TW202244039A - Resin composition, cured product, laminate, method for producing cured product, semiconductor device, and base generator - Google Patents

Resin composition, cured product, laminate, method for producing cured product, semiconductor device, and base generator Download PDF

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TW202244039A
TW202244039A TW111111703A TW111111703A TW202244039A TW 202244039 A TW202244039 A TW 202244039A TW 111111703 A TW111111703 A TW 111111703A TW 111111703 A TW111111703 A TW 111111703A TW 202244039 A TW202244039 A TW 202244039A
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resin composition
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浅川大輔
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日商富士軟片股份有限公司
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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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Abstract

Provided are: a resin composition including a precursor of a cyclized resin and a base generator, wherein the base generated by the base generator is a base that cyclizes within the same molecule and becomes a tertiary amine, and the base generated by the base generator is neither an [alpha],[beta]-unsaturated carbonyl compound nor an [alpha],[beta]-unsaturated imine compound; a cured product obtained by curing the resin composition; a laminate including the cured product; a method for producing the cured product; a semiconductor device including the cured product or the laminate; and a base generator.

Description

樹脂組成物、硬化物、積層體、硬化物的製造方法及半導體裝置、以及鹼產生劑Resin composition, cured product, laminate, method for producing cured product, semiconductor device, and base generator

本發明係有關一種樹脂組成物、硬化物、積層體、硬化物的製造方法及半導體裝置、以及鹼產生劑。The present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a semiconductor device, and an alkali generator.

聚醯亞胺等環化樹脂由於耐熱性及絕緣性等優異，因此可用於各種用途。作為上述用途，並沒有特別限定，若以實際安裝用半導體裝置為例，則可以舉出作為絕緣膜、密封材料的素材或保護膜的利用。又，亦可用作可撓性基板的基底膜、覆蓋膜等。Cyclized resins such as polyimides are used in various applications because they are excellent in heat resistance and insulation properties. The above application is not particularly limited, and if a semiconductor device for actual mounting is taken as an example, use as an insulating film, a sealing material material, or a protective film can be mentioned. Moreover, it can also be used as a base film, a cover film, etc. of a flexible substrate.

例如，在上述用途中，聚醯亞胺等環化樹脂以包含聚醯亞胺前驅物等環化樹脂的前驅物之樹脂組成物的形態使用。 例如藉由塗佈等將該種樹脂組成物適用於基材上形成感光膜，之後根據需要進行曝光、顯影、加熱等，藉此能夠在基材上形成硬化物。 聚醯亞胺前驅物等上述環化樹脂的前驅物例如藉由加熱被環化而在硬化物中成為聚醯亞胺等環化樹脂。 樹脂組成物能夠藉由公知的塗佈方法等適用，因此，可以說例如所適用之樹脂組成物的適用時的形狀、大小、適用位置等設計自由度高等製造上的適應性優異。從除了聚醯亞胺等環化樹脂所具有之高性能以外，該種製造上的適應性亦優異的觀點考慮，上述樹脂組成物在產業上的應用拓展愈發令人期待。 For example, in the above application, the cyclized resin such as polyimide is used in the form of a resin composition containing a precursor of the cyclized resin such as a polyimide precursor. For example, by applying such a resin composition to a base material to form a photosensitive film by coating or the like, and then performing exposure, development, heating, etc. as necessary, a cured product can be formed on the base material. Precursors of the above-mentioned cyclized resins such as polyimide precursors are cyclized by heating, for example, and become cyclized resins such as polyimides in cured products. Since the resin composition can be applied by known coating methods and the like, it can be said that, for example, the applicable resin composition has a high degree of design freedom in the application of the shape, size, application position, etc., and has excellent manufacturing adaptability. In addition to the high performance of cyclized resins such as polyimides, it is expected that the industrial application of the above-mentioned resin compositions will expand from the viewpoint of excellent manufacturing adaptability.

例如，在專利文獻1中，記載有一種樹脂組成物，其特徵在於，含有：高分子前驅物，其藉由鹼性物質或藉由鹼性物質存在下的加熱來促進向最終生成物的反應；以及鹼產生劑，其特徵在於，藉由電磁波的照射和/或加熱而產生特定結構的鹼，並且所產生之鹼因加熱而在同一分子內進行麥可加成。For example, Patent Document 1 describes a resin composition characterized by containing a polymer precursor that promotes the reaction to the final product by a basic substance or by heating in the presence of a basic substance. ; and a base generating agent, characterized in that a base of a specific structure is generated by electromagnetic wave irradiation and/or heating, and the generated base undergoes Michael addition in the same molecule due to heating.

[專利文獻1]日本特開2010-254982號公報[Patent Document 1] Japanese Patent Laid-Open No. 2010-254982

在用於獲得硬化物的樹脂組成物中，要求所獲得之硬化物圖案的矩形性優異。In a resin composition for obtaining a cured product, it is required that the pattern of the obtained cured product has excellent rectangularity.

本發明的目的在於提供一種可以獲得圖案的矩形性優異之硬化物之樹脂組成物、硬化上述樹脂組成物而成之硬化物、包含上述硬化物之積層體、上述硬化物的製造方法及包含上述硬化物或上述積層體之半導體裝置、以及新型鹼產生劑。An object of the present invention is to provide a resin composition capable of obtaining a cured product having excellent pattern rectangularity, a cured product obtained by curing the above resin composition, a laminate including the above cured product, a method for producing the above cured product, and a Semiconductor devices of hardened products or the above-mentioned laminates, and novel base generators.

以下，示出本發明的代表性實施態樣的例子。 ＜1＞一種樹脂組成物，其係包含環化樹脂的前驅物和鹼產生劑，其中 從上述鹼產生劑產生之鹼係在同一分子內環化而成為三級胺之鹼， 從上述鹼產生劑產生之鹼不是α、β-不飽和羰基化合物及α、β-不飽和亞胺化合物中的任一種。 ＜2＞如＜1＞所述之樹脂組成物，其中，從上述鹼產生劑產生之鹼係包含選自包括環氧化物、氧環丁烷、醛、酮及鹵素基之群組中之至少一種基團之胺。 ＜3＞如＜1＞或＜2＞所述之樹脂組成物，其中，上述鹼產生劑係非離子性的鹼產生劑。 ＜4＞一種樹脂組成物，其係包含環化樹脂的前驅物和式（1-1）所表示之鹼產生劑。 [化學式1]

Figure 02_image001
式（1-1）中，L 1表示n+m價的連結基，R 1分別獨立地表示1價的有機基團，R 1中的至少一個包含環氧化物、氧環丁烷、醛、酮或鹵素基，X分別獨立地為羥基或羧基，m表示1以上的整數，n表示1以上的整數。 ＜5＞如＜1＞至＜4＞之任一項所述之樹脂組成物，其係包含光自由基聚合起始劑。 ＜6＞如＜1＞至＜5＞之任一項所述之樹脂組成物，其係包含聚合性化合物。 ＜7＞如＜1＞至＜6＞之任一項所述之樹脂組成物，其係用於形成再配線層用層間絕緣膜。 ＜8＞一種硬化物，其係硬化＜1＞至＜7＞之任一項所述之樹脂組成物而成。 ＜9＞一種積層體，其係包含2層以上由＜8＞所述之硬化物構成之層，在由上述硬化物構成之任意層彼此之間包含金屬層。 ＜10＞一種硬化物的製造方法，其係包括在基材上適用＜1＞至＜7＞之任一項所述之樹脂組成物來形成膜之膜形成步驟。 ＜11＞如＜10＞所述之硬化物的製造方法，其係包括： 曝光步驟，對上述膜進行選擇性曝光；及 顯影步驟，使用顯影液對上述膜進行顯影來形成圖案。 ＜12＞如＜10＞或＜11＞所述之硬化物的製造方法，其係包括在50～450℃下加熱上述膜之加熱步驟。 ＜13＞一種半導體裝置，其係包含＜8＞所述之硬化物或＜9＞所述之積層體。 ＜14＞一種鹼產生劑，其中，所產生之鹼係在同一分子內環化而成為三級胺之鹼，所產生之鹼不是α、β-不飽和羰基化合物及α、β不飽和亞胺化合物中的任一種。 ＜15＞一種鹼產生劑，其由下述式（1-1）表示， [化學式2]
Figure 02_image001
式（1-1）中，L 1表示n+m價的連結基，R 1分別獨立地表示1價的有機基團，R 1中的至少一個包含環氧化物、氧環丁烷、醛、酮或鹵素基，X分別獨立地為羥基或羧基，m表示1以上的整數，n表示1以上的整數。 [發明效果] Examples of representative embodiments of the present invention are shown below. <1> A resin composition comprising a precursor of a cyclized resin and a base generator, wherein the base generated from the base generator is cyclized in the same molecule to become a base of a tertiary amine, generated from the base The base generated by the agent is not any of α, β-unsaturated carbonyl compounds and α, β-unsaturated imine compounds. <2> The resin composition as described in <1>, wherein the base generated from the above-mentioned base generator contains at least A group of amines. <3> The resin composition according to <1> or <2>, wherein the base generator is a nonionic base generator. <4> A resin composition comprising a precursor of a cyclized resin and a base generator represented by formula (1-1). [chemical formula 1]
Figure 02_image001
In formula (1-1), L 1 represents a linking group with n+m valence, R 1 each independently represents a monovalent organic group, and at least one of R 1 includes epoxy, oxetane, aldehyde, Ketone or halogen group, X each independently represents a hydroxyl group or a carboxyl group, m represents an integer of 1 or more, and n represents an integer of 1 or more. <5> The resin composition according to any one of <1> to <4>, which contains a photoradical polymerization initiator. <6> The resin composition according to any one of <1> to <5>, which contains a polymerizable compound. <7> The resin composition according to any one of <1> to <6>, which is used for forming an interlayer insulating film for a rewiring layer. <8> A cured product obtained by curing the resin composition described in any one of <1> to <7>. <9> A laminate comprising two or more layers composed of the cured product described in <8>, and a metal layer is included between arbitrary layers composed of the above cured product. <10> A method for producing a cured product, comprising a film forming step of applying the resin composition described in any one of <1> to <7> to form a film on a substrate. <11> The method for producing a cured product according to <10>, comprising: an exposing step of selectively exposing the film; and a developing step of developing the film using a developer to form a pattern. <12> The method for producing a cured product according to <10> or <11>, which includes a heating step of heating the film at 50 to 450°C. <13> A semiconductor device comprising the cured product described in <8> or the laminate described in <9>. <14> A base generating agent, wherein the generated base is cyclized in the same molecule to become a base of a tertiary amine, and the generated base is not an α, β-unsaturated carbonyl compound or an α, β-unsaturated imine any of the compounds. <15> A base generator represented by the following formula (1-1), [Chemical formula 2]
Figure 02_image001
In formula (1-1), L 1 represents a linking group with n+m valence, R 1 each independently represents a monovalent organic group, and at least one of R 1 includes epoxy, oxetane, aldehyde, Ketone or halogen group, X each independently represents a hydroxyl group or a carboxyl group, m represents an integer of 1 or more, and n represents an integer of 1 or more. [Invention effect]

依據本發明，提供一種可以獲得圖案的矩形性優異之硬化物之樹脂組成物、硬化上述樹脂組成物而成之硬化物、包含上述硬化物之積層體、上述硬化物的製造方法及包含上述硬化物或上述積層體之半導體裝置、以及新型鹼產生劑。According to the present invention, there are provided a resin composition capable of obtaining a cured product having excellent pattern rectangularity, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, and a cured product including the cured product. A semiconductor device of a product or the above-mentioned laminate, and a novel base generator.

以下，對本發明的主要實施形態進行說明。然而，本發明並不限定於所明示之實施形態。 本說明書中，利用“～”記號表示之數值範圍係指，將記載於“～”的前後之數值分別作為下限值及上限值包括之範圍。 在本說明書中，“步驟”這一術語係指，不僅包括獨立的步驟，只要能夠達成該步驟的預期作用，則亦包括無法與其他步驟明確區分之步驟。 在本說明書中之基團（原子團）的標記中，未標有經取代及未經取代之標記包括不具有取代基之基團（原子團）的同時亦包括具有取代基之基團（原子團）。例如，“烷基”不僅包括不具有取代基之烷基（未經取代之烷基），亦包括具有取代基之烷基（經取代之烷基）。 在本說明書中，只要沒有特別說明，則“曝光”不僅包括利用光之曝光，亦包括利用電子束、離子束等粒子束之曝光。又，作為用於曝光之光，可以舉出水銀燈的明線光譜、以準分子雷射為代表之遠紫外線、極紫外線（EUV光）、X射線、電子束等活性光線或放射線。 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”這兩者或其中任一者，“（甲基）丙烯酸”表示“丙烯酸”及“甲基丙烯酸”這兩者或其中任一者，“（甲基）丙烯醯基”表示“丙烯醯基”及“甲基丙烯醯基”這兩者或其中任一者。 在本說明書中，結構式中的Me表示甲基，Et表示乙基，Bu表示丁基，Ph表示苯基。 在本說明書中，總固體成分係指組成物的所有成分中除溶劑之外的成分的總質量。又，在本說明書中，固體成分濃度為除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，重量平均分子量（Mw）及數量平均分子量（Mn）為利用凝膠滲透層析（GPC）法測定之值，定義為聚苯乙烯換算值。在本說明書中，例如，利用HLC-8220GPC（TOSOH CORPORATION製），將保護管柱HZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000及TSKgel Super HZ2000（以上為TOSOH CORPORATION製）串聯而用作管柱，藉此能夠求出重量平均分子量（Mw）及數量平均分子量（Mn）。只要沒有特別說明，該等分子量使用THF（四氫呋喃）作為洗提液進行測定。其中，溶解性較低的情況等，在THF不適合作為溶離液的情況下，亦能夠使用NMP（N-甲基-2-吡咯啶酮）。又，只要沒有特別說明，GPC測定中的檢測使用波長254nm的UV射線（紫外線）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，只要在所關注的複數層中成為基準之層的上側或下側存在其他層即可。亦即，在成為基準之層與上述其他層之間可進一步夾有第3層或第3元素，成為基準之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”，或在存在樹脂組成物層的情況下，將從基材朝向樹脂組成物層的方向稱為“上”，將其相反方向稱為“下”。此外，該等上下方向的設定係為了便於說明本說明書，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，作為組成物中所包含之各成分，組成物亦可以包含對應於該成分之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係指對應於該成分之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），相對濕度為50%RH。 在本說明書中，較佳態樣的組合為更佳態樣。 Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the illustrated embodiments. In this specification, the numerical range represented by the symbol "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit, respectively. In this specification, the term "step" means not only an independent step, but also a step that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved. In the notation of a group (atomic group) in this specification, the notation of being substituted and unsubstituted includes both a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group), but also an alkyl group having a substituent (substituted alkyl group). In this specification, unless otherwise specified, "exposure" includes not only exposure by light but also exposure by particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include bright line spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams and other active rays or radiation. In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate" or either, and "(meth)acrylic" means "acrylic" and "methacrylic". "Both or either of them, and "(meth)acryl" means both or either of "acryl" and "methacryl". In this specification, Me in the structural formulas 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 components other than the solvent among all the components of the composition. In addition, in this specification, the solid content concentration is the mass percentage of other components except a solvent with respect to the total mass of a composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are the values measured by the gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. In this specification, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION) is used to connect guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) in series By using it as a column, weight average molecular weight (Mw) and number average molecular weight (Mn) can be obtained. Unless otherwise specified, these molecular weights were measured using THF (tetrahydrofuran) as an eluent. Among them, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as an eluent, such as when the solubility is low. In addition, unless otherwise specified, a UV ray (ultraviolet) detector with a wavelength of 254 nm was used for detection in the GPC measurement. In this specification, when "upper" or "lower" is described as "upper" or "lower" regarding the positional relationship of the layers constituting the laminate, other layers may exist above or below the reference layer among the plurality of layers concerned. That is, a third layer or a third element may be further interposed between the reference layer and the above-mentioned other layers, and the reference layer and the above-mentioned other layers do not need to be in contact. In addition, unless otherwise specified, the direction of stacking layers on the substrate is referred to as "upper", or when there is a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper", and Its opposite direction is called "down". In addition, the setting of these up and down directions is for the convenience of explaining this specification. In an actual situation, the "up" direction in this specification may also be different from the vertical direction. In this specification, unless otherwise specified, as each component contained in the composition, the composition may contain two or more compounds corresponding to the component. In addition, unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23° C., the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, the combination of preferable aspects is a more preferable aspect.

（樹脂組成物） 本發明的第一態樣之樹脂組成物包含環化樹脂的前驅物（以下，亦稱為“特定樹脂”。）與鹼產生劑，並且從上述鹼產生劑產生之鹼係在同一分子內環化而成為三級胺之鹼，從上述鹼產生劑產生之鹼不是α、β-不飽和羰基化合物及α、β不飽和亞胺化合物中的任一種。 本發明的第二態樣之樹脂組成物包含環化樹脂的前驅物（特定樹脂）與式（1-1）所表示之鹼產生劑。 [化學式3]

Figure 02_image001
式（1-1）中，L 1表示n+m價的連結基，R 1分別獨立地表示1價的有機基團，R 1中的至少一個包含環氧化物、氧環丁烷、醛、酮或鹵素基，X分別獨立地為羥基或羧基，m表示1以上的整數，n表示1以上的整數。 在本發明中，將第一態樣之樹脂組成物與第二態樣之樹脂組成物統稱為“樹脂組成物”。 又，將對應於本發明的第一態樣之樹脂組成物中所包含之上述鹼產生劑和本發明的第二態樣之樹脂組成物中所包含之上述鹼產生劑中的任意一個之鹼產生劑亦稱為“特定熱鹼產生劑”。 (Resin Composition) The resin composition of the first aspect of the present invention includes a precursor of a cyclized resin (hereinafter also referred to as "specific resin") and a base generator, and the base generated from the base generator is The base that is cyclized in the same molecule to form a tertiary amine is not any of the α, β-unsaturated carbonyl compound and the α, β-unsaturated imine compound. The resin composition of the second aspect of the present invention includes a precursor of a cyclized resin (specific resin) and a base generator represented by formula (1-1). [chemical formula 3]
Figure 02_image001
In formula (1-1), L 1 represents a linking group with n+m valence, R 1 each independently represents a monovalent organic group, and at least one of R 1 includes epoxy, oxetane, aldehyde, Ketone or halogen group, X each independently represents a hydroxyl group or a carboxyl group, m represents an integer of 1 or more, and n represents an integer of 1 or more. In the present invention, the resin composition of the first aspect and the resin composition of the second aspect are collectively referred to as "resin composition". Also, a base corresponding to any one of the above-mentioned base generators contained in the resin composition of the first aspect of the present invention and the above-mentioned base generators contained in the resin composition of the second aspect of the present invention Generators are also referred to as "specific thermal base generators".

本發明的樹脂組成物用於形成供曝光及顯影之感光膜為較佳，用於形成供曝光及使用包含有機溶劑之顯影液之顯影之膜為較佳。 本發明的樹脂組成物例如能夠用於形成半導體裝置的絕緣膜、再配線層用層間絕緣膜、應力緩衝膜等，用於形成再配線層用層間絕緣膜為較佳。 又，本發明的樹脂組成物可以用於形成供正型顯影之感光膜，亦可以用於形成供負型顯影之感光膜。 在本發明中，在曝光及顯影中，負型顯影係指藉由顯影去除非曝光部之顯影，正型顯影係指藉由顯影去除曝光部之顯影。 作為上述曝光方法、上述顯影液及上述顯影方法，例如，可以使用在後述之硬化物的製造方法的說明中的曝光步驟中所說明之曝光方法、在顯影步驟中所說明之顯影液及顯影方法。 The resin composition of the present invention is preferably used for forming a photosensitive film for exposure and development, and is preferably used for forming a film for exposure and development using a developing solution containing an organic solvent. The resin composition of the present invention can be used, for example, to form an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used for forming an interlayer insulating film for a rewiring layer. Moreover, the resin composition of this invention can be used for forming the photosensitive film for positive tone development, and can also be used for forming the photosensitive film for negative tone development. In the present invention, in exposure and development, negative tone development refers to development in which non-exposed portions are removed by development, and positive tone development refers to development in which exposed portions are removed by development. As the above-mentioned exposure method, the above-mentioned developing solution, and the above-mentioned developing method, for example, the exposing method described in the exposing step in the description of the production method of the cured product described later, the developing solution and the developing method described in the developing step can be used. .

依據本發明的樹脂組成物，可以獲得圖案的矩形性優異之硬化膜。 對染獲得上述效果之機理尚不明確，但推測為如下。 According to the resin composition of this invention, the cured film excellent in the rectangularity of a pattern can be obtained. The mechanism by which counter-dyeing achieves the above effect is not clear, but it is speculated as follows.

一直以來，包含樹脂及鹼產生劑等之樹脂組成物被用於各種領域中。 例如，使用包含聚醯亞胺前驅物等環化樹脂的前驅物及鹼產生劑之組成物，對上述組成物進行加熱而從上述鹼產生劑產生鹼，藉此使環化樹脂的前驅物環化而獲得包含聚醯亞胺樹脂等環化樹脂之硬化物。 在此，本發明人等進行研究之結果，發現使用以往的鹼產生劑的情況下，硬化物的圖案矩形性中存在改善的餘地。 考慮這是因為，從以往的鹼產生劑產生之二級胺等鹼與樹脂中的羰基、C=C基等進行加成反應等，從而阻礙鹼的擴散，因此其結果，樹脂的環化難以在由組成物構成之層的內部均勻地進行。 本發明的第一態樣之樹脂組成物中所包含之鹼產生劑產生環化而成為三級胺之鹼來作為鹼。又，本發明的第二態樣之樹脂組成物包含式（1-1）所表示之鹼產生劑。認為從該鹼產生劑產生之鹼包含環氧化物、氧環丁烷、醛、酮或鹵素基，並且這些基團與所產生之二級胺的胺基進行反應，從而產生三級胺。認為由於三級胺與上述樹脂的反應性低，因此容易在組成物膜內擴散。 因此，樹脂的環化容易在膜內均勻地進行，且圖案矩形性獲得提高。 又，例如專利文獻1中所公開之組成物中所包含之鹼產生劑產生α、β-不飽和羰基化合物或α、β-不飽和亞胺化合物來作為鹼。認為這是因為，所產生之鹼雖然係藉由麥可加成而形成三級胺之鹼，但使用該等鹼產生劑之情況下，存在如下情況：例如在自由基聚合體系中，樹脂或聚合性化合物的C=C基與鹼產生劑的C=C基進行聚合反應等，原本就不環化或者鹼不能充分地擴散從而圖案的矩形性不充分。 Conventionally, a resin composition including a resin, a base generator, and the like has been used in various fields. For example, using a composition comprising a precursor of a cyclized resin such as a polyimide precursor and a base generator, the composition is heated to generate a base from the base generator, thereby cyclizing the precursor of the cyclized resin. To obtain a cured product containing cyclized resins such as polyimide resins. Here, as a result of studies conducted by the present inventors, it was found that there is room for improvement in the pattern rectangularity of the cured product when a conventional base generator is used. This is considered to be because bases such as secondary amines generated from conventional base generators undergo addition reactions with carbonyl groups and C=C groups in the resin, etc., thereby inhibiting the diffusion of bases, and as a result, the cyclization of the resin is difficult. It is carried out uniformly inside the layer composed of the composition. The base generating agent contained in the resin composition of the 1st aspect of this invention generates the base which cyclizes and becomes a tertiary amine as a base. Moreover, the resin composition of the 2nd aspect of this invention contains the base generator represented by formula (1-1). It is believed that the base generated from the base generator contains epoxide, oxetane, aldehyde, ketone, or halo groups, and these groups react with the amine groups of the secondary amine generated to generate a tertiary amine. It is considered that the tertiary amine diffuses easily in the composition film because of its low reactivity with the resin. Therefore, the cyclization of the resin tends to proceed uniformly in the film, and the pattern squareness is improved. Also, for example, the base generator contained in the composition disclosed in Patent Document 1 generates an α, β-unsaturated carbonyl compound or an α, β-unsaturated imine compound as a base. This is considered to be because, although the generated base is a base that forms a tertiary amine by the addition of Myco, in the case of using such a base generator, there are cases where, for example, in a radical polymerization system, the resin or The C=C group of the polymerizable compound is polymerized with the C=C group of the base generating agent, etc., and the squareness of the pattern is insufficient because the cyclization is not performed or the base cannot sufficiently diffuse.

又，由於在本發明中所使用之鹼產生劑的結構接近中性，因此認為組成物的保存穩定性優異。 除此以外，如上所述，由於樹脂的環化容易均勻地進行，其結果認為樹脂的環化率亦獲得提高，並且硬化物的斷裂伸長率亦優異。 又，認為由於樹脂、聚合性化合物等中所包含之C=C基等聚合性基可以抑制因與上述的鹼的反應而減少的情況，因此硬化膜中的交聯密度變得容易提高，並且耐藥品性亦優異。 In addition, since the structure of the base generator used in the present invention is close to neutral, it is considered that the storage stability of the composition is excellent. In addition, as described above, since the cyclization of the resin proceeds easily and uniformly, the cyclization rate of the resin is also considered to be improved as a result, and the cured product is also considered to be excellent in elongation at break. In addition, it is considered that the crosslinking density in the cured film can be easily increased due to the fact that the polymerizable groups such as C=C groups contained in resins, polymerizable compounds, etc. can suppress the reduction due to the reaction with the above-mentioned alkali, and Chemical resistance is also excellent.

在此，在專利文獻1中，未記載有特定鹼產生劑。Here, Patent Document 1 does not describe a specific base generating agent.

以下，對本發明的樹脂組成物中所包含之成分進行詳細說明。Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

＜特定樹脂＞ 本發明的樹脂組成物包含環化樹脂的前驅物（特定樹脂）。 環化樹脂係在主鏈結構中包含醯亞胺環結構或㗁唑環結構之樹脂為較佳。 在本發明中，主鏈係指樹脂分子中相對最長的鍵結鏈。 作為環化樹脂，可以舉出聚醯亞胺、聚苯并㗁唑、聚醯胺醯亞胺等。 環化樹脂的前驅物係指化學結構藉由外部刺激發生變化而成為環化樹脂之樹脂，化學結構藉由熱發生變化而成為環化樹脂之樹脂為較佳，藉由利用熱產生閉環反應而形成環結構來成為環化樹脂之樹脂為更佳。 作為環化樹脂的前驅物，可以舉出聚醯亞胺前驅物、聚苯并㗁唑前驅物、聚醯胺醯亞胺前驅物等。 亦即，本發明的樹脂組成物包含選自包括聚醯亞胺前驅物、聚苯并㗁唑前驅物及聚醯胺醯亞胺前驅物之群組中之至少1種樹脂（特定樹脂）作為特定樹脂為較佳。 本發明的樹脂組成物包含聚醯亞胺前驅物作為特定樹脂為較佳。 又，特定樹脂具有聚合性基為較佳，包含自由基聚合性基為更佳。 在特定樹脂具有自由基聚合性基的情況下，本發明的樹脂組成物包含後述自由基聚合起始劑為較佳，包含後述之自由基聚合起始劑且包含後述之自由基交聯劑為更佳。能夠根據需要進一步包含後述之增感劑。例如，由該等本發明的樹脂組成物可以形成負型感光膜。 又，特定樹脂可以具有酸分解性基等極性轉換基。 在特定樹脂具有酸分解性基的情況下，本發明的樹脂組成物包含後述之光酸產生劑為較佳。例如，由該等本發明的樹脂組成物可以形成作為化學增幅型的正型感光膜或負型感光膜。 ＜Specific resin＞ The resin composition of the present invention contains a precursor (specific resin) of a cyclized resin. The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure. In the present invention, the main chain refers to the relatively longest bonded chain in the resin molecule. Examples of the cyclized resin include polyimide, polybenzoxazole, polyamideimide, and the like. The precursor of the cyclized resin refers to the resin whose chemical structure is changed to become a cyclized resin by external stimuli, and the resin whose chemical structure is changed to become a cyclized resin by heat is better. A resin that forms a ring structure to be a cyclized resin is more preferable. Examples of the precursor of the cyclized resin include polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, and the like. That is, the resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors as Certain resins are preferred. It is preferable that the resin composition of the present invention contains a polyimide precursor as a specific resin. Moreover, it is preferable that a specific resin has a polymerizable group, and it is more preferable that it contains a radical polymerizable group. In the case where the specific resin has a radical polymerizable group, it is preferable that the resin composition of the present invention contains the radical polymerization initiator described later, and the radical polymerization initiator described later and the radical crosslinking agent described later are better. A sensitizer described later can be further included as needed. For example, a negative photosensitive film can be formed from the resin composition of the present invention. In addition, the specific resin may have a polarity conversion group such as an acid decomposable group. When a specific resin has an acid-decomposable group, it is preferable that the resin composition of this invention contains the photoacid generator mentioned later. For example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film can be formed from the resin composition of the present invention.

〔聚醯亞胺前驅物〕 在本發明中所使用之聚醯亞胺前驅物並不特別限定其種類等，但包含下述式（2）所表示之重複單元為較佳。 [化學式4]

Figure 02_image004
式（2）中，A 1及A 2分別獨立地表示氧原子或-NH-，R 111表示2價有機基團，R 115表示4價有機基團，R 113及R 114分別獨立地表示氫原子或1價有機基團。 [Polyimide Precursor] The polyimide precursor used in the present invention is not particularly limited in its type, but preferably contains a repeating unit represented by the following formula (2). [chemical formula 4]
Figure 02_image004
In formula (2), A 1 and A 2 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 independently represent hydrogen atom or a monovalent organic group.

