TW202104368A

TW202104368A - Curable resin composition, cured film, multilayer body, method for producing cured film, and semiconductor device

Info

Publication number: TW202104368A
Application number: TW109114839A
Authority: TW
Inventors: 青島俊栄
Original assignee: 日商富士軟片股份有限公司
Priority date: 2019-05-08
Filing date: 2020-05-05
Publication date: 2021-02-01
Also published as: WO2020226132A1; JPWO2020226132A1; JP7277573B2

Abstract

The present invention provides: a curable resin composition which contains at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, wherein the polymer precursor comprises an aromatic ring to which an optionally substituted vinyl group is directly bonded; a cured film which is obtained by curing the curable resin composition; a multilayer body which contains the cured film; a method for producing the cured film; and a semiconductor device which comprises the cured film or the multilayer body.

Description

硬化性樹脂組成物、硬化膜、積層體、硬化膜的製造方法及半導體器件Curable resin composition, cured film, laminate, cured film manufacturing method and semiconductor device

本發明有關一種硬化性樹脂組成物、硬化膜、積層體、硬化膜的製造方法及半導體器件。The present invention relates to a method for manufacturing a curable resin composition, a cured film, a laminate, a cured film, and a semiconductor device.

對聚醯亞胺樹脂、聚苯并㗁唑樹脂等聚合物的前驅物（以下，亦將聚醯亞胺樹脂的前驅物及聚苯并㗁唑樹脂的前驅物統稱為“含雜環聚合物前驅物”。）進行環化來硬化之樹脂的耐熱性及絕緣性優異，因此可適用於各種用途。作為上述用途並無特別限定，但若以實際安裝用半導體器件為例，則可舉出作為絕緣膜或密封材料的素材或保護膜的利用。又，亦用作撓性基板的基底膜或覆蓋膜等。The precursors of polymers such as polyimide resins and polybenzoxazole resins (hereinafter, the precursors of polyimide resins and polybenzoxazole resins are also collectively referred to as "heterocyclic polymer Precursor".) The resin cured by cyclization has excellent heat resistance and insulation, so it can be applied to various applications. The use is not particularly limited, but if a semiconductor device for actual mounting is taken as an example, the use as a material for an insulating film or a sealing material or a protective film can be cited. It is also used as a base film or cover film for flexible substrates.

例如，在上述用途中，將含雜環聚合物前驅物以含有含雜環聚合物前驅物之硬化性樹脂組成物的形態使用。將該種硬化性樹脂組成物例如藉由塗佈等適用於基材上，之後，藉由加熱等環化上述含雜環聚合物前驅物，能夠在基材上形成已硬化之樹脂。能夠藉由公知的塗佈方法等適用硬化性樹脂組成物，因此，可以說例如所適用的硬化性樹脂組成物的形狀、大小、適用位置等設計的自由度高等製造上的適應性優異。從除了聚醯亞胺樹脂等所具有的高性能以外，製造上的適應性亦優異的觀點考慮，越來越期待含有含雜環聚合物前驅物之硬化性樹脂組成物的產業上的應用拓展。For example, in the above application, the heterocyclic-containing polymer precursor is used in the form of a curable resin composition containing the heterocyclic-containing polymer precursor. This curable resin composition is applied to a substrate, for example, by coating or the like, and then the heterocyclic-containing polymer precursor is cyclized by heating or the like to form a cured resin on the substrate. The curable resin composition can be applied by a known coating method or the like. Therefore, it can be said that, for example, the applied curable resin composition has a high degree of freedom in design, such as the shape, size, and application position, and has excellent manufacturing adaptability. In addition to the high performance of polyimide resins, etc., it also has excellent manufacturing adaptability, and there is an increasing expectation for the expansion of industrial applications of curable resin compositions containing heterocyclic polymer precursors. .

例如，專利文獻1中記載有一種包括特定製程之用於劃分形成於第1電極層堆疊及第2電極層堆疊間之收容空間之隔壁的製造方法，該收容空間包含互不混溶的極性液體及非極性液體。專利文獻2中記載有一種感光性聚合物組成物，其含有（a）聚醯亞胺前驅物及聚醯亞胺、（b）光聚合起始劑及（c）芳香族二胺化合物而成。For example, Patent Document 1 describes a method of manufacturing partition walls for dividing a storage space formed between a first electrode layer stack and a second electrode layer stack, including a specific process, and the storage space contains immiscible polar liquids. And non-polar liquids. Patent Document 2 describes a photosensitive polymer composition containing (a) a polyimide precursor and polyimide, (b) a photopolymerization initiator, and (c) an aromatic diamine compound .

[專利文獻1]日本特開2017-015811號公報 [專利文獻2]日本特開2006-201670號公報[Patent Document 1] JP 2017-015811 A [Patent Document 2] JP 2006-201670 A

在藉由硬化包含聚醯亞胺前驅物等含雜環聚合物前驅物之硬化性樹脂組成物而成之硬化膜的形成中，例如，在藉由在硬化膜上進一步適用並硬化硬化性樹脂組成物而製作積層體時等，存在首先形成之硬化膜與顯影液或其他組成物接觸的情況。因此，在硬化性樹脂組成物中，例如，從對硬化膜的顯影液的耐性或抑制由與其他組成物的接觸導致之硬化膜的溶解等觀點考慮，期待提供一種所獲得之硬化膜的耐藥品性優異之硬化性樹脂組成物。In the formation of a cured film formed by curing a curable resin composition containing a heterocyclic polymer precursor such as a polyimide precursor, for example, by further applying and curing the curable resin on the cured film When the composition is used to produce a layered body, etc., the cured film formed first may come into contact with a developer or other composition. Therefore, in the curable resin composition, for example, from the viewpoint of resistance to the developer of the cured film or suppression of the dissolution of the cured film caused by contact with other components, it is expected to provide a cured film that is resistant to A curable resin composition with excellent chemical properties.

本發明的目的在於提供一種所獲得之硬化膜的耐藥品性優異之硬化性樹脂組成物、藉由硬化上述硬化性樹脂組成物而成之硬化膜、包含上述硬化膜之積層體、上述硬化膜的製造方法及包含上述硬化膜或上述積層體之半導體器件。The object of the present invention is to provide a curable resin composition having excellent chemical resistance of the obtained cured film, a cured film formed by curing the curable resin composition, a laminate including the cured film, and the cured film The manufacturing method of and the semiconductor device including the above-mentioned cured film or the above-mentioned laminate.

以下，示出本發明的代表性實施態樣的例子。＜1＞一種硬化性樹脂組成物，其係包含選自包括聚醯亞胺前驅物及聚苯并㗁唑前驅物之群組中之至少1種聚合物前驅物，上述聚合物前驅物包含由可以被取代的乙烯基直接鍵結之芳香環。＜2＞如＜1＞所述之硬化性樹脂組成物，其中上述聚合物前驅物係具有由下述式（1）表示之重複單元之聚醯亞胺前驅物或具有由下述式（2）表示之重複單元之聚苯并㗁唑前驅物， [化學式1]

在式（1）或式（2）中，A¹ 及A² 分別獨立地表示氧原子或-NH-，R¹¹¹ 表示2價有機基團，R¹¹⁵ 表示4價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團，R¹¹³ 及R¹¹⁴ 中的至少一個包含由可以被取代的乙烯基直接鍵結之芳香環，R¹²¹ 表示2價有機基團，R¹²² 表示4價有機基團，R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價有機基團，R¹²³ 及R¹²⁴ 中的至少一個包含由可以被取代的乙烯基直接鍵結之芳香環。＜3＞如＜1＞或＜2＞所述之硬化性樹脂組成物，其係包含由下述式（S-1）表示之基團作為具有上述由可以被取代的乙烯基直接鍵結之芳香環之基團， [化學式2]

在式（S-1）中，R^S1 表示氫原子或甲基，R^S2 表示取代基，L^S1 表示單鍵或2價連結基，n表示0～4的整數，*表示與其他結構的鍵結部位。＜4＞如＜1＞～＜3＞之任一項所述之硬化性樹脂組成物，其中上述由可以被取代的乙烯基直接鍵結之芳香環的量相對於上述聚合物前驅物的總質量為1～8mol/g。＜5＞如＜1＞～＜4＞之任一項所述之硬化性樹脂組成物，其係進一步包含在分子內具有2個以上乙烯性不飽和基之化合物。＜6＞如＜5＞所述之硬化性樹脂組成物，其中上述在分子內具有2個以上的乙烯性不飽和基之化合物係在分子內具有2個以上由可以被取代的乙烯基直接鍵結之芳香環之化合物。＜7＞如＜6＞所述之硬化性樹脂組成物，其中上述在分子內具有2個以上由可以被取代的乙烯基直接鍵結之芳香環之化合物係由下述式（1-1）表示之化合物， [化學式3]

在式（1-1）中，Z係選自包括2價以上的飽和脂肪族烴基、2價以上的不飽和脂肪族烴基、2價以上的烴環基、-O-、-S-、-N（R^A ）-、-C（=O）-O-、-C（R^A ）=N-、-C（=O）-、-S（=O）₂ -、2價以上的雜環基及該等鍵結2個以上之基團之群組中之m價連結基，R^A 表示氫原子、烷基或芳基，R^A 存在複數個時，複數個R^A 可以相同，亦可以不同，R¹ 分別獨立地表示氫原子或甲基，m表示2～6的整數。＜8＞如＜1＞～＜7＞之任一項所述之硬化性樹脂組成物，其係進一步包含光自由基聚合起始劑。＜9＞如＜1＞～＜8＞之任一項所述之硬化性樹脂組成物，其係進一步包含鎓鹽。＜10＞如＜1＞～＜9＞之任一項所述之硬化性樹脂組成物，其係用於形成再配線層用層間絕緣膜。＜11＞一種硬化膜，其係藉由硬化＜1＞～＜10＞之任一項所述之硬化性樹脂組成物而成。＜12＞一種積層體，其係包含2層以上＜11＞所述之硬化膜，在任意上述硬化膜彼此之間包含金屬層。＜13＞一種硬化膜的製造方法，其係包括將＜1＞～＜10＞之任一項所述之硬化性樹脂組成物適用於基材而形成膜之膜形成製程。＜14＞如＜13＞所述之硬化膜的製造方法，其係包括對上述膜進行曝光之曝光製程及對上述膜進行顯影之顯影製程。＜15＞如＜13＞或＜14＞所述之硬化膜的製造方法，其係包括在50～450℃下加熱上述膜之加熱製程。＜16＞一種半導體器件，其係包含＜11＞所述之硬化膜或＜12＞所述之積層體。 [發明效果]Hereinafter, examples of representative embodiments of the present invention are shown. <1> A curable resin composition comprising at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, and the polymer precursors include The aromatic ring to which the substituted vinyl group is directly bonded. <2> The curable resin composition according to <1>, wherein the polymer precursor is a polyimide precursor having a repeating unit represented by the following formula (1) or a polyimide precursor having a repeating unit represented by the following formula (2) ) Represents the polybenzoxazole precursor of the repeating unit, [Chemical formula 1]

In formula (1) or 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, R ¹¹³ and R ¹¹⁴ each independently represents a hydrogen atom or a monovalent organic group, ^{at least one of R 113} and R ¹¹⁴ contains an aromatic ring directly bonded with a vinyl ^{group that may be substituted, R 121} represents a divalent organic group, and R ¹²² represents A tetravalent organic group, R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, ^{and at least one of R 123} and R ¹²⁴ includes an aromatic ring directly bonded with a vinyl group that may be substituted. <3> The curable resin composition as described in <1> or <2>, which contains a group represented by the following formula (S-1) as a direct bond with the above-mentioned vinyl group which may be substituted Aromatic ring group, [Chemical formula 2]

In formula (S-1), R ^S1 represents a hydrogen atom or a methyl group, R ^S2 represents a substituent, L ^S1 represents a single bond or a divalent linking group, n represents an integer from 0 to 4, and * represents a bond with other structures Knot site. <4> The curable resin composition according to any one of <1> to <3>, wherein the amount of the aromatic ring directly bonded to the substituted vinyl group is relative to the total amount of the polymer precursor The mass is 1～8mol/g. <5> The curable resin composition according to any one of <1> to <4>, which further includes a compound having two or more ethylenically unsaturated groups in the molecule. <6> The curable resin composition according to <5>, wherein the compound having two or more ethylenically unsaturated groups in the molecule has two or more direct bonds with a vinyl group that may be substituted in the molecule The compound of the aromatic ring of the knot. <7> The curable resin composition according to <6>, wherein the compound having two or more aromatic rings directly bonded with a vinyl group that may be substituted in the molecule is represented by the following formula (1-1) The compound represented, [Chemical formula 3]

In formula (1-1), Z is selected from the group consisting of saturated aliphatic hydrocarbon groups with a valence of two or more, unsaturated aliphatic hydrocarbon groups with a valence of two or more, a hydrocarbon ring group with a valence of two or more, -O-, -S-,- N(R ^A )-, -C(=O)-O-, -C(R ^A )=N-, -C(=O)-, -S(=O) ₂ -, heterocyclic rings with more than divalent m group and these divalent groups are bonded two or more of the group of the linking group, R ^A represents a hydrogen atom, an alkyl group or an aryl group, in the presence of a plurality of R ^A, R ^A plurality may be the same, can also Different, R ¹ each independently represents a hydrogen atom or a methyl group, and m represents an integer of 2-6. <8> The curable resin composition according to any one of <1> to <7>, which further contains a photoradical polymerization initiator. <9> The curable resin composition according to any one of <1> to <8>, which further contains an onium salt. <10> The curable resin composition according to any one of <1> to <9>, which is used for forming an interlayer insulating film for a rewiring layer. <11> A cured film formed by curing the curable resin composition described in any one of <1> to <10>. <12> A laminate comprising two or more layers of the cured film described in <11>, and a metal layer between any of the cured films. <13> A method for producing a cured film, which includes a film formation process of applying the curable resin composition described in any one of <1> to <10> to a substrate to form a film. <14> The method for producing a cured film as described in <13>, which includes an exposure process for exposing the film and a development process for developing the film. <15> The method for producing a cured film as described in <13> or <14>, which includes a heating process of heating the film at 50 to 450°C. <16> A semiconductor device comprising the cured film described in <11> or the laminated body described in <12>. [Effects of the invention]

根據本發明，提供一種所獲得之硬化膜的耐藥品性優異之硬化性樹脂組成物、藉由硬化上述硬化性樹脂組成物而成之硬化膜、包含上述硬化膜之積層體、上述硬化膜的製造方法及包含上述硬化膜或上述積層體之半導體器件。According to the present invention, there is provided a curable resin composition having excellent chemical resistance of the obtained cured film, a cured film formed by curing the curable resin composition, a laminate including the cured film, and a composite of the cured film Manufacturing method and semiconductor device including the above-mentioned cured film or the above-mentioned laminate.

以下，對本發明的主要實施形態進行說明。然而，本發明並不限於所明示之實施形態。在本說明書中利用“～”記號表示之數值範圍表示將記載於“～”的前後之數值分別作為下限值及上限值包括之範圍。在本說明書中“製程”這一術語不僅表示獨立的製程，只要能夠實現該製程的所需作用，則亦表示包括無法與其他製程明確區分之製程。關於本說明書中的基團（原子團）的標記，未標註經取代及未經取代之標記同時包括不具有取代基之基團（原子團）和具有取代基之基團（原子團）。例如，“烷基”不僅包括不具有取代基之烷基（未經取代的烷基），還包括具有取代基之烷基（取代烷基）。在本說明書中，“曝光”只要無特別限定，除了利用光的曝光以外，還包括利用電子束、離子束等粒子束之曝光。又，作為用於曝光之光，可舉出水銀燈的明線光譜、以準分子雷射為代表之遠紫外線、極紫外線（EUV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”表示“丙烯酸酯”及“甲基丙烯酸酯”這兩者或其中任1個，“（甲基）丙烯酸”表示“丙烯酸”及“甲基丙烯酸”這兩者或其中任1個，“（甲基）丙烯醯基”表示“丙烯醯基”及“甲基丙烯醯基”這兩者或其中任1個。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，總固體成分表示從組成物的總成分去除溶劑之成分的總質量。又，在本說明書中，固體成分濃度係除了溶劑以外的其他成分相對於組成物的總質量的質量百分率。在本說明書中，只要沒有特別說明，則重量平均分子量（Mw）及數量平均分子量（Mn）基於凝膠滲透層析法（GPC測定），並定義為聚苯乙烯換算值。在本說明書中，重量平均分子量（Mw）及數量平均分子量（Mn）例如能夠利用HLC-8220GPC（TOSOH CORPORATION製），並使用保護管柱HZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000、TSKgel Super HZ2000（TOSOH CORPORATION製）作為管柱來求出。該等分子量只要沒有特別說明，將使用THF（四氫呋喃）測定者作為洗提液。又，只要沒有特別說明，GPC測定中的檢測使用UV線（紫外線）的波長254nm檢測器。在本說明書中，關於構成積層體之各層的位置關係，記載為“上”或“下”時，所關注的複數層中成為基準的層的上側或下側存在其他層即可。亦即，在成為基準的層與上述其他層之間可進一步夾有第3層或第3要件，而成為基準的層與上述其他層無需接觸。又，只要沒有特別說明，將對基材堆疊層之方向稱為“上”，或在存在感光層時，將從基材朝向感光層的方向稱為“上”，將其相反方向稱為“下”。此外，該等上下方向的設定是為了本說明書中的便利，在實際態樣中，本說明書中的“上”方向亦可以與鉛垂上朝向不同。在本說明書中，只要沒有特別說明，作為組成物中包含之各成分，組成物可以包含符合該成分的2種以上的化合物。又，只要沒有特別說明，組成物中的各成分的含量表示符合該成分的所有化合物的合計含量。在本說明書中，只要沒有特別說明，溫度為23℃，氣壓為101,325Pa（1氣壓）。在本說明書中，較佳態樣的組合為更佳態樣。Hereinafter, the main embodiment of the present invention will be described. However, the present invention is not limited to the illustrated embodiment. In this specification, the numerical range indicated by the symbol "～" means the range that includes the numerical values described before and after the "～" as the lower limit and the upper limit, respectively. In this specification, the term "process" not only refers to an independent process, but as long as it can achieve the required effect of the process, it also means a process that cannot be clearly distinguished from other processes. Regarding the label of the group (atomic group) in this specification, the label not labeling substituted and unsubstituted includes both a group without a substituent (atomic group) and a group with a substituent (atomic group). For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl). In this specification, "exposure" is not particularly limited, and includes exposure with particle beams such as electron beams and ion beams in addition to exposure with light. In addition, as the light used for exposure, actinic rays or radiations such as the bright line spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams can be cited. In this specification, "(meth)acrylate" means both or any of "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" "These two or any one of them, and "(meth)acryloyl" means both or any one 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 except the solvent from the total components of the composition. In addition, in this specification, the solid content concentration is the mass percentage of components other than the solvent with respect to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are based on gel permeation chromatography (GPC measurement), and are defined as polystyrene conversion values. In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel can be used Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) were obtained as the column. Unless otherwise specified, these molecular weights will be measured using THF (tetrahydrofuran) as the eluent. In addition, unless otherwise specified, the detection in the GPC measurement uses a UV ray (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting the layered body is described as "upper" or "lower", it is only necessary that another layer exists on the upper side or the lower side of the reference layer among the plurality of layers of interest. That is, the third layer or the third element may be further sandwiched between the layer serving as the reference and the other layer described above, and the layer serving as the reference need not be in contact with the other layer described above. In addition, unless otherwise specified, the direction of the stacked layers of the base material is referred to as "up", or when the photosensitive layer is present, the direction from the base material to the photosensitive layer is referred to as "up", and the opposite direction is referred to as "up". under". In addition, the setting of these up and down directions is for the convenience of this specification. In an actual aspect, the "up" direction in this specification may also be different from the vertical up direction. In this specification, unless otherwise specified, as each component contained in the composition, the composition may contain two or more compounds that conform to the component. In addition, unless otherwise specified, the content of each component in the composition indicates the total content of all compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23°C and the air pressure is 101,325 Pa (1 atmosphere). In this specification, a combination of preferred aspects is a more optimal aspect.

（硬化性樹脂組成物）本發明的硬化性樹脂組成物包含選自包括聚醯亞胺前驅物及聚苯并㗁唑前驅物之群組中之至少1種聚合物前驅物，上述聚合物前驅物包含由可以被取代的乙烯基直接鍵結之芳香環。本發明的硬化性樹脂組成物進一步包含在分子內具有2個以上後述之乙烯性不飽和基之化合物為較佳。又，本發明的硬化性樹脂組成物進一步包含後述之光自由基聚合起始劑為較佳。(Curable resin composition) The curable resin composition of the present invention includes at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, and the polymer precursors include those that can be substituted Aromatic ring directly bonded to vinyl. The curable resin composition of the present invention preferably further contains a compound having two or more ethylenically unsaturated groups described later in the molecule. Furthermore, it is preferable that the curable resin composition of the present invention further contains a radical photopolymerization initiator described later.

藉由本發明的硬化性樹脂組成物獲得之硬化膜的耐藥品性優異。獲得上述效果之機制尚不明確，但可推測如下。The cured film obtained from the curable resin composition of the present invention has excellent chemical resistance. The mechanism for obtaining the above effects is not clear, but it can be presumed as follows.

以往，在含有含雜環聚合物前驅物之硬化性樹脂組成物中，使用具有自由基聚合性基團之含雜環聚合物前驅物，藉由曝光、加熱等使上述自由基聚合性基團自由基聚合來獲得硬化膜。其中，已知上述自由基聚合在氧的存在下會受到聚合阻礙，認為在氧的存在下進行上述曝光、加熱等時，具有未反應的自由基聚合性基團之化合物殘留在硬化膜內。然而，本發明的硬化性樹脂組成物中的含雜環聚合物前驅物包含由可以被取代的乙烯基直接鍵結之芳香環。以下，將包含由可以被取代的乙烯基直接鍵結之芳香環之含雜環聚合物前驅物亦稱為“特定含雜環聚合物前驅物”。認為特定含雜環聚合物前驅物中的由可以被取代的乙烯基直接鍵結之芳香環中的上述乙烯基不易受到氧存在下的聚合阻礙，因此即使在氧存在下，曝光時、加熱時等的自由基聚合進行迅速。其結果，在硬化膜中未反應的自由基聚合性基團的量減少，因此根據本發明的硬化性樹脂組成物，認為可獲得有機溶劑的滲透性、對有機溶劑的溶解性等低的硬化膜。又，如上所述，上述乙烯基不易受到氧存在下的聚合阻礙，因此認為本發明的硬化性樹脂組成物的曝光靈敏度亦容易優異。Conventionally, in a curable resin composition containing a heterocyclic polymer precursor, a heterocyclic polymer precursor having a radical polymerizable group is used, and the radical polymerizable group is made by exposure, heating, etc. Free radical polymerization to obtain a cured film. Among them, it is known that the above-mentioned radical polymerization is inhibited by polymerization in the presence of oxygen, and it is considered that when the above-mentioned exposure, heating, etc. are performed in the presence of oxygen, a compound having an unreacted radical polymerizable group remains in the cured film. However, the heterocyclic ring-containing polymer precursor in the curable resin composition of the present invention contains an aromatic ring directly bonded with a vinyl group which may be substituted. Hereinafter, a heterocyclic-containing polymer precursor containing an aromatic ring directly bonded by a vinyl group that may be substituted is also referred to as a "specific heterocyclic-containing polymer precursor". It is considered that the above-mentioned vinyl group in the aromatic ring directly bonded by the substituted vinyl group in the specific heterocyclic-containing polymer precursor is not easily inhibited by polymerization in the presence of oxygen. Therefore, even in the presence of oxygen, during exposure and heating The free radical polymerization of others proceeds rapidly. As a result, the amount of unreacted radical polymerizable groups in the cured film is reduced. Therefore, according to the curable resin composition of the present invention, it is considered that low curing properties such as permeability and solubility to organic solvents can be obtained. membrane. In addition, as described above, the above-mentioned vinyl group is less likely to be inhibited by polymerization in the presence of oxygen, and therefore it is considered that the curable resin composition of the present invention is also likely to be excellent in exposure sensitivity.

其中，在專利文獻1或2中，並未對包含由可以被取代的乙烯基直接鍵結之芳香環含雜環聚合物前驅物（特定含雜環聚合物前驅物）進行記載或提示。以下，對本發明的硬化性樹脂組成物中包含之成分進行詳細說明。Among them, Patent Document 1 or 2 does not describe or suggest an aromatic ring heterocyclic ring-containing polymer precursor (specific heterocyclic ring-containing polymer precursor) directly bonded by a substituted vinyl group. Hereinafter, the components contained in the curable resin composition of the present invention will be described in detail.

＜特定含雜環聚合物前驅物＞本發明的硬化性樹脂組成物含有特定含雜環聚合物前驅物。作為特定含雜環聚合物前驅物，本發明的硬化性樹脂組成物包含選自包括聚醯亞胺前驅物及聚苯并㗁唑前驅物之群組中之至少1種前驅物，包含聚醯亞胺前驅物為較佳。特定含雜環聚合物前驅物包含由可以被取代的乙烯基直接鍵結之芳香環。在本說明書中，由可以被取代的乙烯基直接鍵結之芳香環表示可以被取代的乙烯基的雙鍵中的一個碳原子直接鍵結於芳香環結構上的結構。上述芳香環可以具有烷基、鹵素基等公知的取代基。上述芳香環可以為芳香族烴環，亦可以為芳香族雜環，在上述芳香族烴環或芳香族雜環上可以縮合有芳香族烴環或脂肪族烴環、或者芳香族雜環或脂肪族雜環。又，該等芳香族烴環、脂肪族烴環、芳香族雜環或脂肪族雜環可以分別具有烷基、鹵素基等公知的取代基。上述由可以被取代的乙烯基直接鍵結之芳香環中的芳香環係芳香族烴環為較佳，苯環為更佳。亦即，特定含雜環聚合物前驅物包含乙烯基苯基作為包含乙烯基直接鍵結之芳香環之基團為較佳。＜Specific heterocyclic polymer precursors＞ The curable resin composition of the present invention contains a specific heterocyclic-containing polymer precursor. As a specific heterocyclic-containing polymer precursor, the curable resin composition of the present invention includes at least one precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, including polyamide The imine precursor is preferred. The specific heterocyclic-containing polymer precursor contains an aromatic ring directly bonded by a vinyl group which may be substituted. In this specification, the aromatic ring directly bonded by a vinyl group that may be substituted means a structure in which one carbon atom in the double bond of the vinyl group that may be substituted is directly bonded to the aromatic ring structure. The said aromatic ring may have well-known substituents, such as an alkyl group and a halogen group. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The aromatic hydrocarbon ring or the aromatic heterocyclic ring may be condensed with an aromatic hydrocarbon ring or aliphatic hydrocarbon ring, or an aromatic heterocyclic ring or aliphatic ring. Group heterocycle. In addition, the aromatic hydrocarbon ring, aliphatic hydrocarbon ring, aromatic heterocyclic ring, or aliphatic heterocyclic ring may each have a known substituent such as an alkyl group and a halogen group. The aromatic ring system aromatic hydrocarbon ring in the aromatic ring directly bonded by the optionally substituted vinyl group is preferable, and the benzene ring is more preferable. That is, it is preferable that the specific heterocyclic-containing polymer precursor contains a vinyl phenyl group as a group containing an aromatic ring directly bonded to a vinyl group.

〔由式（S-1）表示之基團〕特定含雜環聚合物前驅物包含由下述式（S-1）表示之基團作為具有由可以被取代的乙烯基直接鍵結之芳香環之基團為較佳。 [化學式4]

在式（S-1）中，R^S1 表示氫原子或甲基，R^S2 表示取代基，L^S1 表示單鍵或2價連結基，n表示0～4的整數，*表示與其他結構的鍵結部位。[Group represented by formula (S-1)] The specific heterocyclic-containing polymer precursor contains a group represented by the following formula (S-1) as having an aromatic ring directly bonded with a vinyl group which may be substituted The group is preferred. [Chemical formula 4]

In formula (S-1), R ^S1 represents a hydrogen atom or a methyl group, R ^S2 represents a substituent, L ^S1 represents a single bond or a divalent linking group, n represents an integer from 0 to 4, and * represents a bond with other structures Knot site.

在式（S-1）中，R^S1 表示氫原子或甲基，係氫原子為較佳。In the formula (S-1), R ^S1 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

在式（S-1）中，R^S2 係鹵素原子、烷基或芳基為較佳，鹵素原子、碳數1～4的烷基或苯基為更佳。In the formula (S-1), R ^S2 is preferably a halogen atom, an alkyl group, or an aryl group, and a halogen atom, an alkyl group having 1 to 4 carbons, or a phenyl group is more preferable.

