TW202112910A - Organic film and manufacturing method therefor, composition, laminate, and semiconductor device - Google Patents

Organic film and manufacturing method therefor, composition, laminate, and semiconductor device Download PDF

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TW202112910A
TW202112910A TW109132315A TW109132315A TW202112910A TW 202112910 A TW202112910 A TW 202112910A TW 109132315 A TW109132315 A TW 109132315A TW 109132315 A TW109132315 A TW 109132315A TW 202112910 A TW202112910 A TW 202112910A
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室祐継
松井高史
青島俊栄
嶋田和人
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日商富士軟片股份有限公司
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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    • C08G73/22—Polybenzoxazoles
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H—ELECTRICITY
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
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Abstract

The purpose of the present invention is to provide: an organic film having excellent solvent resistance and a manufacturing method therefor; a composition used for forming said organic film; a laminate including said organic film; and a semiconductor device including said organic film or said laminate. Provided are: an organic film satisfying at least one expression selected from the group consisting of expression (1) and expression (2) and a manufacturing method therefor; a composition used for forming said organic film; a laminate including said organic film; and a semiconductor device including said organic film or said laminate, wherein expression (1) is I/A ≥ 2.5 and expression (2) is I/B ≥ 0.5 (in expression (1) or expression (2), I is the maximum relative intensity value when small-angle neutron scattering measurement is performed on said organic film within the q range of 0.030 Å<SP>-1</SP> to 0.065 Å<SP>-1</SP>, A is the minimum relative intensity value within the q range of 0.200 Å<SP>-1</SP> to 0.300 Å<SP>-1</SP>, and B is the minimum relative intensity value within the q range of 0.017 Å-1 to 0.025 Å-1).

Description

有機膜及其製造方法、組成物、積層體及半導體器件Organic film and its manufacturing method, composition, laminated body and semiconductor device

本發明係有關一種有機膜及其製造方法、組成物、積層體及半導體器件。The present invention relates to an organic film and its manufacturing method, composition, laminate and semiconductor device.

有機膜能夠使用塗佈法、印刷法、轉印法等容易的成膜方法來形成。又，藉由調節膜中所包含之各成分（例如，樹脂等）的結構、膜中所包含之各成分的含量等，還能夠容易地設計膜的斷裂伸長率等力學特性、膜的絕緣性等物理特性等。因此，近年來，作為用於各種用途的器件之膜，在各領域中使用了包含有機材料之有機膜。 例如，關於包含聚醯亞胺、苯并㗁唑等樹脂之有機膜，由於耐熱性及絕緣性優異，因此適用於各種用途。作為上述用途，並無特別限定，但是若以安裝用半導體器件為例，則可舉出作為絕緣膜、密封材料的材料或保護膜的用途。又，還可用作撓性基板的基底膜、覆蓋層等。 關於這種有機膜，越來越期待在產業上的應用發展。The organic film can be formed using an easy film forming method such as a coating method, a printing method, and a transfer method. In addition, by adjusting the structure of each component (for example, resin, etc.) contained in the film, the content of each component contained in the film, etc., it is also possible to easily design the mechanical properties such as the elongation at break of the film, and the insulating properties of the film. And other physical properties. Therefore, in recent years, as a film for devices for various purposes, organic films containing organic materials have been used in various fields. For example, regarding organic films containing resins such as polyimide and benzoxazole, they are suitable for various applications because they are excellent in heat resistance and insulating properties. The use is not particularly limited, but if a semiconductor device for mounting is taken as an example, the use as a material of an insulating film, a sealing material, or a protective film can be exemplified. In addition, it can also be used as a base film, a cover layer, etc. of a flexible substrate. With regard to this kind of organic film, more and more applications and development in industry are expected.

例如，在專利文獻1中記載了一種感光性樹脂組成物，其特徵為，係含有作為感光性聚醯亞胺前驅物之（A）成分和特定的結構的（B）成分。For example, Patent Document 1 describes a photosensitive resin composition characterized by containing the (A) component as a photosensitive polyimide precursor and the (B) component of a specific structure.

[專利文獻1]國際公開第2017/033833號[Patent Document 1] International Publication No. 2017/033833

隨著在各領域中使用有機膜，期望提供一種耐溶劑性優異的有機膜。As organic films are used in various fields, it is desired to provide an organic film having excellent solvent resistance.

本發明的目的為提供一種耐溶劑性優異的有機膜及其製造方法、供於上述有機膜的形成之組成物、包含上述有機膜之積層體、以及包含上述有機膜或上述積層體之半導體器件。The object of the present invention is to provide an organic film excellent in solvent resistance and a method of manufacturing the same, a composition for forming the organic film, a laminate including the organic film, and a semiconductor device including the organic film or the laminate .

以下，記載本發明的代表性實施態樣的例子。 ＜1＞一種有機膜，其係滿足選自包括下述式（1）及下述式（2）之群組中之至少1個式， 式（1）：I/A≧2.5 式（2）：I/B≧0.5 在上述式（1）或上述式（2）中，I係以q在0.030Å-1 ～0.065Å-1 的範圍內對上述有機膜進行中子小角度散射測量時的相對強度值的最大值，A係以q在0.200Å-1 ～0.300Å-1 的範圍內對上述有機膜進行中子小角度散射測量時的相對強度值的最小值，B係以q在0.017Å-1 ～0.025Å-1 的範圍內對上述有機膜進行中子小角度散射測量時的相對強度值的最小值，q為在小角度散射中由下述式（Q）定義之值， 式（Q）：q=（4π/λ）sinθ 式（Q）中，λ為中子束的波長，θ為中子束的散射角。 ＜2＞如＜1＞所述之有機膜，其係包含選自包括聚醯亞胺、聚苯并㗁唑、聚醯亞胺前驅物及聚苯并㗁唑前驅物之群組中之至少1種樹脂之組成物的塗佈膜的硬化物。 ＜3＞如＜2＞所述之有機膜，其中上述組成物包含光敏劑。 ＜4＞一種組成物，其係供於＜1＞至＜3＞之任一項所述之有機膜的形成。 ＜5＞一種積層體，其係包含2層以上的＜1＞至＜3＞之任一項所述之有機膜，且在任一上述有機膜彼此之間包含金屬層。 ＜6＞一種半導體器件，其係包含＜1＞至＜3＞之任一項所述之有機膜或＜5＞所述之積層體。 ＜7＞一種有機膜之製造方法，其係製造＜1＞至＜3＞之任一項所述之有機膜，前述製造方法包括將組成物適用於基板而形成膜之膜形成步驟。 ＜8＞如＜7＞所述之有機膜之製造方法，其係包括在50～450℃的條件下對上述膜進行加熱之步驟。 [發明效果]Hereinafter, examples of representative embodiments of the present invention will be described. <1> An organic film that satisfies at least one formula selected from the group consisting of the following formula (1) and the following formula (2), formula (1): I/A≧2.5 formula (2) ：I/B≧0.5 In the above formula (1) or the above formula (2), I is based on q in the range of 0.030Å -1 ～0.065Å -1 for the measurement of small-angle neutron scattering of the organic film The maximum value of the relative intensity value, A is the minimum value of the relative intensity value when q is in the range of 0.200Å -1 ～0.300Å -1 for the above organic film when neutron small-angle scattering is measured, and B is q at 0.017 The minimum value of the relative intensity value of the organic film in the range of Å -1 ～0.025Å -1 when the neutron small-angle scattering measurement is performed on the organic film, q is the value defined by the following formula (Q) in the small-angle scattering, (Q): q=(4π/λ)sinθ In formula (Q), λ is the wavelength of the neutron beam, and θ is the scattering angle of the neutron beam. <2> The organic film as described in <1>, which contains at least one selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor A cured product of a coating film made of a resin composition. <3> The organic film according to <2>, wherein the composition includes a photosensitizer. <4> A composition for forming the organic film described in any one of <1> to <3>. <5> A laminated body including two or more layers of the organic film described in any one of <1> to <3>, and including a metal layer between any of the organic films. <6> A semiconductor device comprising the organic film described in any one of <1> to <3> or the laminated body described in <5>. <7> A method of manufacturing an organic film, which manufactures the organic film described in any one of <1> to <3>, the above-mentioned manufacturing method including a film forming step of applying the composition to a substrate to form a film. <8> The method of manufacturing an organic film as described in <7>, which includes the step of heating the film at 50 to 450°C. [Effects of the invention]

依本發明，提供一種耐溶劑性優異的有機膜及其製造方法、供於上述有機膜的形成之組成物、包含上述有機膜之積層體、以及包含上述有機膜或上述積層體之半導體器件。According to the present invention, an organic film excellent in solvent resistance and a method of manufacturing the same, a composition for forming the organic film, a laminate including the organic film, and a semiconductor device including the organic film or the laminate are provided.

以下，對本發明的主要實施形態進行說明。然而，本發明並不限於明示之實施形態。 在本說明書中，使用“～”的標記表示之數值範圍係指將記載於“～”的前後之數值分別作為下限值及上限值而包含之範圍。 在本說明書中，“步驟”這一用語不僅包括獨立之步驟，只要能夠實現該步驟的所期待的作用，則還包括無法與其他步驟明確地進行區分之步驟。 在本說明書中的基團（原子團）的標記中，未標有經取代及未經取代之標記包含不具有取代基之基團（原子團），並且還包含具有取代基之基團（原子團）。例如，“烷基”不僅包含不具有取代基之烷基（未經取代之烷基），而且還包含具有取代基之烷基（經取代之烷基）。 在本說明書中，所謂“曝光”，只要無特別說明，則不僅包含使用了光之曝光，還包含使用了電子束、離子束等粒子束之曝光。又，作為曝光中所使用之光，可舉出以水銀燈的明線光譜、準分子雷射為代表之遠紫外線、極紫外線（EUV光）、X射線、電子束等光化射線或放射線。 在本說明書中，“（甲基）丙烯酸酯”係指“丙烯酸酯”及“丙烯酸甲酯”這兩者或任一者，“（甲基）丙烯酸”係指“丙烯酸”及“甲基丙烯酸”兩者或任一者，“（甲基）丙烯醯基”係指“丙烯醯基”及“甲基丙烯醯基”這兩者或任一者。 在本說明書中，結構式中的Me表示甲基，Et表示乙基，Bu表示丁基，Ph表示苯基。 在本說明書中，總固體成分係指從組成物的所有成分中去除溶劑之成分的總質量。又，在本說明書中，固體成分濃度係指除溶劑以外的其他成分的質量相對於組成物的總質量的百分比。 在本說明書中，關於重量平均分子量（Mw）及數平均分子量（Mn），只要無特別敘述，則按照凝膠滲透層析術（GPC測量），作為聚苯乙烯換算值來定義。在本說明書中，重量平均分子量（Mw）及數平均分子量（Mn）例如能夠藉由使用HLC-8220GPC（TOSOH CORPORATION製造），且使用保護管柱HZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000、TSKgel Super HZ2000（TOSOH CORPORATION製造）作為管柱來求出。關於該等的分子量，只要無特別敘述，則作為溶析液而使用THF（四氫呋喃）來進行測量。又，關於GPC測量中的檢測，只要無特別敘述，則使用UV射線（紫外線）的波長為254nm的檢測器。 在本說明書中，關於構成積層體之各層的位置關係，在記載為“上”或“下”時，只要在所關注之複數個層中作為基準之層的上側或下側具有其他層即可。亦即，可以在作為基準之層與上述其他層之間進一步插入第3層、要素，作為基準之層與上述其他層無需接觸。又，只要無特別說明，則將相對於基材堆積層之方向稱為“上”，或者在具有組成物層之情形下，將從基材朝向組成物層之方向稱為“上”，並將其相反方向稱為“下”。另外，在本說明書中，這種上下方向的設定係為了方便，在實際態樣中，本說明書中的“上”方向有時還與鉛直向上方向不同。 在本說明書中，只要無特別記載，則組成物作為組成物中所包含之各成分而可以包含對應於該成分之2種以上的化合物。又，只要無特別記載，則組成物中的各成分的含量係指對應於該成分之所有化合物的總含量。 在本說明書中，只要無特別敘述，則溫度為23℃，氣壓為101,325Pa（1個大氣壓）。 在本說明書中，較佳的態樣的組合為更佳的態樣。Hereinafter, the main embodiment of the present invention will be described. However, the present invention is not limited to the explicit embodiment. In this specification, the numerical range indicated by the mark "～" refers to the range that includes the numerical values described before and after "～" as the lower limit and the upper limit, respectively. In this specification, the term "step" not only includes independent steps, but also includes steps that cannot be clearly distinguished from other steps as long as they can achieve the expected effect of the step. In the label of the group (atomic group) in this specification, the label that is not labeled substituted and unsubstituted includes a group (atomic group) without a substituent, and also includes a group (atomic group) with a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl). In this specification, the term "exposure", unless otherwise specified, includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. In addition, as the light used in the exposure, there can be exemplified actinic rays or radiation such as extreme ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, electron beams, etc. represented by the bright-ray spectrum of mercury lamps and excimer lasers. In this specification, "(meth)acrylate" refers to both or either of "acrylate" and "methyl acrylate", and "(meth)acrylic acid" refers to "acrylic acid" and "methacrylic acid". "Both or either, "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of the components with the solvent removed from all the components of the composition. In addition, in this specification, the solid content concentration means the percentage of the mass of other components other than the solvent to the total mass of the composition. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC measurement) unless otherwise stated. In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be used, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION), and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000 , TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) are calculated as the column. As for these molecular weights, unless otherwise stated, they are measured using THF (tetrahydrofuran) as an eluent. In addition, as for the detection in the GPC measurement, unless otherwise stated, a detector with a wavelength of UV rays (ultraviolet rays) of 254 nm is used. In this specification, regarding the positional relationship of the layers constituting the laminate, when it is described as "upper" or "lower", it is only necessary to have another layer on the upper or lower side of the reference layer among the plurality of layers of interest. . In other words, a third layer or element may be further inserted between the reference layer and the other layer described above, and the layer used as the reference layer does not need to be in contact with the other layer described above. In addition, unless otherwise specified, the direction of the deposited layer with respect to the substrate is called "up", or in the case of a composition layer, the direction from the substrate to the composition layer is called "up", and The opposite direction is called "down". In addition, in this specification, the setting of this vertical direction is for convenience, and in actual conditions, the "up" direction in this specification is sometimes different from the vertical upward direction. In this specification, unless otherwise stated, the composition may include two or more compounds corresponding to the components as each component contained in the composition. In addition, unless otherwise stated, the content of each component in the composition means the total content of all compounds corresponding to the component. In this specification, unless otherwise stated, the temperature is 23°C and the pressure is 101,325 Pa (1 atmosphere). In this specification, a combination of better aspects is a better aspect.

（有機膜） 本發明的有機膜滿足選自包括下述式（1）及下述式（2）之群組中之至少1個式。 式（1）：I/A≧2.5 式（2）：I/B≧0.5 在上述式（1）或上述式（2）中，I係以q在0.030Å-1 ～0.065Å-1 的範圍內對上述有機膜進行中子小角度散射測量時的相對強度值的最大值，A係以q在0.200Å-1 ～0.300Å-1 的範圍內對上述有機膜進行中子小角度散射測量時的相對強度值的最小值，B係以q在0.017Å-1 ～0.025Å-1 的範圍內對上述有機膜進行中子小角度散射測量時的相對強度值的最小值，q為在小角度散射中由下述式（Q）定義之值。 式（Q）：q=（4π/λ）sinθ 式（Q）中，λ為中子束的波長（Å），θ為中子束的散射角（°）。 又，1Å為0.1nm。(Organic film) The organic film of the present invention satisfies at least one formula selected from the group consisting of the following formula (1) and the following formula (2). Formula (1): I/A≧2.5 Formula (2): I/B≧0.5 In the above formula (1) or the above formula (2), I is based on q in the range of 0.030Å -1 to 0.065Å -1 The maximum value of the relative intensity value during the small-angle neutron scattering measurement of the above-mentioned organic film, A is when q is in the range of 0.200Å -1 ～0.300Å -1 for the above-mentioned organic film when the small-angle neutron scattering measurement is performed The minimum value of the relative intensity value of B is the minimum value of the relative intensity value when q is in the range of 0.017Å -1 ～0.025Å -1 for the small-angle neutron scattering measurement of the above organic film, and q is the minimum value of the relative intensity value at a small angle. The value of scattering is defined by the following formula (Q). Formula (Q): q=(4π/λ)sinθ In formula (Q), λ is the wavelength of the neutron beam (Å), and θ is the scattering angle of the neutron beam (°). In addition, 1Å is 0.1 nm.

本發明的有機膜的耐溶劑性優異。 依本發明，例如，認為提供一種對二甲基亞碸（DMSO）、N-甲基吡咯啶酮（NMP）等極性溶劑之溶解性得到抑制之、耐溶劑性優異的有機膜。 關於耐溶劑性優異的有機膜，例如，即使在用於當使用時、保管時或製造時等有可能與溶劑接觸之產品等之情形、將包含溶劑之組成物進一步適用於有機膜上之情形、對形成於有機膜上之膜進行溶劑顯影之情形等情形下，有機膜在溶劑中的溶解亦得到抑制，因此認為是有用的。The organic film of the present invention is excellent in solvent resistance. According to the present invention, for example, it is considered to provide an organic film having excellent solvent resistance with suppressed solubility to polar solvents such as dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP). Regarding organic films with excellent solvent resistance, for example, even when used in products that may come into contact with solvents during use, storage, or manufacturing, and when a solvent-containing composition is further applied to an organic film , In the case of solvent development of the film formed on the organic film, the dissolution of the organic film in the solvent is also suppressed, so it is considered useful.

本發明的有機膜的耐溶劑性優異的理由尚不清楚，但是推測如下。 滿足式（1）係指相對於以q在0.200Å-1 ～0.300Å-1 的範圍內進行中子小角度散射測量時的相對強度值的最小值A，以q在0.030Å-1 ～0.065Å-1 的範圍內進行中子小角度散射測量時的相對強度值的最大值I為2.5倍以上。 滿足式（2）係指相對於以q在0.017Å-1 ～0.025Å-1 的範圍內進行中子小角度散射測量時的相對強度值的最小值B，上述最大值I為0.5倍以上。 本發明人等進行深入研究之結果，發現q在0.030Å-1 ～0.065Å-1 的範圍內的最大值I係上述最小值A的2.5倍以上、或是上述最小值B的0.5倍以上、或者滿足該兩者之有機膜中，耐溶劑性優異。 在此，認為以q在0.030Å-1 ～0.065Å-1 的範圍內進行中子小角度散射測量時的相對強度值的最大值I係依據有機膜中所包含之樹脂等成分的排列狀態、締合狀態等而發生變化之值。 作為一例，在有機膜包含聚醯亞胺樹脂等具有環結構（例如，雜環結構）之樹脂之情形下，例如，若在有機膜中包含較多的積層上述環結構彼此之狀態，則上述最大值I增大，認為滿足選自包括上述式（1）及式（2）之群組中之至少1個。 又，例如，若在有機膜中包含較多的積層上述環結構彼此之狀態，則樹脂彼此的相互作用強、或有機膜中的樹脂的密度存在偏差，認為由於在有機膜中存在樹脂密度高的部分等的理由，有機膜的耐溶劑性優異。 依據以上見解等，本發明人等發現藉由有機膜滿足選自包括式（1）及式（2）之群組中之至少1個式，可獲得耐溶劑性優異的有機膜，從而完成了本發明。 又，由於上述樹脂彼此的相互作用等的理由，認為藉由有機膜滿足選自包括式（1）及式（2）之群組中之至少1個式，容易獲得斷裂伸長率大，且機械特性優異的有機膜。The reason why the organic film of the present invention is excellent in solvent resistance is not clear, but it is estimated as follows. Satisfying formula (1) refers to the minimum value A of the relative intensity value when q is in the range of 0.200Å -1 ～0.300Å -1 for neutron small-angle scattering measurement, and q is between 0.030Å -1 ～0.065 The maximum value I of the relative intensity value when the neutron small-angle scattering measurement is performed in the range of Å -1 is 2.5 times or more. Satisfying formula (2) means that the minimum value B of the relative intensity value when the neutron small-angle scattering measurement is performed with q in the range of 0.017Å -1 ～0.025Å -1, the above-mentioned maximum value I is 0.5 times or more. As a result of intensive research, the inventors found that the maximum value I of q in the range of 0.030Å -1 to 0.065Å -1 is 2.5 times or more of the above-mentioned minimum value A, or 0.5 times or more of the above-mentioned minimum value B, Or an organic film that satisfies both of these has excellent solvent resistance. Here, it is considered that the maximum value I of the relative intensity value when the neutron small-angle scattering measurement is performed with q in the range of 0.030Å -1 to 0.065Å -1 is based on the arrangement state of the resin and other components contained in the organic film, A value that changes due to the state of association, etc. As an example, in the case where the organic film contains a resin having a ring structure (for example, a heterocyclic structure) such as polyimide resin, for example, if the organic film contains a large number of layers of the above-mentioned ring structures, the above The maximum value I increases, and it is considered that it satisfies at least one selected from the group consisting of the above-mentioned formula (1) and formula (2). Also, for example, if the organic film contains a large number of layers of the above-mentioned ring structures, the interaction between the resins is strong or the density of the resin in the organic film varies. It is considered that the resin density in the organic film is high. The organic film has excellent solvent resistance. Based on the above findings, the inventors found that by satisfying at least one formula selected from the group consisting of formula (1) and formula (2), an organic film with excellent solvent resistance can be obtained, thereby completing this invention. In addition, due to the interaction of the above-mentioned resins and other reasons, it is considered that when the organic film satisfies at least one formula selected from the group consisting of formula (1) and formula (2), it is easy to obtain a large elongation at break and a mechanical Organic film with excellent properties.

＜中子小角度散射（SANS）測量＞ 中子小角度散射測量藉由後述實施例中所記載之方法來實施。 又，本發明中的相對強度值係指對測量用試樣進行中子小角度散射測量，並從所測量之計數減去使用未放入試樣之空白單元（例如，未填充測量用試樣之空樣品架）測量之背景計數而得之值。＜Small-angle neutron scattering (SANS) measurement＞ The small-angle neutron scattering measurement is carried out by the method described in the following examples. In addition, the relative intensity value in the present invention refers to the measurement of small-angle neutron scattering of the sample for measurement, and the use of blank cells not placed in the sample (for example, unfilled measurement sample) is subtracted from the measured count. The empty sample rack) is the value obtained from the background count of the measurement.

本發明的有機膜只要滿足選自包括式（1）及式（2）之群組中之至少1個式即可，但是滿足式（1）及式（2）這兩者亦為較佳的態樣之一。The organic film of the present invention only needs to satisfy at least one formula selected from the group consisting of formula (1) and formula (2), but it is also preferable to satisfy both formula (1) and formula (2) One aspect.

〔I/A〕 式（1）中所記載之I/A的值為2.5以上，2.6以上為較佳，2.7以上為更佳，2.8以上為進一步較佳，3.0以上為進一步較佳，4.0以上為特佳，4.2以上為最佳。 上述I/A的值的上限並無特別限定，但是例如只要係100以下即可。 認為上述I/A的值例如依據有機膜中所包含之樹脂的結構、有機膜中所包含之樹脂以外的成分的結構、具有特定的結構之成分的組合、有機膜中所包含之各成分的含量、有機膜之製造方法（例如，硬化方法）、有機膜的膜厚、形成有有機膜之基材的種類等來確定。〔I/A〕 The value of I/A described in the formula (1) is 2.5 or more, preferably 2.6 or more, more preferably 2.7 or more, more preferably 2.8 or more, more preferably 3.0 or more, particularly preferably 4.0 or more, 4.2 The above is the best. The upper limit of the value of the aforementioned I/A is not particularly limited, but it may be, for example, 100 or less. It is considered that the above-mentioned I/A value is based on, for example, the structure of the resin contained in the organic film, the structure of components other than the resin contained in the organic film, the combination of components having a specific structure, and the composition of each component contained in the organic film. The content, the manufacturing method of the organic film (for example, the curing method), the film thickness of the organic film, the type of substrate on which the organic film is formed, etc. are determined.

〔I/B〕 式（2）中所記載之I/B的值為0.5以上，0.55以上為較佳，0.60以上為更佳，0.65以上為進一步較佳，0.70以上為進一步較佳，0.80以上為特佳，0.84以上為最佳。 上述I/B的值的上限並無特別限定，但是例如只要係20以下即可。 認為上述I/B的值例如依據有機膜中所包含之樹脂的結構、有機膜中所包含之樹脂以外的成分的結構、具有特定的結構之成分的組合、有機膜中所包含之各成分的含量、有機膜之製造方法（例如，硬化方法）、有機膜的膜厚、形成有有機膜之基材的種類等來確定。〔I/B〕 The value of I/B described in the formula (2) is 0.5 or more, 0.55 or more is preferable, 0.60 or more is more preferable, 0.65 or more is more preferable, 0.70 or more is more preferable, 0.80 or more is particularly preferable, 0.84 The above is the best. The upper limit of the value of the aforementioned I/B is not particularly limited, but it may be, for example, 20 or less. It is considered that the value of the above-mentioned I/B is based on, for example, the structure of the resin contained in the organic film, the structure of components other than the resin contained in the organic film, the combination of components having a specific structure, and the composition of each component contained in the organic film. The content, the manufacturing method of the organic film (for example, the curing method), the film thickness of the organic film, the type of substrate on which the organic film is formed, etc. are determined.

〔最大值I〕 關於q在0.030Å-1 ～0.065Å-1 的範圍內的最大值I，只要以q在0.030Å-1 ～0.065Å-1 的範圍內存在即可，但是以q在0.032Å-1 ～0.065Å-1 的範圍內存在上述最大值I為較佳，以q在0.034Å-1 ～0.065Å-1 的範圍內存在上述最大值I為更佳。[Maximum value I] Regarding the maximum value I of q in the range of 0.030Å -1 to 0.065Å -1 , it is sufficient if q exists in the range of 0.030Å -1 to 0.065Å -1 , but q is in the range of 0.032 range Å -1 ~ 0.065Å -1 is preferred in the memory the maximum value I, in q memory is more preferably in the range of the maximum value I 0.034Å -1 ~ 0.065Å -1's.

〔I12 /A、I13 /A〕 在本發明的有機膜滿足式（1）之情形下，進一步滿足下述式（1-2）為較佳，進一步滿足下述式（1-3）為更佳。 式（1-2）：I12 /A≧2.5 式（1-3）：I13 /A≧2.5 在上述式（1-2）或上述式（1-3）中，I12 為以q在0.035Å-1 ～0.065Å-1 的範圍內對上述有機膜進行中子小角度散射測量時的相對強度值的最大值，I13 為以q在0.040Å-1 ～0.065Å-1 的範圍內對上述有機膜進行中子小角度散射測量時的相對強度值的最大值，A及q與式（1）中的A及q含義相同。[I 12 /A, I 13 /A] When the organic film of the present invention satisfies the formula (1), it is preferable to further satisfy the following formula (1-2), and further satisfy the following formula (1-3) For better. Formula (1-2): I 12 /A≧2.5 Formula (1-3): I 13 /A≧2.5 In the above formula (1-2) or the above formula (1-3), I 12 is expressed by q In the range of 0.035Å -1 ～0.065Å -1 , the relative intensity value of the above organic film during small-angle neutron scattering measurement is the maximum value, and I 13 is the range of 0.040Å -1 ～0.065Å -1 with q The maximum value of the relative intensity value when the neutron small-angle scattering measurement is performed on the organic film, A and q have the same meaning as A and q in formula (1).

〔I22 /B、I23 /B〕 在本發明的有機膜滿足式（2）之情形下，進一步滿足下述式（2-2）為較佳，進一步滿足下述式（2-3）為更佳。 式（2-2）：I22 /B≧0.5 式（2-3）：I23 /B≧0.5 在上述式（1-2）或上述式（1-3）中，I22 為以q在0.035Å-1 ～0.065Å-1 的範圍內對上述有機膜進行中子小角度散射測量時的相對強度值的最大值，I23 為以q在0.040Å-1 ～0.065Å-1 的範圍內對上述有機膜進行中子小角度散射測量時的相對強度值的最大值，B及q與式（2）中的A及q含義相同。[I 22 /B, I 23 /B] When the organic film of the present invention satisfies the formula (2), it is preferable to further satisfy the following formula (2-2), and further satisfy the following formula (2-3) For better. Formula (2-2): I 22 /B≧0.5 Formula (2-3): I 23 /B≧0.5 In the above formula (1-2) or the above formula (1-3), I 22 is expressed by q In the range of 0.035Å -1 ～0.065Å -1 , the maximum value of the relative intensity value of the above organic film during small-angle neutron scattering measurement, I 23 is the range of 0.040Å -1 ～0.065Å -1 with q The maximum value of the relative intensity value when the neutron small-angle scattering measurement is performed on the organic film, B and q have the same meaning as A and q in formula (2).

＜成分＞ 本發明的有機膜只要係包含有機成分之膜即可，但是包含樹脂之膜為較佳。 作為樹脂，具有環結構之樹脂為較佳，具有雜環結構之樹脂為更佳。 又，作為樹脂，並無特別限定，可舉出聚醯亞胺、聚醯亞胺前驅物、聚苯并㗁唑、聚苯并㗁唑前驅物、聚矽氧烷、包含矽氧烷結構之樹脂、環氧樹脂、（甲基）丙烯酸樹脂、聚乙烯、聚丙烯等烯烴系樹脂、聚氯乙烯、聚乙烯酯等乙烯基系樹脂、聚胺酯、聚脲、聚醯胺、聚碳酸酯、聚酯、聚苯乙烯、聚縮醛、纖維素樹脂、酚樹脂、聚四氟乙烯等氟系樹脂等。 該等中，就有機膜的絕緣性、耐熱性的觀點而言，有機膜包含聚醯亞胺或聚苯并㗁唑作為上述樹脂為較佳，包含聚醯亞胺為更佳。 上述聚醯亞胺或聚苯并㗁唑係後述組成物中所包含之聚醯亞胺、後述組成物中所包含之聚苯并㗁唑、由後述組成物中所包含之聚醯亞胺前驅物形成之聚醯亞胺、或由後述組成物中所包含之聚苯并㗁唑前驅物形成之聚苯并㗁唑為較佳。 有機膜還可以包含後述之組成物中所包含之各成分作為其他成分。又，例如，在將有機膜形成為硬化物等、使組成物中的各成分中的至少1種成分進行反應而獲得有機膜之情形下，後述之組成物中所包含之各成分（例如，光聚合起始劑、聚合性化合物等）可以以反應後的形態（例如，感光後的光聚合起始劑、聚合後的聚合性化合物等）包含。＜Ingredients＞ The organic film of the present invention may be a film containing organic components, but a film containing resin is preferred. As the resin, a resin having a ring structure is preferable, and a resin having a heterocyclic structure is more preferable. In addition, the resin is not particularly limited, and examples include polyimines, polyimide precursors, polybenzoxazole, polybenzoxazole precursors, polysiloxanes, and those containing a silicone structure. Resin, epoxy resin, (meth)acrylic resin, olefin resin such as polyethylene and polypropylene, vinyl resin such as polyvinyl chloride and polyvinyl ester, polyurethane, polyurea, polyamide, polycarbonate, poly Fluorine resins such as ester, polystyrene, polyacetal, cellulose resin, phenol resin, polytetrafluoroethylene, etc. Among them, from the viewpoint of the insulation and heat resistance of the organic film, the organic film preferably contains polyimide or polybenzoxazole as the above-mentioned resin, and more preferably contains polyimide. The above-mentioned polyimide or polybenzoxazole is the polyimide contained in the composition described later, the polybenzoxazole contained in the composition described later, and the polyimide precursor contained in the composition described later Preferably, the polyimide is formed from a compound or the polybenzoxazole formed from the polybenzoxazole precursor contained in the composition described later. The organic film may also contain each component contained in the composition described later as other components. Also, for example, when an organic film is formed into a cured product, etc., and at least one of the components in the composition is reacted to obtain an organic film, each component contained in the composition described later (for example, A photopolymerization initiator, a polymerizable compound, etc.) can be contained in a form after the reaction (for example, a photopolymerization initiator after exposure, a polymerizable compound after polymerization, etc.).

有機膜係由組成物的塗佈膜形成之有機膜為較佳，組成物的塗佈膜的硬化物為更佳，包含上述樹脂之組成物的塗佈膜的硬化物為進一步較佳，包含選自包括聚醯亞胺、聚苯并㗁唑、聚醯亞胺前驅物及聚苯并㗁唑前驅物之群組中之至少1種樹脂（以下，還稱為“特定樹脂”。）之組成物的塗佈膜的硬化物為特佳。 以下，對組成物中所包含之各成分進行說明。The organic film is preferably an organic film formed from a coating film of the composition, and a cured product of the coating film of the composition is more preferred, and a cured product of the coating film of the composition containing the above resin is even more preferred, including At least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor (hereinafter, also referred to as "specific resin"). The cured product of the coating film of the composition is particularly preferred. Hereinafter, each component contained in the composition will be described.

＜樹脂＞ 作為組成物中所包含之樹脂，可舉出上述有機膜中所包含之樹脂、或在硬化物中成為上述有機膜中所包含之樹脂之樹脂等，但是選自包括聚醯亞胺、聚醯亞胺前驅物、聚苯并㗁唑及聚苯并㗁唑前驅物之群組中之至少1種為較佳，選自包括聚醯亞胺及聚醯亞胺前驅物之群組中之至少1種樹脂為更佳，聚醯亞胺前驅物為進一步較佳。＜Resin＞ Examples of the resin contained in the composition include the resin contained in the above-mentioned organic film, or the resin that becomes the resin contained in the above-mentioned organic film in the cured product, etc., but is selected from the group consisting of polyimide and polyamide. At least one of the group of imine precursors, polybenzoxazole and polybenzoxazole precursors is preferred, and at least one selected from the group consisting of polyimines and polyimines precursors One type of resin is more preferable, and the polyimide precursor is still more preferable.

〔聚醯亞胺前驅物〕 關於本發明中所使用之聚醯亞胺前驅物，其種類等並無特別限定，但是包含由下述式（2）表示之重複單元為較佳。 式（2） [化學式1]

Figure 02_image001
式（2）中，A1 及A2 分別獨立地表示氧原子或NH，R111 表示2價的有機基，R115 表示4價的有機基，R113 及R114 分別獨立地表示氫原子或1價的有機基。[Polyimine precursor] Regarding the polyimine precursor used in the present invention, the type and the like are not particularly limited, but it is preferable to include a repeating unit represented by the following formula (2). Formula (2) [Chemical Formula 1]
Figure 02_image001
In formula (2), A 1 and A 2 each independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, and R 113 and R 114 each independently represent a hydrogen atom or Monovalent organic group.

式（2）中的A1 及A2 分別獨立地表示氧原子或NH，氧原子為較佳。 式（2）中的R111 表示2價的有機基。作為2價的有機基，可例示包含直鏈或支鏈的脂肪族基、環狀的脂肪族基及芳香族基之基團，碳數2～20的直鏈或支鏈的脂肪族基、碳數6～20的環狀的脂肪族基、碳數6～20的芳香族基或由該等的組合組成之基團為較佳，包含碳數6～20的芳香族基之基團為更佳。作為本發明的特佳的實施形態，可例示由-Ar-L-Ar-表示之基團。其中，Ar分別獨立地為芳香族基，L為可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO2 -或NHCO-或由上述2個以上的組合組成之基團。該等的較佳的範圍如上述。 A 1 and A 2 in formula (2) each independently represent an oxygen atom or NH, and an oxygen atom is preferred. R 111 in the formula (2) represents a divalent organic group. Examples of divalent organic groups include groups including linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group with 6 to 20 carbons, an aromatic group with 6 to 20 carbons, or a group composed of a combination of these are preferred, and the group containing an aromatic group with 6 to 20 carbons is Better. As a particularly preferred embodiment of the present invention, a group represented by -Ar-L-Ar- can be exemplified. Wherein, Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group with 1 to 10 carbons, -O-, -CO-, -S-, -SO 2 -or NHCO- which may be substituted by fluorine atoms, or A group composed of a combination of two or more of the above. The preferable ranges of these are as described above.

R111 衍生自二胺為較佳。作為用於聚醯亞胺前驅物的製造之二胺，可舉出直鏈或支鏈的脂肪族、環狀的脂肪族或芳香族二胺等。二胺可以僅使用1種，亦可以使用2種以上。 具體而言，包含碳數2～20的直鏈或支鏈的脂肪族基、碳數6～20的環狀的脂肪族基、碳數6～20的芳香族基或由該等的組合組成之基團之二胺為較佳，包含由碳數6～20的芳香族基組成之基團之二胺為更佳。作為芳香族基的例子，可舉出下述。Preferably, R 111 is derived from diamine. As the diamine used in the production of the polyimide precursor, linear or branched aliphatic, cyclic aliphatic, or aromatic diamines can be cited. Only one type of diamine may be used, or two or more types may be used. Specifically, it contains a linear or branched aliphatic group with 2 to 20 carbons, a cyclic aliphatic group with 6 to 20 carbons, an aromatic group with 6 to 20 carbons, or a combination of these The diamine of the group is preferred, and the diamine containing a group composed of an aromatic group with 6 to 20 carbon atoms is more preferred. As an example of an aromatic group, the following can be mentioned.

[化學式2]

Figure 02_image003
式中，A係單鍵或選自可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-SO2 -、NHCO-或該等的組合中之基團為較佳，單鍵、選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-或-SO2 -中之基團為更佳，-CH2 -、-O-、-S-、-SO2 -、-C（CF3 ）2 -或-C（CH3 ）2 -為進一步較佳。[Chemical formula 2]
Figure 02_image003
In the formula, A is a single bond or is selected from aliphatic hydrocarbon groups with 1 to 10 carbons that can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO 2 -, NHCO- or The groups in these combinations are preferred, single bonds, selected from alkylene groups with 1 to 3 carbons which may be substituted by fluorine atoms, -O-, -C(=O)-, -S- or- The group in SO 2 -is more preferred, and -CH 2 -, -O-, -S-, -SO 2 -, -C(CF 3 ) 2 -or -C(CH 3 ) 2 -are further preferred .

作為二胺，具體而言，可舉出選自1,2-二胺基乙烷、1,2-二胺基丙烷、1,3-二胺基丙烷、1,4-二胺基丁烷及1,6-二胺基己烷；1,2-二胺基環戊烷或1,3-二胺基環戊烷、1,2-二胺基環己烷、1,3-二胺基環己烷或1,4-二胺基環己烷、1,2-雙（胺基甲基）環己烷、1,3-雙（胺基甲基）環己烷或1,4-雙（胺基甲基）環己烷、雙-（4-胺基環己基）甲烷、雙-（3-胺基環己基）甲烷、4,4’-二胺基-3,3’-二甲基環己基甲烷及異佛爾酮二胺；間苯二胺或對苯二胺、二胺基甲苯、4,4’-二胺基聯苯或3,3’-二胺基聯苯、4,4’-二胺基二苯醚、3,3-二胺基二苯醚、4,4’-二胺基二苯基甲烷及3,3’-二胺基二苯基甲烷、4,4’-二胺基二苯碸及3,3’-二胺基二苯碸、4,4’-二胺基二苯硫醚及3,3’-二胺基二苯硫醚、4,4’-二胺基二苯基酮或3,3’-二胺基二苯基酮、3,3’-二甲基-4,4’-二胺基聯苯、2,2’-二甲基-4,4’-二胺基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、2,2-雙（4-胺基苯基）丙烷、2,2-雙（4-胺基苯基）六氟丙烷、2,2-雙（3-羥基-4-胺基苯基）丙烷、2,2-雙（3-羥基-4-胺基苯基）六氟丙烷、2,2-雙（3-胺基-4-羥基苯基）丙烷、2,2-雙（3-胺基-4-羥基苯基）六氟丙烷、雙（3-胺基-4-羥基苯基）碸、雙（4-胺基-3-羥基苯基）碸、4,4’-二胺基對三聯苯、4,4’-雙（4-胺基苯氧基）聯苯、雙[4-（4-胺基苯氧基）苯基]碸、雙[4-（3-胺基苯氧基）苯基]碸、雙[4-（2-胺基苯氧基）苯基]碸、1,4-雙（4-胺基苯氧基）苯、9,10-雙（4-胺基苯基）蒽、3,3’-二甲基-4,4’-二胺基二苯碸、1,3-雙（4-胺基苯氧基）苯、1,3-雙（3-胺基苯氧基）苯、1,3-雙（4-胺基苯基）苯、3,3’-二乙基-4,4’-二胺基二苯基甲烷、3,3’-二甲基-4,4’-二胺基二苯基甲烷、4,4’-二胺基八氟聯苯、2,2-雙[4-（4-胺基苯氧基）苯基]丙烷、2,2-雙[4-（4-胺基苯氧基）苯基]六氟丙烷、9,9-雙（4-胺基苯基）-10-氫蒽、3,3’,4,4’-四胺基聯苯、3,3’,4,4’-四胺基二苯醚、1,4-二胺基蒽醌、1,5-二胺基蒽醌、3,3-二羥基-4,4’-二胺基聯苯、9,9’-雙（4-胺基苯基）茀、4,4’-二甲基-3,3’-二胺基二苯碸、3,3’,5,5’-四甲基-4,4’-二胺基二苯基甲烷、2,4-二胺基枯烯及2,5-二胺基枯烯、2,5-二甲基-對苯二胺、乙醯胍胺、2,3,5,6-四甲基-對苯二胺、2,4,6-三甲基-間苯二胺、雙（3-胺基丙基）四甲基二矽氧烷、2,7-二胺基茀、2,5-二胺基吡啶、1,2-雙（4-胺基苯基）乙烷、二胺基苯醯苯胺、二胺基苯甲酸的酯、1,5-二胺基萘、二胺基三氟甲苯、1,3-雙（4-胺基苯基）六氟丙烷、1,4-雙（4-胺基苯基）八氟丁烷、1,5-雙（4-胺基苯基）十氟戊烷、1,7-雙（4-胺基苯基）十四氟庚烷、2,2-雙[4-（3-胺基苯氧基）苯基]六氟丙烷、2,2-雙[4-（2-胺基苯氧基）苯基]六氟丙烷、2,2-雙[4-（4-胺基苯氧基）-3,5-二甲基苯基]六氟丙烷、2,2-雙[4-（4-胺基苯氧基）-3,5-雙（三氟甲基）苯基]六氟丙烷、對雙（4-胺基-2-三氟甲基苯氧基）苯、4,4’-雙（4-胺基-2-三氟甲基苯氧基）聯苯、4,4’-雙（4-胺基-3-三氟甲基苯氧基）聯苯、4,4’-雙（4-胺基-2-三氟甲基苯氧基）二苯碸、4,4’-雙（3-胺基-5-三氟甲基苯氧基）二苯碸、2,2-雙[4-（4-胺基-3-三氟甲基苯氧基）苯基]六氟丙烷、3,3’,5,5’-四甲基-4,4’-二胺基聯苯、4,4’-二胺基-2,2’-雙（三氟甲基）聯苯、2,2’,5,5’,6,6’-六氟聯甲苯胺及4,4’-二胺基四聯苯中之至少1種二胺。Specific examples of diamines include those selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, and 1,4-diaminobutane And 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diamine Cyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4- Bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-di Methylcyclohexylmethane and isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4 ,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4 ,4'-diaminodiphenyl ketone or 3,3'-diaminodiphenyl ketone, 3,3'-dimethyl-4,4'-diaminodiphenyl, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane , 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-amine Phenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis( 3-amino-4-hydroxyphenyl), bis(4-amino-3-hydroxyphenyl), 4,4'-diamino-p-terphenyl, 4,4'-bis(4-amine Phenyloxy) biphenyl, bis[4-(4-aminophenoxy)phenyl] chrysene, bis[4-(3-aminophenoxy) phenyl] chrysene, bis[4-(2 -Aminophenoxy) phenyl] chrysene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl -4,4'-diaminodiphenyl benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3- Bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diamino Diphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4 -Aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3 ,3',4,4'-tetraamino diphenyl ether, 1,4-diamino anthraquinone, 1,5-diamino anthraquinone, 3,3-dihydroxy-4,4'-diamine Biphenyl, 9,9'-bis(4-aminophenyl ) Fu, 4,4'-dimethyl-3,3'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane , 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetguanamine, 2,3,5,6-tetramethyl -P-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminopyridine, 2,5 -Diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminophenaniline, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotri Fluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl) ) Decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2 ,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl ]Hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2 -Trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3- Trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfide, 4,4'-bis(3-amino-5 -Trifluoromethylphenoxy) diphenyl sulfide, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5 ,5'-Tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5, At least one diamine among 5',6,6'-hexafluorotolidine and 4,4'-diaminotetraphenyl.

又，下述所示之二胺（DA-1）～（DA-18）亦為較佳。In addition, the diamines (DA-1) to (DA-18) shown below are also preferable.

[化學式3]

Figure 02_image005
[Chemical formula 3]
Figure 02_image005

[化學式4]

Figure 02_image007
[Chemical formula 4]
Figure 02_image007

又，還可舉出在主鏈上具有至少2個伸烷基二醇單元之二胺作為較佳的例子。更佳為在一分子中共計包含2個以上的乙二醇鏈、丙二醇鏈中的任一個或兩者之二胺，進一步較佳為不含芳香環之二胺。作為具體例，可舉出JEFFAMINE（註冊商標）KH-511、ED-600、ED-900、ED-2003、EDR-148、EDR-176、D-200、D-400、D-2000、D-4000（以上為商品名稱，HUNTSMAN公司製造）、1-（2-（2-（2-胺基丙氧基）乙氧基）丙氧基）丙烷-2-胺、1-（1-（1-（2-胺基丙氧基）丙烷-2-基）氧基）丙烷-2-胺等，但是並不限定於該等。 以下示出JEFFAMINE（註冊商標）KH-511、ED-600、ED-900、ED-2003、EDR-148、EDR-176的結構。In addition, a diamine having at least two alkylene glycol units in the main chain can also be cited as a preferable example. More preferably, a diamine containing two or more of ethylene glycol chains and propylene glycol chains or both in total is more preferable in one molecule, and a diamine containing no aromatic ring is still more preferable. As specific examples, JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D- 4000 (the above are the product names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1 -(2-Aminopropoxy)propan-2-yl)oxy)propane-2-amine and the like, but are not limited to these. The structures of JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.