式（2）中的A 1及A 2分別獨立地表示氧原子或-NH-，氧原子為較佳。 式（2）中的R 111表示2價有機基團。作為2價有機基團，可以例示出直鏈或支鏈的脂肪族基、環狀的脂肪族基及包含芳香族基之基團，碳數2～20的直鏈或支鏈的脂肪族基、碳數3～20的環狀的脂肪族基、碳數3～20的芳香族基或由該等的組合構成之基團為較佳，包含碳數6～20的芳香族基之基團為更佳。上述直鏈或支鏈的脂肪族基的鏈中的烴基可以被含雜原子之基團取代，上述環狀的脂肪族基及芳香族基的員環的烴基可以被含雜原子之基團取代。作為本發明的較佳之實施形態，可以例示出-Ar-及-Ar-L-Ar-所表示之基團，特佳為-Ar-L-Ar-所表示之基團。其中，Ar分別獨立地為芳香族基，L為單鍵或可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO 2-或-NHCO-、或者由上述2個以上的組合構成之基團。該等的較佳範圍如上所述。 A 1 and A 2 in the formula (2) each independently represent an oxygen atom or -NH-, preferably an oxygen atom. R 111 in formula (2) represents a divalent organic group. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups, and groups containing aromatic groups, and linear or branched aliphatic groups having 2 to 20 carbon atoms. , a cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 3 to 20 carbons, or a combination thereof is preferred, and a group including an aromatic group with 6 to 20 carbons for better. The hydrocarbon group in the chain of the above-mentioned linear or branched aliphatic group may be substituted by a group containing a heteroatom, and the hydrocarbon group of the above-mentioned cyclic aliphatic group and aromatic group may be substituted by a group containing a heteroatom . As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, and groups represented by -Ar-L-Ar- are particularly preferable. Among them, Ar is independently an aromatic group, L is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO 2 - or - NHCO-, or a group consisting of a combination of two or more of the above. Such preferred ranges are as described above.

R 111由二胺衍生為較佳。作為在聚醯亞胺前驅物的製造中所使用之二胺，可以舉出直鏈或支鏈脂肪族、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。 具體而言，包含碳數2～20的直鏈或支鏈的脂肪族基、碳數3～20的環狀的脂肪族基、碳數3～20的芳香族基或由該等的組合構成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。上述直鏈或支鏈的脂肪族基的鏈中的烴基可以被含雜原子之基團取代，上述環狀的脂肪族基及芳香族基的員環的烴基亦可以被含雜原子之基團取代。作為包含芳香族基之基團的例子，可以舉出下述基團。 R 111 is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Diamine may use only 1 type, and may use 2 or more types. Specifically, it includes a straight-chain or branched aliphatic group having 2 to 20 carbons, a cyclic aliphatic group having 3 to 20 carbons, an aromatic group having 3 to 20 carbons, or a combination thereof The diamine of the group is preferable, and the diamine containing the aromatic group of 6-20 carbons is more preferable. The hydrocarbon group in the chain of the above-mentioned linear or branched aliphatic group can be replaced by a group containing a heteroatom, and the hydrocarbon group of the above-mentioned cyclic aliphatic group and aromatic group can also be replaced by a group containing a heteroatom replace. Examples of the group containing an aromatic group include the following groups.

[化學式5]

Figure 02_image006
式中，A表示單鍵或2價的連結基，單鍵或選自可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-SO 2-、-NHCO-或該等的組合之基團為較佳，單鍵或選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-或-SO 2-之基團為更佳，-CH 2-、-O-、-S-、-SO 2-、-C（CF 3） 2-或-C（CH 3） 2-為進一步較佳。 式中，*表示與其他結構的鍵結部位。 [chemical formula 5]
Figure 02_image006
In the formula, A represents a single bond or a divalent linking group, a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -C(=O)-, -S- , -SO 2 -, -NHCO- or the combination of these groups are preferred, single bond or selected from C1-C3 alkylene groups which may be substituted by fluorine atoms, -O-, -C (= O)-, -S- or -SO 2 - groups are more preferred, -CH 2 -, -O-, -S-, -SO 2 -, -C(CF 3 ) 2 - or -C(CH 3 ) 2- is further preferred. In the formula, * represents a bonding site with other structures.

作為二胺，具體而言可以舉出選自1,2-二胺基乙烷、1,2-二胺基丙烷、1,3-二胺基丙烷、1,4-二胺基丁烷或1,6-二胺基己烷；1,2-或1,3-二胺基環戊烷、1,2-、1,3-或1,4-二胺基環己烷、1,2、1,3-或1,4-雙（胺基甲基）環己烷、雙-（4-胺基環己基）甲烷、雙-（3-胺基環己基）甲烷、4,4’-二胺基-3,3’-二甲基環己基甲烷及異佛爾酮二胺；間苯二胺或對苯二胺、二胺基甲苯、4,4’-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’-或3,3’-二胺基二苯基甲烷、4,4’-或3,3’-二胺基二苯基碸、4,4’-或3,3’-二胺基二苯硫醚、4,4’-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、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、2,4-及2,5-二胺基枯烯、2,5-二甲基-對苯二胺、乙醯胍胺、2,3,5,6-四甲基-對苯二胺、2,4,6-三甲基-間苯二胺、雙（3-胺基丙基）四甲基二矽氧烷、雙（對胺基苯基）八甲基五矽氧烷、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, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, or 1,6-Diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2 , 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'- Diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diamine Aminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4 '- or 3,3'-diaminodiphenylsulfide, 4,4'- or 3,3'-diaminodiphenylsulfide, 4,4'- or 3,3'-diaminodiphenylsulfide Benzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl Methoxy-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)pyridine, bis(4-amino-3 -Hydroxyphenyl) p-terphenyl, 4,4'-diamino-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy) Phenyl]pyridine, bis[4-(3-aminophenoxy)phenyl]pyridine, bis[4-(2-aminophenoxy)phenyl]pyridine, 1,4-bis(4-amine phenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylphenene, 1,3-bis( 4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl- 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-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) terpine, 4,4'-Dimethyl-3,3'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2 ,4- and 2,5-diaminocumene, 2, 5-Dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis( 3-Aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diamino terpene, 2,5-diaminopyridine, 1 ,2-bis(4-aminophenyl)ethane, diaminobenzaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3 -Bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 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-trifluoromethylbenzene oxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy) base) biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethyl phenoxy)diphenylphenoxide, 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',5,5',6 , at least one diamine selected from 6'-hexafluorobenzidine and 4,4'-diaminoquaterphenyl.

又，國際公開第2017/038598號的0030～0031段中所記載之二胺（DA-1）～（DA-18）亦為較佳。Moreover, the diamines (DA-1)-(DA-18) described in paragraph 0030-0031 of International Publication No. 2017/038598 are also preferable.

又，亦可較佳地使用國際公開第2017/038598號的0032～0034段中所記載之在主鏈上具有2個以上的伸烷基二醇單元之二胺。Moreover, the diamine which has 2 or more alkylene glycol units in a main chain as described in paragraph 0032-0034 of International Publication No. 2017/038598 can also be used preferably.

從所獲得之有機膜的柔軟性的觀點考慮，R 111由-Ar-L-Ar-表示為較佳。其中，Ar分別獨立地為芳香族基，L為可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO 2-或-NHCO-、或者由上述2個以上的組合構成之基團。Ar為伸苯基為較佳，L為可以被氟原子取代之碳數1或2的脂肪族烴基、-O-、-CO-、-S-或-SO 2-為較佳。此處的脂肪族烴基為伸烷基為較佳。 From the viewpoint of the flexibility of the obtained organic film, R 111 is preferably represented by -Ar-L-Ar-. Among them, Ar is independently an aromatic group, L is an aliphatic hydrocarbon group with 1 to 10 carbons which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO 2 - or -NHCO-, Or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group with 1 or 2 carbons which may be substituted by a fluorine atom, -O-, -CO-, -S- or -SO 2 -. The aliphatic hydrocarbon group here is preferably an alkylene group.

又，從i射線透射率的觀點考慮，R 111係下述式（51）或式（61）所表示之2價有機基團為較佳。尤其，從i射線透射率、易獲得性的觀點考慮，係式（61）所表示之2價有機基團為更佳。 式（51） [化學式6]

Figure 02_image008
在式（51）中，R 50～R 57分別獨立地為氫原子、氟原子或1價有機基團，R 50～R 57中的至少1個為氟原子、甲基或三氟甲基，*分別獨立地表示與式（2）中的氮原子的鍵結部位。 作為R 50～R 57的1價有機基團，可以舉出碳數1～10（較佳為碳數1～6）的未經取代之烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式7]
Figure 02_image010
式（61）中，R 58及R 59分別獨立地為氟原子、甲基或三氟甲基，*分別獨立地表示與式（2）中的氮原子的鍵結部位。 作為賦予式（51）或（61）的結構之二胺，可以舉出2,2'-二甲基對聯苯胺、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。該等可以使用1種或組合使用2種以上。 Also, from the viewpoint of i-ray transmittance, R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by the formula (61) is more preferable. Formula (51) [Chemical Formula 6]
Figure 02_image008
In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoromethyl group, * Each independently represents a bonding site with a nitrogen atom in formula (2). Examples of monovalent organic groups for R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), 1 to 6) fluorinated alkyl groups, etc. [chemical formula 7]
Figure 02_image010
In formula (61), R 58 and R 59 are each independently a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represent a bonding site with a nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or (61) include 2,2'-dimethyl-p-benzidine, 2,2'-bis(trifluoromethyl)-4,4'-diamine Biphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used 1 type or in combination of 2 or more types.

式（2）中的R 115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，下述式（5）或式（6）所表示之基團為更佳。 式（5）或式（6）中，*分別獨立地表示與其他結構的鍵結部位。 [化學式8]

Figure 02_image012
式（5）中，R 112為單鍵或2價連結基，單鍵或選自可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO 2-及-NHCO-、以及該等的組合之基團為較佳，單鍵、選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-CO-、-S-及-SO 2-中之基團為更佳，選自包括-CH 2-、-C（CF 3） 2-、-C（CH 3） 2-、-O-、-CO-、-S-及-SO 2-之群組中之2價基團為進一步較佳。 R 115 in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group including an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), * each independently represents a bonding site with another structure. [chemical formula 8]
Figure 02_image012
In formula (5), R 112 is a single bond or a divalent linking group, a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO 2 - and -NHCO-, and the combination of these groups are preferred, and the single bond is selected from the group consisting of alkylene groups with 1 to 3 carbon atoms that may be substituted by fluorine atoms, -O-, -CO-, The groups in -S- and -SO 2 - are more preferred, selected from the group including -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -O-, -CO-, The divalent group in the group of -S- and -SO 2 - is more preferable.

具體而言，R 115可以舉出從四羧酸二酐去除酸酐基之後而殘留之四羧酸殘基等。作為對應於R 115之結構，聚醯亞胺前驅物可以僅包含1種四羧酸二酐殘基，亦可以包含2種以上。 四羧酸二酐係下述式（O）所表示為較佳。 [化學式9]

Figure 02_image014
在式（O）中，R 115表示4價有機基團。R 115的較佳範圍與式（2）中的R 115的含義相同，較佳範圍亦相同。 Specifically, R 115 includes a tetracarboxylic acid residue remaining after removing an acid anhydride group from tetracarboxylic dianhydride, and the like. As a structure corresponding to R115 , the polyimide precursor may contain only one kind of tetracarboxylic dianhydride residues, and may contain two or more kinds. It is preferable that tetracarboxylic dianhydride is represented by following formula (O). [chemical formula 9]
Figure 02_image014
In formula (O), R 115 represents a tetravalent organic group. The preferable range of R 115 has the same meaning as that of R 115 in the formula (2), and the preferable range is also the same.

作為四羧酸二酐的具體例，可以舉出焦蜜石酸二酐（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’-氧雙鄰苯二甲酸二酐、2,3,6,7-萘四羧酸二酐、1,4,5,7-萘四羧酸二酐、2,2-雙（3,4-二羧基苯基）丙烷二酐、2,2-雙（2,3-二羧基苯基）丙烷二酐、2,2-雙（3,4-二羧基苯基）六氟丙烷二酐、1,3-二苯基六氟丙烷-3,3,4,4-四羧酸二酐、1,4,5,6-萘四羧酸二酐、2,2’,3,3’-二苯基四羧酸二酐、3,4,9,10-苝四羧酸二酐、1,2,4,5-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、1,8,9,10-菲四羧酸二酐、1,1-雙（2,3-二羧基苯基）乙烷二酐、1,1-雙（3,4-二羧基苯基）乙烷二酐、1,2,3,4-苯四羧酸二酐以及該等的碳數1～6的烷基及碳數1～6的烷氧基衍生物。Specific examples of tetracarboxylic dianhydride include pyromelite dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride , 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4' -Biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7 -naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic 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-naphthalene tetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylene Tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride , 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,2,3,4-benzene Tetracarboxylic dianhydride and these alkyl groups having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

又，作為較佳例，亦可以舉出國際公開第2017/038598號的0038段中所記載之四羧酸二酐（DAA-1）～（DAA-5）。Moreover, tetracarboxylic dianhydride (DAA-1) - (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can also be mentioned as a preferable example.

在式（2）中，亦可以為R 111及R 115中的至少1個具有OH基。更具體而言，作為R 111，可以舉出雙胺基苯酚衍生物的殘基。 In formula (2), at least one of R 111 and R 115 may have an OH group. More specifically, R 111 includes a residue of a bisaminophenol derivative.

式（2）中的R 113及R 114分別獨立地表示氫原子或1價有機基團。作為1價有機基團，包含直鏈或支鏈的烷基、環狀烷基、芳香族基或聚伸烷氧基為較佳。又，R 113及R 114中的至少1個包含聚合性基為較佳，兩者均包含聚合性基為更佳。R 113及R 114中的至少1個包含2個以上的聚合性基亦為較佳。作為聚合性基，係能夠藉由熱、自由基等的作用進行交聯反應之基團，自由基聚合性基為較佳。作為聚合性基的具體例，可以舉出具有乙烯性不飽和鍵之基團、烷氧基甲基、羥基甲基、醯氧基甲基、環氧基、氧雜環丁基、苯并㗁唑基、封端異氰酸酯基、胺基。作為聚醯亞胺前驅物所具有之自由基聚合性基，具有乙烯性不飽和鍵之基團為較佳。 作為具有乙烯性不飽和鍵之基團，可以舉出乙烯基、烯丙基、異烯丙基、2-甲基烯丙基、具有與乙烯基直接鍵結之芳香環之基團（例如，乙烯基苯基等）、（甲基）丙烯醯胺基、（甲基）丙烯醯氧基、下述式（III）所表示之基團等，下述式（III）所表示之基團為較佳。 R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferable to contain a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. Also, it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and it is more preferable that both of them contain a polymerizable group. It is also preferable that at least one of R 113 and R 114 contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, free radicals, etc., and a radical polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, and a benzoyl group. Azolyl, blocked isocyanate, amine. As the radical polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable. As the group having an ethylenically unsaturated bond, vinyl, allyl, isoallyl, 2-methallyl, and a group having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl, etc.), (meth)acrylamide, (meth)acryloxy, groups represented by the following formula (III), etc., the group represented by the following formula (III) is better.

[化學式10]

Figure 02_image016
[chemical formula 10]
Figure 02_image016

在式（III）中，R 200表示氫原子、甲基、乙基或羥甲基，氫原子或甲基為較佳。 在式（III）中，*表示與其他結構的鍵結部位。 在式（III）中，R 201表示碳數2～12的伸烷基、-CH 2CH（OH）CH 2-、伸環烷基或聚伸烷氧基。 R 201的較佳例可以舉出乙烯基、丙烯基、三亞甲基、四亞甲基、五亞甲基、六亞甲基、八亞甲基、十二亞甲基等的伸烷基、1,2-丁烷二基、1,3-丁烷二基、-CH 2CH（OH）CH 2-、聚伸烷氧基，乙烯基、丙烯基等伸烷基、-CH 2CH（OH）CH 2-、環己基、聚伸烷氧基為更佳，乙烯基、丙烯基等伸烷基或聚伸烷氧基為進一步較佳。 在本發明中，聚伸烷氧基係指2個以上的伸烷氧基直接鍵結之基團。聚伸烷氧基中所包含之複數個伸烷氧基中的伸烷基分別可以相同或不同。 聚伸烷氧基包含伸烷基不同之複數種伸烷氧基的情況下，聚伸烷氧基中的伸烷氧基的排列可以為隨機排列，可以為具有嵌段之排列，亦可以為具有交替等圖案之排列。 上述伸烷基的碳數（伸烷基具有取代基的情況下，包括取代基的碳數）為2以上為較佳，2～10為更佳，2～6為更佳，2～5為進一步較佳，2～4為更進一步較佳，2或3為特佳，2為最佳。 又，上述伸烷基可以具有取代基。作為較佳之取代基，可以舉出烷基、芳基、鹵素原子等。 又，聚伸烷氧基中所包含之伸烷氧基的數量（聚伸烷氧基的重複數）係2～20為較佳，2～10為更佳，2～6為進一步較佳。 作為聚伸烷氧基，從溶劑溶解性及耐溶劑性的觀點考慮，聚乙烯氧基、聚丙烯氧基、聚三亞甲氧基、聚四亞甲氧基或複數個乙烯氧基與複數個丙烯氧基鍵結之基團為較佳，聚乙烯氧基或聚丙烯氧基為更佳，聚乙烯氧基為進一步較佳。在上述複數個乙烯氧基與複數個丙烯氧基鍵結之基團中，乙烯氧基和丙烯氧基可以隨機排列，可以形成嵌段而排列，亦可以排列成交替等圖案狀。該等基團中的乙烯氧基等的重複數之較佳態樣如上所述。 In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site with other structures. In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 -, a cycloalkylene group, or a polyalkylene group. Preferred examples of R201 include alkylene groups such as vinyl, propenyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH 2 CH(OH)CH 2 -, polyalkyleneoxy, vinyl, propenyl and other alkylene, -CH 2 CH( OH) CH 2 -, cyclohexyl, and polyalkyleneoxy are more preferred, and alkylene or polyalkylene such as vinyl and propenyl are still more preferred. In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plural alkyleneoxy groups included in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or a Arrangements with alternating patterns. The carbon number of the above-mentioned alkylene group (when the alkylene group has a substituent, including the carbon number of the substituent) is preferably 2 or more, more preferably 2-10, more preferably 2-6, and 2-5. More preferably, 2 to 4 are still more preferable, 2 or 3 are particularly preferable, and 2 is most preferable. Moreover, the said alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. are mentioned. Moreover, the number of the alkyleneoxy groups contained in a polyalkyleneoxy group (repetition number of a polyalkyleneoxy group) is 2-20 preferably, 2-10 are more preferable, 2-6 are still more preferable. As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy, or a plurality of ethyleneoxy groups and a plurality of A group bonded with propyleneoxy group is preferable, polyethyleneoxy group or polypropyleneoxy group is more preferable, and polyethyleneoxy group is still more preferable. In the above-mentioned groups in which a plurality of ethyleneoxy groups are bonded to a plurality of propyleneoxy groups, the ethyleneoxy groups and the propyleneoxy groups can be arranged randomly, arranged in blocks, or arranged in alternate patterns. Desirable aspects of the repeating numbers of ethyleneoxy groups and the like in these groups are as described above.

在式（2）中，在R 113為氫原子的情況或R 114為氫原子的情況下，聚醯亞胺前驅物可以與具有乙烯性不飽和鍵之三級胺化合物形成共軛鹽。作為該種具有乙烯性不飽和鍵之三級胺化合物的例子，可以舉出N,N-二甲胺基丙基甲基丙烯酸酯。 In formula (2), when R 113 is a hydrogen atom or R 114 is a hydrogen atom, the polyimide precursor can form a conjugated salt with a tertiary amine compound having an ethylenically unsaturated bond. N,N- dimethylaminopropyl methacrylate is mentioned as an example of the tertiary amine compound which has such an ethylenically unsaturated bond.

在式（2）中，R 113及R 114中的至少1個可以為酸分解性基等極性轉換基。作為酸分解性基，只要藉由酸的作用分解並產生酚性羥基、羧基等鹼可溶性基，則並沒有特別限定，縮醛基、縮酮基、矽基、矽基醚基、三級烷基酯基等為較佳，從曝光靈敏度的觀點考慮，縮醛基或縮酮基為更佳。 作為酸分解性基的具體例，可以舉出三級丁氧基羰基、異丙氧基羰基、四氫哌喃基、四氫呋喃基、乙氧基乙基、甲氧基乙基、乙氧基甲基、三甲基矽基、三級丁氧基羰基甲基、三甲基矽基醚基等。從曝光靈敏度的觀點考慮，乙氧基乙基或四氫呋喃基為較佳。 In formula (2), at least one of R 113 and R 114 may be a polarity switching group such as an acid decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group. An ester group or the like is preferable, and an acetal group or a ketal group is more preferable from the viewpoint of exposure sensitivity. Specific examples of acid-decomposable groups include tertiary butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuryl, ethoxyethyl, methoxyethyl, ethoxymethyl group, trimethylsilyl group, tertiary butoxycarbonylmethyl group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuryl group is preferable.

又，聚醯亞胺前驅物在結構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，又，20質量%以下為更佳。Moreover, it is also preferable that the polyimide precursor has a fluorine atom in the structure. The content of fluorine atoms in the polyimide precursor is preferably at least 10% by mass, more preferably at most 20% by mass.

又，以提高與基板的密接性為目的，聚醯亞胺前驅物可以與具有矽氧烷結構之脂肪族基共聚。具體而言，作為二胺，可以舉出使用雙（3-胺基丙基）四甲基二矽氧烷、雙（對胺基苯基）八甲基五矽氧烷等之態樣。Also, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving the adhesion to the substrate. Specifically, examples of the diamine include those in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like are used.

式（2）所表示之重複單元係式（2-A）所表示之重複單元為較佳。亦即，在本發明中所使用之聚醯亞胺前驅物中的至少1種係具有式（2-A）所表示之重複單元之前驅物為較佳。藉由聚醯亞胺前驅物包含式（2-A）所表示之重複單元，能夠進一步增加曝光寬容度的幅度。 式（2-A） [化學式11]

Figure 02_image018
式（2-A）中，A 1及A 2表示氧原子，R 111及R 112分別獨立地表示2價有機基團，R 113及R 114分別獨立地表示氫原子或1價有機基團，R 113及R 114中的至少1個為包含聚合性基之基團，兩者均為包含聚合性基之基團為較佳。 The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention has a repeating unit represented by formula (2-A). The range of exposure latitude can be further increased by the polyimide precursor comprising the repeating unit represented by formula (2-A). Formula (2-A) [Chemical Formula 11]
Figure 02_image018
In formula (2-A), A 1 and A 2 represent an oxygen atom, R 111 and R 112 independently represent a divalent organic group, R 113 and R 114 independently represent a hydrogen atom or a monovalent organic group, At least one of R 113 and R 114 is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.

A 1、A 2、R 111、R 113及R 114分別獨立地與式（2）中的A 1、A 2、R 111、R 113及R 114的含義相同，較佳範圍亦相同。 R 112與式（5）中的R 112的含義相同，較佳範圍亦相同。 A 1 , A 2 , R 111 , R 113 and R 114 independently have the same meanings as A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and the preferred ranges are also the same. R 112 has the same meaning as R 112 in formula (5), and the preferred range is also the same.

聚醯亞胺前驅物可以包含1種式（2）所表示之重複單元，亦可以包含2種以上。又，可以包含式（2）所表示之重複單元的結構異構物。又，除上述式（2）的重複單元以外，聚醯亞胺前驅物顯然亦可以包含其他種類的重複單元。The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. Moreover, the structural isomer of the repeating unit represented by formula (2) may be included. Moreover, besides the repeating unit of the above-mentioned formula (2), the polyimide precursor may obviously also contain other types of repeating units.

作為本發明中的聚醯亞胺前驅物的一實施形態，可以舉出式（2）所表示之重複單元的含量為所有重複單元的50莫耳%以上之態樣。上述合計含量係70莫耳%以上為更佳，90莫耳%以上為進一步較佳，大於90莫耳%為特佳。上述合計含量的上限並沒有特別限定，除了末端以外的聚醯亞胺前驅物中的所有重複單元可以為式（2）所表示之重複單元。As one embodiment of the polyimide precursor in the present invention, an aspect in which the content of the repeating unit represented by formula (2) is 50 mol% or more of all the repeating units is mentioned. The above-mentioned total content is more than 70 mol %, more preferably 90 mol %, and more than 90 mol % is particularly preferred. The upper limit of the above-mentioned total content is not particularly limited, and all the repeating units in the polyimide precursor except the terminal may be the repeating unit represented by formula (2).

聚醯亞胺前驅物的重量平均分子量（Mw）較佳為5,000～100,000，更佳為10,000～50,000，進一步較佳為15,000～40,000。又，數量平均分子量（Mn）較佳為2,000～40,000，更佳為3,000～30,000，進一步較佳為4,000～20,000。 上述聚醯亞胺前驅物的分子量的分散度係1.5以上為較佳，1.8以上為更佳，2.0以上為進一步較佳。聚醯亞胺前驅物的分子量的分散度的上限值並沒有特別限定，例如，7.0以下為較佳，6.5以下為更佳，6.0以下為進一步較佳。 在本說明書中，分子量的分散度為藉由重量平均分子量/數量平均分子量計算出之值。 又，樹脂組成物包含複數種聚醯亞胺前驅物作為特定樹脂的情況下，至少1種聚醯亞胺前驅物的重量平均分子量、數量平均分子量及分散度在上述範圍為較佳。又，將上述複數種聚醯亞胺前驅物作為1種樹脂所計算出之重量平均分子量、數量平均分子量及分散度分別在上述範圍內亦為較佳。 The weight average molecular weight (Mw) of the polyimide precursor is preferably from 5,000 to 100,000, more preferably from 10,000 to 50,000, even more preferably from 15,000 to 40,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 2,000-40,000, More preferably, it is 3,000-30,000, More preferably, it is 4,000-20,000. The molecular weight dispersion of the polyimide precursor is preferably at least 1.5, more preferably at least 1.8, and still more preferably at least 2.0. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited. For example, 7.0 or less is preferable, 6.5 or less is more preferable, and 6.0 or less is still more preferable. In the present specification, the degree of dispersion of molecular weight is a value calculated from weight average molecular weight/number average molecular weight. Moreover, when the resin composition contains plural polyimide precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide precursor are in the said range. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the above plural polyimide precursors as one resin are within the above ranges.

〔聚苯并㗁唑前驅物〕 關於在本發明中所使用之聚苯并㗁唑前驅物，對其結構並沒有特別限定，較佳為包含下述式（3）所表示之重複單元。 [化學式12]

Figure 02_image020
在式（3）中，R 121表示2價有機基團，R 122表示4價有機基團，R 123及R 124分別獨立地表示氫原子或1價有機基團。 [Polybenzoxazole precursor] The structure of the polybenzoxazole precursor used in the present invention is not particularly limited, but preferably includes a repeating unit represented by the following formula (3). [chemical formula 12]
Figure 02_image020
In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group.

在式（3）中，R 123及R 124分別與式（2）中的R 113的含義相同，較佳範圍亦相同。亦即，至少1個為聚合性基為較佳。 式（3）中，R 121表示2價有機基團。作為2價有機基團，包含脂肪族基及芳香族基中的至少1個之基團為較佳。作為脂肪族基，直鏈脂肪族基為較佳。R 121為二羧酸殘基為較佳。二羧酸殘基可以僅使用1種，亦可以使用2種以上。 In formula (3), R 123 and R 124 have the same meanings as R 113 in formula (2), and their preferred ranges are also the same. That is, at least one of them is preferably a polymerizable group. In formula (3), R 121 represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a straight-chain aliphatic group is preferable. R 121 is preferably a dicarboxylic acid residue. As for dicarboxylic acid residues, only 1 type may be used, and 2 or more types may be used.

作為二羧酸殘基，包含脂肪族基之二羧酸及包含芳香族基之二羧酸殘基為較佳，包含芳香族基之二羧酸殘基為更佳。 作為包含脂肪族基之二羧酸，包含直鏈或支鏈（較佳為直鏈）的脂肪族基之二羧酸為較佳，由直鏈或支鏈（較佳為直鏈）的脂肪族基和2個-COOH構成之二羧酸為更佳。直鏈或支鏈（較佳為直鏈）的脂肪族基的碳數係2～30為較佳，2～25為更佳，3～20為進一步較佳，4～15為更進一步較佳，5～10為特佳。直鏈脂肪族基為伸烷基為較佳。 作為包含直鏈脂肪族基之二羧酸，可以舉出丙二酸、二甲基丙二酸、乙基丙二酸、異丙基丙二酸、二-正丁基丙二酸、琥珀酸、四氟琥珀酸、甲基琥珀酸、2,2-二甲基琥珀酸、2,3-二甲基琥珀酸、二甲基甲基琥珀酸、戊二酸、六氟戊二酸、2-甲基戊二酸、3-甲基戊二酸、2,2-二甲基戊二酸、3,3-二甲基戊二酸、3-乙基-3-甲基戊二酸、己二酸、八氟己二酸、3-甲基己二酸、庚二酸、2,2,6,6-四甲基庚二酸、辛二酸、十二氟辛二酸、壬二酸、癸二酸、十六氟癸二酸、1,9-壬二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸、十七烷二酸、十八烷二酸、十九烷二酸、二十烷二酸、二十一烷二酸、二十二烷二酸、二十三烷二酸、二十四烷二酸、二十五烷二酸、二十六烷二酸、二十七烷二酸、二十八烷二酸、二十九烷二酸、三十烷二酸、三十一烷二酸、三十二烷二酸、二乙醇酸、以及由下述式表示之二羧酸等。 As the dicarboxylic acid residue, an aliphatic group-containing dicarboxylic acid residue and an aromatic group-containing dicarboxylic acid residue are preferable, and an aromatic group-containing dicarboxylic acid residue is more preferable. As the dicarboxylic acid containing aliphatic group, dicarboxylic acid containing straight chain or branched (preferably straight chain) aliphatic group is preferred, from straight chain or branched (preferably straight chain) fatty A dicarboxylic acid composed of a group group and two -COOH is more preferable. The carbon number of the straight-chain or branched (preferably straight-chain) aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, and still more preferably 4 to 15 , 5-10 is particularly good. The linear aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing straight-chain aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, and succinic acid. , tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2 -Methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, Adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid Acid, Sebacic Acid, Hexadecanedioic Acid, 1,9-Azelaic Acid, Dodecanedioic Acid, Tridecanedioic Acid, Tetradecanedioic Acid, Pentadecanedioic Acid, Hexadecandioic Acid , heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, docosanedioic acid, tricosanedioic acid, tetradecanedioic acid Diacid, pentadecanedioic acid, hexacanedioic acid, heptacanedioic acid, octacosanedioic acid, nonacanedioic acid, triacanedioic acid, triundecanedioic acid , docosanedioic acid, diglycolic acid, dicarboxylic acid represented by the following formula, etc.

[化學式13]

Figure 02_image022
（式中，Z為碳數1～6的烴基，n為1～6的整數。） [chemical formula 13]
Figure 02_image022
(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

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

[化學式14]

Figure 02_image024
式中，A表示選自包括-CH 2-、-O-、-S-、-SO 2-、-CO-、-NHCO-、-C（CF 3） 2-及-C（CH 3） 2-之群組中之2價基團，*分別獨立地表示與其他結構的鍵結部位。 [chemical formula 14]
Figure 02_image024
In the formula, A represents the group consisting of -CH 2 -, -O-, -S-, -SO 2 -, -CO-, -NHCO-, -C(CF 3 ) 2 - and -C(CH 3 ) 2 The divalent groups in the group of -, * each independently represent a bonding site with another structure.

