 1 being hydrogen atoms), DPCA-60 (same formula, m=1, the number of groups represented by formula (Z-2) = 6, compounds with all R 1 being hydrogen atoms), DPCA -120 (in the same formula, m=2, the number of groups represented by formula (Z-2)=6, and a compound in which all R 1 is a hydrogen atom), etc.

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

Figure 106104991-A0305-02-0051-11
Figure 106104991-A0305-02-0051-11

通式(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、氫原子或羧基。 In the general formulas (Z-4) and (Z-5), E independently represents -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)-, y each independently represents an integer of 0-10, and X each independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxyl group.

通式(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 general formula (Z-4), the total of (meth)acrylic groups is 3 or 4, m each independently represents an integer of 0-10, and the total of each m is an integer of 0-40.

通式(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 general formula (Z-5), the total of (meth)acrylic groups is 5 or 6, n each independently represents an integer of 0-10, and the total of each n is an integer of 0-60.

通式(Z-4)中，m為0~6的整數為較佳，0~4的整數為更佳。 In the general formula (Z-4), m is preferably an integer of 0-6, and 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, it is preferable that the total of each m is an integer of 2 to 40, an integer of 2 to 16 is more preferable, and an integer of 4 to 8 is more preferable.

通式(Z-5)中，n為0~6的整數為較佳，0~4的整數為更佳。 In the general formula (Z-5), n is preferably an integer of 0-6, and 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。 Furthermore, it is preferable that the total of each n is an integer of 3 to 60, an integer of 3 to 24 is more preferable, and an integer of 6 to 12 is more preferable.

並且，通式(Z-4)或通式(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 general formula (Z-4) or general formula (Z-5) is an oxygen atom The form in which the end of the side is bonded to X is preferred.

以通式(Z-4)或通式(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，通式(Z-5)中的6個X全部為丙烯醯基之形態、通式(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様為較佳。藉由設為該種結構，能夠更加提高顯影性。 The compound represented by general formula (Z-4) or general formula (Z-5) may be used singly, or two or more of them may be used in combination. In particular, all the six Xs in the general formula (Z-5) are in the form of acryloyl groups, the compound in which all the six Xs in the general formula (Z-5) are acryloyl groups, and at least one of the six Xs The state of the mixture of compounds that are hydrogen atoms is preferred. With this structure, the developability can be further improved.

並且，作為以通式(Z-4)或通式(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, as the total content of the compound represented by the general formula (Z-4) or the general formula (Z-5) in the polymerizable compound, 20% by mass or more is preferable, and 50% by mass or more is more preferable.

以通式(Z-4)或通式(Z-5)表示之化合物能夠藉由作為以往公知的製程之製程合成：藉由開環加成反應，使環氧乙烷或環氧丙烷與季戊四醇或雙季戊四醇鍵結之製程；及例如使(甲基)丙烯醯氯與開環骨架的末端羥基反應來導入(甲基)丙烯醯基之製程。各製程係廣為人知之製程，本領域技術人員能夠輕鬆合成以通式(Z-4)或(Z-5)表示之化合物。 The compound represented by the general formula (Z-4) or the general formula (Z-5) can be synthesized by a conventionally known process: through a ring-opening addition reaction, ethylene oxide or propylene oxide is combined with pentaerythritol Or the process of bonding dipentaerythritol; and, for example, the process of introducing (meth)acrylic acid groups by reacting (meth)acrylic acid chloride with the terminal hydroxyl groups of the ring-opening skeleton. Each process is a well-known process, and those skilled in the art can easily synthesize the compound represented by the general formula (Z-4) or (Z-5).

以通式(Z-4)或通式(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 general formula (Z-4) or general formula (Z-5), pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferred.

具體而言，可舉出以下述式(a)~(f)表示之化合物(以下，還稱作“例示化合物(a)~(f)”。)，其中，例示化合物(a)、(b)、(e)、(f)為較佳。 Specifically, compounds represented by the following formulas (a) to (f) (hereinafter, also referred to as "exemplary compounds (a) to (f)") can be given, among which, the exemplified compounds (a) and (b) ), (e), (f) are preferred.

[化學式12]

Figure 106104991-A0305-02-0053-12
[Chemical formula 12]
Figure 106104991-A0305-02-0053-12

[化學式13]

Figure 106104991-A0305-02-0054-13
[Chemical formula 13]
Figure 106104991-A0305-02-0054-13

作為以通式(Z-4)、(Z-5)表示之聚合性化合物的市售品，例如可舉出Sartomer company Inc.製造的具有4個氧化乙烯鏈之4官能丙烯酸酯亦即SR-494、Nippon Kayaku Co.,Ltd.製造的具有6個亞戊基氧(pentyleneoxy)鏈之6官能丙烯酸酯亦即DPCA-60、具有3個異丁烯氧鏈之3官能丙烯酸酯亦即TPA-330等。 As a commercially available product of the polymerizable compound represented by the general formula (Z-4) and (Z-5), for example, SR- is a 4-functional acrylate having 4 ethylene oxide chains manufactured by Sartomer Company Inc. 494, Nippon Kayaku Co., Ltd. made a 6-functional acrylate with 6 pentyleneoxy chains, namely DPCA-60, and a 3-functional acrylate with 3 isobutyleneoxy chains, namely TPA-330, etc. .

作為聚合性化合物，除了如日本特公昭48-41708號公報、日本特開昭51-37193號公報、日本特公平2-32293號公報、日本特公平2-16765號公報中記載之氨酯丙烯酸酯類和日本特公昭58-49860號公報、日本特公昭 56-17654號公報、日本特公昭62-39417號公報、日本特公昭62-39418號公報中記載之具有環氧乙烷系骨架之氨酯化合物類亦較佳。並且，還能夠藉由使用日本特開昭63-277653號公報、日本特開昭63-260909號公報、日本特開平1-105238號公報中記載之、在分子內具有胺基結構和硫醚結構之加成聚合性化合物類，獲得感光速度非常優異之組成物。 As polymerizable compounds, except for the urethane acrylates described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765 Class and Japanese Special Public Bulletin No. 58-49860, Japanese Special Public Bulletin Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also preferable. In addition, it is also possible to use JP-A 63-277653, JP-A 63-260909, and JP-A 1-105238, which have an amino structure and a thioether structure in the molecule. Addition of polymerizable compounds to obtain a composition with very excellent photosensitive speed.

作為市售品，可舉出氨酯低聚物UAS-10、UAB-140(Sanyo Kokusaku Pulp Co.,Ltd.製造)、UA-7200(Shin-Nakamura Chemical Co.,Ltd製造)、DPHA-40H(Nippon Kayaku Co.,Ltd.製造)、UA-306H、UA-306T、UA-306I、AH-600、T-600及AI-600(KYOEISHA CHEMICAL Co.,LTD製造)等。 As commercially available products, urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by KYOEISHA CHEMICAL Co., LTD), etc.

並且，本發明中使用之聚合性化合物的SP(溶解度參數)值為9.50以上為較佳，10.40以上為更佳，10.60以上為進一步較佳。 In addition, the SP (solubility parameter) value of the polymerizable compound used in the present invention is preferably 9.50 or more, more preferably 10.40 or more, and still more preferably 10.60 or more.

另外，本說明書中，關於SP值，除非另有指明，則藉由Hoy法求出(H.L.Hoy Journal of Painting，1970，Vol.42，76-118)。並且，對於SP值，省略單位而示出，但其單位為cal1/2cm-3/2。 In addition, in this specification, the SP value is calculated by the Hoy method (HL Hoy Journal of Painting, 1970, Vol. 42, 76-118) unless otherwise specified. In addition, the SP value is shown without the unit, but the unit is cal 1/2 cm -3/2 .

並且，從改善顯影殘渣的觀點考慮，組成物包含具有卡多骨架之聚合性化合物亦較佳。 In addition, from the viewpoint of improving the development residue, the composition preferably contains a polymerizable compound having a cardo skeleton.

作為具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，以下述式(Q3)表示之化合物為更佳。 As the polymerizable compound having a cardo skeleton, a polymerizable compound having a 9,9-diarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.

通式(Q3) General formula (Q3)

[化學式14]

Figure 106104991-A0305-02-0056-14
[Chemical formula 14]
Figure 106104991-A0305-02-0056-14

上述通式(Q3)中，Ar11~Ar14分別獨立地表示包含以虛線包圍之苯環之芳基。X1~X4分別獨立地表示具有聚合性基團之取代基，上述取代基中的碳原子可被雜原子取代。a及b分別獨立地表示1~5的整數，c及d分別獨立地表示0~4的整數。R1~R4分別獨立地表示取代基，e、f、g及h分別獨立地表示0以上的整數，e、f、g及h的上限值分別為從Ar11~Ar14能夠具有之取代基的數減去a、b、c或d之值。其中，Ar11~Ar14分別獨立地為作為稠環之一而包含以虛線包圍之苯環之多環芳香族烴基時，X1~X4及R1~R4可分別獨立地取代為以虛線包圍之苯環，亦可取代為以虛線包圍之苯環以外的環。 In the general formula (Q3), Ar 11 to Ar 14 each independently represent an aryl group including a benzene ring surrounded by a dotted line. X 1 to X 4 each independently represent a substituent having a polymerizable group, and the carbon atom in the substituent may be substituted by a heteroatom. a and b each independently represent an integer of 1 to 5, and c and d each independently represent an integer of 0 to 4. R 1 to R 4 each independently represent a substituent, e, f, g, and h each independently represent an integer greater than or equal to 0, and the upper limits of e, f, g, and h are those that can have from Ar 11 to Ar 14 The number of substituents minus the value of a, b, c or d. Wherein, when Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a dotted line as one of the fused rings, X 1 to X 4 and R 1 to R 4 may be independently substituted with The benzene ring enclosed by the dotted line may be substituted with a ring other than the benzene ring enclosed by the dotted line.

上述通式(Q3)中，Ar11~Ar14所表示之包含以虛線包圍之苯環之芳基為碳原子數6~14的芳基為較佳，碳原子數6~10的芳基(例如，苯基、萘基)為更佳，苯基(限於以虛線包圍之苯環)為進一步較佳。 In the above general formula (Q3), the aryl group represented by Ar 11 to Ar 14 containing a benzene ring surrounded by a dotted line is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms ( For example, phenyl and naphthyl) are more preferable, and phenyl (limited to the benzene ring surrounded by a dotted line) is still more preferable.

上述通式(Q3)中，X1~X4分別獨立地表示具有聚合性基團之取代基，上述取代基中的碳原子可被雜原子取代。作為X1~X4所表示之具有聚合性基團之取代基，並無特別限制，但具有聚合性基團之脂肪族基為較佳。 In the above general formula (Q3), X 1 to X 4 each independently represent a substituent having a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom. The substituent having a polymerizable group represented by X 1 to X 4 is not particularly limited, but an aliphatic group having a polymerizable group is preferred.

作為具有X1~X4所表示之聚合性基團之脂肪族基，並無特別限制，但聚合性基團以外的碳原子數為1~12的亞烷基為較佳，碳原子數2~10的 亞烷基為更佳，碳原子數2~5的亞烷基為進一步較佳。 The aliphatic group having the polymerizable group represented by X 1 to X 4 is not particularly limited, but an alkylene group having 1 to 12 carbon atoms other than the polymerizable group is preferred, and the number of carbon atoms is 2 An alkylene group of ~10 is more preferable, and an alkylene group of 2 to 5 carbon atoms is more preferable.

並且，具有X1~X4所表示之聚合性基團之脂肪族基中，上述脂肪族基被雜原子取代時，被-NR-(R為取代基)、氧原子、硫原子取代為較佳，上述脂肪族基中不相鄰之-CH2-被氧原子或硫原子取代為更佳，上述脂肪族基中不相鄰之-CH2-被氧原子取代為進一步較佳。具有X1~X4所表示之聚合性基團之脂肪族基的1~2處被雜原子取代為較佳，被雜原子取代1處為更佳，與Ar11~Ar14所表示之包含以虛線包圍之苯環之芳基相鄰之1處被雜原子取代為進一步較佳。 In addition, in the aliphatic group having a polymerizable group represented by X 1 to X 4 , when the aliphatic group is substituted with a hetero atom, it is replaced by -NR- (R is a substituent), an oxygen atom, and a sulfur atom. Jia, the aliphatic group of non-adjacent -CH 2 - is substituted with an oxygen atom or a sulfur atom is more preferably the aliphatic group of non-adjacent -CH 2 - is substituted with an oxygen atom is further preferred. The aliphatic group having a polymerizable group represented by X 1 ~X 4 is preferably substituted by a heteroatom at 1 to 2 points, and it is more preferred to be substituted by a heteroatom at 1 point. It is included with Ar 11 ~ Ar 14 It is more preferable that one adjacent aryl group of the benzene ring surrounded by a dotted line is substituted with a heteroatom.

作為具有X1~X4所表示之聚合性基團之脂肪族基中包含之聚合性基團，能夠進行自由基聚合或陽離子聚合之聚合性基團(以下，還分別稱作自由基聚合性基團及陽離子聚合性基團)為較佳。 As the polymerizable group contained in the aliphatic group having the polymerizable group represented by X 1 to X 4 , a polymerizable group capable of radical polymerization or cationic polymerization (hereinafter, also referred to as radical polymerizable group, respectively) Group and cationically polymerizable group) are preferred.

作為自由基聚合性基團，能夠使用通常周知之自由基聚合性基團，作為較佳者，可舉出具有能夠進行自由基聚合之烯屬不飽和鍵之聚合性基團，具體而言，可舉出乙烯基、(甲基)丙烯醯氧基等。其中，(甲基)丙烯醯氧基為較佳，丙烯醯氧基為更佳。 As the radical polymerizable group, a generally known radical polymerizable group can be used. Preferably, a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization can be mentioned. Specifically, A vinyl group, (meth)acryloxy group, etc. can be mentioned. Among them, (meth)acryloxy is preferred, and acryloxy is more preferred.

作為陽離子聚合性基團，能夠使用通常周知之陽離子聚合性基團，具體而言，可舉出脂環式醚基、環狀縮醛基、環狀內酯基、環狀硫醚基、螺環原酸酯基、乙烯氧基等。其中，脂環式醚基、乙烯氧基為較佳，環氧基、氧雜環丁基、乙烯氧基尤為佳。 As the cationically polymerizable group, commonly known cationically polymerizable groups can be used. Specifically, alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, and spiro Cyclic orthoester group, vinyloxy group, etc. Among them, alicyclic ether groups and vinyloxy groups are preferred, and epoxy groups, oxetanyl groups, and vinyloxy groups are particularly preferred.

Ar1~Ar4所包含之取代基所具有之上述聚合性基團為自由基聚合性基團為較佳。 The above-mentioned polymerizable group contained in the substituents contained in Ar 1 to Ar 4 is preferably a radical polymerizable group.

Ar1~Ar4中的2個以上包含具有聚合性基團之取代基，Ar1~Ar4中的2~4個包含具有聚合性基團之取代基為較佳，Ar1~Ar4中的2或3個包含具有聚合性基團之取代基為更佳，Ar1~Ar4中的2個包含具有聚合性基團之取代基為進一步較佳。 Ar 1 ~ Ar 4 comprising two or more of the substituent having a polymerizable group of the group, Ar 1 ~ Ar 4 is 2 to 4 comprises a substituent having a polymerizable group is preferably the group, Ar 1 ~ Ar 4 in It is more preferable that 2 or 3 of the substituents contain a polymerizable group, and two of Ar 1 to Ar 4 contain a substituent that has a polymerizable group.

Ar11~Ar14分別獨立地為作為稠環之一包含以虛線包圍之苯環之多環芳香族烴基時，X1~X4可分別獨立地取代為以虛線包圍之苯環，亦可取代為以虛線包圍之苯環以外的環。 When Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a dotted line as one of the fused rings, X 1 to X 4 can be independently substituted with a benzene ring surrounded by a dotted line, or substituted It is a ring other than the benzene ring surrounded by a dotted line.

上述通式(Q3)中，a及b分別獨立地表示1~5的整數，1或2為較佳，a及b均為1為更佳。 In the general formula (Q3), a and b each independently represent an integer of 1 to 5, preferably 1 or 2, and more preferably both a and b are 1.

上述通式(Q3)中，c及d分別獨立地表示0~5的整數，0或1為較佳，c及d均為0為更佳。 In the above general formula (Q3), c and d each independently represent an integer of 0 to 5, preferably 0 or 1, and more preferably both c and d are 0.

上述通式(Q3)中，R1~R4分別獨立地表示取代基。作為R1~R4所表示之取代基，並無特別限制，例如，可舉出鹵原子、鹵化烷基、烷基、鏈烯基、醯基、羥基、羥基烷基、烷氧基、芳基、雜芳基、脂環基等。 R1~R4所表示之取代基為烷基、烷氧基或芳基為較佳，碳原子數1~5的烷基、碳原子數1~5的烷氧基或苯基為更佳，甲基、甲氧基或苯基為進一步較佳。 In the general formula (Q3), R 1 to R 4 each independently represent a substituent. The substituents represented by R 1 to R 4 are not particularly limited, and examples include halogen atoms, halogenated alkyl groups, alkyl groups, alkenyl groups, hydroxy groups, hydroxyalkyl groups, alkoxy groups, and aromatic groups. Group, heteroaryl group, alicyclic group, etc. The substituent represented by R 1 to R 4 is preferably an alkyl group, an alkoxy group or an aryl group, and more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group or a phenyl group having 1 to 5 carbon atoms , Methyl, methoxy or phenyl is further preferred.

上述通式(Q3)中，Ar11~Ar14分別獨立地為作為稠環之一包含以虛線包圍之苯環之多環芳香族烴基時，R1~R4可分別獨立地取代為以虛線包圍之苯環，亦可取代為以虛線包圍之苯環以外的環。 In the above general formula (Q3), when Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a dotted line as one of the condensed rings, R 1 to R 4 may be independently substituted with a dotted line The surrounding benzene ring may be substituted with a ring other than the benzene ring surrounded by a dotted line.

上述通式(Q3)中，e、f、g及h分別獨立地表示0以上的整數， e、f、g及h的上限值分別為從Ar11~Ar14能夠具有之取代基的數減去a、b、c或d之值。 In the above general formula (Q3), e, f, g, and h each independently represent an integer of 0 or more, and the upper limit of e, f, g, and h is the number of substituents that can have from Ar 11 to Ar 14 respectively Subtract the value of a, b, c, or d.

e、f、g及h分別獨立地0~8為較佳，0~2為更佳，0為進一步較佳。 e, f, g, and h are each independently 0-8 preferably, 0-2 is more preferable, and 0 is even more preferable.

Ar11~Ar14分別獨立地為作為稠環之一包含以虛線包圍之苯環之多環芳香族烴基時，e、f、g及h為0或1為較佳，0為更佳。 When Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a dotted line as one of the condensed rings, it is preferable that e, f, g, and h are 0 or 1, and 0 is more preferable.

作為以上述式(Q3)表示之化合物，例如，可舉出9，9‘-二[4-(2-丙烯醯氧基乙氧基)苯基]芴等。作為具有9，9-二芳基芴骨架之聚合性化合物，還能夠較佳地使用日本特開2010-254732號公報記載之化合物類。 As the compound represented by the above formula (Q3), for example, 9,9'-bis[4-(2-propenyloxyethoxy)phenyl]fluorene and the like can be cited. As the polymerizable compound having a 9,9-diarylfluorene skeleton, the compounds described in JP 2010-254732 A can also be preferably used.

作為該種具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。 The polymerizable compound having a cardo skeleton is not limited, and examples thereof include Oncoat EX series (manufactured by NAGASE & CO., LTD) and Ogsol (manufactured by Osaka Gas Chemicals Co., Ltd.).

本發明的組成物含有聚合性化合物時，聚合性化合物的含量相對於組成物的總固體含量，0.1~40質量%為較佳。下限例如為0.5質量%以上為更佳，1質量%以上為進一步較佳。上限例如為30質量%以下為更佳，20質量%以下為進一步較佳。 When the composition of the present invention contains a polymerizable compound, the content of the polymerizable compound is preferably 0.1 to 40% by mass relative to the total solid content of the composition. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 20% by mass or less.

聚合性化合物可以係單獨1種，亦可併用2種以上。併用2種以上時，合計量成為上述範圍為較佳。 A polymerizable compound may be used individually by 1 type, and may use 2 or more types together. When two or more types are used in combination, the total amount is preferably in the above range.

<聚合起始劑> <Polymerization initiator>

本發明的組成物具有聚合起始劑為較佳。 The composition of the present invention preferably has a polymerization initiator.

作為聚合起始劑，並無特別限制，能夠從公知的聚合起始劑中適當選擇，例如，具有感光性者(所謂的光聚合起始劑)為較佳。 The polymerization initiator is not particularly limited, and can be appropriately selected from known polymerization initiators. For example, those having photosensitivity (so-called photopolymerization initiators) are preferred.

本發明的組成物除了含氮化鈦粒子以外，還含有光聚合起始劑及上述聚合性化合物時，藉由活性光線或放射線的照射而硬化，故有時被稱作“感光性組成物”。 When the composition of the present invention contains not only titanium nitride particles, but also a photopolymerization initiator and the above-mentioned polymerizable compound, it is cured by irradiation with active light or radiation, so it is sometimes referred to as a "photosensitive composition." .

作為光聚合起始劑，只要具有引發聚合性化合物的聚合之能力，則並無特別限制，能夠從公知的光聚合起始劑中適當選擇。例如，對從紫外線區域至可見光線具有感光性者為較佳。並且，聚合起始劑可以係與被光激發之光敏劑產生某些作用，並生成活性自由基之活性劑，亦可以係依據單體的種類而引發陽離子聚合之起始劑。 The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and it can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have photosensitivity from ultraviolet region to visible light. In addition, the polymerization initiator can be an active agent that has some effect with a photosensitizer excited by light and generates active free radicals, or it can be an initiator that initiates cationic polymerization according to the type of monomer.

並且，光聚合起始劑含有至少1種於約300nm~800nm(330nm~500nm為更佳。)的範圍內具有至少約50莫耳吸光系數之化合物為較佳。 In addition, the photopolymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 mol in the range of about 300 nm to 800 nm (330 nm to 500 nm is more preferable).

作為光聚合起始劑，例如，可舉出鹵化烴衍生物(例如，具有三嗪骨架者、具有噁二唑骨架者等)、醯基氧化膦等醯基膦化合物、六芳基雙咪唑、肟衍生物等肟化合物、有機過氧化物、硫代化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮化合物、羥基苯乙酮等。作為上述具有三嗪骨架之鹵代烴化合物，例如，可舉出若林等著、Bull.Chem.Soc.Japan，42、2924(1969)記載之化合物、英國專利1388492號說明書記載之化合物、日本特開昭53-133428號公報記載之化合物、德國專利3337024號說明書記載之化合物、基於F.C.Schaefer等之J.Org.Chem.；29、1527(1964)記載之化合物、日本特開昭62-58241號公報記載之化合物、日本特開平5-281728號公報記載之化合物、日本特開平5-34920號公報記載之化合物、美國專利第4212976號說明書中記載之化合物等。 As the photopolymerization initiator, for example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), phosphine compounds such as phosphine oxide, hexaarylbisimidazole, Oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, etc. As the halogenated hydrocarbon compound having a triazine skeleton, for example, the compound described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), the compound described in the specification of British Patent No. 1388492, and the Japanese patent The compound described in Japanese Patent Publication No. 53-133428, the compound described in German Patent No. 3337024, the compound described in J. Org. Chem. based on FC Schaefer et al.; 29, 1527 (1964), Japanese Patent Application Publication No. 62-58241 The compound described in the publication, the compound described in JP 5-281728, the compound described in JP 5-34920, the compound described in the specification of U.S. Patent No. 4212976, and the like.