在式（S-1）中，L^S1 係單鍵或選自包括伸烷基、伸烯基、2價烴環基、-O-、-S-、-N（R^A ）-、-C（=O）-O-、-C（R^A ）=N-、-C（=O）-、-S（=O）₂ -、-CH₂ CH（OH）CH₂ -2價雜環基及該等鍵結2個以上之基團之群組中之連結基為較佳，單鍵或選自包括伸烷基、2價芳香族烴環基、-O-、-S-、-N（R^A ）-、-C（=O）-O-、-C（=O）-及該等鍵結2個以上之基團之群組中之連結基為更佳。又，上述連結基包含碳數1～30的（聚）氧伸烷基作為組合了伸烷基及-O-之連結基亦較佳。（聚）氧伸烷基表示氧伸烷基或聚氧伸烷基。上述（聚）氧伸烷基中的伸烷基的碳數為1～12為較佳，1～6為更佳，1～3為特佳。尤其，上述（聚）氧伸烷基係聚氧伸烷基時，伸烷基係伸乙基或伸丙基為較佳。又，上述（聚）氧伸烷基中的氧伸烷基結構的重複數為1～12為較佳，1～6為更佳，1～3為特佳。作為L^S1 中的伸烷基，碳數1～10的伸烷基為較佳，碳數1～8的伸烷基為更佳。作為L^S1 中的伸烯基，碳數2～8的伸烯基為較佳，碳數2～6的伸烯基為更佳。作為L^S1 中的烴環基，從烴環去除2～4個氫原子之2～4價基團為較佳。作為L^S1 中的烴環基中的烴環的環員數，6～20為較佳，6～12為更佳，6為進一步較佳。作為L^S1 中的2價烴環基，芳香族烴環為較佳，苯環為更佳。作為L^S1 中的2價雜環基中的雜環，芳香族雜環為較佳，環員數5～20的芳香族雜環為較佳，5～20的芳香族雜環為更佳。上述雜環可以為複數個雜環的縮合環，亦可以為雜環與芳香族烴環的縮合環。雜環係縮合環時，作為縮合環中包含之單環的雜環的環員數為5～6為較佳。又，作為L^S1 中的2價雜環基中的雜環，吡咯環、吡唑環、咪唑環、***環、四唑環、異㗁唑環、㗁唑環、㗁二唑環、異噻唑環、噻唑環、噻二唑環、噻***環、吲哚環、吲唑環、苯并咪唑環、苯并***環、苯并㗁唑環、苯并噻唑環、苯并硒唑環、苯并噻二唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、三𠯤環、喹啉環、喹㗁啉環、呋喃環或噻吩環為較佳。In formula ^(S1), L S1 system comprising a single bond or is selected from alkylene, alkenylene group, a divalent hydrocarbon ring group, -O -, - S -, - N (R A) -, - C (= O) -O -, - C (R A) = N -, - C (= O) -, - S (= O) 2 -, - CH 2 CH (OH) CH 2 -2 divalent heterocyclic group And the linking group in the group that binds two or more groups is preferable, and the single bond may be selected from alkylene group, divalent aromatic hydrocarbon ring group, -O-, -S-, -N (R ^A )-, -C(=O)-O-, -C(=O)- and the linking group in the group of these bonding two or more groups are more preferable. In addition, it is also preferable that the above-mentioned linking group includes a (poly)oxyalkylene group having 1 to 30 carbon atoms as a linking group combining an alkylene group and -O-. (Poly)oxyalkylene means oxyalkylene or polyoxyalkylene. The carbon number of the alkylene group in the above-mentioned (poly)oxyalkylene group is preferably 1-12, more preferably 1-6, and particularly preferably 1-3. In particular, in the case of the above-mentioned (poly)oxyalkylene-based polyoxyalkylene, the alkylene-based ethylene or propylene is preferred. In addition, the number of repetitions of the oxyalkylene structure in the (poly)oxyalkylene group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. As the ^{alkylene group in L S1} , an alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 1 to 8 carbon atoms is more preferred. As the ^{alkenylene group in L S1} , an alkenylene group having 2 to 8 carbon atoms is preferable, and an alkenylene group having 2 to 6 carbon atoms is more preferable. As ^{the hydrocarbon ring group in L S1} , a 2- to 4-valent group obtained by removing 2 to 4 hydrogen atoms from the hydrocarbon ring is preferable. As the ^{number of ring members of the hydrocarbon ring in the hydrocarbon ring group in L S1} , 6 to 20 are preferable, 6 to 12 are more preferable, and 6 is still more preferable. As the ^{divalent hydrocarbon ring group in L S1} , an aromatic hydrocarbon ring is preferable, and a benzene ring is more preferable. As the ^{heterocyclic ring in the divalent heterocyclic group in L S1} , an aromatic heterocyclic ring is preferable, an aromatic heterocyclic ring having 5 to 20 ring members is preferable, and an aromatic heterocyclic ring having 5 to 20 ring members is more preferable. The heterocyclic ring may be a condensed ring of a plurality of heterocyclic rings, or a condensed ring of a heterocyclic ring and an aromatic hydrocarbon ring. When a heterocyclic ring is a condensed ring, the number of ring members of the heterocyclic ring as a monocyclic ring contained in the condensed ring is preferably 5-6. In addition, as the ^{heterocyclic ring in the divalent heterocyclic group in L S1} , a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an isoazole ring, an azole ring, a diazole ring, and iso Thiazole ring, thiazole ring, thiadiazole ring, thiatriazole ring, indole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzoselazole A ring, a benzothiadiazole ring, a pyridine ring, a pyrimidine ring, a pyrimidine ring, a pyridine ring, a tripyridine ring, a quinoline ring, a quinoline ring, a furan ring or a thiophene ring are preferred.

在式（S-1）中，n表示0～4的整數，0～2的整數為較佳，0為更佳。In formula (S-1), n represents an integer of 0-4, preferably an integer of 0-2, and more preferably 0.

從所獲得之硬化膜的耐藥品性及保存穩定性的觀點考慮，由可以被取代的乙烯基直接鍵結之芳香環的量相對於特定含雜環聚合物前驅物的總質量為0.1～12mol/g為較佳，0.5～10mol/g為更佳，1～8mol/g為進一步較佳。From the viewpoint of the chemical resistance and storage stability of the cured film obtained, the amount of aromatic rings directly bonded by the vinyl group that can be substituted is 0.1-12 mol relative to the total mass of the specific heterocyclic-containing polymer precursor. /g is preferable, 0.5-10 mol/g is more preferable, and 1-8 mol/g is still more preferable.

〔由式（1）表示之重複單元或由式（2）表示之重複單元〕特定含雜環聚合物前驅物係具有由下述式（1）表示之重複單元之聚醯亞胺前驅物或具有由下述式（2）表示之重複單元之聚苯并㗁唑前驅物為較佳。 [化學式5]

在式（1）或式（2）中，A¹ 及A² 分別獨立地表示氧原子或-NH-，R¹¹¹ 表示2價有機基團，R¹¹⁵ 表示4價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團，R¹¹³ 及R¹¹⁴ 中的至少一個包含由可以被取代的乙烯基直接鍵結之芳香環，R¹²¹ 表示2價有機基團，R¹²² 表示4價有機基團，R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價有機基團，R¹²³ 及R¹²⁴ 中的至少一個包含由可以被取代的乙烯基直接鍵結之芳香環。[Repeating unit represented by formula (1) or repeating unit represented by formula (2)] The specific heterocyclic-containing polymer precursor is a polyimide precursor having a repeating unit represented by the following formula (1) or A polybenzoxazole precursor having a repeating unit represented by the following formula (2) is preferred. [Chemical formula 5]

In formula (1) or 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, R ¹¹³ and R ¹¹⁴ each independently represents a hydrogen atom or a monovalent organic group, ^{at least one of R 113} and R ¹¹⁴ contains an aromatic ring directly bonded with a vinyl ^{group that may be substituted, R 121} represents a divalent organic group, and R ¹²² represents A tetravalent organic group, R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, ^{and at least one of R 123} and R ¹²⁴ includes an aromatic ring directly bonded with a vinyl group that may be substituted.

〔聚醯亞胺前驅物〕聚醯亞胺前驅物包含由上述式（1）表示之重複單元為較佳。〔Polyimide precursor〕 The polyimide precursor preferably contains a repeating unit represented by the above formula (1).

-A¹ 及A² - 式（1）中的A¹ 及A² 分別獨立地表示氧原子或-NH-，氧原子為較佳。-A ¹ and A ² - Formula A (1) ¹ and A ² each independently represent an oxygen atom or -NH-, an oxygen atom is preferred.

-R¹¹¹ - 式（1）中的R¹¹¹ 表示2價有機基團。作為2價有機基團，例示直鏈狀或支鏈狀的脂肪族基、環狀的脂肪族基及芳香族基、雜芳香族基或將該等組合2個以上之基團，碳數2～20的直鏈的脂肪族基、碳數3～20的支鏈的脂肪族基、碳數3～20的環狀的脂肪族基、碳數6～20的芳香族基或將該等組合2個以上之基團為較佳，碳數6～20的芳香族基為更佳。-R ¹¹¹ - of formula (1), R ¹¹¹ represents a divalent organic group. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or a combination of two or more groups, with a carbon number of 2 -20 linear aliphatic groups, branched aliphatic groups with 3-20 carbons, cyclic aliphatic groups with 3-20 carbons, aromatic groups with 6-20 carbons, or a combination of these Two or more groups are preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.

式（1）中的R¹¹¹ 衍生自二胺為較佳。作為在聚醯亞胺前驅物的製造中所使用之二胺，可舉出直鏈狀或支鏈狀脂肪族、環狀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。 ^{Preferably, R 111} in the formula (1) is derived from a diamine. Examples of diamines used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.

具體而言，二胺係包含碳數2～20的直鏈脂肪族基、碳數3～20的支鏈狀或環狀脂肪族基、碳數6～20的芳香族基或將該等組合2個以上之基團之二胺為較佳，包含碳數6～20的芳香族基之二胺為更佳。作為芳香族基的例子，可舉出下述芳香族基。Specifically, the diamine contains a linear aliphatic group with 2 to 20 carbons, a branched or cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 6 to 20 carbons, or a combination of these Diamines having two or more groups are preferred, and diamines containing aromatic groups having 6 to 20 carbon atoms are more preferred. As an example of an aromatic group, the following aromatic groups can be mentioned.

[化學式6]

[Chemical formula 6]

式中，A係單鍵或可以經氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-S（=O）₂ -、-NHC（=O）-或將該等組合2個以上之基團為較佳，單鍵或選自可以經氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-及S（=O）₂ -中之基團為更佳，選自包括-CH₂ -、-O-、-S-、-S（=O）₂ -、-C（CF₃ ）₂ -及-C（CH₃ ）₂ -之群組中之2價基團為進一步較佳。In the formula, A is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons that can be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -,- NHC(=O)- or a combination of 2 or more groups of these are preferred, single bond or selected from alkylene groups with 1 to 3 carbons which may be substituted by fluorine atoms, -O-, -C(= The group in O)-, -S- and S(=O) ₂ -is more preferably selected from the group including -CH ₂ -, -O-, -S-, -S(=O) ₂ -, -C The divalent group in the group of (CF ₃ ) ₂ -and -C(CH ₃ ) _{2-is 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、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’-二甲基環己基甲烷或異佛爾酮二胺；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’-二胺基二苯基甲烷或3,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基碸或3,3’-二胺基二苯基碸、4,4’-二胺基二苯硫醚或3,3’-二胺基二苯硫醚、4,4’-二胺基二苯甲酮或3,3’-二胺基二苯甲酮、3,3’-二甲基-4,4’-二胺基聯苯、2,2’-二甲基-4,4’-二胺基聯苯（4,4’-二胺基-2,2’-二甲基聯苯）、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’-二胺基對聯三苯、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’-二胺基二苯基碸、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’-二胺基二苯基碸、3,3’,5,5’-四甲基-4,4’-二胺基二苯基甲烷、2-（3’,5’-二胺基苯甲醯氧基）甲基丙烯酸乙酯、2,4-二胺基枯烯或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、二胺基苯甲醯苯胺、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）二苯基碸、4,4’-雙（3-胺基-5-三氟甲基苯氧基）二苯基碸、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。As the diamine, specifically selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclopentane 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'-dimethyl Cyclohexylmethane or 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 or 3,3'-diaminodiphenylmethane, 4, 4'-diaminodiphenyl sulfide or 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide or 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2' -Dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 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-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2 , 2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfite, bis(4-amino-3-hydroxyphenyl) sulfite, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] sulfide, 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 sulfide, 1,3-bis(4-aminophenoxy) ) Benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diamine Diphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 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'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1 ,5-Diaminoanthraquinone, 3,3-dihydroxy-4 ,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl) sulfide, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfide, 3, 3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzyloxy) ethyl methacrylate, 2 ,4-diaminocumene or 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-di Aminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzaniline, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluoro Toluene, 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-tris Fluoromethylphenoxy)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，以下所示之二胺（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7]

[Chemical formula 7]

[化學式8]

[Chemical formula 8]

又，作為較佳例，亦可舉出在主鏈具有至少2個伸烷基二醇單元之二胺。較佳為在一分子中組合包含2個以上的乙二醇鏈、丙二醇鏈中的任1個或兩者之二胺，更佳為不包含芳香環之二胺。作為具體例，可舉出JEFFAMINE（註冊商標）KH-511、JEFFAMINE（註冊商標）ED-600、JEFFAMINE（註冊商標）ED-900、JEFFAMINE（註冊商標）ED-2003、JEFFAMINE（註冊商標）EDR-148、JEFFAMINE（註冊商標）EDR-176、D-200、D-400、D-2000、D-4000（以上商品名，HUNTSMAN公司製）、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，但並不限定於該等。Moreover, as a preferable example, the diamine which has at least 2 alkylene glycol units in a main chain can also be mentioned. Preferably, it is a diamine that contains two or more of ethylene glycol chains and propylene glycol chains or both in combination in one molecule, and more preferably does not contain an aromatic ring. As specific examples, JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR- 148, JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (above trade names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropyl) (Oxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., But it is not limited to these.

以下示出JEFFAMINE（註冊商標）KH-511、JEFFAMINE（註冊商標）ED-600、JEFFAMINE（註冊商標）ED-900、JEFFAMINE（註冊商標）ED-2003、JEFFAMINE（註冊商標）EDR-148、JEFFAMINE（註冊商標）EDR-176的結構。The following shows JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE ( Registered trademark) The structure of EDR-176.

[化學式9]

[Chemical formula 9]

上述中，x、y、z為算術平均值。In the above, x, y, and z are the arithmetic averages.

從所得到之硬化膜的柔軟性的觀點考慮，式（1）中的R¹¹¹ 由-Ar⁰ -L⁰ -Ar⁰ -表示為較佳。Ar⁰ 分別獨立地為芳香族烴基（碳數6～22為較佳，6～18為更佳，6～10為特佳），伸苯基為較佳。L⁰ 表示單鍵或可以經氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-S（=O）₂ -、-NHCO-或將該等組合2個以上之基團。L⁰ 的較佳範圍的含義與上述A相同。From the viewpoint of the flexibility of the obtained cured film, R ¹¹¹ in the formula (1) is preferably represented by -Ar ⁰ -L ⁰ -Ar ^{0 -.} Ar ^{0 is} each independently an aromatic hydrocarbon group (the carbon number is preferably 6-22, more preferably 6-18, particularly preferably 6-10), and phenylene is preferred. L ⁰ represents a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons which can be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO- Or these groups can be combined with two or more groups. The meaning of the preferable range of L ⁰ is the same as the above-mentioned A.

從i射線透射率的觀點考慮，式（1）中的R¹¹¹ 係由下述式（51）或式（61）表示之2價有機基團為較佳。尤其，從i射線透射率、易獲得的觀點考慮，由式（61）表示之2價有機基團為更佳。From the viewpoint of i-ray transmittance, R ¹¹¹ in the formula (1) 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 formula (61) is more preferable.

[化學式10]

[Chemical formula 10]

在式（51）中，R⁵⁰ ～R⁵⁷ 分別獨立為氫原子、氟原子或1價有機基團，R⁵⁰ ～R⁵⁷ 中的至少一個為氟原子、甲基、氟甲基、二氟甲基或三氟甲基，*分別獨立地表示與其他結構的鍵結部位。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, a fluoromethyl group, or a difluoromethyl group. Group or trifluoromethyl group, * each independently represents a bonding site with another structure.

作為R⁵⁰ ～R⁵⁷ 的1價有機基團，可舉出碳數1～10（較佳為碳數1～6）的未經取代的烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 ^Examples of the monovalent organic groups of 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.

[化學式11]

[Chemical formula 11]

在式（61）中，R⁵⁸ 及R⁵⁹ 分別獨立地為氟原子、氟甲基、二氟甲基或三氟甲基。In the formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.

作為賦予式（51）或（61）的結構之二胺化合物，可舉出二甲基-4,4’-二胺基聯苯、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。可以使用該等中的1種亦可以組合使用2種以上。As the diamine compound imparting the structure of formula (51) or (61), dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4, 4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. One of these may be used, or two or more of them may be used in combination.

-R¹¹⁵ - 式（1）中的R¹¹⁵ 表示4價有機基團。作為4價有機基團，包含芳香環之4價有機基團為較佳，由下述式（5）或式（6）表示之基團為更佳。-R ¹¹⁵ - of formula (1), R ¹¹⁵ 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.

[化學式12]

[Chemical formula 12]

R¹¹² 的含義與A相同，較佳範圍亦相同。*分別獨立地表示與其他結構的鍵結部位。R ^{112 has} the same meaning as A, and the preferred range is also the same. * Each independently indicates the bonding site with other structures.

關於由式（1）中的R¹¹⁵ 表示之4價有機基團，具體而言，可舉出從四羧酸二酐去除酸二酐基之後殘存之四羧酸殘基等。四羧酸二酐可以僅使用1種亦可以使用2種以上。四羧酸二酐係由下述式（7）表示之化合物為較佳。 ^{Regarding the tetravalent organic group represented by R 115} in the formula (1), specifically, the tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride and the like can be mentioned. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).

[化學式13]

[Chemical formula 13]

R¹¹⁵ 表示4價有機基團。R¹¹⁵ 的含義與式（1）的R¹¹⁵ 相同。R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ is the same meaning as in formula (1) is R ^115.

作為四羧酸二酐的具體例，可例示選自均苯四甲酸、均苯四甲酸二酐（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’-二苯基碸四羧酸二酐、3,3’,4,4’-二苯甲酮四羧酸二酐、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’-二苯甲酮四羧酸二酐、4,4’-氧代二鄰苯二甲酸二酐、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-苯四羧酸二酐及該等的碳數1～6的烷基衍生物及碳數1～6的烷氧基衍生物中之至少1種。As a specific example of tetracarboxylic dianhydride, can be exemplified selected from pyromellitic acid, 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'-diphenylmethyl Ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3 ,3',4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxodiphthalic 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-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10 -Phenanthrene tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1, At least one of 2,3,4-benzenetetracarboxylic dianhydride and alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

又，作為較佳例還可舉出以下所示之四羧酸二酐（DAA-1）～（DAA-5）。In addition, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below can also be cited as preferred examples.

[化學式14]

[Chemical formula 14]

-R¹¹³ 及R¹¹⁴ - 式（1）中的R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團，R¹²³ 及R¹²⁴ 中的至少一個包含由可以被取代的乙烯基直接鍵結之芳香環。作為具有由可以被取代的乙烯基直接鍵結之芳香環之基團，由上述式（S-1）表示之基團為較佳。 R¹²³ 及R¹²⁴ 中的至少一個為由上述式（S-1）表示之基團時，式（S-1）中的*表示與式（1）中的A¹ 或A² 的鍵結部位。-R ¹¹³ and R ¹¹⁴ - of formula (1), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, R ¹²³ and R ¹²⁴ may be substituted by the vinyl group comprises at least a direct bond The aromatic ring of the knot. As the group having an aromatic ring directly bonded with a vinyl group which may be substituted, a group represented by the above formula (S-1) is preferred. When ^{at least one of R 123} and R ¹²⁴ is a group represented by the above formula (S-1), * in the formula (S-1) represents the bonding site ^{with A 1} or A ^{2 in the formula (1)} .

R¹¹³ 及R¹¹⁴ 的其中一個可以不包含由可以被取代的乙烯基直接鍵結之芳香環。 R¹¹³ 及R¹¹⁴ 中，不包含由可以被取代的乙烯基直接鍵結之芳香環時，R¹¹³ 及R¹¹⁴ 的其中一個可以為具有除了由可以被取代的乙烯基直接鍵結之芳香環以外的乙烯性不飽和鍵之基團，不具有乙烯性不飽和鍵之基團為較佳。One of R ¹¹³ and R ¹¹⁴ may not include an aromatic ring directly bonded with a vinyl group which may be substituted. When R ¹¹³ and R ¹¹⁴ do not contain an aromatic ring directly bonded by a vinyl group that may be substituted, one of R ¹¹³ and R ¹¹⁴ may have an aromatic ring other than the aromatic ring directly bonded by a vinyl group that may be substituted The group with ethylenically unsaturated bond is preferably a group without ethylenically unsaturated bond.

作為R¹¹³ 及R¹¹⁴ 中的具有除了由可以被取代的乙烯基直接鍵結之芳香環以外的乙烯性不飽和鍵之基團，可舉出乙烯基、烯丙基、（甲基）丙烯醯基、由下述式（III）表示之基團等。Examples of groups in R ¹¹³ and R ¹¹⁴ having an ethylenically unsaturated bond other than the aromatic ring directly bonded to the vinyl group which may be substituted include vinyl group, allyl group, and (meth)acrylic acid group. Group, a group represented by the following formula (III), etc.

[化學式15]

[Chemical formula 15]

在式（III）中，R²⁰⁰ 表示氫原子或甲基，甲基為較佳。In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is preferred.

在式（III）中，R²⁰¹ 表示碳數2～12的伸烷基、-CH₂ CH（OH）CH₂ -或碳數4～30的（聚）氧伸烷基（作為伸烷基，碳數1～12為較佳，1～6為更佳，1～3為特佳；重複數為1～12為較佳，1～6為更佳，1～3為特佳）。此外，（聚）氧伸烷基表示氧伸烷基或聚氧伸烷基。關於較佳之R²⁰¹ 的例子，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 -，伸乙基、伸丙基、三亞甲基、-CH₂ CH（OH）CH₂ -為更佳。特佳為R²⁰⁰ 係甲基，R²⁰¹ 係伸乙基。在式（III）中，*表示與其他結構的鍵結部位。In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -or a (poly)oxyalkylene group having 4 to 30 carbon atoms (as an alkylene group, The carbon number is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 to 3; the repeating number is preferably from 1 to 12, preferably from 1 to 6 and particularly preferably from 1 to 3). In addition, (poly)oxyalkylene means oxyalkylene or polyoxyalkylene. Examples of preferred R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene Methylene, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, ethylene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ -are more good. Particularly preferably, R ²⁰⁰ is a methyl group, and R ²⁰¹ is an ethylene group. In formula (III), * represents the bonding site with other structures.

作為R¹¹³ 及R¹¹⁴ 中的不具有乙烯性不飽和鍵之基團，可舉出具有1個、2個或3個（較佳為1個）酸基之脂肪族基、芳香族基及芳烷基等。具體而言，可舉出具有酸基之碳數6～20的芳香族基、具有酸基之碳數7～25的芳烷基。更具體而言，可舉出具有酸基之苯基及具有酸基之苄基。酸基係羥基為較佳。亦即，R¹¹³ 或R¹¹⁴ 係具有羥基之基團為較佳。作為R¹¹³ 及R¹¹⁴ 中的不具有乙烯性不飽和鍵之基團，可較佳地利用提高顯影液的溶解度之取代基。 ^Examples of the groups having no ethylenically unsaturated bond in R ¹¹³ and R 114 include aliphatic groups, aromatic groups, and aromatic groups having 1, 2, or 3 (preferably 1) acid groups. Alkyl and so on. Specifically, an aromatic group having 6 to 20 carbon atoms having an acid group, and an aralkyl group having 7 to 25 carbon atoms having an acid group can be mentioned. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is preferably a hydroxyl group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxyl group. As ^{the group having no ethylenically unsaturated bond in R 113} and R ¹¹⁴ , a substituent that improves the solubility of the developer can be preferably used.

從對水性顯影液的溶解性的觀點考慮，R¹¹³ 或R¹¹⁴ 係氫原子、2-羥基芐基、3-羥基芐基及4-羥基芐基為更佳。From the viewpoint of solubility in an aqueous developer, R ¹¹³ or R ¹¹⁴ is preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, and 4-hydroxybenzyl.

從對有機溶劑的溶解度的觀點考慮，R¹¹³ 及R¹¹⁴ 中的不具有乙烯性不飽和鍵之基團係1價有機基團為較佳。作為1價有機基團，直鏈或支鏈的烷基、環狀烷基、芳香族基為較佳，被芳香族基取代之烷基為更佳。From the viewpoint of solubility in an organic solvent, the group having no ethylenically unsaturated bond among ^{R 113} and R ^{114 is preferably a monovalent organic group.} As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group are preferable, and an alkyl group substituted with an aromatic group is more preferable.

烷基的碳數係1～30為較佳（當為環狀時為3以上）。烷基可以為直鏈、支鏈、環狀中的任1個。作為直鏈或支鏈烷基，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、第二丁基、第三丁基、1-乙基戊基及2-乙基己基。環狀烷基可以為單環環狀烷基，亦可以為多環環狀烷基。作為單環環狀的烷基，例如，可舉出環丙基、環丁基、環戊基、環己基、環庚基及環辛基。作為多環環狀的烷基，例如，可舉出金剛烷基、降莰基、莰基、莰烯基（camphenyl）、十氫萘基、三環癸烷基、四環癸烷基、莰二醯基、二環己基及蒎烯基（pinenyl）。又，作為被芳香族基取代之烷基，被以下所述之芳香族基取代之直鏈烷基為較佳。The carbon number of the alkyl group is preferably 1 to 30 (when it is cyclic, it is 3 or more). The alkyl group may be any one of linear, branched, and cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl Alkyl, octadecyl, isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or 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 (camphenyl), decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and camphenyl. Diacyl, dicyclohexyl and pinenyl (pinenyl). In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable.

作為芳香族基，具體而言為經取代或未經取代的芳香族烴基（作為構成基團之環狀結構，可舉出苯環、萘環、聯苯環、茀環、戊搭烯環、茚環、薁環、庚搭烯環、茚烯環、苝環、稠五苯環、苊烯環、菲環、蒽環、稠四苯環、䓛環、三伸苯環等）或經取代或未經取代的芳香族雜環基（作為構成基團之環狀結構，茀環、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、吲口巾環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹口巾環、喹啉環、呔𠯤環、萘啶環、喹㗁啉環、喹唑啉環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環、色烯環、口山口星環、啡㗁噻環、啡噻𠯤環或啡𠯤環）。The aromatic group is specifically a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a sulphur ring, a pentene ring, Indene ring, azulene ring, heptene ring, indenene ring, perylene ring, fused pentaphenyl ring, acenaphthylene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, tetraphenyl ring, terylene ring, etc.) or substituted Or unsubstituted aromatic heterocyclic group (as the cyclic structure constituting the group, 茀 ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyridine ring, pyrrole ring, pyrimidine ring) Ring, scalp ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, quinoline ring, naphthyridine ring, quinoline Phinyl ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thiaxanthene ring, chromene ring, Kouyamakou star ring, phenanthrene ring, phenanthrene ring Ring or brown 𠯤 ring).

又，聚醯亞胺前驅物中，在重複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為10質量%以上為較佳，20質量%以上為更佳。上限並無特別限制，實際上為50質量%以下。In addition, in the polyimide precursor, it is also preferable to have a fluorine atom in the repeating unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit is not particularly limited, but is actually 50% by mass or less.

又，以提高與基材的密接性為目的，可以使具有矽氧烷結構之脂肪族基與由式（1）表示之重複單元共聚合。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, for the purpose of improving the adhesion to the substrate, the aliphatic group having a siloxane structure and the repeating unit represented by formula (1) can be copolymerized. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

由式（1）表示之重複單元係由式（1-A）或式（1-B）表示之重複單元為較佳。The repeating unit represented by formula (1) is preferably a repeating unit represented by formula (1-A) or formula (1-B).

[化學式16]

[Chemical formula 16]

A¹¹ 及A¹² 表示氧原子或-NH-，R¹¹¹ 及R¹¹² 分別獨立地表示2價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團，R¹¹³ 及R¹¹⁴ 中的至少一個包含由可以被取代的乙烯基直接鍵結之芳香環。A ¹¹ and A ¹² represent an oxygen atom or -NH-, 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, R ¹¹³ and R ^{At least one of 114} contains an aromatic ring directly bonded with a vinyl group which may be substituted.

A¹¹ 、A¹² 、R¹¹¹ 、R¹¹³ 及R¹¹⁴ 的較佳範圍的含義分別與式（1）中的A¹ 、A² 、R¹¹¹ 、R¹¹³ 及R¹¹⁴ 的較佳範圍相同。The meanings of the preferred ranges of A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ^{114 are the same} ^{as the preferred ranges of A 1} , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1), respectively.

R¹¹² 的較佳範圍的含義與式（5）中R¹¹² 相同，其中氧原子為更佳。In the preferred range of R is the same R ¹¹² meaning as in formula (5) ^112, wherein the oxygen atoms.

式中羰基在苯環的鍵結位置在式（1-A）中為4、5、3’、4’為較佳。在式（1-B）中，1、2、4、5為較佳。In the formula, the bonding position of the carbonyl group on the benzene ring is preferably 4, 5, 3', 4'in the formula (1-A). In formula (1-B), 1, 2, 4, and 5 are preferred.

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

作為其他種類的重複單元的例子，可舉出由下述式（1-2）表示之重複單元。 [化學式17]

在式（1-2）中，A¹ 及A² 分別獨立地表示氧原子或-NH-，R¹¹¹ 表示2價有機基團，R¹¹⁵ 表示4價有機基團，R^113a 及R^114a 分別獨立地表示氫原子或1價有機基團，R^113a 及R^114a 不包含由可以被取代的乙烯基直接鍵結之芳香環。As an example of another type of repeating unit, a repeating unit represented by the following formula (1-2) can be given. [Chemical formula 17]

In formula (1-2), 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 ^113a and R ^114a are each independently Ground represents a hydrogen atom or a monovalent organic group, and R ^113a and R ^114a do not include an aromatic ring directly bonded with a vinyl group that may be substituted.

在式（1-2）中，A¹ 、A² 、R¹¹¹ 及R¹¹⁵ 的含義分別與式（1）中的A¹ 、A² 、R¹¹¹ 及R¹¹⁵ 相同，較佳態樣亦相同。在式（1-2）中，R^113a 及R^114a 分別為式（1）中的R¹¹³ 及R¹¹⁴ 的說明中記載之R¹¹³ 及R¹¹⁴ 中的具有除了由可以被取代的乙烯基直接鍵結之芳香環以外的乙烯性不飽和鍵之基團或與R¹¹³ 及R¹¹⁴ 中的不具有乙烯性不飽和鍵之基團相同的基團為較佳，與R¹¹³ 及R¹¹⁴ 中的不具有乙烯性不飽和鍵之基團相同的基團為更佳。上述R¹¹³ 及R¹¹⁴ 中的具有除了由可以被取代的乙烯基直接鍵結之芳香環以外的乙烯性不飽和鍵之基團及上述與R¹¹³ 及R¹¹⁴ 中的不具有乙烯性不飽和鍵之基團相同的基團的較佳態樣如上所述。聚醯亞胺前驅物可以單獨包含1種由式（1-2）表示之重複單元，亦可以包含2種以上。In the formula (1-2), (1) A ^1, A ^2, R ^111, and the same as ^{^{^{R 115 A 1, A 2,}}} R 111 and R ^115, respectively, and the meanings of formula, preferred aspects are also the same. In the formula (1-2), R ^113a and R ^114a ^{are respectively the R 113} and R ¹¹⁴ in the formula (1). The R 113 and R 114 described in the description of R ¹¹³ and R ¹¹⁴ have a direct bond except by a vinyl group which may be substituted. other than the ethylenically unsaturated aromatic ring structure of the bond group or R ¹¹³ and R ¹¹⁴ is not having an ethylenically unsaturated bond group of the same groups are preferred, and does not R ¹¹³ R ¹¹⁴ is The groups having the same ethylenically unsaturated bond are more preferred. In the above R ¹¹³ and R ¹¹⁴ , the group having an ethylenically unsaturated bond other than the aromatic ring directly bonded by the vinyl group which may be substituted, and the above and R ¹¹³ and R ¹¹⁴ do not have an ethylenically unsaturated bond The preferred aspects of the same groups are as described above. The polyimide precursor may include one type of repeating unit represented by formula (1-2) alone, or two or more types.