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

式（3）中，R 122表示4價有機基團。作為4價有機基團，與上述式（2）中的R 115的含義相同，較佳範圍亦相同。 又，R 122係源自雙胺基苯酚衍生物之基團為較佳，作為源自雙胺基苯酚衍生物之基團，例如，可以舉出3,3’-二胺基-4,4’-二羥基聯苯基、4,4’-二胺基-3,3’-二羥基聯苯基、3,3’-二胺基-4,4’-二羥基二苯基碸、4,4’-二胺基-3,3’-二羥基二苯基碸、雙-（3-胺基-4-羥基苯基）甲烷、2,2-雙（3-胺基-4-羥基苯基）丙烷、2,2-雙-（3-胺基-4-羥基苯基）六氟丙烷、2,2-雙-（4-胺基-3-羥基苯基）六氟丙烷、雙-（4-胺基-3-羥基苯基）甲烷、2,2-雙-（4-胺基-3-羥基苯基）丙烷、4,4’-二胺基-3,3’-二羥基二苯甲酮、3,3’-二胺基-4,4’-二羥基二苯甲酮、4,4’-二胺基-3,3’-二羥基二苯醚、3,3’-二胺基-4,4’-二羥基二苯醚、1,4-二胺基-2,5-二羥基苯、1,3-二胺基-2,4-二羥基苯、1,3-二胺基-4,6-二羥基苯等。該等雙胺基苯酚可以單獨使用或混合使用。 In formula (3), R 122 represents a tetravalent organic group. The tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferred range is also the same. In addition, R 122 is preferably a group derived from a bisaminophenol derivative. As a group derived from a bisaminophenol derivative, for example, 3,3'-diamino-4,4 '-Dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl, 4 ,4'-Diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxy phenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis -(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-di Hydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3 '-Diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1 , 3-diamino-4,6-dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

在雙胺基苯酚衍生物中，具有下述芳香族基之雙胺基苯酚衍生物為較佳。Among the bisaminophenol derivatives, those having the following aromatic groups are preferred.

[化學式15]

Figure 02_image026
式中，X 1表示-O-、-S-、-C（CF 3） 2-、-CH 2-、-SO 2-、-NHCO-，*及#分別表示與其他結構的鍵結部位。R表示氫原子或1價取代基，氫原子或烴基為較佳，氫原子或烷基為更佳。又，R 122係由上述式所表示之結構亦為較佳。R 122為由上述式所表示之結構的情況下，共計4個*及#中，任意2個為與式（3）中的R 122所鍵結之氮原子的鍵結部位且另2個為與式（3）中的R 122所鍵結之氧原子的鍵結部位為較佳，2個*為與式（3）中的R 122所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R 122所鍵結之氮原子的鍵結部位或2個*為與式（3）中的R 122所鍵結之氮原子的鍵結部位且2個#為與式（3）中的R 122所鍵結之氧原子的鍵結部位為更佳，2個*為與式（3）中的R 122所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R 122所鍵結之氮原子的鍵結部位為進一步較佳。 [chemical formula 15]
Figure 02_image026
In the formula, X 1 represents -O-, -S-, -C(CF 3 ) 2 -, -CH 2 -, -SO 2 -, -NHCO-, and * and # represent bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. In addition, it is also preferable that R 122 is a structure represented by the above formula. When R 122 is a structure represented by the above formula, among the total 4 * and #, any 2 are the bonding sites of the nitrogen atom to which R 122 is bonded in the formula (3), and the other 2 are The bonding site of the oxygen atom bonded to R 122 in formula (3) is preferred, and 2 * are bonded sites of the oxygen atom bonded to R 122 in formula (3) and 2 # It is the bonding site of the nitrogen atom bonded to R 122 in formula (3) or 2 * are the bonding sites of the nitrogen atom bonded to R 122 in formula (3) and 2 # are The bonding position of the oxygen atom bonded by R 122 in the formula (3) is more preferable, and the 2 * are the bonding sites of the oxygen atom bonded to the R 122 in the formula (3) and the 2 #s are The bonding site to the nitrogen atom to which R 122 in formula (3) is bonded is more preferable.

雙胺基苯酚衍生物係式（A-s）所表示之化合物亦為較佳。 [化學式16]

Figure 02_image028
Bisaminophenol derivatives represented by the formula (As) are also preferred. [chemical formula 16]
Figure 02_image028

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

[化學式17]

Figure 02_image030
（在式（A-sc）中，*表示與上述式（A-s）所表示之雙胺基苯酚衍生物的胺基苯酚基的芳香環鍵結。） [chemical formula 17]
Figure 02_image030
(In the formula (A-sc), * indicates that it is bonded to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

認為在上述式（A-s）中，在酚性羥基的鄰位亦即在R 3亦具有取代基會使醯胺鍵的羰基碳與羥基的距離更接近，並且從進一步提高低溫下硬化時環化率變高的效果方面考慮，為特佳。 It is believed that in the above formula (As), having a substituent at the ortho position of the phenolic hydroxyl group, that is, at R3 will make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and further improve the cyclization during hardening at low temperature. Considering the effect of increasing the rate, it is especially good.

又，在上述式（A-s）中，R 2為烷基且R 3為烷基能夠維持對i射線的高透明性和在低溫下硬化時環化率高等的效果，因此較佳。 In addition, in the above formula (As), it is preferable that R 2 is an alkyl group and R 3 is an alkyl group because it can maintain high transparency to i-rays and high cyclization rate when hardened at low temperature.

又，在上述式（A-s）中，R 1為伸烷基或取代伸烷基為進一步較佳。作為與R 1相關之伸烷基及取代伸烷基的具體例，可以舉出碳數1～8的直鏈狀或支鏈狀烷基，其中，從維持對i射線的高透明性和在低溫下硬化時環化率高等之效果，並且能夠獲得在溶劑中具有充分的溶解性且平衡優異之聚苯并㗁唑前驅物的方面考慮，-CH 2-、-CH（CH 3）-、-C（CH 3） 2-為更佳。 Also, in the above formula (As), R 1 is further preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and substituted alkylene group related to R1 include straight-chain or branched-chain alkyl groups having 1 to 8 carbon atoms. -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 - is more preferred.

作為上述式（A-s）所表示之雙胺基苯酚衍生物的製造方法，例如，能夠參考日本特開2013-256506號公報的0085～0094段及實施例1（0189～0190段），該等內容編入本說明書中。As a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A-2013-256506 can be referred to. incorporated into this manual.

作為式（A-s）所表示之雙胺基苯酚衍生物的結構的具體例，可以舉出日本特開2013-256506號公報的0070～0080段中所記載之內容，該等內容編入本說明書中。當然並不限於該等。Specific examples of the structure of the bisaminophenol derivative represented by the formula (A-s) include those described in paragraphs 0070 to 0080 of JP-A-2013-256506, which are incorporated in this specification. Of course it is not limited to these.

除上述式（3）的重複單元以外，聚苯并㗁唑前驅物亦可以包含其他種類的重複單元。 從能夠抑制伴隨閉環而產生之翹曲的方面考慮，聚苯并㗁唑前驅物包含下述式（SL）所表示之二胺殘基作為其他種類的重複單元為較佳。 In addition to the repeating units of the above formula (3), the polybenzoxazole precursor may also contain other types of repeating units. It is preferable that the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another type of repeating unit from the viewpoint of being able to suppress warpage accompanying ring closure.

[化學式18]

Figure 02_image032
在式（SL）中，Z具有a結構和b結構，R 1s為氫原子或碳數1～10的烴基，R 2s為碳數1～10的烴基，R 3s、R 4s、R 5s、R 6s中的至少1個為芳香族基，剩餘部分為氫原子或碳數1～30的有機基團且分別可以相同，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。關於Z部分的莫耳%，a結構為5～95莫耳%，b結構為95～5莫耳%，a+b為100莫耳%。 [chemical formula 18]
Figure 02_image032
In formula (SL), Z has structure a and structure b, R 1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbons, R 2s is a hydrocarbon group with 1 to 10 carbons, R 3s , R 4s , R 5s , R At least one of 6s is an aromatic group, and the rest is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and they may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. The molar % of the Z moiety is 5 to 95 molar % for the a structure, 95 to 5 molar % for the b structure, and 100 molar % for a+b.

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

包含式（SL）所表示之二胺殘基作為其他種類的重複單元的情況下，進一步包含從四羧酸二酐去除酸酐基之後而殘留之四羧酸殘基作為重複單元亦為較佳。作為該種四羧酸殘基的例子，可以舉出式（2）中的R 115的例子。 When including the diamine residue represented by formula (SL) as another type of repeating unit, it is also preferable to further include, as a repeating unit, a tetracarboxylic acid residue remaining after removing an acid anhydride group from tetracarboxylic dianhydride. An example of such a tetracarboxylic acid residue includes an example of R 115 in formula (2).

例如，聚苯并㗁唑前驅物的重量平均分子量（Mw）較佳為18,000～30,000，更佳為20,000～29,000，進一步較佳為22,000～28,000。又，數量平均分子量（Mn）較佳為7,200～14,000，更佳為8,000～12,000，進一步較佳為9,200～11,200。 上述聚苯并㗁唑前驅物的分子量的分散度係1.4以上為較佳，1.5以上為更佳，1.6以上為進一步較佳。聚苯并㗁唑前驅物的分子量的分散度的上限值並沒有特別限定，例如，2.6以下為較佳，2.5以下為更佳，2.4以下為進一步較佳，2.3以下為更進一步較佳，2.2以下為再進一步較佳。 又，在樹脂組成物包含複數種聚苯并㗁唑前驅物作為特定樹脂的情況下，至少1種聚苯并㗁唑前驅物的重量平均分子量、數量平均分子量及分散度在上述範圍內為較佳。又，將上述複數種聚苯并㗁唑前驅物作為1種樹脂所計算出之重量平均分子量、數量平均分子量及分散度分別在上述範圍內亦為較佳。 For example, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000-30,000, more preferably 20,000-29,000, further preferably 22,000-28,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 7,200-14,000, More preferably, it is 8,000-12,000, More preferably, it is 9,200-11,200. The molecular weight dispersion of the polybenzoxazole precursor is preferably at least 1.4, more preferably at least 1.5, and still more preferably at least 1.6. The upper limit of the molecular weight dispersion of the polybenzoxazole precursor is not particularly limited, for example, 2.6 or less is preferred, 2.5 or less is more preferred, 2.4 or less is further preferred, 2.3 or less is still more preferred, Below 2.2 is further preferred. In addition, when the resin composition contains plural polybenzoxazole precursors as the specific resin, it is relatively preferable that the weight average molecular weight, number average molecular weight and dispersity of at least one polybenzoxazole precursor are within the above-mentioned ranges. good. Furthermore, it is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated by using the above plural polybenzoxazole precursors as one resin are within the above ranges.

〔聚醯胺醯亞胺前驅物〕 聚醯胺醯亞胺前驅物包含下述式（PAI-2）所表示之重複單元為較佳。 [化學式19]

Figure 02_image034
在式（PAI-2）中，R 117表示3價有機基團，R 111表示2價有機基團，A 2表示氧原子或-NH-，R 113表示氫原子或1價有機基團。 [Polyamideimide Precursor] The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2). [chemical formula 19]
Figure 02_image034
In the formula (PAI-2), R 117 represents a trivalent organic group, R 111 represents a divalent organic group, A 2 represents an oxygen atom or -NH-, and R 113 represents a hydrogen atom or a monovalent organic group.

式（PAI-2）中，R 117可以例示出直鏈狀或支鏈狀脂肪族基、環狀的脂肪族基及芳香族基、雜芳香族基或者藉由單鍵或連結基將該等連結2個以上而成之基團，碳數2～20的直鏈脂肪族基、碳數3～20的支鏈脂肪族基、碳數3～20的環狀的脂肪族基、碳數6～20的芳香族基或藉由單鍵或連結基將該等組合2個以上而成之基團為較佳，碳數6～20的芳香族基或藉由單鍵或連結基將碳數6～20的芳香族基組合2個以上而成之基團為更佳。 作為上述連結基，-O-、-S-、-C（=O）-、-S（=O） 2-、伸烷基、鹵化伸烷基、伸芳基或將該等鍵結2個以上而成之連結基為較佳，-O-、-S-、伸烷基、鹵化伸烷基、伸芳基或將該等鍵結2個以上而成之連結基為更佳。 作為上述伸烷基，碳數1～20的伸烷基為較佳，碳數1～10的伸烷基為更佳，碳數1～4的伸烷基為進一步較佳。 作為上述鹵化伸烷基，碳數1～20的鹵化伸烷基為較佳，碳數1～10的鹵化伸烷基為更佳，碳數1～4的鹵化伸烷基為更佳。又，作為上述鹵化伸烷基中的鹵素原子，可以舉出氟原子、氯原子、溴原子、碘原子等，氟原子為較佳。上述鹵化伸烷基可以具有氫原子，亦可以所有氫原子被鹵素原子取代，但所有氫原子被鹵素原子取代為較佳。作為較佳之鹵化伸烷基的例子，可以舉出（二三氟甲基）亞甲基等。 作為上述伸芳基，伸苯基或伸萘基為較佳，伸苯基為更佳，1,3-伸苯基或1,4-伸苯基為進一步較佳。 In the formula (PAI-2), R 117 can be exemplified by a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a single bond or a linking group. A group formed by linking two or more, straight-chain aliphatic group with 2 to 20 carbons, branched aliphatic group with 3 to 20 carbons, cyclic aliphatic group with 3 to 20 carbons, 6 carbons An aromatic group of ~20 or a combination of two or more of these through a single bond or a linking group is preferred, and an aromatic group with 6 to 20 carbons or a combination of two or more carbons via a single bond or a linking group is preferred. A combination of two or more aromatic groups of 6 to 20 is more preferable. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) 2 -, alkylene group, halogenated alkylene group, arylylene group, or a combination of two of these The above linking group is preferred, and -O-, -S-, alkylene, halogenated alkylene, arylylene or a linking group in which two or more of these are bonded is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is still more preferable. As the alkylene halide, a alkylene halide having 1 to 20 carbons is preferable, an alkylene halide having 1 to 10 carbons is more preferable, and an alkylene halide having 1 to 4 carbons is more preferable. Moreover, examples of the halogen atom in the above-mentioned halogenated alkylene group include fluorine atom, chlorine atom, bromine atom, iodine atom and the like, among which fluorine atom is preferred. The aforementioned halogenated alkylene group may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, but all hydrogen atoms are preferably replaced by halogen atoms. Examples of preferable alkylene halides include (bistrifluoromethyl)methylene and the like. As said aryl group, phenylene or naphthylene is preferable, phenylene is more preferable, and 1,3-phenylene or 1,4-phenylene is still more preferable.

又，R 117衍生自至少1個羧基可以被鹵化之三羧酸化合物為較佳。作為上述鹵化，氯化為較佳。 在本發明中，將具有3個羧基之化合物稱為三羧酸化合物。 上述三羧酸化合物的3個羧基中的2個羧基可以被酸酐化。 作為用於製造聚醯胺醯亞胺前驅物之可以被鹵化之三羧酸化合物，可以舉出支鏈狀脂肪族、環狀脂肪族或芳香族三羧酸化合物等。 該等三羧酸化合物可以僅使用1種，亦可以使用2種以上。 Also, R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As the above-mentioned halogenation, chlorination is preferable. In the present invention, a compound having three carboxyl groups is called a tricarboxylic acid compound. Two of the three carboxyl groups of the tricarboxylic acid compound may be anhydrided. Examples of the tricarboxylic acid compound that may be halogenated for the production of the polyamideimide precursor include branched aliphatic, cycloaliphatic, or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used only by 1 type, and may use 2 or more types.

具體而言，作為三羧酸化合物，包含碳數2～20的直鏈脂肪族基、碳數3～20的支鏈脂肪族基、碳數3～20的環狀的脂肪族基、碳數6～20的芳香族基或藉由單鍵或連結基將該等組合2個以上而成之基團之三羧酸化合物為較佳，包含碳數6～20的芳香族基或藉由單鍵或連結基將碳數6～20的芳香族基組合2個以上而成之基團之三羧酸化合物為更佳。Specifically, as a tricarboxylic acid compound, a straight-chain aliphatic group having 2 to 20 carbons, a branched aliphatic group having 3 to 20 carbons, a cyclic aliphatic group having 3 to 20 carbons, a carbon number An aromatic group with 6 to 20 carbon atoms or a tricarboxylic acid compound formed by combining two or more of them through a single bond or a linking group is preferred, and it contains an aromatic group with 6 to 20 carbon atoms or a group with a single carbon number of 6 to 20 The bond or linking group is more preferably a tricarboxylic acid compound in which two or more aromatic groups having 6 to 20 carbon atoms are combined.

又，作為三羧酸化合物的具體例，可以舉出1,2,3-丙烷三羧酸、1,3,5-戊烷三羧酸、檸檬酸、偏苯三甲酸、2,3,6-萘三羧酸、鄰苯二甲酸（或鄰苯二甲酸酐）與苯甲酸藉由單鍵、-O-、-CH 2-、-C（CH 3） 2-、-C（CF 3） 2-、-SO 2-或伸苯基連結而成之化合物等。 該等化合物可以為2個羧基酐化而成之化合物（例如，偏苯三甲酸酐），亦可以為至少1個羧基鹵化而成之化合物（例如，氯化偏苯三甲酸酐）。 Moreover, specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6 -Naphthalene tricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid via single bond, -O-, -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -SO 2 - or compounds formed by linking phenylene groups, etc. These compounds may be compounds in which two carboxyl groups are anhydrided (for example, trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (for example, trimellitic anhydride).

式（PAI-2）中，R 111、A 2、R 113分別與上述式（2）中的R 111、A 2、R 113的含義相同，較佳態樣亦相同。 In formula (PAI-2), R 111 , A 2 , and R 113 have the same meanings as R 111 , A 2 , and R 113 in formula (2), respectively, and preferred embodiments are also the same.

聚醯胺醯亞胺前驅物可以進一步包含其他重複單元。 作為其他重複單元，可以舉出上述式（2）所表示之重複單元、下述式（PAI-1）所表示之重複單元等。 [化學式20]

Figure 02_image036
The polyamideimide precursor may further comprise other repeating units. As another repeating unit, the repeating unit represented by said formula (2), the repeating unit represented by following formula (PAI-1), etc. are mentioned. [chemical formula 20]
Figure 02_image036

在式（PAI-1）中，R 116表示2價有機基團，R 111表示2價有機基團。 式（PAI-1）中，R 116可以例示出直鏈狀或支鏈狀脂肪族基、環狀的脂肪族基及芳香族基、雜芳香族基或者藉由單鍵或連結基將該等連結2個以上而成之基團，碳數2～20的直鏈脂肪族基、碳數3～20的支鏈脂肪族基、碳數3～20的環狀的脂肪族基、碳數6～20的芳香族基或藉由單鍵或連結基將該等組合2個以上而成之基團為較佳，碳數6～20的芳香族基或藉由單鍵或連結基將碳數6～20的芳香族基組合2個以上而成之基團為更佳。 作為上述連結基，-O-、-S-、-C（=O）-、-S（=O） 2-、伸烷基、鹵化伸烷基、伸芳基或將該等鍵結2個以上而成之連結基為較佳，-O-、-S-、伸烷基、鹵化伸烷基、伸芳基或將該等鍵結2個以上而成之連結基為更佳。 作為上述伸烷基，碳數1～20的伸烷基為較佳，碳數1～10的伸烷基為更佳，碳數1～4的伸烷基為進一步較佳。 作為上述鹵化伸烷基，碳數1～20的鹵化伸烷基為較佳，碳數1～10的鹵化伸烷基為更佳，碳數1～4的鹵化伸烷基為更佳。又，作為上述鹵化伸烷基中的鹵素原子，可以舉出氟原子、氯原子、溴原子、碘原子等，氟原子為較佳。上述鹵化伸烷基可以具有氫原子，亦可以所有氫原子被鹵素原子取代，但所有氫原子被鹵素原子取代為較佳。作為較佳之鹵化伸烷基的例子，可以舉出（二三氟甲基）亞甲基等。 作為上述伸芳基，伸苯基或伸萘基為較佳，伸苯基為更佳，1,3-伸苯基或1,4-伸苯基為進一步較佳。 In formula (PAI-1), R 116 represents a divalent organic group, and R 111 represents a divalent organic group. In the formula (PAI-1), R 116 can be exemplified by a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a single bond or a linking group. A group formed by linking two or more, straight-chain aliphatic group with 2 to 20 carbons, branched aliphatic group with 3 to 20 carbons, cyclic aliphatic group with 3 to 20 carbons, 6 carbons An aromatic group of ~20 or a combination of two or more of these through a single bond or a linking group is preferred, and an aromatic group with 6 to 20 carbons or a combination of two or more carbons via a single bond or a linking group is preferred. A combination of two or more aromatic groups of 6 to 20 is more preferable. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) 2 -, alkylene group, halogenated alkylene group, arylylene group, or a combination of two of these The above linking group is preferred, and -O-, -S-, alkylene, halogenated alkylene, arylylene or a linking group in which two or more of these are bonded is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is still more preferable. As the alkylene halide, a alkylene halide having 1 to 20 carbons is preferable, an alkylene halide having 1 to 10 carbons is more preferable, and an alkylene halide having 1 to 4 carbons is more preferable. Moreover, examples of the halogen atom in the above-mentioned halogenated alkylene group include fluorine atom, chlorine atom, bromine atom, iodine atom and the like, among which fluorine atom is preferable. The aforementioned halogenated alkylene group may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, but all hydrogen atoms are preferably replaced by halogen atoms. Examples of preferable alkylene halides include (bistrifluoromethyl)methylene and the like. As said aryl group, phenylene or naphthylene is preferable, phenylene is more preferable, and 1,3-phenylene or 1,4-phenylene is still more preferable.

又，R 116衍生自二羧酸化合物或二羧酸二鹵化物化合物為較佳。 在本發明中，將具有2個羧基之化合物稱為二羧酸化合物，具有2個鹵化羧基之化合物稱為二羧酸二鹵化物化合物。 二羧酸二鹵化物化合物中的羧基可以被鹵化，例如，被氯化為較佳。亦即，二羧酸二鹵化物化合物為二羧酸二氯化物化合物為較佳。 作為用於製造聚醯胺醯亞胺前驅物之可以被鹵化之二羧酸化合物或二羧酸二鹵化物化合物，可以舉出直鏈狀或支鏈狀脂肪族、環狀脂肪族或芳香族二羧酸化合物或二羧酸二鹵化物化合物等。 該等二羧酸化合物或二羧酸二鹵化物化合物可以僅使用1種，亦可以使用2種以上。 Also, R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide compound. The carboxyl group in the dicarboxylic acid dihalide compound may be halogenated, for example, preferably chlorinated. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. Examples of halogenated dicarboxylic acid compounds or dicarboxylic acid dihalide compounds used in the production of polyamideimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic Dicarboxylic acid compound or dicarboxylic acid dihalide compound, etc. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used only by 1 type, and may use 2 or more types.

具體而言，作為二羧酸化合物或二羧酸二鹵化物化合物，包含碳數2～20的直鏈脂肪族基、碳數3～20的支鏈脂肪族基、碳數3～20的環狀的脂肪族基、碳數6～20的芳香族基或者藉由單鍵或連結基將該等組合2個以上而成之基團之二羧酸化合物或二羧酸二鹵化物化合物為較佳，包含碳數6～20的芳香族基或者將2個以上的碳數6～20的芳香族基藉由單鍵或連結基組合而成之基團之二羧酸化合物或二羧酸二鹵化物化合物為更佳。Specifically, as a dicarboxylic acid compound or a dicarboxylic acid dihalide compound, a straight-chain aliphatic group having 2 to 20 carbons, a branched aliphatic group having 3 to 20 carbons, a ring having 3 to 20 carbons, Dicarboxylic acid compound or dicarboxylic acid dihalide compound of aliphatic group, aromatic group with 6 to 20 carbon atoms, or a combination of two or more of these through a single bond or a linking group Preferably, a dicarboxylic acid compound or a dicarboxylic acid dicarboxylic acid compound containing an aromatic group with 6 to 20 carbons or a group formed by combining two or more aromatic groups with 6 to 20 carbons through a single bond or a linking group. Halide compounds are more preferred.

又，作為二羧酸化合物的具體例，可以舉出丙二酸、二甲基丙二酸、乙基丙二酸、異丙基丙二酸、二-正丁基丙二酸、琥珀酸、四氟琥珀酸、甲基琥珀酸、2,2-二甲基琥珀酸、2,3-二甲基琥珀酸、二甲基甲基琥珀酸、戊二酸、六氟戊二酸、2-甲基戊二酸、3-甲基戊二酸、2,2-二甲基戊二酸、3,3-二甲基戊二酸、3-乙基-3-甲基戊二酸、己二酸、八氟己二酸、3-甲基己二酸、庚二酸、2,2,6,6-四甲基庚二酸、辛二酸、十二氟辛二酸、壬二酸、癸二酸、十六氟癸二酸、1,9-壬二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸、十七烷二酸、十八烷二酸、十九烷二酸、二十烷二酸、二十一烷二酸、二十二烷二酸、二十三烷二酸、二十四烷二酸、二十五烷二酸、二十六烷二酸、二十七烷二酸、二十八烷二酸、二十九烷二酸、三十烷二酸、三十一烷二酸、三十二烷二酸、二甘醇酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、4,4’-聯苯羧酸、4,4’-聯苯羧酸、4,4’-二羧基二苯醚、二苯甲酮-4,4’-二羧酸等。 作為二羧酸二鹵化物化合物的具體例，可以舉出上述二羧酸化合物的具體例中的將2個羧基鹵化之結構的化合物。 Further, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, Tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2- Methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, hexane Diacid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid , sebacic acid, hexadecanedioic acid, 1,9- azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, Heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, docosanedioic acid, tricosanedioic acid, tetradecanedioic acid Acid, pentadecanedioic acid, hexacanedioic acid, heptacanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacanedioic acid, triundecanedioic acid, Docosanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4 '-Dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxyl groups are halogenated among the specific examples of the dicarboxylic acid compound described above.

在式（PAI-1）中，R 111與上述式（2）中的R 111的含義相同，較佳態樣亦相同。 In the formula (PAI-1), R 111 has the same meaning as R 111 in the above formula (2), and preferred embodiments are also the same.

又，聚醯胺醯亞胺前驅物在結構中具有氟原子亦為較佳。聚醯胺醯亞胺前驅物中的氟原子含量係10質量%以上為較佳，又，20質量%以下為較佳。Furthermore, it is also preferable that the polyamideimide precursor has a fluorine atom in its structure. The content of fluorine atoms in the polyamideimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

又，以提高與基板的密接性為目的，聚醯胺醯亞胺前驅物可以與具有矽氧烷結構之脂肪族基共聚。具體而言，作為二胺成分，可以舉出使用雙（3-胺基丙基）四甲基二矽氧烷、雙（對胺基苯基）八甲基五矽氧烷等之態樣。Also, for the purpose of improving the adhesion to the substrate, the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as a diamine component, the aspect which used bis(3-aminopropyl) tetramethyldisiloxane, bis(p-aminophenyl) octamethyl pentasiloxane, etc. is mentioned.

作為本發明中的聚醯胺醯亞胺前驅物的一實施形態，可以舉出式（PAI-2）所表示之重複單元、式（PAI-1）所表示之重複單元及式（2）所表示之重複單元的合計含量為所有重複單元的50莫耳%以上之態樣。上述合計含量係70莫耳%以上為更佳，90莫耳%以上為進一步較佳，大於90莫耳%為特佳。上述合計含量的上限並沒有特別限定，除了末端以外的聚醯胺醯亞胺前驅物中的所有重複單元可以為式（PAI-2）所表示之重複單元、式（PAI-1）所表示之重複單元及式（2）所表示之重複單元中的任一種。 又，作為本發明中的聚醯胺醯亞胺前驅物的另一實施形態，可以舉出式（PAI-2）所表示之重複單元及式（PAI-1）所表示之重複單元的合計含量為所有重複單元的50莫耳%以上之態樣。上述合計含量係70莫耳%以上為更佳，90莫耳%以上為進一步較佳，大於90莫耳%為特佳。上述合計含量的上限並沒有特別限定，除了末端以外的聚醯胺醯亞胺前驅物中的所有重複單元可以為式（PAI-2）所表示之重複單元或式（PAI-1）所表示之重複單元中的任一種。 As an embodiment of the polyamide imide precursor in the present invention, the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1) and the compound represented by the formula (2) can be mentioned. The total content of the repeating units indicated is an aspect of 50 mol% or more of all the repeating units. The above-mentioned total content is more than 70 mol %, more preferably 90 mol %, and more than 90 mol % is particularly preferred. The upper limit of the above-mentioned total content is not particularly limited, and all the repeating units in the polyamideimide precursor except the terminal can be the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1) Any one of repeating units and repeating units represented by formula (2). In addition, as another embodiment of the polyamideimide precursor in the present invention, the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) can be mentioned. It is the form of more than 50 mol% of all repeating units. The above-mentioned total content is more than 70 mol %, more preferably 90 mol %, and more than 90 mol % is particularly preferred. The upper limit of the above-mentioned total content is not particularly limited, and all the repeating units in the polyamideimide precursor except the terminal can be the repeating unit represented by the formula (PAI-2) or the repeating unit represented by the formula (PAI-1) any of the repeating units.

聚醯胺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。 聚醯胺醯亞胺前驅物的分子量的分散度為1.5以上為較佳，1.8以上為更佳，2.0以上為進一步較佳。聚醯胺醯亞胺前驅物的分子量的分散度的上限值並沒有特別限定，例如，7.0以下為較佳，6.5以下為更佳，6.0以下為進一步較佳。又，在樹脂組成物包含複數種聚醯胺醯亞胺前驅物作為特定樹脂的情況下，至少1種聚醯胺醯亞胺前驅物的重量平均分子量、數量平均分子量及分散度在上述範圍內為較佳。又，將上述複數種聚醯胺醯亞胺前驅物作為1種樹脂所計算出之重量平均分子量、數量平均分子量及分散度分別在上述範圍內亦為較佳。 The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000-500,000, more preferably 5,000-100,000, further preferably 10,000-50,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 800-250,000, More preferably, it is 2,000-50,000, More preferably, it is 4,000-25,000. The molecular weight dispersion of the polyamideimide precursor is preferably at least 1.5, more preferably at least 1.8, and still more preferably at least 2.0. The upper limit of the molecular weight dispersion of the polyamideimide precursor is not particularly limited, for example, 7.0 or less is preferable, 6.5 or less is more preferable, 6.0 or less is still more preferable. Also, when the resin composition includes a plurality of polyamide imide precursors as a specific resin, the weight average molecular weight, number average molecular weight and degree of dispersion of at least one polyamide imide precursor are within the above range is better. Furthermore, it is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated by using the above-mentioned plural kinds of polyamideimide precursors as one resin are within the above-mentioned ranges, respectively.