[化學式5]

Figure 02_image009
[Chemical formula 5]
Figure 02_image009

上述中，x、y、z為平均值。In the above, x, y, and z are average values.

就所獲得之有機膜的柔軟性的觀點而言，R111 由-Ar-L-Ar-表示為較佳。其中，Ar分別獨立地為芳香族基，L為可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO2 -或NHCO-或由上述2個以上的組合組成之基團。Ar係伸苯基為較佳，L係可以被氟原子取代之碳數1或2的脂肪族烴基、-O-、-CO-、-S-或SO2 -為較佳。此處的脂肪族烴基係伸烷基為較佳。From the viewpoint of the flexibility of the obtained organic film, R 111 is preferably represented by -Ar-L-Ar-. Wherein, Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group with 1 to 10 carbons, -O-, -CO-, -S-, -SO 2 -or NHCO- which may be substituted by fluorine atoms, or A group composed of a combination of two or more of the above. Ar-based phenylene is preferred, and L-based aliphatic hydrocarbon group with 1 or 2 carbon atoms, -O-, -CO-, -S- or SO 2 -which may be substituted by fluorine atom is preferred. The aliphatic hydrocarbon-based alkylene group is preferred here.

又，就i射線透射率的觀點而言，R111 係由下述式（51）或式（61）表示之2價的有機基為較佳。尤其，就i射線透射率、容易獲得之觀點而言，由式（61）表示之2價的有機基為更佳。 式（51） [化學式6]

Figure 02_image011
式（51）中，R50 ～R57 分別獨立地為氫原子、氟原子或1價的有機基，R50 ～R57 中的至少1個為氟原子、甲基或三氟甲基。 作為R50 ～R57 的1價的有機基，可舉出碳數1～10（較佳為碳數1～6）的未經取代之烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式7]
Figure 02_image013
式（61）中，R58 及R59 分別獨立地為氟原子或三氟甲基。 作為賦予式（51）或（61）的結構之二胺化合物，可舉出2,2’-二甲基聯苯胺、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。該等可以使用1種或者可以組合使用2種以上。Moreover, from the viewpoint of i-ray transmittance, R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and easy availability, the divalent organic group represented by the formula (61) is more preferable. Formula (51) [Chemical Formula 6]
Figure 02_image011
In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, or a trifluoromethyl group. Examples of the monovalent organic group R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), and 1 to 10 carbons (preferably carbons 1～6) Fluorinated alkyl groups, etc. [Chemical formula 7]
Figure 02_image013
In the formula (61), R 58 and R 59 are each independently a fluorine atom or a trifluoromethyl group. As the diamine compound imparting the structure of formula (51) or (61), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-bis Aminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used 1 type or in combination of 2 or more types.

式（2）中的R115 表示4價的有機基。作為4價的有機基，包含芳香環之4價的有機基為較佳，由下述式（5）或式（6）表示之基團為更佳。 式（5） [化學式8]

Figure 02_image015
式（5）中，R112 係單鍵或選自可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO2 -及NHCO-以及該等的組合中之基團為較佳，單鍵或選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-CO-、-S-及-SO2 -中之基團為更佳，選自包括-CH2 -、-C（CF3 ）2 -、-C（CH3 ）2 -、-O-、-CO-、-S及SO2 -之群組中之2價的基團為進一步較佳。 R 115 in the formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. Formula (5) [Chemical Formula 8]
Figure 02_image015
In formula (5), R 112 is a single bond or is selected from aliphatic hydrocarbon groups with 1 to 10 carbons which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO 2 -and NHCO- and The groups in these combinations are preferred, single bonds or selected from alkylene groups with 1 to 3 carbons, -O-, -CO-, -S- and -SO 2 -which may be substituted by fluorine atoms The group is more preferably selected from the group including -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -O-, -CO-, -S and SO 2- Among them, the divalent group is more preferable.

式（6） [化學式9]

Figure 02_image017
Formula (6) [Chemical Formula 9]
Figure 02_image017

關於R115 ，具體而言，可舉出從四羧酸二酐去除酐基之後殘留之四羧酸殘基等。四羧酸二酐可以僅使用1種，亦可以使用2種以上。 四羧酸二酐由下述式（O）表示為較佳。 式（O） [化學式10]

Figure 02_image019
式（O）中，R115 表示4價的有機基。R115 的較佳的範圍與式（2）中的R115 含義相同，較佳的範圍亦相同。Specific examples of R 115 include a tetracarboxylic acid residue remaining after removing an anhydride group from tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably represented by the following formula (O). Formula (O) [Chemical Formula 10]
Figure 02_image019
In formula (O), R 115 represents a tetravalent organic group. The same meaning as R 115 (2) and in the preferred range of the formula R 115, preferred ranges are also the same.

作為四羧酸二酐的具體例，可舉出均苯四酸二酐（PMDA）、3,3’,4,4’-聯苯四羧酸二酐、3,3’,4,4’-二苯硫醚四羧酸二酐、3,3’,4,4’-二苯碸四羧酸二酐、3,3’,4,4’-二苯基酮四羧酸二酐、3,3’,4,4’-二苯基甲烷四羧酸二酐、2,2’,3,3’-二苯基甲烷四羧酸二酐、2,3,3’,4’-聯苯四羧酸二酐、2,3,3’,4’-二苯基酮四羧酸二酐、4,4’-氧二鄰苯二甲酸二酐、2,3,6,7-萘四羧酸二酐、1,4,5,7-萘四羧酸二酐、2,2-雙（3,4-二羧基苯基）丙烷二酐、2,2-雙（2,3-二羧基苯基）丙烷二酐、2,2-雙（3,4-二羧基苯基）六氟丙烷二酐、1,3-二苯基六氟丙烷-3,3,4,4-四羧酸二酐、1,4,5,6-萘四羧酸二酐、2,2’,3,3’-二苯基四羧酸二酐、3,4,9,10-苝四羧酸二酐、1,2,4,5-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、1,8,9,10-菲四羧酸二酐、1,1-雙（2,3-二羧基苯基）乙烷二酐、1,1-雙（3,4-二羧基苯基）乙烷二酐、1,2,3,4-苯四羧酸二酐以及該等的碳數1～6的烷基及碳數1～6的烷氧基衍生物。Specific examples of tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-Diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-Diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'- Biphenyl tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ketone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7- Naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3 -Dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4- Tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride Carboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetrahydride Carboxylic dianhydride and these C1-C6 alkyl groups and C1-C6 alkoxy derivatives.

又，還可舉出下述所述之四羧酸二酐（DAA-1）～（DAA-5）作為較佳例。 [化學式11]

Figure 02_image021
In addition, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described below can also be cited as preferred examples. [Chemical formula 11]
Figure 02_image021

R111 和R115 中的至少一方具有OH基亦為較佳。更具體而言，作為R111 ，可舉出雙胺基苯酚衍生物的殘基。It is also preferable that at least one of R 111 and R 115 has an OH group. More specifically, as R 111 , a residue of a diaminophenol derivative can be mentioned.

R113 及R114 分別獨立地表示氫原子或1價的有機基，R113 及R114 中的至少一方包含聚合性基為較佳，兩者包含聚合性基為更佳。作為聚合性基，係能夠藉由熱、自由基等的作用進行交聯反應之基團，且光自由基聚合性基為較佳。作為聚合性基的具體例，可舉出具有乙烯性不飽和鍵之基團、烷氧基甲基、羥甲基、醯氧基甲基、環氧基、氧雜環丁基、苯并㗁唑基、嵌段異氰酸酯基、羥甲基、胺基。作為聚醯亞胺前驅物等所具有之自由基聚合性基，具有乙烯性不飽和鍵之基團為較佳。 作為具有乙烯性不飽和鍵之基團，可舉出乙烯基、（甲基）丙烯醯基、由下述式（III）表示之基團等，由下述式（III）表示之基團為較佳。R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group. It is preferred that at least one of R 113 and R 114 contains a polymerizable group, and it is more preferred that both of them contain a polymerizable group. As the polymerizable group, a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and a photoradical polymerizable group is preferred. Specific examples of the polymerizable group include groups having ethylenically unsaturated bonds, alkoxymethyl, hydroxymethyl, oxymethyl, epoxy, oxetanyl, and benzo Azole group, blocked isocyanate group, methylol group, amine group. As the radical polymerizable group possessed by the polyimide precursor, etc., a group having an ethylenically unsaturated bond is preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)acryloyl group, a group represented by the following formula (III), etc. The group represented by the following formula (III) is Better.

[化學式12]

Figure 02_image023
[Chemical formula 12]
Figure 02_image023

式（III）中，R200 表示氫原子或甲基，氫原子為較佳。 式（III）中，R201 表示碳數2～12的伸烷基、-CH2 CH（OH）CH2 -或聚伸烷氧基。 作為R201 的較佳例，可舉出伸乙基、伸丙基、三亞甲基、四亞甲基、1,2-丁二基、1,3-丁二基、五亞甲基、六亞甲基、八亞甲基、十二亞甲基、-CH2 CH（OH）CH2 -、聚伸烷氧基，伸乙基、伸丙基、三亞甲基、-CH2 CH（OH）CH2 -、聚伸烷氧基為更佳，就在有機膜中容易滿足式（1）或式（2）之觀點而言，聚伸烷氧基為進一步較佳。 在本發明中，聚伸烷氧基係指2個以上的伸烷氧基直接鍵結而成之基團。聚伸烷氧基中所包含之複數個伸烷氧基中的伸烷基可以分別相同，亦可以分別不同。 在聚伸烷氧基包含伸烷基不同的複數種伸烷氧基之情形下，聚伸烷氧基中的伸烷氧基的排列可以為無規排列，亦可以為具有嵌段之排列，還可以為具有交替等的圖案之排列。 上述伸烷基的碳數（在伸烷基具有取代基之情形下，包含取代基的碳數）係2以上為較佳，2～10為更佳，2～6為更佳，2～5為進一步較佳，2～4為進一步較佳，2或3為特佳，2為最佳。 又，上述伸烷基可以具有取代基。作為較佳的取代基，可舉出烷基、芳基、鹵素原子等。 又，聚伸烷氧基中所包含之伸烷氧基的數量（聚伸烷氧基的重複數）係2～20個為較佳，2～10個為更佳，2～6個為進一步較佳。 作為聚伸烷氧基，就溶劑溶解性及耐溶劑性的觀點而言，聚乙烯氧基、聚丙烯氧基、聚三亞甲氧基、聚四亞甲氧基或複數個乙烯氧基與複數個丙烯氧基鍵結而成之基團為較佳，聚乙烯氧基或聚丙烯氧基為更佳，聚乙烯氧基為進一步較佳。在上述複數個乙烯氧基與複數個丙烯氧基鍵結而成之基團中，乙烯氧基和丙烯氧基可以無規排列，亦可以形成嵌段而排列，還可以排列成交替等的圖案狀。該等基團中的乙烯氧基等的重複數的較佳的態樣如上述。In the formula (III), R 200 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred. In the formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 -or a polyalkyleneoxy group. Preferred examples of R 201 include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene Methylene, octamethylene, dodecamethylene, -CH 2 CH(OH)CH 2 -, polyoxyethylene, ethylene, propylene, trimethylene, -CH 2 CH(OH ) CH 2 -and polyalkoxyl group are more preferable, and from the viewpoint of easily satisfying formula (1) or formula (2) in the organic film, polyalkoxyl group is more preferable. In the present invention, the polyalkoxyl group refers to a group formed by directly bonding two or more alkoxyl groups. The alkylene groups in the plural alkoxy groups contained in the polyalkoxy group may be the same or different. In the case where the polyalkoxyl group contains a plurality of alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement or a block arrangement. It may also be an arrangement with alternating patterns and the like. The carbon number of the above-mentioned alkylene group (when the alkylene group has a substituent, the carbon number including the substituent) is preferably 2 or more, more preferably 2-10, more preferably 2-6, more preferably 2-5 To be further preferred, 2 to 4 are further preferred, 2 or 3 is particularly preferred, and 2 is the most preferred. In addition, the above-mentioned alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. can be mentioned. In addition, the number of alkoxyl groups contained in the polyoxyalkylene group (the number of repeating polyoxyalkylene groups) is preferably from 2 to 20, more preferably from 2 to 10, and more preferably from 2 to 6 Better. As the polyoxyethylene group, from the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy or plural ethyleneoxy groups and plural A group formed by bonding a propyleneoxy group is preferable, a polyvinyloxy group or a polypropyleneoxy group is more preferable, and a polyvinyloxy group is further preferable. Among the groups formed by bonding plural ethyleneoxy groups and plural propyleneoxy groups, the ethyleneoxy group and the propyleneoxy group may be arranged randomly, formed into blocks and arranged, or arranged in an alternating pattern. shape. Preferred aspects of the number of repetitions of vinyloxy and the like in these groups are as described above.

R113 及R114 分別獨立地為氫原子或1價的有機基。作為1價的有機基，可舉出在構成芳基之1個、2個或3個碳中、較佳為1個碳中鍵結有酸性基之、芳香族基及芳烷基等。具體而言，可舉出具有酸性基之碳數6～20的芳香族基、具有酸性基之碳數7～25的芳烷基。更具體而言，可舉出具有酸性基之苯基及具有酸性基之苄基。酸性基係OH基為較佳。 R113 或R114 係氫原子、2-羥基苄基、3-羥基苄基及4-羥基苄基亦為更佳。R 113 and R 114 are each independently a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include one, two, or three carbons constituting the aryl group, preferably one carbon having an acidic group, an aromatic group, an aralkyl group, and the like. Specifically, a C6-C20 aromatic group which has an acidic group, and a C7-25 aralkyl group which has an acidic group are mentioned specifically,. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group. R 113 or R 114 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, and 4-hydroxybenzyl are also more preferable.

就對有機溶劑的溶解度的觀點而言，R113 或R114 係1價的有機基為較佳。作為1價的有機基，包含直鏈或支鏈烷基、環狀烷基、芳香族基為較佳，被芳香族基取代之烷基為更佳。 烷基的碳數係1～30為較佳。烷基可以係直鏈、支鏈、環狀中的任一種。作為直鏈或支鏈的烷基，例如，可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十二烷基、十四烷基、十八烷基、異丙基、異丁基、二級丁基、三級丁基、1-乙基戊基、2-乙基己基2-（2-（2-甲氧基乙氧基）乙氧基）乙氧基、2-（2-（2-乙氧基乙氧基）乙氧基）乙氧基）乙氧基、2-（2-（2-（2-甲氧基乙氧基）乙氧基）乙氧基）乙氧基及2-（2-（2-（2-乙氧基乙氧基）乙氧基）乙氧基）乙氧基。環狀烷基可以係單環的環狀烷基，可以係多環的環狀烷基。作為單環的環狀烷基，例如可舉出環丙基、環丁基、環戊基、環己基、環庚基及環辛基。作為多環的環狀烷基，例如可舉出金剛烷基、降莰基、莰基、莰烯基、十氫萘基、三環癸基、四環癸基、莰二醯基、二環己基及蒎烯基。其中，就兼顧高靈敏度化之觀點而言，環己基為最佳。又，作為被芳香族基取代之烷基，被後述之芳香族基取代之直鏈烷基為較佳。 作為芳香族基，具體而言，為經取代或未經取代的苯環、萘環、并環戊二烯環、茚環、薁環、庚搭烯環、茚烯環、苝環、稠五苯環、乙烷合萘環、菲環、蒽環、稠四苯環、䓛環、聯三伸苯環、茀環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑環、㗁唑環、噻唑環、吡啶環、吡𠯤環、嘧啶環、嗒𠯤環、吲𠯤環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹𠯤環、喹啉環、酞𠯤環、萘啶環、喹㗁啉環、喹㗁唑啉（quinoxazoline）環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉（phenanthroline）環、噻嗯環、色烯（chromene）環、𠮿口星（xanthene）環、啡㗁噻（phenoxathiine）環、啡噻𠯤（phenothiazine）環或啡𠯤（phenazine）環。苯環為最佳。From the viewpoint of solubility in an organic solvent, R 113 or R 114 is preferably a monovalent organic group. As the monovalent organic group, it is preferable to include a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and an alkyl group substituted with an aromatic group is more preferable. The carbon number of the alkyl group is preferably 1-30. The alkyl group may be any of linear, branched, and cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and decyl groups. Tetraalkyl, octadecyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, 1-ethylpentyl, 2-ethylhexyl 2-(2-(2-methoxy Ethoxy)ethoxy)ethoxy, 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy, 2-(2-(2-(2- Methoxyethoxy)ethoxy)ethoxy)ethoxy) and 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy. The cyclic alkyl group may be a monocyclic cyclic alkyl group, or may be a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, camphenyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphenyl and bicyclo Hexyl and pinenyl. Among them, from the viewpoint of achieving high sensitivity, cyclohexyl is the most preferred. In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferred. As the aromatic group, specifically, substituted or unsubstituted benzene ring, naphthalene ring, pentacyclopentadiene ring, indene ring, azulene ring, heptene ring, indenene ring, perylene ring, fused five Benzene ring, ethane naphthalene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, tetraphenyl ring, terphenylene ring, pyrene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole Ring, thiazole ring, pyridine ring, pyridine ring, pyrimidine ring, pyrimidine ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring , Phthaloline ring, naphthyridine ring, quinoxazoline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thiamine ring , Chromene ring, xanthene ring, phenoxathiine ring, phenothiazine ring or phenazine ring. The benzene ring is the best.

式（2）中，在R113 為氫原子的情形或R114 為氫原子的情形下，聚醯亞胺前驅物可以形成與具有乙烯性不飽和鍵之三級胺化合物抗衡之鹽。作為這種具有乙烯性不飽和鍵之三級胺化合物的例子，可舉出N,N-二甲基胺基丙基甲基丙烯酸酯。In formula (2), in the case where R 113 is a hydrogen atom or when R 114 is a hydrogen atom, the polyimide precursor can form a salt that competes with a tertiary amine compound having an ethylenically unsaturated bond. As an example of such a tertiary amine compound having an ethylenically unsaturated bond, N,N-dimethylaminopropyl methacrylate can be cited.

又，聚醯亞胺前驅物在結構單元中具有氟原子亦為較佳。聚醯亞胺前驅物中的氟原子含量係10質量%以上為較佳，且20質量%以下為較佳。Moreover, it is also preferable that the polyimide precursor has a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

又，為了提高與基板的密接性，聚醯亞胺前驅物可以與具有矽氧烷結構之脂肪族基共聚。具體而言，作為二胺成分，可舉出雙（3-胺基丙基）四甲基二矽氧烷、雙（對胺基苯基）八甲基五矽氧烷等。In addition, in order to improve the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

由式（2）表示之重複單元係由式（2-A）表示之重複單元為較佳。亦即，本發明中所使用之聚醯亞胺前驅物等中的至少1種係具有由式（2-A）表示之重複單元之前驅物為較佳。藉由設為這種結構，能夠進一步擴大曝光寬容度的寬度。 式（2-A） [化學式13]

Figure 02_image025
式（2-A）中，A1 及A2 表示氧原子，R111 及R112 分別獨立地表示2價的有機基，R113 及R114 分別獨立地表示氫原子或1價的有機基，R113 及R114 中的至少一方係包含聚合性基之基團，兩者係聚合性基為較佳。The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors and the like used in the present invention has a repeating unit represented by the formula (2-A). With this structure, the width of the exposure latitude can be further expanded. Formula (2-A) [Chemical Formula 13]
Figure 02_image025
In the formula (2-A), A 1 and A 2 represent an oxygen atom, R 111 and R 112 each independently represent a divalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, At least one of R 113 and R 114 is a group containing a polymerizable group, and both of them are preferably a polymerizable group.

A1 、A2 、R111 、R113 及R114 分別獨立地與式（2）中的A1 、A2 、R111 、R113 及R114 含義相同，較佳的範圍亦相同。 R112 與式（5）中的R112 含義相同，較佳的範圍亦相同。 A 1, A 2, R 111 , R 113 and R 114 each independently have the formula A 1, A 2, R 111 , R 113 and R 114 have the same meaning (2), the preferred ranges are also the same. Same as (5) in the meaning of R 112 and R 112 type, the preferred ranges are also the same.

聚醯亞胺前驅物可以包含1種由式（2）表示之重複結構單元，但是亦可以包含2種以上。又，還可以包含由式（2）表示之重複單元的結構異構物。又，當然，聚醯亞胺前驅物除了上述式（2）的重複單元以外，還可以包含其他種類的重複結構單元。The polyimide precursor may include one type of repeating structural unit represented by formula (2), but may also include two or more types. In addition, it may also include structural isomers of the repeating unit represented by formula (2). Furthermore, of course, the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (2).

作為本發明中的聚醯亞胺前驅物的一實施形態，可例示所有重複單元的50莫耳%以上、進而係70莫耳%以上、尤其係90莫耳%以上為由式（2）表示之重複單元之聚醯亞胺前驅物。As an embodiment of the polyimide precursor in the present invention, 50 mol% or more, further 70 mol% or more, especially 90 mol% or more of all repeating units can be exemplified as represented by formula (2) The polyimide precursor of the repeating unit.

聚醯亞胺前驅物的重量平均分子量（Mw）較佳為18,000～30,000，更佳為20,000～27,000，進一步較佳為22,000～25,000。在本發明的有機膜形成用組成物包含含有金屬元素之化合物之情形下，還可較佳地舉出重量平均分子量（Mw）為22,000～26,000的態樣。又，數平均分子量（Mn）較佳為7,200～14,000，更佳為8,000～12,000，進一步較佳為9,200～11,200。在本發明的有機膜形成用組成物包含含有金屬元素之化合物之情形下，還可較佳地舉出數平均分子量（Mn）為7,200～20,000的態樣，此時，更佳為8,000～18,000，進一步較佳為10,000～14,000。 上述聚醯亞胺前驅物的分子量的分散度係2.5以上為較佳，2.7以上為更佳，2.8以上為進一步較佳。在本發明的有機膜形成用組成物包含含有金屬元素之化合物之情形下，還可較佳地舉出分子量的分散度為1.5以上的態樣，此時，更佳為1.7以上，進一步較佳為1.8以上。聚醯亞胺前驅物的分子量的分散度的上限值並無特別限定，但是例如4.5以下為較佳，4.0以下為更佳，3.8以下為進一步較佳，3.2以下為進一步較佳，3.1以下為更進一步較佳，3.0以下為更進一步較佳，2.95以下為特佳。 在本說明書中，分子量的分散度係指依據重量平均分子量/數平均分子量計算之值。The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and still more preferably 22,000 to 25,000. In the case where the composition for forming an organic film of the present invention contains a compound containing a metal element, the aspect having a weight average molecular weight (Mw) of 22,000-26,000 can also be preferably mentioned. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200. In the case where the composition for forming an organic film of the present invention contains a compound containing a metal element, the number average molecular weight (Mn) is preferably 7,200 to 20,000. In this case, it is more preferably 8,000 to 18,000. , More preferably 10,000 to 14,000. The dispersion degree of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. In the case where the composition for forming an organic film of the present invention contains a compound containing a metal element, it is also preferable that the molecular weight dispersion is 1.5 or more. In this case, it is more preferably 1.7 or more, and even more preferably It is 1.8 or more. The upper limit of the dispersion of the molecular weight of the polyimide precursor is not particularly limited, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is more preferable, 3.2 or less is more preferable, and 3.1 or less To be more preferable, 3.0 or less is still more preferable, and 2.95 or less is particularly preferable. In this specification, the degree of molecular weight dispersion refers to a value calculated on the basis of weight average molecular weight/number average molecular weight.

〔聚醯亞胺〕 本發明中所使用之聚醯亞胺可以為鹼可溶性聚醯亞胺，亦可以為可溶於以有機溶劑為主要成分之顯影液中之聚醯亞胺。 在本說明書中，鹼可溶性聚醯亞胺係指相對於100g的2.38質量%四甲基銨水溶液在23℃的條件下溶解0.1g以上之聚醯亞胺，就圖案形成性的觀點而言，溶解0.5g以上之聚醯亞胺為較佳，溶解1.0g以上之聚醯亞胺為進一步較佳。上述溶解量的上限並無特別限定，但是100g以下為較佳。 又，就所獲得之有機膜的膜強度及絕緣性的觀點而言，聚醯亞胺係在主鏈上具有複數個醯亞胺結構之聚醯亞胺為較佳。 在本說明書中，“主鏈”係指在構成樹脂之高分子化合物的分子中相對最長的鍵結鏈，“側鏈”係指除此以外的鍵結鏈。〔Polyimide〕 The polyimine used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developer with an organic solvent as the main component. In this specification, the alkali-soluble polyimide means that 0.1 g or more of polyimide is dissolved at 23°C with respect to 100 g of 2.38% by mass tetramethylammonium aqueous solution. From the viewpoint of pattern formation, It is preferable to dissolve 0.5 g or more of polyimide, and it is more preferable to dissolve 1.0 g or more of polyimine. The upper limit of the above-mentioned dissolution amount is not particularly limited, but 100 g or less is preferable. In addition, from the viewpoint of the film strength and insulating properties of the obtained organic film, a polyimide-based polyimide having a plurality of imine structures in the main chain is preferable. In this specification, the "main chain" refers to the relatively longest bonding chain in the molecule of the polymer compound constituting the resin, and the "side chain" refers to other bonding chains.

-氟原子- 就所獲得之有機膜的膜強度的觀點而言，聚醯亞胺具有氟原子為較佳。 氟原子例如包含在後述之由式（4）表示之重複單元中的R132 或後述之由式（4）表示之重複單元中的R131 中為較佳，作為氟化烷基而包含在後述之由式（4）表示之重複單元中的R132 或後述之由式（4）表示之重複單元中的R131 中為更佳。 相對於聚醯亞胺的總質量之氟原子的量係1～50mol/g為較佳，5～30mol/g為更佳。-Fluorine atom- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has a fluorine atom. For example, the fluorine atom is preferably contained in R 132 in the repeating unit represented by formula (4) described later or R 131 in the repeating unit represented by formula (4) described later, and is included as a fluorinated alkyl group. R 132 in the repeating unit represented by formula (4) or R 131 in the repeating unit represented by formula (4) described later is more preferred. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 1-50 mol/g, more preferably 5-30 mol/g.

-矽原子- 就所獲得之有機膜的膜強度的觀點而言，聚醯亞胺具有矽原子為較佳。 矽原子例如包含在後述之由式（4）表示之重複單元中的R131 中為較佳，作為後述之有機改質（聚）矽氧烷結構而包含在後述之由式（4）表示之重複單元中的R131 中為更佳。 又，上述矽原子或上述有機改質（聚）矽氧烷結構可以包含在聚醯亞胺的側鏈中，但是包含在聚醯亞胺的主鏈中為較佳。 相對於聚醯亞胺的總質量之矽原子的量係0.01～5mol/g為較佳，0.05～1mol/g為更佳。-Silicon atom- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has a silicon atom. For example, the silicon atom is preferably contained in R 131 in the repeating unit represented by formula (4) described later, and is included in the structure represented by formula (4) described later as an organic modified (poly)siloxane structure described later R 131 in the repeating unit is more preferable. In addition, the silicon atom or the organic modified (poly)siloxane structure may be contained in the side chain of the polyimide, but it is preferably contained in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 0.01-5 mol/g, and more preferably 0.05-1 mol/g.

-乙烯性不飽和鍵- 就所獲得之有機膜的膜強度的觀點而言，聚醯亞胺具有乙烯性不飽和鍵為較佳。 聚醯亞胺可以在主鏈末端具有乙烯性不飽和鍵，亦可以在側鏈具有乙烯性不飽和鍵，但是在側鏈具有乙烯性不飽和鍵為較佳。 上述乙烯性不飽和鍵具有自由基聚合性為較佳。 乙烯性不飽和鍵包含在後述之由式（4）表示之重複單元中的R132 或後述之由式（4）表示之重複單元中的R131 中為較佳，作為具有乙烯性不飽和鍵之基團而包含在後述之由式（4）表示之重複單元中的R132 或後述之由式（4）表示之重複單元中的R131 中為更佳。 該等中，乙烯性不飽和鍵包含在後述之由式（4）表示之重複單元中的R131 中為較佳，作為具有乙烯性不飽和鍵之基團而包含在後述之由式（4）表示之重複單元中的R131 中為更佳。 作為具有乙烯性不飽和鍵之基團，可舉出乙烯基、烯丙基、與乙烯基苯基等芳香環直接鍵結之、具有可以被取代之乙烯基之基團、（甲基）丙烯醯胺基、（甲基）丙烯醯氧基、由下述式（IV）表示之基團等。-Ethylene unsaturated bond- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has an ethylenic unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain or may have an ethylenically unsaturated bond in the side chain, but it is preferred to have an ethylenically unsaturated bond in the side chain. It is preferable that the above-mentioned ethylenically unsaturated bond has radical polymerizability. It is preferable that the ethylenically unsaturated bond is contained in R 132 in the repeating unit represented by formula (4) described later or R 131 in the repeating unit represented by formula (4) described later, as it has an ethylenically unsaturated bond It is more preferable that the group is contained in R 132 in the repeating unit represented by formula (4) mentioned later or R 131 in the repeating unit represented by formula (4) mentioned later. Among these, it is preferable that the ethylenically unsaturated bond is contained in R 131 in the repeating unit represented by formula (4) described later, and it is contained in the group having ethylenically unsaturated bond in the repeating unit represented by formula (4) described later. ) Is more preferable among R 131 in the repeating unit. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, groups directly bonded to aromatic rings such as vinyl phenyl groups, groups having vinyl groups that may be substituted, and (meth)propylene An amide group, a (meth)acryloxy group, a group represented by the following formula (IV), and the like.

[化學式14]

Figure 02_image027
[Chemical formula 14]
Figure 02_image027

式（IV）中，R20 表示氫原子或甲基，甲基為較佳。In the formula (IV), R 20 represents a hydrogen atom or a methyl group, and a methyl group is preferred.

式（IV）中，R21 表示碳數2～12的伸烷基、-O-CH2 CH（OH）CH2 -、-C（=O）O-、-O（C=O）NH-、碳數2～30的（聚）伸烷氧基（伸烷基的碳數係2～12為較佳，2～6為更佳，2或3為特佳；重複數係1～12為較佳，1～6為更佳，1～3為特佳）或組合該等中的2個以上而成之基團。In the formula (IV), R 21 represents an alkylene having 2 to 12 carbon atoms, -O-CH 2 CH(OH)CH 2 -, -C(=O)O-, -O(C=O)NH- , (Poly) alkoxylate having 2-30 carbon atoms (the carbon number of the alkylene group is preferably 2-12, more preferably 2-6, especially 2 or 3; repeating number 1-12 is Preferably, 1 to 6 are more preferable, and 1 to 3 are particularly preferable) or a group formed by combining two or more of them.

該等中，R21 係由下述式（R1）～式（R3）中的任一個表示之基團為較佳，由式（R1）表示之基團為更佳。 [化學式15]

Figure 02_image029
式（R1）～（R3）中，L表示單鍵或碳數2～12的伸烷基、碳數2～30的（聚）伸烷氧基或將該等中的2個以上鍵結而成之基團，X表示氧原子或硫原子，*表示與其他結構的鍵結部位，●表示與式（III）中的R201 鍵結之氧原子的鍵結部位。 式（R1）～（R3）中，L中的碳數2～12的伸烷基或碳數2～30的（聚）伸烷氧基的較佳的態樣與上述R21 中的、碳數2～12的伸烷基或碳數2～30的（聚）伸烷氧基的較佳的態樣相同。 式（R1）中，X係氧原子為較佳。 式（R1）～（R3）中，*與式（IV）中的*含義相同，較佳的態樣亦相同。 由式（R1）表示之結構例如藉由使具有酚性羥基等羥基之聚醯亞胺與具有異氰酸酯基及乙烯性不飽和鍵之化合物（例如，2-異氰酸基乙基甲基丙烯酸酯等）進行反應來獲得。 由式（R2）表示之結構例如藉由使具有羧基之聚醯亞胺與具有羥基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-羥乙酯等）進行反應來獲得。 由式（R3）表示之結構例如藉由使具有酚性羥基等羥基之聚醯亞胺與具有環氧丙基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸環氧丙酯等）進行反應來獲得。Among these, R 21 is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by the formula (R1). [Chemical formula 15]
Figure 02_image029
In the formulas (R1) to (R3), L represents a single bond or an alkylene group having 2 to 12 carbons, a (poly)alkylene group having 2 to 30 carbons, or two or more of these are bonded. As a group, X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ● represents a bonding site with an oxygen atom bonded to R 201 in formula (III). In formulas (R1) to (R3), the preferred aspect of the alkylene group having 2 to 12 carbons or the (poly)alkylene group having 2 to 30 carbons in L is the same as that of the above-mentioned R 21 , carbon The preferred aspect of the alkylene group having 2 to 12 or the (poly)alkylene group having 2 to 30 carbon atoms is the same. In the formula (R1), the X-based oxygen atom is preferred. In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and the preferred aspects are also the same. The structure represented by the formula (R1), for example, can be obtained by combining a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate Etc.) to obtain by reaction. The structure represented by the formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.). The structure represented by the formula (R3) is formed, for example, by combining a polyimide having a hydroxyl group such as a phenolic hydroxyl group and a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.) Response to get.

式（IV）中，*表示與其他結構的鍵結部位，與聚醯亞胺的主鏈的鍵結部位為較佳。In the formula (IV), * represents the bonding site with other structures, and the bonding site with the main chain of the polyimide is preferred.

相對於聚醯亞胺的總質量之乙烯性不飽和鍵的量係0.05～10mol/g為較佳，0.1～5mol/g為更佳。The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.05-10 mol/g, and more preferably 0.1-5 mol/g.

-除了乙烯性不飽和鍵以外的交聯性基- 聚醯亞胺還可以具有除了乙烯性不飽和鍵以外的交聯性基。 作為除了乙烯性不飽和鍵以外的交聯性基，可舉出環氧基、氧雜環丁基等環狀醚基、甲氧基甲基等烷氧基甲基、羥甲基等。 除了乙烯性不飽和鍵以外的交聯性基例如包含在後述之由式（4）表示之重複單元中的R131 中為較佳。 相對於聚醯亞胺的總質量之除了乙烯性不飽和鍵以外的交聯性基的量係0.05～10mol/g為較佳，0.1～5mol/g為更佳。-Crosslinkable group other than ethylenic unsaturated bond- Polyimide may have a crosslinkable group other than ethylenic unsaturated bond. Examples of crosslinkable groups other than ethylenically unsaturated bonds include cyclic ether groups such as epoxy groups and oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups. The crosslinkable group other than the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by formula (4) described later, for example. The amount of crosslinkable groups other than the ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.05-10 mol/g, and more preferably 0.1-5 mol/g.

-酸值- 在聚醯亞胺被供於鹼性顯影之情形下，就提高顯影性之觀點而言，聚醯亞胺的酸值係30mgKOH/g以上為較佳，50mgKOH/g以上為更佳，70mgKOH/g以上為進一步較佳。 又，上述酸值係500mgKOH/g以下為較佳，400mgKOH/g以下為更佳，200mgKOH/g以下為進一步較佳。 又，在聚醯亞胺被供於使用了以有機溶劑為主要成分之顯影液之顯影（例如，後述之“溶劑顯影”）之情形下，聚醯亞胺的酸值係2～35mgKOH/g為較佳，3～30mgKOH/g為更佳，5～20mgKOH/g為進一步較佳。 上述酸值藉由公知的方法進行測量，例如，藉由JIS K 0070：1992中所記載之方法進行測量。 又，作為聚醯亞胺中所包含之酸基，就兼顧保存穩定性及顯影性之觀點而言，pKa係0～10的酸基為較佳，3～8的酸基為更佳。 pKa係指考慮從酸中釋放氫離子之解離反應而由其負的常用對數pKa表示其平衡常數Ka者。在本說明書中，關於pKa，只要無特別說明，則設為基於ACD/ChemSketch（註冊商標）之計算值。或者，可以參閱日本化學會編輯的“修訂第5版，化學手冊，基礎版”中所刊載之值。 又，在酸基例如為磷酸等多元酸的情形下，上述pKa為第一解離常數。 作為這種酸基，聚醯亞胺包含選自包括羧基及酚性羥基之群組中之至少1種為較佳，包含酚性羥基為更佳。-Acid value- When polyimine is used for alkaline development, from the viewpoint of improving developability, the acid value of polyimine is preferably 30mgKOH/g or more, more preferably 50mgKOH/g or more, and 70mgKOH/ g or more is more preferable. In addition, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. In addition, when polyimide is used for development (for example, "solvent development" described later) using a developer with an organic solvent as the main component, the acid value of polyimide is 2 to 35 mgKOH/g It is more preferable, 3-30 mgKOH/g is more preferable, and 5-20 mgKOH/g is still more preferable. The above-mentioned acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. In addition, as the acid group contained in the polyimide, from the viewpoint of achieving both storage stability and developability, an acid group having a pKa of 0-10 is preferable, and an acid group having a pKa of 3-8 is more preferable. pKa refers to the one whose equilibrium constant Ka is expressed by its negative common logarithm pKa in consideration of the dissociation reaction of hydrogen ion release from acid. In this specification, the pKa is a calculated value based on ACD/ChemSketch (registered trademark) unless otherwise specified. Alternatively, you can refer to the values published in the "Revised 5th Edition, Handbook of Chemistry, Basic Edition" edited by the Chemical Society of Japan. In addition, when the acid group is a polybasic acid such as phosphoric acid, the aforementioned pKa is the first dissociation constant. As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

-酚性羥基- 就使基於鹼性顯影液之顯影速度適當之觀點而言，聚醯亞胺具有酚性羥基為較佳。 聚醯亞胺可以在主鏈末端具有酚性羥基，亦可以在側鏈具有酚性羥基。 酚性羥基例如包含在後述之由式（4）表示之重複單元中的R132 或後述之由式（4）表示之重複單元中的R131 中為較佳。 相對於聚醯亞胺的總質量之酚性羥基的量係0.1～30mol/g為較佳，1～20mol/g為更佳。-Phenolic hydroxyl group- From the viewpoint of making the development speed based on an alkaline developer appropriate, it is preferable that the polyimide has a phenolic hydroxyl group. The polyimide may have a phenolic hydroxyl group at the end of the main chain, or may have a phenolic hydroxyl group at the side chain. The phenolic hydroxyl group is preferably contained in R 132 in the repeating unit represented by formula (4) described later or R 131 in the repeating unit represented by formula (4) described later, for example. The amount of the phenolic hydroxyl group relative to the total mass of the polyimide is preferably 0.1-30 mol/g, and more preferably 1-20 mol/g.

作為本發明中所使用之聚醯亞胺，只要係具有醯亞胺環之高分子化合物，則並無特別限定，但是包含由下述式（4）表示之重複單元為較佳，包含由式（4）表示之重複單元，且具有聚合性基之化合物為更佳。 式（4） [化學式16]

Figure 02_image031
式（4）中，R131 表示2價的有機基，R132 表示4價的有機基。 在具有聚合性基之情形下，聚合性基可以位於R131 及R132 中的至少一方，如下述式（4-1）或式（4-2）所示，亦可以位於聚醯亞胺的末端。 式（4-1） [化學式17]
Figure 02_image033
式（4-1）中，R133 為聚合性基，其他基團與式（4）含義相同。 式（4-2） [化學式18]
Figure 02_image035
R134 及R135 中的至少一方為聚合性基，在不是聚合性基之情形下為有機基，其他基團與式（4）含義相同。The polyimine used in the present invention is not particularly limited as long as it is a polymer compound having an imine ring, but it preferably contains a repeating unit represented by the following formula (4), including (4) The repeating unit shown, and the compound having a polymerizable group is more preferable. Formula (4) [Chemical Formula 16]
Figure 02_image031
In formula (4), R 131 represents a divalent organic group, and R 132 represents a tetravalent organic group. In the case of having a polymerizable group, the polymerizable group may be located in at least one of R 131 and R 132 , as shown in the following formula (4-1) or formula (4-2), or may be located in the polyimide End. Formula (4-1) [Chemical Formula 17]
Figure 02_image033
In the formula (4-1), R 133 is a polymerizable group, and other groups have the same meaning as in the formula (4). Formula (4-2) [Chemical Formula 18]
Figure 02_image035
At least one of R 134 and R 135 is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups have the same meaning as in formula (4).

聚合性基與上述聚醯亞胺前驅物等所具有之聚合性基中敘述之聚合性基含義相同。 R131 表示2價的有機基。作為2價的有機基，可例示與式（2）中的R111 相同者，較佳的範圍亦相同。 又，作為R131 ，可舉出去除二胺的胺基之後殘留之二胺殘基。作為二胺，可舉出脂肪族、環式脂肪族或芳香族二胺等。作為具體例，可舉出聚醯亞胺前驅物的式（2）中的R111 的例子。The polymerizable group has the same meaning as the polymerizable group described in the polymerizable group possessed by the polyimide precursor and the like. R 131 represents a divalent organic group. As a divalent organic group, the same thing as R 111 in Formula (2) can be illustrated, and a preferable range is also the same. Moreover, as R 131 , the diamine residue remaining after removing the amine group of the diamine can be exemplified. Examples of diamines include aliphatic, cycloaliphatic, or aromatic diamines. As a specific example, an example of R 111 in the formula (2) of the polyimide precursor can be given.

就更有效地抑制煅燒時翹曲的發生之觀點而言，R131 係在主鏈具有至少2個伸烷基二醇單元之二胺殘基為較佳。更佳為在一分子中共計包含2個以上的乙二醇鏈、丙二醇鏈中的任一個或兩者之二胺殘基，進一步較佳為不含芳香環之二胺殘基。From the viewpoint of more effectively suppressing the occurrence of warpage during calcination, R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain. It is more preferable that a total of two or more diamine residues of either or both of the ethylene glycol chain and the propylene glycol chain are contained in one molecule, and it is still more preferable that the diamine residue does not contain an aromatic ring.

作為在一分子中共計包含2個以上的乙二醇鏈、丙二醇鏈中的任一個或兩者之二胺，可舉出JEFFAMINE（註冊商標）KH-511、ED-600、ED-900、ED-2003、EDR-148、EDR-176、D-200、D-400、D-2000、D-4000（以上為商品名稱，HUNTSMAN公司製造）、1-（2-（2-（2-胺基丙氧基）乙氧基）丙氧基）丙烷-2-胺、1-（1-（1-（2-胺基丙氧基）丙烷-2-基）氧基）丙烷-2-胺等，但是並不限定於該等。Examples of diamines containing two or more of ethylene glycol chains and propylene glycol chains or both in a molecule include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED -2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (the above are trade names, manufactured by HUNTSMAN), 1-(2-(2-(2-amino group) Propoxy) ethoxy) propoxy) propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc. , But not limited to these.

R132 表示4價的有機基。作為4價的有機基，可例示與式（2）中的R115 相同者，較佳的範圍亦相同。 例如，作為R115 而例示之4價的有機基的4個鍵結鍵與上述式（4）中的4個-C（=O）-的部分鍵結而形成縮合環。 [化學式19]

Figure 02_image037
R 132 represents a tetravalent organic group. As a tetravalent organic group, the same thing as R 115 in Formula (2) can be illustrated, and a preferable range is also the same. For example, the four bonding bonds of the tetravalent organic group exemplified as R 115 are bonded to the four -C(=O)- moieties in the above formula (4) to form a condensed ring. [Chemical formula 19]
Figure 02_image037

又，關於R132 ，可舉出從四羧酸二酐去除酐基之後殘留之四羧酸殘基等。作為具體例，可舉出聚醯亞胺前驅物的式（2）中的R115 的例子。就有機膜的強度的觀點而言，R132 係具有1～4個芳香環之芳香族二胺殘基為較佳。Moreover, as for R 132 , the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride can be mentioned. As a specific example, an example of R 115 in the formula (2) of the polyimide precursor can be given. From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

在R131 和R132 中的至少一方具有OH基亦為較佳。更具體而言，作為R131 ，可舉出2,2-雙（3-羥基-4-胺基苯基）丙烷、2,2-雙（3-羥基-4-胺基苯基）六氟丙烷、2,2-雙（3-胺基-4-羥基苯基）丙烷、2,2-雙（3-胺基-4-羥基苯基）六氟丙烷、上述（DA-1）～（DA-18）作為較佳例，作為R132 ，可舉出上述（DAA-1）～（DAA-5）作為更佳的例子。It is also preferable that at least one of R 131 and R 132 has an OH group. More specifically, as R 131 , 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoro Propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, the above (DA-1)～( DA-18) As a preferable example, as R 132 , the above-mentioned (DAA-1) to (DAA-5) can be cited as more preferable examples.

又，聚醯亞胺在結構單元中具有氟原子亦為較佳。聚醯亞胺中的氟原子的含量係10質量%以上為較佳，且20質量%以下為較佳。In addition, it is also preferable that the polyimide has a fluorine atom in the structural unit. The content of the fluorine atom in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.