聚醯亞胺前驅物的重量平均分子量（Mw）較佳為2,000～500,000，更佳為5,000～100,000，進一步較佳為10,000～50,000。又，數量平均分子量（Mn）較佳為800～250,000，更佳為2,000～50,000，進一步較佳為4,000～25,000，尤其較佳為4,000～24,000。The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. In addition, the number average molecular weight (Mn) is preferably 800-250,000, more preferably 2,000-50,000, still more preferably 4,000-25,000, and particularly preferably 4,000-24,000.

聚醯亞胺前驅物的分子量的分散度為1.5～3.5為較佳，2～3為更佳。在本說明書中，分子量的分散度表示將重量平均分子量除以數量平均分子量之值（重量平均分子量/數量平均分子量）。The molecular weight dispersion of the polyimide precursor is preferably 1.5-3.5, more preferably 2-3. In this specification, the degree of molecular weight dispersion means the value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).

聚醯亞胺前驅物可藉由使二羧酸或二羧酸衍生物與二胺進行反應來獲得。較佳為使用鹵化劑對二羧酸或二羧酸衍生物進行鹵化之後，使其與二胺進行反應來獲得。作為獲得具有由可以被取代的乙烯基直接鍵結之芳香環之聚醯亞胺前驅物之方法，可舉出下述方法。（1）使具有由可以被取代的乙烯基直接鍵結之芳香環之四羧酸衍生物與二胺進行反應之方法（2）使四羧酸衍生物與具有由可以被取代的乙烯基直接鍵結之芳香環之二胺進行反應之方法（3）在使四羧酸衍生物與二胺進行反應之後，使所獲得之反應物與具有羥基、環氧基、異氰酸酯基等之苯乙烯衍生物進行反應之方法上述具有由可以被取代的乙烯基直接鍵結之芳香環之四羧酸衍生物和二胺例如藉由使四羧酸衍生物與具有胺基或羥基之苯乙烯衍生物進行反應來獲得。上述具有由可以被取代的乙烯基直接鍵結之芳香環之二胺例如藉由具有羥基之二胺與具有異氰酸酯基、環氧基等之苯乙烯衍生物進行反應來獲得。The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent, and then reacting it with a diamine. As a method of obtaining a polyimide precursor having an aromatic ring directly bonded with a vinyl group which may be substituted, the following methods can be cited. (1) A method of reacting a tetracarboxylic acid derivative having an aromatic ring directly bonded by a substituted vinyl group with a diamine (2) A method of reacting a tetracarboxylic acid derivative with a diamine having an aromatic ring directly bonded to a vinyl group that can be substituted (3) After reacting a tetracarboxylic acid derivative with a diamine, the obtained reactant is reacted with a styrene derivative having a hydroxyl group, an epoxy group, an isocyanate group, etc. The above-mentioned tetracarboxylic acid derivative and diamine having an aromatic ring directly bonded with a vinyl group which may be substituted are obtained, for example, by reacting a tetracarboxylic acid derivative with a styrene derivative having an amino group or a hydroxyl group. The above-mentioned diamine having an aromatic ring directly bonded with a vinyl group that may be substituted is obtained, for example, by reacting a diamine having a hydroxyl group with a styrene derivative having an isocyanate group, an epoxy group, and the like.

聚醯亞胺前驅物的製造方法中，進行反應時，使用有機溶劑為較佳。有機溶劑可以為1種，亦可以為2種以上。In the production method of the polyimide precursor, 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.

作為有機溶劑，能夠依原料適當設定，可例示吡啶、二乙二醇二甲醚（二甘二甲醚）、N-甲基-2-吡咯啶酮及N-乙基-2-吡咯啶酮。As the organic solvent, it can be appropriately set according to the raw material, and examples include pyridine, diethylene glycol dimethyl ether (diglyme), N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone .

製造聚醯亞胺前驅物時，包括析出固體之製程為較佳。具體而言，使反應液中的聚醯亞胺前驅物沉澱於水中並使其溶解於可溶解四氫呋喃等聚醯亞胺前驅物之溶劑，藉此能夠進行固體析出。When manufacturing the polyimide precursor, a process including the precipitation of solids is preferred. Specifically, the polyimide precursor in the reaction liquid is precipitated in water and dissolved in a solvent that can dissolve the polyimide precursor such as tetrahydrofuran, thereby enabling solid precipitation.

〔聚苯并㗁唑前驅物〕聚苯并㗁唑前驅物包含由上述式（2）表示之重複單元為較佳。〔Polybenzoxazole precursor〕 The polybenzoxazole precursor preferably contains a repeating unit represented by the above formula (2).

-R¹²¹ - 在式（2）中，R¹²¹ 表示2價有機基團。作為2價有機基團，包含脂肪族基（碳數1～24為較佳，1～12為更佳，1～6為特佳）及芳香族基（碳數6～22為較佳，6～14為更佳，6～12為特佳）中的至少1種之基團為較佳。作為構成R¹²¹ 之芳香族基，可舉出上述式（1）的R¹¹¹ 的例子。作為上述脂肪族基，直鏈脂肪族基為較佳。R¹²¹ 源自4,4’-氧代二苯甲醯氯為較佳。-R ¹²¹ -In the formula (2), R ¹²¹ represents a divalent organic group. Divalent organic groups include aliphatic groups (with carbon numbers of 1-24 preferably, more preferably from 1-12, particularly preferably from 1 to 6) and aromatic groups (with carbon numbers of 6-22 being preferred, 6 ~14 is more preferred, and 6~12 are particularly preferred) at least one group is preferred. Examples of the aromatic group constituting R ¹²¹ ^{include R 111} in the above formula (1). As the above-mentioned aliphatic group, a straight-chain aliphatic group is preferred. Preferably, R ^{121 is} derived from 4,4'-oxobenzyl chloride.

-R¹²² - 在式（2）中，R¹²² 表示4價有機基團。作為4價有機基團，含義與上述式（1）中的R¹¹⁵ 相同，較佳範圍亦相同。R¹²² 源自2,2’-雙（3-胺基-4-羥基苯基）六氟丙烷為較佳。-R ¹²² -In the formula (2), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the above formula (1), and the preferred range is also the same. Preferably, R ^{122 is} derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

-R¹²³ 及R¹²⁴ - R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價有機基團，含義與上述式（1）中的R¹¹³ 及R¹¹⁴ 相同，較佳範圍亦相同。-R ¹²³ and R ¹²⁴ -R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferred range is also the same.

除了上述式（2）的重複單元以外，聚苯并㗁唑前驅物還可以包含其他種類的重複單元。In addition to the repeating unit of the above formula (2), the polybenzoxazole precursor may also include other types of repeating units.

作為其他種類的重複單元，可舉出由下述式（2-2）表示之重複單元。 [化學式18]

在式（2-2）中，R¹²¹ 表示2價有機基團，R¹²² 表示4價有機基團，R^123a 及R^124a 分別獨立地表示氫原子或1價有機基團，R^123a 及R^124a 不包含由可以被取代的乙烯基直接鍵結之芳香環。Examples of other types of repeating units include repeating units represented by the following formula (2-2). [Chemical formula 18]

In formula (2-2), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, R ^123a and R ^124a each independently represent a hydrogen atom or a monovalent organic group, and R ^123a and R ^124a It does not contain aromatic rings directly bonded by vinyl groups that may be substituted.

在式（2-2）中，R¹²¹ 及R¹²² 的含義分別與式（2）中的R¹²¹ 及R¹²² 相同，較佳態樣亦相同。在式（2-2）中，R^123a 及R^124a 分別為式（1）中的R¹¹³ 及R¹¹⁴ 的說明中記載之R¹¹³ 及R¹¹⁴ 中的具有除了由可以被取代的乙烯基直接鍵結之芳香環以外的乙烯性不飽和鍵之基團或與R¹¹³ 及R¹¹⁴ 中的不具有乙烯性不飽和鍵之基團相同的基團為較佳，與R¹¹³ 及R¹¹⁴ 中的不具有乙烯性不飽和鍵之基團相同的基團為更佳。上述R¹¹³ 及R¹¹⁴ 中的具有除了由可以被取代的乙烯基直接鍵結之芳香環以外的乙烯性不飽和鍵之基團及上述與R¹¹³ 及R¹¹⁴ 中的不具有乙烯性不飽和鍵之基團相同的基團的較佳態樣如上所述。聚苯并㗁唑前驅物可以單獨包含1種由式（2-2）表示之重複單元，亦可以包含2種以上。In the formula (2-2), R ¹²¹ and meaning ¹²¹ and R ¹²² are the same as the formula R (2) is R ^122, preferred aspects are also the same. In the formula (2-2), R ^123a and R ^124a ^{are respectively the R 113} and R ¹¹⁴ in the formula (1). The description of R ¹¹³ and R ¹¹⁴ has a direct bond except for the vinyl group which may be substituted. other than the ethylenically unsaturated aromatic ring structure of the bond group or R ¹¹³ and R ¹¹⁴ is not having an ethylenically unsaturated bond group of the same groups are preferred, and does not R ¹¹³ R ¹¹⁴ is The groups having the same ethylenically unsaturated bond are more preferred. In the above R ¹¹³ and R ¹¹⁴ , the group having an ethylenically unsaturated bond other than the aromatic ring directly bonded by the vinyl group which may be substituted, and the above and R ¹¹³ and R ¹¹⁴ do not have an ethylenically unsaturated bond The preferred aspects of the same groups are as described above. The polybenzoxazole precursor may include one type of repeating unit represented by formula (2-2) alone, or may include two or more types.

又，從能夠抑制伴隨閉環產生之硬化膜的翹曲的觀點考慮，聚苯并㗁唑前驅物還包含由下述式（SL）表示之二胺殘基來作為其他種類的重複單元為較佳。In addition, from the viewpoint of suppressing the warpage of the cured film caused by ring closure, the polybenzoxazole precursor further contains a diamine residue represented by the following formula (SL) as another type of repeating unit .

[化學式19]

[Chemical formula 19]

Z具有a結構和b結構，R^1s 為氫原子或碳數1～10的烴基（較佳為碳數1～6，更佳為碳數1～3），R^2s 為碳數1～10的烴基（較佳為碳數1～6，更佳為碳數1～3），R^3s 、R^4s 、R^5s 、R^6s 中的至少一個為芳香族基（較佳為碳數6～22，更佳為碳數6～18，特佳為碳數6～10），剩餘部分為氫原子或碳數1～30（較佳為碳數1～18，更佳為碳數1～12，特佳為碳數1～6）的有機基團，且可以分別相同亦可以不同。a結構及b結構的聚合可以為嵌段聚合或隨機聚合。Z部分中，較佳為a結構為5～95莫耳%，b結構為95～5莫耳%，a+b為100莫耳%。Z has a structure and a structure b, R ^1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbons (preferably 1 to 6 carbons, more preferably 1 to 3 carbons), and R ^2s is 1 to 10 carbons Hydrocarbyl group (preferably carbon number 1-6, more preferably carbon number 1-3), ^{at least one of R 3s} , R ^4s , R ^5s , and R ^6s is an aromatic group (preferably carbon number 6-22, It is more preferably carbon number 6-18, particularly preferably carbon number 6-10), the remainder is a hydrogen atom or carbon number 1-30 (preferably carbon number 1-18, more preferably carbon number 1-12, especially It is preferably an organic group having 1 to 6 carbon atoms, which 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 Z part, it is preferable that the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a+b is 100 mol%.

在式（SL）中，作為較佳之Z，可舉出b結構中的R^5s 及R^6s 為苯基者。又，由式（SL）表示之結構的分子量為400～4,000為較佳，500～3,000為更佳。分子量能夠藉由通常所使用之凝膠滲透層析法求出。藉由將上述分子量設為上述範圍，能夠兼備降低聚苯并㗁唑前驅物的脫水閉環後的彈性模數，且抑制翹曲之效果和提高溶解性之效果。In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure 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. The molecular weight can be determined by the gel permeation chromatography method generally used. By setting the above-mentioned molecular weight in the above-mentioned range, it is possible to reduce the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure, and to suppress the warpage and improve the solubility.

聚苯并㗁唑前驅物包含由式（SL）表示之二胺殘基作為其他種類的重複單元時，從可提高硬化性樹脂組成物的鹼溶性的方面考慮，進而包含從四羧酸二酐去除酸二酐基之後殘存之四羧酸殘基來作為重複單元為較佳。作為該種四羧酸殘基的例子，可舉出式（1）中的R¹¹⁵ 的例子。When the polybenzoxazole precursor contains a diamine residue represented by the formula (SL) as another type of repeating unit, from the viewpoint of improving the alkali solubility of the curable resin composition, it further includes tetracarboxylic dianhydride The tetracarboxylic acid residue remaining after removing the acid dianhydride group is preferably used as a repeating unit. As an example of such a tetracarboxylic acid residue, an example of R ¹¹⁵ in the formula (1) can be given.

聚苯并㗁唑前驅物的重量平均分子量（Mw）較佳為2,000～500,000，更佳為5,000～100,000，進一步較佳為10,000～50,000。又，數量平均分子量（Mn）較佳為800～250,000，更佳為2,000～50,000，進一步較佳為4,000～25,000。The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. In addition, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000.

聚苯并㗁唑前驅物的分子量的分散度為1.5～3.5為較佳，2～3為更佳。The molecular weight dispersion of the polybenzoxazole precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

本發明的硬化性樹脂組成物中的特定含雜環聚合物前驅物的含量相對於硬化性樹脂組成物的總固體成分為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，60質量%以上為更進一步較佳，70質量%以上為再進一步較佳。又，本發明的硬化性樹脂組成物中的特定含雜環聚合物前驅物的含量相對於硬化性樹脂組成物的總固體成分為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%以下為又進一步較佳，95質量%以下為更進一步較佳。The content of the specific heterocyclic polymer precursor in the curable resin composition of the present invention relative to the total solid content of the curable resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass % Or more is more preferable, 50 mass% or more is more preferable, 60 mass% or more is still more preferable, and 70 mass% or more is still more preferable. Furthermore, the content of the specific heterocyclic-containing polymer precursor in the curable resin composition of the present invention is preferably 99.5% by mass or less with respect to the total solid content of the curable resin composition, and more preferably 99% by mass or less. 98% by mass or less is more preferable, 97% by mass or less is still more preferable, and 95% by mass or less is even more preferable.

本發明的硬化性樹脂組成物可以僅包含1種特定含雜環聚合物前驅物，亦可以包含2種以上。當包含2種以上時，合計量成為上述範圍為較佳。The curable resin composition of the present invention may include only one type of specific heterocyclic-containing polymer precursor, 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.

＜其他含雜環聚合物前驅物＞本發明的硬化性樹脂組成物可以進一步包含除了上述特定含雜環聚合物前驅物以外的其他含雜環聚合物前驅物。作為其他含雜環聚合物前驅物，不包含由可以被取代的乙烯基直接鍵結之芳香環之聚醯亞胺前驅物或不包含由可以被取代的乙烯基直接鍵結之芳香環之聚苯并㗁唑前驅物為較佳，不包含由可以被取代的乙烯基直接鍵結之芳香環之聚醯亞胺前驅物為更佳。＜Other heterocyclic polymer precursors＞ The curable resin composition of the present invention may further contain other heterocyclic-containing polymer precursors in addition to the above-mentioned specific heterocyclic-containing polymer precursors. As other heterocyclic polymer precursors, polyimide precursors that do not contain aromatic rings directly bonded by vinyl groups that can be substituted or polyimide precursors that do not include aromatic rings directly bonded by vinyl groups that can be substituted Benzoazole precursors are preferred, and polyimide precursors that do not contain an aromatic ring directly bonded by a vinyl group that may be substituted are more preferred.

〔不包含由可以被取代的乙烯基直接鍵結之芳香環之聚醯亞胺前驅物〕不包含由可以被取代的乙烯基直接鍵結之芳香環之聚醯亞胺前驅物具有由上述式（1-2）表示之重複單元為較佳。[Does not include polyimide precursors of aromatic rings directly bonded by vinyl groups that can be substituted] The polyimide precursor which does not contain an aromatic ring directly bonded by a vinyl group which may be substituted preferably has a repeating unit represented by the above formula (1-2).

在不包含由可以被取代的乙烯基直接鍵結之芳香環之聚醯亞胺前驅物中，由式（1-2）表示之重複單元可以為1種，亦可以為2種以上。又，可以包含由式（1-2）表示之重複單元的結構異構物。又，除了由上述式（1-2）表示之重複單元以外，聚醯亞胺前驅物還可以包含其他種類的重複單元。In the polyimide precursor that does not include an aromatic ring directly bonded with a vinyl group that may be substituted, the repeating unit represented by the formula (1-2) may be one type or two or more types. Furthermore, it may contain structural isomers of the repeating unit represented by formula (1-2). Moreover, in addition to the repeating unit represented by the above formula (1-2), the polyimide precursor may also include other types of repeating units.

作為本發明中的不包含由可以被取代的乙烯基直接鍵結之芳香環之聚醯亞胺前驅物的一實施形態，可例示總重複單元的50莫耳%以上（進而為70莫耳%以上，尤其為90莫耳%以上）為由式（1-2）表示之重複單元之聚醯亞胺前驅物。作為上限，實際為100莫耳%以下。As an embodiment of the polyimide precursor of the present invention that does not include an aromatic ring directly bonded by a vinyl group which may be substituted, 50 mol% or more (and further 70 mol%) of the total repeating unit can be exemplified. The above, especially 90 mol% or more) is a polyimide precursor of the repeating unit represented by formula (1-2). As the upper limit, it is actually 100 mol% or less.

不包含由可以被取代的乙烯基直接鍵結之芳香環之聚醯亞胺前驅物的重量平均分子量（Mw）較佳為2,000～500,000，更佳為5,000～100,000，進一步較佳為10,000～50,000。又，數量平均分子量（Mn）較佳為800～250,000，更佳為2,000～50,000，進一步較佳為4,000～25,000。The weight average molecular weight (Mw) of the polyimide precursor that does not contain an aromatic ring directly bonded by a vinyl group that may be substituted is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000 . In addition, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000.

不包含由可以被取代的乙烯基直接鍵結之芳香環之聚醯亞胺前驅物的分子量的分散度為1.5～3.5為較佳，2～3為更佳。The molecular weight dispersion of the polyimide precursor that does not contain an aromatic ring directly bonded by a vinyl group that may be substituted is preferably 1.5 to 3.5, and more preferably 2 to 3.

不包含由可以被取代的乙烯基直接鍵結之芳香環之聚醯亞胺前驅物可藉由使二羧酸或二羧酸衍生物與二胺反應來獲得。較佳為使用鹵化劑對二羧酸或二羧酸衍生物進行鹵化之後，使其與二胺進行反應來獲得。The polyimide precursor that does not contain an aromatic ring directly bonded by a vinyl group that may be substituted can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent, and then reacting it with a diamine.

在不包含由可以被取代的乙烯基直接鍵結之芳香環之聚醯亞胺前驅物的製造方法中，反應時使用有機溶劑為較佳。有機溶劑可以為1種，亦可以為2種以上。作為有機溶劑，能夠根據原料適當確定，可例示與在上述特定含雜環聚合物前驅物亦即聚醯亞胺前驅物的合成中使用的有機溶劑相同的有機溶劑。In the production method of a polyimide precursor that does not include an aromatic ring directly bonded with a vinyl group that may be substituted, it is preferable to use an organic solvent during the reaction. The organic solvent may be one type or two or more types. The organic solvent can be appropriately determined according to the raw material, and the same organic solvent as the organic solvent used in the synthesis of the polyimide precursor that is the precursor of the specific heterocyclic-containing polymer can be exemplified.

在製造不包含由可以被取代的乙烯基直接鍵結之芳香環之聚醯亞胺前驅物時，包括析出固體的製程為較佳。具體而言，使反應液中的聚醯亞胺前驅物沉澱於水中並使其溶解於可溶解四氫呋喃等聚醯亞胺前驅物之溶劑，藉此能夠進行固體析出。When producing a polyimide precursor that does not contain an aromatic ring directly bonded by a vinyl group that can be substituted, a process involving precipitation of solids is preferred. Specifically, the polyimide precursor in the reaction liquid is precipitated in water and dissolved in a solvent that can dissolve the polyimide precursor such as tetrahydrofuran, thereby enabling solid precipitation.

〔不包含由可以被取代的乙烯基直接鍵結之芳香環之聚苯并㗁唑前驅物〕不包含由可以被取代的乙烯基直接鍵結之芳香環之聚苯并㗁唑前驅物具有由上述式（2-2）表示之重複單元為較佳。又，不包含由可以被取代的乙烯基直接鍵結之芳香環之聚苯并㗁唑前驅物進一步包含由上述式（SL）表示之二胺殘基作為其他種類的重複單元為較佳。不包含由可以被取代的乙烯基直接鍵結之芳香環之聚苯并㗁唑前驅物包含由式（SL）表示之二胺殘基作為其他種類的重複單元時，從可提高硬化性樹脂組成物的鹼溶性的方面考慮，進一步包含從四羧酸二酐去除酸二酐基之後殘存之四羧酸殘基來作為重複單元為較佳。作為該種四羧酸殘基的例子，可舉出式（1）中的R¹¹⁵ 的例子。[Polybenzoxazole precursors that do not contain aromatic rings directly bonded to vinyl groups that can be substituted] Polybenzoxazole precursors that do not include aromatic rings that can be directly bonded to vinyl groups that can be substituted The repeating unit represented by the above formula (2-2) is preferred. Moreover, it is preferable that the polybenzoxazole precursor which does not contain the aromatic ring directly bonded by the vinyl group which may be substituted further contains the diamine residue represented by the said formula (SL) as another kind of repeating unit. The polybenzoxazole precursor that does not contain an aromatic ring directly bonded by a vinyl group that can be substituted contains a diamine residue represented by the formula (SL) as another type of repeating unit, which can improve the composition of the curable resin In view of the alkali solubility of the substance, it is preferable to further include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride as a repeating unit. As an example of such a tetracarboxylic acid residue, an example of R ¹¹⁵ in the formula (1) can be given.

不包含由可以被取代的乙烯基直接鍵結之芳香環之聚苯并㗁唑前驅物的重量平均分子量（Mw）較佳為2,000～500,000，更佳為5,000～100,000，進一步較佳為10,000～50,000。又，數量平均分子量（Mn）較佳為800～250,000，更佳為2,000～50,000，進一步較佳為4,000～25,000。The weight average molecular weight (Mw) of the polybenzoxazole precursor that does not contain an aromatic ring directly bonded by a vinyl group that may be substituted is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. In addition, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000.

不包含由可以被取代的乙烯基直接鍵結之芳香環之聚苯并㗁唑前驅物的分子量的分散度為1.5～3.5為較佳，2～3為更佳。The molecular weight dispersion of the polybenzoxazole precursor that does not include an aromatic ring directly bonded with a vinyl group that may be substituted is preferably 1.5 to 3.5, and more preferably 2 to 3.

〔含量〕本發明的硬化性樹脂組成物包含其他含雜環聚合物前驅物時，其他含雜環聚合物前驅物的含量相對於硬化性樹脂組成物的總固體成分為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。又，本發明的硬化性樹脂組成物中的其他含雜環聚合物前驅物的含量相對於硬化性樹脂組成物的總固體成分為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%以下為又進一步較佳，95質量%以下為更進一步較佳。本發明的硬化性樹脂組成物可以僅包含1種其他含雜環聚合物前驅物，亦可以包含2種以上。當包含2種以上時，合計量成為上述範圍為較佳。〔content〕 When the curable resin composition of the present invention contains other heterocyclic-containing polymer precursors, the content of the other heterocyclic-containing polymer precursors is preferably 20% by mass or more relative to the total solid content of the curable resin composition, 30 The mass% or more is more preferable, and 40 mass% or more is more preferable. In addition, the content of the other heterocyclic-containing polymer precursor in the curable resin composition of the present invention is preferably 99.5% by mass or less, and more preferably 99% by mass or less with respect to the total solid content of the curable resin composition. 98% by mass or less is more preferable, 97% by mass or less is still more preferable, and 95% by mass or less is even more preferable. The curable resin composition of the present invention may include only one type of other heterocyclic-containing polymer precursors, 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.

＜在分子內具有2個以上乙烯性不飽和基之化合物＞本發明的硬化性樹脂組成物包含在分子內具有2個以上乙烯性不飽和基之化合物為較佳。在分子內具有2個以上乙烯性不飽和基之化合物係在分子內具有2個以上由可以被取代的乙烯基直接鍵結之芳香環之化合物為較佳。＜Compounds having two or more ethylenically unsaturated groups in the molecule＞ The curable resin composition of the present invention preferably contains a compound having two or more ethylenically unsaturated groups in the molecule. The compound having two or more ethylenically unsaturated groups in the molecule is preferably a compound having two or more aromatic rings in the molecule directly bonded with a vinyl group which may be substituted.

＜在分子內具有2個以上由可以被取代的乙烯基直接鍵結之芳香環之化合物＞從進一步提高耐藥品性的觀點考慮，本發明的硬化性樹脂組成物包含在分子內具有2個以上由可以被取代的乙烯基直接鍵結之芳香環之化合物（以下，亦稱為“特定聚合性化合物”。）為較佳。＜Compounds with two or more aromatic rings directly bonded by a substituted vinyl group in the molecule＞ From the viewpoint of further improving chemical resistance, the curable resin composition of the present invention contains a compound having two or more aromatic rings directly bonded to a vinyl group that may be substituted in the molecule (hereinafter, also referred to as "specific polymerization Sexual compound".) is preferred.

〔由可以被取代的乙烯基直接鍵結之芳香環〕在本說明書中，由可以被取代的乙烯基直接鍵結之芳香環表示可以被取代的乙烯基的雙鍵中的一個碳原子直接鍵結於芳香環結構上的結構。上述芳香環可以具有烷基、鹵素基等公知的取代基。上述芳香環可以為芳香族烴環，亦可以為芳香族雜環，在上述芳香族烴環或芳香族雜環上可以縮合有芳香族烴環或脂肪族烴環、或者芳香族雜環或脂肪族雜環。又，該等芳香族烴環、脂肪族烴環、芳香族雜環或脂肪族雜環可以分別具有烷基、鹵素基等公知的取代基。上述由可以被取代的乙烯基直接鍵結之芳香環中的芳香環係芳香族烴環為較佳，苯環為更佳。亦即，特定聚合性化合物包含乙烯基苯基作為包含上述乙烯基直接鍵結之芳香環之基團為較佳。特定聚合性化合物中的乙烯基直接鍵結之芳香環的數量為2～10為較佳，2～6為更佳，2～4為進一步較佳，2或3為特佳。又，特定聚合性化合物可以具有除了上述乙烯基直接鍵結之芳香環中的乙烯基以外的乙烯性不飽和基，但作為特定聚合性化合物的較佳態樣，可舉出不具有除了上述乙烯基以外的乙烯性不飽和基之態樣。又，特定聚合性化合物中的乙烯基直接鍵結之芳香環中的乙烯基具有自由基聚合性為較佳。又，作為可以被取代的乙烯基中的取代基，可舉出烷基等，例如可舉出乙烯基中的α氫被甲基等取代之態樣。〔Aromatic ring directly bonded by vinyl which can be substituted〕 In this specification, the aromatic ring directly bonded by a vinyl group that may be substituted means a structure in which one carbon atom in the double bond of the vinyl group that may be substituted is directly bonded to the aromatic ring structure. The said aromatic ring may have well-known substituents, such as an alkyl group and a halogen group. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The aromatic hydrocarbon ring or the aromatic heterocyclic ring may be condensed with an aromatic hydrocarbon ring or aliphatic hydrocarbon ring, or an aromatic heterocyclic ring or aliphatic ring. Group heterocycle. In addition, the aromatic hydrocarbon ring, aliphatic hydrocarbon ring, aromatic heterocyclic ring, or aliphatic heterocyclic ring may each have a known substituent such as an alkyl group and a halogen group. The aromatic ring system aromatic hydrocarbon ring in the aromatic ring directly bonded by the optionally substituted vinyl group is preferable, and the benzene ring is more preferable. That is, it is preferable that the specific polymerizable compound contains a vinyl phenyl group as the group containing the aromatic ring to which the above-mentioned vinyl group is directly bonded. The number of aromatic rings to which the vinyl group in the specific polymerizable compound is directly bonded is preferably 2-10, more preferably 2-6, more preferably 2-4, and particularly preferably 2 or 3. In addition, the specific polymerizable compound may have an ethylenically unsaturated group other than the vinyl group in the aromatic ring to which the vinyl group is directly bonded. However, as a preferred aspect of the specific polymerizable compound, there may be no other than the vinyl group. The state of ethylenically unsaturated groups other than the base. Moreover, it is preferable that the vinyl group in the aromatic ring to which the vinyl group in the specific polymerizable compound is directly bonded has radical polymerizability. In addition, examples of the substituent in the vinyl group that may be substituted include an alkyl group and the like. For example, an aspect in which the α hydrogen in the vinyl group is substituted by a methyl group or the like can be mentioned.

又，特定聚合性化合物1g中的上述乙烯基的量（莫耳量）為2～8mol/g為較佳，3～7mol/g為更佳。In addition, the amount (molar amount) of the vinyl group in 1 g of the specific polymerizable compound is preferably 2 to 8 mol/g, and more preferably 3 to 7 mol/g.