並且，從曝光靈敏度的觀點考慮，選自包含三鹵甲基三嗪化合物、苄基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、鎓類化合物、苯并噻唑化合物、二苯甲酮化合物、苯乙酮化合物及其衍生物、環戊二烯-苯-鐵絡合物及其鹽、鹵代甲基噁二唑化合物及3-芳基取代香豆素化合物之組之化合物為較佳。 Also, from the viewpoint of exposure sensitivity, it is selected from the group consisting of trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, phosphine compounds, and phosphine oxide compounds. , Metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes Compounds of the group of salts, halogenated methyl oxadiazole compounds and 3-aryl substituted coumarin compounds are preferred.

三鹵甲基三嗪化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、肟化合物、三芳基咪唑二聚體、鎓類化合物、二苯甲酮化合物、苯乙酮化合物為進一步較佳，選自包含三鹵甲基三嗪化合物、α-胺基酮化合物、肟化合物、三芳基咪唑二聚體及二苯甲酮化合物之組之至少1種化合物尤為佳。 Trihalomethyl triazine compound, α-amino ketone compound, phosphine compound, phosphine oxide compound, oxime compound, triaryl imidazole dimer, onium compound, benzophenone compound, acetophenone compound are further Preferably, at least one compound selected from the group consisting of trihalomethyl triazine compound, α-amino ketone compound, oxime compound, triaryl imidazole dimer and benzophenone compound is particularly preferred.

尤其，使用本發明的樹脂膜製作固態攝影元件的遮光膜時，需要以銳利的形狀形成微細的圖案，故與硬化性一同在未曝光部無殘渣地顯影為重要。從該種觀點考慮，使用肟化合物作為光聚合起始劑尤為佳。尤其，固態攝影元件中形成微細的圖案時，硬化用曝光中利用步進曝光，但該曝光機有時會被鹵素損傷，還需要將光聚合起始劑的添加量抑制得較低，故，若考慮該些方面，則形成如固態攝影元件的微細圖案時，作為光聚合起始劑，使用肟化合物尤為佳。並且，藉由使用肟化合物，能夠使顏色轉移性更優化。 In particular, when the resin film of the present invention is used to produce a light-shielding film of a solid-state imaging element, it is necessary to form a fine pattern in a sharp shape. Therefore, together with the curability, development without residue in the unexposed area is important. From this viewpoint, it is particularly preferable to use an oxime compound as a photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging element, step exposure is used in exposure for curing. However, this exposure machine may be damaged by halogen, and it is necessary to keep the amount of photopolymerization initiator added to a low level. In consideration of these points, when forming a fine pattern such as a solid-state imaging element, it is particularly preferable to use an oxime compound as a photopolymerization initiator. Moreover, by using an oxime compound, the color transfer can be optimized.

作為光聚合起始劑的具體例，例如，能夠參閱日本特開2013-29760號公報的段落0265~0268，該內容編入本申請說明書中。 As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP 2013-29760 A can be referred to, and this content is incorporated in the specification of this application.

作為光聚合起始劑，亦可適當地使用羥基苯乙酮化合物、胺基苯 乙酮化合物及醯基膦化合物。更具體而言，例如，還能夠使用日本特開平10-291969號公報中記載之胺基苯乙酮系起始劑、日本專利第4225898號公報中記載之醯基膦系起始劑。 As the photopolymerization initiator, hydroxyacetophenone compounds and aminobenzene can also be suitably used. Ethyl ketone compounds and phosphine compounds. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and the phosphine-based initiator described in Japanese Patent No. 4225898 can also be used.

作為羥基苯乙酮系起始劑，能夠使用IRGACURE-184、DAROCUR-1173、IRGACURE-500、IRGACURE-2959、IRGACURE-127(商品名、均為BASF公司製造)。 As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (brand names, all manufactured by BASF) can be used.

作為胺基苯乙酮系起始劑，能夠使用作為市售品之IRGACURE-907、IRGACURE-369及IRGACURE-379EG(商品名、均為BASF公司製造)。胺基苯乙酮系起始劑還能夠使用吸收波長與365nm或405nm等長波光源匹配之日本特開2009-191179號公報中記載之化合物。 As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (brand names, all manufactured by BASF Corporation), which are commercially available products, can be used. As the aminoacetophenone-based initiator, the compound described in Japanese Patent Application Laid-Open No. 2009-191179 whose absorption wavelength matches a long-wave light source such as 365 nm or 405 nm can also be used.

作為醯基膦系起始劑，能夠使用作為市售品之IRGACURE-819或DAROCUR-TPO(商品名、均為BASF公司製造)。 As the phosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (brand name, both manufactured by BASF Corporation), which are commercially available products, can be used.

作為光聚合起始劑，可更佳地舉出肟化合物。尤其，肟系起始劑為高靈敏度且聚合效率較高，能夠與色材濃度無關地進行硬化，易將色材的濃度設計為較高，故為較佳。 As the photopolymerization initiator, an oxime compound can be more preferably mentioned. In particular, the oxime-based initiator has high sensitivity and high polymerization efficiency, and can be hardened regardless of the color material concentration, and it is easy to design the color material concentration to be high, which is preferable.

作為肟化合物的具體例，可使用日本特開2001-233842號公報記載之化合物、日本特開2000-80068號公報記載之化合物、日本特開2006-342166號公報記載之化合物。 As specific examples of the oxime compound, the compound described in JP 2001-233842 A, the compound described in JP 2000-80068 A, and the compound described in JP 2006-342166 can be used.

在本發明中作為能夠較佳地使用之肟化合物，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-乙醯氧基亞胺基-1-苯基丙烷-1-酮、 2-苯甲醯氧基亞胺基-1-苯基丙烷-1-酮、3-(4-甲苯磺醯氧基)亞胺基丁烷-2-酮及2-乙氧基羰氧基亞胺基-1-苯基丙烷-1-酮等。 As the oxime compound that can be preferably used in the present invention, for example, 3-benzyloxyiminobutane-2-one, 3-acetoxyiminobutane-2- Ketone, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane- 1-ketone, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyloxy Imino-1-phenylpropan-1-one, etc.

並且，還可舉出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、特表2004-534797號公報、日本特開2006-342166號公報的各公報中記載之化合物等。 In addition, JCSPerkin II (1979) pp.1653-1660), JCSPerkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, Japan The compounds described in JP 2000-66385 A, JP 2000-80068 A, JP 2004-534797 A, and JP 2006-342166 A, etc.

市售品中，亦可較佳地使用IRGACURE-OXE01(BASF SE製造)、IRGACURE-OXE02(BASF SE製造)。並且，還可使用TR-PBG-304(常州強力電子新材料有限公司製造)、Adeka Arkles NCI-831及Adeka Arkles NCI-930(ADEKA CORPORATION製造)、N-1919(含咔唑．肟酯骨架光起始劑(ADEKA CORPORATION製造)。 Among commercially available products, IRGACURE-OXE01 (manufactured by BASF SE) and IRGACURE-OXE02 (manufactured by BASF SE) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (manufactured by ADEKA CORPORATION), N-1919 (containing carbazole and oxime ester skeleton light Starter (manufactured by ADEKA CORPORATION).

並且，作為上述記載以外的肟化合物，可使用在咔唑N位連結有肟之日本特表2009-519904號公報中記載之化合物、在二苯基酮部位導入有雜取代基之美國專利第7626957號公報中記載之化合物、在色素部位導入有硝基之日本特開2010-15025號公報及美國專利公開2009-292039號記載之化合物、國際公開專利2009-131189號公報中記載之酮肟化合物、在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、在405nm具有極大吸收且對g射線光源具有良好的靈敏度之日本特開2009-221114號公報記載之化合物等。 In addition, as oxime compounds other than those described above, compounds described in Japanese Patent Application Publication No. 2009-519904 in which an oxime is linked to the N-position of carbazole, and US Pat. No. 7626957 in which a heterosubstituent is introduced at the diphenylketone site can be used. The compound described in the publication No., the compound described in Japanese Patent Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced into the pigment site, the ketoxime compound described in the International Publication No. 2009-131189, The compound described in U.S. Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule, a compound described in Japanese Patent Application Laid-Open No. 2009-221114, etc., which has a great absorption at 405 nm and has good sensitivity to g-ray light sources.

例如可較佳地參閱日本特開2013-29760號公報的段落0274~0275，該 內容編入本說明書中。 For example, it is better to refer to paragraphs 0274~0275 of JP 2013-29760 A The content is incorporated into this manual.

具體而言，作為肟化合物，以下述式(OX-1)表示之化合物為較佳。另外，肟的N-O鍵可以係(E)體的肟化合物，亦可以係(Z)體的肟化合物，還可以係(E)體與(Z)體的混合物。 Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferred. In addition, the N-O bond of the oxime may be an oxime compound in the (E) form, or an oxime compound in the (Z) form, or a mixture of the (E) form and the (Z) form.

Figure 106104991-A0305-02-0064-15
Figure 106104991-A0305-02-0064-15

通式(OX-1)中，R及B分別獨立地表示一價的取代基，A表示二價的有機基團，Ar表示芳基。 In the general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

作為通式(OX-1)中以R表示之一價的取代基，一價的非金屬原子團為較佳。 As the monovalent substituent represented by R in the general formula (OX-1), a monovalent non-metal atomic group is preferred.

作為一價的非金屬原子團，可舉出烷基、芳基、醯基、烷氧羰基、芳氧羰基、雜環基、烷基硫代羰基、芳基硫代羰基等。並且，該些基團可具有1個以上的取代基。並且，前述取代基可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, an arylthiocarbonyl group, and the like. In addition, these groups may have one or more substituents. In addition, the aforementioned substituent may be further substituted with another substituent.

作為取代基，可舉出鹵原子、芳氧基、烷氧羰基或芳氧羰基、醯氧基、醯基、烷基、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, an aryl group, and the like.

作為通式(OX-1)中以B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。該些基團可具有1個以上的取代基。作為取代基，可例示前述取代基。 As the monovalent substituent represented by B in the general formula (OX-1), an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group is preferred. These groups may have one or more substituents. As the substituent, the aforementioned substituents can be exemplified.

作為通式(OX-1)中以A表示之二價的有機基團，碳原子數1~12的亞烷基、亞環烷基、亞炔基為較佳。該些基團可具有1個以上的取代基。作 為取代基，可例示前述取代基。 As the divalent organic group represented by A in the general formula (OX-1), an alkylene group, cycloalkylene group, and alkynylene group having 1 to 12 carbon atoms are preferred. These groups may have one or more substituents. Make As a substituent, the aforementioned substituents can be exemplified.

本發明中，作為光聚合起始劑，還能夠使用具有氟原子之肟化合物。作為具有氟原子之肟化合物的具體例，可舉出日本特開2010-262028號公報記載之化合物、日本特表2014-500852號公報記載之化合物24、36~40、日本特開2013-164471號公報記載之化合物(C-3)等。該內容編入本說明書中。 In the present invention, as the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include the compounds described in JP 2010-262028 A, the compounds 24, 36 to 40 described in JP 2014-500852 A, and JP 2013-164471 The compound (C-3) etc. described in the bulletin. This content is incorporated into this manual.

本發明中，作為光聚合起始劑，還能夠使用以下述通式(1)或(2)表示之化合物。 In the present invention, as the photopolymerization initiator, a compound represented by the following general formula (1) or (2) can also be used.

Figure 106104991-A0305-02-0065-16
Figure 106104991-A0305-02-0065-16

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的脂環式羥基、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第基，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表示直接鍵結或羰基。 In formula (1), R 1 and R 2 each independently represent an alkyl group with 1 to 20 carbon atoms, an alicyclic hydroxyl group with 4 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or the number of carbon atoms The aralkyl group of 7 to 30, when R 1 and R 2 are phenyl groups, the phenyl groups can be bonded to each other to form a group. R 3 and R 4 each independently represent a hydrogen atom and an alkyl group with 1 to 20 carbon atoms , C 6-30 aryl group, C 7-30 aralkyl group or C 4-20 heterocyclic group, X represents a 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表示直接鍵結或羰基，a表示0~4的整數。 (2), R 1, R 2, 1 , R 2, R 3 and the same formula the meanings of R 4 in the formula R (1) in R 3 and R 4, R 5 represents -R 6, -OR 6, -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6 , -CN, halogen atom or Hydroxyl group, R 6 represents an alkyl group with 1 to 20 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 direct Bonding or carbonyl group, a represents an integer of 0-4.

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為直接鍵結為較佳。 In the above formulas (1) and (2), it is preferred 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. Preferably, R 4 is an alkyl group or phenyl group having 1 to 6 carbon atoms. R 5 is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct 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。 As specific examples of the compounds represented by formula (1) and formula (2), for example, the compounds described in paragraph numbers 0076 to 0079 of JP 2014-137466 A can be cited. This content is incorporated into this manual.

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

[化學式17]

Figure 106104991-A0305-02-0067-17
[Chemical formula 17]
Figure 106104991-A0305-02-0067-17

肟化合物係在350nm~500nm的波長區域具有極大吸收波長者為較佳，在360nm~480nm的波長區域具有極大吸收波長者為更佳，365nm及405nm的吸光度較高者尤為佳。 The oxime compound preferably has a maximum absorption wavelength in the 350nm~500nm wavelength region, preferably the maximum absorption wavelength in the 360nm~480nm wavelength region, and the higher absorbance at 365nm and 405nm is particularly preferred.

肟化合物中，關於365nm或405nm中的莫耳吸光系數，從靈敏度的觀點考慮，1,000~300,000為較佳，2,000~300,000為更佳，5,000~ 200,000尤為佳。 Among oxime compounds, with regard to the molar absorption coefficient at 365 nm or 405 nm, from the viewpoint of sensitivity, 1,000 to 300,000 is preferable, 2,000 to 300,000 is more preferable, and 5,000 to 5,000 200,000 is particularly preferred.

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

本發明中使用之光聚合起始劑可依據需要組合2種以上來使用。 The photopolymerization initiator used in the present invention can be used in combination of two or more types as required.

本發明的組成物含有聚合起始劑時，聚合起始劑的含量相對於組成物中的總固體含量，0.1~30質量%為較佳，1~25質量%為更佳，1~10質量%為進一步較佳。本發明的組成物可僅包含1種聚合起始劑，亦可包含2種以上。包含2種以上時，其合計量成為上述範圍為較佳。 When the composition of the present invention contains a polymerization initiator, the content of the polymerization initiator relative to the total solid content in the composition is preferably 0.1-30% by mass, more preferably 1-25% by mass, and 1-10% by mass. % Is more preferable. The composition of the present invention may include only one type of polymerization initiator, or may include two or more types. When two or more types are contained, the total amount thereof is preferably in the above-mentioned range.

<有機溶劑> <Organic solvent>

本發明的組成物含有有機溶劑為較佳。 The composition of the present invention preferably contains an organic solvent.

作為有機溶劑的例子，例如，可舉出丙酮、甲乙酮、環己烷、乙酸乙酯、二氯乙烯、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、甲氧基乙氧基乙醇、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、乙酸乙酯、乙酸丁酯、乳酸甲酯及乳酸乙酯等，但並不限定於該些。 Examples of organic solvents include, for example, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethylene, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether. , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl Ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxyethoxyethanol, 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-methoxy propyl acetate, N,N-dimethylformamide, dimethyl sulfide , Γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, etc., but not limited to these.

本發明的組成物可含有1種有機溶劑，亦可含有2種以上的有 機溶劑，但從調液本發明的組成物時能夠抑制含氮化鈦粒子的粒徑變動之角度考慮，含有2種以上有機溶劑。 The composition of the present invention may contain one organic solvent, or two or more organic solvents. Organic solvents, but from the viewpoint of suppressing variation in the particle size of titanium nitride-containing particles when the composition of the present invention is adjusted, it contains two or more organic solvents.

含有2種以上的有機溶劑時，由選自上述3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙基溶纖劑乙酸酯、乳酸乙酯、二甘醇二甲醚、乙酸丁酯、3-甲氧基丙酸甲酯、2-庚酮、環己酮、環戊酮、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲醚及丙二醇單甲醚乙酸酯之2種以上構成之混合溶液尤為佳。 When two or more organic solvents are contained, it is selected from the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol diethylene glycol Methyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol mono A mixed solution composed of two or more kinds of methyl ether and propylene glycol monomethyl ether acetate is particularly preferred.

本發明的組成物含有有機溶劑時，作為有機溶劑的含量，相對於組成物的總質量，10~90質量%為較佳，60~90質量%為更佳。包含2種以上的有機溶劑時，其合計量成為上述範圍為較佳。 When the composition of the present invention contains an organic solvent, the content of the organic solvent is preferably 10 to 90% by mass, and more preferably 60 to 90% by mass relative to the total mass of the composition. When two or more kinds of organic solvents are contained, the total amount thereof is preferably in the above range.

<水> <water>

本發明的組成物可含有水。水可以係有目的地添加者，亦可以係藉由添加本發明的組成物中包含之各成分而在組成物中不可避免地含有者。 The composition of the present invention may contain water. Water may be added purposefully, or may be inevitably contained in the composition by adding each component contained in the composition of the present invention.

水的含量相對於組成物100質量%，0.01~1質量%為較佳，0.05~0.8質量%為更佳，0.1~0.7質量%為進一步較佳。藉由水的含量在上述範圍內，能夠在製作硬化膜時抑制產生針孔，或提高硬化膜的耐濕性。 The content of water is preferably 0.01 to 1% by mass relative to 100% by mass of the composition, more preferably 0.05 to 0.8% by mass, and still more preferably 0.1 to 0.7% by mass. When the water content is within the above range, it is possible to suppress the generation of pinholes during the production of the cured film, or to improve the moisture resistance of the cured film.

<其他成分> <Other ingredients>

本發明的組成物中可包含上述成分以外的其他成分。 The composition of the present invention may contain components other than the above-mentioned components.

以下，對各成分進行詳細說明。 Hereinafter, each component is explained in detail.

(著色劑) (Colorant)

本發明的組成物還能夠使用上述含氮化鈦粒子以外的著色劑(以下， 還簡單稱作“著色劑”。)。著色劑例如為了調整組成物的色度而使用，能夠在OD值不下降之範圍內，將氮化鈦的一部分替換為著色劑。作為該種著色劑，可舉出顏料(黑色有機顏料及彩色有機顏料的有機顏料以及無機顏料)及染料等。 The composition of the present invention can also use coloring agents other than the above-mentioned titanium nitride-containing particles (hereinafter, It is also simply referred to as "colorant". ). The colorant is used, for example, to adjust the chromaticity of the composition, and part of the titanium nitride can be replaced with the colorant within a range where the OD value does not decrease. Examples of such coloring agents include pigments (organic pigments of black organic pigments and color organic pigments, and inorganic pigments), dyes, and the like.

作為著色劑，使用顏料為較佳。藉此，易製造波長在400~700nm的範圍的透射率的標準偏差較小之膜。尤其，作為顏料使用黑色顏料(黑色有機顏料及黑色無機顏料)時，易製造上述範圍的透射率的標準偏差為10%以下的膜。 As the colorant, it is preferable to use a pigment. With this, it is easy to manufacture a film with a small standard deviation of transmittance in the range of 400 to 700 nm. In particular, when black pigments (black organic pigments and black inorganic pigments) are used as the pigment, it is easy to produce a film with a standard deviation of transmittance in the above range of 10% or less.

((顏料)) ((pigment))

作為顏料，可舉出以往公知的各種顏料。 As the pigment, various conventionally known pigments can be cited.

作為彩色有機顏料，可舉出以下者。但本發明並不限定於該些。 Examples of the color organic pigments include the following. However, the present invention is not limited to these.

染料索引(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 Dye Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35 :1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94 , 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137 ,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176 , 177,179,180,181,182,185,187,188,193,194,199,213,214 etc. CI Pigment Orange 2,5,13,16,17:1,31,34,36,38 , 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 etc., CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 , 49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3 , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 , 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279 etc., CI pigment Green 7, 10, 36, 37, 58, 59 etc.

C.I.顏料紫1，19，23，27，32，37，42等 C.I. Pigment Violet 1,19,23,27,32,37,42 etc.

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 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.

並且，作為綠色顏料，還能夠使用分子中的鹵原子數為平均10~14個、溴原子為平均8~12個、氯原子為平均2~5個之鹵化鋅酞菁顏料。作為具體例，可舉出國際公開第2015/118720號中記載之化合物。 In addition, as a green pigment, it is also possible to use a halogenated zinc phthalocyanine pigment in which the number of halogen atoms in the molecule is 10 to 14 on average, bromine atoms is on average 8 to 12, and the chlorine atoms are on average 2 to 5. As a specific example, the compound described in International Publication No. 2015/118720 can be mentioned.

該些有機顏料可單獨或者為了提高顏色純度而組合複數種來使用。 These organic pigments can be used alone or in combination of plural kinds in order to improve color purity.

黑色顏料能夠使用各種公知的黑色顏料。例如，可舉出炭黑或以下示出之含黑色金屬有機顏料。作為含黑色金屬有機顏料，可舉出包含選自包含Co、Cr、Cu、Mn，Ru、Fe、Ni、Sn、Ti及Ag之組之1種或2種以上的金屬元素之金屬氧化物、金屬氮化物。該些能夠僅使用1種，並且，還能夠作為2種以上的混合物來使用。並且，可藉由對黑色顏料進一步組合其他色調的無機顏料，製備成具有所希望的遮光性。作為可組合來 使用之具體的無機顏料的例子，例如，可舉出鋅白、鉛白、鋅鋇白、氧化鈦、氧化鉻、氧化鐵、沉降性硫酸鋇及重晶石粉、鉛紅、氧化鐵紅、鉻黃、鋅黃(鋅黃1種、鋅黃2種)、群青藍、普魯士藍(亞鐵氰化鐵鉀)鋯石灰色、鐠黃、鉻鈦黃、鉻綠、孔雀、維多利亞綠、鐵藍(與普魯士藍無關)、釩鋯藍、鉻錫紅、錳紅、橙紅等。尤其，為了顯現紫外至紅外的較廣的波長域中的遮光性，不僅能夠單獨使用該些黑色顏料或其他色調，亦可混合複數種顏料來使用。 As the black pigment, various well-known black pigments can be used. For example, carbon black or the black metal-containing organic pigment shown below can be mentioned. Examples of black metal-containing organic pigments include metal oxides containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag, Metal nitride. These can be used only 1 type, and can also be used as a mixture of 2 or more types. Moreover, it can be prepared to have desired light-shielding properties by further combining inorganic pigments of other colors with black pigments. As combinable Examples of specific inorganic pigments used, for example, zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitating barium sulfate and barite powder, lead red, iron oxide red, chromium Yellow, zinc yellow (1 type of zinc yellow, 2 types of zinc yellow), ultramarine blue, Prussian blue (potassium ferrocyanide) zircon gray, yellow, chrome titanium yellow, chrome green, peacock, Victoria green, iron blue (It has nothing to do with Prussian blue), vanadium zirconium blue, chrome tin red, manganese red, orange red, etc. In particular, in order to express light-shielding properties in a wide wavelength range from ultraviolet to infrared, not only these black pigments or other colors can be used alone, but also plural kinds of pigments can be mixed and used.