又，為了提高與基板的密接性，聚醯亞胺可以使具有矽氧烷結構之脂肪族基共聚。具體而言，作為二胺成分，可舉出雙（3-胺基丙基）四甲基二矽氧烷、雙（對胺基苯基）八甲基五矽氧烷等。In addition, in order to improve the adhesion to the substrate, polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

又，為了提高組成物的保存穩定性，聚醯亞胺用單胺、酸酐、單羧酸、單醯氯化合物、單活性酯化合物等封端劑密封主鏈末端為較佳。該等中，使用單胺為更佳，作為單胺的較佳的化合物，可舉出苯胺、2-乙炔苯胺、3-乙炔苯胺、4-乙炔苯胺、5-胺基-8-羥基喹啉、1-羥基-7-胺萘、1-羥基-6-胺萘、1-羥基-5-胺萘、1-羥基-4-胺萘、2-羥基-7-胺萘、2-羥基-6-胺萘、2-羥基-5-胺萘、1-羧基-7-胺萘、1-羧基-6-胺萘、1-羧基-5-胺萘、2-羧基-7-胺萘、2-羧基-6-胺萘、2-羧基-5-胺萘、2-胺基苯甲酸、3-胺基苯甲酸、4-胺基苯甲酸、4-胺基水楊酸、5-胺基水楊酸、6-胺基水楊酸、2-胺基苯磺酸、3-胺基苯磺酸、4-胺基苯磺酸、3-胺基-4,6-二羥基嘧啶、2-胺基苯酚、3-胺基苯酚、4-胺基苯酚、2-胺基苯硫酚、3-胺基苯硫酚、4-胺基苯硫酚等。可以使用該等中的2種以上，亦可以藉由使複數種封端劑進行反應來導入複數個不同的末端基。Furthermore, in order to improve the storage stability of the composition, it is preferable that the polyimide is sealed with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochlorine compound, a monoactive ester compound, or the like. Among them, it is more preferable to use a monoamine. As a preferable compound of the monoamine, aniline, 2-acetylene aniline, 3-acetylene aniline, 4-acetylene aniline, 5-amino-8-hydroxyquinoline , 1-hydroxy-7-amine naphthalene, 1-hydroxy-6-amine naphthalene, 1-hydroxy-5-amine naphthalene, 1-hydroxy-4-amine naphthalene, 2-hydroxy-7-amine naphthalene, 2-hydroxy- 6-amine naphthalene, 2-hydroxy-5-amine naphthalene, 1-carboxy-7-amine naphthalene, 1-carboxy-6-amine naphthalene, 1-carboxy-5-amine naphthalene, 2-carboxy-7-amine naphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-amine Salicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these can be used, or a plurality of different terminal groups can be introduced by reacting a plurality of end-capping agents.

-醯亞胺化率（閉環率）- 就所獲得之有機膜的膜強度、絕緣性等的觀點而言，聚醯亞胺的醯亞胺化率（還稱為“閉環率”）係70%以上為較佳，80%以上為更佳，90%以上為更佳。 上述醯亞胺化率的上限並無特別限定，只要係100%以下即可。 上述醯亞胺化率例如藉由下述方法進行測量。 測量聚醯亞胺的紅外吸收光譜，並求出源自醯亞胺結構之吸收峰亦即1377cm-1 附近的峰強度P1。接著，在350℃的條件下對該聚醯亞胺進行1小時的熱處理之後，再次測量紅外吸收光譜，並求出1377cm-1 附近的峰強度P2。能夠使用所獲得之峰強度P1、P2，依據下述式，求出聚醯亞胺的醯亞胺化率。 醯亞胺化率（%）=（峰強度P1/峰強度P2）×100-Imidation rate (closed loop rate)- From the viewpoint of the film strength and insulation properties of the obtained organic film, the imidization rate (also referred to as "closed loop rate") of polyimide is 70 % Or more is preferable, 80% or more is more preferable, and 90% or more is more preferable. The upper limit of the above-mentioned imidization rate is not particularly limited as long as it is 100% or less. The above-mentioned imidization rate is measured by the following method, for example. The infrared absorption spectrum of polyimide was measured, and the absorption peak derived from the imine structure, that is, the peak intensity P1 near 1377 cm -1 was obtained. Next, after heat-treating the polyimide for 1 hour at 350°C, the infrared absorption spectrum was measured again, and the peak intensity P2 near 1377 cm -1 was determined. The obtained peak intensities P1 and P2 can be used to obtain the imidization rate of polyimine based on the following formula. The imidization rate (%)=(peak intensity P1/peak intensity P2)×100

聚醯亞胺可以包含含有均為1種的R131 或R132 之上述式（4）的重複結構單元，亦可以包含含有2個以上的不同種類的R131 或R132 之上述式（4）的重複單元。又，聚醯亞胺除了上述式（4）的重複單元以外，還可以包含其他種類的重複結構單元。Comprising both polyimide may comprise one kind of R in the above formula (4) repeating structural units of 131 or R 132, R contains also may comprise two or more different types of R 131, or 132 of the above-described formula (4) The repeating unit. In addition, the polyimide may contain other types of repeating structural units in addition to the repeating unit of the above formula (4).

聚醯亞胺例如能夠利用使用如下方法獲得聚醯亞胺前驅物並使用已知的醯亞胺化反應法使其完全醯亞胺化之方法、或在中途停止醯亞胺化反應並導入局部醯亞胺結構之方法、以及藉由混合完全醯亞胺化之聚合物和該聚醯亞胺前驅物來導入局部醯亞胺結構之方法來合成，該方法為使四羧酸二酐與二胺化合物（一部分被作為單胺的封端劑取代）在低溫中進行反應之方法；使四羧酸二酐（一部分被作為酸酐或單醯氯化合物或單活性酯化合物的封端劑取代）與二胺化合物在低溫中進行反應之方法；由四羧酸二酐和醇獲得二酯，然後在縮合劑存在下與二胺（一部分被作為單胺的封端劑取代）進行反應之方法；由四羧酸二酐和醇獲得二酯，然後將剩餘的二羧酸進行醯氯化，與二胺（一部分被作為單胺的封端劑取代）進行反應之方法等方法。 作為聚醯亞胺的市售品，可例示Durimide（註冊商標）284（FUJIFILM Corporation製造）、Matrimide5218（HUNTSMAN公司製造）。For example, the polyimide can be obtained by using the following method to obtain a polyimide precursor and using a known method for complete imidization of the imidization reaction method, or stop the imidization reaction in the middle and introduce it locally The method of the imine structure and the method of introducing the local imine structure by mixing the fully imidized polymer and the polyimide precursor. The method is to make tetracarboxylic dianhydride and two A method of reacting an amine compound (part of it is replaced by a blocking agent as a monoamine) at low temperature; making tetracarboxylic dianhydride (part of it is replaced by a blocking agent as an acid anhydride or monochloride compound or monoactive ester compound) with A method of reacting diamine compounds at low temperatures; a method of obtaining diesters from tetracarboxylic dianhydrides and alcohols, and then reacting with diamines (part of which are replaced by capping agents as monoamines) in the presence of a condensing agent; by Tetracarboxylic dianhydride and alcohol are used to obtain diesters, and then the remaining dicarboxylic acids are chlorinated and reacted with diamines (part of which are replaced by capping agents as monoamines). As a commercially available product of polyimide, Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by HUNTSMAN) can be exemplified.

聚醯亞胺的重量平均分子量（Mw）係5,000～70,000為較佳，8,000～50,000為更佳，10,000～30,000為進一步較佳。藉由將重量平均分子量設為5,000以上，能夠提高硬化後的膜的耐折性。為了獲得機械特性優異的有機膜，重量平均分子量係20,000以上為特佳。又，在含有2種以上的聚醯亞胺之情形下，至少1種聚醯亞胺的重量平均分子量在上述範圍內為較佳。The weight average molecular weight (Mw) of the polyimide is preferably from 5,000 to 70,000, more preferably from 8,000 to 50,000, and even more preferably from 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. In addition, when two or more types of polyimines are contained, the weight average molecular weight of at least one type of polyimines is preferably within the above-mentioned range.

〔聚苯并㗁唑前驅物〕 關於本發明中所使用之聚苯并㗁唑前驅物，對其結構等並無特別限定，但是較佳為包含由下述式（3）表示之重複單元。 式（3） [化學式20]

Figure 02_image039
式（3）中，R121 表示2價的有機基，R122 表示4價的有機基，R123 及R124 分別獨立地表示氫原子或1價的有機基。[Polybenzoxazole Precursor] Regarding the polybenzoxazole precursor used in the present invention, the structure and the like are not particularly limited, but it preferably contains a repeating unit represented by the following formula (3). Formula (3) [Chemical Formula 20]
Figure 02_image039
In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group.

式（3）中，R123 及R124 分別與式（2）中的R113 含義相同，較佳的範圍亦相同。亦即，其中至少一方係聚合性基為較佳。 式（3）中，R121 表示2價的有機基。作為2價的有機基，包含脂肪族基及芳香族基中的至少一方之基團為較佳。作為脂肪族基，直鏈脂肪族基為較佳。R121 係二羧酸殘基為較佳。二羧酸殘基可以僅使用1種，亦可以使用2種以上。In formula (3), R 123 and R 124 respectively have the same meaning as R 113 in formula (2), and their preferred ranges are also the same. That is, at least one of them is preferably a polymerizable group. In formula (3), R 121 represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a straight-chain aliphatic group is preferred. R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

作為二羧酸殘基，包含脂肪族基之二羧酸及包含芳香族基之二羧酸殘基為較佳，包含芳香族基之二羧酸殘基為更佳。 作為包含脂肪族基之二羧酸，包含直鏈或支鏈（較佳為直鏈）的脂肪族基之二羧酸為較佳，由直鏈或支鏈（較佳為直鏈）的脂肪族基和2個-COOH組成之二羧酸為更佳。直鏈或支鏈（較佳為直鏈）的脂肪族基的碳數係2～30為較佳，2～25為更佳，3～20為進一步較佳，4～15為進一步較佳，5～10為特佳。直鏈的脂肪族基係伸烷基為較佳。 作為包含直鏈的脂肪族基之二羧酸，可舉出丙二酸、二甲基丙二酸、乙基丙二酸、異丙基丙二酸、二-正丁基丙二酸、丁二酸、四氟丁二酸、甲基丁二酸、2,2-二甲基丁二酸、2,3-二甲基丁二酸、二甲基甲基丁二酸、戊二酸、六氟戊二酸、2-甲基戊二酸、3-甲基戊二酸、2,2-二甲基戊二酸、3,3-二甲基戊二酸、3-乙基-3-甲基戊二酸、己二酸、八氟己二酸、3-甲基己二酸、庚二酸、2,2,6,6-四甲基庚二酸、辛二酸、十二氟辛二酸、壬二酸、癸二酸、十六氟癸二酸、1,9-壬二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸、十七烷二酸、十八烷二酸、十九烷二酸、二十烷二酸、二十一烷二酸、二十二烷二酸、二十三烷二酸、二十四烷二酸、二十五烷二酸、二十六烷二酸、二十七烷二酸、二十八烷二酸、二十九烷二酸、三十烷二酸、三十一烷二酸、三十二烷二酸、二乙醇酸、以及由下述式表示之二羧酸等。As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable. As dicarboxylic acids containing aliphatic groups, dicarboxylic acids containing linear or branched aliphatic groups (preferably straight-chain) are preferred. A dicarboxylic acid composed of a family group and 2 -COOH is more preferred. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2-30, more preferably 2-25, more preferably 3-20, and still more preferably 4-15, 5～10 are particularly good. The straight-chain aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, butane Diacid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, Hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3 -Methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecane Fluoroseric acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid Acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, behenicanedioic acid, behenedioic acid, tricosane Diacid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, nonaconanedioic acid, triaconanedioic acid , Tridecanedioic acid, Tridodecanedioic acid, Diglycolic acid, Dicarboxylic acid represented by the following formula, etc.

[化學式21]

Figure 02_image041
（式中，Z為碳數1～6的烴基，n為1～6的整數。）[Chemical formula 21]
Figure 02_image041
(In the formula, Z is a hydrocarbon group having 1 to 6 carbons, and n is an integer of 1 to 6.)

作為包含芳香族基之二羧酸，具有以下芳香族基之二羧酸為較佳，僅由以下芳香族基和2個-COOH組成之二羧酸為更佳。As the dicarboxylic acid containing an aromatic group, the dicarboxylic acid having the following aromatic group is preferable, and the dicarboxylic acid composed only of the following aromatic group and two -COOH is more preferable.

[化學式22]

Figure 02_image043
式中，A表示選自包括-CH2 -、-O-、-S-、-SO2 -、-CO-、-NHCO-、-C（CF3 ）2 -及-C（CH3 ）2 -之群組中之2價的基團。[Chemical formula 22]
Figure 02_image043
In the formula, A represents selected from -CH 2 -, -O-, -S-, -SO 2 -, -CO-, -NHCO-, -C(CF 3 ) 2 -and -C(CH 3 ) 2 -The divalent group in the group.

作為包含芳香族基之二羧酸的具體例，可舉出4,4’-羰基二苯甲酸及4,4’-二羧基二苯醚、對苯二甲酸。Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

式（3）中，R122 表示4價的有機基。作為4價的有機基，與上述式（2）中的R115 含義相同，較佳的範圍亦相同。 R122 係源自雙胺基苯酚衍生物之基團亦為較佳，作為源自雙胺基苯酚衍生物之基團，例如，可舉出3,3’-二胺基-4,4’-二羥基聯苯、4,4’-二胺基-3,3’-二羥基聯苯、3,3’-二胺基-4,4’-二羥基二苯碸、4,4’-二胺基-3,3’-二羥基二苯碸、雙-（3-胺基-4-羥基苯基）甲烷、2,2-雙（3-胺基-4-羥基苯基）丙烷、2,2-雙-（3-胺基-4-羥基苯基）六氟丙烷、2,2-雙-（4-胺基-3-羥基苯基）六氟丙烷、雙-（4-胺基-3-羥基苯基）甲烷、2,2-雙-（4-胺基-3-羥基苯基）丙烷、4,4’-二胺基-3,3’-二羥基二苯甲酮、3,3’-二胺基-4,4’-二羥基二苯甲酮、4,4’-二胺基-3,3’-二羥基二苯醚、3,3’-二胺基-4,4’-二羥基二苯醚、1,4-二胺基-2,5-二羥基苯、1,3-二胺基-2,4-二羥基苯、1,3-二胺基-4,6-二羥基苯等。該等雙胺基苯酚可以單獨使用或混合使用。In formula (3), R 122 represents a tetravalent organic group. The tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferred range is also the same. R 122 is also preferably a group derived from a diaminophenol derivative. As a group derived from a diaminophenol derivative, for example, 3,3'-diamino-4,4' -Dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfide, 4,4'- Diamino-3,3'-dihydroxydiphenyl benzene, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-Bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amine 3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone , 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino -4,4'-Dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamine Group-4,6-dihydroxybenzene, etc. These diaminophenols can be used alone or in combination.

雙胺基苯酚衍生物中具有下述芳香族基之雙胺基苯酚衍生物為較佳。Among the bisaminophenol derivatives, a bisaminophenol derivative having the following aromatic group is preferred.

[化學式23]

Figure 02_image045
式中，X1 表示-O-、-S-、-C（CF3 ）2 -、-CH2 -、-SO2 -、-NHCO-。[Chemical formula 23]
Figure 02_image045
In the formula, X 1 represents -O-, -S-, -C(CF 3 ) 2 -, -CH 2 -, -SO 2 -, -NHCO-.

[化學式24]

Figure 02_image047
[Chemical formula 24]
Figure 02_image047

式（A-s）中，R1 為氫原子、伸烷基、經取代伸烷基、-O-、-S-、-SO2 -、-CO-、-NHCO-、單鍵或選自下述式（A-sc）的群組中之有機基。R2 可以為氫原子、烷基、烷氧基、醯氧基、環狀的烷基中的任一個，可以相同，亦可以不同。R3 為氫原子、直鏈或支鏈的烷基、烷氧基、醯氧基、環狀的烷基中的任一個，可以相同，亦可以不同。In the formula (As), R 1 is a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, -SO 2 -, -CO-, -NHCO-, a single bond or selected from the following The organic group in the group of formula (A-sc). R 2 may be any of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different. R 3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

[化學式25]

Figure 02_image049
（式（A-sc）中，*表示與由上述式（A-s）表示之雙胺基苯酚衍生物的胺基苯酚基的芳香環鍵結。）[Chemical formula 25]
Figure 02_image049
(In the formula (A-sc), * represents the bond to the aromatic ring of the aminophenol group of the diaminophenol derivative represented by the above formula (As).)

上述式（A-s）中，認為在酚性羥基的鄰位亦即R3 亦具有取代基使醯胺鍵的羰基碳與羥基的距離更靠近，就在低溫下硬化時成為高環化率之效果進一步得到提高之觀點而言，為特佳。In the above formula (As), it is believed that the ortho-position of the phenolic hydroxyl group, that is, R 3 also has a substituent to make the carbonyl carbon of the amide bond closer to the hydroxyl group, which has an effect of high cyclization rate when hardened at low temperature. From the viewpoint of further improvement, it is particularly good.

又，上述式（A-s）中，R2 為烷基，且R3 為烷基，這能夠維持相對於i射線之高透明性和在低溫下硬化時高環化率之效果，因此為較佳。In addition, in the above formula (As), R 2 is an alkyl group, and R 3 is an alkyl group, which can maintain high transparency with respect to i-rays and the effect of high cyclization rate when hardened at low temperature, so it is preferable .

又，上述式（A-s）中，R1 係伸烷基或經取代伸烷基為進一步較佳。作為R1 之伸烷基及經取代伸烷基的具體例，可舉出-CH2 -、-CH（CH3 ）-、-C（CH3 ）2 -、-CH（CH2 CH3 ）-、-C（CH3 ）（CH2 CH3 ）-、-C（CH2 CH3 ）（CH2 CH3 ）-、-CH（CH2 CH2 CH3 ）-、-C（CH3 ）（CH2 CH2 CH3 ）-、-CH（CH（CH3 ）2 ）-、-C（CH3 ）（CH（CH3 ）2 ）-、-CH（CH2 CH2 CH2 CH3 ）-、-C（CH3 ）（CH2 CH2 CH2 CH3 ）-、-CH（CH2 CH（CH3 ）2 ）-、-C（CH3 ）（CH2 CH（CH3 ）2 ）-、-CH（CH2 CH2 CH2 CH2 CH3 ）-、-C（CH3 ）（CH2 CH2 CH2 CH2 CH3 ）-、-CH（CH2 CH2 CH2 CH2 CH2 CH3 ）-、-C（CH3 ）（CH2 CH2 CH2 CH2 CH2 CH3 ）-等，其中，就能夠獲得維持相對於i射線之高透明性和在低溫下硬化時的高環化率之效果的同時相對於溶劑具有足夠的溶解性之、平衡優異的聚苯并㗁唑前驅物之觀點而言，-CH2 -、-CH（CH3 ）-、-C（CH3 ）2 -為更佳。In addition, in the above formula (As), R 1 is an alkylene group or a substituted alkylene group is more preferred. Specific examples of the alkylene group and substituted alkylene group of R 1 include -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, -CH(CH 2 CH 3 ) -, -C (CH 3 ) (CH 2 CH 3 ) -, -C (CH 2 CH 3 ) (CH 2 CH 3 ) -, -CH (CH 2 CH 2 CH 3 ) -, -C (CH 3 ) (CH 2 CH 2 CH 3 ) -, -CH (CH (CH 3 ) 2 ) -, -C (CH 3 ) (CH (CH 3 ) 2 ) -, -CH (CH 2 CH 2 CH 2 CH 3 ) -, -C (CH 3 ) (CH 2 CH 2 CH 2 CH 3 ) -, -CH (CH 2 CH (CH 3 ) 2 ) -, -C (CH 3 ) (CH 2 CH (CH 3 ) 2 ) -, -CH (CH 2 CH 2 CH 2 CH 2 CH 3 ) -, -C (CH 3 ) (CH 2 CH 2 CH 2 CH 2 CH 3 ) -, -CH (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 )-, etc., among them, it is possible to maintain high transparency with respect to i-rays and maintain high transparency when hardened at low temperatures From the viewpoint of polybenzoxazole precursors that have a high cyclization rate and have sufficient solubility with respect to solvents and an excellent balance, -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -is better.

作為由上述式（A-s）表示之雙胺基苯酚衍生物之製造方法，例如，能夠參閱日本特開2013-256506號公報的0085～0094段及實施例1（0189～0190段），且該等內容被編入本說明書中。As a method for producing the diaminophenol derivative represented by the above formula (As), for example, refer to paragraphs 0085 to 0094 of JP 2013-256506 A and Example 1 (paragraphs 0189 to 0190), and these The content is compiled into this manual.

作為由上述式（A-s）表示之雙胺基苯酚衍生物的結構的具體例，可舉出日本特開2013-256506號公報的0070～0080段中所記載者，且該等內容被編入本說明書中。當然，不限定於該等是不言而喻的。Specific examples of the structure of the diaminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of JP 2013-256506 A, and these contents are incorporated into this specification in. Of course, it goes without saying that they are not limited to these.

聚苯并㗁唑前驅物除了上述式（3）的重複單元以外，還可以包含其他種類的重複結構單元。 就能夠抑制伴隨閉環之翹曲的發生之觀點而言，包含由下述式（SL）表示之二胺殘基作為其他種類的重複結構單元為較佳。In addition to the repeating unit of the above formula (3), the polybenzoxazole precursor may also include other types of repeating structural units. From the viewpoint of being able to suppress the occurrence of warpage accompanying ring closure, it is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit.

[化學式26]

Figure 02_image051
式（SL）中，Z具有a結構和b結構，R1s 為氫原子或碳數1～10的烴基，R2s 為碳數1～10的烴基，R3s 、R4s 、R5s 、R6s 中的至少1個為芳香族基，且剩餘部分為氫原子或碳數1～30的有機基，並且可以分別相同，亦可以分別不同。a結構及b結構的聚合可以係嵌段聚合，亦可以係無規聚合。Z部分的莫耳%中，a結構係5～95莫耳%，b結構係95～5莫耳%，a+b係100莫耳%。[Chemical formula 26]
Figure 02_image051
In formula (SL), Z has a structure and a structure b, R 1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbons, R 2s is a hydrocarbon group with 1 to 10 carbons, R 3s , R 4s , R 5s , R 6s At least one of them is an aromatic group, and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and they may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the mol% of the Z part, the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a+b is 100 mol%.

式（SL）中，作為較佳的Z，可舉出b結構中的R5s 及R6s 係苯基者。又，由式（SL）表示之結構的分子量係400～4,000為較佳，500～3,000為更佳。藉由將上述分子量設在上述範圍內，更有效地降低聚苯并㗁唑前驅物的脫水閉環後的彈性模數，能夠兼顧能夠抑制翹曲之效果和提高溶劑溶解性之效果。In the formula (SL), preferred Z includes those in which R 5s and R 6s in the structure b are phenyl groups. In addition, the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By setting the above-mentioned molecular weight within the above-mentioned range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be more effectively reduced, and the effect of suppressing warpage and the effect of improving solvent solubility can be both achieved.

在包含由式（SL）表示之二胺殘基作為其他種類的重複結構單元之情形下，還包含從四羧酸二酐去除酐基之後殘留之四羧酸殘基作為重複結構單元亦為較佳。作為這種四羧酸殘基的例子，可舉出式（2）中的R115 的例子。In the case where the diamine residue represented by the formula (SL) is included as another type of repeating structural unit, it is also more important to include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride as the repeating structural unit. good. As an example of such a tetracarboxylic acid residue, an example of R 115 in the formula (2) can be given.

例如，在用於後述之組成物之情形下，聚苯并㗁唑前驅物的重量平均分子量（Mw）較佳為18,000～30,000，更佳為20,000～29,000，進一步較佳為22,000～28,000。又，數平均分子量（Mn）較佳為7,200～14,000，更佳為8,000～12,000，進一步較佳為9,200～11,200。 上述聚苯并㗁唑前驅物的分子量的分散度係1.4以上為較佳，1.5以上為更佳，1.6以上為進一步較佳。聚苯并㗁唑前驅物的分子量的分散度的上限值並無特別限定，但是例如2.6以下為較佳，2.5以下為更佳，2.4以下為進一步較佳，2.3以下為進一步較佳，2.2以下為更進一步較佳。For example, when used in the composition described later, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and still more preferably 22,000 to 28,000. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200. The molecular weight dispersion of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the dispersion of the molecular weight of the polybenzoxazole precursor is not particularly limited, but for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is more preferable, 2.3 or less is more preferable, and 2.2 The following are further preferred.

〔聚苯并㗁唑〕 作為聚苯并㗁唑，只要係具有苯并㗁唑環之高分子化合物，則並無特別限定，但是由下述式（X）表示之化合物為較佳，由下述式（X）表示且具有聚合性基之化合物為更佳。 [化學式27]

Figure 02_image053
式（X）中，R133 表示2價的有機基，R134 表示4價的有機基。 在具有聚合性基之情形下，聚合性基可以位於R133 及R134 中的至少一方，如下述式（X-1）或式（X-2）所示，亦可以位於聚苯并㗁唑的末端。 式（X-1） [化學式28]
Figure 02_image055
式（X-1）中，R135 及R136 中的至少一方為聚合性基，在不是聚合性基之情形下為有機基，其他基團與式（X）含義相同。 式（X-2） [化學式29]
Figure 02_image057
式（X-2）中，R137 為聚合性基，其他為取代基，其他基團與式（X）含義相同。[Polybenzoxazole] As polybenzoxazole, as long as it is a polymer compound having a benzoxazole ring, it is not particularly limited, but a compound represented by the following formula (X) is preferred. The compound represented by the formula (X) and having a polymerizable group is more preferable. [Chemical formula 27]
Figure 02_image053
In formula (X), R 133 represents a divalent organic group, and R 134 represents a tetravalent organic group. In the case of having a polymerizable group, the polymerizable group may be located in at least one of R 133 and R 134 , as shown in the following formula (X-1) or formula (X-2), or may be located in polybenzoxazole The end. Formula (X-1) [Chemical formula 28]
Figure 02_image055
In the formula (X-1), at least one of R 135 and R 136 is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other groups have the same meaning as the formula (X). Formula (X-2) [Chemical Formula 29]
Figure 02_image057
In the formula (X-2), R137 is a polymerizable group, the others are substituents, and the other groups have the same meaning as in the formula (X).

聚合性基與上述聚醯亞胺前驅物等所具有之聚合性基中敘述之聚合性基含義相同。The polymerizable group has the same meaning as the polymerizable group described in the polymerizable group possessed by the polyimide precursor and the like.

R133 表示2價的有機基。作為2價的有機基，可舉出脂肪族或芳香族基。作為具體例，可舉出聚苯并㗁唑前驅物的式（3）中的R121 的例子。又，其較佳例與R121 相同。R 133 represents a divalent organic group. As a divalent organic group, an aliphatic or aromatic group can be mentioned. As a specific example, an example of R 121 in the formula (3) of the polybenzoxazole precursor can be given. In addition, the preferred example is the same as R 121.

R134 表示4價的有機基。作為4價的有機基，可舉出聚苯并㗁唑前驅物的式（3）中的R122 的例子。又，其較佳例與R122 相同。 例如，作為R122 而例示之4價的有機基的4個鍵結鍵與上述式（X）中的氮原子、氧原子鍵結而形成縮合環。例如，在R134 為下述有機基的情形下，形成下述結構。 [化學式30]

Figure 02_image059
R 134 represents a tetravalent organic group. Examples of the tetravalent organic group include R 122 in the formula (3) of the polybenzoxazole precursor. In addition, its preferred example is the same as R 122. For example, the four bonding bonds of the tetravalent organic group exemplified as R 122 are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, when R 134 is the following organic group, the following structure is formed. [Chemical formula 30]
Figure 02_image059

聚苯并㗁唑的㗁唑化率係85%以上為較佳，90%以上為更佳。藉由㗁唑化率為85%以上，基於藉由加熱而㗁唑化時引起之閉環之膜收縮變小，能夠更有效地抑制翹曲的發生。The azolization rate of polybenzoxazole is preferably 85% or more, and more preferably 90% or more. Since the azolization rate is 85% or more, the shrinkage of the film due to the closed loop caused by the azolization by heating is reduced, and the occurrence of warpage can be suppressed more effectively.

聚苯并㗁唑可以包含含有均為1種的R131 或R132 之上述式（X）的重複結構單元，亦可以包含含有2個以上的不同種類的R131 或R132 之上述式（X）的重複單元。又，聚苯并㗁唑除了上述式（X）的重複單元以外，還可以包含其他種類的重複結構單元。Azole may comprise polybenzoxazole㗁contain both kinds of R 131 or the formula (X), the repeating structural units of R 132, R contains also may comprise two or more different types of R 131 or 132 of the above-described formula (X ) Repeating unit. In addition, the polybenzoxazole may include other types of repeating structural units in addition to the repeating unit of the above formula (X).

聚苯并㗁唑例如可藉由使雙胺基苯酚衍生物與選自包含R133 之二羧酸或上述二羧酸的、二羧酸二氯化物及二羧酸衍生物等中之化合物進行反應來獲得聚苯并㗁唑前驅物，並利用已知的㗁唑化反應法來使其㗁唑化而獲得。 另外，在二羧酸的情形下，為了提高反應產率等，可以使用預先使1-羥基-1,2,3-苯并三唑等進行反應而得之活性酯型二羧酸衍生物。Polybenzoxazole can be carried out, for example, by making a diaminophenol derivative and a compound selected from the dicarboxylic acid containing R 133 or the above-mentioned dicarboxylic acid, dicarboxylic acid dichloride and dicarboxylic acid derivative, etc. The polybenzoxazole precursor is obtained by reaction, and it is obtained by azoleizing by a known azoleizing reaction method. In addition, in the case of dicarboxylic acid, in order to increase the reaction yield, etc., an active ester-type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole etc. in advance can be used.

聚苯并㗁唑的重量平均分子量（Mw）係5,000～70,000為較佳，8,000～50,000為更佳，10,000～30,000為進一步較佳。藉由將重量平均分子量設為5,000以上，能夠提高硬化後的膜的耐折性。為了獲得機械特性優異的有機膜，重量平均分子量係20,000以上為特佳。又，在含有2種以上的聚苯并㗁唑之情形下，至少1種聚苯并㗁唑的重量平均分子量在上述範圍內為較佳。The weight average molecular weight (Mw) of the polybenzoxazole is preferably from 5,000 to 70,000, more preferably from 8,000 to 50,000, and even more preferably from 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. Moreover, when two or more types of polybenzoxazole are contained, the weight average molecular weight of at least one type of polybenzoxazole is preferably within the above-mentioned range.

〔聚醯亞胺前驅物等之製造方法〕 聚醯亞胺前驅物等可藉由使二羧酸或二羧酸衍生物與二胺進行反應而獲得。較佳為藉由利用鹵化劑使二羧酸或二羧酸衍生物進行鹵化之後，與二胺進行反應而獲得。 聚醯亞胺前驅物等之製造方法中，進行反應時，使用有機溶劑為較佳。有機溶劑可以係1種，亦可以係2種以上。 作為有機溶劑，能夠依據原材料而適當地確定，但是可例示吡啶、二乙二醇二甲醚（二甘二甲醚）、N-甲基吡咯啶酮及N-乙基吡咯啶酮。 聚醯亞胺可以在合成聚醯亞胺前驅物之後，藉由熱醯亞胺化、化學醯亞胺化（例如，藉由使觸媒發揮作用來促進環化反應）等方法進行環化來製造，亦可以直接合成聚醯亞胺。[Manufacturing methods of polyimide precursors, etc.] The polyimide precursor and the like can be obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent, and then reacting with a diamine. In the production method of the polyimide precursor, etc., it is preferable to use an organic solvent when the reaction is carried out. The organic solvent may be one type or two or more types. The organic solvent can be appropriately determined depending on the raw material, but pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone can be exemplified. Polyimine can be cyclized by methods such as thermal imidization and chemical imidization (for example, by using a catalyst to promote the cyclization reaction) after synthesizing the polyimine precursor. Manufacture, can also directly synthesize polyimide.

-封端劑- 在聚醯亞胺前驅物等之製造方法時，為了進一步提高保存穩定性，用酸酐、單羧酸、單醯氯化合物、單活性酯化合物等封端劑密封聚醯亞胺前驅物等的末端為較佳。作為封端劑，使用單胺為更佳，作為單胺的較佳的化合物，可舉出苯胺、2-乙炔苯胺、3-乙炔苯胺、4-乙炔苯胺、5-胺基-8-羥基喹啉、1-羥基-7-胺萘、1-羥基-6-胺萘、1-羥基-5-胺萘、1-羥基-4-胺萘、2-羥基-7-胺萘、2-羥基-6-胺萘、2-羥基-5-胺萘、1-羧基-7-胺萘、1-羧基-6-胺萘、1-羧基-5-胺萘、2-羧基-7-胺萘、2-羧基-6-胺萘、2-羧基-5-胺萘、2-胺基苯甲酸、3-胺基苯甲酸、4-胺基苯甲酸、4-胺基水楊酸、5-胺基水楊酸、6-胺基水楊酸、2-胺基苯磺酸、3-胺基苯磺酸、4-胺基苯磺酸、3-胺基-4,6-二羥基嘧啶、2-胺基苯酚、3-胺基苯酚、4-胺基苯酚、2-胺基苯硫酚、3-胺基苯硫酚、4-胺基苯硫酚等。可以使用該等中的2種以上，亦可以藉由使複數種封端劑進行反應來導入複數個不同的末端基。-Capping agent- In the production method of polyimide precursors, etc., in order to further improve storage stability, the ends of polyimide precursors, etc. are sealed with end-capping agents such as acid anhydrides, monocarboxylic acids, monochlorine compounds, and monoactive ester compounds. For better. As a blocking agent, it is more preferable to use a monoamine. As a preferable compound of a monoamine, aniline, 2-acetylene aniline, 3-acetylene aniline, 4-acetylene aniline, 5-amino-8-hydroxyquine Morpholine, 1-hydroxy-7-amine naphthalene, 1-hydroxy-6-amine naphthalene, 1-hydroxy-5-amine naphthalene, 1-hydroxy-4-amine naphthalene, 2-hydroxy-7-amine naphthalene, 2-hydroxy -6-Aminonaphthalene, 2-hydroxy-5-aminenaphthalene, 1-carboxy-7-aminenaphthalene, 1-carboxy-6-aminenaphthalene, 1-carboxy-5-aminenaphthalene, 2-carboxy-7-aminenaphthalene , 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5- Aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine , 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these can be used, or a plurality of different terminal groups can be introduced by reacting a plurality of end-capping agents.

-固體析出- 在製造聚醯亞胺前驅物等時，可以包括析出固體之步驟。具體而言，藉由使反應液中的聚醯亞胺前驅物等沉澱於水中，並溶解於四氫呋喃等可溶解聚醯亞胺前驅物等之溶劑中，而能夠析出固體。 然後，對聚醯亞胺前驅物等進行乾燥，而能夠獲得粉末狀的聚醯亞胺前驅物等。-Solid precipitation- In the production of polyimide precursors, etc., a step of precipitation of solids may be included. Specifically, by precipitating the polyimide precursor and the like in the reaction liquid in water and dissolving the polyimide precursor and the like in a solvent such as tetrahydrofuran, the solid can be deposited. Then, by drying the polyimide precursor and the like, a powdery polyimide precursor and the like can be obtained.

〔含量〕 相對於組成物的總固體成分，本發明的組成物中的樹脂的含量係20質量%以上為較佳，30質量%以上為更佳，40質量%以上為進一步較佳，50質量%以上為進一步較佳。又，相對於組成物的總固體成分，本發明的組成物中的樹脂的含量係99.5質量%以下為較佳，99質量%以下為更佳，98質量%以下為進一步較佳，97質量%以下為進一步較佳，95質量%以下為更進一步較佳。 本發明的組成物可以僅包含1種樹脂，亦可以包含2種以上。在包含2種以上之情形下，總量成為上述範圍為較佳。〔content〕 Relative to the total solid content of the composition, the content of the resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and 50% by mass or more Further better. In addition, relative to the total solid content of the composition, the content of the resin in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, more preferably 98% by mass or less, 97% by mass The following is more preferable, and 95% by mass or less is even more preferable. The composition of the present invention may include only one type of resin, or may include two or more types. When two or more types are contained, it is preferable that the total amount falls within the above-mentioned range.

＜其他樹脂＞ 本發明的組成物可以包含上述之特定樹脂和與特定樹脂不同的其他樹脂（以下，還簡稱為“其他樹脂”。）。 作為其他樹脂，可舉出與特定樹脂不同種類的聚醯亞胺、聚醯亞胺前驅物、聚苯并㗁唑、聚苯并㗁唑前驅物、聚醯胺醯亞胺、聚醯胺醯亞胺前驅物、酚樹脂、聚醯胺、環氧樹脂、聚矽氧烷、包含矽氧烷結構之樹脂、丙烯酸樹脂等。 例如，藉由進一步加入丙烯酸樹脂，可獲得塗佈性優異的組成物，且可獲得耐溶劑性優異的有機膜。 例如，代替後述之聚合性化合物或除了後述之聚合性化合物以外，將重量平均分子量為20,000以下的聚合性基值高的丙烯酸系樹脂添加到組成物中，藉此能夠提高組成物的塗佈性、有機膜的耐溶劑性等。＜Other resins＞ The composition of the present invention may include the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also simply referred to as "other resin"). Examples of other resins include polyimide, polyimide precursors, polybenzoxazole, polybenzoxazole precursors, polyimides, and polyimides that are different from the specific resins. Imine precursors, phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing silicone structures, acrylic resins, etc. For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, and an organic film having excellent solvent resistance can be obtained. For example, instead of the polymerizable compound described later or in addition to the polymerizable compound described later, an acrylic resin with a high polymerizable base value having a weight average molecular weight of 20,000 or less is added to the composition, thereby improving the coating properties of the composition , Solvent resistance of organic film, etc.

在本發明的組成物包含其他樹脂之情形下，相對於組成物的總固體成分，其他樹脂的含量係0.01質量%以上為較佳，0.05質量%以上為更佳，1質量%以上為進一步較佳，2質量%以上為進一步較佳，5質量%以上為更進一步較佳，10質量%以上為更進一步較佳。 又，相對於組成物的總固體成分，本發明的組成物中的其他樹脂的含量係80質量%以下為較佳，75質量%以下為更佳，70質量%以下為進一步較佳，60質量%以下為進一步較佳，50質量%以下為更進一步較佳。 又，作為本發明的組成物的較佳的一態樣，還能夠設為其他樹脂的含量低的態樣。在上述態樣中，相對於組成物的總固體成分，其他樹脂的含量係20質量%以下為較佳，15質量%以下為更佳，10質量%以下為進一步較佳，5質量%以下為進一步較佳，1質量%以下為更進一步較佳。上述含量的下限並無特別限定，只要係0質量%以上即可。 本發明的組成物可以僅包含1種其他樹脂，亦可以包含2種以上。在包含2種以上之情形下，總量成為上述範圍為較佳。In the case where the composition of the present invention contains other resins, relative to the total solid content of the composition, the content of the other resin is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 1% by mass or more. Preferably, it is more preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more. In addition, relative to the total solid content of the composition, the content of other resins in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass or less, and 60% by mass % Or less is more preferable, and 50 mass% or less is still more preferable. Moreover, as a preferable aspect of the composition of this invention, it can also be set as the aspect in which the content of other resin is low. In the above aspect, relative to the total solid content of the composition, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less, and 5% by mass or less More preferably, 1% by mass or less is even more preferable. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more. The composition of the present invention may include only one type of other resin, or may include two or more types. When two or more types are contained, it is preferable that the total amount falls within the above-mentioned range.

＜光敏劑＞ 本發明的組成物包含光敏劑為較佳。 作為光敏劑，光聚合起始劑為較佳。＜Photosensitizer＞ The composition of the present invention preferably contains a photosensitizer. As the photosensitizer, a photopolymerization initiator is preferred.

〔光聚合起始劑〕 本發明的組成物包含光聚合起始劑作為光敏劑為較佳。 光聚合起始劑係光自由基聚合起始劑為較佳。作為光自由基聚合起始劑，並無特別限制，能夠適當地選自公知的光自由基聚合起始劑中。例如，針對紫外線區域至可見區域的光線具有感光性之光自由基聚合起始劑為較佳。又，可以係與經光激勵之增感劑產生某種作用並生成活性自由基之活性劑。〔Photopolymerization initiator〕 The composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer. The photopolymerization initiator is preferably a photoradical polymerization initiator. The radical photopolymerization initiator is not particularly limited, and it can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator having photosensitivity for light from the ultraviolet region to the visible region is preferable. In addition, it can be an active agent that has a certain effect with a light-excited sensitizer and generates active free radicals.

在有機膜中，就容易滿足選自包括上述式（1）及式（2）之群組中之至少1個式之觀點而言，本發明的組成物包含後述之含有金屬元素之化合物作為光自由基聚合起始劑為較佳。亦即，在本發明中，後述之含有金屬元素之化合物中，能夠將具有自由基聚合起始能力者用作光自由基聚合起始劑。 在此，具有自由基聚合起始能力係指能夠產生能夠起始自由基聚合之游離基。例如，對包含自由基聚合性單體、黏合劑聚合物及含有金屬元素之化合物之組成物，照射含有金屬元素之化合物吸收光且自由基聚合性單體不吸收光之波長區域的光時，能夠藉由確認自由基聚合性單體是否消失來確認有無聚合起始能力。為了確認是否消失，能夠依據自由基聚合性單體、黏合劑聚合物的種類來選擇適當的方法，但是例如只要藉由IR測量（紅外分光測量）或HPLC測量（高效液相層析術）來確認即可。In the organic film, from the viewpoint of easily satisfying at least one formula selected from the group consisting of the above-mentioned formula (1) and formula (2), the composition of the present invention includes a compound containing a metal element described later as a light A radical polymerization initiator is preferred. That is, in the present invention, among the metal element-containing compounds described later, those having the ability to initiate radical polymerization can be used as a photoradical polymerization initiator. Here, having the ability to initiate radical polymerization refers to the ability to generate free radicals capable of initiating radical polymerization. For example, when a composition containing a radical polymerizable monomer, a binder polymer, and a compound containing a metal element is irradiated with light in a wavelength region where the compound containing the metal element absorbs light and the radical polymerizable monomer does not absorb light, The presence or absence of polymerization initiation ability can be confirmed by confirming whether the radical polymerizable monomer has disappeared. In order to confirm whether it disappears, an appropriate method can be selected according to the types of radically polymerizable monomers and binder polymers, but for example, it can be measured by IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography). Just confirm.

在本發明的組成物包含具有自由基聚合起始能力之含有金屬元素之化合物等之情形下，本發明的組成物實質上不含除了上述含有金屬元素之化合物以外的自由基聚合起始劑亦為較佳。實質上不含除了上述含有金屬元素之化合物以外的自由基聚合起始劑係指在本發明的組成物中，相對於上述含有金屬元素之化合物的總質量，除了上述含有金屬元素之化合物以外的其他自由基聚合起始劑的含量為5質量%以下，3質量%以下為較佳，1質量%以下為更佳，0.1質量%為進一步較佳。 又，在本發明的組成物包含具有自由基聚合起始能力之含有金屬元素之化合物等之情形下，本發明的組成物包含上述含有金屬元素之化合物和其他光自由基聚合起始劑亦為較佳。 在本發明的組成物中，包含含有金屬元素之化合物和其他光自由基聚合起始劑之情形下，相對於含有金屬元素之化合物和其他光自由基聚合起始劑的總含量，含有金屬元素之化合物的含量係20～80質量%為較佳，30～70質量%為更佳。 又，作為上述其他光自由基聚合起始劑，後述肟化合物為較佳。In the case where the composition of the present invention contains a metal element-containing compound having the ability to initiate radical polymerization, the composition of the present invention does not substantially contain any radical polymerization initiator other than the above-mentioned metal element-containing compound. For better. Substantially free of radical polymerization initiators other than the above-mentioned metal element-containing compound means that in the composition of the present invention, relative to the total mass of the above-mentioned metal element-containing compound, excluding the above-mentioned metal element-containing compound The content of the other radical polymerization initiator is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass. In addition, in the case where the composition of the present invention contains a metal element-containing compound having the ability to initiate radical polymerization, the composition of the present invention contains the above-mentioned metal element-containing compound and other photo-radical polymerization initiators. Better. In the composition of the present invention, when a compound containing a metal element and another photo-radical polymerization initiator is included, the metal element is contained relative to the total content of the compound containing the metal element and the other photo-radical polymerization initiator The content of the compound is preferably 20 to 80% by mass, more preferably 30 to 70% by mass. In addition, as the above-mentioned other radical photopolymerization initiator, an oxime compound described later is preferable.

光自由基聚合起始劑含有至少1種在約300～800nm（較佳為330～500nm）的範圍內具有至少約50L·mol-1 ·cm-1 的莫耳吸光係數之化合物為較佳。化合物的莫耳吸光係數能夠利用公知的方法來進行測量。例如，藉由紫外可見分光光度計（Varian公司製造之Cary-5分光光度計（spectrophotometer）），使用乙酸乙酯溶劑以0.01g/L的濃度進行測量為較佳。The photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L·mol -1 ·cm -1 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), it is better to use ethyl acetate solvent to measure at a concentration of 0.01 g/L.

作為光自由基聚合起始劑，能夠任意地使用公知的化合物。例如，可舉出鹵化烴衍生物（例如，具有三𠯤骨架之化合物、具有㗁二唑骨架之化合物、具有三鹵甲基之化合物等）、醯基氧化膦等醯基膦化合物、六芳基雙咪唑、肟衍生物等肟化合物、有機過氧化物、硫化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮化合物、羥基苯乙酮、偶氮系化合物、疊氮化合物、茂金屬化合物、有機硼化合物、鐵芳烴錯合物等。關於該等的詳細內容，能夠參閱日本特開2016-027357號公報的0165～0182段、國際公開第2015/199219號的0138～0151段的記載，且該內容被編入本說明書中。As the photoradical polymerization initiator, a known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazole skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), phosphonium phosphine compounds such as oxyphosphine oxide, and hexaaryl Oxime compounds such as bisimidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, and azide compounds , Metallocene compounds, organoboron compounds, iron arene complexes, etc. For the details, refer to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A, and paragraphs 0138 to 0151 of International Publication No. 2015/199219, and the contents are incorporated in this specification.