〔由式（1-1）表示之化合物〕特定聚合性化合物係由下述式（1-1）表示之化合物為較佳。 [化學式20]

在式（1-1）中，Z係選自包括2價以上的飽和脂肪族烴基、2價以上的不飽和脂肪族烴基、2價以上的烴環基、-O-、-S-、-N（R^A ）-、-C（=O）-O-、-C（R^A ）=N-、-C（=O）-、-S（=O）₂ -、2價以上的雜環基及該等鍵結2個以上之基團之群組中之m價連結基，R^A 表示氫原子、烷基或芳基，R^A 存在複數個時，複數個R^A 可以相同，亦可以不同，R¹ 分別獨立地表示氫原子或甲基，m表示2～6的整數。式（1-1）中的苯環中的氫原子可以被取代基取代。作為取代基，只要可實現本發明的目的，則並不特別限定，能夠使用公知的取代基。又，不具有該等取代基之態樣，在本發明中亦為較佳態樣。[Compound represented by formula (1-1)] The specific polymerizable compound is preferably a compound represented by the following formula (1-1). [Chemical formula 20]

In formula (1-1), Z is selected from the group consisting of saturated aliphatic hydrocarbon groups with a valence of two or more, unsaturated aliphatic hydrocarbon groups with a valence of two or more, a hydrocarbon ring group with a valence of two or more, -O-, -S-,- N(R ^A )-, -C(=O)-O-, -C(R ^A )=N-, -C(=O)-, -S(=O) ₂ -, heterocyclic rings with more than divalent m group and these divalent groups are bonded two or more of the group of the linking group, R ^A represents a hydrogen atom, an alkyl group or an aryl group, in the presence of a plurality of R ^A, R ^A plurality may be the same, can also Different, R ¹ each independently represents a hydrogen atom or a methyl group, and m represents an integer of 2-6. The hydrogen atom in the benzene ring in formula (1-1) may be substituted with a substituent. As a substituent, as long as it can achieve the objective of this invention, it will not specifically limit, A well-known substituent can be used. In addition, the aspect that does not have these substituents is also a preferred aspect in the present invention.

-Z- 作為Z中的2價以上的脂肪族飽和烴基，碳數1～100的脂肪族飽和烴基為較佳，碳數2～30的脂肪族飽和烴基為更佳。上述2價以上的脂肪族飽和烴基係2～20價脂肪族飽和烴基為較佳，2～10價脂肪族飽和烴基為較佳，2～6價脂肪族飽和烴基為更佳。又，只要可獲得本發明的效果，則上述2價以上的脂肪族飽和烴基可以具有公知的取代基。作為Z中的2價以上的脂肪族不飽和烴基，碳數2～100的脂肪族不飽和烴基為較佳，碳數2～30的脂肪族不飽和烴基為更佳。上述2價以上的脂肪族不飽和烴基係2～20價脂肪族不飽和烴基為較佳，2～10價脂肪族不飽和烴基為較佳，2～6價脂肪族不飽和烴基為更佳。又，只要可獲得本發明的效果，則上述2價以上的脂肪族不飽和烴基可以具有公知的取代基。又，在式（1-1）中，Z係包含選自包括2價以上的烴環基及2價以上的雜環基之群組中之至少1種之基團為較佳。-Z- As the aliphatic saturated hydrocarbon group having a valence of 2 or higher in Z, aliphatic saturated hydrocarbon groups having 1 to 100 carbon atoms are preferred, and aliphatic saturated hydrocarbon groups having 2 to 30 carbon atoms are more preferred. The aliphatic saturated hydrocarbon group having a valence of 2 or higher is preferably a 2-20 valent aliphatic saturated hydrocarbon group, a 2-10 valent aliphatic saturated hydrocarbon group is more preferred, and a 2-6 valent aliphatic saturated hydrocarbon group is more preferred. Moreover, as long as the effect of the present invention can be obtained, the aliphatic saturated hydrocarbon group having a valence of 2 or higher may have a known substituent. As the aliphatic unsaturated hydrocarbon group having a valence of 2 or higher in Z, an aliphatic unsaturated hydrocarbon group having 2 to 100 carbon atoms is preferable, and an aliphatic unsaturated hydrocarbon group having 2 to 30 carbon atoms is more preferable. The above-mentioned aliphatic unsaturated hydrocarbon group having a valence of 2 or higher is preferably a 2-20 valence aliphatic unsaturated hydrocarbon group, a 2-10 valence aliphatic unsaturated hydrocarbon group is more preferable, and a 2-6 valence aliphatic unsaturated hydrocarbon group is more preferable. Moreover, as long as the effect of the present invention can be obtained, the aliphatic unsaturated hydrocarbon group having a valence of 2 or higher may have a known substituent. Furthermore, in the formula (1-1), Z preferably includes at least one group selected from the group consisting of a hydrocarbon ring group having a valence of two or more and a heterocyclic group having a valence of two or more.

作為Z中的2價以上的烴環基，從烴環去除2～4個氫原子之2～4價基團為較佳。 Z中的2價以上的烴環基中的烴環的環員數為6～20為較佳，6～12為更佳，6為進一步較佳。作為Z中的2價以上的烴環基中的烴環，芳香族烴環為較佳，苯環為更佳。As the divalent or higher hydrocarbon ring group in Z, a divalent to tetravalent group obtained by removing 2 to 4 hydrogen atoms from the hydrocarbon ring is preferred. The number of ring members of the hydrocarbon ring in the bivalent or higher hydrocarbon ring group in Z is preferably 6-20, more preferably 6-12, and still more preferably 6. As the hydrocarbon ring in the bivalent or higher hydrocarbon ring group in Z, an aromatic hydrocarbon ring is preferred, and a benzene ring is more preferred.

作為Z中的2價以上的雜環基，從雜環去除2～4個氫原子之2～4價基團為較佳。作為上述雜環中的雜原子（hetero atom），係氧原子、氮原子、硫原子或硒原子為較佳。又，作為環員包含在雜環中的雜原子數為1～4為較佳。作為Z中的2價以上的雜環基中的雜環，芳香族雜環為較佳，環員數5～20的芳香族雜環為較佳，5～20的芳香族雜環為更佳。上述雜環可以為複數個雜環的縮合環，亦可以為雜環與芳香族烴環的縮合環。雜環係縮合環時，作為縮合環中包含之單環的雜環的環員數為5～6為較佳。As the divalent or higher heterocyclic group in Z, a divalent to tetravalent group obtained by removing 2 to 4 hydrogen atoms from the heterocyclic ring is preferred. As the hetero atom in the above heterocyclic ring, an oxygen atom, a nitrogen atom, a sulfur atom, or a selenium atom is preferred. Furthermore, the number of heteroatoms contained in the heterocyclic ring as a ring member is preferably 1 to 4. As the heterocyclic ring in the bivalent or higher heterocyclic group in Z, an aromatic heterocyclic ring is preferable, an aromatic heterocyclic ring having 5 to 20 ring members is preferable, and an aromatic heterocyclic ring having 5 to 20 ring members is more preferable . The heterocyclic ring may be a condensed ring of a plurality of heterocyclic rings, or a condensed ring of a heterocyclic ring and an aromatic hydrocarbon ring. When a heterocyclic ring is a condensed ring, the number of ring members of the heterocyclic ring as a monocyclic ring contained in the condensed ring is preferably 5-6.

從提高分子間相互作用，進一步提高耐藥品性之觀點考慮，作為2價以上的雜環基中的雜環，Z包含選自包括吡咯環、吡唑環、咪唑環、***環、四唑環、異㗁唑環、㗁唑環、㗁二唑環、異噻唑環、噻唑環、噻二唑環、噻***環、吲哚環、吲唑環、苯并咪唑環、苯并***環、苯并㗁唑環、苯并噻唑環、苯并硒唑環、苯并噻二唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、三𠯤環、喹啉環、喹㗁啉環、呋喃環及噻吩環之群組中之至少1種雜環為較佳，包含選自包括吡唑環、咪唑環、***環、異㗁唑環、㗁唑環、㗁二唑環、異噻唑環、噻唑環、噻二唑環、噻***環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、三𠯤環、喹啉環、喹㗁啉環、呋喃環及噻吩環之群組中之至少1種雜環為更佳。From the viewpoint of improving the intermolecular interaction and further improving the chemical resistance, as the heterocyclic ring in the heterocyclic group having a valence of more than two, Z is selected from the group consisting of pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole Ring, isoazole ring, azole ring, oxadiazole ring, isothiazole ring, thiazole ring, thiadiazole ring, thiatriazole ring, indole ring, indazole ring, benzimidazole ring, benzotriazole Ring, benzoxazole ring, benzothiazole ring, benzoselenazole ring, benzothiadiazole ring, pyridine ring, pyridine ring, pyrimidine ring, pyrimidine ring, tricyclic ring, quinoline ring, quinoline At least one heterocyclic ring in the group of morpholine ring, furan ring and thiophene ring is preferred, and includes a ring selected from the group consisting of pyrazole ring, imidazole ring, triazole ring, isooxazole ring, oxazole ring, and diazole ring , Isothiazole ring, thiazole ring, thiadiazole ring, thiatriazole ring, pyridine ring, pyrimidine ring, pyrimidine ring, pyridine ring, tricyclic ring, quinoline ring, quinoline ring, furan ring and thiophene ring At least one heterocyclic ring in the group is more preferred.

又，Z係由下述式（Z-1）或式（Z-2）表示之基團為較佳。 [化學式21]

在式（Z-1）或式（Z-2）中，A1及A2分別獨立地表示烴環基或雜環基，L^Z1 ～L^Z5 分別獨立地表示選自包括伸烷基、伸烯基、烴環基、-O-、-S-、-N（R^A ）-、-C（=O）-O-、-C（R^A ）=N-、-C（=O）-、-S（=O）₂ -、雜環基及該等鍵結2個以上之基團之群組中之2價連結基，R^A 表示氫原子、烷基或芳基，R^A 存在複數個時，複數個R^A 可以相同，亦可以不同，*分別獨立地表示與式（1-1）中的苯環的鍵結部位。In addition, Z is preferably a group represented by the following formula (Z-1) or formula (Z-2). [Chemical formula 21]

In formula (Z-1) or formula (Z-2), A1 and A2 each independently represent a hydrocarbon ring group or a heterocyclic group, and L ^Z1 to L ^Z5 each independently represent selected from the group including alkylene and alkenylene , hydrocarbon ring group, -O -, - S -, - N (R A) -, - C (= O) -O -, - C (R A) = N -, - C (= O) -, - S(=O) ₂ -, a heterocyclic group and a divalent linking group in the group of these groups bonding two or more groups, R ^A represents a hydrogen atom, an alkyl group or an aryl group, when there are plural ^{R A groups} , a plurality of R ^a may be the same, may be also different, each independently represent a * bonded portion in the formula (1-1) a benzene ring.

＜＜A1及A2＞＞在式（Z-1）或式（Z-2）中，A1及A2分別獨立地為芳香族烴環基或芳香族雜環基為較佳。作為上述芳香族烴環基中的芳香族烴環，苯環為較佳。作為上述芳香族雜環基中的芳香族雜環，吡咯環、吡唑環、咪唑環、***環、四唑環、異㗁唑環、㗁唑環、㗁二唑環、異噻唑環、噻唑環、噻二唑環、噻***環、吲哚環、吲唑環、苯并咪唑環、苯并***環、苯并㗁唑環、苯并噻唑環、苯并硒唑環、苯并噻二唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、三𠯤環、喹啉環、喹㗁啉環、呋喃環或噻吩環為較佳，吡唑環、咪唑環、***環、異㗁唑環、㗁唑環、㗁二唑環、異噻唑環、噻唑環、噻二唑環、噻***環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、三𠯤環、喹啉環、喹㗁啉環、呋喃環或噻吩環為更佳。＜＜A1 and A2＞＞ In the formula (Z-1) or the formula (Z-2), it is preferable that A1 and A2 are each independently an aromatic hydrocarbon ring group or an aromatic heterocyclic group. As the aromatic hydrocarbon ring in the above-mentioned aromatic hydrocarbon ring group, a benzene ring is preferred. As the aromatic heterocyclic ring in the above-mentioned aromatic heterocyclic group, a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an isoazole ring, an azole ring, a diazole ring, an isothiazole ring, Thiazole ring, thiadiazole ring, thiatriazole ring, indole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzoselazole ring, benzene A thiadiazole ring, a pyridine ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a tricyclic ring, a quinoline ring, a quinoline ring, a furan ring or a thiophene ring are preferred, and the pyrazole ring, imidazole ring, tri Azole ring, isoazole ring, azole ring, diazole ring, isothiazole ring, thiazole ring, thiadiazole ring, thiatriazole ring, pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, triazole ring A ring, a quinoline ring, a quinoline ring, a furan ring or a thiophene ring is more preferable.

在式（Z-1）或式（Z-2）中，L^Z1 ～L^Z5 分別獨立地表示選自包括伸烷基、2價芳香族烴環基、-O-、-S-、-N（R^A ）-、-C（=O）-O-、-C（R^A ）=N-、-C（=O）-、-S（=O）₂ -、2價芳香族雜環基及該等鍵結2個以上之基團之群組中之2價連結基為較佳，2個以上伸烷基、2價芳香族烴環基、-O-、-S-、-N（R^A ）-鍵結之2價連結基為更佳。式（Z-1）或式（Z-2）中的R^A 的含義與上述式（1-1）中的R^A 相同，較佳態樣亦相同。作為上述2價芳香族烴環基，苯基為較佳。作為上述2價芳香族雜環基，從吡咯環、吡唑環、咪唑環、***環、四唑環、異㗁唑環、㗁唑環、㗁二唑環、異噻唑環、噻唑環、噻二唑環、噻***環、吲哚環、吲唑環、苯并咪唑環、苯并***環、苯并㗁唑環、苯并噻唑環、苯并硒唑環、苯并噻二唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、三𠯤環、喹啉環、喹㗁啉環、呋喃環或噻吩環去除2個氫原子之2價芳香族雜環基為較佳，從吡唑環、咪唑環、***環、異㗁唑環、㗁唑環、㗁二唑環、異噻唑環、噻唑環、噻二唑環、噻***環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、三𠯤環、喹啉環、喹㗁啉環、呋喃環或噻吩環去除2個氫原子之2價芳香族雜環基為更佳。In formula (Z-1) or formula (Z-2), L ^Z1 to L ^Z5 are each independently selected from the group consisting of alkylene, divalent aromatic hydrocarbon ring group, -O-, -S-, -N ^{(R A) -, - C} (= O) -O -, - C (R A) = N -, - C (= O) -, - S (= O) 2 -, 2 divalent aromatic heterocyclic group And the divalent linking group in the group bonding two or more groups is preferable, and two or more alkylene groups, divalent aromatic hydrocarbon ring groups, -O-, -S-, -N ( R ^A )-The divalent linking group of the bond is better. Within the meaning of the formula (Z-1) or formula (Z-2) R ^A in the above formula (1-1) R ^A same preferred aspects are also the same. As the above-mentioned divalent aromatic hydrocarbon ring group, a phenyl group is preferred. As the above-mentioned divalent aromatic heterocyclic group, a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an isoazole ring, an azole ring, a diazole ring, an isothiazole ring, a thiazole ring, Thiadiazole ring, thiatriazole ring, indole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzoselazole ring, benzothiadiene Azole ring, pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, tris ring, quinoline ring, quinoline ring, furan ring, or thiophene ring, and the divalent aromatic heterocyclic group with 2 hydrogen atoms removed is more Preferably, from pyrazole ring, imidazole ring, triazole ring, isoazole ring, azole ring, diazole ring, isothiazole ring, thiazole ring, thiadiazole ring, thiatriazole ring, pyridine ring, and Ring, pyrimidine ring, pyridine ring, tricyclic ring, quinoline ring, quinoline ring, furan ring, or thiophene ring are more preferably divalent aromatic heterocyclic groups with two hydrogen atoms removed.

-R^A - 在式（1-1）中，R^A 表示氫原子、烷基或芳基，氫原子、碳數1～4的烷基或苯基為較佳，氫原子為更佳。-R ^A - in the formula (1-1), R ^A represents a hydrogen atom, an alkyl group or an aryl group, a hydrogen atom, a C 1-4 alkyl or phenyl are preferred, more preferably a hydrogen atom.

-R¹ - 在式（1-1）中，R¹ 表示氫原子或甲基，氫原子為更佳。-R ¹ -In the formula (1-1), R ¹ represents a hydrogen atom or a methyl group, more preferably a hydrogen atom.

-m- 在式（1-1）中，m表示2～6的整數，2～4的整數為較佳，2或3為更佳。-m- In formula (1-1), m represents an integer of 2 to 6, preferably an integer of 2 to 4, and more preferably 2 or 3.

在特定聚合性化合物中，sp³ 碳與Z中的除氫原子以外的所有原子數的比例為0.2～0.4為較佳。其中，sp³ 碳與Z中的除氫原子以外的所有原子數的比例係藉由“Z中包含之sp³ 碳數/Z中的除氫原子以外的所有原子數”算出的值。In the specific polymerizable compound, ^{the ratio of the sp 3} carbon to the number of atoms in Z except for hydrogen atoms is preferably 0.2 to 0.4. Wherein the ratio of the number of all atoms excluding hydrogen atom SP ³ and Z is carbon-based, "the number of all atoms other than hydrogen atoms contained in the SP Z ³ carbon atoms / Z of the" value calculated by.

〔分子量〕特定聚合性化合物的分子量例如考慮環化溫度、揮發性等來確定即可，200以上為較佳，250以上為更佳，300以上為更佳，400以上為進一步較佳。作為上限，並無特別限定，2,000以下為較佳。〔Molecular Weight〕 The molecular weight of the specific polymerizable compound may be determined in consideration of, for example, the cyclization temperature, volatility, etc., preferably 200 or more, more preferably 250 or more, more preferably 300 or more, and more preferably 400 or more. The upper limit is not particularly limited, but 2,000 or less is preferable.

〔具體例〕作為特定聚合性化合物，可舉出下述化合物，但並不限定於此。 [化學式22]

[化學式23]

[化學式24]

[Specific Examples] As the specific polymerizable compound, the following compounds may be mentioned, but they are not limited to these. [Chemical formula 22]

[Chemical formula 23]

[Chemical formula 24]

〔合成方法〕例如藉由下述方法合成特定聚合性化合物。例如，（B-1）～（B-5）、（B-8）或（B-12）等化合物可藉由使多價巰基化合物與鹵代甲基苯乙烯進行反應等公知的硫醚化反應來獲得。（B-6）、（B-7）、（B-9）或（B-11）等化合物可藉由使多元醇化合物與鹵代甲基苯乙烯或鹵素化苯乙烯進行反應等公知的醚化反應來獲得。（B-10）等化合物可藉由使多元醇化合物與乙烯基苯甲酸鹵化物進行反應等公知的酯化反應來獲得。〔resolve resolution〕 For example, the specific polymerizable compound is synthesized by the following method. For example, compounds such as (B-1) to (B-5), (B-8) or (B-12) can be thioetherified by reacting a polyvalent mercapto compound with a halogenated methyl styrene, etc. Response to get. Compounds such as (B-6), (B-7), (B-9) or (B-11) can be obtained by reacting a polyol compound with halogenated methyl styrene or halogenated styrene and other known ethers Chemical reaction to obtain. Compounds such as (B-10) can be obtained by a known esterification reaction such as a reaction between a polyol compound and a vinyl benzoic acid halide.

〔含量〕本發明的硬化性樹脂組成物包含特定聚合性化合物時，從提高硬化性樹脂組成物的保存穩定性及所獲得之硬化膜的斷裂伸長率等觀點考慮，特定聚合性化合物的含量相對於硬化性樹脂組成物的總固體成分為0.005～50質量%為較佳。下限為0.05質量%以上為更佳，0.5質量%以上為進一步較佳，1質量%以上為特佳，3質量%以上為最佳。從硬化膜的機械特性的觀點考慮，上述含量的上限為40質量%以下為更佳，30質量%以下為進一步較佳，20質量%以下為特佳。本發明的硬化性樹脂組成物可以僅包含1種特定聚合性化合物，亦可以包含2種以上。當包含2種以上時，合計量成為上述範圍為較佳。〔content〕 When the curable resin composition of the present invention contains a specific polymerizable compound, from the viewpoints of improving the storage stability of the curable resin composition and the elongation at break of the cured film obtained, the content of the specific polymerizable compound is relative to the curability The total solid content of the resin composition is preferably 0.005 to 50% by mass. The lower limit is more preferably 0.05% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and most preferably 3% by mass or more. From the viewpoint of the mechanical properties of the cured film, the upper limit of the content is more preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. The curable resin composition of the present invention may include only one type of specific polymerizable compound, 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.

＜其他多官能聚合性化合物＞在分子內具有2個以上乙烯性不飽和基之化合物可以為具有2個以上除了由可以被取代的乙烯基直接鍵結之芳香環以外的乙烯性不飽和基之化合物（亦稱為“其他多官能聚合性化合物”。）。其他多官能聚合性化合物可以具有1個由可以被取代的乙烯基直接鍵結之芳香環，亦可以不具有由可以被取代的乙烯基直接鍵結之芳香環。將具有2個以上由可以被取代的乙烯基直接鍵結之芳香環且具有2個以上除了由可以被取代的乙烯基直接鍵結之芳香環以外的乙烯性不飽和基之化合物設為符合上述特定聚合性化合物但不符合其他多官能聚合性化合物者。＜Other polyfunctional polymerizable compounds＞ A compound having two or more ethylenically unsaturated groups in the molecule may be a compound having two or more ethylenically unsaturated groups other than the aromatic ring directly bonded by the vinyl group that may be substituted (also referred to as "other multiple Functional polymerizable compound".). The other polyfunctional polymerizable compound may have an aromatic ring directly bonded to the vinyl group that may be substituted, or may not have the aromatic ring directly bonded to the vinyl group that may be substituted. A compound having two or more aromatic rings directly bonded to a vinyl group that may be substituted and two or more ethylenically unsaturated groups other than the aromatic ring directly bonded to a vinyl group that may be substituted is set to meet the above Specific polymerizable compound but not compatible with other polyfunctional polymerizable compounds.

作為其他多官能聚合性化合物中的具有乙烯性不飽和基之基團，可舉出乙烯基、烯丙基、乙烯基苯基、（甲基）丙烯醯基等，該等中（甲基）丙烯醯基為較佳，從反應性的觀點考慮，（甲基）丙烯醯氧基為更佳。Examples of groups having ethylenically unsaturated groups in other polyfunctional polymerizable compounds include vinyl groups, allyl groups, vinyl phenyl groups, (meth)acryloyl groups, and the like, among which (methyl) An acryloyl group is preferable, and from the viewpoint of reactivity, a (meth)acryloyloxy group is more preferable.

其他多官能聚合性化合物中的具有乙烯性不飽和基之基團的數量可以為1個，亦可以為2個以上，3個以上為較佳。上限為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 groups having ethylenically unsaturated groups in other polyfunctional polymerizable compounds may be one or two or more, preferably three or more. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

其他多官能聚合性化合物的分子量為2,000以下為較佳，1,500以下為更佳，900以下為進一步較佳。其他多官能聚合性化合物的分子量的下限為100以上為較佳。The molecular weight of other polyfunctional polymerizable compounds is preferably 2,000 or less, more preferably 1,500 or less, and more preferably 900 or less. The lower limit of the molecular weight of other polyfunctional polymerizable compounds is preferably 100 or more.

從顯影性的觀點考慮，其他多官能聚合性化合物包含至少1種2官能以上的多官能聚合性化合物為較佳，包含至少1種3官能以上的多官能聚合性化合物為更佳。又，亦可以為2官能的多官能聚合性化合物與3官能以上的多官能聚合性化合物的混合物。 2官能的多官能聚合性化合物表示具有2個上述之具有乙烯性不飽和基之基團之多官能聚合性化合物。From the viewpoint of developability, the other polyfunctional polymerizable compound preferably contains at least one type of bifunctional or higher polyfunctional polymerizable compound, and more preferably contains at least one type of trifunctional or higher polyfunctional polymerizable compound. In addition, it may be a mixture of a bifunctional polyfunctional polymerizable compound and a trifunctional or higher polyfunctional polymerizable compound. The bifunctional polyfunctional polymerizable compound means a polyfunctional polymerizable compound having two groups having the above-mentioned ethylenically unsaturated group.

作為其他多官能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、衣康酸、巴豆酸、異巴豆酸、順丁烯二酸等）或其酯類、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、氫硫基等親和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，具有異氰酸酯基或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醇類、胺類、硫醇類的加成反應物，進而具有鹵素基或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醇類、胺類、硫醇類的取代反應物亦為較佳。又，作為另一例，替代上述不飽和羧酸，能夠使用被不飽和膦酸、苯乙烯等乙烯基苯衍生物、乙烯醚、烯丙醚等取代之化合物組。作為具體例，能夠參考日本特開2016-027357號公報的0113～0122段的記載，該等內容編入本說明書中。Specific examples of other polyfunctional polymerizable compounds include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters, The amides are preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reactants of unsaturated carboxylic acid esters or amides having affinity substituents such as hydroxyl groups, amino groups, sulfhydryl groups, and monofunctional or polyfunctional isocyanates or epoxy groups can also be preferably used, Dehydration condensation reaction product with monofunctional or polyfunctional carboxylic acid, etc. In addition, an addition reaction product of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and further having halogen groups Or a substitution reaction product of unsaturated carboxylic acid esters or amides with detachable substituents such as toluene sulfonyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols is also preferred. As another example, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds substituted with unsaturated phosphonic acid, vinyl benzene derivatives such as styrene, vinyl ether, allyl ether, and the like can be used. 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，關於其他多官能聚合性化合物，在常壓下具有100℃以上的沸點的化合物亦較佳。作為其例，可舉出聚乙二醇二（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、新戊四醇三（甲基）丙烯酸酯、新戊四醇四（甲基）丙烯酸酯、二新戊四醇五（甲基）丙烯酸酯、二新戊四醇六（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）異三聚氰酸酯、甘油或三羥甲基乙烷等在多官能醇中加成環氧乙烷或環氧丙烷後進行（甲基）丙烯酸酯化之化合物、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（甲基）丙烯酸胺基甲酸酯類、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）丙烯酸的反應產物的環氧丙烯酸酯類等多官能的丙烯酸酯或甲基丙烯酸酯；以及該等的混合物。又，日本特開2008-292970號公報的0254～0257段中記載之化合物亦較佳。又，還能夠舉出使多官能羧酸與（甲基）丙烯酸縮水甘油酯等具有環狀醚基及乙烯性不飽和鍵之化合物進行反應而獲得的多官能（甲基）丙烯酸酯等。Moreover, with regard to other polyfunctional polymerizable compounds, compounds having a boiling point of 100°C or higher under normal pressure are also preferable. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl erythritol tri (Meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dine pentaerythritol penta (meth) acrylate, dine pentaerythritol hexa (meth) acrylate, hexanediol (meth) Base) acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trimethylolethane, etc. in multifunctional alcohol Compounds in which ethylene oxide or propylene oxide is added and then (meth)acrylated, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Application Publication No. 51-037193, etc. (Meth) acrylic urethanes described in the gazette, JP 48-064183, JP 49-043191, and JP 52-030490, polyester acrylates described in each gazette Types, polyfunctional acrylates or methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid; and mixtures of these. In addition, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also preferable. In addition, a polyfunctional (meth)acrylate 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 can also be mentioned.

又，作為除了上述以外的較佳之其他多官能聚合性化合物，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茀環，且具有2個以上的包含乙烯性不飽和鍵的基團的化合物或卡多（cardo）樹脂。In addition, as other preferred polyfunctional polymerizable compounds other than the above, it is also possible to use those described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, and Japanese Patent No. 4364216. A compound or cardo resin that has a ring and has two or more ethylenically unsaturated bond-containing groups.

進而，作為其他例子，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的化合物。進而，還能夠使用“Journal of the Adhesion Society of Japan”vol.20、No.7、300～308頁（1984年）中作為光硬化性單體及寡聚物所介紹者。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 photocurable 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，亦能夠較佳地使用日本特開2015-034964號公報的0048～0051段中記載之化合物、國際公開第2015/199219號的0087～0131段中記載之化合物，該等內容編入本說明書中。In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Unexamined Patent Publication No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and these contents are incorporated herein. In the manual.

又，在日本特開平10-062986號公報中作為式（1）及式（2）且與其具體例一同記載之如下化合物還能用作其他多官能聚合性化合物，該化合物係在多官能醇中加成環氧乙烷或環氧丙烷後進行（甲基）丙烯酸酯化而成的化合物。In addition, the following compounds described as formula (1) and formula (2) in Japanese Unexamined Patent Publication No. 10-062986 and their specific examples can also be used as other polyfunctional polymerizable compounds, which are in polyfunctional alcohols A compound obtained by adding ethylene oxide or propylene oxide followed by (meth)acrylate esterification.

進而，還能夠使用日本特開2015-187211號公報的0104～0131段中記載之化合物來用作其他其他多官能聚合性化合物，並將該等內容編入本說明書中。Furthermore, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used as other polyfunctional polymerizable compounds, and these contents are incorporated in this specification.