黑色顏料為炭黑、鈦黑為較佳，從具有紫外至紅外的較廣的波長域的遮光性之觀點考慮，鈦黑尤為佳。鈦黑係具有鈦原子之黑色粒子。低次氧化鈦或氧氮化鈦等為較佳。雖無特別限定，但作為氧氮化鈦，能夠使用如國際公開2008/123097號公報、日本特開2009-58946、日本特開2010-14848、日本特開2010-97210及日本特開2011-2274670等的氧氮化鈦，並且，能夠使用如日本特開2010-95716的氧氮化鈦與碳化鈦的混合物等。可為了提高分散性、抑制凝聚性等，依據需要修飾鈦黑粒子的表面。能夠藉由氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鎂、氧化鋯包覆，並且，還能夠進行如日本特開2007-302836號公報所示之藉由疏水性物質的處理。為了調整分散性、著色性等，鈦黑可含有1種Cu、Fe、Mn、V、Ni等的複合氧化物、酸化鈷、氧化鐵、炭黑等黑色顏料，或者以2種以上的組合來含有。 The black pigment is preferably carbon black or titanium black, and titanium black is particularly preferred from the viewpoint of having light-shielding properties in a wide wavelength range from ultraviolet to infrared. Titanium black is a black particle with titanium atoms. Lower titanium oxide, titanium oxynitride, etc. are preferable. Although not particularly limited, as titanium oxynitride, for example, International Publication No. 2008/123097, Japanese Patent Application Publication No. 2009-58946, Japanese Patent Application Publication No. 2010-14848, Japanese Patent Application Publication No. 2010-97210, and Japanese Patent Application Publication No. 2011-2274670 can be used. In addition, a mixture of titanium oxynitride and titanium carbide as disclosed in JP 2010-95716 can be used. The surface of the titanium black particles can be modified as needed in order to improve dispersibility, suppress cohesion, etc. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and can also be treated with a hydrophobic substance as shown in Japanese Patent Application Laid-Open No. 2007-302836. In order to adjust the dispersibility, colorability, etc., titanium black can contain one kind of composite oxides such as Cu, Fe, Mn, V, Ni, and black pigments such as cobalt oxide, iron oxide, and carbon black, or a combination of two or more kinds. contain.

作為鈦黑的製造方法，有藉由還原氣氛對二氧化鈦與金屬鈦的混合體進行加熱還原之方法(日本特開昭49-5432號公報)、在包含氫之還原氣氛中對藉由四氯化鈦的高溫水解來獲得之超微細二氧化鈦進行還原之 方法(日本特開昭57-205322號公報)、在氨存在下對二氧化鈦或氫氧化鈦進行高溫還原之方法(日本特開昭60-65069號公報、日本特開昭61-201610號公報)、使釩化合物附著於二氧化鈦或氫氧化鈦並在氨存在下進行高溫還原之方法(日本特開昭61-201610號公報)等。但本發明並不限定於該些。 As a method of producing titanium black, there are a method of heating and reducing a mixture of titanium dioxide and metallic titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), and a method of heating and reducing a mixture of titanium dioxide and metallic titanium in a reducing atmosphere containing hydrogen. The ultra-fine titanium dioxide obtained by high-temperature hydrolysis of titanium is reduced Method (Japanese Patent Laid-Open No. 57-205322), a method of high-temperature reduction of titanium dioxide or titanium hydroxide in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No. 61-201610), A method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and performing high-temperature reduction in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), etc. However, the present invention is not limited to these.

鈦黑的比表面積並無特別限制，但藉由BET(Brunauer，Emmett，Teller)法測定之值為5m2/g以上150m2/g以下為較佳，20m2/g以上120m2/g以下為更佳。 The specific surface area of titanium black is not particularly limited, but the value measured by the BET (Brunauer, Emmett, Teller) method is preferably 5m 2 /g or more and 150m 2 /g or less, and 20m 2 /g or more and 120m 2 /g or less For better.

作為鈦黑的市售品的例子，可舉出鈦黑10S、12S、13R、13M、13M-C、13R、13R-N、13M-T(商品名：Mitsubishi Materials Corporation製造)、Tilack(Tilack)D(商品名：Ako Kasei Co.,Ltd.製造)等。 As examples of commercially available products of titanium black, titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilack (Tilack) D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.

黑色顏料的平均一次粒徑為5nm以上為較佳，10nm以上為佳。從相同的觀點考慮，作為上限，10μm以下為較佳，1μm以下為更佳，100nm以下為進一步較佳。黑色顏料的平均一次粒徑設為藉由以下方法測定之值。設為，藉由丙二醇單甲醚乙酸酯將包含黑色顏料之混合液稀釋成80倍，對所獲得之稀釋液，利用動態光散射法測定之值。該測定中，設為利用NIKKISO CO.,LTD.製造Microtrac(商品名)UPA-EX150進行來獲得之平均粒徑。 The average primary particle size of the black pigment is preferably 5 nm or more, preferably 10 nm or more. From the same viewpoint, as the upper limit, 10 μm or less is preferable, 1 μm or less is more preferable, and 100 nm or less is more preferable. The average primary particle size of the black pigment is set to the value measured by the following method. It is assumed that the mixed solution containing the black pigment is diluted 80 times with propylene glycol monomethyl ether acetate, and the obtained diluted solution is measured by a dynamic light scattering method. In this measurement, the average particle diameter obtained by NIKKISO CO., LTD. Microtrac (trade name) UPA-EX150 was used.

而且，含有包含鈦黑及Si原子之被分散體作為鈦黑亦較佳。 Furthermore, it is also preferable to contain a dispersed body containing titanium black and Si atoms as titanium black.

該形態中，鈦黑係在組成物中作為被分散體而含有者，被分散體中的Si原子與Ti原子的含有比(Si/Ti)以質量換算計，0.05以上為較佳，0.05~ 0.5為更佳，0.07~0.4為進一步較佳。 In this form, titanium black is contained in the composition as a dispersion, and the content ratio of Si atoms to Ti atoms (Si/Ti) in the dispersion is calculated by mass conversion. 0.05 or more is preferred, 0.05~ 0.5 is more preferable, and 0.07 to 0.4 is still more preferable.

其中，上述被分散體包含鈦黑為一次粒子的狀態者、凝聚體(二次粒子)的狀態者双方。 Here, the above-mentioned dispersed body includes both the titanium black in the state of primary particles and the state of aggregates (secondary particles).

為了變更被分散體的Si/Ti(例如，設為0.05以上)，能夠採用如下手段。 In order to change the Si/Ti of the dispersion (for example, set to 0.05 or more), the following means can be adopted.

首先，藉由利用分散機分散氧化鈦與二氧化矽粒子來獲得分散物，並在高溫(例如，850~1000℃)下對該分散物進行還原處理，藉此獲得以鈦黑粒子作為主成分並含有Si與Ti之被分散體。上述還原處理還能夠在氨等還原性氣體的氣氛下進行。 First, the dispersion is obtained by dispersing titanium oxide and silicon dioxide particles by a disperser, and the dispersion is reduced at a high temperature (for example, 850~1000°C) to obtain titanium black particles as the main component And contains Si and Ti to be dispersed. The above reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia.

作為氧化鈦，可舉出TTO-51N(商品名：Ishihara Sangyo Kaisha,Ltd.製造)等。 As titanium oxide, TTO-51N (trade name: manufactured by Ishihara Sangyo Kaisha, Ltd.) etc. are mentioned.

藉由等離子體法之製作之氧化鈦，其粒徑小於市售的氧化鈦微粒，故能夠較佳地使用(參閱日本金屬學會誌第63卷第1號(1999)74-81的記載)。 The titanium oxide produced by the plasma method has a smaller particle size than commercially available titanium oxide particles, so it can be used preferably (see the description of the Journal of the Japanese Society of Metals, Vol. 63, No. 1 (1999) 74-81).

作為二氧化矽粒子的市售品，可舉出AEROSIL(註冊商標)90、130、150、200、255、300、380(商品名：Evonik Japan Co.,Ltd.製造)等。 Examples of commercially available products of silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name: manufactured by Evonik Japan Co., Ltd.) and the like.

氧化鈦與二氧化矽粒子的分散中還可使用分散劑。作為分散劑可舉出後述之分散劑一欄中說明者。 A dispersant may also be used in the dispersion of titanium oxide and silicon dioxide particles. Examples of the dispersant include those described in the column of the dispersant described later.

上述分散可在溶劑中進行。作為溶劑，可舉出水、有機溶劑。可舉出後述之有機溶劑一欄中說明者。 The above dispersion can be carried out in a solvent. Examples of solvents include water and organic solvents. Examples include those described in the column of organic solvents described later.

Si/Ti例如調整為0.05以上等之鈦黑例如能夠藉由日本特開2008-266045號公報的段落號〔0005〕及段落號〔0016〕~〔0021〕中記載之方 法製作。 For example, titanium black with Si/Ti adjusted to 0.05 or more can be described in paragraph number [0005] and paragraph number [0016] to [0021] of JP 2008-266045. Method production.

藉由將包含鈦黑及Si原子之被分散體中的Si原子與Ti原子的含有比(Si/Ti)調整為適當的範圍(例如，0.05以上)，利用包含該被分散體之組成物形成遮光膜時，遮光膜的形成區域外的源自組成物的殘渣物減少。另外，残渣物係包含源自鈦黑粒子、樹脂成分等組成物之成分者。 By adjusting the content ratio (Si/Ti) of Si atoms to Ti atoms in the dispersion containing titanium black and Si atoms to an appropriate range (for example, 0.05 or more), it is formed from a composition containing the dispersion In the case of the light-shielding film, residues derived from the composition outside the formation area of the light-shielding film are reduced. In addition, the residue includes those derived from components such as titanium black particles and resin components.

雖然尚不明確殘渣物減少之理由，但推斷如下：如上述被分散體具有變成小粒徑之趨勢(例如，粒徑為30nm以下)，而且該被分散體的包含Si原子之成分增加，藉此膜整體與基底的吸附性降低，這有助於提高遮光膜形成時的未硬化的組成物(尤其，鈦黑)的顯影去除性。 Although the reason for the reduction of residues is not clear, it is estimated as follows: as the above-mentioned dispersed body has a tendency to become smaller in particle size (for example, the particle size is 30 nm or less), and the Si atom-containing component of the dispersed body increases, by The overall adhesion of the film to the substrate is reduced, which helps to improve the development and removal of the uncured composition (especially, titanium black) when the light-shielding film is formed.

並且，鈦黑相對於遍及紫外光至紅外光的廣範圍之波長區域的光之遮光性優異，故利用上述包含鈦黑及Si原子之被分散體(Si/Ti以質量換算計，0.05以上者為較佳)來形成之遮光膜發揮優異的遮光性。 In addition, titanium black has excellent light-shielding properties with respect to light in a wide range of wavelengths from ultraviolet light to infrared light. Therefore, the above-mentioned dispersed body containing titanium black and Si atoms (Si/Ti in terms of mass, 0.05 or more) is used (Preferably) The formed light-shielding film exhibits excellent light-shielding properties.

另外，被分散體中的Si原子與Ti原子的含有比(Si/Ti)例如能夠利用日本特開2013-249417號公報的段落0033中記載之方法(1-1)或方法(1-2)測定。 In addition, the content ratio (Si/Ti) of Si atoms to Ti atoms in the dispersion can be, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP 2013-249417 A Determination.

並且，對使組成物硬化來獲得之遮光膜中含有之被分散體，判斷該被分散體中的Si原子與Ti原子的含有比(Si/Ti)是否為0.05以上時，利用日本特開2013-249417號公報的段落0035中記載之方法(2)。 In addition, when determining whether the content ratio of Si atoms to Ti atoms (Si/Ti) in the dispersed body contained in the light-shielding film obtained by curing the composition is 0.05 or more, use JP 2013 -Method (2) described in paragraph 0035 of Bulletin No. 249417.

包含鈦黑及Si原子之被分散體中，鈦黑能夠使用上述者。 Among the dispersions containing titanium black and Si atoms, the above-mentioned titanium black can be used.

並且，該被分散體中，可為了調整分散性、著色性等，與鈦黑一同，組合1種或2種以上的包含Cu、Fe、Mn、V、Ni等的複合氧化物、酸化鈷、 氧化鐵、炭黑、苯胺黑等之黑色顏料，併用作被分散體。 In addition, in order to adjust the dispersibility, coloring properties, etc., the dispersed body can be combined with titanium black with one or more types of composite oxides containing Cu, Fe, Mn, V, Ni, etc., cobalt oxide, Iron oxide, carbon black, aniline black and other black pigments, and used as a dispersion.

此時，包含鈦黑之被分散體佔所有被分散體中的50質量%以上為較佳。 At this time, it is preferable that the dispersed body containing titanium black accounts for 50% by mass or more of the total dispersed body.

並且，該被分散體中，為了調整遮光性等，可在無損本發明的效果之範圍內，依據需要，與鈦黑一同併用其他著色劑(有機顏料或染料等)。 In addition, in order to adjust the light-shielding properties and the like in the dispersion, other colorants (organic pigments, dyes, etc.) may be used in combination with titanium black as needed within a range that does not impair the effects of the present invention.

以下，對向被分散體導入Si原子時使用的材料進行敘述。向被分散體導入Si原子時，使用二氧化矽等含Si物質即可。 Hereinafter, the materials used when introducing Si atoms into the dispersion are described. When introducing Si atoms into the dispersion, Si-containing materials such as silicon dioxide may be used.

作為可使用之二氧化矽，可舉出沈降二氧化矽、氣相二氧化矽、膠體二氧化矽、合成二氧化矽等，可適當選擇該些來使用。 The silica that can be used includes precipitated silica, fumed silica, colloidal silica, synthetic silica, etc., and these can be appropriately selected and used.

而且，若二氧化矽粒子的粒徑在形成遮光膜時為小於膜厚之粒徑，則遮光性更優異，故使用微粒類型的二氧化矽作為二氧化矽粒子為較佳。另外，作為微粒類型的二氧化矽的例子，例如，可舉出日本特開2013-249417號公報的段落0039中記載之二氧化矽，該些內容編入本說明書中。 Furthermore, if the particle size of the silicon dioxide particles is smaller than the film thickness when the light-shielding film is formed, the light-shielding properties are more excellent, so it is preferable to use fine-particle type silicon dioxide as the silicon dioxide particles. In addition, as an example of the fine particle type silica, for example, the silica described in paragraph 0039 of JP 2013-249417 A can be cited, and these contents are incorporated in this specification.

並且，作為顏料，還能夠使用鎢化合物及金屬硼化物。 In addition, as the pigment, tungsten compounds and metal borides can also be used.

鎢化合物及金屬硼化物係相對於紅外線(波長約為800~1200nm的光)吸收較高(亦即，相對於紅外線之遮光性(遮蔽性)較高)，且相對於可見光吸收較低之紅外線遮蔽材。故，本發明的感光性組成物藉由含有鎢化合物和/或金屬硼化物，能夠形成在紅外區域中的遮光性較高且可見光區域中的透光性較高之圖案。 Tungsten compounds and metal borides have higher absorption of infrared light (light with a wavelength of approximately 800 to 1200 nm) (that is, higher light-shielding properties (shielding properties) than infrared light), and lower infrared light absorption than visible light Shading material. Therefore, by containing the tungsten compound and/or the metal boride, the photosensitive composition of the present invention can form a pattern with high light-shielding properties in the infrared region and high light-transmitting properties in the visible light region.

並且，鎢化合物及金屬硼化物針對比用於形成圖像之、高壓水銀燈、KrF及ArF等的曝光中使用之可見區域更短波的光，其吸收亦較小。 In addition, tungsten compounds and metal borides absorb light with a shorter wavelength than the visible region used in exposure of high-pressure mercury lamps, KrF, and ArF, which are used to form images, and have less absorption.

作為鎢化合物，可舉出氧化鎢系化合物、硼化鎢系化合物、硫化 鎢系化合物等，以下述通式(組成式)(I)表示之氧化鎢系化合物為較佳。 Examples of tungsten compounds include tungsten oxide compounds, tungsten boride compounds, sulfide compounds As the tungsten compound etc., a tungsten oxide compound represented by the following general formula (composition formula) (I) is preferred.

MxWyOz......(I) M x W y O z ......(I)

M表示金屬，W表示鎢，O表示氧。 M represents metal, W represents tungsten, and O represents oxygen.

0.001

Figure 106104991-A0305-02-0077-35
x/y
Figure 106104991-A0305-02-0077-36
1.1 0.001
Figure 106104991-A0305-02-0077-35
x/y
Figure 106104991-A0305-02-0077-36
1.1

2.2

Figure 106104991-A0305-02-0077-37
z/y
Figure 106104991-A0305-02-0077-38
3.0 2.2
Figure 106104991-A0305-02-0077-37
z/y
Figure 106104991-A0305-02-0077-38
3.0

作為M的金屬，例如，可舉出鹼金屬、鹼土類金屬、Mg、Zr、Cr、Mn、Fe、Ru、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl、Sn、Pb、Ti、Nb、V、Mo、Ta、Re、Be、Hf、Os、Bi等，鹼金屬為較佳。M的金屬可以係1種，亦可以係2種以上。 Examples of the metal of M include alkali metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd , Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, etc., alkali metals are preferred. The metal of M may be one type or two or more types.

M為鹼金屬為較佳，Rb或Cs為更佳，Cs為進一步較佳。 M is preferably an alkali metal, Rb or Cs is more preferably, and Cs is even more preferably.

藉由x/y為0.001以上，能夠充分遮蔽紅外線，藉由其為1.1以下，能夠可靠地避免鎢化合物中產生雜質相。 When x/y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, the generation of impurity phases in the tungsten compound can be reliably avoided.

藉由z/y為2.2以上，能夠更加提高作為材料的化學穩定性，藉由其為3.0以下，能夠充分遮蔽紅外線。 When z/y is 2.2 or more, the chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.

作為以上述通式(I)表示之氧化鎢系化合物的具體例，可舉出Cs0.33WO3、Rb0.33WO3、K0.33WO3、Ba0.33WO3等，Cs0.33WO3或Rb0.33WO3為較佳，Cs0.33WO3為更佳。 As specific examples of tungsten oxide compounds represented by the above general formula (I), Cs 0.33 WO 3 , Rb 0.33 WO 3 , K 0.33 WO 3 , Ba 0.33 WO 3, etc., Cs 0.33 WO 3 or Rb 0.33 WO 3 is preferred, and Cs 0.33 WO 3 is more preferred.

鎢化合物為微粒為較佳。鎢微粒的平均粒徑為800nm以下為較佳，400nm以下為更佳，200nm以下為進一步較佳。藉由平均粒徑在該種範圍，鎢微粒由於光散射而不易遮蔽可見光，故能可靠地實現可見光區域的透光性。從避免光散射之觀點考慮，平均粒徑越小越佳，但從製造時的操作容 易性等理由考慮，鎢微粒的平均粒徑通常為1nm以上。 The tungsten compound is preferably fine particles. The average particle size of the tungsten particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. With the average particle diameter in this range, the tungsten particles are not easily shielded from visible light due to light scattering, so the light transmittance in the visible light region can be reliably achieved. From the viewpoint of avoiding light scattering, the smaller the average particle size is, the better. Considering workability and other reasons, the average particle size of tungsten fine particles is usually 1 nm or more.

並且，鎢化合物能夠使用2種以上。 In addition, two or more types of tungsten compounds can be used.

鎢化合物能夠作為市售品來獲得，鎢化合物例如為氧化鎢系化合物時，氧化鎢系化合物能夠藉由在惰性氣體氣氛或還原性氣體氣氛中對鎢化合物進行熱處理之方法來獲得(參閱日本專利第4096205號公報)。 Tungsten compounds can be obtained as commercially available products. When the tungsten compound is a tungsten oxide compound, the tungsten oxide compound can be obtained by heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (see Japanese Patent Bulletin No. 4096205).

並且，氧化鎢系化合物亦可作為例如Sumitomo Metal Mining Co.,Ltd.製造的YMF-02等鎢微粒的分散物來獲得。 In addition, the tungsten oxide compound can also be obtained as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

並且，作為金屬硼化物，可舉出硼化鑭(LaB6)、硼化鐠(PrB6)、硼化釹(NdB6)、硼化鈰(CeB6)、硼化釔(YB6)、硼化鈦(TiB2)、硼化鋯(ZrB2)、硼化鉿(HfB2)、硼化釩(VB2)、硼化鉭(TaB2)、硼化鉻(CrB、CrB2)、硼化鉬(MoB2、Mo2B5、MoB)、硼化鎢(W2B5)等的1種或2種以上，硼化鑭(LaB6)為較佳。 In addition, examples of the metal boride include lanthanum boride (LaB 6 ), magma boride (PrB 6 ), neodymium boride (NdB 6 ), cerium boride (CeB 6 ), yttrium boride (YB 6 ), Titanium boride (TiB 2 ), zirconium boride (ZrB 2 ), hafnium boride (HfB 2 ), vanadium boride (VB 2 ), tantalum boride (TaB 2 ), chromium boride (CrB, CrB 2 ), One or more of molybdenum boride (MoB 2 , Mo 2 B 5 , MoB), tungsten boride (W 2 B 5 ), etc., and lanthanum boride (LaB 6 ) is preferred.

金屬硼化物為微粒為較佳。金屬硼化物微粒的平均粒徑為800nm以下為較佳，300nm以下為更佳，100nm以下為進一步較佳。藉由平均粒徑在該種範圍，金屬硼化物微粒由於光散射而變得不易遮斷可見光，故能夠更可靠地實現可見光區域的透光性。從避免光散射之觀點考慮，平均粒徑越小越佳，但從製造時的操作容易性等理由考慮，金屬硼化物微粒的平均粒徑通常為1nm以上。 The metal boride is preferably fine particles. The average particle diameter of the metal boride particles is preferably 800 nm or less, more preferably 300 nm or less, and even more preferably 100 nm or less. When the average particle size is in this range, the metal boride particles are less likely to block visible light due to light scattering, so that the light transmittance in the visible light region can be achieved more reliably. From the viewpoint of avoiding light scattering, the smaller the average particle size is, the better. However, for reasons such as ease of handling during production, the average particle size of the metal boride fine particles is usually 1 nm or more.

並且，金屬硼化物能夠使用2種以上。 In addition, two or more types of metal borides can be used.

金屬硼化物能夠作為市售品來獲得，例如還能夠作為Sumitomo Metal Mining Co.,Ltd.製造的KHF-07AH等金屬硼化物微粒的分散物來獲 得。 The metal boride can be obtained as a commercially available product, for example, it can also be obtained as a dispersion of metal boride particles such as KHF-07AH manufactured by Sumitomo Metal Mining Co., Ltd. Got.

((染料)) ((dye))

作為染料，例如可使用日本特開昭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，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。 As the dye, for example, Japanese Patent Application Publication No. 64-90403, Japanese Patent Application Publication No. 64-91102, Japanese Patent Application Publication No. 1-94301, Japanese Patent Application Publication No. 6-11614, Japanese Patent Publication No. 2592207, United States Patent No. 4808501 Specification, U.S. Patent No. 5,669,920 Specification, U.S. Patent No. 505,950 Specification, U.S. Patent No. 5,667,920 Specification, Japanese Patent Application Publication No. 5-333207, Japanese Patent Application Publication No. 6-35183, Japanese Patent Application Publication No. 6-51115, The pigment disclosed in Japanese Patent Application Laid-Open No. 6-194828, etc. If distinguished as a chemical structure, pyrazole azo compounds, pyrrole methylene compounds, aniline azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazole compounds can be used Azolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. In addition, as the dye, a dye multimer can be used. Examples of the dye multimer include compounds described in Japanese Patent Application Publication No. 2011-213925 and Japanese Patent Application Publication No. 2013-041097.

本發明的組成物可除了著色劑以外，還依據需要包含體質顏料。作為該種體質顏料，例如可舉出硫酸鋇、碳酸鋇、碳酸鈣、二氧化矽、鹼性碳酸鎂、矾土白、光澤白、鈦白及水滑石等。該些體質顏料能夠單獨使用或混合2種以上來使用。體質顏料的使用量相對於著色劑100質量份，通常為0~100質量份，5~50質量份為較佳，10~40質量份為更佳。本發明中，著色劑及體質顏料能夠依情況，藉由聚合物對其表面進行改性來使用。 The composition of the present invention may contain extender pigments as needed in addition to the colorant. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments can be used alone or in combination of two or more kinds. The use amount of the extender pigment relative to 100 parts by mass of the colorant is usually 0-100 parts by mass, preferably 5-50 parts by mass, and more preferably 10-40 parts by mass. In the present invention, the colorant and the extender pigment can be used by modifying the surface of the coloring agent and the extender pigment with a polymer.