作為酮化合物，例如，可例示日本特開2015-087611號公報的0087段中所記載之化合物，且該內容被編入本說明書中。市售品中，亦可較佳地使用KAYACURE DETX（Nippon Kayaku Co.,Ltd.製造）。As the ketone compound, for example, the compound described in paragraph 0087 of JP 2015-087611 A can be exemplified, and the content is incorporated in this specification. Among the commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

在本發明的一實施態樣中，作為光自由基聚合起始劑，能夠較佳地使用羥基苯乙酮化合物、胺基苯乙酮化合物及醯基膦化合物。更具體而言，例如，能夠使用日本特開平10-291969號公報中所記載之胺基苯乙酮系起始劑、日本專利第4225898號中所記載之醯基膦氧化物系起始劑。In one aspect of the present invention, as the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and phosphine compounds can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the phosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.

作為羥基苯乙酮系起始劑，能夠使用IRGACURE 184（IRGACURE為註冊商標）、DAROCUR 1173、IRGACURE 500、IRGACURE-2959、IRGACURE 127（商品名稱：均為BASF公司製造）。As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), 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 379（商品名稱：均為BASF公司製造）。As the aminoacetophenone-based initiator, IRGACURE 907, IRGACURE 369, and IRGACURE 379 (brand names: all manufactured by BASF Corporation), which are commercially available products, can be used.

作為胺基苯乙酮系起始劑，還能夠使用最大吸收波長與365nm或405nm等的波長光源匹配之日本特開2009-191179號公報中所記載之化合物。As the aminoacetophenone-based initiator, it is also possible to use the compound described in JP 2009-191179 A whose maximum absorption wavelength matches a wavelength light source such as 365 nm or 405 nm.

作為醯基氧化膦系起始劑，可舉出2,4,6-三甲基苯甲醯基-二苯基-氧化膦等。又，能夠使用作為市售品之IRGACURE-819、IRGACURE-TPO（商品名稱：均為BASF公司製造）。As an acylphosphine oxide-based initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide and the like can be mentioned. In addition, IRGACURE-819 and IRGACURE-TPO (brand names: all manufactured by BASF Corporation), which are commercially available products, can be used.

作為茂金屬化合物，可例示IRGACURE-784、IRGACURE-784EG（均由BASF公司製造）等。茂金屬化合物中包含後述含有金屬元素之化合物，該化合物具有自由基聚合起始能力。As the metallocene compound, IRGACURE-784, IRGACURE-784EG (all manufactured by BASF Corporation), etc. can be exemplified. The metallocene compound includes a compound containing a metal element described later, and the compound has the ability to initiate radical polymerization.

作為光自由基聚合起始劑，可更佳地舉出肟化合物。藉由使用肟化合物，能夠更有效地提高曝光寬容度。關於肟化合物，由於曝光寬容度（曝光餘裕度（exposure margin））寬，且還作為光硬化促進劑發揮作用，因此為特佳。As the photoradical polymerization initiator, an oxime compound can be more preferably mentioned. By using oxime compounds, the exposure latitude can be improved more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also functions as a photohardening accelerator.

作為肟化合物的具體例，能夠使用日本特開2001-233842號公報中所記載之化合物、日本特開2000-080068號公報中所記載之化合物、日本特開2006-342166號公報中所記載之化合物。As specific examples of the oxime compound, the compound described in JP 2001-233842 A, the compound described in JP 2000-080068 A, and the compound described in JP 2006-342166 can be used. .

作為較佳的肟化合物，例如可舉出下述結構的化合物、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-乙醯氧基亞胺基丁烷-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。本發明的組成物中，尤其，作為光自由基聚合起始劑，使用肟化合物（肟系光聚合起始劑）為較佳。肟系光聚合起始劑在分子內具有＞C=N-O-C（=O）-的連結基。As a preferable oxime compound, for example, a compound having the following structure, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-acetoxyiminobutan-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-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one and the like. In the composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

[化學式31]

Figure 02_image061
[Chemical formula 31]
Figure 02_image061

市售品中，還可較佳地使用IRGACURE OXE 01、IRGACURE OXE 02、IRGACURE OXE 03、IRGACURE OXE 04（以上，BASF公司製造）、Adeka Optomer N-1919（ADEKA CORPORATION製造，日本特開2012-014052號公報中所記載之光自由基聚合起始劑2）。又，還能夠使用TR-PBG-304（Changzhou Tronly New Electronic Materials CO.,LTD.製造）、ADEKA ARKLS NCI-831及ADEKA ARKLS NCI-930（ADEKA CORPORATION製造）。又，能夠使用DFI-091（DAITO CHEMIX Co., Ltd.製造）。Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF Corporation), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, JP 2012-014052) The photo-radical polymerization initiator described in No. 2). In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.

又，還能夠使用具有氟原子之肟化合物。作為這種肟化合物的具體例，可舉出日本特開2010-262028號公報中所記載之化合物、日本特表2014-500852號公報的0345段中所記載之化合物24、化合物36～化合物40、日本特開2013-164471號公報的0101段中所記載之化合物（C-3）等。In addition, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in Japanese Patent Application Publication No. 2010-262028, and the compounds described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, compound 24, compound 36 to compound 40, The compound (C-3) described in paragraph 0101 of JP 2013-164471 A, etc.

作為最佳的肟化合物，可舉出日本特開2007-269779號公報中所示之具有特定取代基之肟化合物、日本特開2009-191061號公報中所示之具有硫基芳基之肟化合物等。As the best oxime compound, oxime compounds having specific substituents shown in Japanese Patent Application Publication No. 2007-269779, and oxime compounds having a thioaryl group shown in Japanese Patent Application Publication No. 2009-191061 Wait.

就曝光靈敏度的觀點而言，光自由基聚合起始劑係選自包括三鹵甲基三𠯤（trihalo methyl triazine）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、三芳基咪唑二聚物、鎓鹽化合物、苯并噻唑化合物、二苯基酮化合物、苯乙酮化合物及其衍生物、環戊二烯-苯-鐵錯合物及其鹽、鹵甲基㗁二唑化合物、3-芳基取代香豆素化合物之群組中之化合物為較佳。From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is selected from the group including trihalo methyl triazine (trihalo methyl triazine) compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, and α-amines. Ketone compounds, phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, diphenyl ketone compounds, acetophenone compounds and their derivatives Cyclopentadiene-benzene-iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferably compounds in the group.

進一步較佳的光自由基聚合起始劑為三鹵甲基三𠯤化合物、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、三芳基咪唑二聚物、鎓鹽化合物、二苯基酮化合物、苯乙酮化合物，選自包括三鹵甲基三𠯤化合物、α-胺基酮化合物、肟化合物、三芳基咪唑二聚物、二苯基酮化合物之群組中之至少1種化合物為進一步較佳，使用茂金屬化合物或肟化合物為更進一步較佳，肟化合物為更進一步較佳。Further preferred photo-radical polymerization initiators are trihalomethyl tri-ketone compounds, α-amino ketone compounds, phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, Onium salt compounds, diphenyl ketone compounds, and acetophenone compounds, selected from the group including trihalomethyl triketone compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and diphenyl ketone compounds At least one compound in the group is more preferable, a metallocene compound or an oxime compound is more preferable, and an oxime compound is still more preferable.

又，光自由基聚合起始劑還能夠使用二苯基酮、N,N’-四甲基-4,4’-二胺基二苯基酮（米蚩酮）等N,N’-四烷基-4,4’-二胺基二苯基酮、2-苄基-2-二甲基胺基-1-（4-口末啉基苯基）-丁酮-1,2-甲基-1-[4-（甲基硫基）苯基]-2-口末啉基-丙酮-1等芳香族酮、烷基蒽醌等與芳香環稠合之醌類、安息香烷基醚等安息香醚化合物、安息香、烷基安息香等安息香化合物、苄基二甲基縮酮等苄基衍生物等。又，還能夠使用由下述式（I）表示之化合物。In addition, the photoradical polymerization initiator can also use N,N'-tetrakis such as diphenyl ketone, N,N'-tetramethyl-4,4'-diaminodiphenyl ketone (Michler’s ketone), etc. Alkyl-4,4'-diaminodiphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-endolinylphenyl)-butanone-1,2-methanone Aromatic ketones such as -1-[4-(methylsulfanyl)phenyl]-2-endolinyl-acetone-1, quinones condensed with aromatic rings such as alkylanthraquinones, and benzoin alkyl ethers Benzoin ether compounds, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. In addition, a compound represented by the following formula (I) can also be used.

[化學式32]

Figure 02_image063
[Chemical formula 32]
Figure 02_image063

式（I）中，RI00 為碳數1～20的烷基、被1個以上的氧原子中斷之碳數2～20的烷基、碳數1～12的烷氧基、苯基、碳數1～20的烷基、碳數1～12的烷氧基、鹵素原子、環戊基、環己基、碳數2～12的烯基、被1個以上的氧原子中斷之碳數2～18的烷基及被至少1個碳數1～4的烷基取代之苯基或聯苯，RI01 為由式（II）表示之基團或者與RI00 相同的基團，RI02 ～RI04 各自獨立地為碳數1～12的烷基、碳數1～12的烷氧基或鹵素。In the formula (I), R I00 is an alkyl group having 1 to 20 carbons, an alkyl group having 2 to 20 carbons interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbons, a phenyl group, a carbon Alkyl groups having 1-20, alkoxy groups having 1-12 carbons, halogen atoms, cyclopentyl, cyclohexyl, alkenyl groups having 2-12 carbons, and carbon numbers 2 to 2 interrupted by one or more oxygen atoms The alkyl group of 18 and the phenyl or biphenyl substituted by at least one alkyl group having 1 to 4 carbons, R I01 is a group represented by formula (II) or the same group as R I00 , R I02 to R I04 is each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or halogen.

[化學式33]

Figure 02_image065
[Chemical formula 33]
Figure 02_image065

式中，RI05 ～RI07 與上述式（I）的RI02 ～RI04 相同。In the formula, R I05 to R I07 are the same as R I02 to R I04 in the above formula (I).

又，光自由基聚合起始劑還能夠使用國際公開第2015/125469號的0048～0055段中所記載之化合物。In addition, the photoradical polymerization initiator can also use the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

在包含光聚合起始劑之情形下，其含量相對於本發明的組成物的總固體成分係0.1～30質量%為較佳，更佳為0.1～20質量%，進一步較佳為0.5～15質量%，進一步較佳為1.0～10質量%。光聚合起始劑可以僅含有1種，亦可以含有2種以上。在含有2種以上的光聚合起始劑之情形下，總量在上述範圍內為較佳。In the case of containing the photopolymerization initiator, its content is preferably 0.1-30% by mass relative to the total solid content of the composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 0.5-15 % By mass, more preferably 1.0 to 10% by mass. The photopolymerization initiator may contain only one type or two or more types. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above-mentioned range.

〔光酸產生劑〕 又，本發明的組成物包含光酸產生劑作為光敏劑亦為較佳。 藉由含有光酸產生劑，例如，在組成物層的曝光部產生酸，上述曝光部相對於顯影液（例如，鹼水溶液）之溶解性增加，能夠獲得曝光部被顯影液去除之正型浮雕圖案。 又，還能夠設為如下態樣：組成物含有光酸產生劑和除了後述之自由基聚合性化合物以外的聚合性化合物，藉此，例如藉由在曝光部產生之酸促進上述聚合性化合物的交聯反應，曝光部相較於非曝光部更難以被顯影液去除。依據這種態樣，能夠獲得負型浮雕圖案。〔Photoacid generator〕 Furthermore, it is also preferable that the composition of the present invention contains a photoacid generator as a photosensitizer. By containing a photoacid generator, for example, acid is generated in the exposed part of the composition layer, the solubility of the exposed part with respect to the developer (for example, an aqueous alkali solution) is increased, and a positive relief in which the exposed part is removed by the developer can be obtained pattern. In addition, it can also be set as an aspect in which the composition contains a photoacid generator and a polymerizable compound other than the radical polymerizable compound described below, whereby, for example, the acid generated in the exposed portion promotes the formation of the polymerizable compound. In the crosslinking reaction, the exposed part is more difficult to be removed by the developer than the non-exposed part. According to this aspect, a negative relief pattern can be obtained.

作為光酸產生劑，只要係藉由曝光產生酸者，則並無特別限定，但是能夠舉出醌二疊氮化物、重氮鹽、鏻鹽、鋶鹽、錪鹽等鎓鹽化合物、醯亞胺基磺酸鹽、肟磺酸鹽、重氮二碸、二碸、鄰硝基苄基磺酸鹽等磺酸鹽化合物等。The photoacid generator is not particularly limited as long as it generates acid by exposure, but it can include onium salt compounds such as quinonediazide, diazonium salt, phosphonium salt, sulfonium salt, and iodonium salt. Sulfonate compounds such as amine sulfonate, oxime sulfonate, diazo disulfonate, disulfonate, o-nitrobenzyl sulfonate, etc.

作為醌二疊氮化物，可舉出醌二疊氮的磺酸藉由酯鍵結於多羥基化合物而成者、醌二疊氮的磺酸藉由磺醯胺鍵結於聚胺基化合物而成者、醌二疊氮的磺酸藉由酯鍵及磺醯胺鍵中的至少一方鍵結於多羥基聚胺基化合物而成者等。在本發明中，例如，該等多羥基化合物、聚胺基化合物的官能基整體的50莫耳%以上被醌二疊氮取代為較佳。As the quinone diazide compound, a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound through an ester, and a sulfonic acid of quinonediazide is bonded to a polyamine compound through a sulfonamide. As a result, the sulfonic acid of quinonediazide is bonded to a polyhydroxypolyamine-based compound through at least one of an ester bond and a sulfonamide bond. In the present invention, for example, it is preferable that 50 mol% or more of the entire functional groups of the polyhydroxy compounds and polyamine compounds are substituted with quinonediazide.

在本發明中，醌二疊氮可較佳地使用5-萘醌二疊氮磺醯基、4-萘醌二疊氮磺醯基中的任一個。4-萘醌二疊氮磺醯酯化合物在水銀燈的i射線區域具有吸收，適於i射線曝光。5-萘醌二疊氮磺醯酯化合物的吸收延伸到水銀燈的g射線區域，適於g射線曝光。在本發明中，依據曝光之波長來選擇4-萘醌二疊氮磺醯酯化合物、5-萘醌二疊氮磺醯酯化合物為較佳。又，可以含有在同一分子中具有4-萘醌二疊氮磺醯基、5-萘醌二疊氮磺醯基之萘醌二疊氮磺醯酯化合物，亦可以含有4-萘醌二疊氮磺醯酯化合物和5-萘醌二疊氮磺醯酯化合物。In the present invention, the quinone diazide can preferably use any of 5-naphthoquinone diazide sulfonyl and 4-naphthoquinone diazide sulfonyl. The 4-naphthoquinone diazide sulfonate compound has absorption in the i-ray region of the mercury lamp and is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazide sulfonate compound extends to the g-ray region of the mercury lamp, which is suitable for g-ray exposure. In the present invention, it is preferable to select 4-naphthoquinone diazide sulfonate compound and 5-naphthoquinone diazide sulfonate compound according to the wavelength of exposure. In addition, it may contain a naphthoquinone diazide sulfonyl ester compound having 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group in the same molecule, or 4-naphthoquinone diazide sulfonyl ester compound Azosulfonate compound and 5-naphthoquinone diazide sulfonate compound.

上述萘醌二疊氮化物能夠藉由具有酚性羥基之化合物與醌二疊氮磺酸化合物的酯化反應來合成，能夠藉由公知的方法來合成。藉由使用該等萘醌二疊氮化物，解析度、靈敏度、殘膜率得到進一步提高。 作為上述萘醌二疊氮化物，例如，可舉出1,2-萘醌-2-二疊氮-5-磺酸或1,2-萘醌-2-二疊氮-4-磺酸、該等化合物的鹽或酯化合物等。The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazides, the resolution, sensitivity, and residual film rate are further improved. As the above-mentioned naphthoquinone diazide compounds, for example, 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, Salts or ester compounds of these compounds, etc.

作為鎓鹽化合物或磺酸鹽化合物，可舉出日本特開2008-013646號公報的0064～0122段中所記載之化合物等。 除此以外，作為光酸產生劑，可以使用市售品。作為市售品，可舉出WPAG-145、WPAG-149、WPAG-170、WPAG-199、WPAG-336、WPAG-367、WPAG-370、WPAG-469、WPAG-638、WPAG-699（均由FUJIFILM Wako Pure Chemical Corporation製造）等。Examples of the onium salt compound or sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP 2008-013646 A, and the like. In addition, as the photoacid generator, a commercially available product can be used. As commercially available products, WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638, WPAG-699 (all made by FUJIFILM Wako Pure Chemical Corporation), etc.

在包含光酸產生劑之情形下，其含量相對於本發明的組成物的總固體成分係0.1～30質量%為較佳，0.1～20質量%為更佳，2～15質量%為進一步較佳。光酸產生劑可以僅含有1種，亦可以含有2種以上。在含有2種以上的光酸產生劑之情形下，其總計在上述範圍內為較佳。In the case of containing the photoacid generator, its content is preferably 0.1-30% by mass relative to the total solid content of the composition of the present invention, more preferably 0.1-20% by mass, and more preferably 2-15% by mass. good. The photoacid generator may contain only 1 type, and may contain 2 or more types. When two or more types of photoacid generators are contained, the total amount is preferably within the above-mentioned range.

＜含有金屬元素之化合物＞ 本發明的組成物還包含含有金屬元素之化合物為較佳。 就進一步提高耐溶劑性之觀點而言，本發明中的含有金屬元素之化合物係上述光自由基聚合起始劑為較佳。 含有金屬元素之化合物係包含金屬元素之有機物為較佳。亦即，有機金屬化合物為較佳。 又，作為本發明中的含有金屬元素之化合物中的金屬元素，可舉出鐵、鈀、鎳、第4族元素等，但是第4族元素為較佳。 亦即，含有金屬元素之化合物係含有第4族元素之化合物為較佳，含有第4族元素之有機化合物為更佳。 作為含有第4族元素之化合物，包含選自包括鈦原子、鋯原子及鉿原子之群組中之至少1個之有機化合物為較佳，包含選自包括鈦原子及鋯原子之群組中之至少1個之有機化合物為更佳，包含鈦原子之有機化合物為進一步較佳。又，包含選自鈦原子及鋯原子中之至少1個之有機化合物較佳為包含有機基和鈦原子或鋯原子之有機化合物，上述有機化合物一分子中所包含之鈦原子及鋯原子的數量以總計係1個為較佳。作為有機基，並無特別限定，但是由烴基或烴基與雜原子的組合組成之基團為較佳。作為雜原子，氧原子、硫原子、氮原子為較佳。 在本發明中，至少1個有機基係環狀基為較佳，至少2個係環狀基為更佳。上述環狀基從5員環的環狀基及6員環的環狀基中選擇為較佳，從5員環的環狀基中選擇為更佳。作為5員環的環狀基，環戊二烯基為較佳。又，本發明中所使用之有機鈦化合物等在一分子中包含2～4個環狀基為較佳。 本發明中的含有第4族元素之化合物係由下述式（P）表示之化合物為較佳。 [化學式34]

Figure 02_image067
式（P）中，M為第4族元素，R分別獨立地表示取代基。 上述R分別獨立地從芳香族基、烷基、鹵素原子及烷基磺醯氧基中選擇為較佳。<Compound containing a metal element> It is preferable that the composition of the present invention further contains a compound containing a metal element. From the viewpoint of further improving the solvent resistance, the metal element-containing compound in the present invention is preferably the aforementioned photoradical polymerization initiator. The compound containing the metal element is preferably an organic substance containing the metal element. That is, organometallic compounds are preferred. In addition, as the metal element in the metal element-containing compound in the present invention, iron, palladium, nickel, group 4 elements, etc. can be cited, but group 4 elements are preferred. That is, the compound containing a metal element is preferably a compound containing a group 4 element, and an organic compound containing a group 4 element is more preferable. As the compound containing group 4 elements, organic compounds containing at least one selected from the group consisting of titanium atoms, zirconium atoms, and hafnium atoms are preferred, including those selected from the group consisting of titanium atoms and zirconium atoms. At least one organic compound is more preferable, and an organic compound containing a titanium atom is even more preferable. In addition, the organic compound containing at least one member selected from the group consisting of titanium and zirconium atoms is preferably an organic compound containing an organic group and a titanium atom or a zirconium atom. The number of titanium and zirconium atoms contained in one molecule of the organic compound is It is better to have one in total. The organic group is not particularly limited, but a group composed of a hydrocarbon group or a combination of a hydrocarbon group and a heteroatom is preferred. As the hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferable. In the present invention, at least one organic cyclic group is preferable, and at least two cyclic groups are more preferable. The above-mentioned cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably selected from a 5-membered cyclic group. As the 5-membered cyclic group, a cyclopentadienyl group is preferred. In addition, the organotitanium compound used in the present invention preferably contains 2 to 4 cyclic groups in one molecule. The compound containing a group 4 element in the present invention is preferably a compound represented by the following formula (P). [Chemical formula 34]
Figure 02_image067
In formula (P), M is a group 4 element, and R each independently represents a substituent. The above-mentioned R is preferably selected independently from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

作為M所表示之第4族元素，鈦原子、鋯原子及鉿原子為較佳，鈦原子及鋯原子為更佳。As the group 4 element represented by M, a titanium atom, a zirconium atom, and a hafnium atom are preferable, and a titanium atom and a zirconium atom are more preferable.

作為上述R中的芳香族基，可舉出碳數6～20的芳香族基，碳數6～20的芳香族烴基為較佳，可舉出苯基、1-萘基或2-萘基等。 作為上述R中的烷基，碳數1～20的烷基為較佳，碳數1～10的烷基為更佳，可舉出甲基、乙基、丙基、辛基、異丙基、三級丁基、異戊基、2-乙基己基、2-甲基己基、環戊基等。 作為上述R中的鹵素原子，可舉出F、Cl、Br、I。 作為構成上述R中的烷基磺醯氧基之烷基鏈，碳數1～20的烷基為較佳，碳數1～10的烷基為更佳，可舉出甲基鏈、乙基鏈、丙基鏈、辛基鏈、異丙基鏈、三級丁基鏈、異戊基鏈、2-乙基己基鏈、2-甲基己基鏈、環戊基鏈等。 上述R還可以具有取代基。作為取代基的例子，可舉出鹵素原子（F、Cl、Br、I）、羥基、羧基、胺基、氰基、芳基、烷氧基、芳氧基、醯基、烷氧基羰基、芳氧基羰基、醯氧基、單烷基胺基、二烷基胺基、單芳基胺基及二芳基胺基等。Examples of the aromatic group in the above R include aromatic groups having 6 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms are preferred, such as phenyl, 1-naphthyl or 2-naphthyl. Wait. As the alkyl group in the above-mentioned R, an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred. Examples include methyl, ethyl, propyl, octyl, and isopropyl. , Tertiary butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. Examples of the halogen atom in the above R include F, Cl, Br, and I. As the alkyl chain constituting the alkylsulfonyloxy group in R, an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred. Examples of the alkyl chain include methyl chain and ethyl group. Chain, propyl chain, octyl chain, isopropyl chain, tertiary butyl chain, isopentyl chain, 2-ethylhexyl chain, 2-methylhexyl chain, cyclopentyl chain, etc. The above-mentioned R may have a substituent. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, Aryloxycarbonyl, acyloxy, monoalkylamino, dialkylamino, monoarylamino and diarylamino groups, etc.

本發明中所使用之含有第4族元素之化合物包含選自包括茂金屬及茂金屬衍生物之群組中之至少1種為較佳。 在本發明中，茂金屬衍生物表示具有2個具有取代基之環戊二烯基陰離子衍生物作為η5-配位體之有機金屬化合物，包含二茂鈦衍生物、鋯茂衍生物、二茂鉿衍生物等。 又，本發明中所使用之含有第4族元素之化合物從二茂鈦化合物、四烷氧基鈦化合物、鈦醯化物、鈦螯合化合物、鋯茂化合物及二茂鉿化合物中選擇為較佳，從二茂鈦化合物、鋯茂化合物及二茂鉿化合物中選擇為更佳，從二茂鈦化合物及鋯茂化合物中選擇為進一步較佳。 又，含有第4族元素之化合物係選自包括二茂鈦、二茂鈦衍生物、鋯茂及鋯茂衍生物之群組中之至少1種為較佳，選自包括二茂鈦及二茂鈦衍生物之群組中之至少1種為更佳。The compound containing group 4 elements used in the present invention preferably contains at least one selected from the group consisting of metallocenes and metallocene derivatives. In the present invention, metallocene derivatives refer to organometallic compounds having two substituted cyclopentadienyl anion derivatives as η5-ligands, including titanocene derivatives, zirconocene derivatives, and Hafnium derivatives and so on. In addition, the compound containing group 4 elements used in the present invention is preferably selected from titanocene compounds, tetraalkoxytitanium compounds, titanium alkoxides, titanium chelate compounds, zirconocene compounds and hafnium compounds It is more preferable to select from titanocene compounds, zirconocene compounds and hafnium compounds, and it is more preferable to select from titanocene compounds and zirconocene compounds. In addition, the compound containing group 4 elements is preferably at least one selected from the group consisting of titanocene, titanocene derivatives, zirconocene and zirconocene derivatives, and is preferably selected from the group consisting of titanocene and two At least one of the group of titanocene derivatives is more preferable.

含有第4族元素之化合物的分子量係50～2,000為較佳，100～1,000為更佳。The molecular weight of the compound containing a group 4 element is preferably 50 to 2,000, and more preferably 100 to 1,000.

作為含有第4族元素之化合物的具體例，可例示四異丙氧基鈦、四（2-乙基己氧基）鈦、二異丙氧基雙（乙醯乙酸乙酯）鈦、二異丙氧基雙（乙醯丙酮）鈦及下述化合物。 [化學式35]

Figure 02_image069
As specific examples of compounds containing group 4 elements, titanium tetraisopropoxide, titanium tetra(2-ethylhexyloxy), titanium diisopropoxybis(ethyl acetate), and diisopropoxy titanium can be exemplified. Propoxy bis(acetone) titanium and the following compounds. [Chemical formula 35]
Figure 02_image069

又，作為含有第4族元素之化合物中包含鈦原子之有機化合物，還能夠使用二-環戊二烯基-二氯化鈦、二-環戊二烯基-雙苯基鈦、二-環戊二烯基-鈦-雙-2,3,4,5,6-五氟苯基-1-基、二-環戊二烯基-鈦-雙-2,3,5,6-四氟苯基-1-基、二-環戊二烯基-鈦-雙-2,4,6-三氟苯基-1-基、二-環戊二烯基-鈦-2,6-二氟苯基-1-基、二-環戊二烯基-鈦-雙-2,4-二氟苯基-1-基、二-甲基環戊二烯基-鈦-雙-2,3,4,5,6-五氟苯基-1-基、二-甲基環戊二烯基-鈦-雙-2,3,5,6-四氟苯基-1-基、二-甲基環戊二烯基-鈦-雙-2,4-二氟苯基-1-基、雙（環戊二烯基）-雙（2,6-二氟-3-（吡啶-1-基）苯基）鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（甲基磺醯胺）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-丁基三甲基乙醯基（Butyl pivaloyl）-胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-乙基乙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-甲基乙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-乙基丙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-乙基-（2,2-二甲基丁醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-丁基-（2,2-二甲基丁醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-戊基-（2,2-二甲基丁醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-己基）-（2,2-二甲基丁醯基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-甲基丁醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-甲基戊醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-乙基環己基羰基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-乙基異丁醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-乙基乙醯胺基）苯基〕鈦、In addition, as an organic compound containing a titanium atom in the compound containing a group 4 element, di-cyclopentadienyl-titanium dichloride, di-cyclopentadienyl-bisphenyl titanium, and di-cyclopentadienyl-titanium dichloride can also be used. Pentadienyl-titanium-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-cyclopentadienyl-titanium-bis-2,3,5,6-tetrafluoro Phenyl-1-yl, di-cyclopentadienyl-titanium-bis-2,4,6-trifluorophenyl-1-yl, di-cyclopentadienyl-titanium-2,6-difluoro Phenyl-1-yl, di-cyclopentadienyl-titanium-bis-2,4-difluorophenyl-1-yl, dimethylcyclopentadienyl-titanium-bis-2,3, 4,5,6-Pentafluorophenyl-1-yl, bis-methylcyclopentadienyl-titanium-bis-2,3,5,6-tetrafluorophenyl-1-yl, bis-methyl Cyclopentadienyl-titanium-bis-2,4-difluorophenyl-1-yl, bis(cyclopentadienyl)-bis(2,6-difluoro-3-(pyridin-1-yl) Phenyl)titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(methylsulfonamide)phenyl]titanium, bis(cyclopentadienyl)bis[2,6- Difluoro-3-(N-Butyl pivaloyl-amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N -Ethylacetamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-methylacetamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-methylacetamido)phenyl]titanium, bis(cyclopentadienyl) Pentadienyl) bis[2,6-difluoro-3-(N-ethylpropanamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (N-ethyl-(2,2-dimethylbutyryl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-( 2,2-Dimethylbutyryl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-pentyl-(2,2-dimethyl) Butyryl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl)-(2,2-dimethylbutyryl)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-methylbutyramido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro -3-(N-methylpentanylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethylcyclohexylcarbonylamino)phenyl ]Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethylisobutyramido)phenyl]titanium, bis(cyclopentadienyl)bis[2, 6-difluoro-3-(N-ethylacetamido)phenyl]titanium,

雙（環戊二烯基）雙〔2,6-二氟-3-（2,2,5,5-四甲基-1,2,5-氮雜二氯-1-基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（辛基磺醯胺）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（4-甲苯磺醯胺）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（4-十二烷基苯基磺醯基醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（4-（1-戊基庚基）苯基磺醯基醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（乙基磺醯基醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（（4-溴苯基）-磺醯基醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（2-萘磺醯基醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（十六烷基磺醯基醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-甲基-（4-十二烷基苯基）磺醯基醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-甲基-4-（1-戊基庚基）苯基）磺醯基醯胺基）〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-己基-（4-甲苯基）-磺醯基醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（吡咯啶-2,5-二酮-1-基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（3,4-二甲基-3-吡咯啶-2,5-二酮-1-基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（鄰苯二甲醯亞胺）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（異丁氧基羰基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（乙氧基羰基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（（2-氯乙氧基）-羰基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（苯氧基羰基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（3-苯硫基脲基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（3-丁硫基脲基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（3-苯基脲基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（3-丁基脲基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N,N-二乙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（3,3-二甲基脲基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（乙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（丁醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（癸醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（十八醯胺基）苯基〕鈦、Bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2,5,5-tetramethyl-1,2,5-azadichloro-1-yl)phenyl] Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(octylsulfonamide)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro- 3-(4-Toluenesulfonamide)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-dodecylphenylsulfonylamide) Phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-(1-pentylheptyl)phenylsulfonylamino)phenyl]titanium, bis (Cyclopentadienyl)bis[2,6-difluoro-3-(ethylsulfonylamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro- 3-((4-Bromophenyl)-sulfonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-naphthalenesulfonylamino) Amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(hexadecylsulfonylamino)phenyl]titanium, bis(cyclopentadiene) Group) bis[2,6-difluoro-3-(N-methyl-(4-dodecylphenyl)sulfonylamino)phenyl]titanium, bis(cyclopentadienyl)bis [2,6-Difluoro-3-(N-methyl-4-(1-pentylheptyl)phenyl)sulfonylamino)]titanium, bis(cyclopentadienyl)bis[2 ,6-Difluoro-3-(N-hexyl-(4-tolyl)-sulfonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3 -(Pyrrolidine-2,5-diketo-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,4-dimethyl-3) -Pyrrolidine-2,5-diketo-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(phthalimide)phenyl ]Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(isobutoxycarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6- Difluoro-3-(ethoxycarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-((2-chloroethoxy)-carbonylamino) )Phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(phenoxycarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2, 6-Difluoro-3-(3-phenylthioureido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-butylthioureido)benzene Base]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-phenylureido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6- Difluoro-3-(3-butylureido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N,N-diacetamido)phenyl ]Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,3-dimethylureido)phenyl]titanium, bis(cyclopentadienyl)bis[2, 6-Difluoro-3-(acetamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(butanoamide) Yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(decamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6 -Difluoro-3-(octadecamido)phenyl]titanium,

雙（環戊二烯基）雙〔2,6-二氟-3-（異丁醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（2-乙基己醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（2-甲基丁醯基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（三甲基乙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（2,2-二甲基丁醯基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（2-乙基-2-甲基庚醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（環己基羰基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（2,2-二甲基-3-氯丙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（3-苯基丙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（2-氯甲基-2-甲基-3-氯丙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（3,4-茬甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（4-乙基苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（2,4,6-三甲苯基羰基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（3-苯丙基）苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（3-乙基庚基）-2,2-二甲基戊醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-異丁基-（4-甲苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-異丁基苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-環己基甲基三甲基乙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（氧戊-2-基甲基）苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（3-乙基庚基）-2,2-二甲基丁醯基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（3-苯丙基-（4-甲苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（氧戊-2-基甲基）-（4-甲苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（4-甲苯甲醯基甲基）苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（4-甲苯甲醯基甲基）-（4-甲苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-丁基苯甲醯胺基）苯基〕鈦、Bis(cyclopentadienyl)bis[2,6-difluoro-3-(isobutyramido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (2-Ethylhexylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-methylbutyrylamino)phenyl]titanium, bis( Cyclopentadienyl)bis[2,6-difluoro-3-(trimethylacetamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (2,2-Dimethylbutyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-ethyl-2-methylheptanylamino) )Phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(cyclohexylcarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6 -Difluoro-3-(2,2-dimethyl-3-chloropropanamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3- Phenylpropionylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-chloromethyl-2-methyl-3-chloropropionylamino) )Phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,4-carboxamido)phenyl]titanium, bis(cyclopentadienyl)bis [2,6-Difluoro-3-(4-ethylbenzamide)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,4, 6-Trimethylolylcarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(benzamide)phenyl]titanium, bis(cyclopentadiene) Alkenyl) bis[2,6-difluoro-3-(N-(3-phenylpropyl)benzamide)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-di Fluoro-3-(N-(3-ethylheptyl)-2,2-dimethylpentylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro- 3-(N-isobutyl-(4-tolyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl) Benzylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyltrimethylacetamido)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(oxopent-2-ylmethyl)benzamide)phenyl]titanium, bis(cyclopentadienyl) ) Bis[2,6-difluoro-3-(N-(3-ethylheptyl)-2,2-dimethylbutyrylamino)phenyl]titanium, bis(cyclopentadienyl)bis[ 2,6-Difluoro-3-(N-(3-phenylpropyl-(4-tolyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-di Fluoro-3-(N-(oxopent-2-ylmethyl)-(4-tolyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro -3-(N-(4-tolylmethyl)benzamide)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-( 4-tolylmethyl)-(4-tolyl)amino)phenyl]titanium, bis(cyclopentadienyl) ) Bis[2,6-difluoro-3-(N-butylbenzamide)phenyl]titanium,

雙（環戊二烯基）雙〔2,6-二氟-3-（N-丁基-（4-甲苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-己基-（4-甲苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（2,4-二甲基戊基）-2,2-二甲基丁醯基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（2,4-二甲基戊基）-2,2-二甲基戊醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（（4-甲苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（2,2-二甲基戊醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（2,2-二甲基-3-乙氧基丙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（2,2-二甲基-3-烯丙氧基丙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-烯丙基乙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（2-乙基丁醯基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-環己基甲基苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-環己基甲基-（4-甲苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（2-乙基己基）苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-異丙基苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（3-苯丙基）-2,2-二甲基戊醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-己基苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-環己基甲基-2,2-二甲基戊醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-丁基苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（2-乙基己基）-2,2-二甲基戊醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-己基-2,2-二甲基戊醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-異丙基-2,2-二甲基戊醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（3-苯丙基）三甲基乙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-丁基-2,2-二甲基戊醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（2-甲氧基乙基）苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-苄基苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-苄基-（4-甲苯甲醯基）胺基）苯基〕鈦、Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4-tolyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis [2,6-Difluoro-3-(N-hexyl-(4-tolyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (N-(2,4-Dimethylpentyl)-2,2-dimethylbutanoylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (2,4-Dimethylpentyl)-2,2-dimethylpentylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(( 4-tolyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethylpentylamino)phenyl] Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2,2-dimethyl-3-ethoxypropanamido)phenyl]titanium, bis(cyclopentadiene) Alkenyl) bis[2,6-difluoro-3-(2,2-dimethyl-3-allyloxypropanamido)phenyl]titanium, bis(cyclopentadienyl)bis[2 ,6-Difluoro-3-(N-allylacetamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-ethylbutanoylamine) Yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethylbenzamide)phenyl]titanium, bis(cyclopentadiene) Yl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-(4-tolyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6 -Difluoro-3-(N-(2-ethylhexyl)benzamide)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-iso Propylbenzamide)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropyl)-2,2-dimethyl Pentanyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexylbenzylamino)phenyl]titanium, bis(cyclopentadienyl) Dienyl) bis[2,6-difluoro-3-(N-cyclohexylmethyl-2,2-dimethylpentanyl)amino)phenyl]titanium, bis(cyclopentadienyl) Bis[2,6-difluoro-3-(N-butylbenzamide)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-( 2-Ethylhexyl)-2,2-Dimethylpentanyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl- 2,2-Dimethylpentamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isopropyl-2,2-dimethyl Pentamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropyl)trimethylacetamido)phenyl] Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-2,2-dimethylpentylamino)phenyl]titanium, bis(cyclopentadiene) Group) Bis[2,6-difluoro-3-(N-(2-methoxyethyl)benzamide)phenyl] Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzylbenzamide)phenyl]titanium, bis(cyclopentadienyl)bis[2,6 -Difluoro-3-(N-benzyl-(4-tolyl)amino)phenyl]titanium,

雙（環戊二烯基）雙〔2,6-二氟-3-（N-（2-甲氧基乙基）-（4-甲苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（4-甲基苯基甲基）-2,2-二甲基戊醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（2-甲氧基乙基）-2,2-二甲基戊醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-環己基甲基-（2-乙基-2-甲基庚醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-丁基-（4-氯苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-己基-（2-乙基-2-甲基丁醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-環己基-2,2-二甲基戊醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（氧戊-2-基甲基）-2,2-二甲基戊醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-環己基-（4-氯苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-環己基-（2-氯苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（3,3-二甲基-2-氮環丁酮-1-基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-異氰酸酯苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-乙基-（4-甲苯基磺醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-己基-（4-甲苯基磺醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-丁基-（4-甲苯基磺醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-異丁基-（4-甲苯基磺醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-丁基-（2,2-二甲基-3-氯丙醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（3-苯基丙醯基）-2,2-二甲基-3-氯丙醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-環己基甲基-（2,2-二甲基-3-氯丙醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-異丁基-（2,2-二甲基-3-氯丙醯基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-丁基-（2-氯甲基-2-甲基-3-氯丙醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（丁硫基羰基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（苯硫基羰基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-異氰酸酯苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-乙基-（4-甲苯基磺醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-己基-（4-甲苯基磺醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-丁基-（4-甲苯基磺醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-異丁基-（4-甲苯基磺醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-丁基-（2,2-二甲基-3-氯丙醯基）胺基）苯基〕鈦、Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-methoxyethyl)-(4-tolyl)amino)phenyl]titanium, bis( Cyclopentadienyl) bis[2,6-difluoro-3-(N-(4-methylphenylmethyl)-2,2-dimethylpentamido)phenyl]titanium, bis( Cyclopentadienyl) bis[2,6-difluoro-3-(N-(2-methoxyethyl)-2,2-dimethylpentamido)phenyl]titanium, bis(cyclo Pentadienyl) bis[2,6-difluoro-3-(N-cyclohexylmethyl-(2-ethyl-2-methylheptanyl)amino)phenyl]titanium, bis(cyclopentyl) Dienyl) bis[2,6-difluoro-3-(N-butyl-(4-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2, 6-Difluoro-3-(N-hexyl-(2-ethyl-2-methylbutanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3 -(N-Cyclohexyl-2,2-Dimethylpentanyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(oxygen) Pent-2-ylmethyl)-2,2-dimethylpentanyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- Cyclohexyl-(4-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexyl-(2-chlorobenzene) Methanoyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3,3-dimethyl-2-azcyclobutanone-1-yl) )Phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-isocyanatephenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3- (N-ethyl-(4-tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4- Tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(4-tolylsulfonyl)amino) )Phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(4-tolylsulfonyl)amino)phenyl]titanium, double (Cyclopentadienyl) bis[2,6-difluoro-3-(N-butyl-(2,2-dimethyl-3-chloropropanyl)amino)phenyl]titanium, bis( Cyclopentadienyl) bis[2,6-difluoro-3-(N-(3-phenylpropionyl)-2,2-dimethyl-3-chloropropionyl)amino)phenyl ]Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-(2,2-dimethyl-3-chloropropanyl)amino)benzene Base]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(2,2-dimethyl-3-chloropropionyl)phenyl]titanium , Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2-chloromethyl-2-methyl-3-chloropropanyl)amino)phenyl ]Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(butylthiocarbonylamino)phenyl ]Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(phenylthiocarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-di Fluoro-3-isocyanate phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(4-tolylsulfonyl)amino)phenyl] Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(4-tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl) ) Bis[2,6-difluoro-3-(N-butyl-(4-tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-di Fluoro-3-(N-isobutyl-(4-tolylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N- Butyl-(2,2-dimethyl-3-chloropropionyl)amino)phenyl]titanium,

雙（環戊二烯基）雙〔2,6-二氟-3-（N-（3-苯基丙醯基）-2,2-二甲基-3-氯丙醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-環己基甲基-（2,2-二甲基-3-氯丙醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-異丁基-（2,2-二甲基-3-氯丙醯基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-丁基-（2-氯甲基-2-甲基-3-氯丙醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（丁硫基羰基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（苯硫基羰基胺基）苯基〕鈦、雙（甲基環戊二烯基）雙〔2,6-二氟-3-（N-己基-2,2-二甲基丁醯基）胺基）苯基〕鈦、雙（甲基環戊二烯基）雙〔2,6-二氟-3-（N-己基-2,2-二甲基戊醯胺基）苯基〕鈦、雙（甲基環戊二烯基）雙〔2,6-二氟-3-（N-乙基乙醯胺基）苯基〕鈦、雙（甲基環戊二烯基）雙〔2,6-二氟-3-（N-乙基丙醯胺基）苯基〕鈦、雙（三甲基矽基戊二烯基）雙〔2,6-二氟-3-（N-丁基-2,2-二甲基丙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（2-甲氧基乙基）-三甲基矽基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-丁基己基二甲基矽基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-乙基-（1,1,2,-三甲基丙基）二甲基矽基胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（3-乙氧基甲基-3-甲基-2-氮環丁酮-1-基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（3-烯丙氧基甲基-3-甲基-2-氮環丁酮-1-基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（3-氯甲基-3-甲基-2-氮環丁酮-1-基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-苄基-2,2-二甲基丙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（5,5-二甲基-2-吡咯啶酮-1-基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（6,6-二苯基-2-哌啶酮-1-基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（2,3-二氫-1,2-苯并噻唑-3-酮（1,1-二氧化物）-2-基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-己基-（4-氯苯甲醯基）胺基）苯基〕鈦、Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-phenylpropionyl)-2,2-dimethyl-3-chloropropionyl)amino) Phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-cyclohexylmethyl-(2,2-dimethyl-3-chloropropanyl)amino) )Phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-isobutyl-(2,2-dimethyl-3-chloropropionyl)phenyl) ]Titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butyl-(2-chloromethyl-2-methyl-3-chloropropanyl)amino) Phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(butylthiocarbonylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6 -Difluoro-3-(phenylthiocarbonylamino)phenyl]titanium, bis(methylcyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-2,2-di Methylbutyryl)amino)phenyl]titanium, bis(methylcyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-2,2-dimethylpentylamino) Phenyl]titanium, bis(methylcyclopentadienyl) bis[2,6-difluoro-3-(N-ethylacetamido)phenyl]titanium, bis(methylcyclopentadienyl) ) Bis[2,6-difluoro-3-(N-ethylpropanamido)phenyl]titanium, bis(trimethylsilylpentadienyl)bis[2,6-difluoro-3- (N-butyl-2,2-dimethylpropanamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-methoxy Ethyl)-trimethylsilylamino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylhexyldimethylsilylamino) )Phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-ethyl-(1,1,2,-trimethylpropyl)dimethylsilyl) Amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-ethoxymethyl-3-methyl-2-azcyclobutanone-1- Yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-allyloxymethyl-3-methyl-2-azacyclobutanone-1- Yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(3-chloromethyl-3-methyl-2-azacyclobutanone-1-yl)benzene Base]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzyl-2,2-dimethylpropanamido)phenyl]titanium, bis(cyclopentadienyl) Dienyl) bis[2,6-difluoro-3-(5,5-dimethyl-2-pyrrolidinone-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2 ,6-Difluoro-3-(6,6-diphenyl-2-piperidone-1-yl)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3 -(N-(2,3-Dihydro-1,2-benzothiazol-3-one(1,1-dioxide)-2-yl)phenyl]titanium, bis(cyclopentadienyl) Bis[2,6-difluoro-3-(N-hexyl-(4-chlorobenzyl)amino)phenyl]titanium,

雙（環戊二烯基）雙〔2,6-二氟-3-（N-己基-（2-氯苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-異丙基-（4-氯苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（4-甲基苯基甲基）-（4-氯苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（4-甲基苯基甲基）-（2-氯苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-丁基-（4-氯苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-苄基-2,2-二甲基戊醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（2-乙基己基）-4-甲苯基-磺醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（3-氧雜庚基）苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（3,6-二氧雜癸基）苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（三氟甲基磺醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（三氟乙醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（2-氯苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（4-氯苯甲醯基）胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（3,6-二氧雜癸基）-2,2-二甲基戊醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-（3,7-二甲基-7-甲氧基辛基）苯甲醯胺基）苯基〕鈦、雙（環戊二烯基）雙〔2,6-二氟-3-（N-環己基苯甲醯胺基）苯基〕鈦等。Bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-hexyl-(2-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis [2,6-Difluoro-3-(N-isopropyl-(4-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro -3-(N-(4-Methylphenylmethyl)-(4-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro -3-(N-(4-methylphenylmethyl)-(2-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro -3-(N-butyl-(4-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-benzyl) -2,2-Dimethylpentamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(2-ethylhexyl)-4- Tolyl-sulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3-oxaheptyl)benzamide) )Phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(N-(3,6-dioxadecyl)benzamide)phenyl]titanium, Bis(cyclopentadienyl)bis[2,6-difluoro-3-(trifluoromethylsulfonyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[2,6- Difluoro-3-(trifluoroacetamido)phenyl]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(2-chlorobenzyl)amino)benzene Base]titanium, bis(cyclopentadienyl)bis[2,6-difluoro-3-(4-chlorobenzyl)amino)phenyl]titanium, bis(cyclopentadienyl)bis[ 2,6-Difluoro-3-(N-(3,6-dioxadecyl)-2,2-dimethylpentamido)phenyl]titanium, bis(cyclopentadienyl)bis [2,6-Difluoro-3-(N-(3,7-dimethyl-7-methoxyoctyl)benzamide)phenyl]titanium, bis(cyclopentadienyl)bis [2,6-Difluoro-3-(N-cyclohexylbenzamide)phenyl]titanium and the like.