〔聚醯亞胺前驅物等的製造方法〕 例如，聚醯亞胺前驅物等能夠利用如下方法獲得：在低溫中使四羧酸二酐與二胺反應之方法、在低溫中使四羧酸二酐與二胺反應來獲得聚醯胺酸並用縮合劑或烷基化劑酯化之方法、藉由四羧酸二酐及醇獲得二酯之後使其在二胺及縮合劑的存在下反應之方法、藉由四羧酸二酐及醇獲得二酯之後用鹵化劑鹵化剩餘的二羧酸並使其與二胺反應之方法等。上述製造方法中，藉由四羧酸二酐與醇獲得二酯之後用鹵化劑鹵化剩餘的二羧酸並使其與二胺反應之方法為更佳。 作為上述縮合劑，例如可以舉出二環己碳二亞胺、二異丙基碳二亞胺、1-乙氧基羰基-2-乙氧基-1,2-二氫喹啉、1,1-羰基二氧基-二-1,2,3-苯并三唑、N,N’-二琥珀醯亞胺碳酸酯、三氟乙酸酐等。 作為上述烷基化劑，可以舉出N,N-二甲基甲醯胺二甲基縮醛、N,N-二甲基甲醯胺二乙基縮醛、N,N-二烷基甲醯胺二烷基縮醛、原甲酸三甲酯、原甲酸三乙酯等。 作為上述鹵化劑，可以舉出亞硫醯氯、草醯氯、磷醯氯等。 在聚醯亞胺前驅物等的製造方法中，在進行反應時，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。 作為有機溶劑，能夠根據原料而適當確定，可以例示出吡啶、二乙二醇二甲醚（二甘二甲醚）、N-甲基吡咯啶酮、N-乙基吡咯啶酮、丙酸乙酯、二甲基乙醯胺、二甲基甲醯胺、四氫呋喃、γ-丁內酯等。 在聚醯亞胺前驅物等的製造方法中，在進行反應時，添加鹼性化合物為較佳。鹼性化合物可以為1種，亦可以為2種以上。 鹼性化合物能夠根據原料而適當確定，可以例示出三乙胺、二異丙基乙胺、吡啶、1,8-二吖雙環[5.4.0]十一-7-烯、N,N-二甲基-4-胺吡啶等。 [Methods for producing polyimide precursors, etc.] For example, a polyimide precursor etc. can be obtained by the method of making tetracarboxylic dianhydride and diamine react at low temperature, making tetracarboxylic dianhydride and diamine react at low temperature to obtain polyamic acid The method of esterifying with a condensing agent or an alkylating agent, the method of obtaining a diester by tetracarboxylic dianhydride and alcohol, and then reacting it in the presence of diamine and condensing agent, using tetracarboxylic dianhydride and alcohol A method of halogenating the remaining dicarboxylic acid with a halogenating agent after obtaining a diester and reacting it with a diamine, etc. Among the above production methods, the method of obtaining a diester from tetracarboxylic dianhydride and alcohol, and then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine is more preferable. Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1, 1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, etc. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide Amide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, etc. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, and the like. In the production method of a polyimide precursor etc., it is preferable to use an organic solvent at the time of 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 examples include pyridine, diglyme (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate Esters, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the production method of a polyimide precursor etc., it is preferable to add a basic compound at the time of reaction. The basic compound may be one type, or two or more types. The basic compound can be appropriately determined according to the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diacribicyclo[5.4.0]undec-7-ene, N,N-di Methyl-4-aminopyridine, etc.

-封端劑- 在製造聚醯亞胺前驅物等時，為了進一步提高保存穩定性，密封殘留在聚醯亞胺前驅物等樹脂末端之羧酸酐、酸酐衍生物或胺基為較佳。密封殘留於樹脂末端之羧酸酐及酸酐衍生物時，作為封端劑，可以舉出單醇、苯酚、硫醇、苯硫酚、單胺等，從反應性、膜的穩定性考慮，使用單醇、酚類或單胺為更佳。作為單醇的較佳之化合物，可以舉出甲醇、乙醇、丙醇、丁醇、己醇、辛醇、十二醇、苯甲醇、2-苯基乙醇、2-甲氧基乙醇、2-氯甲醇、糠醇等一級醇、異丙醇、2-丁醇、環己醇、環戊醇、1-甲氧基-2-丙醇等二級醇、三級丁醇、金剛烷醇等三級醇。作為酚類的較佳之化合物，可以舉出苯酚、甲氧基苯酚、甲基苯酚、萘-1-醇、萘-2-醇、羥基苯乙烯等酚類等。又，作為單胺的較佳之化合物，可以舉出苯胺、2-乙炔基苯胺、3-乙炔基苯胺、4-乙炔基苯胺、5-胺基-8-羥喹啉、1-羥基-7-胺萘、1-羥基-6-胺萘、1-羥基-5-胺萘、1-羥基-4-胺萘、2-羥基-7-胺萘、2-羥基-6-胺萘、2-羥基-5-胺萘、1-羧基-7-胺萘、1-羧基-6-胺萘、1-羧基-5-胺萘、2-羧基-7-胺萘、2-羧基-6-胺萘、2-羧基-5-胺萘、2-胺基苯甲酸、3-胺基苯甲酸、4-胺基苯甲酸、4-胺基水楊酸、5-胺基水楊酸、6-胺基水楊酸、2-胺基苯磺酸、3-胺基苯磺酸、4-胺基苯磺酸、3-胺基-4,6-二羥基嘧啶、2-胺基苯酚、3-胺基苯酚、4-胺基苯酚、2-胺基苯硫酚、3-胺基苯硫酚、4-胺基苯硫酚等。該等可以使用2種以上，亦可以藉由使複數種封端劑反應而導入複數種不同之末端基。 又，在密封樹脂末端的胺基時，能夠用具有可與胺基反應的官能基之化合物進行密封。對胺基較佳之封端劑係羧酸酐、羧酸氯化物、羧酸溴化物、磺酸氯化物、磺酸酐、磺酸羧酸酐等為較佳，羧酸酐、羧酸氯化物為更佳。作為羧酸酐的較佳之化合物，可以舉出乙酸酐、丙酸酐、草酸酐、琥珀酸酐、順丁烯二酸酐、鄰苯二甲酸酐、苯甲酸酐、5-降莰烯-2,3-二羧酸酐等。又，作為羧酸氯化物的較佳之化合物，可以舉出乙醯氯、丙烯醯氯、丙醯氯、甲基丙烯醯氯、新戊醯氯、環己烷甲醯氯、2-乙基己醯氯、桂皮醯氯、1-金剛烷甲醯氯、七氟丁醯氯、硬脂醯氯、苯甲醯氯等。 -Encapping agent- When producing polyimide precursors, etc., in order to further improve storage stability, it is preferable to seal carboxylic anhydrides, acid anhydride derivatives, or amine groups remaining at the ends of resins such as polyimide precursors. When sealing carboxylic acid anhydride and acid anhydride derivatives remaining at the end of the resin, examples of end-capping agents include monoalcohols, phenols, mercaptans, thiophenols, monoamines, etc. Alcohols, phenols or monoamines are more preferred. Preferred compounds of monoalcohol include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloro Methanol, furfuryl alcohol and other primary alcohols, isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, tertiary butanol, adamantanol and other tertiary alcohols alcohol. Preferable compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. In addition, preferred compounds of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7- Aminenaphthalene, 1-hydroxy-6-aminenaphthalene, 1-hydroxy-5-aminenaphthalene, 1-hydroxy-4-aminenaphthalene, 2-hydroxy-7-aminenaphthalene, 2-hydroxy-6-aminenaphthalene, 2- Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-amine Naphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6- Aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3 -Aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. Two or more kinds of these can be used, and a plurality of different terminal groups can also be introduced by reacting a plurality of kinds of end-capping agents. Also, when sealing the amine group at the terminal of the resin, it can be sealed with a compound having a functional group capable of reacting with the amine group. The preferred capping agent for amino group is carboxylic acid anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic acid anhydride, etc., and carboxylic anhydride and carboxylic acid chloride are more preferred. Preferred compounds of carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-di Carboxylic anhydride, etc. In addition, preferred compounds of carboxylic acid chlorides include acetyl chloride, acryl chloride, propionyl chloride, methacryl chloride, pivalyl chloride, cyclohexaneformyl chloride, 2-ethylhexyl chloride, and Acyl chloride, cinnamyl chloride, 1-adamantaneformyl chloride, heptafluorobutyryl chloride, stearyl chloride, benzoyl chloride, etc.

-固體析出- 在製造聚醯亞胺前驅物等時，可以包括固體析出步驟。具體而言，根據需要過濾出反應液中共存之脫水縮合劑的吸水副產物之後，在水、脂肪族低級醇或其混合液等不良溶劑中投入所獲得之聚合物成分並析出聚合物成分，藉此以固體析出並使其乾燥從而能夠獲得聚醯亞胺前驅物等。為了提高純化度，可以對聚醯亞胺前驅物等反覆進行再溶解、再沉澱析出、乾燥等操作。亦可以進一步包括使用離子交換樹脂去除離子性雜質之步驟。 -Solid precipitation- When producing a polyimide precursor and the like, a solid precipitation step may be included. Specifically, after filtering out the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction liquid as needed, the obtained polymer component is put into a poor solvent such as water, aliphatic lower alcohol or a mixture thereof, and the polymer component is precipitated. Thereby, a polyimide precursor etc. can be obtained by depositing as a solid and drying it. In order to improve the degree of purification, operations such as redissolution, reprecipitation, and drying can be repeated on the polyimide precursor. It may further include the step of removing ionic impurities using an ion exchange resin.

〔含量〕 特定樹脂在本發明的樹脂組成物中的含量相對於樹脂組成物的總固體成分係20質量%以上為較佳，30質量%以上為更佳，40質量%以上為進一步較佳，50質量%以上為更進一步較佳。又，本發明的樹脂組成物中的樹脂的含量相對於樹脂組成物的總固體成分係99.5質量%以下為較佳，99質量%以下為更佳，98質量%以下為進一步較佳，97質量%以下為更進一步較佳，95質量%以下為再進一步較佳。 本發明的樹脂組成物可以僅包含1種特定樹脂，亦可以包含2種以上。在包含2種以上的情況下，合計量在上述範圍內為較佳。 〔content〕 The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and 50% by mass relative to the total solid content of the resin composition. The above are further preferred. In addition, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, and 97% by mass relative to the total solid content of the resin composition. % or less is still more preferable, and 95 mass % or less is still more preferable. The resin composition of this invention may contain only 1 type of specific resin, and may contain 2 or more types. When containing 2 or more types, it is preferable that a total amount exists in the said range.

又，本發明的樹脂組成物包含至少2種樹脂亦為較佳。 具體而言，本發明的樹脂組成物可以將特定樹脂和後述之其他樹脂合計包含2種以上，亦可以包含2種以上的特定樹脂，包含2種以上特定樹脂為較佳。 在本發明的樹脂組成物包含2種以上的特定樹脂的情況下，例如包含源自二酐的結構（上述式（2）中的R 115）不同之2種以上的聚醯亞胺前驅物為較佳。 Moreover, it is also preferable that the resin composition of this invention contains at least 2 types of resins. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described later, or may contain two or more specific resins, but preferably contains two or more specific resins. When the resin composition of the present invention contains two or more specific resins, for example, two or more polyimide precursors containing different structures derived from dianhydrides (R 115 in the above formula (2)) are better.

＜其他樹脂＞ 本發明的樹脂組成物可以包含上述特定樹脂及與特定樹脂不同之其他樹脂（以下，亦簡稱為“其他樹脂”）。 作為其他樹脂，可以舉出酚樹脂、聚醯胺、環氧樹脂、聚矽氧烷、包含矽氧烷結構之樹脂、（甲基）丙烯酸樹脂、（甲基）丙烯醯胺樹脂、胺基甲酸酯樹脂、丁醛樹脂、苯乙烯樹脂、聚醚樹脂、聚酯樹脂等。 例如，藉由進一步添加（甲基）丙烯酸樹脂，可以獲得塗佈性優異之樹脂組成物，又，可以獲得耐溶劑性優異之圖案（硬化物）。 例如，藉由代替後述之聚合性化合物或者除了後述之聚合性化合物以外，將重量平均分子量為20,000以下的聚合性基值高（例如，樹脂1g中聚合性基的含有莫耳量為1×10 -3莫耳/g以上）的（甲基）丙烯酸樹脂添加於樹脂組成物中，能夠提高樹脂組成物的塗佈性、圖案（硬化物）的耐溶劑性等。 <Other resins> The resin composition of the present invention may contain the above-mentioned specific resins and other resins different from the specific resins (hereinafter also simply referred to as “other resins”). Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, aminoformaldehyde resins, Ester resin, butyral resin, styrene resin, polyether resin, polyester resin, etc. For example, by further adding a (meth)acrylic resin, a resin composition excellent in applicability can be obtained, and a pattern (cured product) excellent in solvent resistance can be obtained. For example, by substituting or in addition to the polymerizable compound described later, the value of the polymerizable group with a weight average molecular weight of 20,000 or less is increased (for example, the molar amount of the polymerizable group contained in 1 g of resin is 1×10 -3 mol/g or more) (meth)acrylic resin can be added to the resin composition to improve the coatability of the resin composition, the solvent resistance of the pattern (cured product), and the like.

在本發明的樹脂組成物包含其他樹脂的情況下，其他樹脂的含量相對於樹脂組成物的總固體成分係0.01質量%以上為較佳，0.05質量%以上為更佳，1質量%以上為進一步較佳，2質量%以上為進一步較佳，5質量%以上為更進一步較佳，10質量%以上為再進一步較佳。 又，本發明的樹脂組成物中的其他樹脂的含量相對於樹脂組成物的總固體成分係80質量%以下為較佳，75質量%以下為更佳，70質量%以下為進一步較佳，60質量%以下為更進一步較佳，50質量%以下為再進一步較佳。 又，作為本發明的樹脂組成物的較佳之一態樣，亦能夠設為其他樹脂的含量為低含量的態樣。在上述態樣中，其他樹脂的含量相對於樹脂組成物的總固體成分係20質量%以下為較佳，15質量%以下為更佳，10質量%以下為進一步較佳，5質量%以下為更進一步較佳，1質量%以下為再進一步較佳。上述含量的下限並沒有特別限定，0質量%以上即可。 本發明的樹脂組成物可以僅包含1種其他樹脂，亦可以包含2種以上。在包含2種以上的情況下，合計量在上述範圍內為較佳。 When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 1% by mass or more, relative to the total solid content of the resin composition. Preferably, it is more preferably 2% by mass or more, still more preferably 5% by mass or more, and still more preferably 10% by mass or more. In addition, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, and 60% by mass relative to the total solid content of the resin composition. It is still more preferable that it is below mass %, and it is still more preferable that it is below 50 mass %. Moreover, as one preferable aspect of the resin composition of this invention, it can also be set as the aspect which makes content of other resin into low content. In the above-mentioned aspect, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and 5% by mass or less with respect to the total solid content of the resin composition. It is still more preferable, and 1 mass % or less is still more preferable. The lower limit of the content is not particularly limited, and it may be 0% by mass or more. The resin composition of this invention may contain only 1 type of other resins, and may contain 2 or more types. When containing 2 or more types, it is preferable that a total amount exists in the said range.

＜特定鹼產生劑＞ 本發明的樹脂組成物（本發明的第一態樣之樹脂組成物，及本發明的第二態樣之樹脂組成物）包含特定鹼產生劑。 從本發明的第一態樣之鹼產生劑產生之鹼係在同一分子內環化而成為三級胺之鹼，從上述鹼產生劑產生之鹼不是α、β-不飽和羰基化合物及α、β-不飽和亞胺化合物中的任一種。 從本發明的第二態樣之鹼產生劑產生之鹼係在同一分子內環化而成為三級胺之鹼，且從上述鹼產生劑產生之鹼不是α、β-不飽和羰基化合物及α、β-不飽和亞胺化合物中的任一種為較佳。 ＜Specific base generator＞ The resin composition of the present invention (the resin composition of the first aspect of the present invention, and the resin composition of the second aspect of the present invention) contains a specific base generator. The base generated from the base generator of the first aspect of the present invention is cyclized in the same molecule to become a base of a tertiary amine, and the base generated from the above-mentioned base generator is not an α, β-unsaturated carbonyl compound and α, Any of β-unsaturated imine compounds. The base generated from the base generator of the second aspect of the present invention is cyclized in the same molecule to become a base of a tertiary amine, and the base generated from the above-mentioned base generator is not an α, β-unsaturated carbonyl compound and α , β-unsaturated imine compounds are preferred.

特定鹼產生劑藉由250℃的加熱而產生上述鹼為較佳，藉由220℃的加熱而產生上述鹼為更佳，藉由200℃的加熱而產生上述鹼為進一步較佳，藉由190℃的加熱而產生上述鹼為特佳，藉由180℃的加熱而產生上述鹼為最佳。產生上述鹼之溫度的下限並沒有特別限定，從組成物的保存穩定性等觀點考慮，例如，100℃以上為較佳。 又，除此之外，特定鹼產生劑例如亦可以係藉由光而產生鹼者、藉由基於公知的觸媒等之醯胺基切割而產生鹼者等。 藉由下述方法來判斷某化合物A是否顯示在某溫度X℃下產生具有上述特徵之鹼之性質。 將1莫耳的化合物A在密封容器中，在1氣壓下、上述X℃、加熱3小時之後，藉由HPLC（高速液相層析）等的方法定量分解量，在產生0.01莫耳以上的上述鹼之情況下，判定為化合物A藉由X℃的加熱而產生上述鹼。關於所產生之鹼是否係在同一分子內環化而成為三級胺之鹼，例如，可以藉由使用 1H-NMR來確認。上述鹼的產生量為0.1莫耳以上為較佳，0.5莫耳以上為更佳。上述鹼的產生量的上限並沒有特別限定，例如能夠設為1000莫耳以下。 又，藉由上述條件而產生之三級胺的量係0.1莫耳以上為較佳，0.5莫耳以上為更佳。上述鹼的產生量的上限並沒有特別限定，例如能夠設為1000莫耳以下。 It is preferable that the specific base generating agent generate the above-mentioned base by heating at 250° C., it is more preferable that the above-mentioned base is generated by heating at 220° C., and it is still more preferable that the above-mentioned base is generated by heating at 200° C. It is especially preferable to generate the above-mentioned base by heating at 180°C, and it is most preferable to generate the above-mentioned base by heating at 180°C. The lower limit of the temperature at which the base is generated is not particularly limited, but is preferably 100° C. or higher, for example, from the viewpoint of storage stability of the composition. In addition, the specific base generator may be, for example, one that generates a base by light, one that generates a base by cleavage of an amido group by a known catalyst, or the like. Whether a certain compound A exhibits the property of generating a base with the above-mentioned characteristics at a certain temperature X°C is judged by the following method. After heating 1 mole of compound A in a sealed container at 1 atmosphere at the above-mentioned X°C for 3 hours, the amount of decomposition is quantified by a method such as HPLC (high-speed liquid chromatography), and 0.01 mole or more of compound A is produced. In the case of the above-mentioned base, it was determined that compound A produced the above-mentioned base by heating at X°C. It can be confirmed by using 1 H-NMR, for example, whether the generated base is cyclized in the same molecule to become a base of a tertiary amine. The generation amount of the above-mentioned base is preferably 0.1 mol or more, more preferably 0.5 mol or more. The upper limit of the generation amount of the above-mentioned base is not particularly limited, and can be set to, for example, 1000 mol or less. Also, the amount of the tertiary amine produced under the above conditions is preferably 0.1 mole or more, more preferably 0.5 mole or more. The upper limit of the generation amount of the above-mentioned base is not particularly limited, and can be set to, for example, 1000 mol or less.

從本發明的第一態樣之鹼產生劑產生之鹼係在同一分子內環化而成為三級胺之鹼。 又，上述鹼不是α、β-不飽和羰基化合物及α、β-不飽和亞胺化合物中的任一種。 在本發明中，α、β-不飽和羰基化合物係指，下述式（x-1）所表示之結構之化合物，α、β-不飽和亞胺化合物係指，下述式（x-2）所表示之結構之化合物。 [化學式21]

Figure 02_image038
式（x-1）及式（x-2）中，*分別表示與其他結構的鍵結部位。 The base generated from the base generator of the first aspect of the present invention is cyclized in the same molecule to become a base of a tertiary amine. In addition, the above-mentioned base is not any one of α, β-unsaturated carbonyl compounds and α, β-unsaturated imine compounds. In the present invention, the α, β-unsaturated carbonyl compound refers to the compound of the structure represented by the following formula (x-1), and the α, β-unsaturated imine compound refers to the compound of the following formula (x-2 ) Compounds with structures represented by . [chemical formula 21]
Figure 02_image038
In the formula (x-1) and the formula (x-2), * respectively represents a bonding site with another structure.

從特定鹼產生劑產生之鹼係包含選自包括環氧化物、氧環丁烷、醛、酮及鹵素基之群組中之至少一種基團之胺為較佳，包含選自包括環氧化物、氧環丁烷、醛及酮之群組中之至少1種基團之胺為更佳，包含環氧化物或醛之胺為進一步較佳。 上述鹼係下述式（Bs-1）所表示之鹼為較佳。 [化學式22]

Figure 02_image040
式（Bs-1）中，R 1分別獨立地表示1價的有機基團，R 1中的至少一個包含環氧化物、氧環丁烷、醛、酮或鹵素基。 R 1包含環氧化物、氧環丁烷、醛、酮或鹵素基時的較佳之態樣，及不包含該等基團中的任一種時的較佳之態樣與後述的式（1-1）中的R 1的該等較佳之態樣相同。 The base generated from the specific base generator is preferably an amine comprising at least one group selected from the group consisting of epoxides, oxetanes, aldehydes, ketones, and halogen groups, including amines selected from the group consisting of epoxides An amine of at least one group of oxetane, aldehyde, and ketone is more preferred, and an amine containing an epoxide or an aldehyde is still more preferred. The above-mentioned base is preferably a base represented by the following formula (Bs-1). [chemical formula 22]
Figure 02_image040
In formula (Bs-1), R 1 each independently represents a monovalent organic group, and at least one of R 1 contains an epoxy, oxetane, aldehyde, ketone, or halogen group. The preferred aspect when R 1 includes epoxide, oxetane, aldehyde, ketone or halogen group, and the preferred aspect when not including any of these groups is the same as the following formula (1-1 The preferred aspects of R 1 in ) are the same.

作為從特定鹼產生劑產生之鹼的具體例，可以舉出下述鹼，但並不限定於此。該等化合物中，環氧化物、氧環丁烷、醛、酮或鹵素基分別與結構中的2級胺基進行反應並環化而成為三級胺。 [化學式23]

Figure 02_image042
Specific examples of the base generated from the specific base generator include the following bases, but are not limited thereto. In these compounds, epoxides, oxetanes, aldehydes, ketones or halogen groups respectively react with the secondary amine groups in the structure and are cyclized to become tertiary amines. [chemical formula 23]
Figure 02_image042

作為從特定鹼產生劑產生之鹼在同一分子內環化所形成之三級胺，下述式（AM-1）～式（AM-4）中的任一個所表示之三級胺為較佳。 在從特定鹼產生劑產生之鹼具有環氧化物之情況下，式（AM-1）所表示之三級胺為較佳。 在從特定鹼產生劑產生之鹼具有醛或酮之情況下，式（AM-2）所表示之三級胺為較佳。 特定鹼產生劑產生之鹼為氧環丁烷之情況下，式（AM-3）所表示之三級胺為較佳。 在從特定鹼產生劑產生之鹼具有鹵素原子之情況下，式（AM-4）所表示之三級胺為較佳。 [化學式24]

Figure 02_image044
式（AM-1）～式（AM-4）中，L A1表示2價的連結基，L A2表示2價的連結基，R A1表示1價的有機基團，R A2表示氫原子或1價的有機基團。 As the tertiary amine formed by the cyclization of the base generated from a specific base generator in the same molecule, the tertiary amine represented by any one of the following formulas (AM-1) to formula (AM-4) is preferred . In the case where the base generated from the specific base generator has an epoxide, a tertiary amine represented by the formula (AM-1) is preferable. In the case where the base generated from the specific base generator has an aldehyde or a ketone, a tertiary amine represented by the formula (AM-2) is preferable. When the base generated by the specific base generator is oxetane, a tertiary amine represented by formula (AM-3) is preferable. In the case where the base generated from the specific base generator has a halogen atom, a tertiary amine represented by the formula (AM-4) is preferable. [chemical formula 24]
Figure 02_image044
In formulas (AM-1) to (AM-4), L A1 represents a divalent linking group, L A2 represents a divalent linking group, R A1 represents a monovalent organic group, and R A2 represents a hydrogen atom or 1 valent organic groups.

式（AM-1）中，L A1的較佳之態樣與後述的式（R-1）中的L R1的較佳之態樣相同。 式（AM-1）中，R A1的較佳之態樣與後述的式（1-1）中的R 1不包含環氧化物、氧環丁烷、醛、酮及鹵素基中的任一種時的較佳之態樣相同。 又，將式（AM-1）中所記載之氮原子及L A1作為員環而包含之環結構係5員環結構或6員環結構為較佳。 In formula (AM-1), a preferred aspect of L A1 is the same as a preferred aspect of L R1 in formula (R-1) described later. In the formula (AM-1), a preferred aspect of R A1 is when R 1 in the formula (1-1) described later does not contain any one of epoxy, oxetane, aldehyde, ketone, and halogen group The better form of the same. In addition, it is preferable that the ring structure including the nitrogen atom described in the formula (AM-1) and L A1 as a membered ring is a 5-membered ring structure or a 6-membered ring structure.

式（AM-2）中，L A2的較佳之態樣與後述的式（R-3）中的L R3的較佳之態樣相同。 式（AM-2）中，R A1的較佳之態樣與後述的式（1-1）中的R 1不包含環氧化物、氧環丁烷、醛、酮及鹵素基中的任一種時的較佳之態樣相同。 式（AM-2）中，R A2的較佳之態樣與後述的式（R-3）中的R R1的較佳之態樣相同。 In formula (AM-2), a preferred aspect of L A2 is the same as a preferred aspect of L R3 in formula (R-3) described later. In the formula (AM-2), a preferred aspect of R A1 is when R 1 in the formula (1-1) described later does not contain any one of epoxy, oxetane, aldehyde, ketone, and halogen group The better form of the same. In formula (AM-2), a preferred aspect of R A2 is the same as a preferred aspect of R R1 in formula (R-3) described later.

式（AM-3）中，L A1的較佳之態樣與後述的式（R-2）中的L R2的較佳之態樣相同。 式（AM-3）中，R A1的較佳之態樣與後述的式（1-1）中的R 1不包含環氧化物、氧環丁烷、醛、酮及鹵素基中的任一種時的較佳之態樣相同。 In formula (AM-3), a preferred aspect of L A1 is the same as a preferred aspect of L R2 in formula (R-2) described later. In the formula (AM-3), a preferred aspect of R A1 is when R 1 in the formula (1-1) described later does not contain any one of epoxy, oxetane, aldehyde, ketone, and halogen group The better form of the same.

式（AM-4）中，L A1的較佳之態樣與後述的式（R-4）中的L R4的較佳之態樣相同。 式（AM-4）中，R A1的較佳之態樣與後述的式（1-1）中的R 1不包含環氧化物、氧環丁烷、醛、酮及鹵素基中的任一種時的較佳之態樣相同。 In formula (AM-4), a preferred aspect of L A1 is the same as a preferred aspect of L R4 in formula (R-4) described later. In the formula (AM-4), the preferred aspect of R A1 is when R 1 in the formula (1-1) described later does not contain any one of epoxy, oxetane, aldehyde, ketone and halogen group The better form of the same.

上述三級胺中的環結構係5員環結構或6員環結構為較佳。 又，上述三級胺的分子量係80～1,000為較佳，90～500為更佳，100～400為進一步較佳。 上述三級胺在1氣壓下的沸點係50～600℃為較佳，60～500℃為更佳，80～450℃為進一步較佳。 The ring structure in the above-mentioned tertiary amine is preferably a 5-membered ring structure or a 6-membered ring structure. Moreover, the molecular weight of the above-mentioned tertiary amine is preferably 80-1,000, more preferably 90-500, and still more preferably 100-400. The boiling point of the above-mentioned tertiary amine at 1 atmosphere is preferably 50 to 600°C, more preferably 60 to 500°C, and still more preferably 80 to 450°C.

特定鹼產生劑係非離子性的鹼產生劑為較佳。 非離子性係指，不形成具有陰離子結構之有機分子與具有陽離子結構之有機分子接近而形成之締合體的形態，而是以一個分子的形式所表示之化合物。 又，特定鹼產生劑係具有醯胺基之化合物為較佳，藉由加熱而醯胺基開裂從而產生上述的胺之化合物為更佳。 作為醯胺基，可以舉出羧酸醯胺基、磺酸醯胺基等，羧酸醯胺基為較佳。 It is preferable that the specific base generator is a nonionic base generator. Nonionic refers to a compound expressed as a single molecule without forming an association of an organic molecule having an anionic structure and an organic molecule having a cationic structure approaching each other. Also, the specific base generator is preferably a compound having an amide group, and a compound that generates the above-mentioned amine by cleaving the amide group by heating is more preferable. Examples of the amide group include a carboxylic acid amide group, a sulfonic acid amide group, and the like, and a carboxylic acid amide group is preferable.