著色劑可單獨使用1種，亦可併用2種以上。作為著色劑，可含 有紅色、藍色、黃色、綠色及紫色等著色有機顏料。併用遮光性顏料(具體而言，含氮化鈦粒子)與著色有機顏料時，相對於遮光性顏料，使用1~40質量%的著色有機顏料為較佳。從調整色調之觀點考慮，併用紅色顏料與遮光性顏料為較佳，雖並無特別限定，但作為紅色顏料，顏料紅254為較佳。並且，從提高遮光性之觀點考慮，併用黄色顏料與遮光性顏料為較佳，雖然並無特別限定，但作為黄色顏料，顏料黃150為較佳。 A coloring agent may be used individually by 1 type, and may use 2 or more types together. As a colorant, it can contain There are colored organic pigments such as red, blue, yellow, green and purple. When a light-shielding pigment (specifically, titanium nitride particles containing) and a coloring organic pigment are used together, it is preferable to use 1-40% by mass of the coloring organic pigment with respect to the light-shielding pigment. From the viewpoint of adjusting the color tone, it is preferable to use a red pigment and a light-shielding pigment in combination. Although it is not particularly limited, as the red pigment, Pigment Red 254 is preferable. In addition, from the viewpoint of improving the light-shielding properties, it is preferable to use a yellow pigment and a light-shielding pigment in combination. Although it is not particularly limited, as the yellow pigment, Pigment Yellow 150 is preferable.

本發明的組成物含有著色劑時，著色劑的含量相對於組成物的總固體含量，20~80質量%為較佳，30~70質量%為更佳，35~60質量%為進一步較佳。 When the composition of the present invention contains a colorant, the content of the colorant relative to the total solid content of the composition is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and more preferably 35 to 60% by mass .

(顏料衍生物) (Pigment derivatives)

本發明的組成物能夠含有顏料衍生物。作為顏料衍生物，例如，可舉出具有藉由酸性基、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。 The composition of the present invention can contain a pigment derivative. As the pigment derivative, for example, a compound having a structure in which a part of the organic pigment is substituted with an acidic group, a basic group, or a phthalic iminomethyl 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 form pigment derivatives include dioxopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, and dioxazine pigments. , Perylene pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, Shilin pigments, metal complex pigments, etc.

並且，作為顏料衍生物所具有之酸性基，磺酸基、羧酸基及其四級銨鹽基為較佳，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。 In addition, as the acidic group possessed by the pigment derivative, a sulfonic acid group, a carboxylic acid group, and a quaternary ammonium salt group thereof are preferable, the carboxylic acid group and the sulfonic acid group are more preferable, and the sulfonic acid group is particularly preferable. As the basic group possessed by the pigment derivative, an amine group is preferred, and a tertiary amine group is particularly preferred.

作為顏料衍生物的具體例，例如，可舉出下述化合物。並且，可參閱日 本特開2011-252065號公報的段落0162~0183的記載，該內容編入本說明書中。 As specific examples of pigment derivatives, for example, the following compounds can be given. And, you can refer to the The contents of paragraphs 0162 to 0183 of this Japanese Patent Application Publication No. 2011-252065 are incorporated into this manual.

Figure 106104991-A0305-02-0081-18
Figure 106104991-A0305-02-0081-18

本發明的組成物含有顏料衍生物時，顏料衍生物的含量相對於著色劑的總質量，1~30質量%為較佳，3~20質量%為進一步較佳。本發明的組成物可僅包含1種顏料衍生物，亦可包含2種以上。包含2種以上時，其合計量成為上述範圍為較佳。 When the composition of the present invention contains a pigment derivative, the content of the pigment derivative relative to the total mass of the colorant is preferably 1-30% by mass, and more preferably 3-20% by mass. The composition of the present invention may include only one type of pigment derivative or two or more types. When two or more types are contained, the total amount thereof is preferably in the above-mentioned range.

(矽烷偶聯劑) (Silane coupling agent)

矽烷偶聯劑係指在分子中具有水解性基團及其以外的官能基之化合物。另外，烷氧基等水解性基團與矽原子鍵結。 Silane coupling agent refers to a compound having a hydrolyzable group and other functional groups in the molecule. In addition, a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.

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、烯氧基。水解性基團具有碳原子時，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以下的烯氧基尤為佳。 The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by a hydrolysis reaction and/or condensation reaction. As the hydrolyzable group, for example, a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group are mentioned. When the hydrolyzable group has carbon atoms, the number of carbon atoms is preferably 6 or less, and 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 particularly preferred.

並且，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)、被矽原子取代之亞烷基、 碳原子數8以上的直鏈烷基及碳原子數3以上的支鏈烷基為較佳。 Moreover, 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 the silicon atoms bonded by the hydrolyzable groups), and does not contain fluorine atoms and silicon atoms. Atoms (except for the silicon atom bonded by the hydrolyzable group), alkylene substituted by silicon atom, A straight chain alkyl group having 8 or more carbon atoms and a branched chain alkyl group having 3 or more carbon atoms are preferable.

矽烷偶聯劑具有以以下的式(Z)表示之基團為較佳。*表示鍵結位置。 The silane coupling agent preferably has a group represented by the following formula (Z). * Indicates the bonding position.

式(Z)*-Si-(RZ1)3 Formula (Z)*-Si-(R Z1 ) 3

式(Z)中，RZ1表示水解性基團，其定義如上述。 In formula (Z), R Z1 represents a hydrolyzable group, and its definition is as described above.

矽烷偶聯劑具有選自包含(甲基)丙烯醯氧基、環氧基及氧雜環丁基之組之1種以上的硬化性官能基為較佳。硬化性官能基可直接與矽原子鍵結，亦可經由連結基與矽原子鍵結。 The silane coupling agent preferably has one or more curable functional groups selected from the group consisting of (meth)acryloxy groups, epoxy groups, and oxetanyl groups. The hardenable functional group can be directly bonded to the silicon atom, or can be bonded to the silicon atom via a linking group.

另外，作為上述矽烷偶聯劑中包含之硬化性官能基的較佳態樣，還可舉出自由基聚合性基團。 In addition, as a preferable aspect of the curable functional group contained in the silane coupling agent, a radical polymerizable group can also be mentioned.

矽烷偶聯劑的分子量並無特別限制，從操作性觀點考慮，100~1000的情況較多，從本發明的效果更加優異之角度考慮，270以上為較佳，270~1000為更佳。 The molecular weight of the silane coupling agent is not particularly limited. From the viewpoint of operability, it is usually 100 to 1000. From the viewpoint of the effect of the present invention, 270 or more is preferable, and 270 to 1000 is more preferable.

作為矽烷偶聯劑的較佳態樣之一，可舉出以式(W)表示之矽烷偶聯劑X。 As one of the preferred aspects of the silane coupling agent, a silane coupling agent X represented by formula (W) can be cited.

式(W)RZ2-Lz-Si-(RZ1)3 Formula (W) R Z2 -Lz-Si-(R Z1 ) 3

Rz1表示水解性基團，定義如上述。 R z1 represents a hydrolyzable group, and is defined as described above.

Rz2表示硬化性官能基，定義如上述，較佳範圍亦如上述。 R z2 represents a curable functional group, which is defined as described above, and the preferred range is also the same as described above.

Lz表示單鍵或2價的連結基。Lz表示2價的連結基時，作為2價的連結基，可舉出鹵原子可取代之亞烷基、鹵原子可取代之伸芳基、-NR12-、-CONR12-、-CO-、-CO2-、SO2NR12-、-O-、-S-、-SO2-或該些的組合。其中， 選自包含碳原子數2~10的鹵原子可取代之亞烷基及碳原子數6~12的鹵原子可取代之伸芳基之組之至少1種、或包含該些基團與選自包含-NR12-、-CONR12-、-CO-、-CO2-、SO2NR12-、-O-、-S-及SO2-之組之至少1種基團的組合之基團為較佳，包含碳原子數2~10的鹵原子可取代之亞烷基、-CO2-、-O-、-CO-、-CONR12-或該些基團的組合之基團為更佳。其中，上述R12表示氫原子或甲基。 Lz represents a single bond or a divalent linking group. When Lz represents a divalent linking group, examples of the divalent linking group include an alkylene group substituted with a halogen atom, an aryl group substituted with a halogen atom, -NR 12 -, -CONR 12 -, -CO- , -CO 2 -, SO 2 NR 12 -, -O-, -S-, -SO 2 -or a combination of these. Among them, at least one selected from the group consisting of alkylene groups substituted with halogen atoms having 2 to 10 carbon atoms and arylene groups substituted with halogen atoms having 6 to 12 carbon atoms, or containing these groups and A combination of at least one group selected from the group consisting of -NR 12 -, -CONR 12 -, -CO-, -CO 2 -, SO 2 NR 12 -, -O-, -S- and SO 2- Groups are preferred, including alkylene groups with 2-10 carbon atoms that can be substituted with halogen atoms, -CO 2 -, -O-, -CO-, -CONR 12 -or a combination of these groups For better. Here, R 12 above represents a hydrogen atom or a methyl group.

作為矽烷偶聯劑X，可舉出N-(β-胺乙基)-γ-胺丙基-甲基二甲氧基矽烷(Shin-Etsu Chemical Co.,Ltd.製商品名KBM-602)、N-β-胺乙基-γ-胺丙基-三甲氧基矽烷(Shin-Etsu Chemical Co.,Ltd.製商品名KBM-603)、N-β-胺乙基-γ-胺丙基-三乙氧基矽烷(Shin-Etsu Chemical Co.,Ltd.製造商品名KBE-602)、γ-胺丙基-三甲氧基矽烷(Shin-Etsu Chemical Co.,Ltd.製造商品名KBM-903)、γ-胺丙基-三乙氧基矽烷(Shin-Etsu Chemical Co.,Ltd.製造商品名KBE-903)、3-甲基丙烯醯氧基丙基三甲氧基矽烷(Shin-Etsu Chemical Co.,Ltd.製造商品名KBM-503)、縮水甘油醚辛基三甲氧基矽烷(Shin-Etsu Chemical Co.,Ltd.製造商品名KBM-4803)等。 As the silane coupling agent X, N-(β-aminoethyl)-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.) , N-β-aminoethyl-γ-aminopropyl-trimethoxysilane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl -Triethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-trimethoxysilane (trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.) ), γ-aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd. manufactured product name KBM-503), glycidyl ether octyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd. manufactured product name KBM-4803), etc.

作為矽烷偶聯劑的其他較佳態樣，可舉出在分子內至少具有矽原子、氮原子、硬化性官能基，且具有與矽原子鍵結之水解性基團之矽烷偶聯劑Y。 As another preferred aspect of the silane coupling agent, a silane coupling agent Y having at least a silicon atom, a nitrogen atom, and a hardenable functional group in the molecule, and having a hydrolyzable group bonded to the silicon atom is mentioned.

該矽烷偶聯劑Y在分子內具有至少1個矽原子即可，矽原子能夠與以下的原子、取代基鍵結。該些可以係相同的原子、取代基，亦可不同。可鍵結之原子、取代基可舉出氫原子、鹵原子、羥基、碳原子數1至20的烷基、 鏈烯基、炔基、芳基、可用烷基和/或芳基取代之胺基、甲矽烷基、碳原子數1至20的烷氧基、芳氧基等。該些取代基可進一步被甲矽烷基、鏈烯基、炔基、芳基、烷氧基、芳氧基、硫代烷氧基、可用烷基和/或芳基取代的胺基、鹵原子、磺醯胺基、烷氧基羰基、醯胺基、尿素基、銨基、烷基銨基、羧基或其鹽、磺基或其鹽等。 The silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can bond with the following atoms and substituents. These may be the same atom, substituent or different. Examples of bondable atoms and substituents include hydrogen atoms, halogen atoms, hydroxyl groups, alkyl groups with 1 to 20 carbon atoms, Alkenyl groups, alkynyl groups, aryl groups, amine groups that can be substituted with alkyl and/or aryl groups, silyl groups, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups, etc. These substituents may be further substituted by silyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, thioalkoxy groups, amino groups which may be substituted with alkyl groups and/or aryl groups, and halogen atoms , Sulfonamide group, alkoxycarbonyl group, amide group, urea group, ammonium group, alkylammonium group, carboxyl group or its salt, sulfo group or its salt, etc.

另外，矽原子上鍵結有至少1個水解性基團。水解性基團的定義如上述。 In addition, at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above.

矽烷偶聯劑Y中可包含以上述式(Z)表示之基團。 The silane coupling agent Y may contain a group represented by the above formula (Z).

矽烷偶聯劑Y在分子內具有至少1個以上的氮原子，氮原子以2級胺基或者3級胺基的形態存在為較佳，亦即，氮原子作為取代基具有至少1個有機基團為較佳。另外，作為胺基的結構，可以以含氮雜環的部分結構的形態存在於分子內，亦可作為苯胺等取代胺基存在。 Silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably in the form of a secondary or tertiary amino group, that is, the nitrogen atom has at least one organic group as a substituent Group is better. In addition, the structure of the amino group may exist in the molecule as a partial structure of a nitrogen-containing heterocyclic ring, or may exist as a substituted amino group such as aniline.

其中，作為有機基團，可舉出烷基、鏈烯基、炔基、芳基或該些的組合。該些可進一步具有取代基，作為可導入之取代基，可舉出甲矽烷基、鏈烯基、炔基、芳基、烷氧基、芳氧基、硫代烷氧基、胺基、鹵原子、磺醯胺基、烷氧基羰基、羰基氧基、醯胺基、尿素基、亞烷氧基銨基、烷基銨基、羧基或其鹽、磺基等。 Among them, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination of these. These may further have substituents. Examples of the substituents that can be introduced include silyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, thioalkoxy groups, amino groups, and halogen groups. Atom, sulfonamide group, alkoxycarbonyl group, carbonyloxy group, amide group, urea group, alkyleneoxyammonium group, alkylammonium group, carboxyl group or its salt, sulfo group, etc.

並且，氮原子經由任意的有機連結基與硬化性官能基鍵結為較佳。作為較佳之有機連結基，可舉出可導入到上述氮原子及與其鍵結之有機基團之取代基。 In addition, the nitrogen atom is preferably bonded to the curable functional group via an arbitrary organic linking group. As a preferable organic linking group, the substituent which can be introduced into the above-mentioned nitrogen atom and the organic group bonded to it can be mentioned.

矽烷偶聯劑Y中包含之硬化性官能基的定義如上述，較佳範圍亦 如上述。 The definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also As above.

矽烷偶聯劑Y中，在一分子中可以具有至少1個以上的硬化性官能基，但亦可取具有2個以上的硬化性官能基之態樣，從靈敏度、穩定性的觀點考慮，具有2~20個硬化性官能基為較佳，具有4~15個為更佳，在分子內具有6~10個硬化性官能基為進一步較佳。 Silane coupling agent Y may have at least one hardenable functional group in one molecule, but it may also have two or more hardenable functional groups. From the viewpoint of sensitivity and stability, it has 2 It is preferable to have ~20 hardenable functional groups, more preferably 4 to 15 hardenable functional groups, and even more preferably 6 to 10 hardenable functional groups in the molecule.

矽烷偶聯劑X及矽烷偶聯劑Y的分子量並無特別限制，可舉出上述範圍(270以上為較佳)。 The molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, and can include the above-mentioned range (270 or more is preferable).

本發明的樹脂組成物中的矽烷偶聯劑的含量相對於組成物中的總固體含量，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 resin composition of the present invention, relative to the total solid content in the composition, is preferably 0.1-10% by mass, more preferably 0.5-8% by mass, and more preferably 1.0-6% by mass. good.

本發明的組成物可單獨包含1種矽烷偶聯劑，亦可包含2種以上。組成物包含2種以上的矽烷偶聯劑時，其合計在上述範圍內即可。 The composition of the present invention may include one type of silane coupling agent alone, or two or more types. When the composition contains two or more types of silane coupling agents, the total of them should be within the above range.

(紫外線吸收劑) (Ultraviolet absorber)

本發明的組成物中可包含紫外線吸收劑。藉此，能夠將圖案形狀設為更優異(精細)者。 The composition of the present invention may contain an ultraviolet absorber. Thereby, the pattern shape can be made more excellent (fine).

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

此外，二乙基胺基-苯基磺醯基系紫外線吸收劑(DAITO CHEMICAL CO.,LTD.製造、商品名：UV-503)等亦可較佳地使用。 In addition, diethylamino-phenylsulfonyl-based ultraviolet absorbers (manufactured by DAITO CHEMICAL 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。 As the ultraviolet absorber, the compounds exemplified in paragraphs 0134 to 0148 of JP 2012-32556 A can be cited.

本發明的組成物可包含紫外線吸收劑，亦可不包含，但包含時，紫外線吸收劑的含量相對於組成物的總固體含量，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 composition of the present invention may or may not contain an ultraviolet absorber, but when it is included, the content of the ultraviolet absorber relative to the total solid content of the composition is preferably 0.001-15% by mass, more preferably 0.01-10% by mass , 0.1 to 5 mass% is more preferable.

(表面活性劑) (Surfactant)

關於本發明的組成物，從更加提高塗佈性之觀點考慮，可含有各種表面活性劑。作為表面活性劑，可使用氟系表面活性劑、非離子系表面活性劑、陽離子系表面活性劑、陰離子系表面活性劑、矽酮系表面活性劑等各種表面活性劑。 The composition of the present invention may contain various surfactants from the viewpoint of further improving coating properties. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.

藉由使本發明的組成物中含有氟系表面活性劑，製備成塗佈液時的液體特性(尤其，流動性)更加提高，能夠更加改善塗佈厚度的均勻性和省液性。亦即，利用適用含有氟系表面活性劑之組成物之塗佈液來形成膜時，被塗佈面與塗佈液之間的表面張力下降，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，能夠更佳地形成厚度不均較小之均勻厚度的膜。 By including a fluorine-based surfactant in the composition of the present invention, the liquid characteristics (especially fluidity) when the coating liquid is prepared are further improved, and the uniformity of the coating thickness and the liquid-saving property can be further improved. That is, when a film is formed using a coating liquid applied with a composition containing a fluorine-based surfactant, the surface tension between the coated surface and the coating liquid is reduced, and the wettability to the coated surface is improved. The coatability to the coated surface is improved. Therefore, it is possible to better form a uniform thickness film with less uneven thickness.

氟系表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%尤為佳。氟含有率在該範圍內之氟系表面活性劑在塗佈膜的厚度的均勻性和省液性方面有效，組成物中的溶解性亦良好。 The fluorine content in the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in uniformity of the thickness of the coating film and liquid-saving properties, and the solubility in the composition is also good.

作為氟系表面活性劑，例如，可舉出Megafac F171、Megafac F172、Megafac F173、Megafac F176、Megafac F177、Megafac F141、Megafac F142、 Megafac F143、Megafac F144、Megafac R30、Megafac F437、Megafac F475、Megafac F479、Megafac F482、Megafac F554、Megafac F780、RS-72-K(以上，DIC CORPORATION製造)、Fluorado FC430、Fluorado FC431、Fluorado FC171(以上，3M Japan Limited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，ASAHI GLASS CO.,LTD.製造)、PF636、PF656、PF6320、PF6520、PF7002(OMNOVA SOLUTIONS INC.製造)等。氟系表面活性劑還能夠使用日本特開2015-117327號公報的段落0015~0158中記載之化合物。作為氟系表面活性劑，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。 As the fluorine-based surfactant, for example, Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, RS-72-K (above, manufactured by DIC CORPORATION), Fluorado FC430, Fluorado FC431, Fluorado FC171 (above , 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 ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA SOLUTIONS INC.), etc. The fluorine-based surfactant can also use the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A. As the fluorine-based surfactant, a block polymer can also be used. As a specific example, for example, a compound described in JP 2011-89090 A can be cited.

氟系表面活性劑亦可較佳地使用如下含氟高分子化合物，其包含源自具有氟原子之(甲基)丙烯酸酯化合物之重複單元及源自具有2個以上(5個以上為較佳)亞烷氧基(乙烯氧基、丙烯氧基為較佳)之(甲基)丙烯酸酯化合物之重複單元，下述化合物亦作為本發明中使用之氟系表面活性劑來例示。 Fluorine-based surfactants can also preferably use the following fluorine-containing polymer compounds, which contain repeating units derived from (meth)acrylate compounds having fluorine atoms and derived from having 2 or more (5 or more are preferred) ) Repeating units of (meth)acrylate compounds of alkyleneoxy (ethyleneoxy and propyleneoxy are preferred), and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[化學式19]

Figure 106104991-A0305-02-0088-19
[Chemical formula 19]
Figure 106104991-A0305-02-0088-19

上述化合物的重量平均分子量為3,000~50,000為較佳，例如為14,000。 The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.

並且，還能夠將在側鏈具有烯屬不飽和基之含氟聚合物用作氟系表面活性劑。作為具體例，可舉出日本特開2010-164965號公報0050~0090段落及0289~0295段落中記載之化合物，例如DIC CORPORATION製造的Megafac RS-101、RS-102、RS-718K、RS-72-K等。 In addition, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as a fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP 2010-164965 A, such as Megafac RS-101, RS-102, RS-718K, RS-72 manufactured by DIC CORPORATION -K etc.

作為非離子系表面活性劑，具體而言，可舉出甘油、三羥甲基丙烷、三羥甲基乙烷以及該些的乙氧基化物及丙氧基化物(例如，甘油丙氧基化物、甘油乙氧基化物等)、聚氧乙烯月桂基醚、聚氧乙烯硬脂醚、聚氧乙烯油烯醚、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、脫水山梨醇脂肪酸酯(BASF公司製造的Pluronic L10、L31、L61、L62、10R5、17R2、25R2、TETRONIC 304、701、704、901、904、150R1、SOLSPERSE 20000(The Lubrizol corporatin製造)等。並且，還可使用Wako Pure Chemical Industries,Ltd.製造的NCW-101、NCW-1001、NCW-1002。 Specific examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylate). , Glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene Glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, TETRONIC 304, 701, 704, manufactured by BASF 901, 904, 150R1, SOLSPERSE 20000 (manufactured by The Lubrizol Corporatin), etc. In addition, NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

作為陽離子系表面活性劑，具體而言，可舉出酞菁衍生物(商品 名：EFKA-745、MORISHITA & CO.,LTD.製造)、有機矽氧烷聚合物KP341(Shin-Etsu Chemical Co.,Ltd.製造)、(甲基)丙烯酸系(共)聚合物Polyflow No.75、No.90、No.95(KYOEISHA CHEMICAL CO.,LTD製造)、W001(Yusho Co Ltd製造)等。 As the cationic surfactant, specifically, phthalocyanine derivatives (commercial Name: EFKA-745, manufactured by MORISHITA & CO., LTD.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No. 75, No. 90, No. 95 (manufactured by KYOEISHA CHEMICAL CO., LTD), W001 (manufactured by Yusho Co Ltd), etc.

作為陰離子系表面活性劑，具體而言，可舉出W004、W005、W017(Yusho Co Ltd製造)、Sandetto BL(Sanyo Chemical Industries,Ltd.製造)等。 As an anionic surfactant, W004, W005, W017 (manufactured by Yusho Co Ltd), Sandetto BL (manufactured by Sanyo Chemical Industries, Ltd.), etc. are mentioned specifically,.