又，作為含有第4族元素之化合物中包含鋯原子之有機化合物、包含鉿原子之化合物，還能夠使用（環戊二烯基）三甲基鋯、（環戊二烯基）三苯基鋯、（環戊二烯基）三苄基鋯、（環戊二烯基）三氯鋯、（環戊二烯基）三甲氧基鋯、（環戊二烯基）二甲基（甲氧基）鋯、（環戊二烯基）甲基二氯鋯、（甲基環戊二烯基）三甲基鋯、（甲基環戊二烯基）三苯基鋯、（甲基環戊二烯基）三苄基鋯、（甲基環戊二烯基）三氯鋯、（甲基環戊二烯基）二甲基（甲氧基）鋯、（二甲基環戊二烯基）三甲基鋯、（三甲基環戊二烯基）三甲基鋯、（三甲基矽基環戊二烯基）三甲基鋯、（四甲基環戊二烯基）三甲基鋯、（五甲基環戊二烯基）三甲基鋯、（五甲基環戊二烯基）三苯基鋯、（五甲基環戊二烯基）三苄基鋯、（五甲基環戊二烯基）三氯鋯、（五甲基環戊二烯基）三甲氧基鋯、（五甲基環戊二烯基）二甲基（甲氧基）鋯、（環戊二烯基）三乙基鋯、（環戊二烯基）三丙基鋯、（環戊二烯基）三新戊基鋯、（環戊二烯基）三（二苯甲基）鋯、（環戊二烯基）二甲基氫化鋯、（環戊二烯基）三乙氧基鋯、（環戊二烯基）三異丙氧基鋯、（環戊二烯基）三苯氧基鋯、（環戊二烯基）二甲基異丙氧基鋯、（環戊二烯基）二苯基異丙氧基鋯、（環戊二烯基）二甲氧基氯鋯、（環戊二烯基）甲氧基二氯鋯、（環戊二烯基）二苯氧基氯鋯、（環戊二烯基）苯氧基二氯鋯、（環戊二烯基）三（苯基二甲基矽基）鋯、（正丁基環戊二烯基）二甲基正丁氧基鋯、（苄基環戊二烯基）二間甲苯基甲基鋯、（三氟甲基環戊二烯基）三苄基鋯、（二苯基環戊二烯基）二降莰基甲基鋯、（四乙基環戊二烯基）三苄基鋯、（五三甲基矽基環戊二烯基）三苄基鋯、（五甲基環戊二烯基）三新戊基鋯、（五甲基環戊二烯基）甲基二氯鋯、（五甲基環戊二烯基）三乙氧基鋯、（五甲基環戊二烯基）三苯氧基鋯、（五甲基環戊二烯基）甲氧基二氯鋯、（五甲基環戊二烯基）二苯氧基氯鋯、（五甲基環戊二烯基）苯氧基二氯鋯、（茚基）三甲基鋯、（茚基）三苄基鋯、（茚基）三氯鋯、（茚基）三甲氧基鋯、In addition, as organic compounds containing zirconium atoms and compounds containing hafnium atoms among the compounds containing group 4 elements, (cyclopentadienyl) trimethyl zirconium and (cyclopentadienyl) triphenyl zirconium can also be used , (Cyclopentadienyl) tribenzyl zirconium, (cyclopentadienyl) zirconium trichloride, (cyclopentadienyl) trimethoxy zirconium, (cyclopentadienyl) dimethyl (methoxy) ) Zirconium, (cyclopentadienyl) methyl zirconium dichloride, (methyl cyclopentadienyl) trimethyl zirconium, (methyl cyclopentadienyl) triphenyl zirconium, (methyl cyclopentadienyl) Alkenyl) tribenzyl zirconium, (methylcyclopentadienyl) zirconium trichloride, (methylcyclopentadienyl) dimethyl (methoxy) zirconium, (dimethylcyclopentadienyl) Trimethyl zirconium, (trimethylcyclopentadienyl) trimethyl zirconium, (trimethylsilylcyclopentadienyl) trimethyl zirconium, (tetramethylcyclopentadienyl) trimethyl Zirconium, (pentamethylcyclopentadienyl) trimethyl zirconium, (pentamethylcyclopentadienyl) triphenyl zirconium, (pentamethylcyclopentadienyl) tribenzyl zirconium, (pentamethyl Cyclopentadienyl) zirconium trichloride, (pentamethylcyclopentadienyl) zirconium trimethoxy, (pentamethylcyclopentadienyl) dimethyl (methoxy) zirconium, (cyclopentadienyl) Alkenyl) triethyl zirconium, (cyclopentadienyl) tripropyl zirconium, (cyclopentadienyl) trineopentyl zirconium, (cyclopentadienyl) tris(diphenylmethyl) zirconium, ( Cyclopentadienyl) dimethyl zirconium hydride, (cyclopentadienyl) triethoxy zirconium, (cyclopentadienyl) triisopropoxy zirconium, (cyclopentadienyl) triphenoxy Zirconium, (cyclopentadienyl) zirconium dimethyl isopropoxide, (cyclopentadienyl) zirconium diphenyl isopropoxide, (cyclopentadienyl) zirconium dimethoxychloride, (cyclopentadienyl) zirconium Pentadienyl) methoxy zirconium dichloride, (cyclopentadienyl) diphenoxy zirconium chloride, (cyclopentadienyl) phenoxy zirconium dichloride, (cyclopentadienyl) tris(benzene) Dimethylsilyl) zirconium, (n-butyl cyclopentadienyl) dimethyl n-butoxy zirconium, (benzyl cyclopentadienyl) m-tolyl methyl zirconium, (trifluoromethyl) Cyclopentadienyl) tribenzyl zirconium, (diphenylcyclopentadienyl) dinorbornyl methyl zirconium, (tetraethylcyclopentadienyl) tribenzyl zirconium, (pentatrimethyl silicon) Cyclopentadienyl) tribenzyl zirconium, (pentamethylcyclopentadienyl) trineopentyl zirconium, (pentamethylcyclopentadienyl) methyl zirconium dichloride, (pentamethylcyclopentadienyl) Dienyl) zirconium triethoxide, (pentamethylcyclopentadienyl) zirconium triphenoxide, (pentamethylcyclopentadienyl) methoxy zirconium dichloride, (pentamethylcyclopentadienyl) Alkenyl) diphenoxy zirconium chloride, (pentamethylcyclopentadienyl) phenoxy zirconium dichloride, (indenyl) trimethyl zirconium, (indenyl) tribenzyl zirconium, (indenyl) three Zirconium chloride, (indenyl) trimethoxy zirconium,

（茚基）三乙氧基鋯、雙（環戊二烯基）二甲基鋯、雙（環戊二烯基）二苯基鋯、雙（環戊二烯基）二乙基鋯、雙（環戊二烯基）二苄基鋯、雙（環戊二烯基）二甲氧基鋯、雙（環戊二烯基）二氯鋯、雙（環戊二烯基）二氫化鋯、雙（環戊二烯基）氯氫化鋯、雙（甲基環戊二烯基）二甲基鋯、雙（甲基環戊二烯基）二苄基鋯、雙（甲基環戊二烯基）二氯鋯、雙（五甲基環戊二烯基）二甲基鋯、雙（五甲基環戊二烯基）二苄基鋯、雙（五甲基環戊二烯基）二氯鋯、雙（五甲基環戊二烯基）氯甲基鋯、雙（五甲基環戊二烯基）氫化甲基鋯、（環戊二烯基）（五甲基環戊二烯基）二甲基鋯、雙（環戊二烯基）二新戊基鋯、雙（環戊二烯基）二間甲苯基鋯、雙（環戊二烯基）二對甲苯基鋯、雙（環戊二烯基）雙（二苯甲基）鋯、雙（環戊二烯基）二溴鋯、雙（環戊二烯基）甲基氯鋯、雙（環戊二烯基）乙基氯鋯、雙（環戊二烯基）環己基氯鋯、雙（環戊二烯基）苯基氯鋯、雙（環戊二烯基）苄基氯鋯、雙（環戊二烯基）氫化甲基鋯、雙（環戊二烯基）甲氧基氯鋯、(Indenyl) zirconium triethoxy, bis(cyclopentadienyl) dimethyl zirconium, bis(cyclopentadienyl) diphenyl zirconium, bis(cyclopentadienyl) diethyl zirconium, double (Cyclopentadienyl) zirconium dibenzyl, bis(cyclopentadienyl) zirconium dimethoxy, bis(cyclopentadienyl) zirconium dichloride, bis(cyclopentadienyl) zirconium dihydride, Bis(cyclopentadienyl) zirconium hydride, bis(methylcyclopentadienyl) dimethyl zirconium, bis(methylcyclopentadienyl) dibenzyl zirconium, bis(methylcyclopentadiene) Base) zirconium dichloride, bis(pentamethylcyclopentadienyl) dimethyl zirconium, bis(pentamethylcyclopentadienyl) dibenzyl zirconium, bis(pentamethylcyclopentadienyl) two Zirconium chloride, bis(pentamethylcyclopentadienyl) chloromethyl zirconium, bis(pentamethylcyclopentadienyl) methyl zirconium hydride, (cyclopentadienyl)(pentamethylcyclopentadiene) Base) dimethyl zirconium, bis(cyclopentadienyl) dineopentyl zirconium, bis(cyclopentadienyl) di-tolyl zirconium, bis(cyclopentadienyl) di-p-tolyl zirconium, double (Cyclopentadienyl) bis(diphenylmethyl) zirconium, bis(cyclopentadienyl) zirconium dibromide, bis(cyclopentadienyl) methyl zirconium chloride, bis(cyclopentadienyl) ethyl Zirconium chloride, bis(cyclopentadienyl) cyclohexyl zirconium chloride, bis(cyclopentadienyl) phenyl zirconium chloride, bis(cyclopentadienyl) benzyl zirconium chloride, bis(cyclopentadienyl) ) Methyl zirconium hydride, bis (cyclopentadienyl) methoxy zirconium chloride,

雙（環戊二烯基）乙氧基氯鋯、雙（環戊二烯基）（三甲基矽基）甲基鋯、雙（環戊二烯基）雙（三甲基矽基）鋯、雙（環戊二烯基）（三苯基矽基）甲基鋯、雙（環戊二烯基）（三（二甲基矽基）矽基）甲基鋯、雙（環戊二烯基）（三甲基矽基）（三甲基矽基甲基）鋯、雙（甲基環戊二烯基）二苯基鋯、雙（乙基環戊二烯基）二甲基鋯、雙（乙基環戊二烯基）二氯鋯、雙（丙基環戊二烯基）二甲基鋯、雙（丙基環戊二烯基）二氯鋯、雙（正丁基環戊二烯基）二氯鋯、雙（三級丁基環戊二烯基）雙（三甲基矽基）鋯、雙（己基環戊二烯基）二氯鋯、雙（環己基環戊二烯基）二甲基鋯、雙（二甲基環戊二烯基）二甲基鋯、雙（二甲基環戊二烯基）二氯鋯、雙（二甲基環戊二烯基）乙氧基氯鋯、雙（乙基甲基環戊二烯基）二氯鋯、雙（丙基甲基環戊二烯基）二氯鋯、雙（丁基甲基環戊二烯基）二氯鋯、雙（三甲基環戊二烯基）二氯鋯、雙（四甲基環戊二烯基）二氯鋯、雙（環己基甲基環戊二烯基）二苄基鋯、雙（三甲基矽基環戊二烯基）二甲基鋯、雙（三甲基矽基環戊二烯基）二氯鋯、雙（三甲基鍺烷基環戊二烯基）二甲基鋯、雙（三甲基鍺烷基環戊二烯基）二苯基鋯、雙（三甲基錫烷基環戊二烯基）二甲基鋯、雙（三甲基錫烷基環戊二烯基）二苄基鋯、雙（三氟甲基環戊二烯基）二甲基鋯、雙（三氟甲基環戊二烯基）二降莰基鋯、雙（茚基）二苄基鋯、雙（茚基）二氯鋯、雙（茚基）二溴鋯、雙（四氫茚基）二氯鋯、雙（茀基）二氯鋯、（丙基環戊二烯基）（環戊二烯基）二甲基鋯、（環己基甲基環戊二烯基）（環戊二烯基）二苄基鋯、（五三甲基矽基環戊二烯基）（環戊二烯基）二甲基鋯、（三氟甲基環戊二烯基）（環戊二烯基）二甲基鋯、伸乙基雙（茚基）二甲基鋯、伸乙基雙（茚基）二氯鋯、伸乙基雙（四氫茚基）二甲基鋯、伸乙基雙（四氫茚基）二氯鋯、二甲基亞矽基雙（環戊二烯基）二甲基鋯、二甲基亞矽基雙（環戊二烯基）二氯鋯、異亞丙基（環戊二烯基）（9-茀基）二甲基鋯、異亞丙基（環戊二烯基）（9-茀基）二氯鋯、[苯基（甲基）亞甲基]（9-茀基）（環戊二烯基）二甲基鋯、二苯基亞甲基（環戊二烯基）（9-茀基）二甲基鋯、伸乙基（9-茀基）（環戊二烯基）二甲基鋯、亞環己基（9-茀基）（環戊二烯基）二甲基鋯、亞環戊基（9-茀基）（環戊二烯基）二甲基鋯、亞環丁基（9-茀基）（環戊二烯基）二甲基鋯、二甲基亞矽基（9-茀基）（環戊二烯基）二甲基鋯、二甲基亞矽基雙（2,3,5-三甲基環戊二烯基）二甲基鋯、二甲基亞矽基雙（2,3,5-三甲基環戊二烯基）二氯鋯、二甲基亞矽基雙（茚基）二氯鋯、亞甲基雙（環戊二烯基）二甲基鋯、亞甲基雙（環戊二烯基）二（三甲基矽基）鋯、Bis(cyclopentadienyl)ethoxy zirconium chloride, bis(cyclopentadienyl)(trimethylsilyl)methyl zirconium, bis(cyclopentadienyl)bis(trimethylsilyl)zirconium , Bis (cyclopentadienyl) (triphenylsilyl) methyl zirconium, bis (cyclopentadienyl) (tris (dimethylsilyl) silyl) methyl zirconium, bis (cyclopentadiene) Base) (trimethylsilyl) (trimethylsilylmethyl) zirconium, bis(methylcyclopentadienyl) diphenyl zirconium, bis(ethylcyclopentadienyl) dimethyl zirconium, Bis(ethylcyclopentadienyl) zirconium dichloride, bis(propylcyclopentadienyl) dimethyl zirconium, bis(propylcyclopentadienyl) zirconium dichloride, bis(n-butylcyclopentadienyl) Dienyl) zirconium dichloride, bis (tertiary butyl cyclopentadienyl) bis (trimethylsilyl) zirconium, bis (hexyl cyclopentadienyl) zirconium dichloride, bis (cyclohexyl cyclopentadiene) Alkenyl) dimethyl zirconium, bis(dimethylcyclopentadienyl) dimethyl zirconium, bis(dimethylcyclopentadienyl) zirconium dichloride, bis(dimethylcyclopentadienyl) Zirconium chloride ethoxy, bis(ethylmethylcyclopentadienyl) zirconium dichloride, bis(propylmethylcyclopentadienyl) zirconium dichloride, bis(butylmethylcyclopentadienyl) dichloride Zirconium, bis(trimethylcyclopentadienyl) zirconium dichloride, bis(tetramethylcyclopentadienyl) zirconium dichloride, bis(cyclohexylmethylcyclopentadienyl) dibenzyl zirconium, double (Trimethylsilylcyclopentadienyl) dimethyl zirconium, bis(trimethylsilylcyclopentadienyl) zirconium dichloride, bis(trimethylgermanylcyclopentadienyl) dimethyl Zirconium, bis(trimethylgermanylcyclopentadienyl) diphenyl zirconium, bis(trimethylstannylcyclopentadienyl) dimethyl zirconium, bis(trimethylstannyl) Pentadienyl) dibenzyl zirconium, bis(trifluoromethylcyclopentadienyl) dimethyl zirconium, bis(trifluoromethylcyclopentadienyl) dinorbornyl zirconium, bis(indenyl) Dibenzyl zirconium, bis(indenyl) zirconium dichloride, bis(indenyl) zirconium dibromide, bis(tetrahydroindenyl) zirconium dichloride, bis(indenyl) zirconium dichloride, (propylcyclopentadiene) Group) (cyclopentadienyl) dimethyl zirconium, (cyclohexyl methyl cyclopentadienyl) (cyclopentadienyl) dibenzyl zirconium, (pentatrimethylsilyl cyclopentadienyl) (Cyclopentadienyl) dimethyl zirconium, (trifluoromethyl cyclopentadienyl) (cyclopentadienyl) dimethyl zirconium, ethylidene bis(indenyl) dimethyl zirconium, ethylene oxide Bis(indenyl) zirconium dichloride, ethylene bis(tetrahydroindenyl) zirconium dimethyl, ethylene bis(tetrahydroindenyl) zirconium dichloride, dimethylsilylene bis(cyclopentadiene) Alkenyl) dimethyl zirconium, dimethylsilylene bis(cyclopentadienyl) zirconium dichloride, isopropylene (cyclopentadienyl) (9-tyl) dimethyl zirconium, isocyanide Propyl (cyclopentadienyl) (9-pyrenyl) zirconium dichloride, [phenyl (methyl) methylene] (9-pyrenyl) (cyclopentadienyl) zirconium dimethyl, diphenyl Zirconium dimethyl (cyclopentadienyl) (9-茀yl) zirconium dimethyl, ethylene (9-茀yl) (cyclopentadienyl) zirconium dimethyl, cyclohexylene (9-茀) Group) (cyclopentadienyl) dimethyl zirconium, cyclopentylidene (9-tyl) (cyclopentadienyl) dimethyl zirconium, cyclobutylidene (9-tyl) (cyclopentadienyl) Alkenyl) dimethyl zirconium, dimethyl silylene (9-tyl) (cyclopentadienyl) dimethyl zirconium, dimethyl silylene bis (2,3 ,5-Trimethylcyclopentadienyl) dimethyl zirconium, dimethylsilylene bis(2,3,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene Bis(indenyl) zirconium dichloride, methylene bis(cyclopentadienyl) dimethyl zirconium, methylene bis(cyclopentadienyl) bis(trimethylsilyl) zirconium,

亞甲基（環戊二烯基）（四甲基環戊二烯基）二甲基鋯、亞甲基（環戊二烯基）（茀基）二甲基鋯、伸乙基雙（環戊二烯基）二甲基鋯、伸乙基雙（環戊二烯基）二苄基鋯、伸乙基雙（環戊二烯基）二氫化鋯、伸乙基雙（茚基）二苯基鋯、伸乙基雙（茚基）甲基氯鋯、伸乙基雙（四氫茚基）二苄基鋯、異亞丙基（環戊二烯基）（甲基環戊二烯基）二氯鋯、異亞丙基（環戊二烯基）（八氫茀基）二氫化鋯、二甲基亞矽基雙（環戊二烯基）二新戊基鋯、二甲基亞矽基雙（環戊二烯基）二氫化鋯、二甲基亞矽基雙（甲基環戊二烯基）二氯鋯、二甲基亞矽基雙（二甲基環戊二烯基）二氯鋯、二甲基亞矽基雙（四氫茚基）二氯鋯、二甲基亞矽基（環戊二烯基）（茀基）二氯鋯、二甲基亞矽基（環戊二烯基）（茀基）二氫化鋯、二甲基亞矽基（甲基環戊二烯基）（茀基）二氫化鋯、二甲基亞矽基雙（3-三甲基矽基環戊二烯基）二氫化鋯、二甲基亞矽基雙（茚基）二甲基鋯、二苯基亞矽基雙（茚基）二氯鋯、苯基甲基亞矽基雙（茚基）二氯鋯及用鉿原子取代該等化合物的鋯原子而得之化合物等。Methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) dimethyl zirconium, methylene (cyclopentadienyl) (stilbene) dimethyl zirconium, ethylene bis (cyclopentadienyl) Pentadienyl) dimethyl zirconium, ethylene bis (cyclopentadienyl) dibenzyl zirconium, ethylene bis (cyclopentadienyl) zirconium hydride, ethylene bis (indenyl) bis Zirconium phenyl, ethylene bis(indenyl) methyl zirconium chloride, ethylene bis(tetrahydroindenyl) dibenzyl zirconium, isopropylene (cyclopentadienyl) (methylcyclopentadiene) Base) zirconium dichloride, isopropylene (cyclopentadienyl) (octahydropyranyl) zirconium dihydride, dimethylsilylene bis(cyclopentadienyl) dineopentyl zirconium, dimethyl Silylene bis(cyclopentadienyl) zirconium dihydride, dimethylsilylene bis(methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis(dimethylcyclopentadiene) Base) zirconium dichloride, dimethylsilylene bis(tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (stilbene) zirconium dichloride, dimethylsilylene (Cyclopentadienyl) (Tunyl) Zirconium Dihydride, Dimethylsilylene (Methylcyclopentadienyl) (Tunyl) Zirconium Dihydride, Dimethylsilylene bis(3-trimethyl) Cyclopentadienyl) zirconium dihydride, dimethylsilylene bis(indenyl) dimethyl zirconium, diphenylsilyl bis(indenyl) zirconium dichloride, phenyl methyl silylene Bis(indenyl) zirconium dichloride and compounds obtained by substituting hafnium atoms for zirconium atoms of these compounds, etc.

除此以外，作為含有金屬元素之化合物，可舉出包含鐵原子、鈀原子、鎳原子等之化合物等。 作為包含鐵原子之化合物，包含鐵原子之錯合物為較佳，二茂鐵等茂金屬化合物為更佳。 作為包含鈀原子或鎳原子之化合物，包含鈀原子或鎳原子之錯合物為更佳。 包含鐵原子、鈀原子、鎳原子等之化合物可以具有自由基聚合起始能力，亦可以不具有該能力，但是具有自由基聚合起始能力為較佳。In addition, as a compound containing a metal element, a compound containing an iron atom, a palladium atom, a nickel atom, and the like can be cited. As the compound containing an iron atom, a complex containing an iron atom is preferable, and a metallocene compound such as ferrocene is more preferable. As the compound containing a palladium atom or a nickel atom, a complex containing a palladium atom or a nickel atom is more preferable. Compounds containing iron atoms, palladium atoms, nickel atoms, etc. may or may not have the ability to initiate radical polymerization, but it is preferable to have the ability to initiate radical polymerization.

相對於本發明的組成物的總固體成分，含有金屬元素之化合物的含量係0.1～30質量%為較佳。下限係1.0質量%以上為更佳，1.5質量%以上為進一步較佳，3.0質量%以上為特佳。上限係25質量%以下為更佳。 含有金屬元素之化合物能夠使用1種或2種以上。在使用2種以上之情形下，總量在上述範圍內為較佳。The content of the metal element-containing compound is preferably 0.1 to 30% by mass relative to the total solid content of the composition of the present invention. The lower limit is more preferably 1.0% by mass or more, more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less. One type or two or more types of compounds containing metal elements can be used. In the case of using two or more types, the total amount is preferably within the above-mentioned range.

又，本發明的組成物中，含有金屬元素之化合物的含量與後述之鎓鹽或其他熱鹼產生劑的含量的質量比率係含有金屬元素之化合物：鎓鹽或其他熱鹼產生劑=99:1～1:99為較佳，90:10～10:90為更佳，40:60～20:80為更佳。藉由設在這種範圍內，能夠實現前驅物在低溫下的更高的閉環率和更高的玻璃化轉變溫度。In addition, in the composition of the present invention, the mass ratio of the content of the compound containing the metal element to the content of the onium salt or other thermal base generator described later is the compound containing the metal element: onium salt or other thermal base generator=99: 1～1:99 is preferable, 90:10～10:90 is more preferable, and 40:60～20:80 is more preferable. By setting in this range, a higher ring-closure rate and a higher glass transition temperature of the precursor at low temperatures can be achieved.

＜聚合性化合物＞ 〔自由基聚合性化合物〕 本發明的組成物包含聚合性化合物為較佳。 作為聚合性化合物，能夠使用自由基聚合性化合物。自由基聚合性化合物為具有自由基聚合性基之化合物。作為自由基聚合性基，可舉出乙烯基、烯丙基、乙烯基苯基、（甲基）丙烯醯基等具有乙烯性不飽和鍵之基團。自由基聚合性基係（甲基）丙烯醯基為較佳，就反應性的觀點而言，（甲基）丙烯醯氧基為更佳。＜Polymerizable compound＞ [Free radical polymerizable compound] The composition of the present invention preferably contains a polymerizable compound. As the polymerizable compound, a radical polymerizable compound can be used. The radical polymerizable compound is a compound having a radical polymerizable group. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinyl phenyl group, and a (meth)acryloyl group. The radical polymerizable group is preferably a (meth)acryloyl group, and from the viewpoint of reactivity, a (meth)acryloyloxy group is more preferable.

自由基聚合性化合物所具有之自由基聚合性基的數量可以係1個，亦可以係2個以上，但是自由基聚合性化合物具有2個以上的自由基聚合性基為較佳，具有3個以上為更佳。上限係15個以下為較佳，10個以下為更佳，8個以下為進一步較佳。The number of radically polymerizable groups possessed by the radically polymerizable compound may be one or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, with three The above is better. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

自由基聚合性化合物的分子量係2,000以下為較佳，1,500以下為更佳，900以下為進一步較佳，600以下為特佳。自由基聚合性化合物的分子量的下限係100以上為較佳，200以上為更佳，300以上為進一步較佳。The molecular weight of the radically polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, more preferably 900 or less, and particularly preferably 600 or less. The lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more, more preferably 200 or more, and more preferably 300 or more.

就顯影性的觀點而言，本發明的組成物包含至少1種含有2個以上的自由基聚合性基之2官能以上的自由基聚合性化合物為較佳，包含至少1種3官能以上的自由基聚合性化合物為更佳。又，亦可以係2官能的自由基聚合性化合物與3官能以上的自由基聚合性化合物的混合物。例如，2官能以上的聚合性單體的官能基數係指一分子中的自由基聚合性基的數量為2個以上。From the viewpoint of developability, the composition of the present invention preferably contains at least one bifunctional or more radical polymerizable compound containing two or more radical polymerizable groups, and at least one trifunctional or more free radical polymerizable compound is included. The base polymerizable compound is more preferable. In addition, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher radical polymerizable compound. For example, the number of functional groups of a bifunctional or more polymerizable monomer means that the number of radically polymerizable groups in one molecule is two or more.

作為自由基聚合性化合物的具體例，可舉出不飽和羧酸（例如，丙烯酸、甲基丙烯酸、伊康酸、巴豆酸、異巴豆酸、順丁烯二酸等）、其酯類、醯胺類，較佳為不飽和羧酸與多元醇化合物的酯、及不飽和羧酸與多元胺化合物的醯胺類。又，還可較佳地使用具有羥基、胺基、氫硫基（Sulfanyl group）等親核性取代基之不飽和羧酸酯或醯胺類與單官能或多官能異氰酸酯類或環氧類的加成反應物、與單官能或多官能的羧酸的脫水縮合反應物等。又，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醯胺類與單官能或多官能的醇類、胺類、硫醇類的加成反應物、以及具有鹵代基、甲苯磺醯氧基等脫離性取代基之不飽和羧酸酯或醯胺類與單官能或多官能的醇類、胺類、硫醇類的取代反應物亦為較佳。又，作為另一例，還能夠使用取代為不飽和膦酸、苯乙烯等乙烯基苯衍生物、乙烯基醚、烯丙基醚等之化合物群組，來代替上述不飽和羧酸。作為具體例，能夠參閱日本特開2016-027357號公報的0113～0122段的記載，且該等內容被編入本說明書中。Specific examples of radically polymerizable compounds include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters, and The amines are preferably esters of unsaturated carboxylic acids and polyol compounds, and amines of unsaturated carboxylic acids and polyamine compounds. In addition, unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amine, and Sulfanyl group and monofunctional or polyfunctional isocyanate or epoxy can also be preferably used. Addition reactant, dehydration condensation reactant with monofunctional or polyfunctional carboxylic acid, etc. In addition, addition reactants of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and halogens Substitution reactants of unsaturated carboxylic acid esters or amides with detachable substituents such as a substituent and a toluene sulfonyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc., instead of the above-mentioned unsaturated carboxylic acid. As a specific example, the description in paragraphs 0113 to 0122 of JP 2016-027357 A can be referred to, and these contents are incorporated in this specification.

又，自由基聚合性化合物係在常壓下具有100℃以上的沸點之化合物亦為較佳。作為其例子，能夠舉出聚乙二醇二（甲基）丙烯酸酯、三羥甲基乙烷三（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、己二醇（甲基）丙烯酸酯、三羥甲基丙烷三（丙烯醯氧基丙基）醚、三（丙烯醯氧基乙基）異氰脲酸酯、將環氧乙烷、環氧丙烷加成到甘油、三羥甲基乙烷等多官能醇之後進行（甲基）丙烯酸酯化而得之化合物、如日本特公昭48-041708號公報、日本特公昭50-006034號公報、日本特開昭51-037193號各公報中所記載之胺酯（甲基）丙烯酸酯類、日本特開昭48-064183號、日本特公昭49-043191號、日本特公昭52-030490號各公報中所記載之聚酯丙烯酸酯類、作為環氧樹脂與（甲基）丙烯酸的反應產物之環氧丙烯酸酯類等多官能丙烯酸酯、丙烯酸甲酯及該等的混合物。又，日本特開2008-292970號公報的0254～0257段中所記載之化合物亦為較佳。又，還能夠舉出使（甲基）丙烯酸環氧丙酯等具有環狀醚基和乙烯性不飽和鍵之化合物與多官能羧酸進行反應而獲得之多官能（甲基）丙烯酸酯等。In addition, it is also preferable that the radically polymerizable compound has a boiling point of 100°C or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate ) Acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tri( Acrylic acid oxypropyl) ether, tris(acrylic acid oxyethyl) isocyanurate, ethylene oxide, propylene oxide are added to glycerol, trimethylol ethane and other polyfunctional alcohols. (Meth) acrylate compounds, such as the amine ester (methyl) described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Application Publication No. 51-037193. ) Acrylics, JP 48-064183, JP 49-043191, JP 52-030490, and the polyester acrylates described in the respective publications, as epoxy resin and (meth) Polyfunctional acrylates such as epoxy acrylates, methyl acrylate, and mixtures of these are the reaction products of acrylic acid. In addition, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also preferable. In addition, polyfunctional (meth)acrylates obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate with a polyfunctional carboxylic acid and the like can also be mentioned.

又，作為除上述以外的較佳的自由基聚合性化合物，還能夠使用日本特開2010-160418號公報、日本特開2010-129825號公報、日本專利第4364216號公報等中所記載之、具有2個以上的具有茀環且具有乙烯性不飽和鍵之基團之化合物、卡多樹脂。In addition, as preferred radical polymerizable compounds other than the above, those described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, Japanese Patent Publication No. 4364216, etc. can also be used. Two or more compounds with a tungsten ring and an ethylenically unsaturated bond group, cardo resin.

進而，作為其他例，還能夠舉出日本特公昭46-043946號公報、日本特公平01-040337號公報、日本特公平01-040336號公報中所記載之特定的不飽和化合物、日本特開平02-025493號公報中所記載之乙烯基膦酸系化合物等。又，還能夠使用日本特開昭61-022048號公報中所記載之包含全氟烷基之化合物。進而，還能夠使用在日本接著協會誌（Journal of the Adhesion Society of Japan） vol.20、No.7、300～308頁（1984年）中作為光聚合性單體及寡聚物而介紹者。Furthermore, as other examples, there are specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and Japanese Patent Application Publication No. 02 Vinylphosphonic acid-based compounds and the like described in Bulletin -025493. In addition, the perfluoroalkyl group-containing compound described in JP 61-022048 A can also be used. Furthermore, it is also possible to use those introduced as photopolymerizable monomers and oligomers in Journal of the Adhesion Society of Japan vol. 20, No. 7, pages 300 to 308 (1984).

除了上述以外，還能夠較佳地使用日本特開2015-034964號公報的0048～0051段中所記載之化合物、國際公開第2015/199219號的0087～0131段中所記載之化合物，且該等內容被編入本說明書中。In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Laid-Open No. 2015-034964, the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and these The content is compiled into this manual.

又，還能夠使用在日本特開平10-062986號公報中作為式（1）及式（2）而與其具體例一同記載之、將環氧乙烷、環氧丙烷加成到多官能醇之後進行（甲基）丙烯酸酯化而得之化合物，來作為自由基聚合性化合物。In addition, it is also possible to use the formula (1) and formula (2) described in Japanese Patent Application Laid-Open No. 10-062986 together with the specific examples thereof, after adding ethylene oxide and propylene oxide to a polyfunctional alcohol. The compound obtained by esterification of (meth)acrylate is used as a radical polymerizable compound.

進而，還能夠使用日本特開2015-187211號公報的0104～0131段中所記載之化合物作為其他自由基聚合性化合物，且該等內容被編入本說明書中。Furthermore, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used as other radically polymerizable compounds, and these contents are incorporated in this specification.

作為自由基聚合性化合物，二季戊四醇三丙烯酸酯（作為市售品，KAYARAD D-330；Nippon Kayaku Co.,Ltd.製造）、二季戊四醇四丙烯酸酯（作為市售品，KAYARAD D-320；Nippon Kayaku Co.,Ltd.製造，A-TMMT：Shin-Nakamura Chemical Co., Ltd.製造）、二季戊四醇五（甲基）丙烯酸酯（作為市售品，KAYARAD D-310；Nippon Kayaku Co.,Ltd.製造）、二季戊四醇六（甲基）丙烯酸酯（作為市售品，KAYARAD DPHA；Nippon Kayaku Co.,Ltd.製造，A-DPH；Shin-Nakamura Chemical Co., Ltd.製造）、及經由乙二醇殘基或丙二醇殘基而鍵結有該等的（甲基）丙烯醯基之結構為較佳。還能夠使用該等的寡聚物型。As a radically 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 Manufactured by Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; Nippon Kayaku Co., Ltd. . Manufacturing), dipentaerythritol hexa(meth)acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and A structure in which a diol residue or a propylene glycol residue is bonded to these (meth)acrylic groups is preferred. These oligomer types can also be used.

作為自由基聚合性化合物的市售品，例如可舉出Sartomer Company, Inc製造的具有4個伸乙氧基鏈之4官能丙烯酸酯亦即SR-494、具有4個伸乙氧基鏈之2官能丙烯酸甲酯亦即Sartomer Company, Inc製造的SR-209、231、239、Nippon Kayaku Co.,Ltd.製造的具有6個戊烯氧基鏈之6官能丙烯酸酯亦即DPCA-60、具有3個異丁烯氧基鏈之3官能丙烯酸酯亦即TPA-330、胺酯寡聚物UAS-10、UAB-140（NIPPON PAPER INDUSTRIES CO., LTD.製造）、NK酯M-40G、NK酯4G、NK酯M-9300、NK酯A-9300、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、AI-600（Kyoeisha chemical Co.,Ltd.製造）、BLENMER PME400（NOF CORPORATION.製造）等。Commercial products of radically polymerizable compounds include, for example, SR-494, a 4-functional acrylate having 4 ethoxy chains manufactured by Sartomer Company, Inc, and 2 of 4 ethoxy chains. Functional methyl acrylate, namely SR-209, 231, 239 manufactured by Sartomer Company, Inc, 6-functional acrylate with 6 pentenoxy chains manufactured by Nippon Kayaku Co., Ltd., namely DPCA-60, with 3 Three functional acrylates with a methacryloxy chain, namely TPA-330, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, 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.), BLENMER PME400 (manufactured by NOF CORPORATION), etc.

作為自由基聚合性化合物，如日本特公昭48-041708號公報、日本特開昭51-037193號公報、日本特公平02-032293號公報、日本特公平02-016765號公報中所記載之丙烯酸胺酯類、日本特公昭58-049860號公報、日本特公昭56-017654號公報、日本特公昭62-039417號公報、日本特公昭62-039418號公報中所記載之具有環氧乙烷系骨架之胺酯化合物類亦為較佳。作為自由基聚合性化合物，還能夠使用日本特開昭63-277653號公報、日本特開昭63-260909號公報、日本特開平01-105238號公報中所記載之、在分子內具有胺基結構、硫醚結構之化合物。As a radically polymerizable compound, for example, the acrylic amines described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Application Publication No. 02-016765 Esters, Japanese Japanese Patent Publication No. 58-049860, Japanese Japanese Patent Publication No. 56-017654, Japanese Japanese Patent Publication No. 62-039417, Japanese Patent Publication No. 62-039418, which have an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039418, and Japanese Patent Publication No. 62-039418. Amine ester compounds are also preferred. As the radically polymerizable compound, those described in JP 63-277653 A, JP 63-260909 A, and JP 01-105238 A having an amino group structure in the molecule can also be used. , Compounds with thioether structure.

自由基聚合性化合物可以係具有羧基、磷酸基等酸基之自由基聚合性化合物。具有酸基之自由基聚合性化合物係脂肪族多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多羥基化合物的未反應的羥基進行反應而具有酸基之自由基聚合性化合物為更佳。特佳為，在使非芳香族羧酸酐與脂肪族多羥基化合物的未反應的羥基進行反應而具有酸基之自由基聚合性化合物中脂肪族多羥基化合物係季戊四醇或二季戊四醇之化合物。作為市售品，例如可舉出作為TOAGOSEI CO.,LTD.製造的多元酸改質丙烯酸寡聚物之M-510、M-520等。The radical polymerizable compound may be a radical polymerizable compound having an acid group such as a carboxyl group and a phosphoric acid group. The radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. The non-aromatic carboxylic acid anhydride is reacted with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. A radically polymerizable compound is more preferable. Particularly preferably, the aliphatic polyhydroxy compound is a compound of pentaerythritol or dipentaerythritol among the radically polymerizable compounds having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. Examples of commercially available products include M-510 and M-520 which are polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., LTD.

作為具有酸基之自由基聚合性化合物的較佳的酸值，係0.1～40mgKOH/g，特佳為5～30mgKOH/g。若自由基聚合性化合物的酸值在上述範圍內，則製造上的操作性優異，進而顯影性優異。又，聚合性良好。上述酸值依照JIS K 0070:1992的記載進行測量。The preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. If the acid value of the radically polymerizable compound is in the above range, the workability in production is excellent, and the developability is also excellent. In addition, the polymerizability is good. The above acid value is measured in accordance with the description of JIS K 0070:1992.

就伴隨控制有機膜的彈性模數之翹曲抑制的觀點而言，本發明的組成物能夠較佳地使用單官能自由基聚合性化合物作為自由基聚合性化合物。作為單官能自由基聚合性化合物，可較佳地使用正丁基（甲基）丙烯酸酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸2-羥乙酯、丁氧基乙基（甲基）丙烯酸酯、卡必醇（甲基）丙烯酸酯、（甲基）丙烯環己酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸苯氧基乙酯、N-羥甲基（甲基）丙烯酸醯胺、（甲基）丙烯酸環氧丙酯、聚乙二醇單（甲基）丙烯酸酯、聚丙二醇單（甲基）丙烯酸酯等（甲基）丙烯酸衍生物、N-乙烯基吡咯啶酮、N-乙烯基己內醯胺等N-乙烯基化合物類、烯丙基環氧丙基醚、鄰苯二甲酸二烯丙酯、偏苯三酸三烯丙酯等烯丙基化合物類等。作為單官能自由基聚合性化合物，為了抑制曝光前的揮發，在常壓下具有100℃以上的沸點之化合物亦為較佳。From the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the organic film, the composition of the present invention can preferably use a monofunctional radical polymerizable compound as the radical polymerizable compound. As the monofunctional radical polymerizable compound, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy can be preferably used. Ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxyl (Meth)acrylic acid derivatives such as meth(meth)acrylate, glycidyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate And other allyl compounds. As the monofunctional radical polymerizable compound, in order to suppress volatilization before exposure, a compound having a boiling point of 100°C or higher under normal pressure is also preferable.

〔除上述之自由基聚合性化合物以外的聚合性化合物〕 本發明的組成物還能夠包含除上述之自由基聚合性化合物以外的聚合性化合物。作為除上述之自由基聚合性化合物以外的聚合性化合物，可舉出具有羥甲基（methylol group）、烷氧基甲基或醯氧基甲基之化合物；環氧化合物；氧環丁烷化合物；苯并㗁𠯤化合物。[Polymerizable compounds other than the above-mentioned radically polymerizable compounds] The composition of the present invention can also contain a polymerizable compound other than the above-mentioned radical polymerizable compound. Examples of polymerizable compounds other than the above-mentioned radical polymerizable compounds include compounds having methylol group, alkoxymethyl or oxymethyl; epoxy compounds; oxetane compounds ; Benzo 㗁𠯤 compounds.

-具有羥甲基、烷氧基甲基或醯氧基甲基之化合物- 作為具有羥甲基、烷氧基甲基或醯氧基甲基之化合物，由下述式（AM1）、（AM4）或（AM5）表示之化合物為較佳。-Compounds with hydroxymethyl, alkoxymethyl or oxymethyl- As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferred.

[化學式36]

Figure 02_image071
（式中，t表示1～20的整數，R104 表示碳數1～200的t價的有機基，R105 表示由-OR106 或-OCO-R107 表示之基團，R106 表示氫原子或碳數1～10的有機基，R107 表示碳數1～10的有機基。） [化學式37]
Figure 02_image073
（式中，R404 表示碳數1～200的2價的有機基，R405 表示由-OR406 或-OCO-R407 表示之基團，R406 表示氫原子或碳數1～10的有機基，R407 表示碳數1～10的有機基。） [化學式38]
Figure 02_image075
（式中u表示3～8的整數，R504 表示碳數1～200的u價的有機基，R505 表示由-OR506 或-OCO-R507 表示之基團，R506 表示氫原子或碳數1～10的有機基，R507 表示碳數1～10的有機基。）[Chemical formula 36]
Figure 02_image071
(In the formula, t represents an integer from 1 to 20, R 104 represents a t-valent organic group with a carbon number of 1 to 200, R 105 represents a group represented by -OR 106 or -OCO-R 107 , and R 106 represents a hydrogen atom Or an organic group with 1 to 10 carbons, R 107 represents an organic group with 1 to 10 carbons.) [Chemical formula 37]
Figure 02_image073
(In the formula, R 404 represents a divalent organic group with 1 to 200 carbons, R 405 represents a group represented by -OR 406 or -OCO-R 407 , and R 406 represents a hydrogen atom or an organic group with 1 to 10 carbons. R 407 represents an organic group having 1 to 10 carbon atoms.) [Chemical formula 38]
Figure 02_image075
(In the formula, u represents an integer from 3 to 8, R 504 represents an organic group of u valence with 1 to 200 carbon atoms, R 505 represents a group represented by -OR 506 or -OCO-R 507 , and R 506 represents a hydrogen atom or An organic group having 1 to 10 carbons, R 507 represents an organic group having 1 to 10 carbons.)

作為由式（AM4）表示之化合物的具體例，可舉出46DMOC、46DMOEP（以上為商品名稱，ASAHI YUKIZAI CORPORATION製造）、DML-MBPC、DML-MBOC、DML-OCHP、DML-PCHP、DML-PC、DML-PTBP、DML-34X、DML-EP、DML-POP、dimethylolBisOC-P、DML-PFP、DML-PSBP、DML-MTrisPC（以上為商品名稱，Honshu Chemical Industry Co., Ltd.製造）、NIKALAC MX-290（商品名稱，Sanwa Chemical co., LTD.製造）、2,6-二甲氧基甲基-4-三級丁基苯酚（2,6-dimethoxymethyl-4-t-butylphenol）、2,6-二甲氧基甲基-對甲酚（2,6-dimethoxymethyl-p-cresol）、2,6-二乙醯氧基甲基-對甲酚（2,6-diacetoxymethyl-p-cresol）等。Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above are trade names, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC , DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (trade name, manufactured by Sanwa Chemical co., LTD.), 2,6-dimethoxymethyl-4-t-butylphenol, 2 ,6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacetoxymethyl-p-cresol (2,6-diacetoxymethyl-p-cresol) )Wait.

又，作為由式（AM5）表示之化合物的具體例，可舉出TriML-P、TriML-35XL、TML-HQ、TML-BP、TML-pp-BPF、TML-BPA、TMOM-BP、HML-TPPHBA、HML-TPHAP、HMOM-TPPHBA、HMOM-TPHAP（以上為商品名稱，Honshu Chemical Industry Co., Ltd.製造）、TM-BIP-A（商品名稱，ASAHI YUKIZAI CORPORATION製造）、NIKALAC MX-280、NIKALAC MX-270、NIKALAC MW-100LM（以上為商品名稱，Sanwa Chemical co., LTD.製造）。Furthermore, as specific examples of the compound represented by the formula (AM5), TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML- TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade names, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above are trade names, manufactured by Sanwa Chemical co., LTD.).