本發明的第一態樣之鹼產生劑係下述式（1-1）所表示之鹼產生劑為較佳。 本發明的第二態樣之鹼產生劑係下述式（1-1）所表示之鹼產生劑。 [化學式25]

Figure 02_image046
式（1-1）中，L 1表示2價的連結基，R 1分別獨立地表示1價的有機基團，R 1中的至少一個包含環氧化物、氧環丁烷、醛、酮或鹵素基，X分別獨立地為羥基或羧基，m表示1以上的整數，n表示1以上的整數。 The base generator of the first aspect of the present invention is preferably a base generator represented by the following formula (1-1). The base generator of the second aspect of the present invention is a base generator represented by the following formula (1-1). [chemical formula 25]
Figure 02_image046
In formula (1-1), L 1 represents a divalent linking group, R 1 independently represents a monovalent organic group, and at least one of R 1 contains epoxy, oxetane, aldehyde, ketone or In a halogen group, X is each independently a hydroxyl group or a carboxyl group, m represents an integer of 1 or more, and n represents an integer of 1 or more.

式（1-1）中，L 1係烴基或者由1個以上的烴基與選自包括含雜原子環基、-O-、-C（=O）-、-S-、-S（=O 2）-及-NR N-之群組中之至少1個結構的組合所表示之基團為較佳，烴基或者由1個以上的烴基與選自包括-O-、-S-及-NR N-之群組中之至少1個結構的組合所表示之基團為更佳。作為上述含雜原子環基，含雜原子芳香環基為較佳。又，作為含雜原子環基中所包含之含雜原子，可以舉出氧原子、硫原子、氮原子等。上述R N表示氫原子或1價取代基，氫原子或烴基為較佳，氫原子、烷基或芳香族烴基為更佳。 作為上述烴基，可以係脂肪族烴基、芳香族烴基或由其組合所表示之基團中的任一種，但至少包含芳香族烴基為較佳，由芳香族烴基與脂肪族烴基的組合所表示之基團為更佳。 作為上述芳香族烴基，碳數6～20的芳香族烴基為較佳，從苯環去除複數個氫原子之基團為更佳。又，上述芳香族烴基可以具有取代基，亦可以與其他環結構形成縮合環。 作為上述脂肪族烴基，飽和脂肪族烴基為較佳，碳數1～20的飽和脂肪族烴基為更佳，碳數1～10的飽和脂肪族烴基為進一步較佳，碳數1～4的飽和脂肪族烴基為特佳。 In formula (1-1), L1 is a hydrocarbon group or is composed of more than one hydrocarbon group and is selected from the group including heteroatom-containing ring group, -O-, -C(=O)-, -S-, -S(=O 2 ) The group represented by the combination of at least one structure in the group of - and -NR N - is preferably a hydrocarbon group or a hydrocarbon group consisting of more than one hydrocarbon group selected from the group consisting of -O-, -S- and -NR A group represented by a combination of at least one structure in the N -group is more preferable. As the heteroatom-containing ring group, a heteroatom-containing aromatic ring group is preferred. Moreover, examples of the heteroatom contained in the heteroatom-containing ring group include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The above R N represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. As the above-mentioned hydrocarbon group, it can be any one of aliphatic hydrocarbon group, aromatic hydrocarbon group, or groups represented by their combination, but it is better to include at least an aromatic hydrocarbon group, represented by a combination of an aromatic hydrocarbon group and an aliphatic hydrocarbon group Group is better. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, and a group obtained by removing a plurality of hydrogen atoms from a benzene ring is more preferable. Moreover, the said aromatic hydrocarbon group may have a substituent, and may form a condensed ring with another ring structure. As the aforementioned aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is preferred, a saturated aliphatic hydrocarbon group having 1 to 20 carbons is more preferred, a saturated aliphatic hydrocarbon group having 1 to 10 carbons is further preferred, and a saturated aliphatic hydrocarbon group having 1 to 4 carbons is more preferred. Aliphatic hydrocarbon groups are particularly preferred.

又，在式（1-1）中的X為羥基的情況下，L 1中的X與-C（=O）-之間的連結鏈的最短路徑上的原子數（連結鏈長度）係3～6為較佳，3或4為更佳。 在式（1-1）中的X為羧基的情況下，L 1中的X與-C（=O）-之間的連結鏈的最短路徑上的原子數（連結鏈長度）係2～5為較佳，2或3為更佳。 在上述任何一種情況下，L 1在上述最短路徑上包含芳香環（較佳為可以具有取代基或縮合環之伸苯基，更佳為可以具有取代基或縮合環之1,2-伸苯基）為較佳。 又，L 1在上述最短路徑上包含氧原子或硫原子為較佳。 Also, when X in formula (1-1) is a hydroxyl group, the number of atoms (linkage chain length) on the shortest path of the linking chain between X and -C(=O)- in L1 is 3 ~6 is preferred, and 3 or 4 is more preferred. In the case where X in formula (1-1) is a carboxyl group, the number of atoms (chain length) on the shortest path of the connecting chain between X and -C(=O)- in L1 is 2 to 5 is better, 2 or 3 is more preferred. In any of the above cases, L contains an aromatic ring (preferably a phenylene group that may have a substituent or a condensed ring, more preferably a 1,2-phenylene group that may have a substituent or a condensed ring) on the shortest path above. base) is better. In addition, it is preferable that L 1 contains an oxygen atom or a sulfur atom on the above-mentioned shortest path.

L 1可以具有聚合性基，具有自由基聚合性基為較佳。 又，在L 1具有自由基聚合性基之情況下，滿足環化樹脂的前驅物具有自由基聚合性基或樹脂組成物包含後述之自由基交聯劑中的至少一個為較佳。 依據該等態樣，認為由於鹼產生劑嵌入到藉由聚合所形成之聚合體中，因此例如組成物內中的鹼產生劑的分佈成為接近均勻之狀態，並且圖案矩形性進一步提高。 L 1 may have a polymerizable group, preferably a radical polymerizable group. Also, when L 1 has a radical polymerizable group, it is preferable that the precursor of the cyclization resin has a radical polymerizable group or that the resin composition contains at least one of the radical crosslinking agents described later. According to these aspects, it is considered that since the base generator is embedded in the polymer formed by polymerization, for example, the distribution of the base generator in the composition becomes nearly uniform, and the pattern rectangularity is further improved.

作為L 1的具體例，例如可以舉出下述結構，但並不限定於此。下述具體例中，*表示與式（1-1）中的X的鍵結部位，#表示與式（1-1）中的-C（=O）-的鍵結部位。 [化學式26]

Figure 02_image048
Specific examples of L1 include, for example, the following structures, but are not limited thereto. In the following specific examples, * represents a bonding site with X in formula (1-1), and # represents a bonding site with -C(=O)- in formula (1-1). [chemical formula 26]
Figure 02_image048

式（1-1）中，R 1中的至少一個包含環氧化物、氧環丁烷、醛、酮或鹵素基，包含環氧化物、氧環丁烷、醛或酮為較佳，包含環氧化物或醛為較佳。 在R 1包含環氧化物、氧環丁烷、醛、酮或鹵素基之情況下，R 1係下述式（R-1）～式（R-4）中的任一個所表示之基團為較佳。從斷裂伸長率的觀點而言，式（R-1）及式（R-2）中的任一個所表示之基團為較佳，式（R-1）所表示之基團為更佳。 [化學式27]

Figure 02_image050
式（R-1）～式（R-4）中，L R1表示2價的連結基，L R2表示2價的連結基，L R3表示2價的連結基，R R1表示氫原子或烴基，L R4表示2價的連結基，Ha表示鹵素基，*表示與式（1-1）中的氮原子的鍵結部位。 In formula (1-1), at least one of R 1 contains epoxide, oxetane, aldehyde, ketone or halogen group, preferably contains epoxide, oxetane, aldehyde or ketone, and contains ring Oxides or aldehydes are preferred. In the case where R 1 contains epoxy, oxetane, aldehyde, ketone or halogen group, R 1 is a group represented by any one of the following formulas (R-1) to formula (R-4) is better. From the viewpoint of elongation at break, the group represented by any one of formula (R-1) and formula (R-2) is preferable, and the group represented by formula (R-1) is more preferable. [chemical formula 27]
Figure 02_image050
In formulas (R-1) to ( R -4), LR1 represents a divalent linking group, LR2 represents a divalent linking group, LR3 represents a divalent linking group, RR1 represents a hydrogen atom or a hydrocarbon group, L R4 represents a divalent linking group, Ha represents a halogen group, and * represents a bonding site with a nitrogen atom in formula (1-1).

式（R-1）中，L R1係烴基或者由1個以上的烴基與選自包括含雜原子環基、-O-、-C（=O）-、-S-、-S（=O 2）-及-NR N-之群組中之至少1個結構的組合所表示之基團為較佳，烴基或者由1個以上的烴基與選自包括-O-、-S-及-NR N-之群組中之至少1個結構的組合所表示之基團為更佳，由1個以上的烴基與-O-的組合所表示之基團為進一步較佳。作為上述含雜原子環基，含雜原子芳香環基為較佳。又，作為含雜原子環基中所包含之含雜原子，可以舉出氧原子、硫原子、氮原子等。上述R N表示氫原子或1價取代基，氫原子或烴基為較佳，氫原子、烷基或芳香族烴基為更佳。 作為上述烴基，可以係脂肪族烴基、芳香族烴基或由其組合所表示之基團中的任一種，係脂肪族烴基為較佳。 作為上述芳香族烴基，碳數6～20的芳香族烴基為較佳，從苯環去除複數個氫原子之基團為更佳。又，上述芳香族烴基可以具有取代基，亦可以與其他環結構形成縮合環。 作為上述脂肪族烴基，伸烷基為較佳，碳數1～20的伸烷基為更佳，碳數1～10的伸烷基為進一步較佳，碳數2～4的伸烷基為特佳。 又，L R1中的*與環氧化物之間的連結鏈的最短路徑上的原子數（連結鏈長度）係3～6為較佳，4為更佳。 又，L R1在上述最短路徑上包含氧原子或硫原子為較佳。 In formula (R-1), L R1 is a hydrocarbon group or is composed of more than one hydrocarbon group and is selected from the group including heteroatom-containing ring group, -O-, -C(=O)-, -S-, -S(=O 2 ) The group represented by the combination of at least one structure in the group of - and -NR N - is preferably a hydrocarbon group or a hydrocarbon group consisting of more than one hydrocarbon group selected from the group consisting of -O-, -S- and -NR A group represented by a combination of at least one structure in the N- group is more preferred, and a group represented by a combination of one or more hydrocarbon groups and -O- is still more preferred. As the heteroatom-containing ring group, a heteroatom-containing aromatic ring group is preferred. Moreover, examples of the heteroatom contained in the heteroatom-containing ring group include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The above R N represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. The above-mentioned hydrocarbon group may be any one of aliphatic hydrocarbon group, aromatic hydrocarbon group or a combination thereof, preferably an aliphatic hydrocarbon group. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, and a group obtained by removing a plurality of hydrogen atoms from a benzene ring is more preferable. Moreover, the said aromatic hydrocarbon group may have a substituent, and may form a condensed ring with another ring structure. As the above-mentioned aliphatic hydrocarbon group, an alkylene group is preferred, an alkylene group having 1 to 20 carbon atoms is more preferred, an alkylene group having 1 to 10 carbon atoms is further preferred, and an alkylene group having 2 to 4 carbon atoms is Excellent. Also, the number of atoms on the shortest path of the linking chain between * in L R1 and the epoxide (linking chain length) is preferably 3-6, more preferably 4. In addition, it is preferable that L R1 contains an oxygen atom or a sulfur atom on the above-mentioned shortest path.

式（R-2）中，L R2係烴基或者由1個以上的烴基與選自包括含雜原子環基、-O-、-C（=O）-、-S-、-S（=O 2）-及-NR N-之群組中之至少1個結構的組合所表示之基團為較佳，烴基或者由1個以上的烴基與選自包括-O-、-S-及-NR N-之群組中之至少1個結構的組合所表示之基團為更佳，係烴基為進一步較佳。作為上述含雜原子環基，含雜原子芳香環基為較佳。又，作為含雜原子環基中所包含之含雜原子，可以舉出氧原子、硫原子、氮原子等。上述R N表示氫原子或1價取代基，氫原子或烴基為較佳，氫原子、烷基或芳香族烴基為更佳。 作為上述烴基，可以係脂肪族烴基、芳香族烴基或由其組合所表示之基團中的任一種，係脂肪族烴基為較佳。 作為上述芳香族烴基，碳數6～20的芳香族烴基為較佳，從苯環去除複數個氫原子之基團為更佳。又，上述芳香族烴基可以具有取代基，亦可以與其他環結構形成縮合環。 作為上述脂肪族烴基，伸烷基為較佳，碳數1～20的伸烷基為更佳，碳數1～10的伸烷基為進一步較佳，碳數2～4的伸烷基為特佳。 又，L R2中的*與環氧化物之間的連結鏈的最短路徑上的原子數（連結鏈長度）係2～5為較佳，2為更佳。 又，L R2可以在上述最短路徑上包含氧原子或硫原子。 In formula (R-2), L R2 is a hydrocarbon group or is composed of more than one hydrocarbon group and is selected from the group including heteroatom-containing ring group, -O-, -C(=O)-, -S-, -S(=O 2 ) The group represented by the combination of at least one structure in the group of - and -NR N - is preferably a hydrocarbon group or a hydrocarbon group consisting of more than one hydrocarbon group selected from the group consisting of -O-, -S- and -NR A group represented by a combination of at least one structure in the N -group is more preferable, and a hydrocarbon group is still more preferable. As the heteroatom-containing ring group, a heteroatom-containing aromatic ring group is preferred. Moreover, examples of the heteroatom contained in the heteroatom-containing ring group include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The above R N represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. The above-mentioned hydrocarbon group may be any one of aliphatic hydrocarbon group, aromatic hydrocarbon group or a combination thereof, preferably an aliphatic hydrocarbon group. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, and a group obtained by removing a plurality of hydrogen atoms from a benzene ring is more preferable. Moreover, the said aromatic hydrocarbon group may have a substituent, and may form a condensed ring with another ring structure. As the above-mentioned aliphatic hydrocarbon group, an alkylene group is preferred, an alkylene group having 1 to 20 carbon atoms is more preferred, an alkylene group having 1 to 10 carbon atoms is further preferred, and an alkylene group having 2 to 4 carbon atoms is Excellent. Also, the number of atoms (linkage chain length) on the shortest path of the linking chain between * in L R2 and the epoxide is preferably 2-5, more preferably 2. In addition, L R2 may contain an oxygen atom or a sulfur atom on the above-mentioned shortest path.

式（R-3）中，L R3係烴基或者由1個以上的烴基與選自包括含雜原子環基、-O-、-C（=O）-、-S-、-S（=O 2）-及-NR N-之群組中之至少1個結構的組合所表示之基團為較佳，烴基或者由1個以上的烴基與選自包括-O-、-S-及-NR N-之群組中之至少1個結構的組合所表示之基團為更佳，係烴基為進一步較佳。作為上述含雜原子環基，含雜原子芳香環基為較佳。又，作為含雜原子環基中所包含之含雜原子，可以舉出氧原子、硫原子、氮原子等。上述R N表示氫原子或1價取代基，氫原子或烴基為較佳，氫原子、烷基或芳香族烴基為更佳。 作為上述烴基，可以係脂肪族烴基、芳香族烴基或由其組合所表示之基團中的任一種，係脂肪族烴基為較佳。 作為上述芳香族烴基，碳數6～20的芳香族烴基為較佳，從苯環去除複數個氫原子之基團為更佳。又，上述芳香族烴基可以具有取代基，亦可以與其他環結構形成縮合環。 作為上述脂肪族烴基，伸烷基為較佳，碳數1～20的伸烷基為更佳，碳數1～10的伸烷基為進一步較佳，碳數2～4的伸烷基為特佳。 又，L R3中的*與環氧化物之間的連結鏈的最短路徑上的原子數（連結鏈長度）係2～5為較佳，3為更佳。 又，L R3可以在上述最短路徑上包含氧原子或硫原子。 式（R-3）中，R R1係烴基為較佳，烷基為更佳，碳數1～4的烷基為進一步較佳。 In formula (R-3), L R3 is a hydrocarbon group or is composed of more than one hydrocarbon group and is selected from the group including heteroatom-containing ring group, -O-, -C(=O)-, -S-, -S(=O 2 ) The group represented by the combination of at least one structure in the group of - and -NR N - is preferably a hydrocarbon group or a hydrocarbon group consisting of more than one hydrocarbon group selected from the group consisting of -O-, -S- and -NR A group represented by a combination of at least one structure in the N -group is more preferable, and a hydrocarbon group is still more preferable. As the heteroatom-containing ring group, a heteroatom-containing aromatic ring group is preferred. Moreover, examples of the heteroatom contained in the heteroatom-containing ring group include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The above R N represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. The above-mentioned hydrocarbon group may be any one of aliphatic hydrocarbon group, aromatic hydrocarbon group or a combination thereof, preferably an aliphatic hydrocarbon group. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, and a group obtained by removing a plurality of hydrogen atoms from a benzene ring is more preferable. Moreover, the said aromatic hydrocarbon group may have a substituent, and may form a condensed ring with another ring structure. As the above-mentioned aliphatic hydrocarbon group, an alkylene group is preferred, an alkylene group having 1 to 20 carbon atoms is more preferred, an alkylene group having 1 to 10 carbon atoms is further preferred, and an alkylene group having 2 to 4 carbon atoms is Excellent. Also, the number of atoms (linkage chain length) on the shortest path of the linking chain between * in LR3 and the epoxide is preferably 2-5, more preferably 3. In addition, LR3 may contain an oxygen atom or a sulfur atom on the above-mentioned shortest path. In the formula (R-3), R R1 is preferably a hydrocarbon group, more preferably an alkyl group, and still more preferably an alkyl group having 1 to 4 carbon atoms.

式（R-4）中，L R4係烴基或者由1個以上的烴基與選自包括含雜原子環基、-O-、-C（=O）-、-S-、-S（=O 2）-及-NR N-之群組中之至少1個結構的組合所表示之基團為較佳，烴基或者由1個以上的烴基與選自包括-O-、-S-及-NR N-之群組中之至少1個結構的組合所表示之基團為更佳，係烴基為進一步較佳。作為上述含雜原子環基，含雜原子芳香環基為較佳。又，作為含雜原子環基中所包含之含雜原子，可以舉出氧原子、硫原子、氮原子等。上述R N表示氫原子或1價取代基，氫原子或烴基為較佳，氫原子、烷基或芳香族烴基為更佳。 作為上述烴基，可以係脂肪族烴基、芳香族烴基或由其組合所表示之基團中的任一種，係脂肪族烴基為較佳。 作為上述芳香族烴基，碳數6～20的芳香族烴基為較佳，從苯環去除複數個氫原子之基團為更佳。又，上述芳香族烴基可以具有取代基，亦可以與其他環結構形成縮合環。 作為上述脂肪族烴基，伸烷基為較佳，碳數1～20的伸烷基為更佳，碳數1～10的伸烷基為進一步較佳，碳數3～5的伸烷基為特佳。 又，L R4中的*與鹵素基之間的連結鏈的最短路徑上的原子數（連結鏈長度）係3～6為較佳，4為更佳。 又，L R4可以在上述最短路徑上包含氧原子或硫原子。 式（R-4）中，Ha係F、Cl、Br或I為較佳，Cl或Br為較佳。 In formula (R-4), L R4 is a hydrocarbon group or is composed of more than one hydrocarbon group and is selected from the group including heteroatom-containing ring group, -O-, -C(=O)-, -S-, -S(=O 2 ) The group represented by the combination of at least one structure in the group of - and -NR N - is preferably a hydrocarbon group or a hydrocarbon group consisting of more than one hydrocarbon group selected from the group consisting of -O-, -S- and -NR A group represented by a combination of at least one structure in the N -group is more preferable, and a hydrocarbon group is still more preferable. As the heteroatom-containing ring group, a heteroatom-containing aromatic ring group is preferred. Moreover, examples of the heteroatom contained in the heteroatom-containing ring group include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The above R N represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. The above-mentioned hydrocarbon group may be any one of aliphatic hydrocarbon group, aromatic hydrocarbon group or a combination thereof, preferably an aliphatic hydrocarbon group. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, and a group obtained by removing a plurality of hydrogen atoms from a benzene ring is more preferable. Moreover, the said aromatic hydrocarbon group may have a substituent, and may form a condensed ring with another ring structure. As the above-mentioned aliphatic hydrocarbon group, an alkylene group is preferred, an alkylene group having 1 to 20 carbon atoms is more preferred, an alkylene group having 1 to 10 carbon atoms is further preferred, and an alkylene group having 3 to 5 carbon atoms is Excellent. Also, the number of atoms on the shortest path of the linking chain between * in LR4 and the halogen group (linking chain length) is preferably 3-6, more preferably 4. In addition, LR4 may contain an oxygen atom or a sulfur atom on the above-mentioned shortest path. In formula (R-4), Ha is preferably F, Cl, Br or I, more preferably Cl or Br.

式（1-1）中，在R 1不包含環氧化物、氧環丁烷、醛、酮及鹵素基中的任一種之情況下，R 1係烴基為較佳，烷基為更佳，碳數1～10的烷基為進一步較佳。作為上述烷基，例如，可以舉出乙基、異丙基、環己基等。 In formula (1-1), when R does not contain any one of epoxide, oxetane, aldehyde, ketone and halogen group, R is preferably a hydrocarbon group, more preferably an alkyl group, An alkyl group having 1 to 10 carbon atoms is further preferred. As said alkyl group, an ethyl group, an isopropyl group, a cyclohexyl group etc. are mentioned, for example.

式（1-1）中，R 1中的一個包含環氧化物、氧環丁烷、醛、酮或鹵素基，另一個不包含環氧化物、氧環丁烷、醛、酮及鹵素基中的任一種之態樣亦係本發明的較佳之態樣之一。 In formula (1-1), one of R 1 contains epoxide, oxetane, aldehyde, ketone or halogen group, and the other does not contain epoxide, oxetane, aldehyde, ketone and halogen group Any one of the aspects is also one of the preferred aspects of the present invention.

式（1-1）中，X分別獨立地表示羥基或羧基，羥基為較佳。 式（1-1）中，n係1～4的整數為較佳，1或2為更佳，1為進一步較佳。 式（1-1）中，m係1～4的整數為較佳，1或2為更佳，1為進一步較佳。 In formula (1-1), X each independently represent a hydroxyl group or a carboxyl group, preferably a hydroxyl group. In formula (1-1), n is preferably an integer of 1 to 4, more preferably 1 or 2, and further preferably 1. In formula (1-1), m is preferably an integer of 1 to 4, more preferably 1 or 2, and further preferably 1.

又，特定鹼產生劑係下述式（1-2）所表示之化合物為較佳。 [化學式28]

Figure 02_image052
式（1-2）中，L 2及L 3分別獨立地表示單鍵或2價的連結基，Ar表示可以具有取代基之芳香族基，R 1分別獨立地表示1價的有機基團，R 1中的至少一個包含環氧化物、氧環丁烷、醛、酮或鹵素基，X分別獨立地為羥基或羧基，x表示1以上的整數，y表示1以上的整數。 Furthermore, it is preferable that the specific base generator is a compound represented by the following formula (1-2). [chemical formula 28]
Figure 02_image052
In formula (1-2), L 2 and L 3 independently represent a single bond or a divalent linking group, Ar represents an aromatic group that may have a substituent, R 1 represents a monovalent organic group independently, At least one of R 1 contains an epoxide, oxetane, aldehyde, ketone or halogen group, X is each independently a hydroxyl group or a carboxyl group, x represents an integer of 1 or more, and y represents an integer of 1 or more.

式（1-2）中，R 1及X分別與式（1-1）中的R 1及X含義相同，較佳之態樣亦相同。 In formula (1-2), R 1 and X have the same meanings as R 1 and X in formula (1-1), respectively, and preferred embodiments are also the same.

式（1-2）中，L 2係單鍵、烴基、或者由1個以上的烴基與選自包括-O-、-C（=O）-、-S-、-S（=O 2）-及-NR N-之群組中之至少1個結構的組合所表示之基團為較佳，單鍵或烴基為更佳，單鍵或伸烷基為進一步較佳。 作為上述烴基，碳數1～10的烴基為較佳，碳數1～4的烴基為較佳。 作為上述伸烷基，碳數1～10的伸烷基為較佳，碳數1～4的伸烷基為更佳。 In formula (1-2), L 2 is a single bond, hydrocarbon group, or more than one hydrocarbon group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O 2 ) A group represented by a combination of at least one structure in the group of - and -NR N - is preferable, a single bond or a hydrocarbon group is more preferable, and a single bond or an alkylene group is still more preferable. As the above-mentioned hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms is preferable, and a hydrocarbon group having 1 to 4 carbon atoms is more preferable. As the above-mentioned alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 4 carbon atoms is more preferable.

式（1-2）中，Ar係可以具有取代基及縮合環中的至少一個之芳香族烴基為較佳，從可以具有取代基及縮合環的至少一個之苯環結構去除複數個氫原子之基團為較佳。 作為Ar中的取代基，可以舉出硝基、乙烯基、酯基等。 作為具有縮合環之芳香族烴基，可以舉出苯并呋喃環、苯并噻吩環、吲哚環等，但並不限定於此。 In formula (1-2), Ar is preferably an aromatic hydrocarbon group that may have at least one of a substituent and a condensed ring, and it is preferable to remove a plurality of hydrogen atoms from a benzene ring structure that may have at least one of a substituent and a condensed ring. group is preferred. Examples of the substituent in Ar include a nitro group, a vinyl group, an ester group, and the like. Examples of the aromatic hydrocarbon group having a condensed ring include, but are not limited to, a benzofuran ring, a benzothiophene ring, and an indole ring.

式（1-2）中，L 3係單鍵、或選自包括烴基、-O-、-C（=O）-、-S-、-S（=O 2）-及-NR N-之群組中之至少1個基團、或者由它們的鍵結所表示之基團為較佳，選自包括烴基、-O-及-C（=O）-之群組中之至少1個基團、或者由它們的鍵結所表示之基團為更佳。R N如上所述。 In formula (1-2), L 3 is a single bond, or is selected from hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O 2 )- and -NR N - At least one group in the group, or the group represented by their bond is preferably at least one group selected from the group including hydrocarbon group, -O- and -C(=O)- Groups, or groups represented by their bonds are more preferred. R N is as described above.

又，在式（1-2）中的X為羥基的情況下，-L 2-Ar-L 3-中的X與-C（=O）-之間的連結鏈的最短路徑上的原子數（連結鏈長度）係3～6為較佳，3或4為更佳。 在式（1-2）中的X為羧基的情況下，-L 2-Ar-L 3-中的X與-C（=O）-之間的連結鏈的最短路徑上的原子數（連結鏈長度）係2～5為較佳，2或3為更佳。 又，L 3在上述最短路徑上包含氧原子或硫原子為較佳。 Also, when X in formula (1-2) is a hydroxyl group, the number of atoms on the shortest path of the connecting chain between X and -C(=O)- in -L 2 -Ar-L 3 - (Linking chain length) is preferably 3 to 6, more preferably 3 or 4. In the case where X in formula (1-2) is a carboxyl group, the number of atoms on the shortest path of the connecting chain between X in -L 2 -Ar-L 3 - and -C(=O)- (link Chain length) is preferably 2 to 5, more preferably 2 or 3. In addition, it is preferable that L 3 contains an oxygen atom or a sulfur atom on the above-mentioned shortest path.

式（1-2）中，x係1～4的整數為較佳，1或2為更佳，1為進一步較佳。 式（1-2）中，y係1～4的整數為較佳，1或2為更佳，1為進一步較佳。 In the formula (1-2), x is an integer of 1 to 4. Preferably, 1 or 2 is more preferable, and 1 is still more preferable. In formula (1-2), it is preferable that y is an integer of 1 to 4, more preferably 1 or 2, and 1 is still more preferable.

又，特定鹼產生劑係下述式（1-3）所表示之化合物為較佳。 [化學式29]

Figure 02_image054
式（1-3）中，L 3表示單鍵或2價的連結基，R 1分別獨立地表示1價的有機基團，R 1中的至少一個包含環氧化物、氧環丁烷、醛、酮或鹵素基，R 2分別獨立地表示氫原子或1價的有機基團，2以上的R 2可以鍵結而形成環結構。 式（1-3）中，R 1及L 3分別與式（1-2）中的R 1及L 3含義相同，較佳之態樣亦相同。 式（1-3）中，R 2分別獨立地表示氫原子或1價的有機基團，氫原子為較佳。 在R 2為1價的有機基團的情況下，R 2可以舉出烴基、羥基、羧基、硝基、醯胺基等。 Also, the specific base generator is preferably a compound represented by the following formula (1-3). [chemical formula 29]
Figure 02_image054
In formula (1-3), L 3 represents a single bond or a divalent linking group, R 1 independently represents a monovalent organic group, at least one of R 1 includes epoxy, oxetane, aldehyde , a ketone or a halogen group, R 2 each independently represent a hydrogen atom or a monovalent organic group, and 2 or more R 2 may be bonded to form a ring structure. In formula (1-3), R 1 and L 3 have the same meanings as R 1 and L 3 in formula (1-2), respectively, and preferred embodiments are also the same. In the formula (1-3), R 2 each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom. When R 2 is a monovalent organic group, examples of R 2 include a hydrocarbon group, a hydroxyl group, a carboxyl group, a nitro group, an amido group, and the like.

〔分子量〕 特定鹼產生劑的分子量為150～1,000為較佳，180～800為更佳，200～700為進一步較佳。 〔Molecular weight〕 The molecular weight of the specific base generator is preferably from 150 to 1,000, more preferably from 180 to 800, and still more preferably from 200 to 700.

〔合成方法〕 例如，能夠藉由後述實施例中的合成例中所記載之方法合成特定鹼產生劑。又，亦可以使用其他公知的合成方法進行合成，關於合成方法並沒有特別限制。 〔resolve resolution〕 For example, the specific base generator can be synthesized by the method described in the synthesis examples in the examples described later. In addition, it can also be synthesized using other known synthesis methods, and the synthesis method is not particularly limited.

作為特定鹼產生劑的具體例，並沒有特別限定，可以舉出在實施例中所使用之A-1～A-40。Although it does not specifically limit as a specific example of a specific base generator, A-1 - A-40 used in an Example are mentioned.