作為其他多官能聚合性化合物，二新戊四醇三丙烯酸酯（作為市售品為KAYARAD D-330；Nippon Kayaku Co.,Ltd.製）、二新戊四醇四丙烯酸酯（作為市售品為KAYARAD D-320；Nippon Kayaku Co.,Ltd.製、A-TMMT：Shin-Nakamura Chemical Co.,Ltd.製）、二新戊四醇五（甲基）丙烯酸酯（作為市售品為KAYARAD D-310；Nippon Kayaku Co.,Ltd.製）、二新戊四醇六（甲基）丙烯酸酯（作為市售品為KAYARAD DPHA；Nippon Kayaku Co.,Ltd.製、A-DPH；Shin-Nakamura Chemical Co.,Ltd.製）及該等的（甲基）丙烯醯基經由乙二醇殘基或丙二醇殘基鍵結之結構為較佳。亦能夠使用該等的寡聚物類型。As other polyfunctional polymerizable compounds, dineopentaerythritol triacrylate (as a commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dineopentaerythritol tetraacrylate (as a commercially available product) It is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd., dineopentylene pentaerythritol penta(meth)acrylate (as a commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dineopentaerythritol hexa(meth)acrylate (as a commercially available product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin- Nakamura Chemical Co., Ltd. (manufactured by Nakamura Chemical Co., Ltd.) and a structure in which these (meth)acrylic groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

作為其他多官能聚合性化合物的市售品，例如可舉出Sartomer Company, Inc製的作為具有4個伸乙氧基鏈之4官能丙烯酸酯之SR-494、作為具有4個乙烯氧基鏈之2官能丙烯酸甲酯之Sartomer Company, Inc製SR-209、231、239、Nippon Kayaku Co.,Ltd.製的作為具有6個伸戊氧基鏈之6官能丙烯酸酯之DPCA-60、作為具有3個異伸丁氧基鏈之3官能丙烯酸酯之TPA-330、胺基甲酸酯寡聚物UAS-10、UAB-140（NIPPON PAPER INDUSTRIES CO.,LTD.製）、NK酯M-40G、NK酯4G、NK酯M-9300、NK酯A-9300、UA-7200（Shin-Nakamura Chemical Co.,Ltd製）、DPHA-40H（Nippon Kayaku Co.,Ltd.製）、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600（Kyoeisha chemical Co.,Ltd.製）、BLEMMER PME400（NOF CORPORATION.製）等。Commercial products of other polyfunctional polymerizable compounds include, for example, SR-494 manufactured by Sartomer Company, Inc as a 4-functional acrylate having 4 ethoxy chains, and SR-494 as a 4 ethyleneoxy chain. 2-functional methyl acrylate made by Sartomer Company, Inc. SR-209, 231, 239, made by Nippon Kayaku Co., Ltd. as a 6-functional acrylate with 6 pentoxyl chains, as DPCA-60, as having 3 TPA-330, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ester M-40G, three functional acrylates with a single isobutoxy chain 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.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

作為其他多官能聚合性化合物，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號公報中所記載之那樣的胺基甲酸酯丙烯酸酯類、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基甲酸酯化合物類亦為較佳。進而，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或硫化物結構之化合物。As other polyfunctional polymerizable compounds, as 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 Urethane acrylates, Japanese Japanese Patent Publication No. 58-049860, Japanese Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, Japanese Patent Publication No. 62-039418 Urethane compounds with ethylene oxide-based skeletons are also preferred. Furthermore, as the radically polymerizable compound, those described in JP 63-277653, JP 63-260909, and 01-105238 having an amino group in the molecule can also be used. Structure or sulfide structure compound.

其他多官能聚合性化合物可以為具有羧基、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中，脂肪族多羥基化合物與不飽和羧酸的酯為較佳，使脂肪族多羥基化合物的未反應的羥基與非芳香族羧酸酐反應而具有酸基之自由基聚合性化合物為更佳。特佳為使脂肪族多羥基化合物的未反應的羥基與非芳香族羧酸酐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新戊四醇或二新戊四醇之化合物。作為市售品，例如，作為TOAGOSEI CO.,Ltd.製多元酸改質丙烯酸類寡聚物，可舉出M-510、M-520等。The other polyfunctional polymerizable compound may be a radical polymerizable compound having an acid group such as a carboxyl group and a phosphoric acid group. Among the radically polymerizable compounds having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred. The unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to form an acid group. A radically polymerizable compound is more preferable. Particularly preferably, the unreacted hydroxyl group of the aliphatic polyhydroxy compound reacts with the non-aromatic carboxylic anhydride to have an acid group. Among the radically polymerizable compounds having an acid group, the aliphatic polyhydroxy compound is one of neopentyl erythritol or dineopentaerythritol. Compound. As a commercially available product, for example, M-510, M-520, etc. are mentioned as polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd..

具有酸基之其他多官能聚合性化合物的較佳之酸值為0.1～40mgKOH/g，特佳為5～30mgKOH/g。其他多官能聚合性化合物的酸值只要在上述範圍內，則製造上的操作性優異，進而顯影性優異。又，聚合性良好。上述酸值遵照JIS K 0070：1992的記載進行測定。The other polyfunctional polymerizable compound having an acid group preferably has an acid value of 0.1-40 mgKOH/g, particularly preferably 5-30 mgKOH/g. As long as the acid value of the other polyfunctional polymerizable compound is within the above-mentioned 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.

含有其他多官能聚合性化合物時，其含量相對於本發明的硬化性樹脂組成物的總固體成分為大於0質量%且60質量%以下為較佳。下限為5質量%以上為更佳。上限為50質量%以下為更佳，30質量%以下為進一步較佳。其他多官能聚合性化合物可以單獨使用1種，亦可以混合使用2種以上。當同時使用2種以上時，其合計量成為上述範圍為較佳。When other polyfunctional polymerizable compounds are contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and more preferably 30% by mass or less. The other polyfunctional polymerizable compounds may be used singly, or two or more of them may be mixed and used. When two or more types are used at the same time, it is preferable that the total amount thereof falls within the above-mentioned range.

＜其他聚合性化合物＞本發明的硬化性樹脂組成物可進一步包含除了上述之特定聚合性化合物及其他多官能聚合性化合物以外的其他聚合性化合物。作為其他聚合性化合物，可舉出單官能自由基聚合性化合物；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；氧雜環丁烷化合物；苯并㗁𠯤化合物。＜Other polymerizable compounds＞ The curable resin composition of the present invention may further contain other polymerizable compounds in addition to the above-mentioned specific polymerizable compound and other polyfunctional polymerizable compounds. Examples of other polymerizable compounds include monofunctional radical polymerizable compounds; compounds having hydroxymethyl, alkoxymethyl, or oxymethyl; epoxy compounds; oxetane compounds; benzos 𠯤 Compound.

〔單官能自由基聚合性化合物〕從伴隨彈性模數控制之硬化膜的翹曲抑制的觀點考慮，本發明的硬化性樹脂組成物可進一步包含單官能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、2-乙基己基（甲基）丙烯酸酯、2-羥乙基（甲基）丙烯酸酯、丁氧基乙基（甲基）丙烯酸酯、卡必醇（甲基）丙烯酸酯、環己基（甲基）丙烯酸酯、芐基（甲基）丙烯酸酯、苯氧基乙基（甲基）丙烯酸酯、N-羥甲基（甲基）丙烯醯胺、縮水甘油基（甲基）丙烯酸酯、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、烯丙基縮水甘油醚、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。[Monofunctional radical polymerizable compound] From the viewpoint of suppressing warpage of the cured film accompanying elastic modulus control, the curable resin composition of the present invention may further contain a monofunctional radical polymerizable compound. As the monofunctional radical polymerizable compound, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy Ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. (meth)acrylic acid Derivatives, N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate Allyl compounds such as esters, etc. 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.

〔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25]

（式中，t表示1～20的整數，R¹⁰⁴ 表示碳數1～200的t價有機基團，R¹⁰⁵ 表示由-OR¹⁰⁶ 或-OCO-R¹⁰⁷ 表示之基團，R¹⁰⁶ 表示氫原子或碳數1～10的有機基團，R¹⁰⁷ 表示碳數1～10的有機基團。） [化學式26]

（式中，R⁴⁰⁴ 表示碳數1～200的2價有機基團，R⁴⁰⁵ 表示由-OR⁴⁰⁶ 或-OCO-R⁴⁰⁷ 表示之基團，R⁴⁰⁶ 表示氫原子或碳數1～10的有機基團，R⁴⁰⁷ 表示碳數1～10的有機基團。） [化學式27]

（式中，u表示3～8的整數，R⁵⁰⁴ 表示碳數1～200的u價有機基團，R⁵⁰⁵ 表示由-OR⁵⁰⁶ 或、-OCO-R⁵⁰⁷ 表示之基團，R⁵⁰⁶ 表示氫原子或碳數1～10的有機基團，R⁵⁰⁷ 表示碳數1～10的有機基團。）[Chemical formula 25]

(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 26]

(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. Group, R ⁴⁰⁷ represents an organic group having 1 to 10 carbons.) [Chemical formula 27]

(In the formula, u represents an integer from 3 to 8, R ⁵⁰⁴ represents a U-valent organic group with a carbon number of 1 to 200, R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ⁵⁰⁷ , and R ⁵⁰⁶ represents hydrogen Atom or an organic group with 1 to 10 carbon atoms, R ⁵⁰⁷ represents an organic group with 1 to 10 carbon atoms.)

作為由式（AM4）表示之化合物的具體例，可舉出46DMOC、46DMOEP（以上商品名，ASAHI YUKIZAI CORPORATION製）、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（以上商品名，Honshu Chemical Industry Co.,Ltd.製）、NIKALAC MX-290（商品名，Sanwa Chemical Co.,Ltd.製）、2,6-dimethoxymethyl-4-三級butylphenol（2,6-二甲氧基甲基-4-第三丁基苯酚）、2,6-dimethoxymethyl-p-cresol（2,6-二甲氧基甲基-對甲酚）、2,6-diacetoxymethyl-p-cresol（2,6-二乙醯氧基甲基-對甲酚）等。Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above 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 product names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX- 290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-tertiary butylphenol (2,6-dimethoxymethyl-4-tertiary butylphenol), 2,6 -dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacetoxymethyl-p-cresol (2,6-diacetoxymethyl-p-cresol), etc. .

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（以上商品名，Honshu Chemical Industry Co.,Ltd.製）、TM-BIP-A（商品名，ASAHI YUKIZAI CORPORATION製）、NIKALAC MX-280、NIKALAC MX-270、NIKALAC MW-100LM（以上商品名，Sanwa Chemical Co.,Ltd.製）。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 (trade name above, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above 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，係在一分子中具有2個以上的環氧基之化合物為較佳。環氧基在200℃以下進行交聯反應，並且由於不發生源自交聯之脫水反應而不易引起膜收縮。因此，藉由含有環氧化合物，可有效地抑制硬化性樹脂組成物的低溫硬化及翹曲。[Epoxy compounds (compounds with epoxy groups)] As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a cross-linking reaction below 200°C, and it is unlikely to cause film shrinkage because the dehydration reaction derived from the cross-linking does not occur. Therefore, by containing the epoxy compound, the low-temperature curing and warpage of the curable resin composition can be effectively suppressed.

環氧化合物含有聚環氧乙烷基為較佳。藉此，彈性模數進一步降低，並且能夠抑制翹曲。聚環氧乙烷基表示環氧乙烷的重複單元數為2以上者，重複單元數為2～15為較佳。The epoxy compound preferably contains a polyethylene oxide group. Thereby, the modulus of elasticity is 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；丙二醇二縮水甘油醚等伸烷基二醇型環氧樹脂；聚丙二醇二縮水甘油醚等聚伸烷基二醇型環氧樹脂；聚甲基（縮水甘油氧基丙基）矽氧烷等含環氧基矽酮等，但並不限定於該等。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（以上商品名，DIC Corporation製）、RIKARESIN（註冊商標）BEO-60E（商品名，New Japan Chemical Co.,Ltd.製）、EP-4003S、EP-4000S（以上商品名，ADEKA CORPORATION製）等。其中，從抑制翹曲及耐熱性優異之方面考慮，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，因此較佳。Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; Alkylene glycol type epoxy resin; epoxy-containing silicone such as polymethyl (glycidoxypropyl) silicone, etc., but 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 (above trade name, manufactured by DIC Corporation), RIKARESIN (registered trademark) ) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (trade name above, manufactured by ADEKA CORPORATION), etc. Among them, from the viewpoints of suppressing 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 and are therefore preferred.

〔氧雜環丁烷化合物（具有氧雜環丁基之化合物）〕作為氧雜環丁烷化合物，能夠舉出在一分子中具有2個以上的氧雜環丁烷環之化合物、3-乙基-3-羥甲氧雜環丁烷、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）氧雜環丁烷、1,4-苯二羧酸-雙[（3-乙基-3-氧雜環丁基）甲基]酯等。作為具體的例子，能夠較佳地使用TOAGOSEI CO.,LTD.製ARON OXETANE系列（例如，OXT-121、OXT-221、OXT-191、OXT-223），該等可以單獨使用，或者可以混合2種以上。[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-hydroxymethoxetane, and 1,4-bis{ [(3-Ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4- Benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl] ester and the like. As a specific example, the 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. More than species.

-苯并㗁𠯤化合物（具有聚苯并㗁唑基之化合物）- 苯并㗁𠯤化合物因源自開環加成反應之交聯反應而在硬化時不產生脫氣，進而減少熱收縮而抑制產生翹曲，因此較佳。-Benzo 㗁𠯤 compounds (compounds with polybenzo azole groups)- The benzoglucan compound is preferred because of the cross-linking reaction derived from the ring-opening addition reaction and does not produce outgassing during hardening, thereby reducing thermal shrinkage and suppressing warpage.

作為苯并㗁𠯤化合物的較佳例子，可舉出B-a型苯并㗁𠯤、B-m型苯并㗁𠯤（以上商品名，Shikoku Chemicals Corporation製）、聚羥基苯乙烯樹脂的苯并㗁𠯤加成物、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 benzophenone compound, there can be mentioned Ba type benzophenone, Bm type benzophenone (the above trade name, manufactured by Shikoku Chemicals Corporation), and benzophenone addition of polyhydroxystyrene resin. Compounds, novolac-type dihydrobenzo 㗁𠯤 compounds. These can be used individually or in mixture of 2 or more types.

含有其他聚合性化合物時，其含量相對於本發明的硬化性樹脂組成物的總固體成分為大於0質量%且60質量%以下為較佳。下限為5質量%以上為更佳。上限為50質量%以下為更佳，30質量%以下為進一步較佳。又，本發明的硬化性樹脂組成物亦能夠設為實質上不包含其他聚合性化合物之態樣。在該種態樣中，例如，其他聚合性化合物的含量相對於本發明的硬化性樹脂組成物的總固體成分為0～5質量%為較佳，0～1質量%為更佳，0～0.1質量%為進一步較佳。又，上述含量亦可以為0質量%。其他聚合性化合物可以單獨使用1種，亦可以混合使用2種以上。當同時使用2種以上時，其合計量成為上述範圍為較佳。When other polymerizable compounds are contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and more preferably 30% by mass or less. In addition, the curable resin composition of the present invention can also be in a form that does not substantially contain other polymerizable compounds. In this aspect, for example, the content of other polymerizable compounds relative to the total solid content of the curable resin composition of the present invention is preferably 0 to 5% by mass, more preferably 0 to 1% by mass, and 0 to 0.1% by mass is more preferable. In addition, the aforementioned content may also be 0% by mass. The other polymerizable compounds may be used singly or in combination of two or more kinds. When two or more types are used at the same time, it is preferable that the total amount thereof falls within the above-mentioned range.

＜鎓鹽＞本發明的硬化性樹脂組成物包含鎓鹽為較佳。鎓鹽的種類等並無特別限定，可較佳地舉出銨鹽、亞胺鹽、鋶鹽、錪鹽或鏻鹽。其中，從熱穩定性高的觀點考慮，銨鹽或亞胺鹽為較佳，從與聚合物的相溶性的觀點考慮，鋶鹽、錪鹽或鏻鹽為較佳。＜Onium salt＞ The curable resin composition of the present invention preferably contains an onium salt. The kind of onium salt and the like are not particularly limited, and preferably ammonium salt, imine salt, sulfonium salt, iodonium salt, or phosphonium salt can be mentioned. Among them, from the viewpoint of high thermal stability, an ammonium salt or an imine salt is preferable, and from the viewpoint of compatibility with a polymer, a sulfonium salt, an phosphonium salt, or a phosphonium salt is preferable.

又，鎓鹽係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鍵結，亦可以不經由共價鍵鍵結。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，亦可以為分別係不同分子的陽離子分子與陰離子分子進行離子鍵結之分子間鹽，分子間鹽為較佳。又，在本發明的硬化性樹脂組成物中，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 can be an intramolecular salt having a cation part and an anion part in the same molecular structure, or an intermolecular salt in which cationic molecules and anion molecules of different molecules are ionically bonded. good. In addition, in the curable resin 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, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferred, and at least one cation selected from the group consisting of tetraalkylammonium cations, sulfonium cations and iodonium cations is Better.

本發明中使用的鎓鹽亦可以為後述之熱鹼產生劑。熱鹼產生劑表示藉由加熱產生鹼之化合物，例如，可舉出若加熱至40℃以上則產生鹼之化合物等。The onium salt used in the present invention may also be a thermal base generator described later. The thermal base generator means a compound that generates a base by heating, and for example, a compound that generates a base when heated to 40°C or higher, and the like.

〔銨鹽〕在本發明中，銨鹽表示銨陽離子與陰離子的鹽。〔Ammonium salt〕 In the present invention, ammonium salt means a salt of an ammonium cation and an anion.

-銨陽離子- 作為銨陽離子，第四銨陽離子為較佳。又，作為銨陽離子，由下述式（101）表示之陽離子為較佳。 [化學式28]

在式（101）中，R¹ ～R⁴ 分別獨立地表示氫原子或烴基，R¹ ～R⁴ 中的至少2個可以分別鍵結而形成環。-Ammonium cation- As the ammonium cation, a fourth ammonium cation is preferred. In addition, as the ammonium cation, a cation represented by the following formula (101) is preferred. [Chemical formula 28]

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.

在式（101）中，R¹ ～R⁴ 分別獨立為烴基為較佳，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 可具有取代基，作為取代基，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。 R¹ ～R⁴ 中的至少2個分別鍵結而形成環時，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 are each independently 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 a substituent, and 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, and an acyloxy group. Base and so on. When ^{at least two of R 1} to R ⁴ are bonded to each other to form a ring, the 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1個表示為較佳。 [化學式29]

The ammonium cation is preferably represented by either of the following formulas (Y1-1) and (Y1-2). [Chemical formula 29]

在式（Y1-1）及（Y1-2）中，R¹⁰¹ 表示n價有機基團，R¹ 的含義與式（101）中的R¹ 相同，Ar¹⁰¹ 及Ar¹⁰² 分別獨立地表示芳基，n表示1以上的整數。在式（Y1-1）中，R¹⁰¹ 係脂肪族烴、芳香族烴或從該等所鍵結之結構去除n個氫原子之基團為較佳，碳數2～30的飽和脂肪族烴、從苯或萘去除n個氫原子之基團為更佳。在式（Y1-1）中，n為1～4為較佳，1或2為更佳，1為進一步較佳。在式（Y1-2）中，Ar¹⁰¹ 及Ar¹⁰² 分別獨立為苯基或萘基為較佳，苯基為更佳。In Formula (Y1-1) and (Y1-2), R ¹⁰¹ represents a n-valent organic group, with the same meaning as R in formula (101) R ¹ is ^1, Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group , 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 with n hydrogen atoms removed from the bonded structure, preferably a saturated aliphatic hydrocarbon with 2-30 carbons , It is more preferable to remove n hydrogen atoms from benzene or naphthalene. In the formula (Y1-1), n is preferably 1 to 4, 1 or 2 is more preferably, and 1 is more preferably. In the formula (Y1-2), Ar ¹⁰¹ and Ar ¹⁰² are each independently preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

-陰離子- 作為銨鹽中的陰離子，選自羧酸根陰離子、苯酚陰離子、磷酸根陰離子及硫酸根陰離子中的1種為較佳，從兼顧鹽的穩定性和熱分解性的理由考慮，羧酸根陰離子為更佳。亦即，銨鹽係銨陽離子與羧酸根陰離子的鹽為更佳。羧酸根陰離子係具有2個以上的羧基之2價以上的羧酸的陰離子為較佳，2價羧酸的陰離子為更佳。根據該態樣，能夠進一步提高硬化性樹脂組成物的穩定性、硬化性及顯影性。尤其，藉由使用2價羧酸的陰離子，能夠進一步提高硬化性樹脂組成物的穩定性、硬化性及顯影性。-Anion- As the anion in the ammonium salt, one selected from the group consisting of carboxylate anion, phenol anion, phosphate anion and sulfate anion is preferred. From the viewpoint of the stability and thermal decomposition of the salt, the carboxylate anion is more preferred. good. That is, a salt of an ammonium cation and a carboxylate anion is more preferable. The carboxylate 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 curable resin composition can be further improved. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the curable resin composition can be further improved.

羧酸根陰離子由下述式（X1）表示為較佳。 [化學式30]

在式（X1）中，EWG表示拉電子基團。The carboxylate anion is preferably represented by the following formula (X1). [Chemical formula 30]

In formula (X1), EWG represents an electron withdrawing group.

本實施形態中拉電子基團係指哈密特取代基常數σm表示正的值者。其中，σm在都野雄甫總說、Journal of Synthetic Organic Chemistry, Japan第23卷第8號（1965）p.631-642中有詳細說明。此外，本實施形態中的拉電子基團並不限定於上述文獻中所記載之取代基。作為σm表示正的值之取代基的例子，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。此外，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 withdrawing group refers to a Hammett substituent constant σm showing a positive value. Among them, σm is described in detail in Tono Yufu, Journal of Synthetic Organic Chemistry, Japan Volume 23, No. 8 (1965) p.631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituents described in the above-mentioned documents. Examples of substituents in which σm represents a positive value include 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. (Following, the same).

EWG係由下述式（EWG-1）～（EWG-6）表示之基團為較佳。 [化學式31]

在式（EWG-1）～（EWG-6）中，R^x1 ～R^x3 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 31]

In 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，羧酸根陰離子由下述式（XA）表示為較佳。 [化學式32]

在式（XA）中，L¹⁰ 表示單鍵或選自包括伸烷基、伸烯基、芳香族基、-NR^X -及該等的組合中的2價連結基，R^X 表示氫原子、烷基、烯基或芳基。In the present invention, the carboxylate anion is preferably represented by the following formula (XA). [Chemical formula 32]

In formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an aromatic group, -NR ^X -and combinations thereof, and R ^X represents a hydrogen atom, Alkyl, alkenyl or aryl.

作為羧酸根陰離子的具體例，可舉出順丁烯二酸根陰離子、鄰苯二甲酸根陰離子、N-苯基亞胺基二乙酸根陰離子及草酸根陰離子。Specific examples of the carboxylate anion include maleate anion, phthalate anion, N-phenyliminodiacetate anion, and oxalate anion.

從特定前驅物的環化容易在低溫下進行且容易提高硬化性樹脂組成物的保存穩定性的觀點考慮，本發明中的鎓鹽包含銨陽離子作為陽離子且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，從所產生之鹼不易中和且改善特定前驅物等的環化效率的觀點考慮，-3以上為較佳，-2以上為更佳。作為上述pKa，能夠參考Determination of Organic Structures by Physical Methods（著者：Brown,H.C.,McDaniel,D.H.,Hafliger,O.,Nachod,F.C.；編著：Braude,E.A.,Nachod, F.C.；Academic Press,New York,1955）或Data for Biochemical Research（著者：Dawson,R.M.C.et al；Oxford,Clarendon Press,1959）中記載之值。關於未記載於該等文獻之化合物，使用利用ACD/pKa（ACD/Labs製）的軟體並藉由結構式算出的值。From the viewpoint that the cyclization of the specific precursor easily proceeds at low temperature and the storage stability of the curable resin 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 of the conjugate acid ( An anion having a pKaH) of 2.5 or less is preferable as an anion, and an anion having a pKaH) of 1.8 or less is more preferable. The lower limit of the above-mentioned pKa is not particularly limited. From the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of the specific precursor 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 Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Edited: Braude, EA, Nachod, FC; Academic Press, New York, 1955 ) Or Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using software using ACD/pKa (manufactured by ACD/Labs) is used.

作為銨鹽的具體例，能夠舉出以下的化合物，但本發明並不限定於此。 [化學式33]

As a specific example of an ammonium salt, the following compounds can be mentioned, but this invention is not limited to this. [Chemical formula 33]

〔亞胺鹽〕在本發明中，亞胺鹽表示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，較佳態樣亦相同。[Imine salt] In the present invention, imine salt means 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 preferred aspects are 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）表示之陽離子亦較佳。 [化學式34]

-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 34]

在式（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個可以分別鍵結而形成環。在式（102）中，R⁵ 及R⁶ 的含義與上述式（101）中的R¹ ～R⁴ 相同，較佳態樣亦相同。在式（102）中，R⁷ 與R⁵ 及R⁶ 中的至少一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 the 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 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. Furthermore, 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1個表示者為較佳。 [化學式35]

在式（Y1-3）～（Y1-5）中，R¹⁰¹ 表示n價有機基團，R⁵ 的含義與式（102）中的R⁵ 相同，R⁷ 的含義與式（102）中的R⁷ 相同，n及m表示1以上的整數。在式（Y1-3）中，R¹⁰¹ 係脂肪族烴、芳香族烴或從該等所鍵結之結構去除n個氫原子之基團為較佳，碳數2～30的飽和脂肪族烴、從苯或萘去除n個氫原子之基團為更佳。在式（Y1-3）中，n為1～4為較佳，1或2為更佳，1為進一步較佳。在式（Y1-5）中，m為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 35]

In Formula (Y1-3) ~ (Y1-5) are, R ¹⁰¹ represents a n-valent organic group, with the same meaning as R in formula (102) ⁵ R ^5, and R in the meaning of formula (102) ⁷ R ^{7 is the} same, and n and m represent an integer of 1 or more. In the formula (Y1-3), R ¹⁰¹ is preferably an aliphatic hydrocarbon, aromatic hydrocarbon or a group with n hydrogen atoms removed from the bonded structure, and a saturated aliphatic hydrocarbon with 2 to 30 carbon atoms , It is more preferable to remove n hydrogen atoms from benzene or naphthalene. 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 from 0 to 4, 1 or 2 is more preferably, and 1 is even more preferably.

作為亞胺鹽的具體例，能夠舉出以下化合物，但本發明並不限定於此。 [化學式36]

As specific examples of the imine salt, the following compounds can be cited, but the present invention is not limited to these. [Chemical formula 36]

〔鋶鹽〕在本發明中，鋶鹽表示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，較佳態樣亦相同。〔Salt〕 In the present invention, a sulfonium salt means 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 preferred aspects are also the same.

-鋶陽離子- 作為鋶陽離子，第三鋶陽離子為較佳，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37]

-Alium cation- As the alumnium cation, the third alumnium cation is preferred, and the triaryl alumnium cation is more preferred. Moreover, as a cation, a cation represented by the following formula (103) is preferable. [Chemical formula 37]

在式（103）中，R⁸ ～R¹⁰ 分別獨立地表示烴基。 R⁸ ～R¹⁰ 分別獨立為烷基或芳基為較佳，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。其中，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 可以為同一基團，亦可以為不同的基團，從合成適性上的觀點考慮，同一基團為較佳。In formula (103), R ⁸ to R ¹⁰ each independently represent a hydrocarbon group. Preferably, R ⁸ to R ¹⁰ are independently an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbons or an aryl group having 6 to 12 carbons, and even more preferably an aryl group having 6 to 12 carbons , 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 them, as the substituent, an alkyl group or an alkoxy group is preferred, and a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbons or an alkoxy group having 1 to 10 carbons is more preferred. The base is further preferred. R ⁸ to R ¹⁰ may be the same group or different groups. From the viewpoint of synthetic suitability, the same group is preferred.

作為鋶鹽的具體例，能夠舉出以下化合物，但本發明並不限定於此。 [化學式38]

As specific examples of the alumium salt, the following compounds can be cited, but the present invention is not limited to these. [Chemical formula 38]

〔錪鹽〕在本發明中，錪鹽表示錪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，較佳態樣亦相同。〔Salt〕 In the present invention, the iodonium salt means a salt of an iodonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt can be exemplified, and preferred aspects are also the same.

-錪陽離子- 作為錪陽離子，二芳基錪陽離子為較佳。又，作為錪陽離子，由下述式（104）表示之陽離子為較佳。 [化學式39]

-Iiodonium cation- As the iodonium cation, a diaryl iodonium cation is preferred. In addition, as the iodonium cation, a cation represented by the following formula (104) is preferred. [Chemical formula 39]

在式（104）中，R¹¹ 及R¹² 分別獨立地表示烴基。 R¹¹ 及R¹² 分別獨立為烷基或芳基為較佳，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 可具有取代基，作為取代基，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。其中，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 可以為同一基團，亦可以為不同的基團，從合成適性上的觀點考慮，同一基團為較佳。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, more preferably an alkyl group having 1 to 10 carbons or an aryl group having 6 to 12 carbons, and even more preferably an aryl group having 6 to 12 carbons , Phenyl is further preferred. R ¹¹ and R ¹² 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, and an oxyoxy group. Base and so on. Among them, as the substituent, an alkyl group or an alkoxy group is preferred, and a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbons or an alkoxy group having 1 to 10 carbons is more preferred. The base is further preferred. R ¹¹ and R ¹² may be the same group or different groups. From the viewpoint of synthetic suitability, the same group is preferred.

作為錪鹽的具體例，能夠舉出以下化合物，但本發明並不限定於此。 [化學式40]

As specific examples of the iodonium salt, the following compounds can be cited, but the present invention is not limited to these. [Chemical formula 40]

〔鏻鹽〕在本發明中，鏻鹽表示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，較佳態樣亦相同。〔Phosphonium salt〕 In the present invention, the phosphonium salt means a salt of a phosphonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt can be exemplified, and preferred aspects are also the same.

-鏻陽離子- 作為鏻陽離子，第四鏻陽離子為較佳，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41]

-Phosphonium cation- As the phosphonium cation, a fourth phosphonium cation is preferred, and tetraalkyl phosphonium cations, triaryl monoalkyl phosphonium cations and the like can be mentioned. In addition, as the phosphonium cation, a cation represented by the following formula (105) is preferred. [Chemical formula 41]

在式（105）中，R¹³ ～R¹⁶ 分別獨立地表示氫原子或烴基。 R¹³ ～R¹⁶ 分別獨立為烷基或芳基為較佳，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 可具有取代基，作為取代基，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。其中，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 可以為同一基團，亦可以為不同的基團，從合成適性上的觀點考慮，同一基團為較佳。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 even more preferable , 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, and an acetoxy group. Base and so on. Among them, as the substituent, an alkyl group or an alkoxy group is preferred, and a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbons or an alkoxy group having 1 to 10 carbons is more preferred. The base is further preferred. R ¹³ to R ¹⁶ may be the same group or different groups. From the viewpoint of synthetic suitability, the same group is preferred.

作為鏻鹽的具體例，能夠舉出以下化合物，但本發明並不限定於此。 [化學式42]

As specific examples of the phosphonium salt, the following compounds can be cited, but the present invention is not limited to these. [Chemical formula 42]

本發明的硬化性樹脂組成物包含鎓鹽時，鎓鹽的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.1～50質量%為較佳。下限為0.5質量%以上為更佳，0.85質量%以上為進一步較佳，1質量%以上為再進一步較佳。上限為30質量%以下為更佳，20質量%以下為進一步較佳，10質量%以下為再進一步較佳，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。使用2種以上時，合計量為上述範圍為較佳。When the curable resin 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 curable resin 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 even 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 still more preferably 10% by mass or less, and may be 5% by mass or less or 4% by mass or less. One type or two or more types of onium salts can be used. When two or more types are used, the total amount is preferably in the above-mentioned range.