-環氧化合物（具有環氧基之化合物）- 作為環氧化合物，在一分子中具有2個以上的環氧基之化合物為較佳。環氧基在200℃以下的條件下進行交聯反應，且不產生源自交聯之脫水反應，因此難以引起膜收縮。因此，含有環氧化合物對於組成物的低溫硬化及抑制翹曲係有效的。-Epoxy compound (compound with epoxy group)- As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a crosslinking reaction under the conditions of 200°C or less, and does not generate a dehydration reaction derived from the crosslinking, so it is difficult to cause film shrinkage. Therefore, containing the epoxy compound is effective for low-temperature hardening of the composition and suppression of warpage.

環氧化合物含有聚環氧乙烷基為較佳。藉此，能夠進一步降低彈性模數，且能夠抑制翹曲。聚環氧乙烷基係指環氧乙烷的重複單元數為2以上者，且重複單元數係2～15為較佳。The epoxy compound preferably contains a polyethylene oxide group. Thereby, the modulus of elasticity can be further reduced, and warpage can be suppressed. The polyethylene oxide group means the number of repeating units of ethylene oxide of 2 or more, and the number of repeating units is preferably 2-15.

作為環氧化合物的例子，能夠舉出雙酚A型環氧樹脂；雙酚F型環氧樹脂；丙二醇二環氧丙基醚等伸烷基二醇型環氧樹脂；聚丙二醇二環氧丙基醚等聚伸烷基二醇型環氧樹脂；聚甲基（環氧丙基氧丙基）矽氧烷等含有環氧基之聚矽氧等，但是並不限定於該等。具體而言，可舉出EPICLON（註冊商標）850-S、EPICLON（註冊商標）HP-4032、EPICLON（註冊商標）HP-7200、EPICLON（註冊商標）HP-820、EPICLON（註冊商標）HP-4700、EPICLON（註冊商標）EXA-4710、EPICLON（註冊商標）HP-4770、EPICLON（註冊商標）EXA-859CRP、EPICLON（註冊商標）EXA-1514、EPICLON（註冊商標）EXA-4880、EPICLON（註冊商標）EXA-4850-150、EPICLON（註冊商標）EXA-4850-1000、EPICLON（註冊商標）EXA-4816、EPICLON（註冊商標）EXA-4822（以上為商品名稱，DIC Corporation製造）、RIKARESIN（註冊商標）BEO-60E（商品名稱，New Japan Chemical Co., Ltd.製造）、EP-4003S、EP-4000S（以上為商品名稱，ADEKA CORPORATION製造）等。其中，就翹曲的抑制及耐熱性優異之觀點而言，含有聚環氧乙烷基之環氧樹脂為較佳。例如，EPICLON（註冊商標）EXA-4880、EPICLON（註冊商標）EXA-4822、RIKARESIN（註冊商標）BEO-60E含有聚環氧乙烷基，因此為較佳。Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polypropylene glycol diglycidyl ether Polyalkylene glycol type epoxy resins such as base ethers; epoxy-containing polysiloxanes such as polymethyl (glycidoxypropyl) silicone, etc., but are not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP- 4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered Trademarks) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (the above are product names, manufactured by DIC Corporation), RIKARESIN (registered Trademarks) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the above are trade names, manufactured by ADEKA CORPORATION), etc. Among them, from the viewpoint of suppression of warpage and excellent heat resistance, epoxy resins containing polyethylene oxide groups are preferred. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups, so they are preferred.

-氧環丁烷化合物（具有氧雜環丁基之化合物）- 作為氧環丁烷化合物，能夠舉出在一分子中具有2個以上的氧環丁烷環之化合物、3-乙基-3-羥甲基氧環丁烷、1,4-雙{[（3-乙基-3-氧雜環丁基）甲氧基]甲基}苯、3-乙基-3-（2-乙基己基甲基）氧環丁烷、1,4-苯二羧酸-雙[（3-乙基-3-氧雜環丁基）甲基]酯等。作為具體例，能夠較佳地使用TOAGOSEI CO.,LTD.製造的ARON OXETANE系列（例如，OXT-121、OXT-221、OXT-191、OXT-223），該等可以單獨使用，或者亦可以混合2種以上來使用。-Oxetane compounds (compounds with oxetanyl groups)- Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyl oxetane, and 1,4-bis{[( 3-Ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylate Acid-bis[(3-ethyl-3-oxetanyl)methyl] ester and the like. As a specific example, ARON OXETANE series manufactured by TOAGOSEI CO., LTD. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or in combination. Two or more kinds are used.

-苯并㗁𠯤化合物（具有苯并㗁唑基之化合物）- 關於苯并㗁𠯤化合物，因源自開環加成反應之交聯反應，在硬化時未發生除氣，進而減小熱收縮以抑制翹曲的發生，藉此為較佳。-Benzo 㗁 𠯤 compounds (compounds with benzo azole groups)- Regarding the benzoglyph compound, because of the crosslinking reaction derived from the ring-opening addition reaction, outgassing does not occur during curing, and thermal shrinkage is reduced to suppress the occurrence of warpage, which is preferred.

作為苯并㗁𠯤化合物的較佳例，可舉出B-a型苯并㗁𠯤、B-m型苯并㗁𠯤（以上為商品名稱，SHIKOKU CHEMICALS CORPORATION製造）、多羥基苯乙烯樹脂的苯并㗁𠯤加成物、苯酚酚醛清漆型二氫苯并㗁𠯤化合物。該等可以單獨使用，或者可以混合2種以上。As preferred examples of the benzoglyph compound, there may be mentioned Ba-type benzoglyph, Bm-type benzoglyph (the above are the trade names, manufactured by SHIKOKU CHEMICALS CORPORATION), and the benzoglyster addition of polyhydroxy styrene resin. The finished product, the phenol novolac type dihydrobenzo 㗁 𠯤 compound. These can be used individually or in mixture of 2 or more types.

相對於本發明的組成物的總固體成分，聚合性化合物的含量超過0質量%且60質量%以下為較佳。下限係5質量%以上為更佳。上限係50質量%以下為更佳，30質量%以下為進一步較佳。With respect to the total solid content of the composition of the present invention, the content of the polymerizable compound is preferably more than 0% by mass and 60% by mass or less. More preferably, the lower limit is 5% by mass or more. The upper limit is more preferably 50% by mass or less, and more preferably 30% by mass or less.

聚合性化合物可以單獨使用1種，但是亦可以混合2種以上來使用。在併用2種以上之情形下，總量在上述範圍內為較佳。A polymerizable compound may be used individually by 1 type, and may mix and use 2 or more types. When two or more types are used in combination, the total amount is preferably within the above-mentioned range.

＜溶劑＞ 本發明的組成物含有溶劑為較佳。溶劑能夠任意地使用公知的溶劑。溶劑係有機溶劑為較佳。作為有機溶劑，可舉出酯類、醚類、酮類、芳香族烴類、亞碸類、醯胺類等的化合物。＜Solvent＞ The composition of the present invention preferably contains a solvent. A well-known solvent can be used arbitrarily as a solvent. Solvent-based organic solvents are preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfenes, and amines.

作為酯類，例如可舉出乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁內酯、ε-己內酯、δ-戊內酯、烷氧基乙酸烷基酯（例如，烷氧基乙酸甲酯、烷氧基乙酸乙酯、烷氧基乙酸丁酯（例如，甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯等））、3-烷氧基丙酸烷基酯類（例如，3-烷氧基丙酸甲酯、3-烷氧基丙酸乙酯等（例如，3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯等））、2-烷氧基丙酸烷基酯類（例如，2-烷氧基丙酸甲酯、2-烷氧基丙酸乙酯、2-烷氧基丙酸丙酯等（例如，2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯））、2-烷氧基-2-甲基丙酸甲酯及2-烷氧基-2-甲基丙酸乙酯（例如，2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯等）、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸甲酯、2-氧代丁酸乙酯等作為較佳者。Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. Ester, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, ethyl alkoxyacetate Ester, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3 -Alkoxy propionic acid alkyl esters (for example, 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (for example, 3-methoxy propionic acid methyl ester, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (for example, 2-alkoxypropionic acid Methyl ester, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkoxy-2 -Ethyl methyl propionate (for example, methyl 2-methoxy-2-methyl propionate, ethyl 2-ethoxy-2-methyl propionate, etc.), methyl pyruvate, ethyl pyruvate Ester, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. are preferred.

作為醚類，例如可舉出二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單乙醚、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯等作為較佳者。As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, two Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. As the better.

作為酮類，例如可舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮等作為較佳者。As ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. are mentioned as preferable ones, for example.

作為芳香族烴類，例如可舉出甲苯、二甲苯、苯甲醚、檸檬烯等作為較佳者。As aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are preferred.

作為亞碸類，例如可舉出二甲基亞碸作為較佳者。As the sulfenite, for example, dimethyl sulfenite is preferable.

作為醯胺類，可舉出N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺等作為較佳者。Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide. Amines etc. are preferable.

關於溶劑，就改善塗佈面性狀等的觀點而言，混合2種以上之形態亦為較佳。Regarding the solvent, from the viewpoint of improving coating surface properties, etc., a form in which two or more types are mixed is also preferable.

在本發明中，選自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、二乙二醇二甲醚、乙酸丁酯、3-甲氧基丙酸甲酯、2-庚酮、環己酮、環戊酮、γ-丁內酯、二甲基亞碸、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、N-甲基-2-吡咯啶酮、丙二醇甲醚及丙二醇甲醚乙酸酯中之1種溶劑或由其中2種以上構成之混合溶劑為較佳。併用二甲基亞碸和γ-丁內酯為特佳。In the present invention, it is selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfene, ethyl carbitol acetate, butyl carbitol One solvent of alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or a mixed solvent composed of two or more of them is preferred. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone in combination.

就塗佈性的觀點而言，將溶劑的含量設為本發明的組成物的總固體成分濃度成為5～80質量%之量為較佳，設為本發明的組成物的總固體成分濃度成為5～75質量%之量為更佳，設為本發明的組成物的總固體成分濃度成為10～70質量%之量為進一步較佳，設為本發明的組成物的總固體成分濃度成為40～70質量%之量為進一步較佳。溶劑含量只要依據塗膜的所期望的厚度和塗佈方法來進行調節即可。From the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the composition of the present invention is 5 to 80% by mass, and the total solid content concentration of the composition of the present invention is The amount is more preferably from 5 to 75% by mass, and the total solid content concentration of the composition of the present invention is more preferably from 10 to 70% by mass, and the total solid content concentration of the composition of the present invention is 40%. The amount of -70% by mass is more preferable. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

溶劑可以僅含有1種，亦可以含有2種以上。在含有2種以上的溶劑之情形下，總量在上述範圍內為較佳。The solvent may contain only one type or two or more types. When two or more kinds of solvents are contained, the total amount is preferably within the above-mentioned range.

＜熱聚合起始劑＞ 本發明的組成物可以包含熱聚合起始劑，尤其，可以包含熱自由基聚合起始劑。熱自由基聚合起始劑為藉由熱能而產生自由基且起始或促進具有聚合性之化合物的聚合反應之化合物。藉由添加熱自由基聚合起始劑，還能夠在後述之加熱步驟中，進行樹脂及聚合性化合物的聚合反應，因此能夠進一步提高耐溶劑性。＜Thermal polymerization initiator＞ The composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or promotes the polymerization reaction of the polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed in the heating step described later, so that the solvent resistance can be further improved.

作為熱自由基聚合起始劑，具體而言，可舉出日本特開2008-063554號公報的0074～0118段中所記載之化合物。Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A.

在包含熱聚合起始劑之情形下，相對於本發明的組成物的總固體成分，其含量係0.1～30質量%為較佳，更佳為0.1～20質量%，進一步較佳為5～15質量%。熱聚合起始劑可以僅含有1種，亦可以含有2種以上。在含有2種以上的熱聚合起始劑之情形下，其總量在上述範圍內為較佳。In the case of including the thermal polymerization initiator, the content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 5 to 30% by mass relative to the total solid content of the composition of the present invention. 15% by mass. The thermal polymerization initiator may contain only one type or two or more types. When two or more kinds of thermal polymerization initiators are contained, the total amount thereof is preferably within the above-mentioned range.

＜熱酸產生劑＞ 本發明的組成物可以包含熱酸產生劑。 熱酸產生劑藉由加熱產生酸，且具有促進選自具有羥甲基、烷氧基甲基或醯氧基甲基之化合物、環氧化合物、氧環丁烷化合物及苯并㗁𠯤化合物中之至少1種化合物的交聯反應之效果。＜Hot acid generator＞ The composition of the present invention may contain a thermal acid generator. The thermal acid generator generates acid by heating, and has a promotion selected from the group consisting of hydroxymethyl, alkoxymethyl, or oxymethyl compounds, epoxy compounds, oxetane compounds, and benzophenone compounds The effect of the cross-linking reaction of at least one compound.

熱酸產生劑的熱解開始溫度係50℃～270℃為較佳，50℃～250℃為更佳。又，若選擇在將組成物塗佈於基板上之後的乾燥（預烘烤：約70～140℃）時不產生酸而在之後的曝光、顯影中進行圖案化之後的最終加熱（硬化：約100～400℃）時產生酸者作為熱酸產生劑，則能夠抑制顯影時的靈敏度下降，因此為較佳。 關於熱解開始溫度，在將熱酸產生劑在耐壓膠囊中以5℃/分鐘加熱至500℃之情形下，作為最低溫度的發熱峰的峰溫度而求出。 作為測量熱解開始溫度時使用之設備，可舉出Q2000（TA Instruments Japan Inc.製造）等。The pyrolysis start temperature of the thermal acid generator is preferably 50°C to 270°C, and more preferably 50°C to 250°C. In addition, if the composition is applied to the substrate after drying (pre-baking: about 70-140°C), no acid is generated, and the final heating after patterning in subsequent exposure and development (curing: about 100 to 400°C), which generates acid at 100 to 400°C), is preferably used as a thermal acid generator to suppress the decrease in sensitivity during development. Regarding the pyrolysis start temperature, when the thermal acid generator is heated to 500°C at 5°C/min in a pressure-resistant capsule, it is determined as the peak temperature of the heat generation peak at the lowest temperature. As a device used when measuring the pyrolysis start temperature, Q2000 (manufactured by TA Instruments Japan Inc.) and the like can be cited.

由熱酸產生劑產生之酸係強酸為較佳，例如，對甲苯磺酸、苯磺酸等芳基磺酸、甲烷磺酸、乙烷磺酸、丁烷磺酸等烷基磺酸、或三氟甲烷磺酸等鹵烷基磺酸等為較佳。作為這種熱酸產生劑的例子，可舉出日本特開2013-072935號公報的0055段中所記載者。Strong acids produced by thermal acid generators are preferred, for example, aryl sulfonic acids such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acids such as methane sulfonic acid, ethane sulfonic acid, butane sulfonic acid, or Haloalkylsulfonic acids such as trifluoromethanesulfonic acid and the like are preferred. As an example of such a thermal acid generator, the one described in paragraph 0055 of JP 2013-072935 A can be cited.

其中，就有機膜中的殘留物少且不易使有機膜物性下降之觀點而言，產生碳數1～4的烷基磺酸、碳數1～4的鹵烷基磺酸者為更佳，甲烷磺酸（4-羥基苯基）二甲基鋶、甲烷磺酸（4-（（甲氧基羰基）氧基）苯基）二甲基鋶、甲烷磺酸苄基（4-羥基苯基）甲基鋶、甲烷磺酸苄基（4-（（甲氧基羰基）氧基）苯基）甲基鋶、甲烷磺酸（4-羥基苯基）甲基（（2-甲基苯基）甲基）鋶、三氟甲烷磺酸（4-羥基苯基）二甲基鋶、三氟甲烷磺酸（4-（（甲氧基羰基）氧基）苯基）二甲基鋶、三氟甲烷磺酸苄基（4-羥基苯基）甲基鋶、三氟甲烷磺酸苄基（4-（（甲氧基羰基）氧基）苯基）甲基鋶、三氟甲烷磺酸（4-羥基苯基）甲基（（2-甲基苯基）甲基）鋶、3-（5-（（（丙基磺醯基）氧基）亞胺基）噻吩-2（5H）-亞基）-2-（鄰甲苯基）丙腈、2,2-雙（3-（甲磺醯基胺基）-4-羥基苯基）六氟丙烷作為熱酸產生劑而較佳。Among them, from the viewpoint that there are few residues in the organic film and the physical properties of the organic film are not easily reduced, it is more preferable to produce alkyl sulfonic acid having 1 to 4 carbon atoms and haloalkyl sulfonic acid having 1 to 4 carbon atoms. Methanesulfonic acid (4-hydroxyphenyl) dimethyl sulfonium, methanesulfonic acid (4-((methoxycarbonyl)oxy) phenyl) dimethyl sulfonic acid, methanesulfonate benzyl (4-hydroxyphenyl) ) Methanesulfonate, benzyl methanesulfonate (4-((methoxycarbonyl)oxy)phenyl)methylsulfonate, methanesulfonate (4-hydroxyphenyl) methyl ((2-methylphenyl) ) Methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethyl sulfonium, trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy) phenyl) dimethyl sulfonium, three Benzyl fluoromethanesulfonate (4-hydroxyphenyl) methyl alumite, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl)oxy) phenyl) methyl alumite, trifluoromethanesulfonic acid ( 4-Hydroxyphenyl)methyl((2-methylphenyl)methyl)aluminium, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)- Subunit)-2-(o-tolyl)propionitrile and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane are preferred as the thermal acid generator.

又，日本特開2013-167742號公報的0059段中所記載之化合物亦作為熱酸產生劑而較佳。In addition, the compound described in paragraph 0059 of JP 2013-167742 A is also preferable as a thermal acid generator.

相對於樹脂100質量份，熱酸產生劑的含量係0.01質量份以上為較佳，0.1質量份以上為更佳。藉由含有0.01質量份以上，可促進交聯反應，因此能夠進一步提高有機膜的機械特性及耐溶劑性。又，就有機膜的電絕緣性的觀點而言，20質量份以下為較佳，15質量份以下為更佳，10質量份以下為進一步較佳。Relative to 100 parts by mass of the resin, the content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more. By containing 0.01 parts by mass or more, the crosslinking reaction can be promoted, and therefore the mechanical properties and solvent resistance of the organic film can be further improved. In addition, from the viewpoint of the electrical insulation of the organic film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is more preferable.

＜鎓鹽＞ 本發明的組成物包含鎓鹽為較佳。 尤其，在作為其他樹脂而包含聚醯亞胺前驅物之情形下，組成物包含鎓鹽為較佳。 鎓鹽的種類等並無特別限定，但是可較佳地舉出銨鹽、亞胺鹽、鋶鹽、錪鎓鹽或鏻鹽。 該等中，就熱穩定性高的觀點而言，銨鹽或亞胺鹽為較佳，就與聚合物的相容性的觀點而言，鋶鹽、錪鎓鹽或鏻鹽為較佳。＜Onium salt＞ The composition of the present invention preferably contains an onium salt. In particular, when a polyimide precursor is included as another resin, the composition preferably includes an onium salt. The type of onium salt and the like are not particularly limited, but preferably ammonium salt, imine salt, sulfonium salt, phosphonium salt, or phosphonium salt can be mentioned. Among them, an ammonium salt or an imine salt is preferable from the viewpoint of high thermal stability, and a sulfonium salt, an phosphonium salt, or a phosphonium salt is preferable from the viewpoint of compatibility with the polymer.

又，鎓鹽為具有鎓結構之陽離子與陰離子的鹽，上述陽離子與陰離子可以經由共價鍵而鍵結，亦可以不經由共價鍵而鍵結。 亦即，鎓鹽可以為在同一分子結構內具有陽離子部和陰離子部之分子內鹽，亦可以為分別為不同分子之陽離子分子與陰離子分子離子鍵結之分子間鹽，但是分子間鹽為較佳。又，本發明的組成物中，上述陽離子部或陽離子分子與上述陰離子部或陰離子分子可以藉由離子鍵而鍵結，亦可以解離。 作為鎓鹽中的陽離子，銨陽離子、吡啶鎓陽離子、鋶陽離子、錪鎓陽離子或鏻陽離子為較佳，選自包括四烷基銨陽離子、鋶陽離子及錪鎓陽離子之群組中之至少1種陽離子為更佳。In addition, the onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may be bonded via a covalent bond or may not be bonded via a covalent bond. That is, the onium salt may be an intramolecular salt having a cation part and an anion part in the same molecular structure, or may be an intermolecular salt in which cationic molecules and anion molecules of different molecules are ionically bonded, but intermolecular salts are relatively high. good. Furthermore, in the composition of the present invention, the cation portion or cation molecule and the anion portion or anion molecule may be bonded by an ionic bond, or may be dissociated. As the cation in the onium salt, ammonium cation, pyridinium cation, sulfonium cation, phosphonium cation or phosphonium cation is preferred, and at least one selected from the group consisting of tetraalkylammonium cation, sulfonium cation and phosphonium cation Cation is more preferable.

本發明中所使用之鎓鹽可以為熱鹼產生劑。 熱鹼產生劑係指藉由加熱產生鹼基之化合物，例如，可舉出若加熱至40℃以上則產生鹼基之酸性化合物等。The onium salt used in the present invention may be a thermal base generator. The thermal base generator refers to a compound that generates a base by heating, and for example, an acidic compound that generates a base when heated to 40° C. or higher can be mentioned.

〔銨鹽〕 在本發明中，銨鹽係指銨陽離子與陰離子的鹽。〔Ammonium salt〕 In the present invention, ammonium salt refers to a salt of ammonium cation and anion.

-銨陽離子- 作為銨陽離子，四級銨陽離子為較佳。 又，作為銨陽離子，由下述式（101）表示之陽離子為較佳。 [化學式39]

Figure 02_image077
式（101）中，R1 ～R4 分別獨立地表示氫原子或烴基，R1 ～R4 中的至少2個可以彼此鍵結而形成環。-Ammonium cation- As the ammonium cation, a quaternary ammonium cation is preferred. In addition, as the ammonium cation, a cation represented by the following formula (101) is preferred. [Chemical formula 39]
Figure 02_image077
In formula (101), R 1 to R 4 each independently represent a hydrogen atom or a hydrocarbon group, and at least two of R 1 to R 4 may be bonded to each other to form a ring.

式（101）中，R1 ～R4 分別獨立地表示烴基為較佳，烷基或芳基為更佳，碳數1～10的烷基或碳數6～12的芳基為進一步較佳。R1 ～R4 可以具有取代基，作為取代基的例子，可舉出羥基、芳基、烷氧基、芳氧基、芳基羰基、烷基羰基、烷氧基羰基、芳氧基羰基、醯氧基等。 在R1 ～R4 中的至少2個彼此鍵結而形成環之情形下，上述環可以包含雜原子。作為上述雜原子，可舉出氮原子。In formula (101), R 1 to R 4 each independently represent a hydrocarbon group, preferably, an alkyl group or an aryl group is more preferable, and an alkyl group having 1 to 10 carbons or an aryl group having 6 to 12 carbons is more preferable . R 1 to R 4 may have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, Oxo and so on. In the case where at least two of R 1 to R 4 are bonded to each other to form a ring, the above-mentioned ring may include a hetero atom. As said hetero atom, a nitrogen atom can be mentioned.

銨陽離子由下述式（Y1-1）及（Y1-2）中的任一個表示為較佳。 [化學式40]

Figure 02_image079
The ammonium cation is preferably represented by either of the following formulas (Y1-1) and (Y1-2). [Chemical formula 40]
Figure 02_image079

式（Y1-1）及（Y1-2）中，R101 表示n價的有機基，R1 與式（101）中的R1 含義相同，Ar101 及Ar102 分別獨立地表示芳基，n表示1以上的整數。 式（Y1-1）中，R101 係脂肪族烴、芳香族烴或從該等鍵結而成之結構去除n個氫原子而成之基團為較佳，從碳數2～30的飽和脂肪族烴、苯或萘去除n個氫原子而成之基團為更佳。 式（Y1-1）中，n係1～4為較佳，1或2為更佳，1為進一步較佳。 式（Y1-2）中，Ar101 及Ar102 分別獨立地表示苯基或萘基為較佳，苯基為更佳。In formulas (Y1-1) and (Y1-2), R 101 represents an n-valent organic group, R 1 has the same meaning as R 1 in formula (101) , Ar 101 and Ar 102 each independently represent an aryl group, and n Represents an integer of 1 or more. In the formula (Y1-1), R 101 is an aliphatic hydrocarbon, an aromatic hydrocarbon or a group formed by removing n hydrogen atoms from the structure formed by such bonding, preferably from a saturated carbon number of 2-30 Aliphatic hydrocarbons, benzene or naphthalene is more preferably a group formed by removing n hydrogen atoms. In the formula (Y1-1), n is preferably 1 to 4, 1 or 2 is more preferable, and 1 is even more preferable. In the formula (Y1-2), it is preferable that Ar 101 and Ar 102 each independently represent a phenyl group or a naphthyl group, and a phenyl group is more preferable.

-陰離子- 作為銨鹽中的陰離子，選自羧酸陰離子、苯酚陰離子、磷酸陰離子及硫酸陰離子中之1種為較佳，就可兼顧鹽的穩定性和熱解性之理由而言，羧酸陰離子為更佳。亦即，銨鹽係銨陽離子與羧酸陰離子的鹽為更佳。 羧酸陰離子係具有2個以上的羧基之2價以上的羧酸的陰離子為較佳，2價的羧酸的陰離子為更佳。依該態樣，能夠進一步提高組成物的穩定性、硬化性及顯影性。尤其，藉由使用2價的羧酸的陰離子，能夠進一步提高組成物的穩定性、硬化性及顯影性。-Anion- As the anion in the ammonium salt, one selected from the group consisting of carboxylic acid anion, phenol anion, phosphoric acid anion, and sulfuric acid anion is preferred. In terms of the stability and pyrolysis of the salt, the carboxylic acid anion is more good. That is, a salt of an ammonium cation and a carboxylic anion is more preferable. The carboxylic acid anion is preferably an anion of a divalent or more carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, the stability, curability, and developability of the composition can be further improved. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the composition can be further improved.

羧酸陰離子由下述式（X1）表示為較佳。 [化學式41]

Figure 02_image081
式（X1）中，EWG表示電子吸引基。The carboxylic acid anion is preferably represented by the following formula (X1). [Chemical formula 41]
Figure 02_image081
In formula (X1), EWG represents the electron attracting base.

本實施形態中，電子吸引基係指哈米特取代基常數σm表示正值者。在此，關於σm，在都野雄甫總說、Journal of Synthetic Organic Chemistry，Japan第23卷第8號（1965）p.631-642中詳細進行說明。另外，本實施形態中的電子吸引基並不限定於上述文獻中所記載之取代基。 作為σm表示正值之取代基的例子，可舉出CF3 基（σm=0.43）、CF3 C（=O）基（σm=0.63）、HC≡C基（σm=0.21）、CH2 =CH基（σm=0.06）、Ac基（σm=0.38）、MeOC（=O）基（σm=0.37）、MeC（=O）CH=CH基（σm=0.21）、PhC（=O）基（σm=0.34）、H2 NC（=O）CH2 基（σm=0.06）等。另外，Me表示甲基，Ac表示乙醯基，Ph表示苯基（以下相同）。In this embodiment, the electron attracting group refers to a Hammett substituent constant σm showing a positive value. Here, σm will be described in detail in Tono Yufu, Journal of Synthetic Organic Chemistry, Japan Volume 23, No. 8 (1965) p.631-642. In addition, the electron attracting group in this embodiment is not limited to the substituents described in the above-mentioned documents. As an example of a substituent whose σm represents a positive value, CF 3 group (σm=0.43), CF 3 C(=O) group (σm=0.63), HC≡C group (σm=0.21), CH 2 = CH base (σm=0.06), Ac base (σm=0.38), MeOC (=O) base (σm=0.37), MeC (=O) CH=CH base (σm=0.21), PhC (=O) base ( σm=0.34), H 2 NC (=O) CH 2 base (σm=0.06), etc. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (the same applies hereinafter).

EWG係由下述式（EWG-1）～（EWG-6）表示之基團為較佳。 [化學式42]

Figure 02_image083
式（EWG-1）～（EWG-6）中，Rx1 ～Rx3 分別獨立地表示氫原子、烷基、烯基、芳基、羥基或羧基，Ar表示芳香族基。EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6). [Chemical formula 42]
Figure 02_image083
In the formulas (EWG-1) to (EWG-6), R x1 to R x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxyl group, and Ar represents an aromatic group.

在本發明中，羧酸陰離子由下述式（XA）表示為較佳。 [化學式43]

Figure 02_image085
式（XA）中，L10 表示單鍵或選自包括伸烷基、伸烯基、芳香族基、-NRX -及該等的組合之群組中之2價的連結基，RX 表示氫原子、烷基、烯基或芳基。In the present invention, the carboxylic acid anion is preferably represented by the following formula (XA). [Chemical formula 43]
Figure 02_image085
In formula (XA), L 10 represents a single bond or a divalent linking group selected from the group consisting of alkylene, alkenylene, aromatic, -NR X -and combinations thereof, R X represents A hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

作為羧酸陰離子的具體例，可舉出順丁烯二酸陰離子、鄰苯二甲酸陰離子、N-苯基亞胺基二乙酸陰離子及草酸陰離子。Specific examples of the carboxylic acid anion include maleic acid anion, phthalic acid anion, N-phenyliminodiacetic acid anion, and oxalic acid anion.

就在低溫下容易進行特定樹脂的環化，且組成物的保存穩定性容易提高之觀點而言，本發明中的鎓鹽包含銨陽離子作為陽離子，上述鎓鹽包含共軛酸的pKa（pKaH）為2.5以下的陰離子作為陰離子為較佳，包含1.8以下的陰離子為更佳。 上述pKa的下限並無特別限定，但是就所產生之鹼基不易被中和，改善特定樹脂等的環化效率之觀點而言，-3以上為較佳，-2以上為更佳。 作為上述pKa，能夠參閱有機結構的物理鑑定法（作者：Brown, H. C.,McDaniel, D. H.,Hafliger, O.,Nachod, F. C.；編輯：Braude, E. A.,Nachod, F. C.；學術出版社，紐約，1955）、生化研究資料（作者：Dawson，R.M.C.等；牛津，克拉侖敦出版社，1959）中所記載之值。關於該等文獻中未記載之化合物，使用利用ACD/pKa（ACD/Labs製造）的軟體依據結構式計算出之值。From the viewpoints that the cyclization of the specific resin is easily carried out at low temperature and the storage stability of the composition is easily improved, the onium salt in the present invention contains an ammonium cation as a cation, and the onium salt contains the pKa (pKaH) of the conjugate acid An anion of 2.5 or less is preferable as an anion, and an anion of 1.8 or less is more preferable. The lower limit of the above-mentioned pKa is not particularly limited, but from the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of a specific resin or the like is improved, -3 or more is preferable, and -2 or more is more preferable. As the above pKa, you can refer to the physical identification method of organic structure (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Editor: Braude, EA, Nachod, FC; Academic Press, New York, 1955) , The value recorded in the biochemical research materials (Author: Dawson, RMC, etc.; Oxford, Clarendon Press, 1959). Regarding compounds not described in these documents, the values calculated based on the structural formula using software ACD/pKa (manufactured by ACD/Labs) are used.

作為銨鹽的具體例，能夠舉出以下化合物，但是本發明並不限定於該等。 [化學式44]

Figure 02_image087
As a specific example of an ammonium salt, the following compounds can be mentioned, but this invention is not limited to these. [Chemical formula 44]
Figure 02_image087

〔亞胺鹽〕 在本發明中，亞胺鹽係指亞胺陽離子與陰離子的鹽。作為陰離子，可例示與上述銨鹽中的陰離子相同者，較佳的態樣亦相同。[Imine salt] In the present invention, imine salt refers to a salt of imine cation and anion. As the anion, the same as the anion in the above-mentioned ammonium salt can be exemplified, and the preferred aspect is also the same.

-亞胺陽離子- 作為亞胺陽離子，吡啶鎓陽離子為較佳。 又，作為亞胺陽離子，由下述式（102）表示之陽離子亦為較佳。 [化學式45]

Figure 02_image089
-Imine cation- As the imine cation, pyridinium cation is preferred. Moreover, as the imine cation, a cation represented by the following formula (102) is also preferable. [Chemical formula 45]
Figure 02_image089

式（102）中，R5 及R6 分別獨立地表示氫原子或烴基，R7 表示烴基，R5 ～R7 中的至少2個可以彼此鍵結而形成環。 式（102）中，R5 及R6 與上述式（101）中的R1 ～R4 含義相同，較佳的態樣亦相同。 式（102）中，R7 與R5 及R6 中的至少1個鍵結而形成環為較佳。上述環可以包含雜原子。作為上述雜原子，可舉出氮原子。又，作為上述環，吡啶環為較佳。In formula (102), R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group, R 7 represents a hydrocarbon group, and at least two of R 5 to R 7 may be bonded to each other to form a ring. In formula (102), R 5 and R 6 have the same meanings as R 1 to R 4 in the above formula (101), and preferred aspects are also the same. In the formula (102), it is preferable that R 7 is bonded to at least one of R 5 and R 6 to form a ring. The aforementioned ring may contain heteroatoms. As said hetero atom, a nitrogen atom can be mentioned. In addition, as the above-mentioned ring, a pyridine ring is preferred.

亞胺陽離子係由下述式（Y1-3）～（Y1-5）中的任一個表示者為較佳。 [化學式46]

Figure 02_image091
式（Y1-3）～（Y1-5）中，R101 表示n價的有機基，R5 與式（102）中的R5 含義相同，R7 與式（102）中的R7 含義相同，n表示1以上的整數，m表示0以上的整數。 式（Y1-3）中，R101 係脂肪族烴、芳香族烴或從該等鍵結而成之結構去除n個氫原子而成之基團為較佳，從碳數2～30的飽和脂肪族烴、苯或萘去除n個氫原子而成之基團為更佳。 式（Y1-3）中，n係1～4為較佳，1或2為更佳，1為進一步較佳。 式（Y1-5）中，m係0～4為較佳，1或2為更佳，1為進一步較佳。The imine cation system is preferably represented by any one of the following formulas (Y1-3) to (Y1-5). [Chemical formula 46]
Figure 02_image091
Formula (Y1-3) (Y1-5) in ~, R 101 represents the same meaning as R 5 in the n-valent organic group, and R 5 of formula (102), R 7 are the same as in the formula (102) the meaning of R 7 , N represents an integer of 1 or more, and m represents an integer of 0 or more. In the formula (Y1-3), R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon or a group formed by removing n hydrogen atoms from the structure formed by such bonding, and it is preferably a saturated group with 2-30 carbon atoms. Aliphatic hydrocarbons, benzene or naphthalene is more preferably a group formed by removing n hydrogen atoms. In the formula (Y1-3), n is preferably 1 to 4, 1 or 2 is more preferable, and 1 is even more preferable. In formula (Y1-5), m is preferably 0-4, 1 or 2 is more preferable, and 1 is still more preferable.

作為亞胺鹽的具體例，能夠舉出以下化合物，但是本發明並不限定於該等。 [化學式47]

Figure 02_image093
As specific examples of the imine salt, the following compounds can be cited, but the present invention is not limited to these. [Chemical formula 47]
Figure 02_image093

〔鋶鹽〕 在本發明中，鋶鹽係指鋶陽離子與陰離子的鹽。作為陰離子，可例示與上述銨鹽中的陰離子相同者，較佳的態樣亦相同。〔Salt〕 In the present invention, a sulfonium salt refers to a salt of sulfonium cation and anion. As the anion, the same as the anion in the above-mentioned ammonium salt can be exemplified, and the preferred aspect is also the same.

-鋶陽離子- 作為鋶陽離子，三級鋶陽離子為較佳，三芳基鋶陽離子為更佳。 又，作為鋶陽離子，由下述式（103）表示之陽離子為較佳。 [化學式48]

Figure 02_image095
-Aluminium cation- As alumnium cation, tertiary alumnium cation is preferred, and triaryl alumnium cation is more preferred. Moreover, as a cation, a cation represented by the following formula (103) is preferable. [Chemical formula 48]
Figure 02_image095

式（103）中，R8 ～R10 分別獨立地表示烴基。 R8 ～R10 分別獨立地係烷基或芳基為較佳，碳數1～10的烷基或碳數6～12的芳基為更佳，碳數6～12的芳基為進一步較佳，苯基為進一步較佳。 R8 ～R10 可以具有取代基，作為取代基的例子，可舉出羥基、芳基、烷氧基、芳氧基、芳基羰基、烷基羰基、烷氧基羰基、芳氧基羰基、醯氧基等。該等中，作為取代基，具有烷基或烷氧基為較佳，具有支鏈烷基或烷氧基為更佳，具有碳數3～10的支鏈烷基或碳數1～10的烷氧基為進一步較佳。 R8 ～R10 可以為相同的基團，亦可以為不同的基團，但是就合成適合性上的觀點而言，相同的基團為較佳。In formula (103), R 8 to R 10 each independently represent a hydrocarbon group. R 8 to R 10 are each independently an alkyl group or an aryl group, preferably, an alkyl group having 1 to 10 carbons or an aryl group having 6 to 12 carbons is more preferable, and an aryl group having 6 to 12 carbons is more preferable. Preferably, phenyl is further preferred. R 8 to R 10 may have a substituent. Examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Oxo and so on. Among these, as the substituent, it is preferable to have an alkyl group or an alkoxy group, and it is more preferable to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbons or one having 1 to 10 carbons Alkoxy is further preferred. R 8 to R 10 may be the same group or different groups, but from the viewpoint of synthesis suitability, the same group is preferred.

〔錪鎓鹽〕 在本發明中，錪鎓鹽係指錪鎓陽離子與陰離子的鹽。作為陰離子，可例示與上述銨鹽中的陰離子相同者，較佳的態樣亦相同。〔Ionium salt〕 In the present invention, the ionium salt refers to a salt of ionium cation and anion. As the anion, the same as the anion in the above-mentioned ammonium salt can be exemplified, and the preferred aspect is also the same.

-錪鎓陽離子- 作為錪鎓陽離子，二芳基錪鎓陽離子為較佳。 又，作為錪鎓陽離子，由下述式（104）表示之陽離子為較佳。 [化學式49]

Figure 02_image097
-Ibidinium cation- As the Ibonium cation, a diarylionium cation is preferred. Moreover, as the iodonium cation, a cation represented by the following formula (104) is preferable. [Chemical formula 49]
Figure 02_image097

式（104）中，R11 及R12 分別獨立地表示烴基。 R11 及R12 分別獨立地係烷基或芳基為較佳，碳數1～10的烷基或碳數6～12的芳基為更佳，碳數6～12的芳基為進一步較佳，苯基為進一步較佳。 R11 及R12 可以具有取代基，作為取代基的例子，可舉出羥基、芳基、烷氧基、芳氧基、芳基羰基、烷基羰基、烷氧基羰基、芳氧基羰基、醯氧基等。該等中，作為取代基，具有烷基或烷氧基為較佳，具有支鏈烷基或烷氧基為更佳，具有碳數3～10的支鏈烷基或碳數1～10的烷氧基為進一步較佳。 R11 及R12 可以為相同的基團，亦可以為不同的基團，但是就合成適合性上的觀點而言，相同的基團為較佳。In formula (104), R 11 and R 12 each independently represent a hydrocarbon group. Preferably, R 11 and R 12 are independently an alkyl group or an aryl group. An alkyl group having 1 to 10 carbons or an aryl group having 6 to 12 carbons is more preferable, and an aryl group having 6 to 12 carbons is more preferable. Preferably, phenyl is further preferred. R 11 and R 12 may have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, Oxo and so on. Among these, as the substituent, it is preferable to have an alkyl group or an alkoxy group, and it is more preferable to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbons or one having 1 to 10 carbons Alkoxy is further preferred. R 11 and R 12 may be the same group or different groups, but from the viewpoint of synthesis suitability, the same group is preferred.

〔鏻鹽〕 在本發明中，鏻鹽係指鏻陽離子與陰離子的鹽。作為陰離子，可例示與上述銨鹽中的陰離子相同者，較佳的態樣亦相同。〔Phosphonium salt〕 In the present invention, phosphonium salt refers to a salt of phosphonium cation and anion. As the anion, the same as the anion in the above-mentioned ammonium salt can be exemplified, and the preferred aspect is also the same.

-鏻陽離子- 作為鏻陽離子，四級鏻陽離子為較佳，可舉出四烷基鏻陽離子、三芳基單烷基鏻陽離子等。 又，作為鏻陽離子，由下述式（105）表示之陽離子為較佳。 [化學式50]

Figure 02_image099
-Phosphonium cation- As the phosphonium cation, a quaternary phosphonium cation is preferred, and examples thereof include tetraalkylphosphonium cations, triarylmonoalkylphosphonium cations, and the like. In addition, as the phosphonium cation, a cation represented by the following formula (105) is preferred. [Chemical formula 50]
Figure 02_image099

式（105）中，R13 ～R16 分別獨立地表示氫原子或烴基。 R13 ～R16 分別獨立地係烷基或芳基為較佳，碳數1～10的烷基或碳數6～12的芳基為更佳，碳數6～12的芳基為進一步較佳，苯基為進一步較佳。 R13 ～R16 可以具有取代基，作為取代基的例子，可舉出羥基、芳基、烷氧基、芳氧基、芳基羰基、烷基羰基、烷氧基羰基、芳氧基羰基、醯氧基等。該等中，作為取代基，具有烷基或烷氧基為較佳，具有支鏈烷基或烷氧基為更佳，具有碳數3～10的支鏈烷基或碳數1～10的烷氧基為進一步較佳。 R13 ～R16 可以為相同的基團，亦可以為不同的基團，但是就合成適合性上的觀點而言，相同的基團為較佳。In formula (105), R 13 to R 16 each independently represent a hydrogen atom or a hydrocarbon group. R 13 to R 16 are each independently an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbons or an aryl group having 6 to 12 carbons, and an aryl group having 6 to 12 carbons is more preferred. Preferably, phenyl is further preferred. R 13 to R 16 may have a substituent. Examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Oxo and so on. Among these, as the substituent, it is preferable to have an alkyl group or an alkoxy group, and it is more preferable to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbons or one having 1 to 10 carbons Alkoxy is further preferred. R 13 to R 16 may be the same group or different groups, but from the viewpoint of synthesis suitability, the same group is preferred.

在本發明的組成物包含鎓鹽之情形下，相對於本發明的組成物的總固體成分，鎓鹽的含量係0.1～50質量%為較佳。下限係0.5質量%以上為更佳，0.85質量%以上為進一步較佳，1質量%以上為進一步較佳。上限係30質量%以下為更佳，20質量%以下為進一步較佳，10質量%以下為進一步較佳，可以為5質量%以下，亦可以為4質量%以下。 鎓鹽能夠使用1種或2種以上。在使用2種以上之情形下，總量在上述範圍內為較佳。When the composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass relative to the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, more preferably 0.85% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, and may be 5% by mass or less, or may be 4% by mass or less. One type or two or more types of onium salts can be used. In the case of using two or more types, the total amount is preferably within the above-mentioned range.

＜熱鹼產生劑＞ 本發明的組成物可以包含熱鹼產生劑。 尤其，在組成物包含聚醯亞胺前驅物作為其他樹脂之情形下，組成物包含熱鹼產生劑為較佳。 熱鹼產生劑可以為對應於上述鎓鹽之化合物，亦可以為除了上述鎓鹽以外的其他熱鹼產生劑。 作為其他熱鹼產生劑，可舉出非離子系熱鹼產生劑。 作為非離子系熱鹼產生劑，可舉出由式（B1）或式（B2）表示之化合物。 [化學式51]

Figure 02_image101
<Thermal base generator> The composition of the present invention may contain a thermal base generator. In particular, when the composition contains a polyimide precursor as another resin, it is preferable that the composition contains a thermal base generator. The thermal base generator may be a compound corresponding to the above-mentioned onium salt, or may be another thermal base generator other than the above-mentioned onium salt. Examples of other hot alkali generators include nonionic hot alkali generators. Examples of the nonionic thermal base generator include compounds represented by formula (B1) or formula (B2). [Chemical formula 51]
Figure 02_image101

式（B1）及式（B2）中，Rb1 、Rb2 及Rb3 分別獨立地為不具有三級胺結構之有機基、鹵素原子或氫原子。但是，Rb1 及Rb2 不會同時成為氫原子。又，Rb1 、Rb2 及Rb3 均不具有羧基。另外，在本說明書中，三級胺結構係指3價的氮原子的3個鍵結鍵均與烴系碳原子共價鍵結之結構。因此，在鍵結之碳原子係形成羰基之碳原子的情形、亦即與氮原子一起形成醯胺基之情形下，不限於此。In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 are each independently an organic group without a tertiary amine structure, a halogen atom, or a hydrogen atom. However, Rb 1 and Rb 2 do not simultaneously become hydrogen atoms. Moreover, none of Rb 1 , Rb 2 and Rb 3 has a carboxyl group. In addition, in this specification, the tertiary amine structure refers to a structure in which all three bonding bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when it forms an amido group together with a nitrogen atom, it is not limited to this.

式（B1）、（B2）中，Rb1 、Rb2 及Rb3 中的至少1個包含環狀結構為較佳，至少2個包含環狀結構為更佳。作為環狀結構，可以為單環及縮合環中的任一種，單環或2個單環縮合而成之縮合環為較佳。單環係5員環或6員環為較佳，6員環為較佳。單環係環己環及苯環為較佳，環己環為更佳。In formulas (B1) and (B2), at least one of Rb 1 , Rb 2 and Rb 3 preferably includes a cyclic structure, and more preferably at least two include a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring formed by condensing two monocyclic rings is preferable. A single ring is preferably a 5-membered ring or a 6-membered ring, and a 6-membered ring is more preferred. The monocyclic cyclohexyl ring and the benzene ring are preferred, and the cyclohexyl ring is more preferred.