特定鹼產生劑的含量相對於本發明的樹脂組成物的總固體成分係0.5～20質量%為較佳。下限係1質量%以上為更佳。上限係15質量%以下為更佳，10質量%以下為進一步較佳。 特定鹼產生劑可以單獨使用1種，亦可以並用2種以上。在並用2種以上的情況下，其合計量在上述範圍內為較佳。 又，在本發明的樹脂組成物包含特定鹼產生劑及後述之鹼產生劑（與特定鹼產生劑不同之鹼產生劑）的情況下，特定鹼產生劑與鹼產生劑（特定鹼產生劑不同之鹼產生劑）的合計含量係0.5～20質量%為較佳。下限係1質量%以上為更佳。上限係15質量%以下為更佳，10質量%以下為進一步較佳。 又，本發明的樹脂組成物中的相對於特定樹脂100質量份之特定鹼產生劑的含量係1～30質量份為較佳，2～20質量份為較佳。 It is preferable that content of a specific base generator is 0.5-20 mass % with respect to the total solid content of the resin composition of this invention. The lower limit is more preferably at least 1% by mass. The upper limit is more preferably 15 mass % or less, and is still more preferably 10 mass % or less. A specific base generator may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that the total amount exists in the said range. Also, when the resin composition of the present invention includes a specific base generator and a base generator (different from the specific base generator) described later, the specific base generator and the base generator (different from the specific base generator) The total content of the base generator) is preferably 0.5 to 20% by mass. The lower limit is more preferably at least 1% by mass. The upper limit is more preferably 15 mass % or less, and is still more preferably 10 mass % or less. In addition, the content of the specific base generator in the resin composition of the present invention is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, relative to 100 parts by mass of the specific resin.

＜有機金屬錯合物＞ 從耐藥品性的觀點考慮，本發明的樹脂組成物可以包含有機金屬錯合物。 有機金屬錯合物只要為包含金屬原子之有機錯合物化合物即可，包含金屬原子及有機基團之錯合物化合物為較佳，有機基團與金屬原子配位之化合物為更佳，茂金屬化合物為進一步較佳。 在本發明中，茂金屬化合物係指，具有2個可以具有取代基之環戊二烯基陰離子衍生物作為η5-配位體之有機金屬錯合物。 作為上述有機基團，並沒有特別限定，烴基或由烴基與雜原子的組合構成之基團為較佳。作為雜原子，氧原子、硫原子、氮原子為較佳。 本發明中，有機基團中的至少1個係環狀基為較佳，至少2個係環狀基為更佳。 上述環狀基選自5員環的環狀基及6員環的環狀基為較佳，5員環的環狀基為更佳。 上述環狀基可以為烴環，亦可以為雜環，烴環為較佳。 作為5員環的環狀基，環戊二烯基為較佳。 又，在本發明中所使用之有機金屬錯合物在1分子中包含2～4個環狀基為較佳。 ＜Organometallic complexes＞ From the viewpoint of chemical resistance, the resin composition of the present invention may contain an organometallic complex. As long as the organometallic complex is an organic complex compound containing a metal atom, a complex compound containing a metal atom and an organic group is preferred, and a compound in which an organic group coordinates with a metal atom is more preferred. Metal compounds are further preferred. In the present invention, the metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives which may have substituents as η5-ligands. Although it does not specifically limit as said organic group, The group which consists of a hydrocarbon group or a combination of a hydrocarbon group and a heteroatom is preferable. As the hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferable. In the present invention, at least one of the organic groups is preferably a cyclic group, and at least two are more preferably a cyclic group. The above-mentioned cyclic group is preferably selected from a cyclic group of a 5-membered ring and a cyclic group of a 6-membered ring, more preferably a cyclic group of a 5-membered ring. The above-mentioned cyclic group may be a hydrocarbon ring or a heterocycle, preferably a hydrocarbon ring. A cyclopentadienyl group is preferable as the cyclic group of a 5-membered ring. Also, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

作為有機金屬錯合物中所包含之金屬，並沒有特別限定，對應於第4族元素之金屬為較佳，選自包括鈦、鋯及鉿之群組中之至少1種金屬為更佳，選自包括鈦及鋯之群組中之至少1種金屬為進一步較佳，鈦為特佳。The metal contained in the organometallic complex is not particularly limited, but metals corresponding to Group 4 elements are preferred, and at least one metal selected from the group consisting of titanium, zirconium, and hafnium is more preferred, At least one metal selected from the group consisting of titanium and zirconium is further preferred, and titanium is particularly preferred.

有機金屬錯合物可以包含2個以上金屬原子，亦可以僅包含1個金屬原子，但僅包含1個金屬原子為較佳。在有機金屬錯合物包含2個以上金屬原子的情況下，可以僅包含1種金屬原子，亦可以包含2種以上的金屬原子。The organometallic complex may contain two or more metal atoms, or only one metal atom, but preferably only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one kind of metal atom, or may contain two or more kinds of metal atoms.

有機金屬錯合物係二茂鐵化合物、二茂鈦化合物、二茂鋯化合物或二茂鉿化合物為較佳，二茂鈦化合物、二茂鋯化合物或二茂鉿化合物為更佳，二茂鈦化合物或二茂鋯化合物為進一步較佳，二茂鈦化合物為特佳。Organometallic complexes are preferably ferrocene compounds, titanocene compounds, zirconocene compounds or hafnocene compounds, more preferably titanocene compounds, zirconocene compounds or hafnocene compounds, and titanocene compounds Compounds or zirconocene compounds are further preferred, and titanocene compounds are particularly preferred.

有機金屬錯合物具有光自由基聚合起始能力之態樣亦為本發明的較佳態樣之一。 在本發明中，具有光自由基聚合起始能力係指，能夠藉由光的照射而產生能夠引發自由基聚合之自由基。例如，對包含自由基交聯劑及有機金屬錯合物之組成物照射有機金屬錯合物吸收光且自由基交聯劑不吸收光之波長區域的光時，藉由確認自由基交聯劑是否消失，能夠確認有無光自由基聚合起始能力。確認有無消失時，能夠根據自由基交聯劑的種類而選擇適當的方法，例如藉由IR測定（紅外分光測定）或HPLC測定（高效液相層析法）確認即可。 在有機金屬錯合物具有光自由基聚合起始能力的情況下，有機金屬錯合物係茂金屬化合物為較佳，二茂鈦化合物、二茂鋯化合物或二茂鉿化合物為更佳，二茂鈦化合物或二茂鋯化合物為進一步較佳，二茂鈦化合物為特佳。 在有機金屬錯合物不具有光自由基聚合起始能力的情況下，有機金屬錯合物係選自包括二茂鈦化合物、四烷氧基鈦化合物、醯化鈦化合物、螯合鈦化合物、二茂鋯化合物及二茂鉿化合物之群組中之至少1種化合物為較佳，選自包括二茂鈦化合物、二茂鋯化合物及二茂鉿化合物之群組中之至少1種化合物為更佳，選自包括二茂鈦化合物及二茂鋯化合物之群組中之至少1種化合物為進一步較佳，二茂鈦化合物為特佳。 The aspect in which the organometallic complex has the ability to initiate photoradical polymerization is also one of the preferred aspects of the present invention. In the present invention, having the capability of initiating photoradical polymerization means that a radical capable of initiating radical polymerization can be generated by irradiation of light. For example, when a composition containing a radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region in which the organometallic complex absorbs light and the radical crosslinking agent does not absorb light, by confirming that the radical crosslinking agent Whether or not it disappears, it is possible to confirm the presence or absence of photoradical polymerization initiating ability. When confirming the presence or absence of disappearance, an appropriate method can be selected according to the type of radical crosslinking agent, for example, IR measurement (infrared spectroscopy measurement) or HPLC measurement (high performance liquid chromatography) may be used for confirmation. In the case where the organometallic complex has the ability to initiate photoradical polymerization, the organometallic complex metallocene compound is preferred, the titanocene compound, the zirconocene compound or the hafnocene compound are more preferred, and the two A titanocene compound or a zirconocene compound is further preferred, and a titanocene compound is particularly preferred. In the case where the organometallic complex does not have the ability to initiate photoradical polymerization, the organometallic complex is selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, chelated titanium compounds, At least one compound selected from the group of zirconocene compounds and hafnocene compounds is preferred, and at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds and hafnocene compounds is more preferred Preferably, at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds is even more preferred, and titanocene compounds are particularly preferred.

有機金屬錯合物的分子量係50～2,000為較佳，100～1,000為更佳。The molecular weight of the organometallic complex is preferably 50-2,000, more preferably 100-1,000.

作為有機金屬錯合物，可較佳地舉出下述式（P）所表示之化合物。 [化學式30]

Figure 02_image056
式（P）中，M為金屬原子，R分別獨立地為取代基。 上述R分別獨立地選自芳香族基、烷基、鹵素原子及烷基磺醯氧基為較佳。 Preferable examples of the organometallic complex include compounds represented by the following formula (P). [chemical formula 30]
Figure 02_image056
In the formula (P), M is a metal atom, and R are each independently a substituent. The above-mentioned Rs are preferably independently selected from aromatic groups, alkyl groups, halogen atoms and alkylsulfonyloxy groups.

式（P）中，作為M所表示之金屬原子，鐵原子、鈦原子、鋯原子或鉿原子為較佳，鈦原子、鋯原子或鉿原子為更佳，鈦原子或鋯原子為進一步較佳，鈦原子為特佳。 作為式（P）中的R中的芳香族基，可以舉出碳數6～20的芳香族基，碳數6～20的芳香族烴基為較佳，可以舉出苯基、1-萘基或2-萘基等。 作為式（P）中的R中的烷基，碳數1～20的烷基為較佳，碳數1～10的烷基為更佳，可以舉出甲基、乙基、丙基、辛基、異丙基、三級丁基、異戊基、2-乙基己基、2-甲基己基、環戊基等。 作為上述R中的鹵素原子，可以舉出F、Cl、Br、I。 作為構成上述R中的烷基磺醯氧基之烷基，碳數1～20的烷基為較佳，碳數1～10的烷基為更佳，可以舉出甲基、乙基、丙基、辛基、異丙基、三級丁基、異戊基、2-乙基己基、2-甲基己基、環戊基等。 上述R可以進一步具有取代基。作為取代基的例子，可以舉出鹵素原子（F、Cl、Br、I）、羥基、羧基、胺基、氰基、芳基、烷氧基、芳氧基、醯基、烷氧基羰基、芳氧基羰基、醯氧基、單烷基胺基、二烷基胺基、單芳胺基及二芳胺基等。 In formula (P), as the metal atom represented by M, iron atom, titanium atom, zirconium atom or hafnium atom is preferable, titanium atom, zirconium atom or hafnium atom is more preferable, titanium atom or zirconium atom is still more preferable , titanium atoms are particularly preferred. As the aromatic group in R in the formula (P), an aromatic group having 6 to 20 carbon atoms is mentioned, preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, such as phenyl, 1-naphthyl Or 2-naphthyl etc. As the alkyl group in R in the formula (P), an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable, such as methyl, ethyl, propyl, octane, etc. Base, isopropyl, tertiary butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. F, Cl, Br, I are mentioned as a halogen atom in said R. As the alkyl group constituting the alkylsulfonyloxy group in the above R, an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable, such as methyl, ethyl, propyl, etc. Base, octyl, isopropyl, tertiary butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. Said R may further have a substituent. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, amino, cyano, aryl, alkoxy, aryloxy, acyl, alkoxycarbonyl, Aryloxycarbonyl, acyloxy, monoalkylamino, dialkylamino, monoarylamino and diarylamino, etc.

作為有機金屬錯合物的具體例，並沒有特別限定，可以例示出四異丙氧基鈦、四（2-乙基己氧基）鈦、二異丙氧基雙（乙醯乙酸乙酯）鈦、二異丙氧基雙（乙醯丙酮）鈦、雙（η5-2,4-環戊二烯-1-基）雙（2,6-二氟-3-（1H-吡咯-1-基）苯基）鈦、五甲基環戊二烯三甲氧基鈦、雙（η5-2,4-環戊二烯-1-基）雙（2,6-二氟苯基）鈦及下述化合物。 [化學式31]

Figure 02_image058
Specific examples of the organometallic complex are not particularly limited, and tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethyl acetate) Titanium, diisopropoxybis(acetylacetonate)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1- base) phenyl) titanium, pentamethylcyclopentadienetrimethoxytitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium and the following said compound. [chemical formula 31]
Figure 02_image058

此外，亦能夠使用國際公開第2018/025738號的0078～0088段中所記載之化合物，但並不限定於此。In addition, compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 can also be used, but are not limited thereto.

有機金屬錯合物的含量相對於本發明的樹脂組成物的總固體成分，0.1～30質量%為較佳。下限係1.0質量%以上為更佳，1.5質量%以上為進一步較佳，3.0質量%以上為特佳。上限係25質量%以下為更佳。 有機金屬錯合物能夠使用1種或2種以上。在使用2種以上的情況下，合計量在上述範圍內為較佳。 The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 1.0% by mass or more, still more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less. One type or two or more types of organometallic complexes can be used. When using 2 or more types, it is preferable that a total amount exists in the said range.

＜聚合性化合物＞ 本發明的樹脂組成物包含聚合性化合物為較佳。 作為聚合性化合物，可以舉出自由基交聯劑或其他交聯劑。 ＜Polymerizable compound＞ It is preferable that the resin composition of this invention contains a polymeric compound. Examples of the polymerizable compound include radical crosslinking agents and other crosslinking agents.

〔自由基交聯劑〕 本發明的樹脂組成物包含自由基交聯劑為較佳。 自由基交聯劑係具有自由基聚合性基之化合物。作為自由基聚合性基，包含乙烯性不飽和鍵之基團為較佳。作為包含上述乙烯性不飽和鍵之基團，可以舉出乙烯基、烯丙基、乙烯基苯基、（甲基）丙烯醯基、順丁烯二醯亞胺基、（甲基）丙烯醯胺基等具有乙烯性不飽和鍵之基團。 在該等之中，作為包含上述乙烯性不飽和鍵之基團，（甲基）丙烯醯基、（甲基）丙烯醯胺基、乙烯基苯基為較佳，從反應性的觀點考慮，（甲基）丙烯醯基為更佳。 〔Free radical crosslinking agent〕 It is preferable that the resin composition of the present invention contains a radical crosslinking agent. The free radical crosslinking agent is a compound having a free radical polymerizable group. As the radical polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of groups containing the aforementioned ethylenically unsaturated bonds include vinyl, allyl, vinylphenyl, (meth)acryl, maleimide, (meth)acryl A group having an ethylenically unsaturated bond such as an amino group. Among them, (meth)acryl, (meth)acrylamide, and vinylphenyl are preferable as the group containing the aforementioned ethylenically unsaturated bond. From the viewpoint of reactivity, (Meth)acryloyl is more preferred.

自由基交聯劑係具有1個以上乙烯性不飽和鍵之化合物為較佳，具有2個以上乙烯性不飽和鍵之化合物為更佳。自由基交聯劑可以具有3個以上乙烯性不飽和鍵。 作為具有2個以上的上述乙烯性不飽和鍵之化合物，具有2～15個乙烯性不飽和鍵之化合物為較佳，具有2～10個乙烯性不飽和鍵之化合物為更佳，具有2～6個乙烯性不飽和鍵之化合物為進一步較佳。 又，從所獲得之圖案（硬化物）的膜強度的觀點考慮，本發明的樹脂組成物包含具有2個乙烯性不飽和鍵之化合物和具有3個以上的上述乙烯性不飽和鍵之化合物亦為較佳。 The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. As a compound having two or more of the above-mentioned ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferred, a compound having 2 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 2 to 10 ethylenically unsaturated bonds is more preferred. A compound having 6 ethylenically unsaturated bonds is further preferred. Also, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention includes a compound having two ethylenically unsaturated bonds and a compound having three or more of the above-mentioned ethylenically unsaturated bonds. is better.

自由基交聯劑的分子量係2,000以下為較佳，1,500以下為更佳，900以下為進一步較佳。自由基交聯劑的分子量的下限為100以上為較佳。The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

作為自由基交聯劑的具體例，可以舉出不飽和羧酸（例如，丙烯酸、甲基丙烯酸、伊康酸、巴豆酸、異巴豆酸、順丁烯二酸等）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價胺化合物的醯胺類。又，亦可較佳地使用具有羥基或胺基、氫硫基等親核性取代基之不飽和羧酸酯或醯胺類與單官能或多官能異氰酸酯類或環氧類的加成反應物、與單官能或多官能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，作為其他例，亦能夠代替上述不飽和羧酸而使用取代為不飽和膦酸、苯乙烯等乙烯基苯衍生物、乙烯醚、烯丙醚之化合物群組。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，該內容編入本說明書中。Specific examples of radical crosslinking agents include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters, acyl acids, etc. The amines are preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, addition reactants of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl groups, amine groups, and mercapto groups and monofunctional or polyfunctional isocyanates or epoxides can also be preferably used. , Dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. Also, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and further have halogen groups Or the substitution reactants of unsaturated carboxylic acid esters or amides with detachable substituents such as toluenesulfonyloxy and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, instead of the above-mentioned unsaturated carboxylic acid, a compound group substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, and allyl ether can also be used. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the content is incorporated in this specification.

又，自由基交聯劑為在常壓下具有100℃以上的沸點之化合物亦為較佳。作為其例，能夠舉出聚乙二醇二（甲基）丙烯酸酯、三羥甲基乙烷三（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、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、己二醇二（甲基）丙烯酸酯、三羥甲基丙烷三（丙烯醯氧基丙基）醚、三（丙烯醯氧基乙基）異氰脲酸酯、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胺基甲酸酯（甲基）丙烯酸酯類、日本特開昭48-064183號、日本特公昭49-043191號、日本特公昭52-030490號各公報中所記載之聚酯丙烯酸酯類，作為環氧樹脂與（甲基）丙烯酸的反應生成物的環氧丙烯酸酯類等多官能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段中所記載之化合物亦為較佳。又，亦能夠舉出使多官能羧酸與（甲基）丙烯酸環氧丙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, it is also preferable that a radical crosslinking agent is a compound which has a boiling point of 100 degreeC or more under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol tri (Meth)acrylate, Neopentylthritol tetra(meth)acrylate, Dineopentylthritol penta(meth)acrylate, Dineopentylthritol hexa(meth)acrylate, Hexylene glycol di( Meth) acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trimethylolethane, etc. in polyfunctional alcohols Compounds that undergo (meth)acrylation after adding ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Application Publication No. 51-037193 Urethane (meth)acrylates described in the gazettes, polyesters described in the gazettes of JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490 Acrylates, polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid; and mixtures thereof. Also, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also preferable. Moreover, the polyfunctional (meth)acrylate obtained by making polyfunctional carboxylic acid and the compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, react, etc. are also mentioned.

又，作為上述以外的較佳之自由基交聯劑，亦能夠使用日本特開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個以上的具有乙烯性不飽和鍵之基團的化合物、卡多（cardo）樹脂。In addition, as a preferable radical crosslinking agent other than the above, those described in JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. having an oxene ring can also be used. Compounds and cardo resins having two or more groups having ethylenically unsaturated bonds.

進而，作為其他例子，亦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，亦能夠使用日本特開昭61-022048號公報中所記載之包含全氟烷基之化合物。進而，亦能夠使用Journal of the Adhesion Society of Japan vol.20，No.7,300～308頁（1984年）中作為光聚合性單體及寡聚物而介紹者。Further, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, Japanese Patent Laid-Open No. 02- Vinylphosphonic acid-based compounds described in Publication No. 025493, etc. Moreover, the compound containing a perfluoroalkyl group described in Unexamined-Japanese-Patent No. 61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in Journal of the Adhesion Society of Japan vol. 20, No. 7, pages 300 to 308 (1984) can also be used.

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段中所記載之化合物、國際公開第2015/199219號的0087～0131段中所記載之化合物，該等內容編入本說明書中。In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used. incorporated into this manual.

又，在日本特開平10-062986號公報中作為式（1）及式（2）而與其具體例一同記載之化合物亦能夠用作自由基交聯劑，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）丙烯酸酯化而成之化合物。In addition, the compounds described in Japanese Patent Application Laid-Open No. 10-062986 as formula (1) and formula (2) together with their specific examples can also be used as radical crosslinking agents. A compound obtained by (meth)acrylic esterification of ethylene oxide or propylene oxide.

進而，日本特開2015-187211號公報的0104～0131段中所記載之化合物亦能夠用作自由基交聯劑，該等內容編入本說明書中。Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as a radical crosslinking agent, and these contents are incorporated in this specification.

作為自由基交聯劑，二新戊四醇三丙烯酸酯（市售品為KAYARAD D-330（Nippon Kayaku Co.,Ltd.）製）、二新戊四醇四丙烯酸酯（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（市售品為KAYARAD D-310（Nippon Kayaku Co.,Ltd.）製）、二新戊四醇六（甲基）丙烯酸酯（市售品為KAYARAD DPHA（Nippon Kayaku Co.,Ltd.）製）、A-DPH（Shin-Nakamura Chemical Co.,Ltd.製）及該等（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 a free radical cross-linking agent, diperythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.), dipiperythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), diperythritol penta(meth)acrylate (commercially available as KAYARAD) D-310 (manufactured by Nippon Kayaku Co., Ltd.), diperythritol hexa(meth)acrylate (commercially available is KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)), A-DPH ( Shin-Nakamura Chemical Co., Ltd.) and a structure in which (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues is preferable. These oligomer types can also be used.

作為自由基交聯劑的市售品，例如可以舉出Sartomer Company,Inc製的作為具有4個乙烯氧基鏈之4官能丙烯酸酯的SR-494、作為具有4個乙烯氧基鏈之2官能甲基丙烯酸酯的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官能丙烯酸酯的DPCA-60、作為具有3個異伸丁氧基鏈之3官能丙烯酸酯的TPA-330、胺基甲酸酯寡聚物UAS-10、UAB-140（NIPPON PAPER INDUSTRIES CO.,LTD.製）、NK ESTER M-40G、NK ESTER 4G、NK ESTER M-9300、NK ESTER 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（以上，Kyoeisha chemical Co.,Ltd.製）、BLEMMER PME400（NOF CORPORATION.製）等。Commercially available free radical crosslinking agents include, for example, SR-494 manufactured by Sartomer Company, Inc., which is a tetrafunctional acrylate having four ethyleneoxy chains, and SR-494, which is a bifunctional acrylate having four ethyleneoxy chains. SR-209, 231, 239 manufactured by Sartomer Company, Inc. of methacrylate, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, DPCA-60 as a hexafunctional acrylate having 3 Trifunctional acrylate TPA-330 of isobutoxy chain, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (above, manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), etc.

作為自由基交聯劑，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，作為自由基交聯劑，亦能夠使用日本特開昭63-277653號公報、日本特開昭63-260909號公報、日本特開平01-105238號公報中所記載之在分子內具有胺基結構、硫醚結構之化合物。As a free radical crosslinking agent, the aminomethyl group described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765 Ester acrylates, Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 have ethylene oxide Urethane compounds with skeletons are also preferred. Furthermore, as a radical crosslinking agent, it is also possible to use those having an amino group in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-01-105238. Structure, compound of thioether structure.

自由基交聯劑可以為具有羧基、磷酸基等酸基之自由基交聯劑。具有酸基之自由基交聯劑中，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羥基與非芳香族羧酸酐反應而使其具有酸基之自由基交聯劑為更佳。特佳為使脂肪族多羥基化合物的未反應羥基與非芳香族羧酸酐反應而使其具有酸基之自由基交聯劑中，脂肪族多羥基化合物為新戊四醇或二新戊四醇。作為市售品，例如，可以舉出TOAGOSEI CO.,LTD.製多元酸改質丙烯酸寡聚物M-510、M-520等。The free radical crosslinking agent may be a free radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. Among free radical crosslinking agents with acid groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, and unreacted hydroxyl groups of aliphatic polyhydroxy compounds are reacted with non-aromatic carboxylic acid anhydrides to have acid groups A free radical crosslinking agent is more preferred. Among the free radical crosslinking agents which react the unreacted hydroxyl group of the aliphatic polyhydroxy compound with the non-aromatic carboxylic acid anhydride to make it have an acid group, the aliphatic polyhydroxy compound is neopentyl glycol or dipentyl glycol . As a commercial item, polybasic-acid-modified acrylic oligomer M-510, M-520 etc. by TOAGOSEI CO., LTD. are mentioned, for example.

具有酸基之自由基交聯劑的較佳酸值為0.1～300mgKOH/g，特佳為1～100mgKOH/g。自由基交聯劑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。上述酸值按照JIS K 0070:1992的記載進行測定。The preferred acid value of the free radical crosslinking agent with acid groups is 0.1-300 mgKOH/g, particularly preferably 1-100 mgKOH/g. If the acid value of a radical crosslinking agent exists in the said range, it will be excellent in workability|operativity in manufacture, and also will be excellent in developability. Also, the polymerizability is good. The said acid value is measured according to description of JISK0070:1992.

從圖案的解析度和膜的伸縮性的觀點考慮，樹脂組成物使用2官能甲基丙烯酸酯或丙烯酸酯為較佳。 作為具體化合物，能夠使用三乙二醇二丙烯酸酯、三乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、四乙二醇二丙烯酸酯、PEG（聚乙二醇）200二丙烯酸酯、PEG200二甲基丙烯酸酯、PEG600二丙烯酸酯、PEG600二甲基丙烯酸酯、聚四乙二醇二丙烯酸酯、聚四乙二醇二甲基丙烯酸酯、新戊二醇二丙烯酸酯、新戊二醇二甲基丙烯酸酯、3-甲基-1,5-戊二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、二羥甲基-三環癸烷二丙烯酸酯、二羥甲基-三環癸烷二甲基丙烯酸酯、雙酚A的EO（環氧乙烷）加成物二丙烯酸酯、雙酚A的EO加成物二甲基丙烯酸酯、雙酚A的PO加成物二丙烯酸酯、雙酚A的PO加成物二甲基丙烯酸酯、2-羥基-3-丙烯醯氧基丙基甲基丙烯酸酯、異氰脲酸EO改質二丙烯酸酯、異氰脲酸改質二甲基丙烯酸酯、其他具有胺基甲酸酯鍵之2官能丙烯酸酯、具有胺基甲酸酯鍵之2官能甲基丙烯酸酯。該等可以根據需要混合使用2種以上。 此外，例如PEG200二丙烯酸酯係指聚乙二醇鏈的式量為200左右的聚乙二醇二丙烯酸酯。 從抑制伴隨圖案（硬化物）的彈性模數控制而產生之翹曲的觀點考慮，本發明的樹脂組成物能夠將單官能自由基交聯劑較佳地用作自由基交聯劑。作為單官能自由基交聯劑，可較佳地使用（甲基）丙烯酸正丁酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸2-羥乙酯、（甲基）丙烯酸丁氧基乙酯、（甲基）丙烯酸卡必醇酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸芐酯、（甲基）丙烯酸苯氧基乙酯、N-羥甲基（甲基）丙烯醯胺、（甲基）丙烯酸環氧丙酯、單（甲基）丙烯酸聚乙二醇酯、單（甲基）丙烯酸聚丙二醇酯等（甲基）丙烯酸衍生物、N-乙烯基吡咯啶酮、N-乙烯基己內醯胺等N-乙烯基化合物類、烯丙基環氧丙醚。作為單官能自由基交聯劑，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。 此外，作為2官能以上的自由基交聯劑，可以舉出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。 From the viewpoint of pattern resolution and film stretchability, it is preferable to use bifunctional methacrylate or acrylate for the resin composition. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 Diacrylate, PEG200 Dimethacrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate , Neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate , dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct of bisphenol A diacrylate, bisphenol A EO adduct dimethacrylate, PO adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloxypropyl methyl acrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylate with urethane bond, 2 functional acrylate with urethane bond Functional methacrylate. These can mix and use 2 or more types as needed. In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a polyethylene glycol chain formula weight of about 200. The resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as the radical crosslinking agent from the viewpoint of suppressing warpage accompanying elastic modulus control of the pattern (cured product). As monofunctional radical crosslinking agents, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth) Butoxyethyl acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (Meth)acrylic acid derivatives such as (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc., N- N-vinyl compounds such as vinylpyrrolidone and N-vinylcaprolactam, and allylglycidyl ether. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable. Moreover, allyl compounds, such as diallyl phthalate and triallyl trimellitate, are mentioned as a difunctional or more radical crosslinking agent.

在含有自由基交聯劑的情況下，其含量相對於本發明的樹脂組成物的總固體成分，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。When a radical crosslinking agent is contained, its content is preferably more than 0 mass % and 60 mass % or less with respect to the total solid content of the resin composition of this invention. The lower limit is more preferably at least 5% by mass. The upper limit is more preferably at most 50% by mass, and more preferably at most 30% by mass.

自由基交聯劑可以單獨使用1種，亦可以混合使用2種以上。在並用2種以上的情況下，其合計量在上述範圍內為較佳。A radical crosslinking agent may be used individually by 1 type, and may mix and use 2 or more types. When using 2 or more types together, it is preferable that the total amount exists in the said range.