作為矽酮系表面活性劑，例如，可舉出Toray Silicone DC3PA、Toray Silicone SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone SH8400(以上，Dow Corning Toray Co.,Ltd.製造)、TSF-4440、TSF-4300、TSF-4445、TSF-4460、TSF-4452(以上，Momentive Performance Materials Inc.製造)、KP341、KF6001、KF6002(以上，Shin-Etsu Chemical Co.,Ltd.製造)、BYK307、BYK323、BYK330(以上，BYK Additives & Instruments製造)等。 Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (above, Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (above, manufactured by BYK Additives & Instruments), etc.

表面活性劑可僅使用1種，亦可組合2種以上。表面活性劑的含量相對於本發明的組成物的總固體含量，0.001~2.0質量%為較佳，0.005~1.0質量%為更佳。 Surfactant may use only 1 type, and may combine 2 or more types. The content of the surfactant relative to the total solid content of the composition of the present invention is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass.

(聚合抑制劑) (Polymerization inhibitor)

本發明的組成物可含有聚合抑制劑。作為聚合抑制劑，可舉出對苯二酚、對甲氧基苯酚、二-叔丁基-對甲酚、鄰苯三酚、叔丁基鄰苯二酚、對苯醌、 4，4’-硫代雙(3-甲基-6-叔丁基苯酚)、2，2’-亞甲基雙(4-甲基-6-叔丁基苯酚)、N-亞硝基苯基羥基胺亞鈰鹽等。 The composition of the present invention may contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso Phenylhydroxylamine cerium salt, etc.

本發明的組成物含有聚合抑制劑時，聚合抑制劑的含量相對於組成物的總固體含量，0.01~5質量%為較佳。本發明的組成物可僅包含1種聚合抑制劑，亦可包含2種以上。包含2種以上時，其合計量成為上述範圍為較佳。 When the composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the composition. The composition of the present invention may include only one type of polymerization inhibitor, or may include two or more types. When two or more types are contained, the total amount thereof is preferably in the above-mentioned range.

並且，可依據需要，為了防止氧引起之聚合阻礙，添加如山嵛酸或山嵛酸醯胺的高級脂肪酸衍生物等，在塗佈之後的乾燥過程中使其局部存在於塗佈膜的表面。含有高級脂肪酸衍生物的添加量時，高級脂肪酸衍生物的含量相對於組成物的總固體含量，0.5~10質量%為較佳。 Furthermore, if necessary, in order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenylamide can be added to make it locally present on the surface of the coating film during the drying process after coating. When the addition amount of the higher fatty acid derivative is contained, the content of the higher fatty acid derivative relative to the total solid content of the composition is preferably 0.5-10% by mass.

除了上述成分以外，本發明的組成物中亦可進一步添加以下成分。例如，敏化劑、共敏化劑、交聯劑、硬化促進劑、填料、熱硬化促進劑、增塑劑、稀釋劑及感脂化劑等，而且，還可依據需要添加對基板表面的黏附促進劑及其他助劑類(例如，導電性粒子、填充劑、消泡劑、阻燃劑、流平劑、剝離促進劑、抗氧化劑、香料、表面張力調節劑及鏈轉移劑等)等公知的添加劑。 In addition to the above-mentioned components, the following components may be further added to the composition of the present invention. For example, sensitizers, co-sensitizers, crosslinking agents, hardening accelerators, fillers, thermal hardening accelerators, plasticizers, diluents, and fat-sensitizing agents, etc., and can be added to the substrate surface as needed Adhesion promoters and other additives (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling promoters, antioxidants, fragrances, surface tension regulators, chain transfer agents, etc.), etc. Well-known additives.

該些成分例如能夠參閱日本特開2012-003225號公報的段落號0183~0228(對應之美國專利出願公開第2013/0034812號說明書的<0237>~<0309>)、日本特開2008-250074號公報的段落號0101~0102、段落號0103~0104、段落號0107~0109、日本特開2013-195480號公報的段落號0159~0184等的記載，該些內容編入本說明書中。 These ingredients can be referred to, for example, Japanese Patent Application Publication No. 2012-003225, paragraph numbers 0183 to 0228 (corresponding to U.S. Patent Application Publication No. 2013/0034812 Specification <0237> to <0309>), Japanese Patent Application Publication No. 2008-250074 Paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and paragraph numbers 0159 to 0184 of JP 2013-195480 A are described in the bulletin, and these contents are incorporated into this specification.

本發明的組成物的固體含量為10~40質量%為較佳，12~30質量%為更佳。藉由組成物的固體含量為10質量%以上，硬化膜的遮光性得到提高。並且，藉由組成物的固體含量為40質量%以下，組成物的經時穩定性變得良好。 The solid content of the composition of the present invention is preferably 10-40% by mass, and more preferably 12-30% by mass. When the solid content of the composition is 10% by mass or more, the light-shielding property of the cured film is improved. In addition, when the solid content of the composition is 40% by mass or less, the stability of the composition over time becomes good.

<組成物的製造方法> <Method of manufacturing composition>

本發明的組成物能夠藉由公知的混合方法(例如，攪拌機、均質器、高壓乳化裝置、濕式粉碎機、濕式分散機)混合上述各種成分來製造。 The composition of the present invention can be produced by mixing the above-mentioned various components by a known mixing method (for example, a mixer, a homogenizer, a high-pressure emulsifying device, a wet mill, a wet disperser).

製造組成物時，可集中配合構成組成物之各種成分，亦可在將各種成分溶解或分散於有機溶劑之後依次配合。並且，配合時的投入順序及作業條件並不特別受限。 When manufacturing the composition, the various components constituting the composition may be blended collectively, or the various components may be dissolved or dispersed in an organic solvent and then blended sequentially. In addition, the order of input and working conditions during cooperation are not particularly limited.

並且，使顏料分散之工藝中，作為用於顏料的分散之機械力，可舉出壓縮、壓榨、衝擊、裁斷或氣蝕等。作為該些工藝的具體例，可舉出珠磨、砂磨、輥磨、高速葉輪、混砂、噴射流混合、高壓濕式微粒化、超聲波分散及微射流等。並且，能夠適當使用“分散技術大全、株式會社資訊機構發行、2005年7月15日”及“以懸浮液(suspension)(固/液分散系統)為中心之分散技術與工業應用的實際 綜合資料集、經營開發Center出版部發行、1978年10月10日”中記載之工藝及分散機。 In addition, in the process of dispersing the pigment, as the mechanical force used for the dispersion of the pigment, compression, pressing, impact, cutting, or cavitation can be mentioned. Specific examples of these processes include bead milling, sand milling, roller milling, high-speed impeller, sand mixing, jet mixing, high-pressure wet micronization, ultrasonic dispersion, and microjets. In addition, it is possible to appropriately use the "Dispersion Technology Encyclopedia, issued by the Information Agency Co., Ltd., July 15, 2005" and "suspension (solid/liquid dispersion system)-centered dispersion technology and actual comprehensive data on industrial applications. Collection, management and development Center Publishing Department issued, October 10, 1978 "process and dispersion machine".

並且，在使顏料分散之工藝中，可進行基於鹽磨製程之顏料的微細化處理。用於鹽磨製程之原材料、設備及處理條件等例如能夠使用日本特開2015-194521號及日本特開2012-046629號中記載者。 In addition, in the process of dispersing the pigment, the miniaturization of the pigment based on the salt milling process can be performed. The raw materials, equipment, and processing conditions used in the salt milling process can be those described in Japanese Patent Application Publication No. 2015-194521 and Japanese Patent Application Publication No. 2012-046629, for example.

並且，本發明的組成物的製造方法包含藉由熱等離子體法獲得上述含 氮化鈦粒子之製程為較佳。獲得含氮化鈦粒子之製程在混合上述各種成分之前實施。基於熱等離子體法之含氮化鈦微粒的具體製造製程如在上述的含氮化鈦粒子一項中進行說明，故省略其說明。 Furthermore, the method for producing the composition of the present invention includes obtaining the above-mentioned containing by a thermal plasma method The manufacturing process of titanium nitride particles is better. The process of obtaining titanium nitride-containing particles is carried out before mixing the above-mentioned various components. The specific manufacturing process of the titanium nitride-containing particles based on the thermal plasma method is described in the item of the above-mentioned titanium nitride-containing particles, so the description is omitted.

而且，關於藉由熱等離子體法獲得之含氮化鈦粒子，在製造含氮化鈦粒子之後(亦即，熱等離子體處理之後)並不立刻暴露於大氣，而是在氧濃度得到控制之密封容器內，靜置規定時間(12~72小時為較佳，12~48小時為更佳，12~24小時為進一步較佳)來獲得者為較佳。並且，若密封容器內的水分的含量得到控制，則更佳，藉此已進行熱等離子體處理之含氮化鈦粒子的表面及晶界變得穩定，可推斷為組成物的性能優化者。具體而言，能夠抑制產生使用本發明的組成物來獲得之硬化膜的針孔。 Moreover, with regard to the titanium nitride-containing particles obtained by the thermal plasma method, after the titanium nitride-containing particles are manufactured (that is, after the thermal plasma treatment), they are not exposed to the atmosphere immediately, but after the oxygen concentration is controlled. In a sealed container, let it stand for a predetermined time (12 to 72 hours is preferable, 12 to 48 hours is more preferable, and 12 to 24 hours is more preferable), whichever is better. In addition, it is better if the moisture content in the sealed container is controlled, whereby the surface and grain boundaries of the titanium nitride-containing particles that have been subjected to thermal plasma treatment become stable, and it can be inferred that the composition is optimized for performance. Specifically, the occurrence of pinholes in the cured film obtained using the composition of the present invention can be suppressed.

密封容器內的氧(O2)濃度及水分的含量分別為100ppm以下為較佳，10ppm以下為更佳，1ppm以下為進一步較佳。 The oxygen (O 2 ) concentration and moisture content in the sealed container are preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less.

密封容器內的氧(O2)濃度及水分的含量能夠藉由調整供給至密封容器內之惰性氣體中的氧濃度及水分量來進行調整。作為惰性氣體，使用氮氣及氬氣為較佳，其中，使用氮氣為更佳。藉此，已進行熱等離子體處理之含氮化鈦粒子的表面及晶界變得穩定，可推斷為組成物的性能得到優化。具體而言，能夠抑制產生使用本發明的組成物來獲得之硬化膜的針孔。 The oxygen (O 2 ) concentration and moisture content in the sealed container can be adjusted by adjusting the oxygen concentration and moisture content in the inert gas supplied into the sealed container. As the inert gas, nitrogen and argon are preferable, and among them, nitrogen is more preferable. Thereby, the surface and grain boundaries of the titanium nitride-containing particles that have been subjected to the thermal plasma treatment become stable, and it can be inferred that the performance of the composition is optimized. Specifically, the occurrence of pinholes in the cured film obtained using the composition of the present invention can be suppressed.

為了去除異物或減少缺陷等，用過濾器過濾本發明的組成物為較佳。作為過濾器，只要係一直以來用於過濾用途等者，則可不特別受限地使用。例如，可舉出基於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)等聚烯烴樹脂(包括高密度、超高分子量)等之過濾器。 該些原材料中，聚丙烯(包括高密度聚丙烯)、尼龍為較佳。 In order to remove foreign matter or reduce defects, etc., it is preferable to filter the composition of the present invention with a filter. As the filter, as long as it has been used for filtering purposes, etc., it can be used without particular limitation. Examples include filters based on fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight). . Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

過濾器的孔徑為0.1~7.0μm程度為較適宜，0.2~2.5μm程度為較佳，0.2~1.5μm程度為更佳，0.3~0.7μm為進一步較佳。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或凝聚物等微細的異物。 The pore size of the filter is preferably 0.1 to 7.0 μm, preferably 0.2 to 2.5 μm, more preferably 0.2 to 1.5 μm, and further preferably 0.3 to 0.7 μm. By setting it as this range, the filter clogging of the pigment can be suppressed, and fine foreign substances such as impurities and aggregates contained in the pigment can be reliably removed.

使用過濾器時，可組合不同過濾器。此時，藉由第1過濾器的過濾可僅進行1次，亦可進行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，可從由NIHON PALL LTD.、Toyo Roshi 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, filtration by the first filter may be performed only once, or may be performed twice or more. When combining different filters to perform more than two filtrations, it is preferable that the pore size after the second filtration is the same or larger than the pore size of the first filtration. In addition, it is also possible to combine first filters with different pore diameters within the above-mentioned range. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL LTD., Toyo Roshi Kaisha, Ltd., Nihon Entegris K.K. (formerly Mykrolis Corpration), or KITZ MICROFILTER CORPORATION.

第2過濾器能夠使用與上述第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程度為較適宜，0.2~7.0μm程度為較佳，0.3~6.0μm程度為進一步較佳。 The second filter can be made of the same material as the above-mentioned first filter. The pore size of the second filter is preferably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm.

〔硬化膜(遮光膜)〕 〔Cure Film (Shading Film)〕

本發明的硬化膜使用上述組成物來獲得。本發明的硬化膜中主要包含上述含氮化鈦粒子。本發明的硬化膜適宜用作遮光膜，具體而言，適宜用於圖像感測器的受光部周邊部分的遮光。 The cured film of the present invention is obtained using the above-mentioned composition. The cured film of the present invention mainly contains the above-mentioned titanium nitride-containing particles. The cured film of the present invention is suitably used as a light-shielding film, and specifically, is suitably used for light-shielding the peripheral portion of the light-receiving portion of an image sensor.

以下，作為一例，對硬化膜用作圖像感測器的受光部周邊部分的遮光膜之情況進行說明。 Hereinafter, as an example, a case where a cured film is used as a light-shielding film in the peripheral portion of the light-receiving portion of an image sensor will be described.

本發明的遮光膜係使用上述組成物(尤其，上述感光性組成物)來形成者。使用本發明的組成物來獲得之遮光膜的圖案形成性及電極的防腐性優異。 The light-shielding film of this invention is formed using the said composition (especially, the said photosensitive composition). The light-shielding film obtained by using the composition of the present invention is excellent in pattern formability and electrode corrosion resistance.

作為遮光膜的膜厚，並無特備限定，從能夠更有效地獲得基於本發明之效果之觀點考慮，以乾燥後的膜厚計，0.2μm以上50μm以下為較佳，0.3μm以上10μm以下為更佳，0.3μm以上5μm以下為進一步較佳。本發明的組成物的每單位體積的光學濃度較高，故與以往使用黑色顏料之組成物相比，還能夠更加減小膜厚。 The film thickness of the light-shielding film is not particularly limited. From the viewpoint of more effectively obtaining the effects based on the present invention, in terms of the film thickness after drying, 0.2μm or more and 50μm or less is preferred, and 0.3μm or more and 10μm or less More preferably, it is more preferably 0.3 μm or more and 5 μm or less. Since the composition of the present invention has a high optical density per unit volume, it is possible to further reduce the film thickness compared to a composition using a black pigment in the past.

作為遮光膜的尺寸(設置於感測器受光部周邊之遮光膜的一邊的長度)，從可更加有效地獲得基於本發明的效果之觀點考慮，0.001mm以上10mm以下為較佳，0.05mm以上7mm以下為更佳，0.1mm以上3.5mm以下為進一步較佳。本發明的組成物的每單位體積的光學濃度較高，故減少塗佈量等，有利於微細加工，且圖案形成性及電極的防腐性優異，故能夠上述範圍內尤其較佳地使用。 As the size of the light-shielding film (length of one side of the light-shielding film provided around the light-receiving part of the sensor), from the viewpoint of more effectively obtaining the effects of the present invention, 0.001mm or more and 10mm or less is preferable, and 0.05mm or more 7 mm or less is more preferable, and 0.1 mm or more and 3.5 mm or less is more preferable. The composition of the present invention has a high optical density per unit volume, so it is advantageous for microfabrication by reducing the coating amount, etc., and is excellent in pattern formation and electrode corrosion resistance, so it can be used particularly preferably within the above range.

<硬化膜的製造方法> <Method of manufacturing cured film>

接著，作為本發明的硬化膜(遮光膜)的製造方法的一例，利用具有黑矩陣之濾色器及其製造方法進行說明。 Next, as an example of the manufacturing method of the cured film (light-shielding film) of the present invention, a color filter having a black matrix and a manufacturing method thereof will be described.

具有本發明的黑矩陣之濾色器的特徵為，在基板上具有使用上述組成物來獲得之硬化膜(黑矩陣)。 The color filter having the black matrix of the present invention is characterized by having a cured film (black matrix) obtained by using the above composition on the substrate.

以下，對具有本發明的黑矩陣之濾色器，藉由其製造方法進行詳細說明。 Hereinafter, the color filter having the black matrix of the present invention will be described in detail by its manufacturing method.

具有本發明的黑矩陣之濾色器的製造方法，其特徵為包含：在基 板上塗佈本發明的組成物來形成組成物層(塗佈膜)之製程(以下，適當簡稱為“組成物層形成製程”。)；經由遮罩對上述組成物層進行曝光之製程(以下，適當簡稱為“曝光製程”。)；及對曝光之後的組成物層進行顯影來形成圖案狀的硬化膜之製程(以下，適當簡稱為“顯影製程”。)。 The method for manufacturing a black matrix color filter of the present invention is characterized by including: A process of applying the composition of the present invention to a plate to form a composition layer (coating film) (hereinafter, referred to as "composition layer forming process" as appropriate); a process of exposing the composition layer through a mask ( Hereinafter, it is appropriately abbreviated as "exposure process".); and a process of developing a composition layer after exposure to form a patterned cured film (hereinafter, appropriately abbreviated as "development process").

具體而言，直接或經由其他層，將本發明的組成物塗佈於基板上來形成組成物層(組成物層形成製程)，經由規定的遮罩圖案進行曝光，僅使被光照射之塗佈膜部分硬化(曝光製程)，藉由用顯影液進行顯影(顯影製程)，形成包含像素之圖案狀的硬化膜，藉此能夠製造本發明的濾色器。 Specifically, directly or through other layers, the composition of the present invention is coated on a substrate to form a composition layer (composition layer formation process), and exposure is performed through a prescribed mask pattern, and only the coating irradiated by light The film is partially cured (exposure process), and developed with a developer (development process) to form a patterned cured film containing pixels, thereby making it possible to manufacture the color filter of the present invention.

以下，對具有本發明的黑矩陣之濾色器的製造方法中的各製程進行說明。 Hereinafter, each process in the manufacturing method of the color filter with the black matrix of the present invention will be described.

(組成物層形成製程) (Composition layer formation process)

組成物層形成製程中，在基板上塗佈本發明的組成物來形成組成物層(塗佈膜)。 In the composition layer forming process, the composition of the present invention is applied on a substrate to form a composition layer (coating film).

作為基板，例如，用於液晶顯示裝置等之無鹼玻璃、鈉玻璃、Pyrex(註冊商標)玻璃、石英玻璃及對該些附著透明導電膜者、用於固態攝影元件等之光電轉換元件基板(例如，矽酮基板等)、CCD(Charge Coupled Device)基板、以及CMOS(Complementary Metal-Oxide Semiconductor)基板等。 As the substrate, for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display devices, etc., and photoelectric conversion element substrates used for solid-state imaging devices, etc. ( For example, silicone substrates, etc.), CCD (Charge Coupled Device) substrates, and CMOS (Complementary Metal-Oxide Semiconductor) substrates, etc.

並且，為了改善與上部層的黏附、防止物質的擴散或者基板表面的平坦化，可在該些基板上，依據需要設置底塗層。 In addition, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface of the substrate, a primer layer can be provided on these substrates as needed.

作為向基板上塗佈本發明的組成物之塗佈方法，可適用狹縫塗佈法、噴墨法、旋塗法、流延塗佈法、輥塗法、網版印刷法等各種塗佈方法。 As a coating method for applying the composition of the present invention to a substrate, various coating methods such as slit coating method, inkjet method, spin coating method, cast coating method, roll coating method, and screen printing method are applicable. method.

製造固態攝影元件用的具有黑矩陣之濾色器時，作為組成物的塗佈膜厚，從分辨率與顯影性的觀點考慮，0.35μm以上1.5μm以下為較佳，0.40μm以上1.0μm以下為更佳。 When manufacturing a color filter with a black matrix for solid-state imaging devices, the coating film thickness of the composition is preferably 0.35 μm or more and 1.5 μm or less from the viewpoint of resolution and developability, and 0.40 μm or more and 1.0 μm or less For better.

塗佈於基板上之組成物通常在70℃以上110℃以下，在2分鐘以上4分鐘以下程度的條件下進行乾燥。藉此，能夠形成組成物層。 The composition coated on the substrate is usually dried at a temperature above 70°C and below 110°C, for 2 minutes or more and 4 minutes or less. Thereby, a composition layer can be formed.

(曝光製程) (Exposure process)

曝光製程中，經由遮罩對在組成物層形成製程中形成之組成物層(塗佈膜)進行曝光，僅使被光照射之塗佈膜部分硬化。 In the exposure process, the composition layer (coating film) formed in the composition layer forming process is exposed through a mask, and only the part of the coating film irradiated with light is hardened.

曝光藉由活性光線或放射線的照射來進行為較佳，尤其，可較佳地適用g射線、h射線、i射線等紫外線，高壓水銀燈為更佳。照射強度為5~1500mJ/cm2為較佳，10~1000mJ/cm2為更佳。並且，從提高分析性的觀點考慮，固態攝影元件用的遮光膜形成中，基於i射線步進機之曝光為較佳。 The exposure is preferably carried out by irradiation of active light or radiation. In particular, ultraviolet rays such as g-rays, h-rays, and i-rays can be preferably applied, and a high-pressure mercury lamp is more preferable. The irradiation intensity is 5 ~ 1500mJ / cm 2 is preferred, 10 ~ 1000mJ / cm 2 is more preferred. In addition, from the viewpoint of improving analytical performance, in the formation of a light-shielding film for solid-state imaging devices, exposure by an i-ray stepper is preferable.

(顯影製程) (Development process)

接著曝光製程進行鹼顯影處理(顯影製程)，使曝光製程中的光未照射部分溶出於鹼水溶液。藉此，僅殘留已光硬化之部分(被光照射之塗佈膜部分)。 The exposure process is followed by an alkali development process (development process), so that the portion not irradiated by the light in the exposure process is dissolved in the alkali aqueous solution. Thereby, only the photohardened part (the part of the coating film irradiated with light) remains.

作為顯影液，製作固態攝影元件用的具有黑矩陣之遮光性濾色器時，不會對基底的電路等帶來損傷之有機鹼顯影液為較佳。作為顯影溫度，通常為20~30℃，顯影時間為20~90秒。 As the developer, an organic alkali developer that does not cause damage to the circuit of the substrate and the like when manufacturing a light-shielding color filter having a black matrix for a solid-state imaging element is preferable. The development temperature is usually 20 to 30°C, and the development time is 20 to 90 seconds.

作為鹼性水溶液，例如，可舉出無機系顯影液及有機系顯影液。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、偏矽酸鈉，溶解成濃度為0.001~10質量%，較佳地為0.01~1質量%之鹼性水溶液。作為有機系顯影液，可舉出將氨水、乙胺、二乙胺、二甲基乙醇胺、四甲基氫氧化銨、四乙基氫氧化銨、膽鹼、吡咯、哌啶、1，8-二氮雜雙環-[5.4.0]-7-十一碳烯等有機鹼性化合物，溶解成濃度為0.001~10質量%，較佳地為0.01~1質量%之鹼性水溶液。鹼性水溶液中，例如還能夠添加適量的甲醇、乙醇等水溶性有機溶劑和/或表面活性劑等。另外，使用包含該種鹼性水溶液之顯影液時，通常在顯影後以純水清洗(沖洗)為較佳。 As an alkaline aqueous solution, an inorganic type developer and an organic type developer are mentioned, for example. As an inorganic developer, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, silicon Sodium and sodium metasilicate are dissolved into an alkaline aqueous solution with a concentration of 0.001-10% by mass, preferably 0.01-1% by mass. Examples of organic developer solutions include ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8- Organic basic compounds such as diazabicyclo-[5.4.0]-7-undecene are dissolved into an alkaline aqueous solution with a concentration of 0.001-10% by mass, preferably 0.01-1% by mass. In the alkaline aqueous solution, for example, an appropriate amount of water-soluble organic solvents such as methanol and ethanol and/or surfactants can be added. In addition, when using a developer containing such an alkaline aqueous solution, it is generally preferable to wash (rinse) with pure water after development.