更具體而言，Rb1 及Rb2 係氫原子、烷基（碳數1～24為較佳，2～18為更佳，3～12為進一步較佳）、烯基（碳數2～24為較佳，2～18為更佳，3～12為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、或芳烷基（碳數7～25為較佳，7～19為更佳，7～12為進一步較佳）為較佳。該等基團可以在發揮本發明的效果之範圍內具有取代基。Rb1 與Rb2 可以相互鍵結而形成環。作為所形成之環，4～7員的含氮雜環為較佳。Rb1 及Rb2 尤其係可以具有取代基之直鏈、支鏈或環狀的烷基（碳數1～24為較佳，2～18為更佳，3～12為進一步較佳）為較佳，可以具有取代基之環烷基（碳數3～24為較佳，3～18為更佳，3～12為進一步較佳）為更佳，可以具有取代基之環己基為進一步較佳。More specifically, Rb 1 and Rb 2 are hydrogen atoms, alkyl groups (the carbon number is preferably 1-24, 2-18 is more preferably, and 3-12 is more preferably), alkenyl (carbon number 2-24 Is preferred, 2-18 is more preferred, 3-12 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred), or aromatic Alkyl groups (7 to 25 carbon atoms are preferred, 7 to 19 are more preferred, and 7 to 12 are more preferred) are preferred. These groups may have substituents within the range in which the effects of the present invention are exhibited. Rb 1 and Rb 2 may be bonded to each other to form a ring. As the ring formed, a 4- to 7-membered nitrogen-containing heterocyclic ring is preferred. Rb 1 and Rb 2 are especially linear, branched or cyclic alkyl groups which may have substituents (1-24 carbon atoms are preferred, 2-18 are more preferred, and 3-12 are further preferred). Preferably, a cycloalkyl group that may have a substituent (the carbon number is preferably 3-24, more preferably 3-18, and even more preferably 3-12) is more preferable, and a cyclohexyl group that may have a substituent is even more preferable .

作為Rb3 ，可舉出烷基（碳數係1～24為較佳，2～18為更佳，3～12為進一步較佳）、芳基（碳數係6～22為較佳，6～18為更佳，6～10為進一步較佳）、烯基（碳數係2～24為較佳，2～12為更佳，2～6為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～12為進一步較佳）、芳烯基（碳數8～24為較佳，8～20為更佳，8～16為進一步較佳）、烷氧基（碳數1～24為較佳，2～18為更佳，3～12為進一步較佳）、芳氧基（碳數6～22為較佳，6～18為更佳，6～12為進一步較佳）、或芳烷氧基（碳數7～23為較佳，7～19為更佳，7～12為進一步較佳）。其中，環烷基（碳數3～24為較佳，3～18為更佳，3～12為進一步較佳）、芳烯基、芳烷氧基為較佳。Rb3 還可以在發揮本發明的效果之範圍內具有取代基。Examples of Rb 3 include alkyl groups (the carbon number system is preferably 1-24, 2-18 is more preferable, and 3-12 is even more preferable), and aryl groups (the carbon number is preferably 6-22, 6 ～18 is more preferable, 6-10 is more preferable), alkenyl group (the carbon number is 2-24 is preferable, 2-12 is more preferable, 2-6 is more preferable), aralkyl (the carbon number is 7-23 is preferred, 7-19 is more preferred, 7-12 is more preferred), aralkenyl (carbon number 8-24 is preferred, 8-20 is more preferred, 8-16 is further preferred) ), Alkoxy (C 1-24 is preferable, 2-18 is more preferable, 3-12 is more preferable), Aryloxy (C 6-22 is preferable, 6-18 is more preferable , 6-12 is more preferable), or aralkyloxy (the carbon number is 7-23 is preferable, 7-19 is more preferable, and 7-12 is more preferable). Among them, cycloalkyl (3 to 24 carbon atoms is preferred, 3 to 18 is more preferred, and 3 to 12 is more preferred), aralkenyl, and aralkoxy are preferred. Rb 3 may have a substituent within the range in which the effects of the present invention are exhibited.

由式（B1）表示之化合物係由下述式（B1-1）或下述式（B1-2）表示之化合物為較佳。 [化學式52]

Figure 02_image103
The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical formula 52]
Figure 02_image103

式中，Rb11 及Rb12 、以及Rb31 及Rb32 分別與式（B1）中的Rb1 及Rb2 相同。 Rb13 為烷基（碳數1～24為較佳，2～18為更佳，3～12為進一步較佳）、烯基（碳數2～24為較佳，2～18為更佳，3～12為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～12為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～12為進一步較佳），可以在發揮本發明的效果之範圍內具有取代基。其中，Rb13 係芳烷基為較佳。In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively. Rb 13 is an alkyl group (the carbon number is preferably 1-24, 2-18 is more preferable, and 3-12 is more preferable), alkenyl group (the carbon number is 2-24 is preferable, and 2-18 is more preferable, 3-12 is more preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl group (carbon number 7-23 is preferred, 7 to 19 are more preferable, and 7 to 12 are more preferable), and may have a substituent within the range where the effects of the present invention are exhibited. Among them, Rb 13 is preferably an aralkyl group.

Rb33 及Rb34 分別獨立地為氫原子、烷基（碳數1～12為較佳，1～8為更佳，1～3為進一步較佳）、烯基（碳數2～12為較佳，2～8為更佳，2～3為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳），氫原子為較佳。Rb 33 and Rb 34 are each independently a hydrogen atom, an alkyl group (the carbon number is preferably 1 to 12, and 1 to 8 is more preferable, and 1 to 3 is more preferable), and an alkenyl group (the carbon number is 2 to 12 is more preferable). Preferably, 2-8 is more preferable, 2-3 is more preferable), aryl (carbon number 6-22 is preferable, 6-18 is more preferable, 6-10 is more preferable), aralkyl ( The carbon number is preferably 7 to 23, more preferably 7 to 19, and even more preferably 7 to 11), and preferably a hydrogen atom.

Rb35 為烷基（碳數1～24為較佳，1～12為更佳，3～8為進一步較佳）、烯基（碳數2～12為較佳，2～10為更佳，3～8為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～12為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～12為進一步較佳），芳基為較佳。Rb 35 is an alkyl group (the carbon number is preferably 1-24, 1-12 is more preferable, and 3-8 is even more preferable), alkenyl (the carbon number is preferably 2-12, more preferably 2-10, 3-8 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 is more preferred, 7-12 is further preferred), aryl is preferred.

由式（B1-1）表示之化合物係由式（B1-1a）表示之化合物亦為較佳。 [化學式53]

Figure 02_image105
It is also preferable that the compound represented by the formula (B1-1) is a compound represented by the formula (B1-1a). [Chemical formula 53]
Figure 02_image105

Rb11 及Rb12 與式（B1-1）中的Rb11 及Rb12 含義相同。 Rb15 及Rb16 為氫原子、烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、烯基（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳），氫原子或甲基為較佳。 Rb17 為烷基（碳數1～24為較佳，1～12為更佳，3～8為進一步較佳）、烯基（碳數2～12為較佳，2～10為更佳，3～8為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～12為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～12為進一步較佳），其中，芳基為較佳。The Rb and Rb. 11 and 12 of formula (B1-1) Rb 11 and Rb are the same meaning as 12. Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (1 to 12 carbon atoms are preferred, 1 to 6 are more preferred, and 1 to 3 are more preferred), alkenyl groups (carbon number 2 to 12 are preferred, 2 ～6 is more preferable, 2～3 are more preferable), aryl group (carbon number 6-22 is preferable, 6-18 is more preferable, 6-10 is more preferable), aralkyl group (carbon number is 7 -23 is preferred, 7-19 is more preferred, 7-11 is further preferred), hydrogen atom or methyl is preferred. Rb 17 is an alkyl group (the carbon number is preferably 1 to 24, 1 to 12 is more preferable, and 3 to 8 is more preferable), alkenyl group (the carbon number is 2 to 12 is preferable, and 2 to 10 is more preferable, 3-8 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 is more preferred, 7-12 is further preferred), among which aryl is preferred.

非離子系熱鹼產生劑的分子量係800以下為較佳，600以下為更佳，500以下為進一步較佳。作為下限，100以上為較佳，200以上為更佳，300以上為進一步較佳。The molecular weight of the nonionic thermal base generator is preferably 800 or less, more preferably 600 or less, and more preferably 500 or less. As a lower limit, 100 or more is preferable, 200 or more is more preferable, and 300 or more is more preferable.

作為上述鎓鹽中作為熱鹼產生劑之化合物的具體例或其他熱鹼產生劑的具體例，能夠舉出以下化合物。 [化學式54]

Figure 02_image107
[化學式55]
Figure 02_image109
The following compounds can be mentioned as specific examples of the compound as a thermal base generator among the above-mentioned onium salts or other specific examples of other thermal base generators. [Chemical formula 54]
Figure 02_image107
[Chemical formula 55]
Figure 02_image109

[化學式56]

Figure 02_image111
[Chemical formula 56]
Figure 02_image111

相對於本發明的組成物的總固體成分，熱鹼產生劑的含量係0.1～50質量%為較佳。下限係0.5質量%以上為更佳，1質量%以上為進一步較佳。上限係30質量%以下為更佳，20質量%以下為進一步較佳。熱鹼產生劑能夠使用1種或2種以上。在使用2種以上之情形下，總量在上述範圍內為較佳。The content of the thermal alkali generator is preferably 0.1-50% by mass relative to the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. One kind or two or more kinds of thermal base generators can be used. In the case of using two or more types, the total amount is preferably within the above-mentioned range.

＜遷移抑制劑＞ 本發明的組成物還包含遷移抑制劑為較佳。藉由包含遷移抑制劑，能夠有效地抑制源自金屬層（金屬配線）之金屬離子遷移到組成物層內。＜Migration inhibitor＞ Preferably, the composition of the present invention further contains a migration inhibitor. By including the migration inhibitor, the migration of metal ions originating from the metal layer (metal wiring) into the composition layer can be effectively suppressed.

作為遷移抑制劑，並無特別限制，但是可舉出具有雜環（吡咯環、呋喃環、噻吩環、咪唑環、㗁唑環、噻唑環、吡唑環、異㗁唑環、異噻唑環、四唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、哌啶環、哌𠯤環、口末啉環、2H-哌喃環及6H-哌喃環、三𠯤環）之化合物、硫脲類及具有硫基之化合物、受阻酚系化合物、水楊酸衍生物系化合物、醯肼衍生物系化合物。尤其，能夠較佳地使用1,2,4-三唑、苯并三唑等三唑系化合物、1H-四唑、5-苯基四唑等四唑系化合物。There are no particular limitations on the migration inhibitor, but examples include heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, Tetrazole ring, pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, oromoline ring, 2H-piperan ring and 6H-piperan ring, tricyclic ring) compounds, Thioureas and compounds having sulfur groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazine derivative compounds. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

或者，還能夠使用捕獲鹵素離子等陰離子之離子捕獲劑。Alternatively, an ion-trapping agent that traps anions such as halogen ions can also be used.

作為其他遷移抑制劑，能夠使用日本特開2013-015701號公報的0094段中所記載之防鏽劑、日本特開2009-283711號公報的0073～0076段中所記載之化合物、日本特開2011-059656號公報的0052段中所記載之化合物、日本特開2012-194520號公報的0114段、0116段及0118段中所記載之化合物、國際公開第2015/199219號的0166段中所記載之化合物等。As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711, and JP 2011 can be used. -059656, the compound described in paragraph 0052 of JP 2012-194520, the compound described in paragraph 0114, paragraph 0116, and paragraph 0118 of JP 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015/199219 Compound etc.

作為遷移抑制劑的具體例，能夠舉出下述化合物。As specific examples of migration inhibitors, the following compounds can be given.

[化學式57]

Figure 02_image113
[Chemical formula 57]
Figure 02_image113

在組成物具有遷移抑制劑之情形下，相對於組成物的總固體成分，遷移抑制劑的含量係0.01～5.0質量%為較佳，0.05～2.0質量%為更佳，0.1～1.0質量%為進一步較佳。When the composition has a migration inhibitor, relative to the total solid content of the composition, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0% by mass Further better.

遷移抑制劑可以係僅1種，亦可以係2種以上。在遷移抑制劑為2種以上的情形下，總量在上述範圍內為較佳。The migration inhibitor may be only one type or two or more types. When there are two or more migration inhibitors, the total amount is preferably within the above range.

＜聚合抑制劑＞ 本發明的組成物包含聚合抑制劑為較佳。＜Polymerization inhibitor＞ The composition of the present invention preferably contains a polymerization inhibitor.

作為聚合抑制劑，例如可較佳地使用氫醌、對甲氧基苯酚、二-三級丁基-對甲酚、五倍子酚、對三級丁基兒茶酚、1,4-苯醌、二苯基-對苯醌、4,4’-硫代雙（3-甲基-6-三級丁基苯酚）、2,2’-亞甲基雙（4-甲基-6-三級丁基苯酚）、N-亞硝基-N-苯基羥基胺鋁鹽、啡噻𠯤、N-亞硝基二苯胺、N-苯基萘基胺、乙二胺四乙酸、1,2-環己烷二胺四乙酸、乙二醇醚二胺四乙酸、2,6-二-三級丁基-4-甲基苯酚、5-亞硝基-8-羥基喹啉、1-亞硝基-2-萘酚、2-亞硝基-1-萘酚、2-亞硝基-5-（N-乙基-N-磺丙基胺基）苯、N-亞硝基-N-（1-萘基）羥基胺銨鹽、雙（4-羥基-3,5-三級丁基）苯基甲烷等。又，還能夠使用日本特開2015-127817號公報的0060段中所記載之聚合抑制劑、及國際公開第2015/125469號的0031～0046段中所記載之化合物。As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, gallic phenol, p-tertiary butylcatechol, 1,4-benzoquinone, Diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylene bis(4-methyl-6-tertiary Butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothionine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2- Cyclohexane diamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tertiary butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso 2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)benzene, N-nitroso-N- (1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tertiarybutyl)phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A, and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

又，能夠使用下述化合物（Me為甲基）。In addition, the following compounds (Me is a methyl group) can be used.

[化學式58]

Figure 02_image115
[Chemical formula 58]
Figure 02_image115

在本發明的組成物具有聚合抑制劑之情形下，相對於本發明的組成物的總固體成分，聚合抑制劑的含量係0.01～5質量%為較佳，0.02～3質量%為更佳，0.05～2.5質量%為進一步較佳。In the case where the composition of the present invention has a polymerization inhibitor, relative to the total solid content of the composition of the present invention, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, and more preferably 0.02 to 3% by mass. 0.05 to 2.5% by mass is more preferable.

聚合抑制劑可以係僅1種，亦可以係2種以上。在聚合抑制劑為2種以上的情形下，總量在上述範圍內為較佳。The polymerization inhibitor may be only one type or two or more types. When there are two or more polymerization inhibitors, the total amount is preferably within the above-mentioned range.

＜金屬接著性改良劑＞ 本發明的組成物包含用於提高與電極、配線等中所使用之金屬材料的接著性之金屬接著性改良劑為較佳。作為金屬接著性改良劑，可舉出矽烷偶合劑等。＜Metal adhesion improver＞ The composition of the present invention preferably contains a metal adhesion improver for improving adhesion with metal materials used in electrodes, wiring, and the like. As the metal adhesion improver, a silane coupling agent and the like can be mentioned.

作為矽烷偶合劑的例子，可舉出國際公開第2015/199219號的0167段中所記載之化合物、日本特開2014-191002號公報的0062～0073段中所記載之化合物、國際公開第2011/080992號的0063～0071段中所記載之化合物、日本特開2014-191252號公報的0060～0061段中所記載之化合物、日本特開2014-041264號公報的0045～0052段中所記載之化合物、國際公開第2014/097594號的0055段中所記載之化合物。又，如日本特開2011-128358號公報的0050～0058段中所記載那樣使用不同的2種以上的矽烷偶合劑亦為較佳。又，矽烷偶合劑使用下述化合物亦為較佳。以下式中，Et表示乙基。Examples of silane coupling agents include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and International Publication No. 2011/ The compound described in paragraphs 0063 to 0071 of 080992, the compound described in paragraphs 0060 to 0061 of JP 2014-191252, and the compound described in paragraphs 0045 to 0052 of JP 2014-041264 , The compound described in paragraph 0055 of International Publication No. 2014/097594. In addition, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP 2011-128358 A. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulae, Et represents an ethyl group.

[化學式59]

Figure 02_image117
[Chemical formula 59]
Figure 02_image117

又，作為金屬接著性改良劑，還能夠使用日本特開2014-186186號公報的0046～0049段中所記載之化合物、日本特開2013-072935號公報的0032～0043段中所記載之硫醚系化合物。In addition, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A, and the sulfides described in paragraphs 0032 to 0043 of JP 2013-072935 can also be used. Department of compounds.

相對於特定樹脂100質量份，金屬接著性改良劑的含量較佳為0.1～30質量份，更佳為0.5～15質量份的範圍，進一步較佳為0.5～5質量份的範圍。藉由設為上述下限值以上，硬化步驟後的有機膜與金屬層的接著性變得良好，藉由設為上述上限值以下，硬化步驟後的有機膜的耐熱性、機械特性變得良好。金屬接著性改良劑可以係僅1種，亦可以係2種以上。在使用2種以上之情形下，總量在上述範圍內為較佳。The content of the metal adhesion improver is preferably 0.1-30 parts by mass relative to 100 parts by mass of the specific resin, more preferably in the range of 0.5-15 parts by mass, and still more preferably in the range of 0.5-5 parts by mass. The adhesion between the organic film and the metal layer after the curing step becomes better by setting it to the above lower limit value or more, and by setting it below the above upper limit value, the heat resistance and mechanical properties of the organic film after the curing step become good. The metal adhesion improver may be one type or two or more types. In the case of using two or more types, the total amount is preferably within the above-mentioned range.

＜其他添加劑＞ 本發明的組成物能夠依需要摻合各種添加物、例如N-苯基二乙醇胺等增感劑、鏈轉移劑、界面活性劑、高級脂肪酸衍生物、無機粒子、硬化劑、硬化觸媒、填充劑、抗氧化劑、紫外線吸收劑、抗凝聚劑等。在摻合該等添加劑之情形下，將總摻合量設為組成物的固體成分的3質量%以下為較佳。＜Other additives＞ The composition of the present invention can be blended with various additives as needed, such as sensitizers such as N-phenyldiethanolamine, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers Agents, antioxidants, ultraviolet absorbers, anti-agglomeration agents, etc. In the case of blending these additives, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

〔增感劑〕 本發明的組成物可以包含增感劑。增感劑吸收特定的活性放射線而成為電子激勵狀態。成為電子激勵狀態之增感劑與熱硬化促進劑、熱自由基聚合起始劑、光自由基聚合起始劑等接觸，而產生電子遷移、能量遷移、發熱等的作用。藉此，熱硬化促進劑、熱自由基聚合起始劑、光自由基聚合起始劑引起化學變化並進行分解，而生成自由基、酸或鹼基。 作為增感劑，可舉出N-苯基二乙醇胺等增感劑。 又，作為增感劑，可以使用增感色素。 關於增感色素的詳細內容，能夠參閱日本特開2016-027357號公報的0161～0163段的記載，且該內容被編入本說明書中。〔Sensitizer〕 The composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in an electronically excited state comes into contact with a thermal hardening accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, etc., to produce effects such as electron transfer, energy transfer, and heat generation. Thereby, the thermal hardening accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator cause chemical changes and decompose to generate free radicals, acids, or bases. Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine. In addition, as a sensitizer, a sensitizing dye can be used. For the details of the sensitizing dye, refer to the description in paragraphs 0161 to 0163 of JP 2016-027357 A, and this content is incorporated in this specification.

在本發明的組成物包含增感劑之情形下，相對於本發明的組成物的總固體成分，增感劑的含量係0.01～20質量%為較佳，0.1～15質量%為更佳，0.5～10質量%為進一步較佳。增感劑可以單獨使用1種，亦可以併用2種以上。When the composition of the present invention contains a sensitizer, relative to the total solid content of the composition of the present invention, the content of the sensitizer is preferably 0.01-20% by mass, more preferably 0.1-15% by mass, 0.5 to 10% by mass is more preferable. A sensitizer may be used individually by 1 type, and may use 2 or more types together.

〔鏈轉移劑〕 本發明的組成物可以含有鏈轉移劑。鏈轉移劑例如在高分子詞典（Kobunshi Jiten）第三版（高分子學會（The Society of Polymer Science，Japan）編，2005年）683-684頁中被定義。作為鏈轉移劑，例如使用在分子內具有SH、PH、SiH及GeH之化合物群組。該等化合物群組對低活性自由基供給氫而生成自由基、或者藉由在氧化之後進行去質子而能夠生成自由基。尤其，能夠較佳地使用硫醇化合物。〔Chain transfer agent〕 The composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Kobunshi Jiten third edition (edited by The Society of Polymer Science (Japan), 2005), pages 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. These groups of compounds can generate free radicals by supplying hydrogen to low-activity free radicals, or can generate free radicals by deprotonation after oxidation. In particular, thiol compounds can be preferably used.

又，鏈轉移劑還能夠使用國際公開第2015/199219號的0152～0153段中所記載之化合物。In addition, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used.

在本發明的組成物具有鏈轉移劑之情形下，相對於本發明的組成物的總固體成分100質量份，鏈轉移劑的含量係0.01～20質量份為較佳，1～10質量份為更佳，1～5質量份為進一步較佳。鏈轉移劑可以係僅1種，亦可以係2種以上。在鏈轉移劑為2種以上的情形下，總量在上述範圍內為較佳。In the case where the composition of the present invention has a chain transfer agent, relative to 100 parts by mass of the total solid content of the composition of the present invention, the content of the chain transfer agent is preferably 0.01-20 parts by mass, and 1-10 parts by mass More preferably, 1 to 5 parts by mass is still more preferable. The chain transfer agent may be only one type or two or more types. When there are two or more chain transfer agents, the total amount is preferably within the above-mentioned range.

〔界面活性劑〕 就進一步提高塗佈性之觀點而言，可以在本發明的組成物中添加各種界面活性劑。作為界面活性劑，能夠使用氟系界面活性劑、非離子系界面活性劑、陽離子系界面活性劑、陰離子系界面活性劑、聚矽氧系界面活性劑等各種界面活性劑。又，下述界面活性劑亦為較佳。下述式中，表示主鏈的重複單元之括號表示各重複單元的含量（莫耳%），表示側鏈的重複單元之括號表示各重複單元的重複數。 [化學式60]

Figure 02_image119
又，界面活性劑還能夠使用國際公開第2015/199219號的0159～0165段中所記載之化合物。[Surfactant] From the viewpoint of further improving coating properties, various surfactants can be added to the composition of the present invention. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. In addition, the following surfactants are also preferable. In the following formula, the parentheses representing the repeating units of the main chain represent the content (mol %) of each repeating unit, and the parentheses representing the repeating units of the side chain represent the repeating number of each repeating unit. [Chemical formula 60]
Figure 02_image119
In addition, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.

在本發明的組成物具有界面活性劑之情形下，相對於本發明的組成物的總固體成分，界面活性劑的含量係0.001～2.0質量%為較佳，更佳為0.005～1.0質量%。界面活性劑可以係僅1種，亦可以係2種以上。在界面活性劑為2種以上的情形下，總量在上述範圍內為較佳。When the composition of the present invention has a surfactant, 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, more preferably 0.005 to 1.0% by mass. The surfactant may be only one type or two or more types. When there are two or more surfactants, the total amount is preferably within the above-mentioned range.

〔高級脂肪酸衍生物〕 關於本發明的組成物，為了防止由氧引起之聚合抑制，可以添加如二十二酸、二十二酸醯胺之高級脂肪酸衍生物，在塗佈後的乾燥過程中偏在於組成物的表面。〔Higher fatty acid derivatives〕 Regarding the composition of the present invention, in order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as behenic acid and behenic acid amide can be added to the surface of the composition during the drying process after coating. .

又，高級脂肪酸衍生物還能夠使用國際公開第2015/199219號的0155段中所記載之化合物。In addition, the higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015/199219.

在本發明的組成物具有高級脂肪酸衍生物之情形下，相對於本發明的組成物的總固體成分，高級脂肪酸衍生物的含量係0.1～10質量%為較佳。高級脂肪酸衍生物可以係僅1種，亦可以係2種以上。在高級脂肪酸衍生物為2種以上的情形下，總量在上述範圍內為較佳。When the composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the composition of the present invention. The higher fatty acid derivative may be one type or two or more types. When there are two or more higher fatty acid derivatives, the total amount is preferably within the above range.

＜對其他含有物質的限制＞ 就塗佈面性狀的觀點而言，本發明的組成物的水分含量小於5質量%為較佳，小於1質量%為更佳，小於0.6質量%為進一步較佳。＜Restrictions on other contained substances＞ From the viewpoint of coating surface properties, the moisture content of the composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and more preferably less than 0.6% by mass.

就絕緣性的觀點而言，本發明的組成物的金屬含量小於5質量ppm（parts per million（百萬分之一））為較佳，小於1質量ppm為更佳，小於0.5質量ppm為進一步較佳。作為金屬，可舉出鈉、鉀、鎂、鈣、鐵、鉻、鎳等。在包含複數種金屬之情形下，該等金屬的總計在上述範圍內為較佳。From the viewpoint of insulation, the metal content of the composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and more preferably less than 0.5 mass ppm. Better. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. In the case where a plurality of metals are included, the total of these metals is preferably within the above-mentioned range.

又，作為降低在本發明的組成物中無意間包含之金屬雜質之方法，能夠舉出：選擇金屬含量少的原材料作為構成本發明的組成物之原材料；利用過濾器對構成本發明的組成物之原材料進行過濾；利用聚四氟乙烯等襯覆裝置內部並在盡可能抑制污染之條件下進行蒸餾等的方法。In addition, as a method of reducing the metal impurities unintentionally contained in the composition of the present invention, there can be mentioned: selecting a raw material with a low metal content as the raw material constituting the composition of the present invention; using a filter to form the composition of the present invention The raw materials are filtered; using polytetrafluoroethylene and other lining inside the device and distilling under the condition of suppressing pollution as much as possible.

關於本發明的組成物，若考慮作為半導體材料的用途，則就配線腐蝕性的觀點而言，鹵素原子的含量小於500質量ppm為較佳，小於300質量ppm為更佳，小於200質量ppm為進一步較佳。其中，以鹵素離子的狀態存在者小於5質量ppm為較佳，小於1質量ppm為更佳，小於0.5質量ppm為進一步較佳。作為鹵素原子，可舉出氯原子及溴原子。氯原子及溴原子、或氯離子及溴離子的總計分別在上述範圍內為較佳。Regarding the composition of the present invention, considering the use as a semiconductor material, from the viewpoint of wiring corrosion, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm Further better. Among them, less than 5 mass ppm is preferable in the state of halogen ions, less than 1 mass ppm is more preferable, and less than 0.5 mass ppm is more preferable. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atoms and bromine atoms, or chloride ions and bromide ions are within the above-mentioned ranges, respectively.

作為本發明的組成物的收容容器，能夠使用以往公知的收容容器。又，作為收容容器，為了抑制雜質混入原材料、組成物中，使用由6種6層的樹脂構成容器內壁之多層瓶子或將6種樹脂製成7層結構之瓶子亦為較佳。作為這種容器，例如可舉出日本特開2015-123351號公報中所記載的容器。As the storage container of the composition of the present invention, a conventionally known storage container can be used. In addition, as the container, in order to prevent impurities from mixing into the raw materials and the composition, it is also preferable to use a multi-layer bottle in which the inner wall of the container is composed of 6 kinds of 6-layer resins or a 7-layer structure bottle made of 6 kinds of resins. As such a container, for example, the container described in JP 2015-123351 A can be cited.

＜組成物的製備＞ 本發明的組成物能夠藉由混合上述各成分來製備。混合方法並無特別限定，能夠藉由以往公知的方法進行。＜Preparation of composition＞ The composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and it can be performed by a conventionally known method.

又，為了去除組成物中的垃圾、微粒等異物，進行使用了過濾器之過濾為較佳。過濾器孔徑係1μm以下為較佳，0.5μm以下為更佳，0.1μm以下為進一步較佳。過濾器的材質係聚四氟乙烯、聚乙烯或尼龍為較佳。過濾器可以使用利用有機溶劑預先清洗者。過濾器過濾步驟中，可以將複數種過濾器串聯連接或並聯連接而使用。在使用複數種過濾器之情形下，可以組合孔徑或材質不同的過濾器而使用。又，可以對各種材料進行複數次過濾。在進行複數次過濾之情形下，可以係循環過濾。又，可以進行加壓並過濾。在進行加壓並過濾之情形下，進行加壓之壓力係0.05MPa以上且0.3MPa以下為較佳。 除了使用了過濾器之過濾之外，還可以進行使用了吸附材料之雜質的去除處理。可以將過濾器過濾和使用了吸附材料之雜質去除處理進行組合。作為吸附材料，能夠使用公知的吸附材料。例如，可舉出二氧化矽凝膠、沸石等無機系吸附材料、活性碳等有機系吸附材料。In addition, in order to remove foreign matter such as garbage and particulates in the composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be cleaned in advance with an organic solvent. In the filter filtration step, a plurality of filters can be connected in series or in parallel for use. When multiple filters are used, filters with different pore sizes or materials can be combined and used. In addition, various materials can be filtered multiple times. In the case of multiple times of filtering, it can be cyclic filtering. In addition, it can be pressurized and filtered. In the case of pressurization and filtration, the pressure for pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using filters, it can also be used to remove impurities using adsorbents. It is possible to combine filter filtration and impurity removal treatment using adsorbent material. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.

＜有機膜的用途＞ 本發明的有機膜用於再配線層用層間絕緣膜為較佳。 又，除此以外，還能夠用於半導體器件的絕緣膜或應力緩衝膜。＜Use of organic film＞ The organic film of the present invention is preferably used as an interlayer insulating film for a rewiring layer. Moreover, in addition to this, it can also be used for an insulating film or a stress buffer film of a semiconductor device.

（組成物） 本發明的組成物為供於本發明的有機膜的形成之組成物。 本發明的組成物中所包含之各成分與上述有機膜中說明之組成物中的各成分含義相同，較佳的態樣亦相同。 本發明的組成物係藉由曝光、加熱等硬化之硬化性組成物為較佳。(Composition) The composition of the present invention is a composition used for the formation of the organic film of the present invention. Each component contained in the composition of the present invention has the same meaning as each component in the composition described in the above organic film, and preferred aspects are also the same. The composition of the present invention is preferably a curable composition cured by exposure, heating, etc.

（有機膜、積層體、半導體器件及該等之製造方法） 接著，對有機膜、積層體、半導體器件及該等之製造方法進行說明。(Organic films, laminates, semiconductor devices and their manufacturing methods) Next, the organic film, the laminate, the semiconductor device, and the manufacturing method thereof will be described.

本發明的有機膜係組成物的塗佈膜的硬化物為較佳。本發明的有機膜的膜厚例如能夠設為0.5μm以上，還能夠設為1μm以上。又，作為上限值，能夠設為100μm以下，還能夠設為30μm以下。The cured product of the coating film of the organic film-based composition of the present invention is preferred. The film thickness of the organic film of the present invention can be, for example, 0.5 μm or more, and can also be 1 μm or more. Moreover, as an upper limit, it can be 100 micrometers or less, and can also be 30 micrometers or less.

可以將本發明的有機膜積層2層以上、進而積層3～7層而製成積層體。本發明的積層體係具有2層以上的有機膜且在有機膜之間具有金屬層之積層體為較佳。又，本發明的積層體係包含2層以上的有機膜且在任一上述有機膜彼此之間包含金屬層之態樣為較佳。例如，可較佳地舉出至少包含依序積層第一有機膜、金屬層、第二有機膜這3個層而成之層結構之積層體。上述第一有機膜及上述第二有機膜均為本發明的有機膜，例如，可較佳地舉出上述第一有機膜及上述第二有機膜均為使本發明的組成物硬化而成之膜之態樣。用於上述第一有機膜的形成之本發明的組成物與用於上述第二有機膜的形成之本發明的組成物可以為組成相同的組成物，亦可以為組成不同的組成物，但是就製造適合性上的觀點而言，組成相同的組成物為較佳。這種金屬層可較佳地用作再配線層等金屬配線。Two or more layers of the organic film of the present invention can be laminated, and 3 to 7 layers can be laminated to form a laminated body. The laminated system of the present invention is preferably a laminated body having two or more organic films and a metal layer between the organic films. In addition, it is preferable that the layered system of the present invention includes two or more organic films, and a metal layer is included between any of the above-mentioned organic films. For example, a laminated body including at least a layer structure in which three layers of a first organic film, a metal layer, and a second organic film are sequentially laminated can be preferably used. The first organic film and the second organic film are both organic films of the present invention. For example, it can be preferably mentioned that both the first organic film and the second organic film are formed by curing the composition of the present invention. The state of the membrane. The composition of the present invention used for the formation of the above-mentioned first organic film and the composition of the present invention used for the formation of the above-mentioned second organic film may be a composition of the same composition or a composition of a different composition. From the viewpoint of manufacturing suitability, a composition having the same composition is preferable. Such a metal layer can be preferably used as a metal wiring such as a rewiring layer.

作為能夠適用本發明的有機膜之領域，可舉出半導體器件的絕緣膜、再配線層用層間絕緣膜、應力緩衝膜等。除此以外，還可舉出藉由蝕刻將密封膜、基板材料（撓性印刷電路板的基底膜、覆蓋層、層間絕緣膜）、或如上述般的用於安裝之絕緣膜形成圖案等。關於該等用途，例如，能夠參閱Science&Technology Co.,Ltd.“聚醯亞胺的高功能化與應用技術”2008年4月、柿本雅明/主編、CMC Publishing Co.,Ltd.“聚醯亞胺材料的基礎和開發”2011年11月發行、日本聚醯亞胺·芳香族系高分子研究會/編“最新聚醯亞胺 基礎與應用”NTS Inc.，2010年8月等。Examples of the field to which the organic film of the present invention can be applied include insulating films of semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition to this, patterning of a sealing film, substrate material (base film, cover layer, and interlayer insulating film of a flexible printed circuit board), or an insulating film for mounting as described above, by etching, etc., can also be mentioned. For these uses, for example, you can refer to Science&Technology Co., Ltd. "High-functionalization and Application Technology of Polyimide" April 2008, Kakimoto Yamin/Editor, CMC Publishing Co., Ltd. "Polyimide Material Foundation and Development" issued in November 2011, Japan Polyimide·Aromatic Polymer Research Association/Edition "The latest polyimide basics and applications" NTS Inc., August 2010, etc.

又，本發明中的有機膜還能夠用於膠印版面或網版版面等版面的製造、針對成形構件的蝕刻的使用、電子、尤其係微電子中的保護漆及介電層的製造等。In addition, the organic film in the present invention can also be used for the production of offset printing plates or screen plates, the use of etching for forming members, the production of protective paints and dielectric layers in electronics, especially microelectronics, and the like.

本發明的有機膜之製造方法（以下，還簡稱為“本發明之製造方法”。）包括將組成物（本發明的組成物）適用於基材而形成膜之膜形成步驟為較佳。 進而，本發明的有機膜之製造方法包括上述膜形成步驟，且還包括對上述膜進行曝光之曝光步驟及對上述膜進行顯影之（對上述膜進行顯影處理之）顯影步驟為更佳。 進而，本發明的有機膜之製造方法包括上述膜形成步驟（及依需要的上述顯影步驟），且還包括在50～450℃的條件下對上述膜進行加熱之加熱步驟為更佳。 具體而言，包括以下（a）～（d）的步驟亦為較佳。 （a）將組成物適用於基材而形成膜（組成物層）之膜形成步驟 （b）膜形成步驟之後，對膜進行曝光之曝光步驟 （c）對經曝光之上述膜進行顯影處理之顯影步驟 （d）在50～450℃的條件下對經顯影之上述膜進行加熱之加熱步驟 藉由在上述加熱步驟中進行加熱，能夠使顯影後的組成物層進一步硬化。在該加熱步驟中，例如，上述熱鹼產生劑分解而獲得足夠的硬化性。The manufacturing method of the organic film of the present invention (hereinafter, also referred to simply as "the manufacturing method of the present invention".) preferably includes a film forming step of applying the composition (the composition of the present invention) to a substrate to form a film. Furthermore, the manufacturing method of the organic film of the present invention includes the above-mentioned film forming step, and further includes an exposure step of exposing the above-mentioned film and a development step of developing the above-mentioned film (for developing the above-mentioned film). Furthermore, the manufacturing method of the organic film of the present invention includes the above-mentioned film forming step (and the above-mentioned development step if necessary), and further includes a heating step of heating the above-mentioned film under the condition of 50-450°C. Specifically, it is also preferable to include the following steps (a) to (d). (A) Film formation step of applying the composition to the substrate to form a film (composition layer) (B) Exposure step of exposing the film after the film formation step (C) The developing step of developing the exposed film (D) Heating step of heating the developed film at 50～450℃ By heating in the above heating step, the developed composition layer can be further hardened. In this heating step, for example, the above-mentioned hot alkali generator is decomposed to obtain sufficient hardenability.

本發明的較佳的實施形態之積層體之製造方法包括本發明的有機膜之製造方法。本實施形態的積層體之製造方法按照上述有機膜之製造方法，形成有機膜之後，進而，再次進行（a）的步驟、或（a）～（c）的步驟、或（a）～（d）的步驟。尤其，依序進行複數次、例如2～5次（亦即，總計3～6次）上述各步驟為較佳。藉由如此積層有機膜，能夠製成積層體。在本發明中，尤其在設置有有機膜之部分的上側或有機膜之間或者該兩者設置金屬層為較佳。另外，在積層體的製造中，無需重複進行（a）～（d）的所有步驟，如上所述，進行複數次至少（a）、較佳為（a）～（c）或（a）～（d）的步驟，藉此能夠獲得有機膜的積層體。The manufacturing method of the laminated body of the preferable embodiment of this invention includes the manufacturing method of the organic film of this invention. The manufacturing method of the laminated body of this embodiment is in accordance with the above-mentioned organic film manufacturing method. After the organic film is formed, step (a), or (a) to (c), or (a) to (d) is performed again. )A step of. In particular, it is preferable to perform the above-mentioned steps plural times in sequence, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating organic films in this way, a laminate can be produced. In the present invention, it is particularly preferable to provide a metal layer on the upper side of the portion where the organic film is provided, between the organic films, or both. In addition, in the production of the laminate, it is not necessary to repeat all the steps (a) to (d). As described above, perform at least (a), preferably (a) to (c) or (a) to multiple times. In the step (d), a laminate of an organic film can be obtained by this.

＜膜形成步驟（層形成步驟）＞ 本發明的較佳的實施形態之製造方法包括將組成物適用於基材而製成膜（層狀）之膜形成步驟（層形成步驟）。<Film formation step (layer formation step)> The manufacturing method of the preferred embodiment of the present invention includes a film formation step (layer formation step) in which the composition is applied to a substrate to form a film (layered).

基材的種類能夠依據用途而適當地確定，矽、氮化矽、多晶矽、氧化矽、非晶質矽等半導體製作基材、石英、玻璃、光學薄膜、陶瓷材料、蒸鍍膜、磁性膜、反射膜、Ni、Cu、Cr、Fe等金屬基材、紙、SOG（Spin On Glass：旋塗式玻璃）、TFT（薄膜電晶體）陣列基材、電漿顯示面板（PDP）的電極板等並無特別限制。 在本發明中，尤其，半導體製作基材為較佳，矽基材為更佳。 又，作為基材，例如，可使用板狀的基材（基板）。The type of substrate can be appropriately determined according to the application. Semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflections, etc. Film, Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, etc. There are no special restrictions. In the present invention, in particular, a semiconductor manufacturing substrate is preferable, and a silicon substrate is more preferable. In addition, as the base material, for example, a plate-shaped base material (substrate) can be used.

又，在組成物層等樹脂層的表面、金屬層的表面形成組成物層之情形下，樹脂層、金屬層成為基材。Moreover, when a composition layer is formed on the surface of a resin layer, such as a composition layer, or the surface of a metal layer, the resin layer and the metal layer become a base material.

作為將組成物適用於基材之方法，塗佈為較佳。As a method of applying the composition to a substrate, coating is preferred.

具體而言，作為應用之方法，可例示浸塗法、氣刀塗佈法、簾式塗佈法、繞線棒塗法、凹版塗佈法、擠壓塗佈法、噴塗法、旋塗法、狹縫塗佈法及噴墨法等。就組成物層的厚度的均勻性的觀點而言，更佳為旋塗法、狹縫塗佈法、噴塗法、噴墨法。藉由依據方法調節適合的固體成分濃度、塗佈條件，能夠獲得所期望的厚度的樹脂層。又，亦能夠依據基材的形狀適當地選擇塗佈方法，若為晶圓等圓形基材，則旋塗法、噴塗法、噴墨法等為較佳，若為矩形基材，則狹縫塗佈法、噴塗法、噴墨法等為較佳。在旋塗法的情形下，例如，能夠以500～2,000rpm（revolutions per minute：每分鐘旋轉數）的轉速，適用10秒～1分鐘左右。 又，還能夠適用將預先藉由上述施加方法施加於偽支撐體上而形成之塗膜轉印到基材上之方法。 關於轉印方法，在本發明中還能夠較佳地使用日本特開2006-023696號公報的0023、0036～0051段、日本特開2006-047592號公報的0096～0108段中所記載之製作方法。Specifically, as the application method, dipping method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method can be exemplified. , Slit coating method and inkjet method, etc. From the viewpoint of the uniformity of the thickness of the composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. By adjusting the appropriate solid content concentration and coating conditions according to the method, a resin layer with a desired thickness can be obtained. In addition, the coating method can also be appropriately selected according to the shape of the substrate. If it is a round substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and if it is a rectangular substrate, it is narrow. The slit coating method, spraying method, inkjet method, etc. are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm (revolutions per minute) for about 10 seconds to 1 minute. In addition, it is also possible to apply a method of transferring a coating film formed by applying the above-mentioned application method to a pseudo support in advance to a substrate. Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of JP 2006-023696 and paragraphs 0096 to 0108 of JP 2006-047592 can also be preferably used in the present invention. .

＜乾燥步驟＞ 本發明之製造方法可以在形成上述膜（組成物層）之後且膜形成步驟（層形成步驟）之後，包括為了去除溶劑而進行乾燥之步驟。較佳的乾燥溫度為50～150℃，70℃～130℃為更佳，90℃～110℃為進一步較佳。作為乾燥時間，可例示30秒鐘～20分鐘，1分鐘～10分鐘為較佳，3分鐘～7分鐘為更佳。＜Drying step＞ The manufacturing method of the present invention may include a step of drying in order to remove the solvent after the film (composition layer) is formed and after the film formation step (layer formation step). The preferred drying temperature is 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

＜曝光步驟＞ 本發明之製造方法可以包括對上述膜（組成物層）進行曝光之曝光步驟。關於曝光量，只要能夠使組成物硬化，則並無特別限定，但是例如以波長365nm下的曝光能量換算計照射100～10,000mJ/cm2 為較佳，照射200～8,000mJ/cm2 為更佳。<Exposure Step> The manufacturing method of the present invention may include an exposure step of exposing the above-mentioned film (composition layer). The exposure dose is not particularly limited as long as the composition can be cured. For example, it is better to irradiate 100 to 10,000 mJ/cm 2 in terms of exposure energy at a wavelength of 365 nm, and more preferably to irradiate 200 to 8,000 mJ/cm 2 good.

曝光波長能夠在190～1,000nm的範圍內適當地確定，240～550nm為較佳。The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

關於曝光波長，就與光源的關係而言，可舉出（1）半導體雷射（波長為830nm、532nm、488nm、405nm等）、（2）金屬鹵化物燈、（3）高壓水銀燈、g射線（波長為436nm）、h射線（波長為405nm）、i射線（波長為365nm）、寬頻（g射線，h射線，i射線這3種波長）、（4）準分子雷射、KrF準分子雷射（波長為248nm）、ArF準分子雷射（波長為193nm）、F2準分子雷射（波長為157nm）、（5）極端紫外線；EUV（波長為13.6nm）、（6）電子束等。關於本發明的組成物，尤其，基於高壓水銀燈之曝光為較佳，其中，基於i射線之曝光為較佳。藉此，可獲得特別高的曝光靈敏度。Regarding the exposure wavelength, in terms of the relationship with the light source, (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamps, (3) high pressure mercury lamps, g-rays (Wavelength is 436nm), h-ray (wavelength is 405nm), i-ray (wavelength is 365nm), broadband (g-ray, h-ray, i-ray three wavelengths), (4) excimer laser, KrF excimer laser Radiation (wavelength is 248nm), ArF excimer laser (wavelength is 193nm), F2 excimer laser (wavelength is 157nm), (5) extreme ultraviolet; EUV (wavelength is 13.6nm), (6) electron beam, etc. Regarding the composition of the present invention, in particular, exposure based on a high-pressure mercury lamp is preferable, and exposure based on i-rays is preferable. In this way, a particularly high exposure sensitivity can be obtained.

＜顯影步驟＞ 本發明之製造方法可以包括對經曝光之膜（組成物層）進行顯影處理之顯影步驟。藉由進行顯影，未曝光之部分（未曝光部）被去除。關於顯影方法，只要能夠形成所期望的圖案，則並無特別限制，例如，能夠採用旋覆浸沒、噴霧、浸漬、超音波等顯影方法。<Development step> The manufacturing method of the present invention may include a development step of developing the exposed film (composition layer). By performing development, the unexposed part (unexposed part) is removed. The development method is not particularly limited as long as the desired pattern can be formed. For example, development methods such as spin immersion, spray, dipping, and ultrasonic can be used.