〔其他交聯劑〕 本發明的樹脂組成物包含與上述自由基交聯劑不同之其他交聯劑亦為較佳。 在本發明中，其他交聯劑係指，上述自由基交聯劑以外的交聯劑，在分子內具有複數個藉由光酸產生劑或光鹼產生劑的感光而促進（在與組成物中的其他化合物或其反應生成物之間形成共價鍵之）反應之基團之化合物為較佳，在分子內具有複數個藉由酸或鹼的作用促進（在與組成物中的其他化合物或其反應生成物之間形成共價鍵之）反應之基團之化合物為更佳。 上述酸或鹼係在曝光步驟中從光酸產生劑或光鹼產生劑產生之酸或鹼為較佳。 作為其他交聯劑，具有選自包括醯氧基甲基、羥甲基及烷氧基甲基之群組中之至少1種基團之化合物為較佳，具有選自包括醯氧基甲基、羥甲基及烷氧基甲基之群組中之至少1種基團直接鍵結於氮原子之結構之化合物為更佳。 作為其他交聯劑，例如可以舉出具有如下結構之化合物：使三聚氰胺、乙炔脲、脲、伸烷基脲、苯并胍胺等含胺基化合物與甲醛進行反應或使甲醛與醇進行反應並用醯氧基甲基、羥甲基或烷氧基甲基取代上述胺基的氫原子之結構。該等化合物的製造方法並沒有特別限定，只要為具有與藉由上述方法製造之化合物相同結構之化合物即可。又，可以為該等化合物的羥甲基彼此自縮合而成之寡聚物。 作為上述含胺基化合物，將使用三聚氰胺之交聯劑稱為三聚氰胺系交聯劑，將使用乙炔脲、脲或伸烷基脲之交聯劑稱為脲系交聯劑，將使用伸烷基脲之交聯劑稱為伸烷基脲系交聯劑，將使用苯并胍胺之交聯劑稱為苯并胍胺系交聯劑。 在該等之中，本發明的樹脂組成物包含選自包括脲系交聯劑及三聚氰胺系交聯劑之群組中之至少1種化合物為較佳，包含選自包括後述乙炔脲系交聯劑及三聚氰胺系交聯劑之群組中之至少1種化合物為更佳。 〔Other crosslinking agents〕 It is also preferable that the resin composition of the present invention contains other crosslinking agents different from the above radical crosslinking agents. In the present invention, other cross-linking agents refer to cross-linking agents other than the above-mentioned free radical cross-linking agents, which have a plurality of cross-linking agents in the molecule that are promoted by the photosensitization of photoacid generators or photobase generators (in combination with the composition) The compound that forms a covalent bond between other compounds or their reaction products in the compound is preferred, and has multiple groups in the molecule that are promoted by the action of acid or base (with other compounds in the composition) A compound of a reactive group that forms a covalent bond between its reaction products is more preferable. It is preferable that the above-mentioned acid or base is an acid or base generated from a photoacid generator or a photobase generator in the exposure step. As other crosslinking agents, compounds having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl and alkoxymethyl groups are preferred, and compounds having groups selected from the group consisting of acyloxymethyl A compound having a structure in which at least one group of the group of hydroxymethyl, alkoxymethyl, and alkoxymethyl is directly bonded to a nitrogen atom is more preferable. Examples of other crosslinking agents include compounds having a structure in which formaldehyde is reacted with an amino group-containing compound such as melamine, acetylene urea, urea, alkylene urea, or benzoguanamine, or formaldehyde is used in combination with an alcohol. A structure in which the hydrogen atom of the above-mentioned amine group is replaced by an acyloxymethyl group, a hydroxymethyl group or an alkoxymethyl group. The production method of these compounds is not particularly limited, as long as it is a compound having the same structure as the compound produced by the above-mentioned method. Moreover, it may be an oligomer obtained by self-condensing the methylol groups of these compounds. As the above-mentioned amine group-containing compound, the cross-linking agent using melamine is called melamine-based cross-linking agent, the cross-linking agent using acetylene carbamide, urea or alkylene urea is called urea-based cross-linking agent, and the cross-linking agent using alkylene urea A urea crosslinking agent is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. Among them, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, including acetylene carbamide crosslinking agents as described later. More preferably, at least one compound selected from the group consisting of crosslinking agents and melamine-based crosslinking agents.

作為本發明中的含有烷氧基甲基及醯氧基甲基中的至少1個之化合物，能夠舉出烷氧基甲基或醯氧基甲基直接在芳香族基或下述脲結構的氮原子上或者在三口井上取代之化合物作為結構例。 關於上述化合物所具有之烷氧基甲基或醯氧基甲基，碳數2～5為較佳，碳數2或3為更佳，碳數2為進一步較佳。 上述化合物所具有之烷氧基甲基及醯氧基甲基的總數係1～10為較佳，更佳為2～8，特佳為3～6。 上述化合物的分子量較佳為1500以下，180～1200為較佳。 As a compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention, those in which an alkoxymethyl group or an acyloxymethyl group is directly attached to an aromatic group or the following urea structure can be mentioned. Compounds substituted on the nitrogen atom or on the three wells are shown as structural examples. Regarding the alkoxymethyl group or acyloxymethyl group possessed by the above-mentioned compounds, the number of carbon atoms is preferably 2 to 5, more preferably 2 or 3 carbon atoms, and still more preferably 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups in the above compounds is preferably 1-10, more preferably 2-8, particularly preferably 3-6. The molecular weight of the above compound is preferably 1500 or less, more preferably 180-1200.

[化學式32]

Figure 02_image060
[chemical formula 32]
Figure 02_image060

R 100表示烷基或醯基。 R 101及R 102分別獨立地表示1價有機基團，可以相互鍵結而形成環。 R 100 represents an alkyl or acyl group. R 101 and R 102 each independently represent a monovalent organic group, which may be bonded to each other to form a ring.

作為烷氧基甲基或醯氧基甲基直接在芳香族基上取代之化合物，例如能夠舉出下述通式之類的化合物。Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds of the following general formula.

[化學式33]

Figure 02_image062
[chemical formula 33]
Figure 02_image062

式中，X表示單鍵或2價有機基團，各R 104分別獨立地表示烷基或醯基，R 103表示氫原子、烷基、烯基、芳基、芳烷基或藉由酸的作用分解並生成鹼可溶性基之基團（例如，藉由酸的作用脫離之基團、由-C（R 4） 2COOR 5表示之基團（R 4分別獨立地表示氫原子或碳數1～4的烷基，R 5表示藉由酸的作用脫離之基團。））。 R 105各自獨立地表示烷基或烯基，a、b及c各自獨立地為1～3，d為0～4，e為0～3，f為0～3，a+d為5以下，b+e為4以下，c+f為4以下。 關於藉由酸的作用分解並生成鹼可溶性基之基團、藉由酸的作用脫離之基團、-C（R 4） 2COOR 5所表示之基團中的R 5，例如，能夠舉出-C（R 36）（R 37）（R 38）、-C（R 36）（R 37）（OR 39）、-C（R 01）（R 02）（OR 39）等。 式中，R 36～R 39分別獨立地表示烷基、環烷基、芳基、芳烷基或烯基。R 36與R 37可以相互鍵結而形成環。 作為上述烷基，碳數1～10的烷基為較佳，碳數1～5的烷基為更佳。 上述烷基可以為直鏈狀、支鏈狀中的任一種。 作為上述環烷基，碳數3～12的環烷基為較佳，碳數3～8的環烷基為更佳。 上述環烷基可以為單環結構，亦可以為縮合環等多環結構。 上述芳基為碳數6～30的芳香族烴基為較佳，苯基為更佳。 作為上述芳烷基，碳數7～20的芳烷基為較佳，碳數7～16的烷基為更佳。 上述芳烷基係指被烷基取代之芳基，該等烷基及芳基的較佳態樣與上述烷基及芳基的較佳態樣相同。 上述烯基為碳數3～20的烯基為較佳，碳數3～16的烯基為更佳。 又，該等基團可以在獲得本發明的效果之範圍內進一步具有公知的取代基。 In the formula, X represents a single bond or a divalent organic group, each R 104 independently represents an alkyl or acyl group, and R 103 represents a hydrogen atom, an alkyl, an alkenyl, an aryl, an aralkyl, or A group that decomposes and generates an alkali-soluble group (for example, a group detached by the action of an acid, a group represented by -C(R 4 ) 2 COOR 5 (R 4 independently represents a hydrogen atom or a carbon number 1 ~4 alkyl groups, R 5 represents the group that is removed by the action of acid.)). R 105 each independently represent an alkyl or alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. As for R 5 in the group decomposed by the action of acid to form an alkali-soluble group, the group detached by the action of acid, and the group represented by -C(R 4 ) 2 COOR 5 , for example, -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(R 01 )(R 02 )(OR 39 ), etc. In the formula, R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R 36 and R 37 may be bonded to each other to form a ring. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. The above-mentioned alkyl group may be either linear or branched. As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable. The above-mentioned cycloalkyl group may have a monocyclic structure or may have a polycyclic structure such as a condensed ring. The above-mentioned aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group. As the above-mentioned aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an alkyl group having 7 to 16 carbon atoms is more preferable. The aforementioned aralkyl group refers to an aryl group substituted with an alkyl group, and preferred aspects of the alkyl group and aryl group are the same as those of the aforementioned alkyl group and aryl group. The aforementioned alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms. In addition, these groups may further have known substituents within the range in which the effects of the present invention are obtained.

R 01及R 02分別獨立地表示氫原子、烷基、環烷基、芳基、芳烷基或烯基。 R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

作為藉由酸的作用分解並生成鹼可溶性基之基團或者藉由酸的作用脫離之基團，較佳為三級烷基酯基、縮醛基、枯基酯基、烯醇酯基等。進一步較佳為三級烷基酯基、縮醛基。As a group decomposed by the action of an acid to form an alkali-soluble group or a group detached by the action of an acid, tertiary alkyl ester groups, acetal groups, cumyl ester groups, enol ester groups, etc. are preferred . Further preferred are tertiary alkyl ester groups and acetal groups.

作為具有烷氧基甲基之化合物，具體能夠舉出以下結構。關於具有醯氧基甲基之化合物，能夠舉出將下述化合物的烷氧基甲基變更為醯氧基甲基之化合物。作為在分子內具有烷氧基甲基或醯氧基甲基之化合物，能夠舉出以下化合物，但並不限定於此。Specific examples of the compound having an alkoxymethyl group include the following structures. Examples of compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compounds is changed to an acyloxymethyl group. Examples of compounds having an alkoxymethyl group or an acyloxymethyl group in the molecule include the following compounds, but are not limited thereto.

[化學式34]

Figure 02_image064
[chemical formula 34]
Figure 02_image064

[化學式35]

Figure 02_image066
[chemical formula 35]
Figure 02_image066

含有烷氧基甲基及醯氧基甲基中的至少1個之化合物可以使用市售品，亦可以使用藉由公知的方法合成者。 從耐熱性的觀點考慮，烷氧基甲基或醯氧基甲基直接在芳香環或三口井環上取代之化合物為較佳。 As a compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercial product may be used, or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a three-well ring is preferable.

作為三聚氰胺系交聯劑的具體例，可以舉出六甲氧基甲基三聚氰胺、六乙氧基甲基三聚氰胺、六丙氧基甲基三聚氰胺、六丁氧基丁基三聚氰胺等。Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, and the like.

作為脲系交聯劑的具體例，例如，可以舉出單羥基甲基化乙炔脲、二羥基甲基化乙炔脲、三羥基甲基化乙炔脲、四羥基甲基化乙炔脲、單甲氧基甲基化乙炔脲，二甲氧基甲基化乙炔脲、三甲氧基甲基化乙炔脲、四甲氧基甲基化乙炔脲、單乙氧基甲基化乙炔脲、二乙氧基甲基化乙炔脲、三乙氧基甲基化乙炔脲、四乙氧基甲基化乙炔脲、單丙氧基甲基化乙炔脲、二丙氧基甲基化乙炔脲、三丙氧基甲基化乙炔脲、四丙氧基甲基化乙炔脲、單丁氧基甲基化乙炔脲、二丁氧基甲基化乙炔脲、三丁氧基甲基化乙炔脲或四丁氧基甲基化乙炔脲等乙炔脲系交聯劑； 雙甲氧基甲基脲、雙乙氧基甲基脲、雙丙氧基甲基脲、雙丁氧基甲基脲等脲系交聯劑、 單羥基甲基化乙烯脲或二羥基甲基化乙烯脲、單甲氧基甲基化乙烯脲、二甲氧基甲基化乙烯脲、單乙氧基甲基化乙烯脲、二乙氧基甲基化乙烯脲、單丙氧基甲基化乙烯脲、二丙氧基甲基化乙烯脲、單丁氧基甲基化乙烯脲或二丁氧基甲基化乙烯脲等乙烯脲系交聯劑、 單羥基甲基化丙烯脲、二羥基甲基化丙烯脲、單甲氧基甲基化丙烯脲、二甲氧基甲基化丙烯脲、單乙氧基甲基化丙烯脲、二乙氧基甲基化丙烯脲、單丙氧基甲基化丙烯脲、二丙氧基甲基化丙烯脲、單丁氧基甲基化丙烯脲或二丁氧基甲基化丙烯脲等丙烯脲系交聯劑、 1,3-二（甲氧基甲基）4,5-二羥基-2-咪唑啶酮、1,3-二（甲氧基甲基）-4,5-二甲氧基-2-咪唑啶酮等。 Specific examples of urea-based crosslinking agents include, for example, monohydroxymethylated acetylene carbamide, dihydroxymethylated acetylene carbamide, trishydroxymethylated acetylene carbamide, tetrahydroxymethylated acetylene carbamide, monomethoxy Dimethoxymethylated acetylene carbamide, dimethoxymethylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetramethoxymethylated acetylene carbamide, monoethoxymethylated acetylene carbamide, diethoxy Methylated acetylene carbamide, triethoxymethylated acetylene carbamide, tetraethoxymethylated acetylene carbamide, monopropoxymethylated acetylene carbamide, dipropoxymethylated acetylene carbamide, triproxymethylated acetylene carbamide Methylated acetylene carbamide, tetrapropoxymethylated acetylene carbamide, monobutoxymethylated acetylene carbamide, dibutoxymethylated acetylene carbamide, tributoxymethylated acetylene carbamide or tetrabutoxy Acetylene carbamide cross-linking agents such as methylated acetylene carbamide; Bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea and other urea-based crosslinking agents, Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxy Methylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea, etc. joint agent, Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxy Propylene urea, such as methylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea, etc. joint agent, 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole pyridone etc.

作為苯并胍胺系交聯劑的具體例，例如，可以舉出單羥基甲基化苯并胍胺、二羥基甲基化苯并胍胺、三羥基甲基化苯并胍胺、四羥基甲基化苯并胍胺、單甲氧基甲基化苯并胍胺、二甲氧基甲基化苯并胍胺、三甲氧基甲基化苯并胍胺、四甲氧基甲基化苯并胍胺、單乙氧基甲基化苯并胍胺、二乙氧基甲基化苯并胍胺、三乙氧基甲基化苯并胍胺、四乙氧基甲基化苯并胍胺、單丙氧基甲基化苯并胍胺、二丙氧基甲基化苯并胍胺、三丙氧基甲基化苯并胍胺、四丙氧基甲基化苯并胍胺、單丁氧基甲基化苯并胍胺、二丁氧基甲基化苯并胍胺、三丁氧基甲基化苯并胍胺、四丁氧基甲基化苯并胍胺等。Specific examples of benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trishydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, and tetrahydroxymethylated benzoguanamine. Methylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine Benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine Guanamine, Monopropoxymethylated Benzoguanamine, Dipropoxymethylated Benzoguanamine, Tripropoxymethylated Benzoguanamine, Tetrapropoxymethylated Benzoguanamine , Monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc.

此外，作為具有選自包括羥甲基及烷氧基甲基之群組中之至少1種基團之化合物，亦可較佳地使用選自包括羥甲基及烷氧基甲基之群組中之至少1種基團直接鍵結於芳香環（較佳為苯環）之化合物。 作為該種化合物的具體例，可以舉出苯二甲醇、雙（羥基甲基）甲酚、雙（羥基甲基）二甲氧基苯、雙（羥基甲基）二苯醚、雙（羥基甲基）二苯甲酮、羥基甲基苯甲酸羥基甲基苯、雙（羥基甲基）聯苯、二甲基雙（羥基甲基）聯苯、雙（甲氧基甲基）苯、雙（甲氧基甲基）甲酚、雙（甲氧基甲基）二甲氧基苯、雙（甲氧基甲基）二苯醚、雙（甲氧基甲基）二苯甲酮、甲氧基甲基苯甲酸甲氧基甲基苯、雙（甲氧基甲基）聯苯、二甲基雙（甲氧基甲基）聯苯、4,4’,4’’-亞乙基三[2,6-雙（甲氧基甲基）苯酚]、5,5’-[2,2,2‐三氟‐1‐（三氟甲基）亞乙基]雙[2‐羥基‐1,3‐苯二甲醇]、3,3’,5,5’-四（甲氧基甲基）-1,1’-聯苯-4,4’-二醇等。 In addition, as a compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl groups, it is also preferable to use A compound in which at least one group is directly bonded to an aromatic ring (preferably a benzene ring). Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl) base) benzophenone, hydroxymethylbenzoate, hydroxymethylbenzene, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis( Methoxymethyl) cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxy Methoxymethylbenzene, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylene triphenyl [2,6-Bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1 ,3‐benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

作為其他交聯劑，可以使用市售品，作為較佳之市售品，可以舉出46DMOC、46DMOEP（以上為ASAHI YUKIZAI CORPORATION製）、DML-PC、DML-PEP、DML-OC、DML-OEP、DML-34X、DML-PTBP、DML-PCHP、DML-OCHP、DML-PFP、DML-PSBP、DML-POP、DML-MBOC、DML-MBPC、DML-MTrisPC、DML-BisOC-Z、DML-BisOCHP-Z、DML-BPC、DMLBisOC-P、DMOM-PC、DMOM-PTBP、DMOM-MBPC、TriML-P、TriML-35XL、TML-HQ、TML-BP、TML-pp-BPF、TML-BPE、TML-BPA、TML-BPAF、TML-BPAP、TMOM-BP、TMOM-BPE、TMOM-BPA、TMOM-BPAF、TMOM-BPAP、HML-TPPHBA、HML-TPHAP、HMOM-TPPHBA、HMOM-TPHAP（以上為Honshu Chemical Industry Co.,Ltd.製）、NIKALAC（註冊商標，以下相同）MX-290、NIKALAC MX-280、NIKALAC MX-270、NIKALAC MX-279、NIKALAC MW-100LM、NIKALAC MX-750LM（以上為SANWA CHEMICAL CO.,LTD製）等。As other crosslinking agents, commercially available products can be used, and preferred commercially available products include 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP- Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML- BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, the same below) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (the above are SANWA CHEMICAL CO.,LTD), etc.

又，本發明的樹脂組成物包含選自包括環氧化合物、氧環丁烷化合物及苯并㗁口井化合物之群組中之至少1種化合物作為其他交聯劑亦為較佳。Furthermore, it is also preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxetane compounds as other crosslinking agents.

-環氧化合物（具有環氧基之化合物）- 作為環氧化合物，在一分子中具有2個以上的環氧基之化合物為較佳。環氧基在200℃以下進行交聯反應且不會因交聯而引發脫水反應，因此不易引起膜收縮。因此，藉由含有環氧化合物，可有效地抑制本發明的樹脂組成物的低溫硬化及翹曲。 -Epoxy compounds (compounds with epoxy groups)- As an epoxy compound, the compound which has 2 or more epoxy groups in one molecule is preferable. The epoxy group undergoes cross-linking reaction below 200°C and does not cause dehydration reaction due to cross-linking, so it is not easy to cause film shrinkage. Therefore, low-temperature hardening and warpage of the resin composition of this invention can be suppressed effectively by containing an epoxy compound.

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，又，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 that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2-15.

作為環氧化合物的例子，可以舉出雙酚A型環氧樹脂；雙酚F型環氧樹脂；丙二醇二環氧丙醚、新戊二醇二環氧丙醚、乙二醇二環氧丙醚、丁二醇二環氧丙醚、己二醇二環氧丙醚、三羥甲基丙烷三環氧丙醚等伸烷基二醇型環氧樹脂或多元醇烴型環氧樹脂；聚丙二醇二環氧丙醚等聚伸烷基二醇型環氧樹脂；聚甲基（環氧丙氧基丙基）矽氧烷等含有環氧基之聚矽氧等，但並不限定於該等。具體而言，可以舉出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）HP-4770、EPICLON（註冊商標）EXA-830LVP、EPICLON（註冊商標）EXA-8183、EPICLON（註冊商標）EXA-8169、EPICLON（註冊商標）N-660、EPICLON（註冊商標）N-665-EXP-S、EPICLON（註冊商標）N-740（以上為商品名，DIC Corporation製）、RIKARESIN（註冊商標）BEO-20E、RIKARESIN（註冊商標）BEO-60E、RIKARESIN（註冊商標）HBE-100、RIKARESIN（註冊商標）DME-100、RIKARESIN（註冊商標）L-200（商品名，New Japan Chemical Co.,Ltd.製）、EP-4003S、EP-4000S、EP-4088S、EP-3950S（以上為商品名，ADEKA CORPORATION製）、CELLOXIDE（註冊商標）2021P、CELLOXIDE（註冊商標）2081、CELLOXIDE（註冊商標）2000、EHPE3150、EPOLEAD（註冊商標）GT401、EPOLEAD（註冊商標）PB4700、EPOLEAD（註冊商標）PB3600（以上為商品名，Daicel Corporation製）、NC-3000、NC-3000-L、NC-3000-H、NC-3000-FH-75M、NC-3100、CER-3000-L、NC-2000-L、XD-1000、NC-7000L、NC-7300L、EPPN-501H、EPPN-501HY、EPPN-502H、EOCN-1020、EOCN-102S、EOCN-103S、EOCN-104S、CER-1020、EPPN-201、BREN-S、BREN-10S（以上為商品名，Nippon Kayaku Co.,Ltd.製）等。又，亦可較佳地使用以下化合物。Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, Ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; Polyalkylene glycol-type epoxy resins such as propylene glycol diglycidyl ether; polymethyl (glycidoxypropyl) siloxane and other polysiloxanes containing epoxy groups, but not limited to this Wait. 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) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are product names, manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) Trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700 , EPOLEAD (registered trademark) PB3600 (the above are trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000- L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER- 1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. Moreover, the following compounds can also be preferably used.

[化學式36]

Figure 02_image068
[chemical formula 36]
Figure 02_image068

式中，n為1～5的整數，m為1～20的整數。In the formula, n is an integer of 1-5, and m is an integer of 1-20.

在上述結構中，從兼顧耐熱性及提高拉伸率的方面考慮，n為1～2，m為3～7為較佳。In the above structure, it is preferable that n is 1-2 and m is 3-7 from the viewpoint of achieving both heat resistance and elongation.

-氧環丁烷化合物（具有氧環丁烷基之化合物）- 作為氧環丁烷化合物，能夠舉出在一分子中具有2個以上的氧環丁烷環之化合物、3-乙基-3-羥基甲基氧環丁烷、1,4-雙{[（3-乙基-3-氧環丁烷基）甲氧基]甲基}苯、3-乙基-3-（2-乙基己基甲基）氧環丁烷、1,4-苯二羧酸-雙[（3-乙基-3-氧環丁烷基）甲基]酯等。作為具體例，能夠較佳地使用TOAGOSEI CO.,LTD.製ARON OXETANE系列（例如，OXT-121、OXT-221），該等可以單獨使用，或者亦可以混合2種以上。 -Oxetane compounds (compounds having an oxetane group)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyl oxetane, 1,4-bis{[( 3-Ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxy Acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these may be used individually, or may mix 2 or more types.

-苯并㗁口井化合物（具有苯并㗁唑基之化合物）- 苯并㗁口井化合物因開環加成反應所引起之交聯反應而在硬化時不發生脫氣，進而減少熱收縮而抑制產生翹曲，因此較佳。 -Benzazolium compounds (compounds having a benzoxazolyl group)- The benzodiazepine compound is preferable because the crosslinking reaction caused by the ring-opening addition reaction does not cause degassing during hardening, thereby reducing heat shrinkage and suppressing warpage.

作為苯并㗁口井化合物的較佳例子，可以舉出P-d型苯并㗁口井、F-a型苯并㗁口井（以上為商品名，Shikoku Chemicals Corporation製）、多羥基苯乙烯樹脂的苯并㗁口井加成物、酚醛清漆型二氫苯并㗁口井化合物。該等可以單獨使用，或者可以混合2種以上。Preferable examples of benzodiazepine compounds include P-d-type benzodiazepines, F-a-type benzodiazepines (the above are trade names, manufactured by Shikoku Chemicals Corporation), and benzos of polyhydroxystyrene resins.㗁Well adducts, novolac type dihydrobenzo 㗁Well compounds. These can be used individually or in mixture of 2 or more types.

其他交聯劑的含量相對於本發明的樹脂組成物的總固體成分係0.1～30質量%為較佳，0.1～20質量%為更佳，0.5～15質量%為進一步較佳，1.0～10質量%為特佳。其他交聯劑可以僅含有1種，亦可以含有2種以上。在含有2種以上其他交聯劑的情況下，其合計在上述範圍內為較佳。The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and 1.0 to 10% by mass relative to the total solid content of the resin composition of the present invention. Quality % is especially good. Other crosslinking agents may contain only 1 type, and may contain 2 or more types. When two or more types of other crosslinking agents are contained, the total of them is preferably within the above range.

〔聚合起始劑〕 本發明的樹脂組成物包含能夠藉由光和/或熱開始聚合之聚合起始劑為較佳。尤其，包含光聚合起始劑為較佳。 光聚合起始劑係光自由基聚合起始劑為較佳。作為光自由基聚合起始劑，並沒有特別限制，能夠適當選自公知的光自由基聚合起始劑。例如，對紫外線區域至可見區域的光線具有感光性之光自由基聚合起始劑為較佳。又，可以為與被光激發之增感劑產生一些作用並生成活性自由基之活性劑。 〔polymerization initiator〕 The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it is preferable to include a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited, and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to rays from an ultraviolet region to a visible region is preferable. Also, it may be an active agent that interacts with a sensitizer excited by light to generate active radicals.

光自由基聚合起始劑至少含有1種在波長約240～800nm（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測定。例如，藉由紫外可見分光光度計（Varian公司製Cary-5 spectrophotometer），使用乙酸乙酯溶劑，在0.01g/L的濃度下進行測定為較佳。 It is preferable that the photoradical polymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 L·mol -1 ·cm -1 in the wavelength range of about 240-800 nm (preferably 330-500 nm). The molar absorptivity of a compound can be measured by a known method. For example, it is preferable to measure at a concentration of 0.01 g/L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

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，可以舉出鹵化烴衍生物（例如具有三口井骨架之化合物、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、胺基苯乙酮等α-胺基酮化合物、羥基苯乙酮等α-羥基酮化合物、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。又，可以舉出日本特開2014-130173號公報的0065～0111段、日本專利第6301489號公報中所記載之化合物、MATERIAL STAGE 37～60p，vol.19，No.3,2019中所記載之過氧化物系光聚合起始劑、國際公開第2018/221177號中所記載之光聚合起始劑、國際公開第2018/110179號中所記載之光聚合起始劑、日本特開2019-043864號公報中所記載之光聚合起始劑、日本特開2019-044030號公報中所記載之光聚合起始劑、日本特開2019-167313號公報中所記載之過氧化物系起始劑，該等內容編入本說明書中。As a photoradical polymerization initiator, a well-known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (such as compounds having a three-well skeleton, compounds having a oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbis Oxime compounds such as imidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxyl compounds such as hydroxyacetophenone Ketone compounds, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. For details of these, the descriptions in paragraphs 0165 to 0182 of JP-A-2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and these contents are incorporated in this specification. Also, the compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in JP-A-6301489, and those described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019 can be mentioned. Peroxide-based photopolymerization initiator, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, Japanese Patent Laid-Open No. 2019-043864 The photopolymerization initiator described in the Publication No. 2019-044030, the photopolymerization initiator described in the Japanese Patent Application Publication No. 2019-044030, and the peroxide-based initiator described in the Japanese Patent Application Publication No. 2019-167313, These contents are compiled into this manual.

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

在本發明的一實施態樣中，作為光自由基聚合起始劑，能夠較佳地使用羥基苯乙酮化合物、胺基苯乙酮化合物及醯基膦化合物。更具體而言，例如，能夠使用日本特開平10-291969號公報中所記載之胺基苯乙酮系起始劑、日本專利第4225898號中所記載之醯基氧化膦系起始劑，該內容編入本說明書中。In one embodiment of the present invention, as photoradical polymerization initiators, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used. The content is incorporated into this manual.

作為α-羥基酮系起始劑，能夠使用Omnirad 184、Omnirad 1173、Omnirad 2959、Omnirad 127（以上為IGM Resins B.V.製）、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 α-hydroxyketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959 can be used , IRGACURE 127 (trade name: both manufactured by BASF Corporation).

作為α-胺基酮系起始劑，能夠使用Omnirad 907、Omnirad 369、Omnirad 369E、Omnirad 379EG（以上為IGM Resins B.V.製）、IRGACURE 907、IRGACURE 369及IRGACURE 379（商品名：均為BASF公司製）。As the α-aminoketone-based initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (the above are manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF Corporation) can be used. ).

作為胺基苯乙酮系起始劑，亦能夠使用極大吸收波長與365nm或405nm等波長光源匹配之日本特開2009-191179號公報中所記載之化合物，該內容編入本說明書中。As the aminoacetophenone-based initiator, compounds described in Japanese Patent Application Laid-Open No. 2009-191179 whose maximum absorption wavelength matches a light source with a wavelength of 365 nm or 405 nm can also be used, and the content is incorporated in this specification.

作為醯基氧化膦系起始劑，可以舉出2,4,6-三甲基苯甲醯基-二苯基-氧化膦等。又，能夠使用Omnirad 819、Omnirad TPO（以上為IGM Resins B.V.製）、IRGACURE-819、IRGACURE-TPO（商品名：均為BASF公司製）。Examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. In addition, Omnirad 819, Omnirad TPO (the above are manufactured by IGM Resins B.V.), IRGACURE-819, and IRGACURE-TPO (trade names: all are manufactured by BASF Corporation) can be used.

作為茂金屬化合物，可以例示出IRGACURE-784、IRGACURE-784EG（均為BASF公司製）、Keycure VIS 813（King Brother Chem Co.,Ltd.製）等。Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF Corporation), Keycure VIS 813 (manufactured by King Brother Chem Co., Ltd.), and the like.

作為光自由基聚合起始劑，可更佳地舉出肟化合物。藉由使用肟化合物，能夠進一步有效地提高曝光寬容度。肟化合物的曝光寬容度（曝光餘裕）較廣且亦起到作為光硬化促進劑的作用，因此特佳。More preferably, an oxime compound is mentioned as a photoradical polymerization initiator. By using an oxime compound, exposure latitude can be improved more effectively. Since the exposure latitude (exposure margin) of an oxime compound is wide and it also functions as a photocuring accelerator, it is especially preferable.

作為肟化合物的具體例，可以舉出日本特開2001-233842號公報中所記載之化合物、日本特開2000-080068號公報中所記載之化合物、日本特開2006-342166號公報中所記載之化合物、J.C.S.Perkin II（1979年，第1653-1660頁）中所記載之化合物、J.C.S.Perkin II（1979年，第156-162頁）中所記載之化合物、Journal of Photopolymer Science and Technology（1995年，第202-232頁）中所記載之化合物、日本特開2000-066385號公報中所記載之化合物、日本特表2004-534797號公報中所記載之化合物、日本特開2017-019766號公報中所記載之化合物、日本專利第6065596號公報中所記載之化合物、國際公開第2015/152153號中所記載之化合物、國際公開第2017/051680號中所記載之化合物、日本特開2017-198865號公報中所記載之化合物、國際公開第2017/164127號的0025～0038段中所記載之化合物、國際公開第2013/167515號中所記載之化合物等，該內容編入本說明書中。Specific examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, and compounds described in JP-A-2006-342166. Compounds, Compounds described in J.C.S.Perkin II (1979, pp. 1653-1660), Compounds described in J.C.S.Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2004-534797, the compound described in JP-A-2017-019766 Compounds described, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015/152153, compounds described in International Publication No. 2017/051680, Japanese Patent Application Publication No. 2017-198865 The compounds described in, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, the compounds described in International Publication No. 2013/167515, etc., are incorporated in this specification.