作為顯影方法，例如能夠利用旋覆浸沒顯影方法及噴淋顯影方法等。 As the development method, for example, a spin-on immersion development method, a shower development method, etc. can be utilized.

另外，具有本發明的硬化膜(黑矩陣)之濾色器的製造方法中，可在進行上述之組成物層形成製程、曝光製程及顯影製程之後，依據需要，包含藉由加熱和/或曝光對所形成之硬化膜進行硬化之硬化製程。 In addition, in the method of manufacturing a color filter having a cured film (black matrix) of the present invention, after the above-mentioned composition layer formation process, exposure process, and development process are performed, as necessary, heating and/or exposure may be included. The hardening process of hardening the formed hardened film.

具有本發明的硬化膜(黑矩陣)之濾色器中使用本發明的組成物，因此所形成之硬化膜的圖案形成性及電極的防腐性優異。 Since the composition of the present invention is used in a color filter having the cured film (black matrix) of the present invention, the formed cured film has excellent pattern formability and electrode corrosion resistance.

藉此，能夠較佳地用於液晶顯示裝置及CCD等固態攝影元件，尤其適於超過100万像素之高分辨率的CCD元件或CMOS等。亦即，具備本發明的硬化膜之濾色器適用於固態攝影元件為較佳。並且，濾色器可具有如下結構，亦即，在藉由隔壁例如分割成格子狀之空間，埋入形成各顏色像素之硬化膜。 Therefore, it can be preferably used in solid-state imaging devices such as liquid crystal display devices and CCDs, and is particularly suitable for CCD devices or CMOS devices with high resolution over 1 million pixels. That is, the color filter provided with the cured film of the present invention is preferably suitable for solid-state imaging devices. In addition, the color filter may have a structure in which a cured film forming pixels of each color is buried in a space divided into a grid shape by a partition wall, for example.

本發明的硬化膜(黑矩陣)例如配置於構成CCD或CMOS之各像素的 受光部與用於聚光的微透鏡之間。 The cured film (black matrix) of the present invention is, for example, arranged on the pixels constituting the CCD or CMOS. Between the light receiving part and the micro lens for condensing light.

〔固態攝影元件〕 〔Solid-state imaging element〕

本發明的固態攝影元件具有上述之本發明的硬化膜(黑矩陣)。本發明的固態攝影元件具備具有黑矩陣及依據需要而包含其他顏色(3色或者4色)的像素之圖案狀皮膜之濾色器而構成為較佳。 The solid-state imaging device of the present invention has the above-mentioned cured film (black matrix) of the present invention. The solid-state imaging device of the present invention is preferably configured to include a color filter having a black matrix and a patterned film containing pixels of other colors (three colors or four colors) as necessary.

作為本發明的固態攝影元件的結構，係具備本發明的黑矩陣之結構，只要係作為固態攝影元件發揮作用之結構，則並無特別限定，例如，可舉出在基板上具有包含構成固態攝影元件(CCD圖像感測器、CMOS圖像感測器等)的受光區之複數個光電二極體及多晶矽等之受光元件，在基板的受光元件形成面的相反側的面具備本發明的黑矩陣之結構等。並且，濾色器亦可具有如下結構，亦即，在藉由隔壁例如分割成格子狀之空間埋入有形成各顏色像素之硬化膜。此時的隔壁相對於各顏色像素為低折射率為較佳。作為具有該種結構之攝像元件的例子，可舉出日本特開2012-227478號公報及日本特開2014-179577號公報中記載之装置。 The structure of the solid-state imaging device of the present invention is a structure having the black matrix of the present invention. As long as it functions as a solid-state imaging device, it is not particularly limited. A plurality of photodiodes, polysilicon and other light-receiving elements in the light-receiving area of the element (CCD image sensor, CMOS image sensor, etc.) are provided on the surface of the substrate opposite to the light-receiving element forming surface of the present invention The structure of the black matrix, etc. In addition, the color filter may have a structure in which a cured film forming pixels of each color is buried in a space divided into a grid shape by a partition wall, for example. In this case, the partition wall preferably has a low refractive index with respect to each color pixel. As an example of an imaging element having such a structure, there are devices described in Japanese Patent Application Publication No. 2012-227478 and Japanese Patent Application Publication No. 2014-179577.

〔附帶遮光膜的紅外光截止濾波器、固態攝像裝置〕 [Infrared cut filter with light shielding film, solid-state imaging device]

上述之硬化膜能夠較佳地適用作所謂的遮光膜。並且，該種遮光膜能夠較佳地適用於附帶遮光膜的紅外光截止濾波器及固態攝像裝置。作為該種固態攝像裝置，例如，可舉出日本特開2015-034983號公報中記載之段落0011~0033及段落0125~0127中記載之固態攝像裝置。 The above-mentioned cured film can be suitably used as a so-called light-shielding film. In addition, the light-shielding film can be preferably applied to infrared light cut filters and solid-state imaging devices with light-shielding films. As such a solid-state imaging device, for example, the solid-state imaging device described in paragraphs 0011 to 0033 and paragraphs 0125 to 0127 described in JP 2015-034983 A can be cited.

〔圖像顯示裝置、濾色器〕 [Image display device, color filter]

上述之硬化膜能夠用於液晶顯示裝置及有機電致發光顯示裝置等圖像 顯示裝置。並且，硬化膜能夠用於濾色器。 The above-mentioned cured film can be used for images such as liquid crystal display devices and organic electroluminescence display devices Display device. Also, the cured film can be used for color filters.

對於圖像顯示裝置的定義或各圖像顯示裝置的詳細內容，例如記載於“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)”等中。並且，對於液晶顯示裝置，例如記載於“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)”。能夠適用本發明之液晶顯示裝置並無特別限制，例如能夠適用於上述“第二代液晶顯示器技術”中記載之各種方式的液晶顯示裝置。 The definition of the image display device or the details of each image display device are described in, for example, "Electronic Display Device (by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd. in 1990)", "Display Device (Junaki Ibuki) "Industrial Books (published in the first year of Heisei)" etc. In addition, the liquid crystal display device is described in, for example, "Second Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd. in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Second Generation Liquid Crystal Display Technology".

其中，本發明的液晶顯示裝置具有上述硬化膜。 Among them, the liquid crystal display device of the present invention has the above-mentioned cured film.

作為本發明的液晶顯示裝置的一態様，例如，至少1個係在光透射性的一對基板之間至少具備濾色器、液晶層及液晶駆動機構(包括單純矩陣驅動方式及有源矩陣駆動方式)者，作為濾色器，使用具有複數個像素組，構成該像素組之各像素係相互藉由本發明的黑矩陣分離之濾色器者。 As one aspect of the liquid crystal display device of the present invention, for example, at least one is provided between a pair of light-transmissive substrates at least with a color filter, a liquid crystal layer, and a liquid crystal actuator (including a simple matrix driving method and an active matrix actuator). Mode), as the color filter, a color filter having a plurality of pixel groups is used, and the pixels constituting the pixel group are separated from each other by the black matrix of the present invention.

並且，作為本發明的液晶顯示裝置的其他態様，至少1個係在光透射性的一對基板之間至少具備濾色器、液晶層及液晶駆動機構，液晶駆動機構具有有源元件(例如，TFT(Thin Film Transistor))，且各有源元件之間具備使用本發明的組成物來獲得之濾色器者。 In addition, as another aspect of the liquid crystal display device of the present invention, at least one is provided with at least a color filter, a liquid crystal layer, and a liquid crystal actuator between a pair of light-transmitting substrates, and the liquid crystal actuator has an active element (for example, TFT (Thin Film Transistor)), and a color filter obtained by using the composition of the present invention is provided between each active element.

使用本發明的組成物來獲得之濾色器可用於彩色TFT(Thin Film Transistor)方式的液晶顯示裝置。對於彩色TFT方式的液晶顯示裝置，例如記載於“彩色TFT液晶顯示器(KYORITSU SHUPPAN CO.,LTD.1996年發行)”。而且，本發明還能夠適用於IPS(In Plane Switching)等橫向電 場驅動方式、MVA(Multi-domain Vertical Alignment)等像素分割方式等視角被擴大之液晶顯示裝置、STN(Super-Twist Nematic)、TN(Twisted Nematic)、VA(Vertical Alignment)、OCS(on-chip spacer)、FFS(fringe field switching)及R-OCB(Reflective Optically Compensated Bend)等。 The color filter obtained by using the composition of the present invention can be used in a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, "Color TFT Liquid Crystal Display (KYORITSU SHUPPAN CO., LTD. issued in 1996)". Moreover, the present invention can also be applied to horizontal electrical appliances such as IPS (In Plane Switching). Field drive method, MVA (Multi-domain Vertical Alignment) and other pixel division methods such as liquid crystal display devices with enlarged viewing angle, STN (Super-Twist Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip) spacer), FFS (fringe field switching) and R-OCB (Reflective Optically Compensated Bend), etc.

並且，本發明中的濾色器還能夠用於明亮且高精細的COA(Color-filter On Array)方式用。關於COA方式的液晶顯示裝置，對於濾色器之要求特性，除了通常的要求特性以外，有時還要求對於層間絶縁膜之要求特性，亦即，低介電常數及剥離液耐性。本發明的濾色器能夠提供分辨率較高且長期耐久性優異之COA方式的液晶顯示裝置。另外，為了滿足低介電常數的要求特性，可在濾色器層上設置樹脂被膜。 In addition, the color filter in the present invention can also be used in a bright and high-definition COA (Color-filter On Array) method. Regarding the liquid crystal display device of the COA method, in addition to the usual required characteristics of the color filter, the required characteristics of the interlayer insulation film, that is, low dielectric constant and peeling liquid resistance, are sometimes required. The color filter of the present invention can provide a COA mode liquid crystal display device with high resolution and excellent long-term durability. In addition, in order to meet the required characteristics of low dielectric constant, a resin film may be provided on the color filter layer.

對於該些圖像顯示方式，例如記載於“EL、PDP、LCD顯示器-技術與市場的最新動向-(TORAY Research Center,Inc.調查研究部門2001年發行)”的43頁等。並且，濾色器可具有如下結構，亦即，在藉由隔壁例如分割成格子狀之空間，埋入形成各顏色像素之硬化膜。 These image display methods are described, for example, on page 43 of "EL, PDP, LCD Display-Latest Trends in Technology and Market-(issued by TORAY Research Center, Inc. 2001)". In addition, the color filter may have a structure in which a cured film forming pixels of each color is buried in a space divided into a grid shape by a partition wall, for example.

此時的隔壁相對於各顏色像素為低折射率為較佳。作為具有該種結構之攝像装置的例子，可舉出日本特開2012-227478號公報、日本特開2014-179577號公報中記載之装置。 In this case, the partition wall preferably has a low refractive index with respect to each color pixel. As an example of an imaging device having such a structure, there can be mentioned devices described in Japanese Patent Application Publication No. 2012-227478 and Japanese Patent Application Publication No. 2014-179577.

本發明的液晶顯示裝置除了本發明的濾色器以外，亦可由電極基板、偏光膜、相位差膜、背光、間隔物及視角保護膜等各種構件構成。本發明的濾色器能夠適用於由該些公知構件構成之液晶顯示裝置。對於該些構件，例如記載於“’94液晶顯示器周邊材料‧化學製品市場(島 健太郎 CMC-Group.1994年發行)”、“2003液晶関連市場的現狀與未來展望(下卷)(表良吉Fuji Chimera Research Institute,Inc.、2003年發行)”。 In addition to the color filter of the present invention, the liquid crystal display device of the present invention may be composed of various members such as electrode substrates, polarizing films, retardation films, backlights, spacers, and viewing angle protective films. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. For these components, for example, it is described in "'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Shima Kentaro) CMC-Group. Issued in 1994)", "The Status Quo and Future Prospects of the 2003 LCD Related Market (Volume 2) (Oyoshiyoshi Fuji Chimera Research Institute, Inc., Issued in 2003)".

關於背光，除了SID meeting Digest 1380(2005)(A.Konno et.al)以外，記載於月刊顯示器2005年12月號的18~24頁(島 康裕)、記載於SID meeting Digest 1380(2005)25~30頁(八木隆明)等。 Regarding the backlight, in addition to SID meeting Digest 1380 (2005) (A. Konno et.al), it is described on pages 18-24 of the December 2005 issue of Monthly Display (Yangyu Shima) and in SID meeting Digest 1380 (2005) 25 ~30 pages (Yagi Takaaki) etc.

並且，本發明的硬化膜能夠使用於個人計算機、平板電腦、移動電話、智能手機或數碼相機等便攜式設備；多功能打印機及掃描儀等OA(Office Automation)設備；監視相機、條形碼讀取器及自動取款機(ATM)、高速相機及使用人臉圖像認證之本人認證等產業用設備；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部件及遮光層、防反射部件以及防反射層。 In addition, the cured film of the present invention can be used in portable devices such as personal computers, tablet computers, mobile phones, smart phones, or digital cameras; OA (Office Automation) devices such as multifunction printers and scanners; surveillance cameras, barcode readers, and Industrial equipment such as automated teller machines (ATM), high-speed cameras, and personal authentication using facial image authentication; automotive camera equipment; medical camera equipment such as endoscopes, capsule endoscopes, and catheters; biological sensors Optical filtering used in aerospace equipment such as Biosensor, military reconnaissance cameras, stereo map cameras, meteorological and ocean observation cameras, terrestrial resources reconnaissance cameras, and exploration cameras for astronomical and deep space targets in the universe Light-shielding parts and light-shielding layers, anti-reflection parts and anti-reflection layers of devices and modules

並且，本發明的硬化膜還可適用於微型LED(Light Emitting Diode)及微型OLED(Organic Light Emitting Diode)等用途。雖然並無特別限定，但除了微型LED及微型OLED中使用之光學濾波器及光學薄膜以外，可較佳地用於賦予遮光功能或防反射功能之部件。 In addition, the cured film of the present invention can also be applied to applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). Although not particularly limited, in addition to optical filters and optical films used in micro LEDs and micro OLEDs, it can be preferably used for parts that provide light shielding or anti-reflection functions.

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 Japanese Special Form No. 2015-500562 and Japanese Special Form 2014-533890.

並且，使本發明的組成物硬化來獲得之硬化膜還能夠用於量子點 顯示器等用途。雖然並無特別限定，但除了量子點顯示器中使用之光學及光學薄膜以外，還較佳地用於賦予遮光功能及防反射功能之部件。 In addition, the cured film obtained by curing the composition of the present invention can also be used for quantum dots Uses such as displays. Although it is not particularly limited, in addition to optical and optical films used in quantum dot displays, it is also preferably used for parts that provide light-shielding and anti-reflection functions.

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。 As examples of quantum dot displays, 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，利用實施例，對本發明進行詳細說明。但是，本發明並不限定於此。另外，除非另有指明，則“份”、“%”為質量基準。 Hereinafter, the present invention will be described in detail using examples. However, the present invention is not limited to this. In addition, unless otherwise specified, "parts" and "%" are quality standards.

〔組成物〕 〔Composition〕

以下，製備實施例及比較例的組成物時，首先對組成物中包含之各成分進行說明。 Hereinafter, when preparing the compositions of Examples and Comparative Examples, first, each component contained in the composition will be described.

<含氮化鈦粒子> <Titanium Nitride Particles>

作為含氮化鈦粒子，使用了如下製造之含氮化鈦粒子TiN-1~TiN-19。 As the titanium nitride-containing particles, titanium nitride-containing particles TiN-1 to TiN-19 produced as follows were used.

關於各含氮化鈦粒子的製造中使用之成分及添加量，示於表1。表1中，鈦粒子(Ti粒子)的添加量中，“餘量”表示除了添加粒子的含量之量。並且，“wt%”表示質量%。 Table 1 shows the components used in the production of each titanium nitride-containing particle and the addition amount. In Table 1, in the addition amount of titanium particles (Ti particles), the "balance" indicates the amount excluding the content of the added particles. And, "wt%" means mass%.

(含氮化鈦粒子TiN-1) (TiN-1 containing titanium nitride particles)

使用表1中記載之各成分製造了含氮化鈦粒子TiN-1。 Titanium nitride-containing particles TiN-1 were produced using the components described in Table 1.

首先，藉由在Ar氣體中對表1中記載之Ti粒子進行等離子體處理，進行了Ti奈米粒子化。將等離子體處理之後的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24小時之後，在以O2濃 度成為100ppm之方式在向Ar氣氛導入O2氣體之狀態下，進行了30℃、24小時的靜置(Ti粒子的預處理)。 First, the Ti particles described in Table 1 were subjected to plasma treatment in Ar gas to perform Ti nanoparticle formation. Plasma-treated Ti nanoparticles were allowed to stand for 24 hours under the conditions of an O 2 concentration of 50 ppm or less and 30°C under an Ar gas atmosphere, and then O was introduced into the Ar atmosphere so that the O 2 concentration became 100 ppm. 2 In the state of gas, it was allowed to stand at 30°C for 24 hours (pretreatment of Ti particles).

之後，將所獲得之Ti奈米粒子，利用Hosokawa Micron Corporation製造TTSP分離器，以產率成為10%之條件進行分級，獲得了Ti奈米粒子的粉末。藉由TEM觀察，並藉由算術平均求出了100個粒子的平均粒徑，其結果，所獲得之粉末的一次粒徑為120nm。 After that, the obtained Ti nanoparticle was classified with a TTSP separator manufactured by Hosokawa Micron Corporation under the condition that the yield became 10%, and a powder of Ti nanoparticle was obtained. The average particle size of 100 particles was obtained by TEM observation and arithmetic average. As a result, the primary particle size of the obtained powder was 120 nm.

利用依據國際公開第2010/147098的第1圖中記載之黑色複合微粒製造装置之装置製造了含氮化鈦粒子TiN-1。 The titanium nitride-containing particles TiN-1 were manufactured using an apparatus based on the black composite particle manufacturing apparatus described in Figure 1 of International Publication No. 2010/147098.

具體而言，黑色複合微粒製造装置中，對電漿炬的高頻振盪用線圈，施加約4MHz及約80kVA的高頻電壓，從等離子體氣體供給源，作為等離子體氣體，供給氬氣50L/min及氮50L/min的混合氣體，使電漿炬內產生氬-氮熱電漿火焰。並且，從材料供給装置的噴霧氣體供給源供給10L/min的載氣。 Specifically, in the black composite particle manufacturing device, a high-frequency voltage of about 4MHz and about 80kVA is applied to the high-frequency oscillation coil of the plasma torch, and 50L of argon gas is supplied as a plasma gas from a plasma gas supply source. The mixed gas of min and nitrogen 50L/min produces an argon-nitrogen thermal plasma flame in the plasma torch. In addition, 10 L/min of carrier gas was supplied from the spray gas supply source of the material supply device.

並且，以表1中記載之添加量添加如上述那樣獲得之鈦粒子及表1中記載之添加粒子，與作為載氣之氬氣一同，供給至電漿炬內的熱電漿火焰中，使其在熱電漿火焰中蒸發，使其以氣相狀態高度分散。 In addition, the titanium particles obtained as described above and the added particles described in Table 1 were added in the addition amount described in Table 1, together with argon gas as the carrier gas, and supplied to the thermoplasma flame in the plasma torch to make it Evaporate in the thermoplasma flame to make it highly dispersed in the gas phase.

並且，作為藉由氣相供給装置供給至腔室內之氣相，使用了氮。將此時的腔室內的流速設為5m/sec，供給量設為1000L/min。並且，將旋風器內的壓力設為50kPa，並且，將從腔室向旋風器的各原料的供給速度設為10m/s(平均值)。 In addition, nitrogen was used as the gas phase supplied into the chamber by the gas phase supply device. The flow velocity in the chamber at this time was 5 m/sec, and the supply amount was 1000 L/min. In addition, the pressure in the cyclone was set to 50 kPa, and the supply speed of each raw material from the chamber to the cyclone was set to 10 m/s (average value).

如此來獲得了含氮化鈦粒子TiN-1。 In this way, TiN-1 containing titanium nitride particles was obtained.

對所獲得之含氮化鈦粒子TiN-1，藉由ICP發光分光分析法測定了鈦(Ti)原子、Fe(鐵)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發光分光分析装置“SPS3000”(商品名)。 For the obtained titanium nitride-containing particles TiN-1, the contents of titanium (Ti) atoms, Fe (iron) atoms, and silicon (Si) atoms were measured by ICP emission spectrometry. The results are shown in Table 1. In addition, in the ICP emission spectroscopic analysis method, an ICP emission spectroscopic analysis device "SPS3000" (trade name) manufactured by Seiko Instruments Inc. was used.

並且，關於氮原子的含量，利用HORIBA,Ltd.製造的氧/氮分析装置“EMGA-620W/C”(商品名)進行測定，並藉由惰性氣體熔融熱導法計算。將結果示於表1。 In addition, the content of nitrogen atoms was measured using 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，對於後述之含氮化鈦粒子TiN-2~TiN-19，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、氮原子的含量。將結果示於表1。 In addition, for the titanium nitride-containing particles TiN-2 to TiN-19 described later, the contents of Ti atoms, Fe atoms, silicon atoms, and nitrogen atoms were also measured by the same method as the 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射線衍射，將粉末試料裝入鋁製標準試料保持器中，藉由廣角X射線衍射法(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, a powder sample was placed in a standard sample holder made of aluminum, and the measurement was performed by a wide-angle X-ray diffraction method (manufactured by Rigaku Corporation, trade name "RU-200R"). As the measurement conditions, the X-ray source is set to CuKα rays, 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 It is 2°/min.

並且，測定了在衍射角2θ(42.6°)附近觀察到之源自TiN(200)面之峰的衍射角2θ。而且，藉由該源自(200)面之峰的半值幅，利用謝勒(Scherrer)公式，求出了構成粒子之微晶尺寸。將結果示於表1。另外，完全沒有觀察到TiO2引起之X射線衍射峰。 In addition, the diffraction angle 2θ of the peak derived from the TiN (200) plane observed near the diffraction angle 2θ (42.6°) was measured. Furthermore, by using the half-value width of the peak originating from the (200) plane, the size of the crystallites of the constituent particles was calculated using Scherrer's formula. The results are shown in Table 1. In addition, X-ray diffraction peaks caused by TiO 2 were not observed at all.

另外，對於以下的含氮化鈦粒子TiN-2~TiN-19，藉由與含氮化鈦粒子TiN-1相同的方法，測定了衍射角2θ、微晶尺寸。將結果示於表1。另外， 關於任意含氮化鈦粒子，均完全沒有觀察到TiO2引起之X射線衍射峰。 In addition, for the following titanium nitride-containing particles TiN-2 to TiN-19, the diffraction angle 2θ and crystallite size were measured by the same method as the titanium nitride-containing particle TiN-1. The results are shown in Table 1. In addition, with regard to any titanium nitride-containing particles, no X-ray diffraction peak due to TiO 2 was observed.

(含氮化鈦粒子TiN-2) (TiN-2 containing titanium nitride particles)

將TiN-1粒子的製造中使用之原料及添加量設為表1所示，除此以外，與含氮化鈦粒子TiN-1的製造相同地製造了含氮化鈦粒子TiN-2。 Except that the raw materials used in the production of the TiN-1 particles and the addition amount are as shown in Table 1, the same as the production of the titanium nitride-containing particles TiN-1 was carried out to produce the titanium nitride-containing particles TiN-2.