顯影使用顯影液來進行。關於顯影液，能夠無特別限制地使用如下顯影液：若組成物為負型組成物則組成物層的未曝光之部分（未曝光部）被去除者、若組成物為正型組成物則經曝光之部分（曝光部）被去除者。 在本發明中，將作為顯影液而使用鹼性顯影液之情形稱為鹼性顯影，將作為顯影液而使用包含50質量%以上的有機溶劑之顯影液之情形稱為溶劑顯影。The development is performed using a developer. Regarding the developer, the following developer can be used without particular limitation: if the composition is a negative type composition, the unexposed part (unexposed part) of the composition layer is removed, and if the composition is a positive type composition, the The exposed part (exposure part) has been removed. In the present invention, the case where an alkaline developer is used as the developer is referred to as alkaline development, and the case where a developer containing 50% by mass or more of an organic solvent is used as the developer is referred to as solvent development.

在鹼性顯影中，顯影液的有機溶劑的含量相對於顯影液的總質量係10質量%以下為較佳，5質量%以下為更佳，1質量%以下為進一步較佳，不含有機溶劑為特佳。 鹼性顯影中的顯影液係pH為9～14的水溶液為更佳。 作為鹼性顯影中的顯影液中所包含之鹼性化合物，例如，可舉出氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、矽酸鈉、矽酸鉀、偏矽酸鈉、偏矽酸鉀、氨或胺等。作為胺，例如，可舉出乙胺、正丙胺、二乙基胺、二-正丙胺、三乙基胺、甲基二乙基胺、烷醇胺、二甲基乙醇胺、三乙醇胺、四級銨氫氧化物、氫氧化四甲基銨（TMAH）或氫氧化四乙基銨、氫氧化四丁基銨等。其中，不含金屬之鹼性化合物為較佳，銨化合物為更佳。 鹼性化合物可以為僅1種，亦可以為2種以上。在鹼性化合物為2種以上的情形下，總量在上述範圍內為較佳。In alkaline development, the content of the organic solvent in the developer relative to the total mass of the developer is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, and does not contain organic solvents. It is especially good. The developer in alkaline development is more preferably an aqueous solution with a pH of 9-14. Examples of alkaline compounds contained in the developer in alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, and potassium silicate. , Sodium metasilicate, potassium metasilicate, ammonia or amine, etc. As the amine, for example, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary Ammonium hydroxide, tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc. Among them, metal-free basic compounds are preferred, and ammonium compounds are more preferred. The basic compound may be only one type or two or more types. When there are two or more basic compounds, the total amount is preferably within the above range.

在溶劑顯影中，顯影液包含90%以上的有機溶劑為更佳。在本發明中，顯影液包含ClogP值為-1～5的有機溶劑為較佳，包含ClogP值為0～3的有機溶劑為更佳。關於ClogP值，能夠在ChemBioDraw中輸入結構式並作為計算值而求出。In solvent development, it is more preferable that the developer contains 90% or more of organic solvent. In the present invention, the developer preferably contains an organic solvent with a ClogP value of -1 to 5, and more preferably contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting the structural formula in ChemBioDraw.

關於有機溶劑，作為酯類，例如可較佳地舉出乙酸乙酯、乙酸正丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁內酯、ε-己內酯、δ-戊內酯、烷氧基乙酸烷基酯（例如：烷氧基乙酸甲酯、烷氧基乙酸乙酯、烷氧基乙酸丁酯（例如，甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯等））、3-烷氧基丙酸烷基酯類（例如：3-烷氧基丙酸甲酯、3-烷氧基丙酸乙酯等（例如，3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯等））、2-烷氧基丙酸烷基酯類（例如：2-烷氧基丙酸甲酯、2-烷氧基丙酸乙酯、2-烷氧基丙酸丙酯等（例如，2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯））、2-烷氧基-2-甲基丙酸甲酯及2-烷氧基-2-甲基丙酸乙酯（例如，2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯等）、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸甲酯、2-氧代丁酸乙酯等；以及作為醚類，例如可較佳地舉出二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單乙醚、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯等；以及作為酮類，例如可較佳地舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮、N-甲基-2-吡咯啶酮等；以及作為芳香族烴類，例如可較佳地舉出甲苯、二甲苯、苯甲醚、檸檬烯等；作為亞碸類，可較佳地舉出二甲基亞碸。Regarding organic solvents, as esters, for example, ethyl acetate, n-butyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl Ethyl acid, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example: methyl alkoxyacetate Ester, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetic acid Ethyl ester, etc.)), 3-alkoxypropionic acid alkyl esters (for example: 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (for example: Methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropyl propionate, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester)), 2-alkoxy-2-methylpropionic acid methyl ester and Ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), acetone Methyl acrylate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.; and as ethers, For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.; And as the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. can be preferably mentioned; and As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. can be preferably mentioned; as the sulphurite, dimethyl sulphide can be preferably mentioned.

在本發明中，尤其，環戊酮、γ-丁內酯為較佳，環戊酮為更佳。In the present invention, in particular, cyclopentanone and γ-butyrolactone are preferable, and cyclopentanone is more preferable.

關於顯影液，50質量%以上係有機溶劑為較佳，70質量%以上係有機溶劑為更佳，90質量%以上係有機溶劑為進一步較佳。又，亦可以係顯影液的100質量%為有機溶劑。Regarding the developer, an organic solvent of 50% by mass or more is preferable, an organic solvent of 70% by mass or more is more preferable, and an organic solvent of 90% by mass or more is more preferable. In addition, 100% by mass of the developer may be an organic solvent.

作為顯影時間，10秒鐘～5分鐘為較佳。關於顯影時的顯影液的溫度，沒有特別指定，但是通常能夠在20～40℃下進行。As the development time, 10 seconds to 5 minutes are preferred. The temperature of the developer during development is not particularly specified, but it can usually be performed at 20 to 40°C.

在使用了顯影液之處理之後，可以進一步進行沖洗。 在溶劑顯影的情形下，沖洗使用與顯影液不同的有機溶劑來進行為較佳。 在鹼性顯影的情形下，沖洗使用純水來進行為較佳。 沖洗時間係5秒鐘～1分鐘為較佳。After the treatment with the developer, it can be further rinsed. In the case of solvent development, it is better to perform washing using an organic solvent different from the developer. In the case of alkaline development, it is better to use pure water for washing. Preferably, the rinsing time is 5 seconds to 1 minute.

＜加熱步驟＞ 本發明之製造方法包括在50～450℃的條件下對經顯影之上述膜進行加熱之步驟（加熱步驟）為較佳。 在膜形成步驟（層形成步驟）、乾燥步驟及顯影步驟之後包括加熱步驟為較佳。 能夠在該步驟中進行本發明的組成物中所包含之、除了特定樹脂以外的未反應的聚合性化合物的硬化反應、特定樹脂中的未反應的聚合性基的硬化反應等。 又，在特定樹脂為聚醯亞胺前驅物，且組成物包含熱鹼產生劑之情形下，在加熱步驟中，例如，藉由熱鹼產生劑分解而產生鹼基，進行聚醯亞胺前驅物的環化反應。 作為加熱步驟中的層的加熱溫度（最高加熱溫度），50℃以上為較佳，80℃以上為更佳，140℃以上為進一步較佳，150℃以上為特佳，160℃以上為進一步較佳，170℃以上為最佳。作為上限，450℃以下為較佳，350℃以下為更佳，250℃以下為進一步較佳，220℃以下為特佳。＜Heating step＞ The manufacturing method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450°C. It is preferable to include a heating step after the film formation step (layer formation step), the drying step, and the development step. In this step, the curing reaction of unreacted polymerizable compounds other than the specific resin contained in the composition of the present invention, the curing reaction of unreacted polymerizable groups in the specific resin, and the like can be performed. In addition, in the case where the specific resin is a polyimide precursor and the composition contains a thermal base generator, in the heating step, for example, the thermal base generator is decomposed to generate a base, and the polyimide precursor is performed The cyclization reaction of the substance. As the heating temperature (maximum heating temperature) of the layer in the heating step, 50°C or higher is preferred, 80°C or higher is more preferred, 140°C or higher is even more preferred, 150°C or higher is particularly preferred, and 160°C or higher is further preferred. Best, 170°C or higher is the best. As the upper limit, 450°C or lower is preferred, 350°C or lower is more preferred, 250°C or lower is more preferred, and 220°C or lower is particularly preferred.

關於加熱，從加熱開始時的溫度至最高加熱溫度為止以1～12℃/分鐘的升溫速度進行加熱為較佳，2～10℃/分鐘為更佳，3～10℃/分鐘為進一步較佳。藉由將升溫速度設為1℃/分鐘以上，能夠確保生產性的同時防止胺的過度揮發，藉由將升溫速度設為12℃/分鐘以下，能夠緩和有機膜的殘餘應力。Regarding heating, heating is preferably carried out at a heating rate of 1-12°C/min from the temperature at the beginning of the heating to the maximum heating temperature, more preferably 2-10°C/min, and still more preferably 3-10°C/min . By setting the heating rate to 1°C/min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the heating rate to 12°C/min or less, the residual stress of the organic film can be alleviated.

加熱開始時的溫度係20℃～150℃為較佳，20℃～130℃為更佳，25℃～120℃為進一步較佳。加熱開始時的溫度係指開始加熱至最高加熱溫度之步驟時的溫度。例如，在將組成物適用於基材上之後，使其乾燥之情形下，為該乾燥後的膜（層）的溫度，例如，從比組成物中所包含之溶劑的沸點低30～200℃的溫度逐漸升溫為較佳。The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and more preferably 25°C to 120°C. The temperature at the beginning of heating refers to the temperature at the beginning of the step of heating to the highest heating temperature. For example, when the composition is applied to the substrate and then dried, the temperature of the dried film (layer) is, for example, 30 to 200°C lower than the boiling point of the solvent contained in the composition It is better to increase the temperature gradually.

加熱時間（最高加熱溫度下的加熱時間）係10～360分鐘為較佳，20～300分鐘為更佳，30～240分鐘為進一步較佳。The heating time (heating time at the highest heating temperature) is preferably from 10 to 360 minutes, more preferably from 20 to 300 minutes, and even more preferably from 30 to 240 minutes.

尤其，在形成多層的積層體之情形下，就有機膜的層間的密接性的觀點而言，關於加熱溫度，在180℃～320℃的條件下進行加熱為較佳，在180℃～260℃的條件下進行加熱為更佳。雖然其理由尚不清楚，但是認為係因為：藉由設為該溫度，層間的樹脂中的聚合性基彼此進行交聯反應。In particular, in the case of forming a multilayer laminate, from the viewpoint of the adhesion between the layers of the organic film, the heating temperature is preferably 180°C to 320°C, which is 180°C to 260°C. It is better to heat it under the conditions of. Although the reason is not clear, it is thought that it is because the polymerizable groups in the resin between the layers undergo a crosslinking reaction by setting it at this temperature.

加熱可以階段性地進行。作為例子，可以進行如下預處理步驟：以3℃/分鐘從25℃升溫至180℃，並在180℃的條件下保持60分鐘，以2℃/分鐘從180℃升溫至200℃，並在200℃的條件下保持120分鐘。作為預處理步驟的加熱溫度係100～200℃為較佳，110～190℃為更佳，120～185℃為進一步較佳。該預處理步驟中，如美國專利9159547號說明書所記載那樣，一邊照射紫外線一邊進行處理亦為較佳。能夠藉由這種預處理步驟提高膜的特性。預處理步驟以10秒鐘～2小時左右的短時間進行為佳，15秒鐘～30分鐘為更佳。預處理可以設為2個階段以上的步驟，例如，可以在100～150℃的範圍內進行預處理步驟1，然後在150～200℃的範圍內進行預處理步驟2。Heating can be carried out in stages. As an example, the following pretreatment steps can be performed: heating from 25°C to 180°C at 3°C/min, and maintaining at 180°C for 60 minutes, heating from 180°C to 200°C at 2°C/min, and heating at 200°C Keep it at ℃ for 120 minutes. The heating temperature as the pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and even more preferably 120 to 185°C. In this pretreatment step, as described in the specification of U.S. Patent No. 9159547, it is also preferable to perform treatment while irradiating with ultraviolet rays. The characteristics of the membrane can be improved by this pretreatment step. The pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be a two-stage or more step. For example, the pretreatment step 1 may be performed in the range of 100 to 150°C, and then the pretreatment step 2 may be performed in the range of 150 to 200°C.

進而，可以在加熱後進行冷卻，作為此時的冷卻速度，1～5℃/分鐘為較佳。Furthermore, cooling may be performed after heating, and the cooling rate at this time is preferably 1 to 5°C/min.

關於加熱步驟，就防止樹脂的分解之觀點而言，藉由使氮氣、氦氣、氬氣等惰性氣體流動，在氧濃度低的環境中進行為較佳。氧濃度係50ppm（體積比）以下為較佳，20ppm（體積比）以下為更佳。Regarding the heating step, from the viewpoint of preventing decomposition of the resin, it is preferable to perform it in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, and argon. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

＜金屬層形成步驟＞ 本發明之製造方法包括在顯影處理後的膜（組成物層）的表面形成金屬層之金屬層形成步驟為較佳。＜Metal layer formation steps＞ The manufacturing method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the film (composition layer) after development treatment.

作為金屬層，並無特別限定，能夠使用現有的金屬種類，可例示銅、鋁、鎳、釩、鈦、鉻、鈷、金及鎢，銅及鋁為更佳，銅為進一步較佳。The metal layer is not particularly limited, and existing metal types can be used. Examples of copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, copper and aluminum are more preferable, and copper is still more preferable.

關於金屬層之形成方法，並無特別限定，能夠應用現有的方法。例如，能夠使用日本特開2007-157879號公報、日本特表2001-521288號公報、日本特開2004-214501號公報、日本特開2004-101850號公報中所記載之方法。例如，考慮光微影、剝離、電鍍、無電鍍、蝕刻、印刷及組合該等之方法等。更具體而言，可舉出組合濺射、光微影及蝕刻之圖案形成方法、組合光微影和電鍍之圖案形成方法。The method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, and Japanese Patent Application Publication No. 2004-101850 can be used. For example, consider methods such as photolithography, stripping, electroplating, electroless plating, etching, printing, and combinations. More specifically, a pattern forming method combining sputtering, photolithography, and etching, and a pattern forming method combining photolithography and electroplating can be cited.

作為金屬層的厚度，以最厚的部分計，0.1～50μm為較佳，1～10μm為更佳。As the thickness of the metal layer, based on the thickest part, 0.1 to 50 μm is preferable, and 1 to 10 μm is more preferable.

＜積層步驟＞ 本發明之製造方法還包括積層步驟為較佳。＜Layering Steps＞ Preferably, the manufacturing method of the present invention further includes a layering step.

積層步驟係指包括對有機膜（樹脂層）或金屬層的表面再次依序進行（a）膜形成步驟（層形成步驟）、（b）曝光步驟、（c）顯影步驟、（d）加熱步驟之一系列步驟。但是，可以為僅重複進行（a）的膜形成步驟之態樣。又，亦可以設為（d）加熱步驟在積層的最後或中間一併進行之態樣。亦即，亦可以設為如下態樣：重複進行既定次數的（a）～（c）的步驟，然後進行（d）的加熱，藉此將所積層之組成物層一併硬化。又，可以在（c）顯影步驟之後包括（e）金屬層形成步驟，此時亦可以每次進行（d）的加熱，還可以在積層既定次數之後一併進行（d）的加熱。不用說，積層步驟中還可以適當地包括上述乾燥步驟、加熱步驟等。The layering step refers to the step of performing (a) the film formation step (layer formation step), (b) the exposure step, (c) the development step, and (d) the heating step on the surface of the organic film (resin layer) or the metal layer in order. A series of steps. However, it may be an aspect in which only the film formation step of (a) is repeated. In addition, the heating step (d) may be performed collectively at the end or in the middle of the build-up layer. That is, it can also be set to the following aspect: repeat the steps (a) to (c) a predetermined number of times, and then heat (d) to harden the laminated composition layers together. In addition, the (e) metal layer forming step may be included after the (c) development step. In this case, the heating of (d) may be performed each time, or the heating of (d) may be performed after a predetermined number of laminations. Needless to say, the above-mentioned drying step, heating step, etc. may also be appropriately included in the layering step.

在積層步驟之後進而進行積層步驟之情形下，可以在上述加熱步驟之後、上述曝光步驟之後或上述金屬層形成步驟之後，進而進行表面活化處理步驟。作為表面活化處理，可例示電漿處理。In the case where the layering step is further performed after the layering step, the surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer forming step. As the surface activation treatment, plasma treatment can be exemplified.

上述積層步驟進行2～5次為較佳，進行3～5次為更佳。The above-mentioned layering step is preferably performed 2 to 5 times, and more preferably 3 to 5 times.

例如，如樹脂層/金屬層/樹脂層/金屬層/樹脂層/金屬層般的、樹脂層為3層以上且7層以下的結構為較佳，3層以上且5層以下為進一步較佳。For example, a structure such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, where the resin layer has 3 layers or more and 7 layers or less is preferable, and 3 layers or more and 5 layers or less is more preferable .

在本發明中，尤其在設置金屬層之後，進而以覆蓋上述金屬層的方式形成上述組成物的有機膜（樹脂層）之態樣為較佳。具體而言，可舉出如下態樣：依序重複進行（a）膜形成步驟、（b）曝光步驟、（c）顯影步驟、（e）金屬層形成步驟、（d）加熱步驟之態樣或依序重複進行（a）膜形成步驟、（b）曝光步驟、（c）顯影步驟、（e）金屬層形成步驟，並在最後或中間一併設置（d）加熱步驟。藉由交替地進行積層組成物層（樹脂層）之積層步驟和金屬層形成步驟，能夠交替地積層組成物層（樹脂層）和金屬層。In the present invention, it is particularly preferable to form an organic film (resin layer) of the above composition so as to cover the above metal layer after the metal layer is provided. Specifically, the following aspect can be mentioned: the aspect in which (a) film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, and (d) heating step are repeated in order Or repeat (a) the film formation step, (b) the exposure step, (c) the development step, and (e) the metal layer formation step in sequence, and set the (d) heating step at the end or in the middle. By alternately performing the laminating step of the laminated composition layer (resin layer) and the metal layer forming step, the composition layer (resin layer) and the metal layer can be alternately laminated.

本發明還揭示包含本發明的有機膜或積層體之半導體器件。作為將本發明的組成物用於再配線層用層間絕緣膜的形成之半導體器件的具體例，能夠參閱日本特開2016-027357號公報的0213～0218段的記載及圖1的記載，且該等內容被編入本說明書中。 [實施例]The present invention also discloses a semiconductor device including the organic film or laminate of the present invention. As a specific example of a semiconductor device in which the composition of the present invention is used for the formation of an interlayer insulating film for a rewiring layer, refer to the description in paragraphs 0213 to 0218 of JP 2016-027357 A and the description in FIG. 1, and the And other contents are incorporated into this manual. [Example]

以下，舉出實施例對本發明進行進一步具體的說明。以下實施例所示之材料、使用量、比例、處理內容、處理步驟等，只要不脫離本發明的趣旨，則能夠適當變更。因此，本發明的範圍並不限定於以下所示之具體例。以下，只要無特別敘述，則“份”、“%”為質量基準。Hereinafter, the present invention will be further specifically described with examples. The materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Hereinafter, unless otherwise stated, "parts" and "%" are quality standards.

（聚醯亞胺前驅物樹脂PA-1的合成） 一邊在具備安裝有攪拌機、冷凝器及內部溫度計之平底接頭之乾燥反應器中去除水分，一邊使氧二鄰苯二甲酸二酐20.0g（64.5毫莫耳）懸浮於二甘二甲醚140mL中。持續添加甲基丙烯酸2-羥乙酯10.1g（77毫莫耳）、BLEMMER AP-400（NOF CORPORATION.製造）12.6g（39毫莫耳）、氫醌0.05g及吡啶10.7g（135毫莫耳），並在60℃的溫度下攪拌了18小時。接著，將混合物冷卻至-20℃之後，經90分鐘滴加了亞硫醯氯16.1g（135.5毫莫耳）。獲得了鹽酸吡啶鎓的白色沈澱。接著，將混合物加熱至室溫（23℃），並攪拌2小時之後，添加吡啶9.7g（123毫莫耳）及N-甲基吡咯啶酮（NMP）25mL，從而獲得了透明溶液。接著，經1小時藉由滴加在所獲得之透明溶液中添加了將作為二胺的4,4’-二胺基二苯基醚11.7g（58.7毫莫耳）溶解於NMP 100mL中而得者。在添加上述二胺之期間，黏度增加。接著，加入甲醇5.6g（17.5毫莫耳）和3,5-二-三級丁基-4-羥基甲苯0.05g，並將混合物攪拌了2小時。接著，使聚醯亞胺前驅物樹脂在4升的水中沉澱，並以500rpm的速度將水-聚醯亞胺前驅物樹脂混合物攪拌了15分鐘。將聚醯亞胺前驅物樹脂進行過濾而獲取，在4升的水中再次攪拌30分鐘並再次進行了過濾。接著，將所獲得之聚醯亞胺前驅物樹脂在減壓下，在45℃的條件下乾燥了1天。該聚醯亞胺前驅物樹脂PA-1的分子量為Mw=25,100、Mn=13,200。 推測PA-1的結構為由下述式（PA-1）表示之結構。式（PA-1）中，*表示與R鍵結之氧原子的鍵結部位。 [化學式61]

Figure 02_image121
上述（PA-1）中，在C3 H6 的記載中隨機包含1-甲基乙烯基（下述式（P1））和2-甲基乙烯基（下述式（P2））。式（P1）及式（P2）中，*1 與式（PA-1）中的R中的丙烯醯氧基側的結構鍵結，*2 與式（PA-1）中的R中的*側的結構鍵結。 [化學式62]
Figure 02_image123
(Synthesis of polyimide precursor resin PA-1) While removing water in a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, 20.0 g of oxydiphthalic dianhydride ( 64.5 millimoles) suspended in 140 mL of diglyme. Continue to add 10.1g (77 millimoles) of 2-hydroxyethyl methacrylate, 12.6g (39 millimoles) of BLEMMER AP-400 (manufactured by NOF CORPORATION), 0.05g of hydroquinone and 10.7g (135 millimoles) of pyridine Ears) and stirred for 18 hours at a temperature of 60°C. Next, after cooling the mixture to -20°C, 16.1 g (135.5 millimoles) of sulfite chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was heated to room temperature (23° C.) and stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Then, 11.7 g (58.7 millimoles) of 4,4'-diaminodiphenyl ether as a diamine was dissolved in 100 mL of NMP by adding dropwise to the obtained transparent solution over 1 hour. By. During the addition of the above diamine, the viscosity increases. Next, 5.6 g (17.5 millimoles) of methanol and 0.05 g of 3,5-di-tertiarybutyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, and it was stirred again for 30 minutes in 4 liters of water and filtered again. Next, the obtained polyimide precursor resin was dried under reduced pressure at 45°C for 1 day. The molecular weight of the polyimide precursor resin PA-1 is Mw=25,100 and Mn=13,200. The structure of PA-1 is estimated to be a structure represented by the following formula (PA-1). In the formula (PA-1), * represents the bonding site of the oxygen atom bonded to R. [Chemical formula 61]
Figure 02_image121
In the above (PA-1), 1-methylvinyl group (the following formula (P1)) and 2-methylvinyl group (the following formula (P2)) are randomly included in the description of C 3 H 6. In formula (P1) and formula (P2), * 1 is bonded to the structure on the propyleneoxy group side of R in formula (PA-1), and * 2 is bonded to * in R in formula (PA-1) Structural bonding on the side. [Chemical formula 62]
Figure 02_image123

＜實施例及比較例＞ 在各實施例中，分別混合下述表1中所記載之成分，獲得了各組成物。又，在比較例中，分別混合下述表1中所記載之成分，獲得了各比較用組成物。 使所獲得之組成物及比較用組成物通過細孔的寬度為0.8μm的聚四氟乙烯製過濾器並進行了加壓過濾。 表1中，各欄中所記載之數值表示組成物中的各成分的含量（質量%）。 又，“總計”一欄的數值表示組成物中的各成分的含量的合計值（質量%）。 又，表1中，“-”的記載表示不含所對應之成分。<Examples and Comparative Examples> In each example, the components described in the following Table 1 were mixed to obtain each composition. Moreover, in the comparative example, the components described in the following Table 1 were mixed, respectively, and each comparative composition was obtained. The obtained composition and the comparative composition were passed through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm and pressure-filtered. In Table 1, the numerical value described in each column represents the content (mass %) of each component in the composition. In addition, the numerical value in the "total" column indicates the total value (mass %) of the contents of each component in the composition. In addition, in Table 1, the description of "-" means that the corresponding component is not included.

[表1]   實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 比較例1 溶劑 NMP - - - 43.690% 43.690% 43.690% - GBL 43.690% 43.690% 43.690% - - - 43.690% DMSO 10.923% 10.923% 10.923% - - - 10.923% EL - - - 10.923% 10.923% 10.923% - 起始劑 OXE01 - 0.642% - - 0.642% - 1.283% 784EG 1.283% 0.642% 1.283% 1.283% 0.642% 1.283% - 樹脂 PA-1 36.650% 36.650% 36.650% 36.650% 36.650% 36.650% 36.650% 聚合性 化合物 SR 209 5.501% 5.501% - 5.501% 5.501% - 5.501% DPHA - - 5.501% - - 5.501% - 矽烷 偶合劑 S-1 0.733% 0.733% 0.733% - - - 0.733% S-2 - - - 0.733% 0.733% 0.733% - 聚合 抑制劑 F-1 0.073% 0.073% 0.073% - - - 0.073% F-2 - - - 0.073% 0.073% 0.073% - 鎓鹽或熱鹼產生劑 T-1 1.026% 1.026% 1.026% 1.026% 1.026% 1.026% 1.026% 遷移 抑制劑 H-1 0.12% 0.12% 0.12% - - - 0.12% H-2 - - - 0.12% 0.12% 0.12% - 總計 100% 100% 100% 100% 100% 100% 100% I/A 4.514 6.168 10.028 4.233 6.124 9.236 2.413 I/B 1.267 1.164 0.924 1.253 1.111 0.841 0.419 耐溶劑性（單位%） 80 80 100 76 78 97 0 斷裂伸長率（單位%） 60 60 45 58 59 44 30 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1 Solvent NMP - - - 43.690% 43.690% 43.690% - GBL 43.690% 43.690% 43.690% - - - 43.690% DMSO 10.923% 10.923% 10.923% - - - 10.923% EL - - - 10.923% 10.923% 10.923% - Initiator OXE01 - 0.642% - - 0.642% - 1.283% 784EG 1.283% 0.642% 1.283% 1.283% 0.642% 1.283% - Resin PA-1 36.650% 36.650% 36.650% 36.650% 36.650% 36.650% 36.650% Polymeric compound SR 209 5.501% 5.501% - 5.501% 5.501% - 5.501% DPHA - - 5.501% - - 5.501% - Silane coupling agent S-1 0.733% 0.733% 0.733% - - - 0.733% S-2 - - - 0.733% 0.733% 0.733% - Polymerization inhibitor F-1 0.073% 0.073% 0.073% - - - 0.073% F-2 - - - 0.073% 0.073% 0.073% - Onium salt or thermal base generator T-1 1.026% 1.026% 1.026% 1.026% 1.026% 1.026% 1.026% Migration inhibitor H-1 0.12% 0.12% 0.12% - - - 0.12% H-2 - - - 0.12% 0.12% 0.12% - total 100% 100% 100% 100% 100% 100% 100% I/A 4.514 6.168 10.028 4.233 6.124 9.236 2.413 I/B 1.267 1.164 0.924 1.253 1.111 0.841 0.419 Solvent resistance (unit %) 80 80 100 76 78 97 0 Elongation at break (unit %) 60 60 45 58 59 44 30

表1中所記載之各成分的詳細內容如下述。The details of each component described in Table 1 are as follows.

〔溶劑〕 ·NMP：N-甲基吡咯啶酮 ·GBL：γ-丁內酯 ·DMSO：二甲基亞碸 ·EL：乳酸乙酯〔Solvent〕 ·NMP: N-Methylpyrrolidone ·GBL: γ-Butyrolactone ·DMSO: dimethyl sulfide ·EL: Ethyl Lactate

〔起始劑〕 ·OXE01：Irgacure OXE01（BASF公司製造） ·784EG：Irgacure 784 EG（BASF公司製造）〔Initiator〕 ·OXE01: Irgacure OXE01 (manufactured by BASF) ·784EG: Irgacure 784 EG (manufactured by BASF)

〔樹脂〕 ·PA-1：上述合成之聚醯亞胺前驅物樹脂PA-1〔Resin〕 ·PA-1: The polyimide precursor resin PA-1 synthesized above

〔聚合性化合物〕 ·SR 209：SR-209（四乙二醇二甲基丙烯酸酯，Sartomer Company, Inc製造） ·DPHA：二新戊四醇六丙烯酸酯（Shin-Nakamura Chemical Co., Ltd.製造）[Polymerizable compound] ·SR 209: SR-209 (tetraethylene glycol dimethacrylate, manufactured by Sartomer Company, Inc) ·DPHA: Dineopentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

〔矽烷偶合劑〕 ·S-1～S-2：下述結構的化合物 [化學式63]

Figure 02_image125
[Silane coupling agent] ·S-1～S-2: Compounds of the following structure [Chemical formula 63]
Figure 02_image125

〔聚合抑制劑〕 ·F-1：1,4-苯醌 ·F-2：2-亞硝基-1-萘酚（Tokyo Chemical Industry Co., Ltd.製造，下述結構的化合物） [化學式64]

Figure 02_image127
[Polymerization inhibitor] · F-1: 1,4-benzoquinone · F-2: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd., compound with the following structure) [Chemical formula 64]
Figure 02_image127

〔鎓鹽或熱鹼產生劑〕 ·T-1：下述結構的化合物 [化學式65]

Figure 02_image129
[Onium salt or thermal base generator] ·T-1: Compound of the following structure [Chemical formula 65]
Figure 02_image129

〔遷移抑制劑〕 ·H-1：1H-四唑 ·H-2：下述結構的化合物 [化學式66]

Figure 02_image131
[Migration inhibitor] · H-1: 1H-tetrazole · H-2: a compound of the following structure [Chemical formula 66]
Figure 02_image131

＜評價＞ 〔小角度中子散射（SANS）測量〕 分別藉由旋塗法，將各實施例及比較例中製備之組成物或比較用組成物適用於矽晶圓上來形成了樹脂層。 將所獲得之形成有樹脂層之矽晶圓在加熱板上在100℃的條件下乾燥5分鐘，從而在矽晶圓上獲得了約15μm的均勻厚度的組成物層。使用步進器（Nikon NSR 2005 i9C），以500mJ/cm2 的曝光能量將所獲得之組成物層進行了整面曝光。上述曝光之後，在氮環境下，以10℃/分鐘的升溫速度進行升溫，達到180℃之後，加熱了3小時。將硬化後的組成物層（有機膜）浸漬於4.9質量%氫氟酸水溶液中，並從矽晶圓剝離了有機膜。 重疊將藉由上述方法獲得之厚度約15μm的有機膜切成直徑18mm的圓形者，以使厚度成為100～200μm，並設為測量用試樣。測量上述測量用試樣的質量及膜厚之後，填充到J-PARC MLF iMATERIA的SANS測量專用的樣品架中，並進行了密封。<Evaluation> [Small-angle neutron scattering (SANS) measurement] The composition prepared in each of the Examples and Comparative Examples or the comparative composition was applied to a silicon wafer by spin coating to form a resin layer. The obtained silicon wafer with the resin layer formed thereon was dried on a hot plate at 100° C. for 5 minutes to obtain a composition layer with a uniform thickness of about 15 μm on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C), the entire surface of the obtained composition layer was exposed with an exposure energy of 500mJ/cm 2. After the above exposure, the temperature was raised at a temperature increase rate of 10°C/min in a nitrogen environment, and after reaching 180°C, it was heated for 3 hours. The cured composition layer (organic film) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and the organic film was peeled from the silicon wafer. The organic film with a thickness of about 15 μm obtained by the above method was cut into a circle with a diameter of 18 mm so that the thickness became 100 to 200 μm, and the sample was used as a measurement sample. After measuring the mass and film thickness of the above-mentioned measuring sample, it was filled into the J-PARC MLF iMATERIA's sample holder for SANS measurement and sealed.

使用填充有上述測量用試樣之樣品架，利用J-PARC MLF iMATERIA（BL20）進行了小角度中子散射測量。具體而言，將上述樣品架設置於SANS測量專用的40連自動試樣更換器，並進行了自動測量。測量條件如下述。 又，為了計算相對強度值，在與上述測量相同的測量條件下進行了使用了未填充測量用試樣之空樣品架之測量。The small-angle neutron scattering measurement was carried out using the J-PARC MLF iMATERIA (BL20) using the sample holder filled with the above-mentioned measurement sample. Specifically, the above-mentioned sample rack was installed in a 40-unit automatic sample changer dedicated to SANS measurement, and automatic measurement was performed. The measurement conditions are as follows. In addition, in order to calculate the relative strength value, the measurement was performed using an empty sample holder that was not filled with the measurement sample under the same measurement conditions as the above measurement.

-測量條件- MLF中子束輸出：500kW 測量q值區域：0.007～5Å-1 （使用了上述J-PARC MLF iMATERIA（BL20）的小角度檢測器組（0.007～0.5Å-1 ）及低角度檢測器組（0.5～5Å-1 ）。） 測量溫度：室溫（23℃） 累計時間：12～15分鐘/試樣-Measurement conditions- MLF neutron beam output: 500kW Measurement q-value area: 0.007～5Å -1 (using the above-mentioned J-PARC MLF iMATERIA (BL20) small angle detector group (0.007～0.5Å -1 ) and low angle Detector group (0.5～5Å -1 ).) Measuring temperature: room temperature (23℃) Cumulative time: 12～15 minutes/sample

依據測量結果，在各實施例及比較例中，計算I/A及I/B的值，並分別記載於表1的“I/A”或“I/B”一欄中。Based on the measurement results, in each of the Examples and Comparative Examples, the values of I/A and I/B were calculated and recorded in the "I/A" or "I/B" column of Table 1, respectively.

〔耐溶劑性的評價〕 在直徑為4英寸的矽晶圓上，分別藉由旋塗法，將各實施例及比較例中製備之組成物或比較用組成物適用於矽晶圓上來形成了樹脂層。 將所獲得之形成有樹脂層之矽晶圓在加熱板上在100℃的條件下乾燥5分鐘，從而在矽晶圓上獲得了約15μm的均勻厚度的組成物層。使用步進器（Nikon NSR 2005 i9C），以500mJ/cm2 的曝光能量將所獲得之組成物層進行了整面曝光。在上述曝光之後，在氮環境下，以10℃/分鐘的升溫速度進行升溫，達到180℃之後，加熱3小時，從而獲得了形成有有機膜之矽晶圓。 在上述加熱之後，測量了矽晶圓上的有機膜的膜厚（膜厚A）。然後，經3小時將形成有有機膜之矽晶圓浸漬於N-甲基-2-吡咯啶酮中，用異丙醇進行清洗之後，進行了風乾。在上述風乾之後，測量了矽晶圓上的有機膜的膜厚（膜厚B）。 依據下述式，計算有機膜的膜厚的殘留率（%），並將所計算之值記載於表1的“耐溶劑性（單位%）”一欄中。 有機膜的膜厚的殘留率（%）越大，則可以說所獲得之有機膜的耐溶劑性越優異。 有機膜的膜厚的殘留率（%）=膜厚B/膜厚A×100[Evaluation of Solvent Resistance] On a silicon wafer with a diameter of 4 inches, the composition prepared in each of the Examples and Comparative Examples or the comparative composition was applied to the silicon wafer by spin coating to form Resin layer. The obtained silicon wafer with the resin layer formed thereon was dried on a hot plate at 100° C. for 5 minutes to obtain a composition layer with a uniform thickness of about 15 μm on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C), the entire surface of the obtained composition layer was exposed with an exposure energy of 500mJ/cm 2. After the above exposure, the temperature was raised at a temperature increase rate of 10°C/min in a nitrogen environment, and after reaching 180°C, it was heated for 3 hours to obtain a silicon wafer with an organic film formed thereon. After the above heating, the film thickness (film thickness A) of the organic film on the silicon wafer was measured. Then, the silicon wafer on which the organic film was formed was immersed in N-methyl-2-pyrrolidone for 3 hours, washed with isopropanol, and then air-dried. After the above air drying, the film thickness of the organic film on the silicon wafer (film thickness B) was measured. According to the following formula, the residual rate (%) of the film thickness of the organic film was calculated, and the calculated value was described in the "solvent resistance (unit %)" column of Table 1. The larger the residual rate (%) of the film thickness of the organic film, the better the solvent resistance of the obtained organic film. Residual rate of organic film thickness (%) = film thickness B/film thickness A×100

〔斷裂伸長率的評價〕 分別藉由旋塗法，將各實施例及比較例中製備之組成物或比較用組成物適用於矽晶圓上來形成了樹脂層。 將所獲得之形成有樹脂層之矽晶圓在加熱板上在100℃的條件下乾燥5分鐘，從而在矽晶圓上獲得了約15μm的均勻厚度的組成物層。使用步進器（Nikon NSR 2005 i9C），以500mJ/cm2 的曝光能量將所獲得之組成物層進行了整面曝光。上述曝光之後，在氮環境下，以10℃/分鐘的升溫速度進行升溫，達到180℃之後，加熱了3小時。將硬化後的組成物層（有機膜）浸漬於4.9質量%氫氟酸水溶液中，並從矽晶圓剝離了有機膜。 使用沖壓機，對所剝離之有機膜進行沖壓，從而製作了試樣寬度為3mm、試樣長度為30mm的試驗片。使用拉伸試驗機（Tensilon），在十字頭速度為300mm/分鐘、25℃、65%RH（相對濕度）的環境下，依照JIS-K6251測量了所獲得之試驗片的長邊方向的伸長率。各實施5次測量，並將5次測量中的試驗片斷裂時的伸長率（斷裂伸長率）的算術平均值記載於表1的“斷裂伸長率（單位%）”一欄中。 上述算術平均值越大，則可以說所獲得之有機膜的斷裂伸長率越優異。[Evaluation of Elongation at Break] The composition prepared in each of the Examples and Comparative Examples or the comparative composition was applied to a silicon wafer by a spin coating method to form a resin layer. The obtained silicon wafer with the resin layer formed thereon was dried on a hot plate at 100° C. for 5 minutes to obtain a composition layer with a uniform thickness of about 15 μm on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C), the entire surface of the obtained composition layer was exposed with an exposure energy of 500mJ/cm 2. After the above exposure, the temperature was raised at a temperature increase rate of 10°C/min in a nitrogen environment, and after reaching 180°C, it was heated for 3 hours. The cured composition layer (organic film) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and the organic film was peeled from the silicon wafer. Using a punching machine, the peeled organic film was punched to produce a test piece with a sample width of 3 mm and a sample length of 30 mm. A tensile testing machine (Tensilon) was used to measure the elongation in the longitudinal direction of the obtained test piece in an environment with a crosshead speed of 300mm/min, 25°C, and 65%RH (relative humidity) in accordance with JIS-K6251 . The measurement was performed 5 times each, and the arithmetic average value of the elongation at break (elongation at break) of the test piece in the 5 measurements was described in the column of “elongation at break (unit %)” in Table 1. The larger the arithmetic mean value, the better the elongation at break of the obtained organic film.

依據以上結果，可知本發明之有機膜的耐溶劑性優異。 比較例1之比較用組成物中，I/A為2.413，I/B為0.419，均不滿足式（1）及式（2）。可知該比較例1之有機膜的耐溶劑性差。From the above results, it can be seen that the organic film of the present invention is excellent in solvent resistance. In the comparative composition of Comparative Example 1, I/A was 2.413 and I/B was 0.419, neither of which satisfies formula (1) and formula (2). It can be seen that the organic film of Comparative Example 1 has poor solvent resistance.

接著，利用分別使用了閉環型聚醯亞胺樹脂、包含聚苯并㗁唑前驅物之樹脂或閉環型聚苯并㗁唑之3種組成物來代替實施例1的樹脂PA-1，分別藉由與實施例1相同的方法，進行了耐溶劑性及斷裂伸長率的評價。無論在使用上述3種組成物中的哪一種之情形下，都獲得了耐溶劑性、斷裂伸長率均與實施例1同等水平的結果。Next, the resin PA-1 of Example 1 was replaced with three types of compositions using a closed-ring polyimide resin, a resin containing a polybenzoxazole precursor, or a closed-ring polybenzoxazole, respectively. By the same method as in Example 1, the solvent resistance and the elongation at break were evaluated. Regardless of the use of any of the above-mentioned three types of compositions, the solvent resistance and the elongation at break are both at the same level as those of Example 1.

＜實施例101＞ 將實施例1中所記載之組成物旋轉塗佈於表面形成有銅薄層之樹脂基材中的銅薄層的表面上，以使膜厚成為20μm。將塗佈於樹脂基材上之組成物在100℃的條件下乾燥2分鐘之後，使用步進器（Nikon Corporation製造，NSR1505 i6）進行了曝光。經由正方形圖案（縱橫各100μm的正方形圖案、重複數為10）的遮罩，在波長365nm下以400mJ/cm2 的曝光量進行曝光而製作了正方形殘留圖案。曝光之後，用環戊酮進行30秒鐘的顯影，用PGMEA沖洗20秒鐘，從而獲得了圖案。 接著，在氮環境下，以10℃/分鐘的升溫速度進行升溫，達到180℃之後，在該溫度下加熱3小時，從而形成了再配線層用層間絕緣膜。該再配線層用層間絕緣膜的絕緣性優異。又，使用該等再配線層用層間絕緣膜製造半導體器件之結果，確認到沒有問題地進行動作。<Example 101> The composition described in Example 1 was spin-coated on the surface of the copper thin layer in the resin substrate with the copper thin layer formed on the surface so that the film thickness became 20 μm. The composition coated on the resin substrate was dried at 100°C for 2 minutes, and then exposed using a stepper (manufactured by Nikon Corporation, NSR1505 i6). Through a mask of a square pattern (a square pattern of 100 μm in each vertical and horizontal direction, the number of repetitions is 10), exposure was performed at a wavelength of 365 nm with an exposure amount of 400 mJ/cm 2 to produce a square residual pattern. After exposure, development was carried out with cyclopentanone for 30 seconds, and washed with PGMEA for 20 seconds, thereby obtaining a pattern. Next, the temperature was raised at a temperature increase rate of 10°C/min in a nitrogen environment, and after reaching 180°C, it was heated at this temperature for 3 hours to form an interlayer insulating film for a rewiring layer. The interlayer insulating film for the rewiring layer has excellent insulating properties. In addition, as a result of manufacturing a semiconductor device using these interlayer insulating films for rewiring layers, it was confirmed that the operation was performed without any problems.

無no

無。no.

Claims (8)

一種有機膜，其係滿足選自包括下述式（1）及下述式（2）之群組中之至少1個式， 式（1）：I/A≧2.5 式（2）：I/B≧0.5 在前述式（1）或前述式（2）中，I係以q在0.030Å-1 ～0.065Å-1 的範圍內對前述有機膜進行中子小角度散射測量時的相對強度值的最大值，A係以q在0.200Å-1 ～0.300Å-1 的範圍內對前述有機膜進行中子小角度散射測量時的相對強度值的最小值，B係以q在0.017Å-1 ～0.025Å-1 的範圍內對前述有機膜進行中子小角度散射測量時的相對強度值的最小值，q為在小角度散射中由下述式（Q）定義之值， 式（Q）：q=（4π/λ）sinθ 式（Q）中，λ為中子束的波長，θ為中子束的散射角。An organic film that satisfies at least one formula selected from the group consisting of the following formula (1) and the following formula (2), formula (1): I/A≧2.5 formula (2): I/ B≧0.5 In the aforementioned formula (1) or the aforementioned formula (2), I is the relative intensity value when q is in the range of 0.030Å -1 ～0.065Å -1 for the small-angle neutron scattering measurement of the aforementioned organic film The maximum value of A is the minimum value of the relative intensity when q is in the range of 0.200Å -1 ～0.300Å -1 for the aforementioned organic film when neutron small-angle scattering is measured, and B is q at 0.017Å -1 ～0.025Å -1 The minimum value of the relative intensity value of the aforementioned organic film during small-angle neutron scattering measurement, q is the value defined by the following formula (Q) in the small-angle scattering, formula (Q) : Q=(4π/λ)sinθ In formula (Q), λ is the wavelength of the neutron beam, and θ is the scattering angle of the neutron beam. 如請求項1所述之有機膜，其係包含選自包括聚醯亞胺、聚苯并㗁唑、聚醯亞胺前驅物及聚苯并㗁唑前驅物之群組中之至少1種樹脂之組成物的塗佈膜的硬化物。The organic film according to claim 1, which contains at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor The cured product of the coating film of the composition. 如請求項2所述之有機膜，其中 前述組成物包含光敏劑。The organic film according to claim 2, wherein The aforementioned composition contains a photosensitizer. 一種組成物，其係供於請求項1至請求項3之任一項所述之有機膜的形成。A composition used for the formation of the organic film described in any one of Claims 1 to 3. 一種積層體，其係包含2層以上的請求項1至請求項3之任一項所述之有機膜，且在任一前述有機膜彼此之間包含金屬層。A laminate comprising two or more layers of the organic film described in any one of Claims 1 to 3, and a metal layer is included between any of the aforementioned organic films. 一種半導體器件，其係包含請求項1至請求項3之任一項所述之有機膜或請求項5所述之積層體。A semiconductor device comprising the organic film according to any one of claims 1 to 3 or the laminate according to claim 5. 一種有機膜之製造方法，其係製造請求項1至請求項3之任一項所述之有機膜，前述製造方法包括將組成物適用於基板而形成膜之膜形成步驟。A method for manufacturing an organic film, which manufactures the organic film described in any one of claims 1 to 3, the foregoing manufacturing method including a film forming step of applying a composition to a substrate to form a film. 如請求項7所述之有機膜之製造方法，其係包括在50℃～450℃的條件下對上述膜進行加熱之步驟。The method for manufacturing an organic film according to claim 7, which includes the step of heating the film under the conditions of 50°C to 450°C.
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