＜熱鹼產生劑＞本發明的硬化性樹脂組成物可以包含熱鹼產生劑。熱鹼產生劑可以為符合上述鎓鹽之化合物，亦可以為除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43]

<Thermal base generator> The curable resin composition of the present invention may contain a thermal base generator. The thermal base generator may be a compound conforming 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 43]

在式（B1）及式（B2）中，Rb¹ 、Rb² 及Rb³ 分別獨立為不具有第三胺結構之有機基團、鹵素原子或氫原子。其中，Rb¹ 及Rb² 不會同時成為氫原子。又，Rb¹ 、Rb² 及Rb³ 均不具有羧基。此外，在本說明書中，第三胺結構係指3價氮原子的3個鍵結鍵均與烴系的碳原子進行共價鍵結之結構。因此，在所鍵結之碳原子係形成羰基之碳原子時，亦即在與氮原子一同形成醯胺基時，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 third amine structure, a halogen atom, or a hydrogen atom. Among them, 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 third 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 中的至少一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1個，單環或2個單環縮合的縮合環為較佳。單環係5員環或6員環為較佳，6員環為較佳。單環係環己烷環及苯環為較佳，環己烷環為更佳。In the formulas (B1) and (B2), it ^{is preferable that at least one of Rb 1} , Rb ² and Rb ³ contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure. The cyclic structure may be any one of a monocyclic ring and a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed 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 cyclohexane ring and benzene ring are preferred, and the cyclohexane 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。尤其，Rb¹ 及Rb² 係可具有取代基之直鏈、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 aralkyl The group (the carbon number is preferably 7-25, 7-19 is more preferable, and 7-12 is still more preferable) is preferable. 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. In particular, Rb ¹ and Rb ² are 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, the 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 the cyclohexyl group that may have a substituent is more preferable. good.

作為Rb³ ，可舉出烷基（碳數1～24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）、烯基（碳數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。在發揮本發明的效果之範圍內Rb³ 可進一步具有取代基。Examples of Rb ³ include alkyl groups (the carbon number is preferably 1-24, 2-18 is more preferable, and 3-12 is more preferable), and aryl groups (the carbon number is preferably 6-22, 6-18 More preferably, 6-10 is further preferred), alkenyl (carbon number 2-24 is preferred, 2-12 is more preferred, 2-6 is further preferred), aralkyl group (carbon number is 7-23 Is preferred, 7-19 is more preferred, 7-12 is further preferred), aralkenyl (carbon number 8-24 is preferred, 8-20 is more preferred, 8-16 is further preferred), alkane An oxy group (the carbon number is preferably 1-24, 2-18 is more preferable, and 3-12 is more preferable), aryloxy group (the carbon number is 6-22 is preferable, 6-18 is more preferable, 6-18 is more preferable) 12 is more preferred) or aralkyloxy (the carbon number is preferably 7 to 23, 7 to 19 is more preferred, and 7 to 12 is even more preferred). 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 further have a substituent as long as the effect of the present invention is exerted.

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44]

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 44]

式中，Rb¹¹ 及Rb¹² 和Rb³¹ 及Rb³² 的含義分別與式（B1）中的Rb¹ 及Rb² 相同。 Rb¹³ 係烷基（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 have} ^{the same meanings 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 preferably 2-24, more preferably 2-18, 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 preferably 2 to 12) , 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 (carbon The number is preferably from 7 to 23, more preferably from 7 to 19, and even more preferably from 7 to 11), and a hydrogen atom is more preferred.

Rb³⁵ 係烷基（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 more preferable), alkenyl group (the carbon number is 2-12 is preferable, and 2-10 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), aryl is preferred.

由式（B1-1）表示之化合物係由式（B1-1a）表示之化合物亦較佳。 [化學式45]

It is also preferable that the compound represented by the formula (B1-1) is a compound represented by the formula (B1-1a). [Chemical formula 45]

Rb¹¹ 及Rb¹² 的含義與式（B1-1）中Rb¹¹ 及Rb¹² 相同。 Rb¹⁵ 及Rb¹⁶ 係氫原子、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 係烷基（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。Same as Rb Rb ¹¹ and Rb ¹² meaning as in formula (B1-1) ¹¹ and Rb ^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 1-24, 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), of which aryl is preferred.

非離子系熱鹼產生劑的分子量為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 even 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.

關於作為熱鹼產生劑的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46]

[化學式47]

Regarding specific examples of the compound as a thermal base generator or specific examples of other thermal base generators, the following compounds can be given. [Chemical formula 46]

[Chemical formula 47]

[化學式48]

[Chemical formula 48]

熱鹼產生劑的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.1～50質量%為較佳。下限為0.5質量%以上為更佳，1質量%以上為進一步較佳。上限為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。使用2種以上時，合計量為上述範圍為較佳。The content of the thermal base generator is preferably 0.1 to 50% by mass relative to the total solid content of the curable resin 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. When two or more types are used, the total amount is preferably in the above-mentioned range.

＜光聚合起始劑＞本發明的硬化性樹脂組成物包含光聚合起始劑為較佳。光聚合起始劑可以為光陽離子聚合起始劑，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，能夠從公知的光自由基聚合起始劑中適當選擇。例如，對紫外線區域至可見區域的光線具有硬化性之光自由基聚合起始劑為較佳。又，可以為與光激發之敏化劑產生一些作用，並生成活性自由基之活性劑。＜Photopolymerization initiator＞ The curable resin composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator may be a photocationic polymerization initiator, and a photoradical polymerization initiator is preferred. The radical photopolymerization initiator is not particularly limited, and it can be appropriately selected from known radical photopolymerization initiators. For example, a photo-radical polymerization initiator that has curability to light rays from the ultraviolet region to the visible region is preferred. In addition, it can be an active agent that interacts with a sensitizer that is excited by light and generates active free radicals.

光自由基聚合起始劑至少含有1種在約300～800nm（較佳為330～500nm）的範圍內至少具有約50L·mol^-1 ·cm^-1 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定。例如，藉由紫外可見分光光度計（Varian公司製Cary-5 spectrophotometer），並使用乙酸乙酯溶劑而於0.01g/L的濃度下進行測定為較佳。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, it is better to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) and use an ethyl acetate solvent at a concentration of 0.01 g/L.

作為光自由基聚合起始劑，能夠任意使用公知的化合物。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，能夠參考日本特開2016-027357號公報的0165～0182段、國際公開第2015/199219號的0138～0151段的記載，該內容編入本說明書中。As the photoradical polymerization initiator, any 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, hexaaryl bis Oxime compounds such as imidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, Metallocene compounds, organoboron compounds, iron arene complexes, etc. For these details, reference can be made to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A, and paragraphs 0138 to 0151 of International Publication No. 2015/199219, which are incorporated into this specification.

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

作為光自由基聚合起始劑，還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，還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號中所記載之醯基氧化膦系起始劑。As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also 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 also 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：均為BASF公司製）。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：均為BASF公司製）。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，還能夠使用吸收極大波長與365nm或405nm等波長光源匹配之日本特開2009-191179號公報中記載之化合物。As the aminoacetophenone-based initiator, it is also possible to use the compound described in Japanese Patent Application Laid-Open No. 2009-191179, which has an absorption maximum wavelength matched with a light source of wavelengths such as 365nm or 405nm.

作為醯基膦系起始劑，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或IRGACURE-TPO（商品名：均為BASF公司製）。Examples of the phosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. In addition, IRGACURE-819 or IRGACURE-TPO (brand name: both manufactured by BASF Corporation), which are commercially available products, can be used.

作為茂金屬化合物，例示IRGACURE-784（BASF公司製）等。As the metallocene compound, IRGACURE-784 (manufactured by BASF Corporation) and the like are exemplified.

作為光自由基聚合起始劑，更佳為舉出肟化合物。藉由使用肟化合物，能夠進一步有效地提高曝光寬容度。肟化合物中，曝光寬容度（曝光餘量）較廣，且還作為光硬化促進劑而發揮功能，因此特佳。As the photoradical polymerization initiator, an oxime compound is more preferable. By using an oxime compound, the exposure latitude can be further effectively improved. Among the oxime compounds, the exposure latitude (exposure margin) is relatively wide, and it also functions as a photohardening accelerator, so it is particularly preferable.

作為肟化合物的具體例，能夠使用日本特開2001-233842號公報中記載之化合物、日本特開2000-080068號公報中記載之化合物、日本特開2006-342166號公報中記載之化合物。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 A can be used.

作為較佳之肟化合物，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-丙醯氧基亞胺基丁烷-2-酮、2-乙醯氧基亞胺基戊烷-3-酮、2-乙醯氧基亞胺基-1-苯基丙烷-1-酮、2-苯甲醯氧基亞胺基-1-苯基丙烷-1-酮、3-（4-甲苯磺醯氧基）亞胺基丁烷-2-酮以及2-乙氧基羰氧基亞胺基-1-苯基丙烷-1-酮等。在本發明的硬化性樹脂組成物中，尤其作為光自由基聚合起始劑而使用肟化合物（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由＞C=N-O-C（=O）-表示之連結基。As a preferable oxime compound, for example, a compound having the following structure, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3 -Propyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one , 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyloxy Group imino-1-phenylpropan-1-one and so on. In the curable resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group represented by >C=N-O-C(=O)- in the molecule.

[化學式49]

[Chemical formula 49]

市售品中，還可較佳地使用IRGACURE OXE 01、IRGACURE OXE 02、IRGACURE OXE 03、IRGACURE OXE 04（以上為BASF公司製）、ADEKA OPTOMER N-1919（ADEKA CORPORATION製、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，能夠使用TR-PBG-304（Changzhou Tronly New Electronic Materials CO.,LTD.製）、ADEKA ARKLS NCI-831及ADEKA ARKLS NCI-930（ADEKA CORPORATION製）。又，能夠使用DFI-091（DAITO CHEMIX Co.,Ltd.製）。Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF), ADEKA OPTOMER N-1919 (made by ADEKA CORPORATION, Japan Special Publication 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 be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.

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

作為最佳之肟化合物，可舉出日本特開2007-269779號公報中所示出之具有特定取代基之肟化合物或日本特開2009-191061號公報中所示出之具有硫芳基之肟化合物等。As the best oxime compound, oxime compounds with specific substituents shown in Japanese Patent Application Publication No. 2007-269779 or oximes with sulfur aryl groups shown in Japanese Patent Application Publication No. 2009-191061 can be cited Compound etc.

從曝光靈敏度的觀點考慮，光自由基聚合起始劑係選自包括三鹵甲基三𠯤化合物、苄基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、鎓鹽化合物、苯并噻唑化合物、二苯甲酮化合物、苯乙酮化合物及其衍生物、環戊二烯基-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 photo-radical polymerization initiator is selected from the group consisting of trihalomethyl tri ketal compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and ketone compounds. Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl -Benzene-iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferably compounds in the group.

更佳的光自由基聚合起始劑係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、三芳基咪唑二聚體、鎓鹽化合物、二苯甲酮化合物、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、三芳基咪唑二聚體、二苯甲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。More preferable photo-radical polymerization initiators are trihalomethyl tri-ketone compounds, α-amino ketone compounds, phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium Salt compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyltriketone compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds Among them, at least one compound 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甲酮、N,N’-四甲基-4,4’-二胺基二苯甲酮（米其勒酮（Michler’s ketone））等N,N’-四烷基-4,4’-二胺基二苯甲酮，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進行縮環而成之醌類、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 benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. ,N'-Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-porolinylphenyl)-butanone- Aromatic ketones such as 1,2-methyl-1-[4-(methylthio)phenyl]-2-endolinyl-acetone-1, alkylanthraquinones, etc. are condensed with aromatic rings. Quinones, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, a compound represented by the following formula (I) can also be used.

[化學式50]

[Chemical formula 50]

在式（I）中，R^I00 係碳數1～20的烷基、藉由1個以上的氧原子而中斷之碳數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、被藉由因1個以上的氧原子而中斷之碳數2～18的烷基及碳數1～4的烷基中的至少一個取代之苯基或聯苯基，R^I01 係由式（II）表示之基團，或者係與R^I00 相同的基團，R^I02 ～R^I04 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 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, benzene Group, C1-C20 alkyl group, C1-C12 alkoxy group, halogen atom, cyclopentyl group, cyclohexyl group, C2-C12 alkenyl group, which is substituted by one or more oxygen atoms And the interrupted C2-C18 alkyl group and C1-C4 alkyl group substituted by at least one phenyl group or biphenyl group, R ^I01 is a group represented by formula (II), or is combined with R ^The same groups as ^{I00, R I02} to R ^I04 are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or halogen.

[化學式51]

[Chemical formula 51]

式中，R^I05 ～R^I07 與上述式（I）的R^I02 ～R^I04 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.

包含光聚合起始劑時，其含量相對於本發明的硬化性樹脂組成物的總固體成分為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%，更進一步較佳為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。含有2種以上的光聚合起始劑時，其合計為上述範圍為較佳。When the photopolymerization initiator is included, its content is preferably 0.1-30% by mass relative to the total solid content of the curable resin 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 of them is preferably in the above-mentioned range.

＜熱聚合起始劑＞作為聚合起始劑，本發明的硬化性樹脂組成物可包含熱聚合起始劑，尤其可包含熱自由基聚合起始劑。熱自由基聚合起始劑係藉由熱的能量而產生自由基，並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，能夠進行特定含雜環聚合物前驅物的環化，並且進行特定含雜環聚合物前驅物的聚合反應，因此能夠實現更高層次的耐熱化。＜Thermal polymerization initiator＞ As the polymerization initiator, the curable resin composition of the present invention may include a thermal polymerization initiator, and in particular, may include 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 cyclization of the specific heterocyclic-containing polymer precursor can be performed, and the polymerization reaction of the specific heterocyclic-containing polymer precursor can be performed, so a higher level of heat resistance can be achieved.

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.

含有熱自由基聚合起始劑時，其含量相對於本發明的硬化性樹脂組成物的總固體成分為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%。熱自由基聚合起始劑可以僅含有1種亦可以含有2種以上。含有2種以上的熱自由基聚合起始劑時，其合計為上述範圍為較佳。When a thermal radical polymerization initiator is contained, its content is preferably 0.1-30% by mass relative to the total solid content of the curable resin composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 5 ～15% by mass. The thermal radical polymerization initiator may contain only one type or two or more types. When two or more types of thermal radical polymerization initiators are contained, the total amount is preferably in the above-mentioned range.

＜溶劑＞本發明的硬化性樹脂組成物含有溶劑為較佳。溶劑能夠任意使用公知的溶劑。溶劑較佳為有機溶劑。作為有機溶劑，可舉出酯類、醚類、酮類、芳香族烴類、亞碸類、醯胺類等化合物。＜Solvent＞ The curable resin composition of the present invention preferably contains a solvent. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of organic solvents include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfenites, and amines.

作為酯類，例如作為較佳者，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。As esters, for example, preferred ones include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate Ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, Ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate Etc.)), 3-alkoxypropionic acid alkyl esters (for example, 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (for example, 3-methoxy propionic acid methyl ester , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (for example, 2- Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , 2-methoxypropionic acid propyl ester, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester)), 2-alkoxy-2-methylpropionic acid methyl ester and 2- Ethyl alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate Ester, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.

作為醚類，例如作為較佳者，可舉出二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單***、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***、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***乙酸酯、丙二醇單丙醚乙酸酯等。As ethers, for example, preferred ones include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve. Acetate, diethylene 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 monopropylene Ether acetate and so on.

作為酮類，例如作為較佳者，可舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮等。As the ketones, for example, preferable ones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and the like.

作為芳香族烴類，例如作為較佳者，可舉出甲苯、二甲苯、苯甲醚、檸檬烯等。As aromatic hydrocarbons, for example, preferable ones include toluene, xylene, anisole, limonene, and the like.

作為亞碸類，例如作為較佳者，可舉出二甲基亞碸。As the sulfenite, for example, a preferable one includes dimethyl sulfenite.

作為醯胺類，作為較佳者，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。As the amides, preferred ones include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- Dimethylformamide and so on.

關於溶劑，從塗佈面性狀的改良等的觀點考慮，混合2種以上之形態亦為較佳。Regarding the solvent, from the viewpoint of improvement of coating surface properties, etc., a form in which two or more types are mixed is also preferable.

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2種以上構成之混合溶劑為較佳。同時使用二甲基亞碸和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 , Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfene, ethyl carbitol acetate, butyl carbitol One solvent or a mixed solvent composed of two or more of acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferred. It is particularly preferable to use dimethyl sulfoxide and γ-butyrolactone at the same time.

關於溶劑的含量，從塗佈性的觀點考慮，設為本發明的硬化性樹脂組成物的總固體成分濃度成為5～80質量%之量為較佳，設為成為5～75質量%之量為更佳，設為成為10～70質量%之量為進一步較佳，設為成為40～70質量%為更進一步較佳。溶劑的含量依所希望的厚度和塗佈方法來進行調節即可。Regarding the content of the solvent, from the viewpoint of coatability, the total solid content concentration of the curable resin composition of the present invention is preferably 5 to 80% by mass, and it is preferably 5 to 75% by mass. More preferably, it is more preferable to set it as 10-70 mass %, and it is still more preferable to set it as 40-70 mass %. The content of the solvent can be adjusted according to the desired thickness and coating method.

溶劑可以僅含有1種亦可以含有2種以上。當含有2種以上溶劑時，其合計為上述範圍為較佳。The solvent may contain only one type or two or more types. When two or more kinds of solvents are contained, the total of them is preferably in the above-mentioned range.

＜遷移抑制劑＞本發明的硬化性樹脂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）的金屬離子轉移到硬化性樹脂組成物層內。＜Migration inhibitor＞ The curable resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the transfer of metal ions originating from the metal layer (metal wiring) into the curable resin composition layer.

作為遷移抑制劑，並無特別限制，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-吡喃環及6H-吡喃環、三𠯤環）之化合物、具有硫脲類及氫硫基之化合物、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-***、苯并***等***系化合物、1H-四唑、5-苯基四唑等四唑系化合物。The migration inhibitor is not particularly limited, and examples include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetra Azole ring, pyridine ring, pyran ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, oromoline ring, 2H-pyran ring and 6H-pyran ring, tri-pyran ring) compounds, having Thiourea and sulfhydryl-based compounds, hindered phenolic 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，亦能夠使用捕捉鹵素離子等陰離子之離子捕捉劑。Alternatively, an ion scavenger 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段中記載之防鏽劑、日本特開2009-283711號公報的0073～0076段中記載之化合物、日本特開2011-059656號公報的0052段中記載之化合物、日本特開2012-194520號公報的0114、0116段及0118段中記載之化合物、國際公開第2015/199219號的0166段中記載之化合物等。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 2011-059656 can be used. The compound described in paragraph 0052 of JP-A-2012-194520, the compound described in paragraphs 0114, 0116, and paragraph 0118 of JP 2012-194520 A, the compound described in paragraph 0166 of International Publication No. 2015/199219, and the like.

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

[化學式52]

[Chemical formula 52]

硬化性樹脂組成物具有遷移抑制劑時，遷移抑制劑的含量相對於硬化性樹脂組成物的總固體成分為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 curable resin composition has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the curable resin composition 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 % Is more preferable.

遷移抑制劑可以為僅1種，亦可以為2種以上。當遷移抑制劑為2種以上時，其合計為上述範圍為較佳。There may be only one type of migration inhibitor, or two or more types. When there are two or more kinds of migration inhibitors, it is preferable that the total of them is in the above range.

＜聚合抑制劑＞本發明的硬化性樹脂組成物包含聚合抑制劑為較佳。＜Polymerization inhibitor＞ The curable resin composition of the present invention preferably contains a polymerization inhibitor.

作為聚合抑制劑，例如可較佳地使用對苯二酚、對甲氧基苯酚、二-第三丁基-對甲酚、鄰苯三酚、對-第三丁基鄰苯二酚、1,4-苯醌、二苯基-對苯醌、4,4’-硫代雙（3-甲基-6-第三丁基苯酚）、2,2’-亞甲基雙（4-甲基-6-第三丁基苯酚）、N-亞硝基-N-苯基羥基胺鋁鹽、啡噻𠯤、N-亞硝基二苯胺、N-苯基萘胺、伸乙基二胺四乙酸、1,2-環己二胺四乙酸、乙二醇醚二胺四乙酸、2,6-二-第三丁基-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-磺基丙基胺）苯酚、N-亞硝基-N-（1-萘基）羥胺銨鹽、雙（4-羥基-3,5-第三丁基）苯基甲烷等。又，亦能夠使用日本特開2015-127817號公報的0060段中記載之聚合抑制劑及國際公開第2015/125469號的0031～0046段中記載之化合物。As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, p-tertiary butylcatechol, 1 ,4-Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl -6-tertiary butyl phenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothionine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine Tetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquine Phenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N- Nitroso-N-(1-naphthyl)hydroxylamine 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53]

[Chemical formula 53]

本發明的硬化性樹脂組成物具有聚合抑制劑時，聚合抑制劑的含量相對於本發明的硬化性樹脂組成物的總固體成分為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。When the curable resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the curable resin composition of the present invention is preferably 0.01 to 5% by mass, and more preferably 0.02 to 3% by mass. Preferably, 0.05 to 2.5% by mass is more preferable.

聚合抑制劑可以為僅1種，亦可以為2種以上。當聚合抑制劑為2種以上時，其合計為上述範圍為較佳。There may be only one type of polymerization inhibitor, or two or more types. When there are two or more kinds of polymerization inhibitors, it is preferable that the total of them is in the above-mentioned range.

＜金屬接著性改良劑＞本發明的硬化性樹脂組成物包含用於提高與使用於電極或配線等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 curable resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion with metal materials used for 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段中記載之化合物、日本特開2014-191002號公報的0062～0073段中記載之化合物、國際公開第2011/080992號的0063～0071段中記載之化合物、日本特開2014-191252號公報的0060～0061段中記載之化合物、日本特開2014-041264號公報的0045～0052段中記載之化合物、國際公開第2014/097594號的0055段中記載之化合物。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. 2011/080992 The compound described in paragraphs 0063 to 0071, the compound described in paragraphs 0060 to 0061 of JP 2014-191252 A, the compound described in paragraphs 0045 to 0052 of JP 2014-041264, International Publication No. 2014 /097594, the compound described in paragraph 0055. 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54]

[Chemical formula 54]

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段中記載之化合物、日本特開2013-072935號公報的0032～0043段中記載之硫化物系化合物。In addition, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A, and sulfide compounds described in paragraphs 0032 to 0043 of JP 2013-072935 can also be used. .

將特定含雜環聚合物前驅物及其他含雜環聚合物前驅物的合計量設為100質量份時，金屬接著性改良劑的含量較佳為0.1～30質量份，更佳為在0.5～15質量份的範圍內，進一步較佳為在0.5～5質量份的範圍內。藉由設為上述下限值以上，硬化製程後的硬化膜與金屬層的接著性變良好，藉由設為上述上限值以下，硬化製程後的硬化膜的耐熱性、機械特性變良好。金屬接著性改良劑可以僅為1種，亦可以為2種以上。使用2種以上時，其合計為上述範圍為較佳。When the total amount of the specific heterocyclic-containing polymer precursor and other heterocyclic-containing polymer precursors is 100 parts by mass, the content of the metal adhesion improver is preferably 0.1-30 parts by mass, more preferably 0.5- Within the range of 15 parts by mass, more preferably within the range of 0.5 to 5 parts by mass. By setting it as the above lower limit or more, the adhesiveness of the cured film after the curing process to the metal layer becomes better, and by setting it as the above upper limit value or less, the heat resistance and mechanical properties of the cured film after the curing process become better. There may be only one type of metal adhesion improver, or two or more types. When using 2 or more types, it is preferable that the sum total is the said range.

＜其他添加劑＞本發明的硬化性樹脂組成物在不損害本發明的效果之範圍內，能夠根據需要配合各種添加物，例如，熱酸產生劑、N-苯基二乙醇胺等敏化劑、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、凝聚抑制劑等。配合該等添加劑時，將其合計配合量設為硬化性樹脂組成物的固體成分的3質量%以下為較佳。＜Other additives＞ The curable resin composition of the present invention can be blended with various additives as necessary, within the range that does not impair the effects of the present invention, such as thermal acid generators, sensitizers such as N-phenyldiethanolamine, chain transfer agents, and interface Active agents, higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.

〔敏化劑〕本發明的硬化性樹脂組成物可包含敏化劑。敏化劑吸收特定的活性放射線而成為電子激發狀態。成為電子激發狀態之敏化劑與熱硬化促進劑、熱自由基聚合起始劑、光自由基聚合起始劑等接觸，而產生電子轉移、能量轉移、發熱等作用。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發生化學變化而分解，並生成自由基、酸或鹼。作為敏化劑，可舉出N-苯基二乙醇胺等。又，作為敏化劑，亦可以使用敏化色素。關於敏化色素的詳細內容，能夠參考日本特開2016-027357號公報的0161～0163段的記載，並將該內容編入本說明書中。〔Sensitizer〕 The curable resin 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 generate electron transfer, energy transfer, heat generation, and the like. Thereby, the thermal hardening accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator undergo chemical changes to decompose and generate free radicals, acids, or bases. Examples of the sensitizer include N-phenyldiethanolamine and the like. In addition, as a sensitizer, a sensitizing dye can also be used. For the details of the sensitizing dye, reference can be made to the descriptions in paragraphs 0161 to 0163 of JP 2016-027357 A, and the contents are incorporated into this specification.

本發明的硬化性樹脂組成物包含敏化劑時，敏化劑的含量相對於本發明的硬化性樹脂組成物的總固體成分為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。敏化劑可以單獨使用1種亦可以併用2種以上。When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer relative to the total solid content of the curable resin composition of the present invention is preferably 0.01-20% by mass, and more preferably 0.1-15% by mass. Preferably, 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〕本發明的硬化性樹脂組成物可含有鏈轉移劑。鏈轉移劑例如於高分子詞典第三版（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。該等向低活性自由基供給氫而生成自由基，或者經氧化之後，藉由去質子而可生成自由基。尤其，能夠較佳地使用硫醇化合物。〔Chain transfer agent〕 The curable resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in pages 683-684 of the third edition of the Polymer Dictionary (Edited by The Society of Polymer Science (Japan), 2005). As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. These provide hydrogen to low-activity free radicals to generate free radicals, or after oxidation, they can generate free radicals by deprotonation. In particular, thiol compounds can be preferably used.

又，鏈轉移劑亦能夠使用國際公開第2015/199219號的0152～0153段中記載之化合物。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.

本發明的硬化性樹脂組成物具有鏈轉移劑時，鏈轉移劑的含量相對於本發明的硬化性樹脂組成物的總固體成分100質量份為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。鏈轉移劑可以為僅1種，亦可以為2種以上。當鏈轉移劑為2種以上時，其合計為上述範圍為較佳。When the curable resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01-20 parts by mass relative to 100 parts by mass of the total solid content of the curable resin composition of the present invention, preferably 1-10 parts by mass Parts are more preferable, and 1 to 5 parts by mass are still more preferable. The chain transfer agent may be only one type or two or more types. When there are two or more kinds of chain transfer agents, it is preferable that the total amount is in the above-mentioned range.

〔界面活性劑〕從進一步提高塗佈性的觀點考慮，本發明的硬化性樹脂組成物中可以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、矽酮系界面活性劑等各種界面活性劑。又，下述界面活性劑亦較佳。在下述式中，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55]

又，界面活性劑亦能夠使用國際公開第2015/199219號的0159～0165段中記載之化合物。[Surfactant] From the viewpoint of further improving coatability, various surfactants can be added to the curable resin 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 unit of the main chain represent the content (mol %) of each repeating unit, and the parentheses representing the repeating unit of the side chain represent the repeating number of each repeating unit. [Chemical formula 55]

In addition, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.

本發明的硬化性樹脂組成物具有界面活性劑時，界面活性劑的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.001～2.0質量%為較佳，更佳為0.005～1.0質量%。界面活性劑可以為僅1種，亦可以為2種以上。當界面活性劑為2種以上時，其合計為上述範圍為較佳。When the curable resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass relative to the total solid content of the curable resin composition of the present invention, more preferably 0.005 to 1.0 mass% %. The surfactant may be only one type or two or more types. When there are two or more surfactants, the total of them is preferably in the above-mentioned range.

〔高級脂肪酸衍生物〕為了防止因氧導致的聚合阻礙，本發明的硬化性樹脂組成物中可以添加二十二酸或二十二酸醯胺之類的高級脂肪酸衍生物而在塗佈後的乾燥過程中偏在於硬化性樹脂組成物的表面。〔Higher fatty acid derivatives〕 In order to prevent polymerization inhibition due to oxygen, the curable resin composition of the present invention may be added with higher fatty acid derivatives such as behenic acid or behenic acid amide to harden during the drying process after coating. The surface of the resin composition.

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

本發明的硬化性樹脂組成物含有高級脂肪酸衍生物時，高級脂肪酸衍生物的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.1～10質量%為較佳。高級脂肪酸衍生物可以為僅1種，亦可以為2種以上。當高級脂肪酸衍生物為2種以上時，其合計為上述範圍為較佳。When the curable resin composition of the present invention contains 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 curable resin composition of the present invention. There may be only one type of higher fatty acid derivative, or two or more types. When there are two or more higher fatty acid derivatives, the total of them is preferably in the above-mentioned range.

＜關於其他含有物質的限制＞從塗佈面性狀的觀點考慮，本發明的硬化性樹脂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。＜Regarding restrictions on other contained substances＞ From the viewpoint of coating surface properties, the water content of the curable resin 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.

從絕緣性的觀點考慮，本發明的硬化性樹脂組成物的金屬含量小於5質量ppm（parts per million（百萬分率））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。包含複數種金屬時，該等金屬的合計為上述範圍為較佳。From the viewpoint of insulation, the metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and less than 0.5 mass ppm. Further better. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are included, the total of these metals is preferably in the above-mentioned range.

又，作為減少意外包含在本發明的硬化性樹脂組成物中的金屬雜質之方法，能夠舉出如下方法：作為構成本發明的硬化性樹脂組成物之原料而選擇金屬含量較少的原料，對構成本發明的硬化性樹脂組成物之原料進行過濾器過濾，用聚四氟乙烯等對裝置內進行內襯而在盡可能抑制污染的條件下進行蒸餾等方法。In addition, as a method of reducing the metal impurities accidentally included in the curable resin composition of the present invention, the following method can be cited: as the raw material constituting the curable resin composition of the present invention, a raw material with a small metal content is selected, and The raw material constituting the curable resin composition of the present invention is filtered by a filter, the inside of the device is lined with polytetrafluoroethylene or the like, and distillation is carried out under conditions that suppress contamination as much as possible.