(含氮化鈦粒子TiN-3) (TiN-3 containing titanium nitride particles)

將TiN-1粒子的製造中使用之原料及添加量設為表1所示，除此以外，與含氮化鈦粒子TiN-1的製造相同地製造了含氮化鈦粒子TiN-3。 Except that the raw materials used in the production of the TiN-1 particles and the addition amounts are as shown in Table 1, the same as the production of the titanium nitride-containing particles TiN-1 was carried out to produce the titanium nitride-containing particles TiN-3.

(含氮化鈦粒子TiN-4) (TiN-4 containing titanium nitride particles)

將TiN-1粒子的製造中使用之原料及添加量設為表1所示，除此以外，與含氮化鈦粒子TiN-1的製造相同地製造了含氮化鈦粒子TiN-4。 Except that the raw materials used in the production of the TiN-1 particles and the addition amounts are as shown in Table 1, the same as the production of the titanium nitride-containing particles TiN-1 was carried out to produce the titanium nitride-containing particles TiN-4.

(含氮化鈦粒子TiN-5) (TiN-5 containing titanium nitride particles)

將TiN-1粒子的製造中使用之原料及添加量設為表1所示，除此以外，與含氮化鈦粒子TiN-1的製造相同地製造了含氮化鈦粒子TiN-5。 Except that the raw materials used in the production of the TiN-1 particles and the addition amount are as shown in Table 1, the same as the production of the titanium nitride-containing particles TiN-1 was carried out to produce the titanium nitride-containing particles TiN-5.

(含氮化鈦粒子TiN-6) (TiN-6 containing titanium nitride particles)

將TiN-1粒子的製造中使用之原料及添加量設為表1所示，除此以外，與含氮化鈦粒子TiN-1的製造相同地製造了含氮化鈦粒子TiN-6。 Except that the raw materials used in the production of the TiN-1 particles and the addition amounts are as shown in Table 1, the same as the production of the titanium nitride-containing particles TiN-1 was carried out to produce the titanium nitride-containing particles TiN-6.

(含氮化鈦粒子TiN-7) (TiN-7 containing titanium nitride particles)

將TiN-6粒子的製造中的從腔室向旋風器的各原料的供給速度變更為8m/s(平均值)，除此以外，與含氮化鈦粒子TiN-6的製造相同地製造了含氮化鈦粒子TiN-7。 In the production of TiN-6 particles, the feed rate of each raw material from the chamber to the cyclone was changed to 8m/s (average value), except that the same as the production of TiN-6 containing titanium nitride particles was produced. Containing titanium nitride particles TiN-7.

(含氮化鈦粒子TiN-8) (TiN-8 containing titanium nitride particles)

將TiN-1粒子的製造中使用之原料及添加量設為表1所示，將從腔室向旋風器的各原料的供給速度變更為15m/s(平均值)，除此以外，與含氮化鈦粒子TiN-1的製造相同地製造了含氮化鈦粒子TiN-8。 The raw materials used in the manufacture of TiN-1 particles and their addition amounts are set as shown in Table 1, and the feed rate of each raw material from the chamber to the cyclone is changed to 15m/s (average value). Production of titanium nitride particles TiN-1 In the same way, titanium nitride particles containing TiN-8 were produced.

(含氮化鈦粒子TiN-9) (TiN-9 containing titanium nitride particles)

將TiN-1粒子的製造中使用之原料及添加量設為表1所示，將從腔室向旋風器的各原料的供給速度變更為20m/s(平均值)，除此以外與含氮化鈦粒子TiN-1的製造相同地製造了含氮化鈦粒子TiN-9。 The raw materials used in the manufacture of TiN-1 particles and their addition amounts are set as shown in Table 1, and the feed rate of each raw material from the chamber to the cyclone is changed to 20m/s (average value). Production of titanium oxide particles TiN-1 In the same manner, titanium nitride-containing particles TiN-9 were produced.

(含氮化鈦粒子TiN-10) (TiN-10 containing titanium nitride particles)

將TiN-1粒子的製造中使用之原料及添加量設為表1所示，除此以外，與含氮化鈦粒子TiN-1的製造相同地製造了含氮化鈦粒子TiN-10。 Except that the raw materials used in the production of the TiN-1 particles and the addition amounts are as shown in Table 1, the same as the production of the titanium nitride-containing particles TiN-1 was carried out to produce the titanium nitride-containing particles TiN-10.

(含氮化鈦粒子TiN-11) (TiN-11 containing titanium nitride particles)

將TiN-1粒子的製造中使用之原料及添加量設為表1所示，未實施Ti粒子的預處理及静置處理，除此以外，與含氮化鈦粒子TiN-1的製造相同地製造了含氮化鈦粒子TiN-11。 The raw materials used in the production of TiN-1 particles and the amount of addition are as shown in Table 1. The pretreatment and standing treatment of Ti particles are not carried out, except for the same as the production of TiN-1 particles containing titanium nitride TiN-11 containing titanium nitride particles was produced.

(含氮化鈦粒子TiN-12) (TiN-12 containing titanium nitride particles)

將TiN-1粒子的製造中使用之原料及添加量設為表1所示，除此以外，與含氮化鈦粒子TiN-1的製造相同地製造了含氮化鈦粒子TiN-12。 Except that the raw materials used in the production of the TiN-1 particles and the addition amount are as shown in Table 1, the same as the production of the titanium nitride-containing particles TiN-1 was carried out to produce the titanium nitride-containing particles TiN-12.

(含氮化鈦粒子TiN-13) (TiN-13 containing titanium nitride particles)

將TiN-1粒子的製造中使用之原料及添加量設為表1所示，除此以外，與含氮化鈦粒子TiN-1的製造相同地製造了含氮化鈦粒子TiN-13。 Except that the raw materials used in the production of TiN-1 particles and the addition amount are as shown in Table 1, the same as the production of TiN-1 containing titanium nitride particles, TiN-13 was produced.

(含氮化鈦粒子TiN-14) (TiN-14 containing titanium nitride particles)

將TiN-1粒子的製造中使用之原料及添加量設為表1所示，除此以外，與含氮化鈦粒子TiN-1的製造相同地製造了含氮化鈦粒子TiN-14。 Except that the raw materials used in the production of the TiN-1 particles and the addition amount are as shown in Table 1, the same as the production of the titanium nitride-containing particles TiN-1 was used to produce the titanium nitride-containing particles TiN-14.

(含氮化鈦粒子TiN-15) (TiN-15 containing titanium nitride particles)

將TiN-1粒子的製造中使用之原料及添加量設為表1所示，除此以外，與含氮化鈦粒子TiN-1的製造相同地製造了含氮化鈦粒子TiN-15。 Except that the raw materials used in the production of TiN-1 particles and the amount of addition were as shown in Table 1, the same as the production of TiN-1 containing titanium nitride particles, TiN-15 was produced.

(含氮化鈦粒子TiN-16) (TiN-16 containing titanium nitride particles)

將TiN-1粒子的製造中使用之原料及添加量設為表1所示，除此以外，與含氮化鈦粒子TiN-1的製造相同地製造了含氮化鈦粒子TiN-16。 Except that the raw materials used in the production of the TiN-1 particles and the addition amounts are as shown in Table 1, the same as the production of the titanium nitride-containing particles TiN-1 was carried out to produce the titanium nitride-containing particles TiN-16.

(含氮化鈦粒子TiN-17、TiN-18及TiN-19) (Containing titanium nitride particles TiN-17, TiN-18 and TiN-19)

將TiN-4粒子的製造中的、後述之含氮化鈦粒子製造之後的氧(O2)濃度控制下的静置時間設為表1所示，除此以外，與含氮化鈦粒子TiN-4相同地製造了含氮化鈦粒子TiN-17、TiN-18及TiN-19。 In the production of TiN-4 particles, the rest time under the control of the oxygen (O 2 ) concentration after the production of the titanium nitride-containing particles described later is set as shown in Table 1. In addition, it is compared with the titanium nitride-containing particles TiN -4 In the same manner, TiN-17, TiN-18 and TiN-19 containing titanium nitride particles were produced.

<製造含氮化鈦粒子之後的氧(O2)濃度控制下的静置期間(製造TiN粒子之後的O2導入下静置)> <Standing period under the control of oxygen (O 2 ) concentration after manufacturing titanium nitride particles (Standing under O 2 introduction after manufacturing TiN particles)>

將如上述那樣獲得之含氮化鈦粒子，以表1~第5表中記載之期間，在氧(O2)濃度及水分的含量分別控制在100ppm以下之導入有氮(N2)氣體之密封容器內静置之後，進行了各組成物的製備。 For the titanium nitride-containing particles obtained as described above, the oxygen (O 2 ) concentration and the moisture content were controlled to below 100 ppm during the period described in Table 1 to Table 5 with nitrogen (N 2 ) gas introduced. After being allowed to stand in the sealed container, each composition was prepared.

另外，表1~表5中，“無”表示將所製造之含氮化鈦粒子立刻向大氣開放來使用。並且，12hr、24hr、48hr及72hr分別表示將所製造之含氮化鈦粒子靜置在氧(O2)濃度100ppm以下的容器內之時間。 In addition, in Tables 1 to 5, "None" means that the manufactured titanium nitride-containing particles were immediately opened to the atmosphere for use. In addition, 12hr, 24hr, 48hr, and 72hr respectively represent the time for the manufactured titanium nitride-containing particles to stand still in a container with an oxygen (O 2 ) concentration of 100 ppm or less.

Figure 106104991-A0305-02-0108-20
Figure 106104991-A0305-02-0108-20

<分散劑> <Dispersant>

作為分散劑，使用了以下結構的分散劑A~G。各結構單元中記載之數值表示相對於所有結構單元之各結構單元的質量%。 As the dispersant, dispersants A to G of the following structures were used. The numerical value described in each structural unit represents the mass% of each structural unit relative to all structural units.

[化學式20]

Figure 106104991-A0305-02-0110-21
[Chemical formula 20]
Figure 106104991-A0305-02-0110-21

<黏結樹脂> <Binder Resin>

作為黏結樹脂亦即樹脂A，使用了Acrycure RD-F8(商品名、NIPPON SHOKUBAI CO.,LTD.製造)。以下示出樹脂A的結構。 Acrycure RD-F8 (trade name, manufactured by NIPPON SHOKUBAI CO., LTD.) was used as resin A, which is a binder resin. The structure of resin A is shown below.

Figure 106104991-A0305-02-0111-22
Figure 106104991-A0305-02-0111-22

<聚合性化合物> <Polymerizable compound>

‧聚合性化合物M1(Nippon Kayaku Co.,Ltd.製造、商品名“KAYARAD DPHA”、參閱下述式) ‧Polymerizable compound M1 (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD DPHA", see the following formula)

‧聚合性化合物M2(Nippon Kayaku Co.,Ltd.製造、商品名“KAYARAD RP-1040”、參閱下述式) ‧Polymerizable compound M2 (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD RP-1040", see the following formula)

Figure 106104991-A0305-02-0111-23
Figure 106104991-A0305-02-0111-23

<聚合起始劑> <Polymerization initiator>

‧OXE-01：Irgacure OXE01(商品名、BASF JAPAN LTD.製造) ‧OXE-01: Irgacure OXE01 (trade name, manufactured by BASF JAPAN LTD.)

‧OXE-02：Irgacure OXE02(商品名、BASF JAPAN LTD.製造) ‧OXE-02: Irgacure OXE02 (trade name, manufactured by BASF JAPAN LTD.)

‧I-1：下述式(I-1)的聚合起始劑 ‧I-1: The polymerization initiator of the following formula (I-1)

‧I-2：下述式(I-2)的聚合起始劑(商品名“B-CIM”、HODOGAYA CHEMICAL CO.,LTD.製造) ‧I-2: The polymerization initiator of the following formula (I-2) (trade name "B-CIM", manufactured by HODOGAYA CHEMICAL CO., LTD.)

‧I-3：下述式(I-3)的聚合起始劑 ‧I-3: The polymerization initiator of the following formula (I-3)

‧I-4：下述式(I-4)的聚合起始劑 ‧I-4: The polymerization initiator of the following formula (I-4)

‧I-5：下述式(I-5)的聚合起始劑 ‧I-5: The polymerization initiator of the following formula (I-5)

‧NCI-831：Adeka Arkles NCI-831(商品名、ADEKA CORPORATION製造) ‧NCI-831: Adeka Arkles NCI-831 (trade name, manufactured by ADEKA CORPORATION)

‧N-1919：商品名、ADEKA CORPORATION製造 ‧N-1919: Trade name, manufactured by ADEKA CORPORATION

[化學式23]

Figure 106104991-A0305-02-0113-24
[Chemical formula 23]
Figure 106104991-A0305-02-0113-24

<有機溶劑> <Organic solvent>

‧PGMEA：丙二醇單甲醚乙酸酯 ‧PGMEA: Propylene glycol monomethyl ether acetate

‧環戊酮 ‧Cyclopentanone

‧乙酸丁酯 ‧Butyl acetate

<表面活性劑> <Surfactant>

F-1：下述混合物(重量平均分子量(Mw)=14000) F-1: The following mixture (weight average molecular weight (Mw) = 14000)

[化學式24]

Figure 106104991-A0305-02-0114-25
[Chemical formula 24]
Figure 106104991-A0305-02-0114-25

<聚合抑制劑> <Polymerization inhibitor>

對甲氧基苯酚 P-Methoxyphenol

<顏料分散物的製備> <Preparation of Pigment Dispersion>

首先，藉由攪拌機(IKA COMPANY製造EUROSTAR)，將含氮化鈦粒子、分散劑及有機溶劑混合15分鐘，由此獲得了分散物。接著，對所獲得之分散物，使用Shinmaru Enterprises Corporation製造的NPM-Pilot，在下述條件下進行分散處理，由此獲得了顏料分散物。另外，以分散劑相對於含氮化鈦粒子之比例(D/P)成為第2表~第5表的各實施例及比較例所示之比例之方式進行添加。 First, the titanium nitride-containing particles, the dispersant, and the organic solvent were mixed with a stirrer (EUROSTAR manufactured by IKA COMPANY) for 15 minutes to obtain a dispersion. Next, using NPM-Pilot manufactured by Shinmaru Enterprises Corporation, the obtained dispersion was subjected to dispersion treatment under the following conditions, thereby obtaining a pigment dispersion. In addition, the ratio (D/P) of the dispersant to the titanium nitride-containing particles was added so that the ratio (D/P) of the respective Examples and Comparative Examples in Table 2 to Table 5 was shown.

(分散條件) (Dispersion condition)

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

‧微珠填充率：65體積% ‧Microbead 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 ‧The 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℃ ‧Processing 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

<組成物的製備> <Preparation of composition>

接著，混合、攪拌上述顏料分散液、黏結樹脂、聚合性化合物、表面活性劑、聚合抑制劑及有機溶劑，獲得了下述第2表~第5表所示之實施例及比較例的各組成物。 Next, the above-mentioned pigment dispersion, binder resin, polymerizable compound, surfactant, polymerization inhibitor, and organic solvent were mixed and stirred to obtain the respective compositions of Examples and Comparative Examples shown in Tables 2 to 5 below Things.

將實施例及比較例的各組成物中包含之各成分的含量(質量%)示於第2表~第5表。 The content (mass %) of each component contained in each composition of the Examples and Comparative Examples is shown in Table 2 to Table 5.

<組成物中的水分量的測定> <Measurement of the amount of moisture in the composition>

關於實施例及比較例的各組成物的水分量，藉由以Karl Fischer方法作為測定原理之MKV-710(商品名、KYOTO ELECTRONICS INDUSTRY CO.,LTD.製造)進行了測定。將結果示於第2表~第5表。 The water content of each composition of the Examples and Comparative Examples was measured by MKV-710 (trade name, manufactured by KYOTO ELECTRONICS INDUSTRY CO., LTD.) using the Karl Fischer method as the measurement principle. The results are shown in Table 2 to Table 5.

〔評價試驗〕 [Evaluation test]

對實施例及比較例的各組成物進行了以下的各評價試驗。 The following evaluation tests were performed on the respective compositions of the examples and comparative examples.

<調液時的粒徑變動> <Variation of particle size during liquid preparation>

製備藉由PGMEA將實施例及比較例的各組成物稀釋成100倍之試驗溶液，將所獲得之試驗溶液在45℃的環境下保存3天。並且，藉由粒度分佈測定裝置(MicrotracBEL Corp.製造、產品名“Nanotrac UPA-150EX”)測定了保存前後的試驗溶液中包含之含氮化鈦粒子的平均粒徑(D90)。依據保存前後的試驗溶液的平均粒徑(D90)的值，藉由以下基準評價了調液時的粒徑變動。 A test solution in which each composition of the Examples and Comparative Examples was diluted 100 times by PGMEA was prepared, and the obtained test solution was stored in an environment at 45°C for 3 days. In addition, the average particle diameter (D90) of the titanium nitride-containing particles contained in the test solution before and after storage was measured with a particle size distribution measuring device (manufactured by MicrotracBEL Corp., product name "Nanotrac UPA-150EX"). Based on the value of the average particle diameter (D90) of the test solution before and after storage, the variation of the particle diameter at the time of liquid adjustment was evaluated by the following criteria.

A：0

Figure 106104991-A0305-02-0116-39
(保存後的含氮化鈦粒子的D90)-(保存前的含氮化鈦粒子的D90)<0.010μm A: 0
Figure 106104991-A0305-02-0116-39
(D90 of titanium nitride particles after storage)-(D90 of titanium nitride particles before storage) <0.010μm

B：0.010μm

Figure 106104991-A0305-02-0116-40
(保存後的含氮化鈦粒子的D90)-(保存前的含氮化鈦粒子的D90)<0.015μm B: 0.010μm
Figure 106104991-A0305-02-0116-40
(D90 of titanium nitride particles after storage)-(D90 of titanium nitride particles before storage) <0.015μm

C：0.015μm

Figure 106104991-A0305-02-0116-41
(保存後的含氮化鈦粒子的D90)-(保存前的含氮化鈦粒子的D90)<0.020μm C: 0.015μm
Figure 106104991-A0305-02-0116-41
(D90 of titanium nitride-containing particles after storage)-(D90 of titanium nitride-containing particles before storage) <0.020μm

D：0.020μm

Figure 106104991-A0305-02-0116-42
(保存後的含氮化鈦粒子的D90)-(保存前的含氮化鈦粒子的D90) D: 0.020μm
Figure 106104991-A0305-02-0116-42
(D90 of titanium nitride particles after storage)-(D90 of titanium nitride particles before storage)

<顆粒的個數> <Number of particles>

製備藉由PGMEA將上述組成物稀釋成500倍之試料溶液，藉由流動式顆粒圖像分析儀(商品名“FPIA”、Malvern Instruments Ltd製造)測定了該試料溶液10ml中包含之10μm以上的尺寸的含氮化鈦粒子的個數。 A sample solution in which the above composition was diluted 500 times by PGMEA was prepared, and the size of 10 μm or more contained in 10 ml of the sample solution was measured by a flow-type particle image analyzer (trade name "FPIA", manufactured by Malvern Instruments Ltd) The number of particles containing titanium nitride.

<過濾性> <Filterability>

對實施例及比較例的各組成物，藉由利用膠囊過濾器DFA(NIHON PALL LTD.製造、尼龍孔徑0.45μm、2inch)之過濾，評價了過濾性。關於過濾，在0.05Mpa的加壓條件下將組成物16kg進行送液來進行。過濾性依據以下的基準進行了評價。 The respective compositions of the Examples and Comparative Examples were filtered with a capsule filter DFA (manufactured by NIHON PALL LTD., nylon pore size 0.45 μm, 2 inches) to evaluate the filterability. The filtration was performed by feeding 16 kg of the composition under pressure of 0.05 MPa. The filterability was evaluated based on the following criteria.

A：能夠對16kg全部進行過濾。 A: It can filter all 16kg.

B：在10kg以上且小於16kg中發生了過濾堵塞。 B: Filter clogging occurred in 10 kg or more and less than 16 kg.

C：在5kg以上且小於10kg中發生了過濾堵塞。 C: Filter clogging occurred in 5 kg or more and less than 10 kg.

D：在小於5kg中發生了過濾堵塞。 D: Filter clogging occurred in less than 5 kg.

<經時黏度穩定性> <Stability of viscosity over time>

將實施例及比較例的各組成物在23℃下保存10天之後，在7℃下保存了90天。之後，利用E型黏度計(Toki Sangyo Co.,Ltd製造、商品名“R85形黏度計”)，在轉速10rpm、23℃的條件下測定了保存前後的各組成物的黏度。並且，計算出〔(組成物的保存後的黏度)-(組成物的保存前的黏度)/(組成物的保存前的黏度)〕×100的值(%)。評價基準如下。 After storing each composition of Examples and Comparative Examples at 23°C for 10 days, they were stored at 7°C for 90 days. After that, the viscosity of each composition before and after storage was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd, trade name "R85 viscometer") under the conditions of a rotation speed of 10 rpm and 23°C. In addition, the value (%) of [(viscosity of the composition after storage)-(viscosity of the composition before storage)/(viscosity of the composition before storage)]×100 was calculated. The evaluation criteria are as follows.

A：±3%以內 A: Within ±3%

B：超過±3%且±5%以內 B: more than ±3% and within ±5%

C：超過±5%且±10%以內 C: more than ±5% and within ±10%

D：超過±10% D: more than ±10%

<電極的防腐性> <Corrosion resistance of electrode>

將實施例及比較例的各組成物用作感光性樹脂組成物，以各組成物的塗佈膜的乾燥膜厚成為0.7μm之方式，在形成於矽晶圓的表面之電極圖案(銅)上進行了旋轉塗佈。塗佈之後保持10分鐘，接著，利用100℃的加熱板，對塗佈有各組成物之矽晶圓進行120秒的加熱處理(預烘)，從而形成了塗佈膜。 The compositions of the Examples and Comparative Examples were used as the photosensitive resin composition, and the electrode pattern (copper) formed on the surface of the silicon wafer so that the dry film thickness of the coating film of each composition became 0.7 μm Spin coating was performed on it. After coating, it was kept for 10 minutes, and then the silicon wafer coated with each composition was heated (pre-baked) for 120 seconds using a hot plate at 100°C to form a coating film.

接著，使用i射線步進曝光装置FPA-3000i5+(Canon Inc.製造)，通過20μm四方的具有島狀圖案之圖案遮罩，以365nm的波長及500mJ/cm2的曝光量對塗佈膜進行了曝光。 Next, using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), the coated film was applied to the coating film with a 20μm square pattern mask with an island pattern with a wavelength of 365nm and an exposure of 500mJ/cm 2 exposure.

另外，實施例及比較例的各組成物係曝光部硬化之負型感光性樹脂組成物。 In addition, each composition of the Examples and Comparative Examples is a negative photosensitive resin composition in which the exposed portion is cured.

之後，將形成有已曝光之塗佈膜之矽晶圓載置於旋轉噴淋顯影機(DW-30型、Chemitronics Co.,Ltd.製造)的水平轉台上，利用CD-2000(FUJIFILM Electronic Materials Co.,Ltd.製造、有機鹼溶液顯影液)，在23℃下進行了60秒的旋覆浸沒顯影。 After that, the silicon wafer with the exposed coating film is placed on the horizontal turntable of a rotary spray developing machine (Model DW-30, manufactured by Chemitronics Co., Ltd.), using CD-2000 (FUJIFILM Electronic Materials Co.) ., Ltd., organic alkali solution developer), the spin immersion development was performed at 23°C for 60 seconds.