若考慮作為半導體材料的用途，且從配線腐蝕性的觀點考慮，本發明的硬化性樹脂組成物中，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合計分別為上述範圍為較佳。Considering the use as a semiconductor material and from the perspective of wiring corrosion, the curable resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm. ppm is more preferable. 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 the chlorine atom and the bromine atom or the chlorine ion and the bromine ion be in the above-mentioned ranges.

作為本發明的硬化性樹脂組成物的收容容器，能夠使用以往公知的收容容器。又，作為收容容器，以抑制雜質混入原材料或硬化性樹脂組成物中為目的，使用由6種6層樹脂構成容器內壁之多層瓶、將6種樹脂形成為7層結構之瓶亦為較佳。作為該種容器，例如可舉出日本特開2015-123351號公報中記載之容器。As the storage container of the curable resin composition of the present invention, a conventionally known storage container can be used. In addition, as a storage container, for the purpose of preventing impurities from mixing into the raw material or curable resin composition, it is also better to use a multi-layer bottle with 6 kinds of 6-layer resins forming the inner wall of the container, and a bottle with 6 kinds of resins into a 7-layer structure. good. As such a container, for example, the container described in JP 2015-123351 A can be cited.

＜硬化性樹脂組成物的製備＞本發明的硬化性樹脂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來進行。<Preparation of curable resin composition> The curable resin 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，以去除硬化性樹脂組成物中的灰塵或微粒等異物為目的，進行使用過濾器之過濾為較佳。過濾器孔徑為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。過濾器可以使用藉由有機溶劑預先清洗者。過濾器的過濾製程中，可以並聯或串聯複數種過濾器而使用。當使用複數種過濾器時，可以組合使用孔徑或材質不同之過濾器。又，可以將各種材料過濾複數次。過濾複數次時，可以為循環過濾。又，可以在加壓之後進行過濾。在加壓之後進行過濾時，進行加壓之壓力為0.05MPa以上且0.3MPa以下為較佳。除了使用過濾器之過濾以外，還可以進行使用吸附材料之雜質去除處理。還可以組合過濾器過濾和使用吸附材料之雜質去除處理。作為吸附材料，能夠使用公知的吸附材料。例如，可舉出矽膠、沸石等無機系吸附材料、活性碳等有機系吸附材料。In addition, for the purpose of removing foreign matter such as dust or particles in the curable resin 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 filtration process of the filter, multiple filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be cyclic filtering. In addition, filtration may be performed after pressurization. When filtering is performed after pressurization, 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 adsorbent materials. It can also be combined with filter filtration and impurity removal treatment using adsorbent materials. 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.

＜硬化性樹脂組成物的用途＞本發明的硬化性樹脂組成物用於形成再配線層用層間絕緣膜為較佳。又，還能夠用於半導體器件的絕緣膜的形成或應力緩衝膜的形成等。<Use of curable resin composition> The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer. In addition, it can also be used for the formation of an insulating film of a semiconductor device, the formation of a stress buffer film, and the like.

（硬化膜、積層體、半導體器件及該等的製造方法）接著，對硬化膜、積層體、半導體裝置及該等的製造方法進行說明。(Cured film, laminate, semiconductor device, and manufacturing methods of these) Next, the cured film, the laminated body, the semiconductor device, and the manufacturing method thereof will be described.

本發明的硬化膜藉由硬化本發明的硬化性樹脂組成物而成。本發明的硬化膜的膜厚例如能夠設為0.5μm以上，且能夠設為1μm以上。又，作為上限值，能夠設為100μm以下，且還能夠設為30μm以下。The cured film of the present invention is formed by curing the curable resin composition of the present invention. The film thickness of the cured film of the present invention can be set to 0.5 μm or more, and can be set to 1 μm or more, for example. Moreover, as an upper limit, it can be 100 micrometers or less, and can also be 30 micrometers or less.

可以將本發明的硬化膜積層2層以上，進而積層3～7層來作為積層體。本發明的積層體包含2層以上的硬化膜，在任意上述硬化膜彼此之間包含金屬層之態樣為較佳。例如，可將至少包含依次積層有第一硬化膜、金屬層、第二硬化膜這3個層之層結構之積層體作為較佳者舉出。上述第一硬化膜及上述第二硬化膜均為本發明的硬化膜，例如，可將上述第一硬化膜及上述第二硬化膜均為藉由硬化本發明的硬化性樹脂組成物而成之膜之態樣作為較佳者舉出。用於形成上述第一硬化膜之本發明的硬化性樹脂組成物和用於形成上述第二硬化膜之本發明的硬化性樹脂組成物可以為組成相同的組成物，亦可以為組成不同之組成物。本發明的積層體中的金屬層可較佳地用作再配線層等的金屬配線。Two or more layers of the cured film of the present invention can be laminated, and 3 to 7 layers can be laminated as a laminated body. The layered product of the present invention includes two or more cured films, and it is preferable to include a metal layer between any of the above-mentioned cured films. For example, a laminate including at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order can be preferably exemplified. The first cured film and the second cured film are both cured films of the present invention. For example, both the first cured film and the second cured film may be formed by curing the curable resin composition of the present invention. The aspect of the film is exemplified as the preferable one. The curable resin composition of the present invention for forming the above-mentioned first cured film and the curable resin composition of the present invention for forming the above-mentioned second cured film may have the same composition or different compositions. Things. The metal layer in the laminate of the present invention can be preferably used as a metal wiring such as a rewiring layer.

作為能夠適用本發明的硬化膜的領域，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，可舉出密封膜、基板材料（柔性印刷電路板的基底膜或覆蓋膜、層間絕緣膜）或藉由對如上述實際安裝用途的絕緣膜進行蝕刻而形成圖案之情況等。關於該等用途，例如，能夠參考Science & Technology Co.,Ltd.“聚醯亞胺的高功能化和應用技術”2008年4月、柿本雅明/監修、CMC技術圖書館“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“最新聚醯亞胺基礎和應用”NTS，2010年8月等。Examples of the field to which the cured 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, a sealing film, a substrate material (a base film or a cover film of a flexible printed circuit board, an interlayer insulating film), or a case where a pattern is formed by etching an insulating film for actual mounting purposes as described above, etc. can 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 Masaki/Supervisor, CMC Technical Library "Polyimide Materials The foundation and development of "Polyimine" issued in November 2011, Japan Polyimine and Aromatic Polymer Research Society/Edition "The latest polyimine basics and applications" NTS, August 2010, etc.

又，本發明中的硬化膜還能夠用於膠印版面或網版版面等版面的製造、蝕刻成型部件的用途、電子尤其微電子中的保護漆及介電層的製造等中。In addition, the cured film in the present invention can also be used for the production of offset printing plates and screen plates, the use of etching molded parts, the production of protective paints and dielectric layers in electronics, especially microelectronics, and the like.

本發明的硬化膜的製造方法（以下，亦簡稱為“本發明的製造方法”。）包括將本發明的硬化性樹脂組成物適用於基材而形成膜之膜形成製程為較佳。本發明的硬化膜的製造方法包括上述膜形成製程以及對上述膜進行曝光之曝光製程及對上述膜進行顯影之顯影製程為較佳。又，本發明的硬化膜的製造方法包括上述膜形成製程及根據需要之上述顯影製程，且包括在50～450℃下加熱上述膜之加熱製程為更佳。具體而言，包括以下的（a）～（d）的製程亦較佳。（a）將硬化性樹脂組成物適用於基材而形成膜（硬化性樹脂組成物層）之膜形成製程（b）膜形成製程之後，對膜進行曝光之曝光製程（c）對經曝光之上述膜進行顯影之顯影製程（d）將經顯影之上述膜在50～450℃下加熱之加熱製程藉由在上述加熱製程中進行加熱，能夠進一步硬化利用曝光硬化之樹脂層。在該加熱製程中，例如上述熱鹼產生劑分解，可獲得充分的硬化性。The production method of the cured film of the present invention (hereinafter, also simply referred to as "the production method of the present invention".) preferably includes a film formation process of applying the curable resin composition of the present invention to a substrate to form a film. The method for producing a cured film of the present invention preferably includes the above-mentioned film formation process, an exposure process for exposing the film, and a development process for developing the film. In addition, the method for producing a cured film of the present invention includes the above-mentioned film forming process and the above-mentioned development process as required, and preferably includes a heating process of heating the above-mentioned film at 50 to 450°C. Specifically, the manufacturing process including the following (a) to (d) is also preferable. (A) Film formation process of applying a curable resin composition to a substrate to form a film (curable resin composition layer) (B) Exposure process for exposing the film after the film formation process (C) Development process for developing the exposed film (D) A heating process in which the developed film is heated at 50～450℃ By heating in the above heating process, the resin layer cured by exposure can be further cured. In this heating process, for example, the above-mentioned hot alkali generator is decomposed, and sufficient hardenability can be obtained.

本發明的較佳實施形態之積層體的製造方法包括本發明的硬化膜的製造方法。本實施形態的積層體的製造方法按照上述之硬化膜的製造方法，形成硬化膜之後，進而再次進行（a）的製程或（a）～（c）的製程、或者（a）～（d）的製程。尤其，依次將上述各製程進行複數次，例如2～5次（亦即，合計3～6次）為較佳。藉由如此對硬化膜進行積層，能夠形成積層體。在本發明中，尤其在設置有硬化膜之部分之上或硬化膜之間或該兩者中設置金屬層為較佳。此外，在積層體的製造中，無需重複（a）～（d）的製程全部，如上述，能夠藉由進行複數次至少（a）、較佳為（a）～（c）或（a）～（d）的製程而獲得硬化膜的積層體。＜膜形成製程（層形成製程）＞本發明的較佳實施形態之製造方法包括將硬化性樹脂組成物適用於基材而形成膜（層狀）之膜形成製程（層形成製程）。The manufacturing method of the laminated body of the preferable embodiment of this invention includes the manufacturing method of the cured film of this invention. The manufacturing method of the laminate of this embodiment follows the above-mentioned method of manufacturing a cured film, after forming a cured film, the process of (a) or the processes of (a) to (c), or (a) to (d) is performed again. The manufacturing process. In particular, it is preferable to sequentially perform the above-mentioned processes a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total). By layering the cured film in this way, a layered body can be formed. In the present invention, it is particularly preferable to provide a metal layer on the part where the cured film is provided, between the cured films, or both. In addition, in the production of the laminate, it is not necessary to repeat all the processes of (a) to (d). As described above, it can be performed multiple times at least (a), preferably (a) to (c) or (a) ~(d) Process to obtain a laminate of cured film. <Film formation process (layer formation process)> The manufacturing method of the preferred embodiment of the present invention includes a film formation process (layer formation process) in which a curable resin composition is applied to a substrate to form a film (layered).

基材的種類能夠依用途而適當設定，但並無特別限制，可舉出矽、氮化矽、多晶矽、氧化矽、非晶矽等半導體製作基材、石英、玻璃、光學膜、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）、TFT（薄膜晶體管）陣列基材、電漿顯示面板（PDP）的電極板等。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，例如使用板狀的基材（基板）。The type of substrate can be appropriately set according to the application, but is not particularly limited. Examples include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, Evaporated film, magnetic film, reflective 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. . In the present invention, semiconductor substrates are particularly preferred, and silicon substrates are more preferred. In addition, as the base material, for example, a plate-shaped base material (substrate) is used.

又，在樹脂層的表面或金屬層的表面形成硬化性樹脂組成物層時，樹脂層或金屬層成為基材。In addition, when the curable resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes the base material.

作為將硬化性樹脂組成物適用於基材之方法，塗佈為較佳。As a method of applying the curable resin composition to the substrate, coating is preferred.

具體而言，作為適用方法，可例示浸塗法、氣刀塗佈法、簾式塗佈法、線棒塗佈法、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。從硬化性樹脂組成物層的厚度均勻性的觀點考慮，更佳為旋塗法、狹縫塗佈法、噴塗法、噴墨法。依方法調整適當的固體成分濃度或塗佈條件，藉此能夠得到所希望的厚度的樹脂層。又，能夠依基材的形狀適當選擇塗佈方法，只要為晶圓等圓形基材，則旋塗法或噴塗法、噴墨法等為較佳，且只要為矩形基材，則狹縫塗佈法或噴塗法、噴墨法等為較佳。在旋塗法的情況下，例如能夠以500～2,000rpm的轉速適用10秒～1分鐘左右。又，亦能夠適用將藉由上述賦予方法預先在偽支撐體上賦予而形成之塗膜轉印在基材上之方法。關於轉印方法，在本發明中，亦能夠較佳地利用日本特開2006-023696號公報的0023、0036～0051段或日本特開2006-047592號公報的0096～0108段中記載之製作方法。Specifically, as applicable methods, there can be exemplified dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, Slit coating method and inkjet method, etc. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, the spin coating method, the slit coating method, the spray method, and the inkjet method are more preferable. By adjusting the appropriate solid content concentration or coating conditions according to the method, a resin layer with a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a round substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and as long as it is a rectangular substrate, 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 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 applying method on a pseudo support in advance to a substrate. Regarding the transfer method, in the present invention, the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can also be preferably used. .

＜乾燥製程＞本發明的製造方法還可以包括在形成上述膜（硬化性樹脂組成物層）之後，膜形成製程（層形成製程）之後，為了去除溶劑而進行乾燥之製程。較佳之乾燥溫度為50～150℃，70℃～130℃為更佳，90℃～110℃為進一步較佳。作為乾燥時間，例示30秒～20分鐘，1分鐘～10分鐘為較佳，3分鐘～7分鐘為更佳。＜Drying process＞ The manufacturing method of the present invention may further include a process of drying in order to remove the solvent after forming the above-mentioned film (curable resin composition layer), followed by a film forming process (layer forming process). 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 are exemplified, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

＜曝光製程＞本發明的製造方法可以包括對上述膜（硬化性樹脂組成物層）進行曝光之曝光製程。曝光量只要能夠使硬化性樹脂組成物硬化，則無特別限定，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 Process> The manufacturing method of the present invention may include an exposure process of exposing the above-mentioned film (curable resin composition layer). The exposure dose is not particularly limited as long as it can harden the curable resin composition. 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的範圍內適當設定，240～550nm為較佳。The exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

關於曝光波長，若以與光源的關係描述，則可舉出（1）半導體雷射（波長830nm、532nm、488nm、405nm etc.）、（2）金屬鹵化物燈、（3）高壓水銀燈、g射線（波長436nm）、h射線（波長405nm）、i射線（波長365nm）、寬（g、h、i射線的3波長）、（4）準分子雷射、KrF準分子雷射（波長248nm）、ArF準分子雷射（波長193nm）、F2準分子雷射（波長157nm）、（5）極紫外線；EUV（波長13.6nm）、（6）電子束等。關於本發明中的硬化性樹脂組成物，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，尤其可得到高的曝光靈敏度。Regarding the exposure wavelength, if it is described in terms of the relationship with the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g Ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, i rays), (4) excimer laser, KrF excimer laser (wavelength 248nm) , ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, etc. Regarding the curable resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is particularly preferred. In this way, particularly high exposure sensitivity can be obtained.

＜顯影製程＞本發明的製造方法可以包括對經曝光之膜（硬化性樹脂組成物層）進行顯影（對上述膜進行顯影）之顯影製程。藉由進行顯影，未曝光之部分（非曝光部）被去除。關於顯影方法，只要能夠形成所希望的圖案，則無特別限制，例如，能夠採用旋覆浸沒、噴霧、浸漬、超音波等顯影方法。＜Development process＞ The manufacturing method of the present invention may include a development process of developing (developing the above-mentioned film) the exposed film (curable resin composition layer). By developing, the unexposed part (non-exposed 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，只要可去除未曝光之部分（非曝光部），則能夠無特別限制地使用。顯影液包含有機溶劑為較佳，顯影液包含90%以上的有機溶劑為更佳。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。ClogP值能夠藉由ChemBioDraw（化學生物圖）輸入結構式而作為計算值來求出。The development is performed using a developer. Regarding the developer, as long as the unexposed part (non-exposed part) can be removed, it can be used without particular limitation. It is preferable that the developer contains an organic solvent, and it is more preferable that the developer contains 90% or more of an 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 calculated as a calculated value by inputting the structural formula from ChemBioDraw (Chemical Biological Diagram).

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：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：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：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***、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***、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、大茴香醚、檸檬烯等，以及作為亞碸類，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 (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 (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 (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 As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. can be preferably cited, and as the sludge, dimethyl sulfoxide can be preferably cited.

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, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred.

顯影液的50質量%以上為有機溶劑為較佳，70質量%以上為有機溶劑為更佳，90質量%以上為有機溶劑為進一步較佳。又，顯影液的100質量%可以為有機溶劑。It is preferable that 50% by mass or more of the developer is an organic solvent, more preferably 70% by mass or more is an organic solvent, and more preferably 90% by mass or more is an organic solvent. In addition, 100% by mass of the developer may be an organic solvent.

作為顯影時間，10秒～5分鐘為較佳。顯影時的顯影液的溫度並無特別限定，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 limited, and it can usually be performed at 20 to 40°C.

在使用顯影液之處理之後，進而可以進行沖洗。沖洗以與顯影液不同之溶劑進行為較佳。例如，能夠使用硬化性樹脂組成物中包含的溶劑進行沖洗。沖洗時間為5秒～1分鐘為較佳。After the treatment with the developer, it can be rinsed. Rinsing is preferably performed with a solvent different from the developer. For example, the solvent contained in the curable resin composition can be used for rinsing. The rinsing time is preferably 5 seconds to 1 minute.

＜加熱製程＞本發明的製造方法包括將經顯影之上述膜在50～450℃下加熱之製程（加熱製程）為較佳。在膜形成製程（層形成製程）、乾燥製程及顯影製程之後包括加熱製程為較佳。在加熱製程中，例如藉由上述熱鹼產生劑分解而產生鹼，並進行特定含雜環聚合物前驅物的環化反應。又，本發明的硬化性樹脂組成物包含在分子內具有2個以上除了特定含雜環聚合物前驅物以外的乙烯性不飽和基之化合物，但在分子內具有2個以上未反應的乙烯性不飽和基之化合物的硬化等亦能夠在該製程中進行。作為加熱製程中層的加熱溫度（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℃以上為更進一步較佳，160℃以上為又進一步較佳，170℃以上為再進一步較佳。作為上限，500℃以下為較佳，450℃以下為更佳，350℃以下為進一步較佳，250℃以下為更進一步較佳，220℃以下為又進一步較佳。＜Heating process＞ The manufacturing method of the present invention preferably includes a process (heating process) in which the developed film is heated at 50 to 450°C. It is preferable to include a heating process after the film forming process (layer forming process), drying process, and developing process. In the heating process, for example, the above-mentioned thermal alkali generator is decomposed to generate alkali, and the cyclization reaction of the specific heterocyclic polymer precursor is carried out. In addition, the curable resin composition of the present invention includes a compound having two or more ethylenic unsaturated groups other than the specific heterocyclic polymer precursor in the molecule, but has two or more unreacted ethylenic groups in the molecule. Hardening of unsaturated group compounds can also be carried out in this process. As the heating temperature (maximum heating temperature) of the layer in the heating process, 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 even more preferred, and 160°C or higher is even further Preferably, 170°C or higher is even more preferable. As the upper limit, 500°C or less is preferred, 450°C or less is more preferred, 350°C or less is more preferred, 250°C or less is even more preferred, and 220°C or less is still more preferred.

關於加熱，從加熱開始時的溫度至最高加熱溫度以1～12℃/分鐘的升溫速度進行為較佳，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，能夠緩和硬化膜的殘存應力。Regarding heating, it is preferable to perform the heating rate from the temperature at the start of heating to the maximum heating temperature at a temperature increase rate of 1-12°C/min, 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 cured film can be alleviated.

加熱開始時的溫度為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製程時的溫度。例如，將硬化性樹脂組成物適用於基材上之後進行乾燥時，為該乾燥後的膜（層）的溫度，例如從比硬化性樹脂組成物中所含有之溶劑的沸點低30～200℃的溫度開始逐漸升溫為較佳。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 process of heating to the highest heating temperature. For example, when the curable resin composition is applied to a 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 curable resin composition It’s better to start to warm up gradually.

加熱時間（最高加熱溫度下的加熱時間）為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 10 to 360 minutes, more preferably 20 to 300 minutes, and more preferably 30 to 240 minutes.

尤其形成多層積層體時，從硬化膜的層間的密接性的觀點考慮，於180℃～320℃的加熱溫度下進行加熱為較佳，於180℃～260℃下進行加熱為更佳。其原因尚不確定，但認為是因為藉由設為該溫度，層間的特定含雜環聚合物前驅物的由可以被取代的乙烯基直接鍵結之芳香環中的乙烯基彼此進行交聯反應。In particular, when forming a multilayer laminate, from the viewpoint of the adhesion between the layers of the cured film, heating at a heating temperature of 180°C to 320°C is preferable, and heating at 180°C to 260°C is more preferable. The reason for this is not certain, but it is believed that by setting the temperature at this temperature, the vinyl groups in the aromatic ring directly bonded with the substituted vinyl group of the specific heterocyclic-containing polymer precursor between the layers undergo cross-linking reaction with each other. .

加熱可以分階段進行。作為例子，可以進行以3℃/分鐘從25℃升溫至180℃，且在180℃下保持60分鐘，以2℃/分鐘從180℃升溫至200℃，且在200℃下保持120分鐘之前處理製程。作為前處理製程之加熱溫度為100～200℃為較佳，110～190℃為更佳，120～185℃為進一步較佳。在該前處理製程中，如美國專利9159547號說明書中所記載，照射紫外線的同時進行處理亦為較佳。藉由該等前處理製程能夠提高膜的特性。前處理製程在10秒～2小時左右的短時間內進行即可，15秒～30分鐘為更佳。前處理可以為兩階段以上的製程，例如可以在100～150℃的範圍內進行前處理製程1，然後於150～200℃的範圍內進行前處理製程2。Heating can be carried out in stages. As an example, it is possible to perform the treatment before raising the temperature from 25°C to 180°C at 3°C/min, and keeping it at 180°C for 60 minutes, heating it from 180°C to 200°C at 2°C/min, and keeping it at 200°C for 120 minutes. Process. The heating temperature of the pretreatment process is preferably 100 to 200°C, more preferably 110 to 190°C, and even more preferably 120 to 185°C. In this pre-treatment process, as described in the specification of US Patent No. 9159547, it is also preferable to perform treatment while irradiating ultraviolet rays. The characteristics of the film can be improved through these pre-treatment processes. The pre-treatment process can be carried out in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pre-treatment may be a two-stage or more process, for example, the pre-treatment process 1 may be performed in the range of 100-150°C, and then the pre-treatment process 2 may be performed in the range of 150-200°C.

進而，可以在加熱之後進行冷卻，作為該情況下的冷卻速度，1～5℃/分鐘為較佳。Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.

關於加熱製程，從防止特定含雜環聚合物前驅物分解的方面考慮，藉由使氮、氦、氬等惰性氣體流過等，在低氧濃度的環境下進行為較佳。氧濃度為50ppm（體積比）以下為較佳，20ppm（體積比）以下為更佳。Regarding the heating process, from the viewpoint of preventing the decomposition of the specific heterocyclic-containing polymer precursor, it is preferable to perform it in an environment of low oxygen concentration by flowing 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.

＜金屬層形成製程＞本發明的製造方法包括在顯影後的膜（硬化性樹脂組成物層）的表面形成金屬層之金屬層形成製程為較佳。＜Metal layer forming process＞ The manufacturing method of the present invention preferably includes a metal layer forming process of forming a metal layer on the surface of the film (curable resin composition layer) after development.

作為金屬層，無特別限定，能夠使用現有的金屬種類，例示出銅、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 include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferable, and copper is still more preferable.

金屬層的形成方法無特別限定，能夠適用現有的方法。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號公報中記載之方法。例如，可考慮光微影、剝離、電解電鍍、無電解電鍍、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化方法、組合光微影與電解電鍍之圖案化方法。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, methods such as photolithography, peeling, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be considered. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating can be cited.

作為金屬層的厚度，在最厚的壁厚部，0.1～50μm為較佳，1～10μm為更佳。As for the thickness of the metal layer, at the thickest part, 0.1 to 50 μm is preferable, and 1 to 10 μm is more preferable.

＜積層製程＞本發明的製造方法還包括積層製程為較佳。＜Layer Process＞ Preferably, the manufacturing method of the present invention also includes a layering process.

積層製程係包括在硬化膜（樹脂層）或金屬層的表面，再次依次進行（a）膜形成製程（層形成製程）、（b）曝光製程、（c）顯影製程、（d）加熱製程之一系列製程。其中，可以為僅重複（a）的膜形成製程之態樣。又，亦可以設為（d）加熱製程在積層的最後或中間統括進行之態樣。亦即，亦可以設為如下態樣：重複進行規定次數的（a）～（c）的製程，之後進行（d）的加熱，藉此將被積層之硬化性樹脂組成物層統括硬化。又，（c）顯影製程之後可以包括（e）金屬層形成製程，此時可以每次進行（d）的加熱，亦可以在積層規定次數之後統括進行（d）的加熱。積層製程中還可以適當包括上述乾燥製程和加熱製程等是毋庸置疑的。The build-up process includes on the surface of the cured film (resin layer) or the metal layer, and then sequentially perform one of (a) film formation process (layer formation process), (b) exposure process, (c) development process, and (d) heating process. A series of manufacturing processes. Among them, it may be a mode in which only the film formation process of (a) is repeated. Moreover, it can also be set as (d) a state in which the heating process is carried out collectively at the end or in the middle of the build-up. That is, it is also possible to adopt a mode in which the processes of (a) to (c) are repeated a predetermined number of times, and then the heating of (d) is performed, thereby collectively curing the laminated curable resin composition layers. In addition, (c) the development process may include (e) the metal layer forming process. In this case, the heating of (d) may be performed each time, or the heating of (d) may be collectively performed after a predetermined number of laminations. There is no doubt that the above-mentioned drying process and heating process can also be appropriately included in the build-up process.

在積層製程之後進而進行積層製程時，可以在上述加熱製程之後，在上述曝光製程之後或在上述金屬層形成製程之後，進而進行表面活化處理製程。作為表面活化處理，例示出電漿處理。When the build-up process is further performed after the build-up process, the surface activation treatment process may be further performed after the above-mentioned heating process, after the above-mentioned exposure process, or after the above-mentioned metal layer formation process. As the surface activation treatment, plasma treatment is exemplified.

上述積層製程進行2～5次為較佳，進行3～5次為更佳。The above-mentioned layering process is preferably carried out 2 to 5 times, and it is more preferable to carry out 3 to 5 times.

例如，如樹脂層/金屬層/樹脂層/金屬層/樹脂層/金屬層等樹脂層為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, resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer are preferably three or more and seven or less resin layers, and more preferably three or more and five or less resin layers.

本發明中，尤其在設置金屬層之後，進一步以覆蓋上述金屬層的方式，形成上述硬化性樹脂組成物的硬化膜（樹脂層）之態樣為較佳。具體而言，可舉出依次重複（a）膜形成製程、（b）曝光製程、（c）顯影製程、（e）金屬層形成製程、（d）加熱製程之態樣或依次重複（a）膜形成製程、（b）曝光製程、（c）顯影製程、（e）金屬層形成製程，並在最後或中間統括設置（d）加熱製程之態樣。藉由交替進行積層硬化性樹脂組成物層（樹脂層）之積層製程和金屬層形成製程，能夠交替積層硬化性樹脂組成物層（樹脂層）和金屬層。In the present invention, it is particularly preferable to form a cured film (resin layer) of the curable resin composition by covering the metal layer after the metal layer is provided. Specifically, it can be mentioned that (a) film formation process, (b) exposure process, (c) development process, (e) metal layer formation process, (d) heating process are repeated in sequence, or (a) is repeated in sequence Film formation process, (b) exposure process, (c) development process, (e) metal layer formation process, and (d) heating process is set at the end or in the middle. By alternately performing the laminating process of laminating the curable resin composition layer (resin layer) and the metal layer forming process, the curable resin composition layer (resin layer) and the metal layer can be alternately laminated.

本發明亦揭示包含本發明的硬化膜或積層體之半導體器件。作為將本發明的硬化性樹脂組成物使用在再配線層用層間絕緣膜的形成中之半導體器件的具體例，能夠參考日本特開2016-027357號公報的0213～0218段的記載及圖1的記載，並將該等內容編入本說明書中。 [實施例]The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the curable resin composition of the present invention is used in 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 FIG. 1 Record and incorporate such content into this manual. [Example]

以下，舉出實施例對本發明進行進一步詳細的說明。以下的實施例中所示出之材料、使用量、比例、處理內容、處理步驟等只要不脫離本發明的宗旨，則能夠適當進行變更。因此，本發明的範圍並不限定於以下所示之具體例。只要無特別說明，則“份”、“%”為質量基準。Hereinafter, the present invention will be described in further detail 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. Unless otherwise specified, "parts" and "%" are quality standards.