接著，將旋覆浸沒顯影後的矽晶圓，以真空吸盤方式固定於上述水平轉台，藉由旋轉装置以轉速50rpm旋轉矽晶圓，並且從其旋轉中心的上方，從噴出噴嘴以噴淋狀供給純水來進行了沖洗處理。之後，對矽晶圓進行噴霧乾燥，從而製作了具有邊框狀的黑矩陣之晶圓。 Then, the silicon wafer after spin-on immersion development is fixed on the above-mentioned horizontal turntable by a vacuum chuck, and the silicon wafer is rotated at a speed of 50 rpm by a rotating device, and from the top of its rotation center, the spray nozzle is sprayed Pure water was supplied to perform the rinsing treatment. After that, the silicon wafer was spray-dried to produce a frame-shaped black matrix wafer.

將具有邊框狀的黑矩陣之晶圓在溫度25℃、濕度65%RH的環境下保存3個月之後，對形成於晶圓上之300個電極墊，藉由光學顯微鏡(Olympus Corporation製、商品名“LEXT OLS4500”)觀察了電極圖案的銹的產生部位數。電極的防腐性依據銹的產生部位數，依據以下基準進行了評價。 After storing a wafer with a frame-shaped black matrix in an environment with a temperature of 25°C and a humidity of 65%RH for 3 months, the 300 electrode pads formed on the wafer were subjected to an optical microscope (manufactured by Olympus Corporation, product (Name "LEXT OLS4500") The number of rust occurrence sites in the electrode pattern was observed. The corrosion resistance of the electrode was evaluated based on the number of sites where rust was generated and based on the following criteria.

A：銹的產生部位為0~5個 A: 0 to 5 rust sites

B：銹的產生部位為6~10個 B: There are 6 to 10 rust sites

C：銹的產生部位為11~20個 C: 11 to 20 rust sites

D：銹的產生部位為21個以上 D: There are 21 or more rust sites

<圖案形成性(顯影殘渣)> <Pattern Formability (Development Residue)>

與上述的“電極的防腐性”相同地，對所獲得之具有邊框狀黑矩陣之晶圓，針對未曝光部，利用掃描型電子顯微鏡(Hitachi High-Technologies Corporation.製造、商品名“SU8010”)，以2万倍的倍率觀察了基板表面，對在所獲得之觀察圖像中確認到之粒子狀的殘渣的個數進行計數，依據以下 基準進行了圖案形成性(顯影殘渣)的評價。 In the same way as the above-mentioned "electrode corrosion resistance", a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, brand name "SU8010") was used for the unexposed part of the obtained wafer with a frame-shaped black matrix. , Observed the surface of the substrate at a magnification of 20,000 times, and counted the number of particulate residues confirmed in the observation image obtained, based on the following Based on the criteria, the pattern formation (development residue) was evaluated.

A：未曝光部中觀察不到顯影殘渣 A: No development residue is observed in the unexposed part

B：未曝光部中粒子狀的顯影殘渣為1~49個 B: Particulate development residues in the unexposed area are 1 to 49

C：未曝光部中粒子狀的顯影殘渣為50~100個 C: There are 50-100 pieces of particulate development residue in the unexposed area

D：未曝光部中粒子狀的顯影殘渣為101個以上 D: There are 101 or more particulate development residues in the unexposed area

<再加工性> <Reworkability>

將與用於電極的防腐性評價之晶圓相同的具有邊框狀黑矩陣之晶圓，在85℃的TMAH(四甲基氫氧化銨)25%水溶液中浸漬5小時，接著，在室溫下，在2L的DIW(純水)槽中浸漬2分鐘，藉此進行了沖洗處理。對所獲得之沖洗處理之後的晶圓，藉由光學顯微鏡(Olympus Corporation製造、商品名“LEXT OLS4500”)觀察了邊框狀黑矩陣的去除狀態，依據以下的評價基準評價了再加工性。 A wafer with a frame-shaped black matrix identical to the wafer used for the evaluation of the corrosion resistance of the electrode was immersed in a 25% aqueous solution of TMAH (tetramethylammonium hydroxide) at 85°C for 5 hours, and then at room temperature , Immersed in a 2L DIW (pure water) tank for 2 minutes to rinse. With respect to the obtained wafer after the rinse treatment, the removal state of the frame-shaped black matrix was observed with an optical microscope (manufactured by Olympus Corporation, trade name "LEXT OLS4500"), and the reworkability was evaluated based on the following evaluation criteria.

A：未觀察到圖案 A: No pattern is observed

B：在圖案形成區域的5%以下中可觀察到粒子狀去除殘渣 B: Particulate removal residue can be observed in 5% or less of the pattern formation area

C：在圖案形成面積的超過5%且10%以下中可觀察到粒子狀的去除殘渣 C: Particulate removal residues can be observed in more than 5% and 10% or less of the pattern formation area

D：在圖案形成面積的超過10%中可觀察到粒子狀去除殘渣，或者可觀察到圖案或圖案的一部分 D: Particulate removal residue can be observed in more than 10% of the pattern formation area, or the pattern or part of the pattern can be observed

<耐濕試驗時的外觀> <Appearance during humidity test>

將與用於電極的防腐性評價之晶圓相同地具有邊框狀黑矩陣之晶圓，在90℃、濕度85%RH的環境下曝光1000小時。針對曝光後的晶圓，藉由 光學顯微鏡(Olympus Corporation製造、商品名“LEXT OLS4500”)觀察黑矩陣的外觀變化，並依據以下評價基準評價了耐濕試驗時的外觀。 A wafer with a frame-shaped black matrix like the wafer used for the evaluation of the corrosion resistance of the electrode was exposed for 1000 hours in an environment of 90°C and a humidity of 85%RH. For the exposed wafer, by The appearance change of the black matrix was observed by an optical microscope (manufactured by Olympus Corporation, trade name "LEXT OLS4500"), and the appearance during the humidity resistance test was evaluated based on the following evaluation criteria.

A：在耐濕試驗前後未觀察到差異，或耐濕試驗之後可觀察到凹凸差10nm以下的表面龜裂。 A: No difference was observed before and after the humidity resistance test, or surface cracks with a difference of 10 nm or less of unevenness were observed after the humidity resistance test.

B：在耐濕試驗之後可觀察到凹凸差超過10nm且50nm以下的表面龜裂。 B: After the humidity resistance test, surface cracks with a difference in unevenness exceeding 10 nm and 50 nm or less were observed.

C在：耐濕試驗之後可觀察到凹凸差超過50nm且100nm以下的表面龜裂。 C: After the humidity resistance test, surface cracks with unevenness exceeding 50 nm and 100 nm or less can be observed.

D：在耐濕試驗之後可觀察到凹凸差超過100nm的表面龜裂。 D: After the humidity resistance test, surface cracks with a difference in unevenness exceeding 100 nm were observed.

<針孔> <pinhole>

用於電極的防腐性評價之晶圓的製作中，代替矽晶圓使用了10cm方形的玻璃基板，未使用具有島狀圖案之圖案遮罩，在玻璃基板的整面形成了塗佈膜，除此以外，與上述的用於電極的防腐性評價之晶圓的製作相同地，在玻璃基板的一個整面形成了使用實施例及比較例的各組成物來獲得之硬化膜。 In the production of wafers used for the evaluation of the corrosion resistance of electrodes, a 10 cm square glass substrate was used instead of a silicon wafer, and a pattern mask with an island pattern was not used. A coating film was formed on the entire surface of the glass substrate. In addition, in the same way as the production of the wafer for evaluation of the corrosion resistance of the electrode described above, a cured film obtained by using the respective compositions of the Examples and Comparative Examples was formed on one entire surface of the glass substrate.

在玻璃基板的設置有硬化膜之一側的相反側設置光源，從設置有光源之一側藉由目視觀察硬化膜的外觀，對玻璃基板中存在之針孔(直徑10μm以上)的個數進行計數。藉由以下基準進行了評價。 A light source was installed on the side of the glass substrate opposite to the side where the cured film was provided, and the appearance of the cured film was visually observed from the side where the light source was provided, and the number of pinholes (10μm or more in diameter) in the glass substrate count. The evaluation was conducted based on the following criteria.

A：針孔為0~1個 A: 0 to 1 pinholes

B：針孔為2~10個 B: 2~10 pinholes

C：針孔為11~20個 C: 11 to 20 pinholes

D：針孔為21個以上 D: 21 or more pinholes

<分光(遮光性)> <Light splitting (shading property)>

在厚度0.7mm、10cm方形的玻璃板(EagleXG，Corning)上，以膜厚成為1.0μm之轉速進行旋轉，藉此塗佈實施例及比較例的各組成物來形成了塗佈膜。接著，利用加熱板，在100℃下，對塗佈膜進行2分鐘的加熱處理來獲得了乾燥膜。對所獲得之乾燥膜，藉由分光光度計U-4100(Hitachi High-Technologies Corporation.製造)，測定了OD(光學濃度)。依據波長400~1200nm中的最低OD，藉由以下基準評價了分光(遮光性)。 On a square glass plate (EagleXG, Corning) with a thickness of 0.7 mm and 10 cm, it was rotated at a rotation speed at which the film thickness was 1.0 μm, thereby coating the respective compositions of the Examples and Comparative Examples to form a coating film. Next, using a hot plate, the coating film was heated at 100°C for 2 minutes to obtain a dry film. With respect to the obtained dry film, the OD (optical density) was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Based on the lowest OD in the wavelength range of 400 to 1200 nm, the spectroscopy (shading property) was evaluated based on the following criteria.

AA：最低OD>4.2 AA: Minimum OD>4.2

A：4.2

Figure 106104991-A0305-02-0121-43
最低OD>4.0 A: 4.2
Figure 106104991-A0305-02-0121-43
Minimum OD>4.0

B：4.0

Figure 106104991-A0305-02-0121-44
最低OD>3.7 B: 4.0
Figure 106104991-A0305-02-0121-44
Minimum OD>3.7

C：3.7

Figure 106104991-A0305-02-0121-45
最低OD>3.5 C: 3.7
Figure 106104991-A0305-02-0121-45
Minimum OD>3.5

D：3.5

Figure 106104991-A0305-02-0121-47
最低OD D: 3.5
Figure 106104991-A0305-02-0121-47
Minimum OD

將以上的各評價結果示於表2~表5。表2~表5中，“分散劑/Fe(含有比例)”表示相對於Fe原子的含量之分散劑的含有比例〔(組成物中的分散劑的含量(質量%))/(組成物中的Fe原子的含量(質量%))〕。並且，“聚合性化合物/Fe(含有比例)”表示相對於上述Fe原子的含量之上述聚合性化合物的含有比例〔(組成物中的聚合性化合物的含量(質量%))/(組成物中的Fe原子的含量(質量%))〕。 The above evaluation results are shown in Tables 2 to 5. In Tables 2 to 5, "dispersant/Fe (content ratio)" means the content ratio of the dispersant relative to the content of Fe atoms [(the content of the dispersant in the composition (mass%))/(in the composition The content of Fe atoms (mass %))]. In addition, "polymerizable compound/Fe (content ratio)" means the content ratio of the polymerizable compound relative to the content of the Fe atom [(the content of the polymerizable compound in the composition (mass%))/(in the composition The content of Fe atoms (mass %))].

Figure 106104991-A0305-02-0122-26
Figure 106104991-A0305-02-0122-26
Figure 106104991-A0305-02-0123-27
Figure 106104991-A0305-02-0123-27

Figure 106104991-A0305-02-0124-28
Figure 106104991-A0305-02-0124-28
Figure 106104991-A0305-02-0125-29
Figure 106104991-A0305-02-0125-29

Figure 106104991-A0305-02-0126-30
Figure 106104991-A0305-02-0126-30
Figure 106104991-A0305-02-0127-31
Figure 106104991-A0305-02-0127-31

Figure 106104991-A0305-02-0128-32
Figure 106104991-A0305-02-0128-32
Figure 106104991-A0305-02-0129-33
Figure 106104991-A0305-02-0129-33

如表2~表5所示，藉由含氮化鈦粒子中的Fe原子的含量在超過0.001質量%且小於0.4質量%的範圍內，能夠製作圖案形成性及電極的防腐性優異之硬化膜(實施例)。 As shown in Tables 2 to 5, when the content of Fe atoms in the titanium nitride-containing particles is within the range of more than 0.001% by mass and less than 0.4% by mass, a cured film with excellent pattern formation and electrode corrosion resistance can be produced (Example).

相對於此，示出了若含氮化鈦粒子中的Fe原子的含量為0.001質量%以下，則圖案形成性較差(比較例1及比較例3)。 In contrast, it was shown that if the content of Fe atoms in the titanium nitride-containing particles is 0.001% by mass or less, the pattern formability is poor (Comparative Example 1 and Comparative Example 3).

並且，示出了若含氮化鈦粒子中的Fe原子的含量為0.4質量%以上，則電極的防腐性較差(比較例2)。 In addition, it was shown that when the content of Fe atoms in the titanium nitride-containing particles is 0.4% by mass or more, the corrosion resistance of the electrode is poor (Comparative Example 2).

實施例1中，將用於製備組成物之聚合性化合物M1變更為聚合性化合物U15HA(Shin-Nakamura Chemical Co.,Ltd製、商品名“U15HA”)，除此以外，相同地製備組成物並進行了各評價。評價結果，得知獲得了與實施例1相同的結果。 In Example 1, the polymerizable compound M1 used to prepare the composition was changed to the polymerizable compound U15HA (manufactured by Shin-Nakamura Chemical Co., Ltd, trade name "U15HA"), except that the composition was prepared in the same manner. Each evaluation was performed. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.

實施例1中，將用於製備組成物之聚合性化合物M1變更為Cardo monomer(Osaka Gas Chemicals Co.,Ltd.製造、商品名“OGSOL”)，除此以外，相同地製備組成物並進行了各評價。評價結果，得知圖案形成性的評價結果為“A”，除此以外，獲得了與實施例1相同的結果。 In Example 1, the polymerizable compound M1 used to prepare the composition was changed to Cardo monomer (manufactured by Osaka Gas Chemicals Co., Ltd., trade name "OGSOL"), except that the composition was prepared in the same manner and carried out Each evaluation. As a result of the evaluation, it was found that the evaluation result of the pattern formability was "A", and the same results as in Example 1 were obtained except for this.

實施例1中，不使用聚合抑制劑而製備了組成物，除此以外，相同地製備組成物並進行了各評價。評價結果，得知獲得了與實施例1相同的結果。 In Example 1, a composition was prepared without using a polymerization inhibitor. Except for this, the composition was prepared in the same manner and each evaluation was performed. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.

實施例1中，不使用表面活性劑F-1而製備了組成物，除此以外，相同地製備組成物並進行了各評價。評價結果，得知獲得了與實施例1相同的結果。 In Example 1, the composition was prepared without using the surfactant F-1, and except for that, the composition was prepared in the same manner and each evaluation was performed. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.

<炭黑分散物(CB分散液)的製備> <Preparation of Carbon Black Dispersion (CB Dispersion)>

上述顏料分散物的製備中，代替含氮化鈦粒子，使用了炭黑(商品名“Color Black S170”、Degussa-Hüls AG製造、平均一次粒徑17nm、BET比表面積200m2/g、藉由氣黑方式製造之炭黑)，除此以外，相同地製備顏料分散物，並獲得了炭黑分散物。 In the preparation of the above-mentioned pigment dispersion, instead of titanium nitride particles, carbon black (trade name "Color Black S170", manufactured by Degussa-Hüls AG, average primary particle size 17nm, BET specific surface area 200m 2 /g, Carbon black manufactured by the gas black method), except for this, the pigment dispersion was prepared in the same manner, and the carbon black dispersion was obtained.

實施例1的組成物的製備中，代替以組成物中含有16質量%的含氮化鈦粒子TiN-1之方式添加之顏料分散液，使用了含有含氮化鈦粒子TiN-1之顏料分散液與上述CB分散液的混合物〔組成物中的含氮化鈦粒子TiN-1：組成物的炭黑=4：1(質量比)(組成物中的含氮化鈦粒子TiN-1與炭黑的合計含量為16質量%)〕，除此以外，相同地製備組成物並進行了各評價。評價結果，得知獲得了與實施例1相同的遮光性。 In the preparation of the composition of Example 1, instead of the pigment dispersion liquid added so that the composition contained 16% by mass of titanium nitride particles TiN-1, a pigment dispersion containing titanium nitride particles TiN-1 was used The mixture of liquid and the above-mentioned CB dispersion liquid [TiN-1 containing titanium nitride particles in the composition: carbon black of the composition = 4:1 (mass ratio) (TiN-1 containing titanium nitride particles in the composition and carbon The total content of black is 16% by mass)] Except for this, the composition was prepared in the same manner and each evaluation was performed. As a result of the evaluation, it was found that the same light shielding properties as in Example 1 were obtained.

<有彩色顏料分散物(PY分散液)的製備> <Preparation of colored pigment dispersion (PY dispersion)>

上述顏料分散物的製備中，代替含氮化鈦粒子，使用了顏料黃150(Hangzhou Star-up Pigment Co.,Ltd.製造、商品名6150顏料黄5GN)，除此以外，藉由相同的方法製作分散物，從而獲得了有彩色顏料分散物(PY分散液)。 In the preparation of the above pigment dispersion, instead of the titanium nitride-containing particles, Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., trade name 6150 Pigment Yellow 5GN) was used, except for this, the same method A dispersion was prepared, thereby obtaining a colored pigment dispersion (PY dispersion).

實施例1的組成物的製備中，代替以組成物中含有16質量%的含氮化鈦粒子TiN-1之方式添加之顏料分散液，使用了含有含氮化鈦粒子TiN-1之顏料分散液與上述PY分散液的混合物〔組成物中的含氮化鈦粒子TiN-1：組成中的顏料黃150=5：1(質量比)(組成物中的含氮化鈦粒子TiN-1與顏料黃150的合計含量為16質量%)〕，除此以外，相同地製備組成物 並進行了各評價。評價結果，得知獲得了與實施例1相同的遮光性，而且獲得了黑色較濃之膜。 In the preparation of the composition of Example 1, instead of the pigment dispersion liquid added so that the composition contained 16% by mass of titanium nitride particles TiN-1, a pigment dispersion containing titanium nitride particles TiN-1 was used The mixture of liquid and the above-mentioned PY dispersion liquid [TiN-1 containing titanium nitride particles in the composition: Pigment Yellow 150=5:1 (mass ratio) in the composition (TiN-1 containing titanium nitride particles in the composition and TiN-1 The total content of Pigment Yellow 150 is 16% by mass)], other than that, the composition was prepared in the same manner And conducted various evaluations. As a result of the evaluation, it was found that the same light-shielding properties as in Example 1 were obtained, and a darker black film was obtained.

Claims (18)

一種組成物，其含有包含Fe原子之含氮化鈦粒子以及聚合起始劑，前述含氮化鈦粒子中的前述Fe原子的含量超過0.001質量%且小於0.4質量%。 A composition containing titanium nitride-containing particles containing Fe atoms and a polymerization initiator, wherein the content of the Fe atoms in the titanium nitride-containing particles exceeds 0.001% by mass and less than 0.4% by mass. 如申請專利範圍第1項所述之組成物，其中將CuKα射線作為X射線源時，前述含氮化鈦粒子的源自(200)面之峰的衍射角2θ超過42.6°且43.5°以下。 The composition described in the first item of the patent application, wherein when CuKα rays are used as an X-ray source, the diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles exceeds 42.6° and 43.5° or less. 如申請專利範圍第1項或第2項所述之組成物，其中前述含氮化鈦粒子還含有Si原子，前述含氮化鈦粒子中的前述Si原子的含量超過0.002質量%且小於0.3質量%。 The composition described in item 1 or item 2 of the scope of patent application, wherein the aforementioned titanium nitride-containing particles further contain Si atoms, and the content of the aforementioned Si atoms in the aforementioned titanium nitride-containing particles exceeds 0.002% by mass and less than 0.3% by mass %. 如申請專利範圍第1項或第2項所述之組成物，其中藉由以下粒子數測定方法求出之10μm以上的尺寸的前述含氮化鈦粒子的數量為100個以下，粒子數測定方法：製備藉由丙二醇單甲醚乙酸酯將前述組成物稀釋為500倍之試料溶液，藉由流動式顆粒圖像分析儀測定前述試料溶液10ml中包含之10μm以上的尺寸的前述含氮化鈦粒子的數量。 The composition described in item 1 or item 2 of the scope of patent application, in which the number of the aforementioned titanium nitride-containing particles with a size of 10 μm or more determined by the following particle number measurement method is 100 or less, the particle number measurement method : Prepare a sample solution prepared by diluting the aforementioned composition 500 times with propylene glycol monomethyl ether acetate, and measure the aforementioned titanium nitride-containing titanium nitride containing a size of 10 μm or more contained in 10 ml of the aforementioned sample solution by a flow-type particle image analyzer The number of particles. 如申請專利範圍第1項或第2項所述之組成物，其還含有2種以上的有機溶劑。 Such as the composition described in item 1 or item 2 of the scope of patent application, it also contains two or more organic solvents. 如申請專利範圍第1項或第2項所述之組成物，其還含有黏結樹脂。 Such as the composition described in item 1 or item 2 of the scope of patent application, it also contains a binding resin. 如申請專利範圍第1項或第2項所述之組成物，其還含有聚合性化合物。 The composition described in item 1 or item 2 of the scope of patent application further contains a polymerizable compound. 如申請專利範圍第1項或第2項所述之組成物，其中前述組成物中的固體含量為10~40質量%。 The composition described in item 1 or item 2 of the scope of patent application, wherein the solid content in the aforementioned composition is 10-40% by mass. 如申請專利範圍第1項或第2項所述之組成物，其中前述含氮化鈦粒子的含量相對於前述組成物的總固體含量，為20~70質量%。 The composition described in item 1 or item 2 of the scope of patent application, wherein the content of the titanium nitride-containing particles is 20 to 70% by mass relative to the total solid content of the composition. 如申請專利範圍第1項或第2項所述之組成物，其還含有水，前述水的含量相對於前述組成物總質量，為0.1~1質量%。 The composition described in item 1 or item 2 of the scope of the patent application further contains water, and the content of the aforementioned water is 0.1-1% by mass relative to the total mass of the aforementioned composition. 如申請專利範圍第1項或第2項所述之組成物，其還含有分散劑，前述分散劑具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組之至少1種結構。 The composition described in item 1 or item 2 of the scope of patent application, which further contains a dispersant, and the aforementioned dispersant is selected from the group consisting of polymethyl acrylate, polymethyl methacrylate and cyclic or chain polyester At least one structure of the group. 如申請專利範圍第11項所述之組成物，其中前述分散劑相對於前述含氮化鈦粒子之含有比例以質量比計為0.05~0.30。 The composition described in item 11 of the scope of patent application, wherein the content ratio of the dispersant to the titanium nitride-containing particles is 0.05 to 0.30 in terms of mass ratio. 一種組成物的製造方法，其為申請專利範圍第1項至第12項中任一項所述之組成物的製造方法，其包含藉由熱等離子體法獲得前述含氮化鈦粒子之製程。 A method for manufacturing a composition is a method for manufacturing the composition described in any one of items 1 to 12 in the scope of the patent application, which includes a process of obtaining the aforementioned titanium nitride-containing particles by a thermal plasma method. 一種硬化膜，其使用申請專利範圍第1項至第12項中任一項所述之組成物來獲得。 A cured film obtained by using the composition described in any one of items 1 to 12 of the scope of patent application. 一種濾色器，其具有申請專利範圍第14項所述之硬化膜。 A color filter having the cured film described in item 14 of the scope of patent application. 一種遮光膜，其具有申請專利範圍第14項所述之硬化膜。 A light-shielding film having the cured film described in item 14 of the scope of patent application. 一種固態攝影元件，其具有申請專利範圍第14項所述之硬化膜。 A solid-state imaging element having the cured film described in item 14 of the scope of patent application. 一種圖像顯示裝置，其具有申請專利範圍第14項所述之硬化膜。 An image display device having the cured film described in item 14 of the scope of patent application.
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