＜合成例1＞〔源自4,4’-氧二鄰苯二甲酸二酐、4,4’-二胺基二苯醚及4-胺基苯乙烯的聚醯亞胺前驅物（A-1）的合成〕將20.0g（64.5毫莫耳）的4,4’-氧二鄰苯二甲酸酐（在140℃下乾燥了12小時）、15.4g（129毫莫耳）的4-胺基苯乙烯、0.05g的對苯二酚、20.4g（258毫莫耳）的吡啶及100g的二甘醇二甲醚進行混合，在0℃下攪拌1小時，繼續在60℃下攪拌1小時，藉此製造了4,4’-氧二鄰苯二甲酸與4-胺基苯乙烯的加成物。將反應混合物冷卻至室溫，並添加了21.43g（270.9毫莫耳）的吡啶及90mL的N-甲基吡咯啶酮。接著，將反應混合物冷卻至-10℃，將溫度保持在-10±4℃的同時經10分鐘添加了16.12g（135.5毫莫耳）的SOCl₂ 。用50mL的N-甲基吡咯啶酮稀釋之後，在室溫下將反應混合物攪拌了2小時。接著，將11.08g（58.7毫莫耳）的4,4’-二胺基二苯醚溶解於100mL的N-甲基吡咯啶酮而成之溶液在保持為-5～0℃的溫度下經20分鐘滴加至反應混合物中。接著，在0℃下使反應混合物反應1小時之後，添加70g的乙醇，並在室溫下攪拌了一晚。接著，使聚醯亞胺前驅物在5升水中沉澱，以5,000rpm的速度將水-聚醯亞胺前驅物混合物攪拌了15分鐘。藉由過濾去除聚醯亞胺前驅物，在4升水中再次攪拌30分鐘，並再次進行了過濾。接著，在減壓下，在45℃下將所獲得之聚醯亞胺前驅物乾燥了3天。該聚醯亞胺前驅物的重量平均分子量為18,000。 [化學式56]

<Synthesis Example 1> [Polyimine precursors derived from 4,4'-oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether, and 4-aminostyrene (A- 1) Synthesis] 20.0g (64.5 millimoles) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 15.4g (129 millimoles) of 4-amine Styrene, 0.05g hydroquinone, 20.4g (258 millimoles) of pyridine and 100g of diglyme were mixed, stirred at 0°C for 1 hour, and continued to stir at 60°C for 1 hour Thus, an adduct of 4,4'-oxydiphthalic acid and 4-aminostyrene was produced. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 millimoles) of SOCl _{2 was} added over 10 minutes while maintaining the temperature at -10±4°C. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred for 2 hours at room temperature. Next, a solution obtained by dissolving 11.08 g (58.7 millimoles) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was maintained at a temperature of -5 to 0°C. Add dropwise to the reaction mixture for 20 minutes. Next, after reacting the reaction mixture at 0°C for 1 hour, 70 g of ethanol was added and stirred at room temperature overnight. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimine precursor mixture was stirred at a speed of 5,000 rpm for 15 minutes. The polyimide precursor was removed by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, under reduced pressure, the obtained polyimide precursor was dried at 45°C for 3 days. The weight average molecular weight of the polyimide precursor was 18,000. [Chemical formula 56]

＜合成例2＞〔源自2,2'-雙（3-胺基-4-羥基苯基）六氟丙烷及4,4'-氧代二苯甲醯氯及4-乙烯基苯甲醯氯的聚苯并㗁唑前驅物（A-2）的合成〕向N-甲基-2-吡咯啶酮100mL添加2,2’-雙（3-胺基-4-羥基苯基）六氟丙烷13.92g並進行了攪拌溶解。接著，將溫度保持在0～5℃的同時經10分鐘滴加11.21g的4,4’-氧代二苯甲醯氯之後，持續攪拌了60分鐘。之後，添加4-乙烯基苯甲醯氯（1.27g），並攪拌了60分鐘。接著，使聚苯并㗁唑前驅物在6升水中沉澱，以5000rpm的速度將水-聚苯并㗁唑前驅物混合物攪拌了15分鐘。過濾去除聚苯并㗁唑前驅物，在6升水中再次攪拌30分鐘，並再次進行了過濾。接著，在減壓下，以45℃將所獲得之聚苯并㗁唑前驅物乾燥了3天。該聚苯并㗁唑前驅物的重量平均分子量為15,000。＜Synthesis example 2＞〔Polybenzoic acid derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxodibenzoic acid chloride and 4-vinylbenzoic acid chloride Synthesis of azole precursor (A-2)] 13.92 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to 100 mL of N-methyl-2-pyrrolidone, and the mixture was stirred and dissolved. Next, 11.21 g of 4,4'-oxobenzyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5°C, and then stirring was continued for 60 minutes. After that, 4-vinylbenzyl chloride (1.27 g) was added and stirred for 60 minutes. Next, the polybenzoxazole precursor was precipitated in 6 liters of water, and the water-polybenzoxazole precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polybenzoxazole precursor was removed by filtration, stirred again for 30 minutes in 6 liters of water, and filtered again. Next, the obtained polybenzoxazole precursor was dried at 45°C for 3 days under reduced pressure. The weight average molecular weight of this polybenzoxazole precursor was 15,000.

＜合成例3＞〔源自4,4’-氧二鄰苯二甲酸酐、4,4’-二胺基二苯醚及甲基丙烯酸-2-羥基乙酯的聚醯亞胺前驅物（A-3：具有自由基聚合性基團之聚醯亞胺前驅物）的合成〕將4,4’-氧二鄰苯二甲酸二酐（ODPA）155.1g放入2升容量的分離式燒瓶中，並添加了甲基丙烯酸-2-羥基乙酯（HEMA）134.0g及γ-丁內酯400ml。一邊在室溫下攪拌，一邊添加吡啶79.1g，藉此獲得了反應混合物。基於反應之發熱結束後，冷卻至室溫，進而靜置了16小時。接著，在冰冷下，將二環己碳二亞胺（DCC）206.3g溶解於γ-丁內酯180ml之溶液一邊攪拌一邊經40分鐘添加到了反應混合物。接著，一邊攪拌一邊經60分鐘添加了將4,4’-二胺基二苯醚93.0g懸浮於γ-丁內酯350ml之懸浮液。進而在室溫下攪拌2小時之後，添加乙醇30ml並攪拌了1小時。之後，添加了γ-丁內酯400ml。藉由過濾去除反應混合物生成之沉澱物，藉此獲得了反應液。將所獲得之反應液添加到3升的乙醇中，生成了由粗聚合物構成之沉澱物。濾取所生成之粗聚合物，溶解於四氫呋喃1.5升，藉此獲得了粗聚合物溶液。將所獲得之粗聚合物溶液滴加於28升水中，使聚合物沉澱，濾取所獲得之沉澱物之後進行真空乾燥，藉此獲得了粉末狀的聚合物A-3。測定該聚合物A-3的重量平均分子量（Mw）之結果，為20,000。＜Synthesis example 3＞ [Polyimine precursors derived from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-3: with Synthesis of polyimide precursors of radical polymerizable groups] Put 155.1g of 4,4'-oxydiphthalic dianhydride (ODPA) into a 2-liter separable flask, and add 134.0g of 2-hydroxyethyl methacrylate (HEMA) and γ- Butyrolactone 400ml. While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After the exotherm due to the reaction was over, it was cooled to room temperature and left to stand for 16 hours. Next, under ice cooling, a solution in which 206.3 g of dicyclohexanecarbodiimide (DCC) was dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Next, while stirring, a suspension in which 93.0 g of 4,4'-diaminodiphenyl ether was suspended in 350 ml of γ-butyrolactone was added over 60 minutes. After further stirring for 2 hours at room temperature, 30 ml of ethanol was added and stirred for 1 hour. After that, 400 ml of γ-butyrolactone was added. The precipitate formed from the reaction mixture was removed by filtration, thereby obtaining a reaction liquid. The obtained reaction liquid was added to 3 liters of ethanol, and a precipitate composed of crude polymer was formed. The produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was filtered and dried in a vacuum, thereby obtaining a powdery polymer A-3. As a result of measuring the weight average molecular weight (Mw) of the polymer A-3, it was 20,000.

＜合成例4＞〔源自3,3’,4,4’-聯苯四羧酸二酐、4,4’-二胺基二苯醚及甲基丙烯酸-2-羥基乙酯的聚醯亞胺前驅物（A-4：具有自由基聚合性基團之聚醯亞胺前驅物）的合成〕在合成例3中，使用3,3’4,4’-聯苯四羧酸二酐147.1g來代替4,4’-氧二鄰苯二甲酸二酐155.1g，除此以外，以與合成例3中記載之方法相同的方法進行反應，藉此獲得了聚合物A-4。測定該聚合物A-4的重量平均分子量（Mw）之結果，為22,000。＜Synthesis example 4＞ [Polyimine precursors derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate ( A-4: Synthesis of polyimide precursors with radical polymerizable groups] In Synthesis Example 3, 147.1g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1g of 4,4'-oxydiphthalic dianhydride. In addition, it was combined with The reaction was carried out in the same manner as the method described in Example 3, thereby obtaining a polymer A-4. As a result of measuring the weight average molecular weight (Mw) of the polymer A-4, it was 22,000.

＜合成例5＞〔化合物B-1的合成〕向三口燒瓶添加甲醇450g、試鉍硫醇（TCI製）15g、三乙胺25.3g，並使其完全溶解。之後，一邊進行冰冷，一邊經20分鐘滴加了溶解於甲醇50g之對氯甲基苯乙烯（AGC SEIMI CHEMICAL CO., LTD.製）30.5g。滴加結束後，一邊進行冰冷，一般攪拌了4小時（在反應液中析出了晶體）。將反應液添加到純水1,000g中，並在室溫下攪拌30分鐘後，濾出了晶體。將所獲得之粗晶體在甲醇300g、乙酸乙酯100g中再次漿化，並在真空下進行乾燥，藉此獲得了11.5g的B-1（產率30%）。＜Synthesis example 5＞ [Synthesis of Compound B-1] To a three-necked flask, 450 g of methanol, 15 g of test bismuth mercaptan (manufactured by TCI), and 25.3 g of triethylamine were added and completely dissolved. Then, while cooling on ice, 30.5 g of p-chloromethylstyrene (manufactured by AGC SEIMI CHEMICAL CO., LTD.) dissolved in 50 g of methanol was added dropwise over 20 minutes. After the dropping was completed, it was generally stirred for 4 hours while cooling on ice (crystals precipitated in the reaction solution). The reaction liquid was added to 1,000 g of pure water, and after stirring at room temperature for 30 minutes, crystals were filtered out. The obtained crude crystals were slurried again in 300 g of methanol and 100 g of ethyl acetate, and dried under vacuum, thereby obtaining 11.5 g of B-1 (yield 30%).

〔化合物B-5及化合物B-12的合成〕將合成原料適當變更，除此以外，以與上述化合物B-1的合成相同的方法合成了化合物B-5及B-12。化合物B-1、B-5及B-12的結構分別如下述式（B-1）、式（B-5）或式（B-12）所示。[Synthesis of Compound B-5 and Compound B-12] Except for appropriately changing the synthesis raw materials, compounds B-5 and B-12 were synthesized by the same method as the synthesis of the above-mentioned compound B-1. The structures of compounds B-1, B-5, and B-12 are as shown in the following formula (B-1), formula (B-5) or formula (B-12), respectively.

[化學式57]

[Chemical formula 57]

＜實施例及比較例＞在各實施例中，分別混合下述表1中記載之成分，藉此獲得了各硬化性樹脂組成物。又，在各比較例中，分別混合下述表1中記載之成分，藉此獲得了各比較用組成物。具體而言，表1中除“溶劑”以外的欄中記載之成分的含量設為表1的“質量份”中記載之量，表1的“溶劑”一欄中記載之成分的含量設為組成物的固體成分濃度成為表1中記載之值的量。又，例如表1的“溶劑”的“I-1/I-2”“80/20”的記載表示I-1與I-2的含量比以質量比計為I-1:I-2=80:20。使所獲得之硬化性樹脂組成物及比較用組成物通過細孔寬度為0.8μm的聚四氟乙烯製過濾器來進行了加壓過濾。又，在表1中，“-”的記載表示組成物不含有該成分。<Examples and Comparative Examples> In each example, the components described in the following Table 1 were mixed to obtain each curable resin composition. In addition, in each comparative example, the components described in the following Table 1 were mixed to obtain each comparative composition. Specifically, the content of the components described in the column other than "solvent" in Table 1 is the amount described in the "parts by mass" of Table 1, and the content of the component described in the "solvent" column of Table 1 is The solid content concentration of the composition becomes the value described in Table 1. Also, for example, the description of "I-1/I-2" and "80/20" of the "solvent" in Table 1 indicates that the content ratio of I-1 to I-2 is I-1: I-2 = 80:20. The obtained curable resin composition and the comparative composition were filtered under pressure through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm. In addition, in Table 1, the description of "-" indicates that the composition does not contain the component.

[表1] 實施例比較例 1 2 3 4 5 6 7 8 9 10 11 12 13 14 1 固體成分濃度（質量%） 42 42 42 42 42 42 42 42 42 42 42 42 42 40 40 聚合物前驅物種類 A-1 A-2 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 /A-4 A-3 /A-4 質量份 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 43 /43 43 /43 由式（1-1）表示之化合物種類 B-1 B-1 B-5 B-12 B-1 B-1 B-1 B-1 B-1 - B-1 B-1 B-1 - - 質量份 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 - 6.06 6.06 6.06 - - 聚合性化合物種類 - - - - - - - - - C-1 C-1 C-2 C-3 C-1 C-1 質量份 - - - - - - - - - 12.12 6.06 6.06 6.06 6.75 6.75 添加劑種類 - - - - - - - - - - - - - J-1 J-1 質量份 - - - - - - - - - - - - - 3.5 3.5 光聚合起始劑種類 D-1 D-1 D-1 D-1 D-2 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 質量份 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 1.75 1.75 鎓鹽或熱鹼產生劑種類 E-1 E-1 E-1 E-1 E-1 E-2 E-1 E-1 E-1 E-1 E-1 E-1 E-1 - - 質量份 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 - - 聚合抑制劑種類 F-1 F-1 F-1 F-1 F-1 F-1 F-2 F-1 F-1 F-1 F-1 F-1 F-1 F-3 F-3 質量份 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.05 0.05 遷移抑制劑種類 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-2 G-1 G-1 G-1 G-1 G-1 - - 質量份 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 - - 金屬接著性改良劑種類 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-2 H-1 H-1 H-1 H-1 H-2 /H-3 H-2 /H-3 質量份 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 0.5 /0.5 0.5 /0.5 溶劑種類 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-3 /I-4 I-3 /I-4 質量比 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 評價結果耐藥品性 A A A B A A A A A B A A A A C [Table 1] Example Comparative example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 1 Solid content concentration (mass%) 42 42 42 42 42 42 42 42 42 42 42 42 42 40 40 Polymer precursor species A-1 A-2 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 /A-4 A-3 /A-4 Mass parts 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 80.74 43 /43 43 /43 Compound represented by formula (1-1) species B-1 B-1 B-5 B-12 B-1 B-1 B-1 B-1 B-1 - B-1 B-1 B-1 - - Mass parts 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 12.12 - 6.06 6.06 6.06 - - Polymeric compound species - - - - - - - - - C-1 C-1 C-2 C-3 C-1 C-1 Mass parts - - - - - - - - - 12.12 6.06 6.06 6.06 6.75 6.75 additive species - - - - - - - - - - - - - J-1 J-1 Mass parts - - - - - - - - - - - - - 3.5 3.5 Photopolymerization initiator species D-1 D-1 D-1 D-1 D-2 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 Mass parts 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 2.83 1.75 1.75 Onium salt or thermal base generator species E-1 E-1 E-1 E-1 E-1 E-2 E-1 E-1 E-1 E-1 E-1 E-1 E-1 - - Mass parts 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 - - Polymerization inhibitor species F-1 F-1 F-1 F-1 F-1 F-1 F-2 F-1 F-1 F-1 F-1 F-1 F-1 F-3 F-3 Mass parts 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.05 0.05 Migration inhibitor species G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-2 G-1 G-1 G-1 G-1 G-1 - - Mass parts 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 0.28 - - Metal adhesion improver species H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-2 H-1 H-1 H-1 H-1 H-2 /H-3 H-2 /H-3 Mass parts 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 1.61 0.5 /0.5 0.5 /0.5 Solvent species I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-1 /I-2 I-3 /I-4 I-3 /I-4 Mass ratio 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 80/20 Evaluation results Chemical resistance A A A B A A A A A B A A A A C

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

〔聚合物前驅物〕・A-1～A-4：以上合成之A-1～A-4〔Polymer precursor〕・A-1～A-4: A-1～A-4 synthesized above

〔特定聚合性化合物〕・B-1、B-5及B-12：以上合成之B-1、B-5及B-12[Specific polymerizable compound] ・B-1, B-5 and B-12: B-1, B-5 and B-12 synthesized above

〔聚合性化合物〕・C-1～C-3：下述結構的化合物 [化學式58]

[Polymerizable compound] ・C-1～C-3: Compounds of the following structure [Chemical formula 58]

〔添加劑〕・J-1：N-苯基二乙醇胺（Tokyo Chemical Industry Co., Ltd.製）〔additive〕・J-1: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

〔光聚合起始劑〕・D-1及D-2：下述結構的化合物 [化學式59]

[Photopolymerization initiator] ・D-1 and D-2: Compounds of the following structure [Chemical formula 59]

〔熱鹼產生劑〕・E-1～E-2：下述結構的化合物 [化學式60]

[Hot alkali generator] ・E-1～E-2: Compounds of the following structure [Chemical formula 60]

〔聚合抑制劑〕・F-1～F-2：下述結構的化合物・F-3：2-亞硝基-1-萘酚（Tokyo Chemical Industry Co., Ltd.製） [化學式61]

[Polymerization inhibitor] ・F-1 to F-2: Compounds of the following structure ・F-3: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) [Chemical formula 61]

〔遷移抑制劑〕・G-1～G-2：下述結構的化合物 [化學式62]

〔金屬接著性改良劑〕・H-1～H-3：下述結構的化合物 [化學式63]

[Migration inhibitor] ・G-1～G-2: Compounds of the following structure [Chemical formula 62]

[Metal Adhesion Improver] ・H-1～H-3: Compounds of the following structure [Chemical formula 63]

〔溶劑〕・I-1：γ-丁內酯（SANWAYUKA INDUSTRY CORPORATION製）・I-2：二甲基亞碸（FUJIFILM Wako Pure Chemical Corporation製）・I-3：N-甲基-2-吡咯啶酮（Ashland公司製）・I-4：乳酸乙酯（Tokyo Chemical Industry Co., Ltd.製）〔Solvent〕・I-1: γ-Butyrolactone (manufactured by SANWAYUKA INDUSTRY CORPORATION) ・I-2: Dimethyl sulfide (manufactured by FUJIFILM Wako Pure Chemical Corporation) ・I-3: N-Methyl-2-pyrrolidone (manufactured by Ashland) ・I-4: Ethyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.)

＜硬化膜的製造＞在各實施例及比較例中，藉由旋塗法，分別將硬化性樹脂組成物或比較用組成物適用於矽晶圓上來形成了樹脂層。將形成有上述樹脂層之矽晶圓在加熱板上，以100℃乾燥4分鐘，在矽晶圓上形成了20μm的均勻厚度的樹脂組成物層。利用寬帶曝光機（USHIO INC.製：UX-1000SN-EH01），以400mJ/cm² 的曝光能對矽晶圓上的樹脂組成物層進行曝光，將經曝光的樹脂組成物層在氮氣氛氣下，以5℃/分鐘的升溫速度升溫，達到180℃之後，在該溫度加熱了2小時。將上述加熱後的樹脂組成物層及矽晶圓浸漬於3質量%氟氫酸水溶液，並從矽晶圓剝離了加熱後的樹脂組成物層。將上述剝離之加熱後的樹脂組成物層作為硬化膜。<Production of Cured Film> In each of the Examples and Comparative Examples, a curable resin composition or a comparative composition was applied to a silicon wafer by a spin coating method to form a resin layer. The silicon wafer on which the resin layer was formed was dried on a hot plate at 100°C for 4 minutes to form a resin composition layer with a uniform thickness of 20 μm on the silicon wafer. The wide exposure device (manufactured by USHIO INC.:. UX-1000SN-EH01) , an exposure 400mJ / cm ² of energy to the resin composition layer on the silicon wafer is exposed through the resin composition layer is exposed in an atmosphere of nitrogen gas Next, the temperature was increased at a temperature increase rate of 5°C/min, and after reaching 180°C, it was heated at that temperature for 2 hours. The heated resin composition layer and the silicon wafer were immersed in a 3% by mass hydrofluoric acid aqueous solution, and the heated resin composition layer was peeled from the silicon wafer. The resin composition layer after the peeling and heating is used as a cured film.

＜評價＞在各實施例及比較例中，分別用所獲得之上述硬化膜，進行了耐藥品性的評價。以下，記載各評價中的評價方法的詳細內容。＜Evaluation＞ In each of the Examples and Comparative Examples, the obtained cured films were used to evaluate the chemical resistance. Hereinafter, the details of the evaluation method in each evaluation are described.

〔耐藥品性〕將所獲得之硬化膜在下述條件下浸漬於下述藥液中，計算了溶解速度。藥品：二甲基亞碸（DMSO）與25質量%的氫氧化四甲基銨（TMAH）水溶液的90:10（質量比）的混合物評價條件：將硬化膜在藥液中，以75℃浸漬15分鐘，比較浸漬前後的膜厚，計算了溶解速度（nm/分鐘）。利用橢偏儀（Foothill公司製KT-22）在塗佈面10處實施膜厚測定，作為其算術平均值求出了膜厚測定。按照下述評價基準進行評價，將評價結果記載於表1。可以說溶解速度值越小，硬化膜的耐藥品性越優異。〔Chemical resistance〕 The obtained cured film was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated. Medicine: 90:10 (mass ratio) mixture of dimethyl sulfide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution Evaluation conditions: The cured film was immersed in the chemical solution at 75°C for 15 minutes, the film thickness before and after the immersion were compared, and the dissolution rate (nm/min) was calculated. The film thickness measurement was performed at 10 places on the coated surface using an ellipsometer (KT-22 manufactured by Foothill), and the film thickness measurement was obtained as an arithmetic mean value. The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in Table 1. It can be said that the smaller the dissolution rate value, the better the chemical resistance of the cured film.

-評價基準- A：溶解速度低於250nm/分鐘。 B：溶解速度為250nm/分鐘以上且低於500nm/分鐘。 C：溶解速度為500nm/分鐘以上。-Evaluation criteria- A: The dissolution rate is lower than 250 nm/min. B: The dissolution rate is 250 nm/min or more and less than 500 nm/min. C: The dissolution rate is 500 nm/min or more.

從以上結果可知，藉由本發明之包含特定含雜環聚合物前驅物之硬化性樹脂組成物獲得之硬化膜的耐藥品性優異。比較例1之硬化性樹脂組成物不包含特定含雜環聚合物前驅物。可知藉由該比較例1之硬化性樹脂組成物獲得之硬化膜的耐藥品性差。From the above results, it can be seen that the cured film obtained from the curable resin composition containing the specific heterocyclic polymer precursor of the present invention has excellent chemical resistance. The curable resin composition of Comparative Example 1 does not include a specific heterocyclic-containing polymer precursor. It can be seen that the cured film obtained from the curable resin composition of Comparative Example 1 has poor chemical resistance.

＜實施例101＞藉由旋塗法將實施例1中使用的硬化性樹脂組成物層狀適用於形成有銅薄層之樹脂基材的表面，在100℃下乾燥5分鐘，藉此形成膜厚20μm的硬化性樹脂組成物層之後，用步進機（Nikon Corporation製，NSR1505 i6）進行了曝光。經由遮罩（圖案為1:1線與空間，線寬為10μm的二元遮罩），在波長365nm下進行了曝光。曝光之後，用環戊酮顯影30秒，用PGMEA沖洗20秒而得到了層的圖案。接著，在230℃下加熱3小時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了半導體器件之結果，確認到正常工作。<Example 101> The curable resin composition used in Example 1 was applied to the surface of a resin substrate with a thin copper layer by spin coating, and dried at 100°C for 5 minutes to form a curable film with a thickness of 20 μm After the resin composition layer, exposure was performed with a stepper (manufactured by Nikon Corporation, NSR1505 i6). Through a mask (a binary mask with a pattern of 1:1 lines and spaces and a line width of 10 μm), exposure was performed at a wavelength of 365 nm. After exposure, it was developed with cyclopentanone for 30 seconds and washed with PGMEA for 20 seconds to obtain a layer pattern. Then, it heated at 230 degreeC for 3 hours, and the interlayer insulating film for rewiring layers was formed. The interlayer insulating film for the rewiring layer has excellent insulating properties. In addition, as a result of fabricating semiconductor devices using these interlayer insulating films for rewiring layers, normal operation was confirmed.

無no

Claims

一種硬化性樹脂組成物，其係包含選自包括聚醯亞胺前驅物及聚苯并㗁唑前驅物之群組中之至少1種聚合物前驅物，前述聚合物前驅物包含由可以被取代的乙烯基直接鍵結之芳香環。A curable resin composition comprising at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, The aforementioned polymer precursor contains an aromatic ring directly bonded with a vinyl group which may be substituted.

如請求項1所述之硬化性樹脂組成物，其中前述聚合物前驅物係具有由下述式（1）表示之重複單元之聚醯亞胺前驅物或具有由下述式（2）表示之重複單元之聚苯并㗁唑前驅物，

在式（1）或式（2）中，A¹ 及A² 分別獨立地表示氧原子或-NH-，R¹¹¹ 表示2價有機基團，R¹¹⁵ 表示4價有機基團，R¹¹³ 及R¹¹⁴ 分別獨立地表示氫原子或1價有機基團，R¹¹³ 及R¹¹⁴ 中的至少一個包含由可以被取代的乙烯基直接鍵結之芳香環，R¹²¹ 表示2價有機基團，R¹²² 表示4價有機基團，R¹²³ 及R¹²⁴ 分別獨立地表示氫原子或1價有機基團，R¹²³ 及R¹²⁴ 中的至少一個包含由可以被取代的乙烯基直接鍵結之芳香環。The curable resin composition according to claim 1, wherein the polymer precursor is a polyimide precursor having a repeating unit represented by the following formula (1) or having a polyimide precursor represented by the following formula (2) Polybenzoxazole precursors of repeating units,

如請求項1或請求項2所述之硬化性樹脂組成物，其係包含由下述式（S-1）表示之基團作為具有前述由可以被取代的乙烯基直接鍵結之芳香環之基團，

在式（S-1）中，R^S1 表示氫原子或甲基，R^S2 表示取代基，L^S1 表示單鍵或2價連結基，n表示0～4的整數，*表示與其他結構的鍵結部位。The curable resin composition according to claim 1 or claim 2, which contains a group represented by the following formula (S-1) as a group having the aforementioned aromatic ring directly bonded with a vinyl group which may be substituted Group,

如請求項1或請求項2所述之硬化性樹脂組成物，其中前述由可以被取代的乙烯基直接鍵結之芳香環的量相對於前述聚合物前驅物的總質量為1mol/g～8mol/g。The curable resin composition according to claim 1 or 2, wherein The amount of the aforementioned aromatic ring directly bonded with the vinyl group that may be substituted is 1 mol/g to 8 mol/g relative to the total mass of the aforementioned polymer precursor.

如請求項1或請求項2所述之硬化性樹脂組成物，其係進一步包含在分子內具有2個以上乙烯性不飽和基之化合物。The curable resin composition according to claim 1 or claim 2, which further includes a compound having two or more ethylenically unsaturated groups in the molecule.

如請求項5所述之硬化性樹脂組成物，其中前述在分子內具有2個以上乙烯性不飽和基之化合物係在分子內具有2個以上由可以被取代的乙烯基直接鍵結之芳香環之化合物。The curable resin composition according to claim 5, wherein The aforementioned compound having two or more ethylenically unsaturated groups in the molecule is a compound having two or more aromatic rings in the molecule directly bonded with a vinyl group which may be substituted.

如請求項6所述之硬化性樹脂組成物，其中前述在分子內具有2個以上由可以被取代的乙烯基直接鍵結之芳香環之化合物係由下述式（1-1）表示之化合物，

在式（1-1）中，Z係選自包括2價以上的飽和脂肪族烴基、2價以上的不飽和脂肪族烴基、2價以上的烴環基、-O-、-S-、-N（R^A ）-、-C（=O）-O-、-C（R^A ）=N-、-C（=O）-、-S（=O）₂ -、2價以上的雜環基及該等鍵結2個以上之基團之群組中之m價連結基，R^A 表示氫原子、烷基或芳基，R^A 存在複數個時，複數個R^A 可以相同，亦可以不同，R¹ 分別獨立地表示氫原子或甲基，m表示2～6的整數。The curable resin composition according to claim 6, wherein the compound having two or more aromatic rings directly bonded to a vinyl group which may be substituted in the molecule is a compound represented by the following formula (1-1) ,

In formula (1-1), Z is selected from the group consisting of saturated aliphatic hydrocarbon groups with a valence of two or more, unsaturated aliphatic hydrocarbon groups with a valence of two or more, a hydrocarbon ring group with a valence of two or more, -O-, -S-,- N(R ^A )-, -C(=O)-O-, -C(R ^A )=N-, -C(=O)-, -S(=O) ₂ -, heterocyclic rings with more than divalent m group and these divalent groups are bonded two or more of the group of the linking group, R ^A represents a hydrogen atom, an alkyl group or an aryl group, in the presence of a plurality of R ^A, R ^A plurality may be the same, can also Different, R ¹ each independently represents a hydrogen atom or a methyl group, and m represents an integer of 2-6.

如請求項1或請求項2所述之硬化性樹脂組成物，其係進一步包含光自由基聚合起始劑。The curable resin composition according to Claim 1 or Claim 2, which further contains a photoradical polymerization initiator.

如請求項1或請求項2所述之硬化性樹脂組成物，其係進一步包含鎓鹽。The curable resin composition according to claim 1 or claim 2, which further contains an onium salt.

如請求項1或請求項2所述之硬化性樹脂組成物，其係用於形成再配線層用層間絕緣膜。The curable resin composition according to claim 1 or claim 2, which is used to form an interlayer insulating film for a rewiring layer.

一種硬化膜，其係藉由硬化請求項1至請求項10之任一項所述之硬化性樹脂組成物而成。A cured film formed by curing the curable resin composition described in any one of claim 1 to claim 10.

一種積層體，其係包含2層以上的請求項11所述之硬化膜，在任意前述硬化膜彼此之間包含金屬層。A laminate comprising two or more layers of the cured film described in claim 11, and including a metal layer between any of the cured films.

一種硬化膜的製造方法，其係包括將請求項1至請求項10之任一項所述之硬化性樹脂組成物適用於基材而形成膜之膜形成製程。A method for producing a cured film, which includes a film forming process of applying the curable resin composition according to any one of claims 1 to 10 to a substrate to form a film.

如請求項13所述之硬化膜的製造方法，其係包括對前述膜進行曝光之曝光製程及對前述膜進行顯影之顯影製程。The method for producing a cured film according to claim 13, which includes an exposure process for exposing the film and a development process for developing the film.

如請求項13或請求項14所述之硬化膜的製造方法，其係包括在50℃～450℃下加熱前述膜之加熱製程。The method for producing a cured film according to claim 13 or claim 14, which includes a heating process of heating the aforementioned film at 50°C to 450°C.

一種半導體器件，其係包含請求項11所述之硬化膜或請求項12所述之積層體。A semiconductor device comprising the cured film described in claim 11 or the laminated body described in claim 12.