作為較佳之肟化合物，例如可以舉出下述結構的化合物、3-（苯甲醯氧基（亞胺基））丁-2-酮、3-（乙醯氧基（亞胺基））丁-2-酮、3-（丙醯氧基（亞胺基））丁-2-酮、2-（乙醯氧基（亞胺基））戊-3-酮、2-（乙醯氧基（亞胺基））-1-苯基丙-1-酮、2-（苯甲醯氧基（亞胺基））-1-苯基丙-1-酮、3-（（4-甲苯磺醯氧基）（亞胺基））丁-2-酮以及2-（乙氧基羰氧基（亞胺基））-1-苯基丙-1-酮等。在本發明的樹脂組成物中，使用肟化合物（肟系光自由基聚合起始劑）來作為光自由基聚合起始劑為特佳。肟系光自由基聚合起始劑在分子內具有連結基＞C=N-O-C（=O）-。Examples of preferred oxime compounds include compounds of the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetyloxy(imino))butyl -2-keto, 3-(propionyloxy(imino))butan-2-one, 2-(acetyloxy(imino))pentan-3-one, 2-(acetyloxy (imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonate Acyloxy)(imino))butan-2-one and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, etc. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based radical photopolymerization initiator) as the radical photopolymerization initiator. The oxime-based photoradical polymerization initiator has a linking group>C=N-O-C(=O)- in the molecule.

[化學式37]

Figure 02_image070
[chemical formula 37]
Figure 02_image070

在市售品中，亦可較佳地使用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，亦能夠使用TR-PBG-304、TR-PBG-305（Changzhou Tronly New Electronic Materials CO.,LTD.製）、ADEKA ARKLS NCI-730、NCI-831及ADEKA ARKLS NCI-930（ADEKA CORPORATION製）。又，能夠使用DFI-091（Daito Chemix Corporation製）、SpeedCure PDO（SARTOMER ARKEMA製）。又，亦能夠使用下述結構的肟化合物。 [化學式38]

Figure 02_image072
Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, JP 2012- Photoradical polymerization initiator 2) described in Gazette No. 014052). In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. . In addition, DFI-091 (manufactured by Daito Chemix Corporation) and SpeedCure PDO (manufactured by Sartomer Arkema) can be used. Moreover, the oxime compound of the following structures can also be used. [chemical formula 38]
Figure 02_image072

作為光自由基聚合起始劑，亦能夠使用具有茀環之肟化合物。作為具有茀環之肟化合物的具體例，可以舉出日本特開2014-137466號公報中所記載之化合物、日本專利06636081號中所記載之化合物，該內容編入本說明書中。An oxime compound having an oxene ring can also be used as a photoradical polymerization initiator. Specific examples of the oxime compound having an oxene ring include compounds described in JP-A-2014-137466 and compounds described in JP-A-06636081, the contents of which are incorporated herein.

作為光自由基聚合起始劑，亦能夠使用具有咔唑環的至少1個苯環成為萘環之骨架之肟化合物。作為該種肟化合物的具體例，可以舉出國際公開第2013/083505號中所記載之化合物，該內容編入本說明書中。As a photoradical polymerization initiator, the oxime compound which has at least one benzene ring which has a carbazole ring as a skeleton of a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505, and the content is incorporated in this specification.

亦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，可以舉出日本特開2010-262028號公報中所記載之化合物、日本特表2014-500852號公報的0345段中所記載之化合物24、36～40、日本特開2013-164471號公報的0101段中所記載之化合物（C-3）等，該內容編入本說明書中。Oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, JP Compound (C-3) and the like described in Paragraph 0101 of Publication No. 2013-164471 are incorporated into this specification.

作為光聚合起始劑，能夠使用具有硝基之肟化合物。具有硝基之肟化合物設為二聚物亦為較佳。作為具有硝基之肟化合物的具體例，可以舉出日本特開2013-114249號公報的0031～0047段、日本特開2014-137466號公報的0008～0012、0070～0079段中所記載之化合物、日本專利4223071號公報的0007～0025段中所記載之化合物，該內容編入本說明書中。又，作為具有硝基之肟化合物，亦可以舉出ADEKA ARKLS NCI-831（ADEKA CORPORATION製）。As a photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferred that the oxime compound having a nitro group be a dimer. Specific examples of oxime compounds having a nitro group include compounds described in paragraphs 0031 to 0047 of JP-A-2013-114249 and in paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466 . The compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, the content of which is incorporated in this specification. Moreover, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION) is also mentioned as an oxime compound which has a nitro group.

作為光自由基聚合起始劑，亦能夠使用具有苯并呋喃骨架之肟化合物。作為具體例，可以舉出國際公開第2015/036910號中所記載之OE-01～OE-75。An oxime compound having a benzofuran skeleton can also be used as a photoradical polymerization initiator. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

作為光自由基聚合起始劑，亦能夠使用在咔唑骨架上鍵結有具有羥基之取代基之肟化合物。作為該種光聚合起始劑，可以舉出國際公開第2019/088055號中所記載之化合物等，該內容編入本說明書中。An oxime compound in which a substituent having a hydroxyl group is bonded to the carbazole skeleton can also be used as the photoradical polymerization initiator. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019/088055, and the content is incorporated in this specification.

作為光聚合起始劑，亦能夠使用具有對芳香族環導入了拉電子基團之芳香族環基Ar OX1之肟化合物（以下，亦稱為肟化合物OX）。作為上述芳香族環基Ar OX1所具有之拉電子基團，可以舉出醯基、硝基、三氟甲基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、氰基，醯基及硝基為較佳，從容易形成耐光性優異之膜的理由考慮，醯基為更佳，苯甲醯基為進一步較佳。苯甲醯基可以具有取代基。作為取代基，鹵素原子、氰基、硝基、羥基、烷基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烯基、烷基氫硫基、芳基氫硫基、醯基或胺基為較佳，烷基、烷氧基、芳基、芳氧基、雜環氧基、烷基氫硫基、芳基氫硫基或胺基為更佳，烷氧基、烷基氫硫基或胺基為進一步較佳。 As the photopolymerization initiator, an oxime compound (hereinafter also referred to as an oxime compound OX) having an aromatic ring group Ar OX1 having an electron-withdrawing group introduced into an aromatic ring can also be used. Examples of the electron-withdrawing group included in the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, An arylsulfonyl group, a cyano group, an acyl group, and a nitro group are preferable, an acyl group is more preferable, and a benzoyl group is still more preferable from the viewpoint of being easy to form a film excellent in light resistance. The benzoyl group may have a substituent. As a substituent, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic epoxy group, an alkenyl group, an alkylthiol group, an arylhydrogen group Thio group, acyl group or amino group are preferred, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic epoxy group, alkyl sulfide group, aryl sulfide group or amine group are more preferred, alkyl group An oxy group, an alkylsulfhydryl group or an amine group is further preferred.

肟化合物OX為選自式（OX1）所表示之化合物及式（OX2）所表示之化合物中之至少1種為較佳，式（OX2）所表示之化合物為更佳。 [化學式39]

Figure 02_image074
式中，R X1表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基氫硫基、芳基氫硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯基、醯氧基、胺基、膦醯基、胺甲醯基或胺磺醯基， R X2表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基氫硫基、芳基氫硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯氧基或胺基， R X3～R X14分別獨立地表示氫原子或取代基； 其中，R X10～R X14中的至少1個為拉電子基團。 The oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and the compound represented by the formula (OX2) is more preferable. [chemical formula 39]
Figure 02_image074
In the formula, R X1 represents an alkyl group, an alkenyl group, an alkoxyl group, an aryl group, an aryloxy group group, a heterocyclic group, a heterocyclic epoxy group group, an alkyl mercapto group, an aryl mercapto group, an alkyl sulfinyl group , arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphonyl, carbamoyl or sulfamoyl, R X2 represents alkyl, Alkenyl, alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylsulfenyl, arylsulfenyl, alkylsulfinyl, arylsulfinyl, alkyl Sulfonyl group, arylsulfonyl group, acyloxy group or amino group, R X3 ~ R X14 independently represent a hydrogen atom or a substituent; wherein, at least one of R X10 ~ R X14 is an electron-withdrawing group .

上述式中，R X12為拉電子基團，R X10、R X11、R X13、R X14為氫原子為較佳。 In the above formula, R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 , and R X14 are preferably hydrogen atoms.

作為肟化合物OX的具體例，可以舉出日本專利第4600600號公報的0083～0105段中所記載之化合物，該內容編入本說明書中。Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, and the contents thereof are incorporated in the present specification.

作為最佳之肟化合物，可以舉出日本特開2007-269779號公報中示出之具有特定取代基之肟化合物、日本特開2009-191061號公報中示出之具有硫芳基之肟化合物等，該內容編入本說明書中。Preferred oxime compounds include oxime compounds having a specific substituent disclosed in JP-A-2007-269779, oxime compounds having a thioaryl group disclosed in JP-A-2009-191061, etc. , which is included in this manual.

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口井化合物、苄基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚物、鎓鹽化合物、苯并噻唑化合物、二苯甲酮化合物、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 photoradical polymerization initiator is selected from the group consisting of trihalomethyl three well compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl Compounds in the group of -benzene-iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

更佳之光自由基聚合起始劑為三鹵甲基三口井化合物、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口井化合物、α-胺基酮化合物、茂金屬化合物、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種化合物為更進一步較佳，使用茂金屬化合物或肟化合物為再進一步較佳。More preferable photoradical polymerization initiators are trihalomethyl three well compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salts Compounds, benzophenone compounds, acetophenone compounds, selected from the group consisting of trihalomethyl three well compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, benzophenone compounds It is still more preferable to use at least one kind of compound in the group, and it is still more preferable to use a metallocene compound or an oxime compound.

又，光自由基聚合起始劑亦能夠使用二苯甲酮、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，亦能夠使用下述式（I）所表示之化合物。In addition, as the photoradical polymerization initiator, N, such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), can also be used. ,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-perolylphenyl)-butanone-1 ,2-methyl-1-[4-(methylthio)phenyl]-2-pornolinyl-acetone-1 and other aromatic ketones, alkylanthraquinones, etc., are quinones formed by condensation with aromatic rings Benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. Moreover, the compound represented by following formula (I) can also be used.

[化學式40]

Figure 02_image076
[chemical formula 40]
Figure 02_image076

在式（I）中，R I00為碳數1～20的烷基、被1個以上的氧原子中斷之碳數2～20的烷基、碳數1～12的烷氧基、苯基、或者碳數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、由被1個以上的氧原子中斷之碳數2～18的烷基及碳數1～4的烷基中的至少1個取代之苯基或聯苯基，R I01為式（II）所表示之基團或者與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的烷氧基或鹵素原子。 In formula (I), R I00 is an alkyl group with 1 to 20 carbons, an alkyl group with 2 to 20 carbons interrupted by one or more oxygen atoms, an alkoxy group with 1 to 12 carbons, a phenyl group, Or alkyl with 1 to 20 carbons, alkoxy with 1 to 12 carbons, halogen atom, cyclopentyl, cyclohexyl, alkenyl with 2 to 12 carbons, carbon interrupted by one or more oxygen atoms A phenyl or biphenyl group substituted by at least one of an alkyl group with 2 to 18 carbon atoms and an alkyl group with 1 to 4 carbon atoms, R I01 is a group represented by formula (II) or the same group as R 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 a halogen atom.

[化學式41]

Figure 02_image078
[chemical formula 41]
Figure 02_image078

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亦能夠使用國際公開第2015/125469號的0048～0055段中所記載之化合物，該內容編入本說明書中。In addition, as the photoradical polymerization initiator, compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used, and the content is incorporated in this specification.

作為光自由基聚合起始劑，可以使用2官能或3官能以上的光自由基起始劑。藉由使用該種光自由基聚合起始劑，從光自由基聚合起始劑的1個分子產生2個以上的自由基，因此可以獲得良好的靈敏度。又，在使用了非對稱結構的化合物的情況下，結晶性下降而在溶劑等中的溶解性變高，隨時間的經過變得不易析出，藉此能夠提高樹脂組成物的經時穩定性。作為2官能或3官能以上的光自由基聚合起始劑的具體例，可以舉出日本特表2010-527339號公報、日本特表2011-524436號公報、國際公開第2015/004565號、日本特表2016-532675號公報的0407～0412段、國際公開第2017/033680號的0039～0055段中所記載之肟化合物的二聚物、日本特表2013-522445號公報中所記載之化合物（E）及化合物（G）、國際公開第2016/034963號中所記載之Cmpd1～7、日本特表2017-523465號公報的0007段中所記載之肟酯類光起始劑、日本特開2017-167399號公報的0020～0033段中所記載之光起始劑、日本特開2017-151342號公報的0017～0026段中所記載之光聚合起始劑（A）、日本專利第6469669號公報中所記載之肟酯光起始劑等，該內容編入本說明書中。As the radical photopolymerization initiator, a difunctional or trifunctional or more photoradical initiator can be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is increased, and precipitation becomes less likely to occur over time, thereby improving the temporal stability of the resin composition. Specific examples of photoradical polymerization initiators with bifunctional or trifunctional or higher functions include JP 2010-527339 A, JP 2011-524436 A, International Publication No. 2015/004565, JP Dimers of oxime compounds described in paragraphs 0407 to 0412 of Table No. 2016-532675, paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds described in Japanese Patent Publication No. 2013-522445 (E ) and compound (G), Cmpd 1-7 described in International Publication No. 2016/034963, the oxime ester photoinitiator described in paragraph 0007 of JP 2017-523465, JP 2017- Photoinitiators described in paragraphs 0020 to 0033 of Japanese Patent Application Publication No. 167399, photopolymerization initiators (A) described in paragraphs 0017 to 0026 of Japanese Patent Application Laid-Open No. 2017-151342, and Japanese Patent Publication No. 6469669 The content of oxime ester photoinitiators and the like described is included in this specification.

在包含光聚合起始劑的情況下，其含量相對於本發明的樹脂組成物的總固體成分係0.1～30質量%為較佳，更佳為0.1～20質量%，進一步較佳為0.5～15質量%，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。在含有2種以上光聚合起始劑的情況下，合計量在上述範圍內為較佳。 此外，有時光聚合起始劑亦會作為熱聚合起始劑而發揮作用，因此有時藉由烘箱、加熱板等的加熱會進一步促進基於光聚合起始劑之交聯。 When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 30% by mass relative to the total solid content of the resin composition of the present invention. 15% by mass, more preferably 1.0 to 10% by mass. A photoinitiator may contain only 1 type, and may contain 2 or more types. When containing 2 or more types of photoinitiators, it is preferable that a total amount exists in the said range. In addition, since a photopolymerization initiator may also function as a thermal polymerization initiator, heating by an oven, a hot plate, etc. may further promote the crosslinking by a photopolymerization initiator.

〔增感劑〕 樹脂組成物可以包含增感劑。增感劑吸收特定的活性放射線而成為電子激發狀態。成為電子激發狀態之增感劑與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，熱自由基聚合起始劑、光自由基聚合起始劑引起化學變化而分解，並生成自由基、酸或鹼。 作為可以使用的增感劑，能夠使用二苯甲酮系、米其勒酮系、香豆素系、吡唑偶氮系、苯胺偶氮系、三苯甲烷系、蒽醌系、蒽系、蒽吡啶酮系、苯亞甲基系、氧雜菁系、吡唑并三唑偶氮系、吡啶酮偶氮系、花青系、啡噻口井系、吡咯并吡唑偶氮次甲基系、口山口星系、酞菁系、苯并哌喃系、靛藍系等化合物。 作為增感劑，例如，可以舉出米其勒酮、4,4’-雙（二乙胺基）二苯甲酮、2,5-雙（4’-二乙胺基亞苄基）環戊烷、2,6-雙（4’-二乙胺基亞苄基）環己酮、2,6-雙（4’-二乙胺基亞苄基）-4-甲基環己酮、4,4’-雙（二甲胺基）查耳酮、4,4’-雙（二乙胺基）查耳酮、對二甲胺基苯亞烯丙基二氫茚酮、對二甲胺基苯亞甲基二氫茚酮、2-（對二甲胺基苯基聯苯）-苯并噻唑、2-（對二甲胺基苯基伸乙烯基）苯并噻唑、2-（對二甲胺基苯基伸乙烯基）異萘基噻唑、1,3-雙（4’-二甲胺基亞苄基）丙酮、1,3-雙（4’-二乙胺基亞苄基）丙酮、3,3’-羰基-雙（7-二乙胺基香豆素）、3-乙醯基-7-二甲胺基香豆素、3-乙氧基羰基-7-二甲胺基香豆素、3-苄氧基羰基-7-二甲胺基香豆素、3-甲氧基羰基-7-二乙胺基香豆素、3-乙氧基羰基-7-二乙胺基香豆素（7-（二乙胺基）香豆素-3-羧酸乙酯）、N-苯基-N’-乙基乙醇胺、N-苯基二乙醇胺、N-對甲苯二乙醇胺、N-苯基乙醇胺、4-口末啉基二苯甲酮、二甲胺基苯甲酸異戊酯、二乙胺基苯甲酸異戊酯、2-巰基苯并咪唑、1-苯基-5-巰基四唑、2-巰基苯并噻唑、2-（對二甲胺基苯乙烯）苯并㗁唑、2-（對二甲胺基苯乙烯）苯并噻唑、2-（對二甲胺基苯乙烯）萘（1,2-d）噻唑、2-（對二甲胺基苯甲醯基）苯乙烯、二苯乙醯胺、苯甲醯苯胺、N-甲基乙醯苯胺、3’,4’-二甲基乙醯苯胺等。 又，亦可以使用增感色素。 關於增感色素的詳細內容，能夠參考日本特開2016-027357號公報的0161～0163段的記載，該內容編入本說明書中。 〔Sensitizer〕 The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and enters an electronically excited state. The sensitizer in an electronically excited state contacts with thermal radical polymerization initiators, photoradical polymerization initiators, etc. to produce electron transfer, energy transfer, and heat generation. Thereby, the thermal radical polymerization initiator and the photoradical polymerization initiator cause a chemical change and decompose to generate radicals, acids, or bases. As sensitizers that can be used, benzophenone series, Michelerone series, coumarin series, pyrazole azo series, aniline azo series, triphenylmethane series, anthraquinone series, anthracene series, Anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenanthylene series, pyrrolopyrazole azomethine series Compounds such as the Kou Yamaguchi system, the phthalocyanine system, the benzopyran system, and the indigo system. Examples of sensitizers include Michelerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene) ring Pentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidene indanone, p-dimethyl Aminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylidene)benzothiazole, 2-(p- Dimethylaminophenylvinylene)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene) Acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylamine Diethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethyl Aminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluene Ethanolamine, N-Phenylethanolamine, 4-Pornolinyl Benzophenone, Isoamyl Dimethylaminobenzoate, Isoamyl Diethylaminobenzoate, 2-Mercaptobenzimidazole, 1-Phenyl -5-Mercaptotetrazole, 2-Mercaptobenzothiazole, 2-(p-Dimethylaminostyrene)benzoxazole, 2-(p-Dimethylaminostyrene)benzothiazole, 2-(p-Dimethylaminostyrene) Methylaminostyrene)naphthalene(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzylaniline, N-methylacetanilide , 3',4'-Dimethylacetaniline, etc. In addition, a sensitizing dye can also be used. For details of the sensitizing dye, reference can be made to the description in paragraphs 0161 to 0163 of JP-A-2016-027357, and the content is incorporated in this specification.

在樹脂組成物包含增感劑的情況下，增感劑的含量相對於樹脂組成物的總固體成分係0.01～20質量%為較佳，0.1～15質量%為更佳，0.5～10質量%為進一步較佳。增感劑可以單獨使用1種，亦可以並用2種以上。When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and 0.5 to 10% by mass relative to the total solid content of the resin composition. for further improvement. A sensitizer may be used individually by 1 type, and may use 2 or more types together.

〔鏈轉移劑〕 本發明的樹脂組成物可以含有鏈轉移劑。鏈轉移劑例如在高分子詞典第三版（高分子學會（The Society of Polymer Science，Japan）編，2005年）683-684頁中有定義。作為鏈轉移劑，例如，可以使用在分子內具有-S-S-、-SO 2-S-、-N-O-、SH、PH、SiH及GeH之化合物群、用於RAFT（Reversible Addition Fragmentation chain Transfer：可逆加成碎斷鏈轉移）聚合之具有硫代羰基硫基之二硫苯甲酸酯、三硫碳酸酯、二硫胺甲酸酯、黃原酸酯化合物等。該等向低活性自由基供給氫而生成自由基，或者可藉由在氧化之後去質子而生成自由基。尤其，能夠較佳地使用硫醇化合物。 [Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in Polymer Dictionary 3rd Edition (edited by The Society of Polymer Science, Japan, 2005) pp. 683-684. As the chain transfer agent, for example, compounds having -SS-, -SO 2 -S-, -NO-, SH, PH, SiH, and GeH in the molecule, used in RAFT (Reversible Addition Fragmentation chain Transfer: reversible Addition fragmentation chain transfer) Polymerized dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds with thiocarbonylthio group. These donate hydrogen to less reactive radicals to generate free radicals, or may generate free radicals by deprotonation after oxidation. 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段中所記載之化合物，該內容編入本說明書中。In addition, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used, and the content is incorporated in this specification.

在本發明的樹脂組成物具有鏈轉移劑的情況下，鏈轉移劑的含量相對於本發明的樹脂組成物的總固體成分100質量份係0.01～20質量份為較佳，0.1～10質量份為更佳，0.5～5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。在鏈轉移劑為2種以上的情況下，其合計在上述範圍內為較佳。When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition of the present invention. More preferably, 0.5-5 mass parts is still more preferable. The chain transfer agent may be only 1 type, or may be 2 or more types. When there are two or more kinds of chain transfer agents, it is preferable that the total thereof is within the above-mentioned range.

＜鹼產生劑＞ 本發明的樹脂組成物可以包含鹼產生劑。在此，鹼產生劑係指能夠藉由物理作用或化學作用產生鹼之化合物。作為對本發明的樹脂組成物較佳之鹼產生劑，可以舉出熱鹼產生劑及光鹼產生劑。 其中，對應於上述特定鹼產生劑之鹼產生劑並不與在此處所說明的鹼產生劑對應。 尤其，在樹脂組成物包含環化樹脂的前驅物的情況下，樹脂組成物包含鹼產生劑為較佳。藉由樹脂組成物含有熱鹼產生劑，例如能夠藉由加熱促進前驅物的環化反應，硬化物的機械特性或耐藥品性變良好，例如作為半導體封裝中所包含之再配線層用層間絕緣膜的性能變良好。 作為鹼產生劑，可以為離子型鹼產生劑，亦可以為非離子型鹼產生劑。作為從鹼產生劑產生之鹼，例如，可以舉出二級胺、三級胺。 本發明之鹼產生劑並沒有特別限制，能夠使用公知的鹼產生劑。作為公知的鹼產生劑，例如，能夠使用胺甲醯基肟化合物、胺甲醯基羥基胺化合物、胺甲酸化合物、甲醯胺化合物、乙醯胺化合物、胺基甲酸酯化合物、苄基胺基甲酸酯化合物、硝基苄基胺基甲酸酯化合物、磺醯胺化合物、咪唑衍生物化合物、胺醯亞胺化合物、吡啶衍生物化合物、α-胺基苯乙酮衍生物化合物、四級銨鹽衍生物化合物、吡啶鎓鹽、α-內酯環衍生物化合物、胺基醯亞胺化合物、鄰苯二甲醯亞胺衍生物化合物、醯氧基亞胺化合物等。 作為非離子型鹼產生劑的具體化合物，可以舉出式（B1）、式（B2）、或式（B3）所表示之化合物。 [化學式42]

Figure 02_image080
<Base Generator> The resin composition of the present invention may contain a base generator. Here, the base generator refers to a compound capable of generating a base by physical action or chemical action. A thermal base generator and a photobase generator are mentioned as a base generator suitable for the resin composition of this invention. However, the base generator corresponding to the said specific base generator does not correspond to the base generator demonstrated here. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. When the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be accelerated by heating, and the mechanical properties and chemical resistance of the cured product will be improved. For example, it can be used as interlayer insulation for rewiring layers included in semiconductor packages. The performance of the membrane becomes better. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator of the present invention is not particularly limited, and known base generators can be used. As known base generators, for example, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamate compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylamines, etc., can be used. carbamate compound, nitrobenzyl carbamate compound, sulfonamide compound, imidazole derivative compound, amidoimide compound, pyridine derivative compound, α-aminoacetophenone derivative compound, tetra Grade ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amidoimide compounds, phthalimide derivative compounds, acyloxyimine compounds, and the like. As a specific compound of a nonionic base generating agent, the compound represented by formula (B1), formula (B2), or formula (B3) is mentioned. [chemical formula 42]
Figure 02_image080

在式（B1）及式（B2）中，Rb 1、Rb 2及Rb 3分別獨立地為不具有三級胺結構之有機基團、鹵素原子或氫原子。其中，Rb 1及Rb 2不會同時成為氫原子。又，Rb 1、Rb 2及Rb 3均不具有羧基。此外，在本說明書中，三級胺結構係指3價氮原子的3個鍵結鍵均與烴系碳原子進行共價鍵結之結構。因此，在所鍵結之碳原子為形成羰基之碳原子的情況下，亦即在與氮原子一同形成醯胺基的情況下，不限於此。 In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 are each independently an organic group not having a tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. Moreover, none of Rb 1 , Rb 2 and Rb 3 has a carboxyl group. In addition, in this specification, a tertiary amine structure means the structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-type carbon atom. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with a nitrogen atom, it is not limited thereto.

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

更具體而言，Rb 1及Rb 2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。Rb 1與Rb 2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，Rb 1及Rb 2係可具有取代基之直鏈、支鏈或環狀烷基（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 (preferably 1 to 24 carbons, more preferably 2 to 18, more preferably 3 to 12), alkenyl (2 to 24 carbons is preferred, 2-18 is more preferred, 3-12 is further preferred), aryl (6-22 carbons is preferred, 6-18 is more preferred, 6-10 is further preferred) or arane A group (preferably 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms) is preferred. These groups may have substituents within the range in which the effects of the present invention are exhibited. Rb 1 and Rb 2 may be bonded to each other to form a ring. As the formed ring, a nitrogen-containing heterocyclic ring with 4 to 7 members is preferable. In particular, Rb 1 and Rb 2 are linear, branched or cyclic alkyl groups that may have substituents (preferably 1 to 24 carbons, more preferably 2 to 18, and further preferably 3 to 12) Preferably, a cycloalkyl group that may have a substituent (preferably 3 to 24 carbons, more preferably 3 to 18, and even more preferably 3 to 12) is more preferred, and a cyclohexyl group that may have a substituent is even more preferred .

作為Rb 3，可以舉出烷基（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。Rb 3可以在發揮本發明的效果之範圍內進一步具有取代基。 Examples of Rb 3 include alkyl (preferably 1-24 carbons, more preferably 2-18, still more preferably 3-12), aryl (preferably 6-22 carbons, 6-18 is more preferred, 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 7-23 is preferred, 7-19 is more preferred, 7-12 is further preferred), aralkenyl (8-24 carbons is preferred, 8-20 is more preferred, 8-16 is further preferred), alkane Oxygen (preferably 1-24 carbons, more preferably 2-18, further preferably 3-12), aryloxy (preferably 6-22 carbons, more preferably 6-18, 6-18 12 is further preferred) or aralkoxy group (with 7 to 23 carbons is preferred, 7 to 19 is more preferred, 7 to 12 is further preferred). Among them, cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and still more preferably having 3 to 12 carbon atoms), aralkenyl groups and aralkoxy groups are preferred. Rb 3 may further have a substituent within the range in which the effects of the present invention are exerted.

式（B1）所表示之化合物為下述式（B1-1）或下述式（B1-2）所表示之化合物為較佳。 [化學式43]

Figure 02_image082
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 43]
Figure 02_image082

式中，Rb 11及Rb 12和Rb 31及Rb 32分別與式（B1）中的Rb 1及Rb 2相同。 Rb 13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），可以在發揮本發明的效果之範圍內具有取代基。其中，Rb 13為芳烷基為較佳。 In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively. Rb 13 is alkyl (preferably 1-24 carbons, more preferably 2-18, further preferably 3-12), alkenyl (preferably 2-24 carbons, more preferably 2-18, 3-12 is more preferred), aryl group (6-22 carbon number is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl group (7-23 carbon number is preferred, 7-19 are more preferable, 7-12 are still more preferable), and may have a substituent within the range which exhibits the effect of this invention. Among them, Rb 13 is preferably an aralkyl group.

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

Rb 35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 alkyl (preferably 1-24 carbons, more preferably 1-12, further preferably 3-8), alkenyl (preferably 2-12 carbons, more preferably 2-10, 3-8 is more preferred), aryl group (6-22 carbon number is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl group (7-23 carbon number is preferred, 7-19 is more preferable, 7-12 is still more preferable), and aryl group is more preferable.

式（B1-1）所表示之化合物為式（B1-1a）所表示之化合物亦為較佳。 [化學式44]

Figure 02_image084
It is also preferable that the compound represented by formula (B1-1) is a compound represented by formula (B1-1a). [chemical formula 44]
Figure 02_image084

Rb 11及Rb 12與式（B1-1）中Rb 11及Rb 12的含義相同。 Rb 15及Rb 16為氫原子、烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、烯基（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳），氫原子或甲基為較佳。 Rb 17為烷基（碳數1～24為較佳，1～12為更佳，3～8為進一步較佳）、烯基（碳數2～12為較佳，2～10為更佳，3～8為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～12為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～12為進一步較佳），其中芳基為較佳。 Rb 11 and Rb 12 have the same meanings as Rb 11 and Rb 12 in formula (B1-1). Rb 15 and Rb 16 are hydrogen atom, alkyl (preferably 1-12 carbons, more preferably 1-6, further preferably 1-3), alkenyl (preferably 2-12 carbons, 2 ～6 is more preferred, 2～3 is further preferred), aryl group (carbon number 6～22 is preferred, 6～18 is more preferred, 6～10 is further preferred), aralkyl group (carbon number 7 ～23 is preferred, 7～19 is more preferred, 7～11 is further preferred), hydrogen atom or methyl group are preferred. Rb 17 is alkyl (preferably 1-24 carbons, more preferably 1-12, further preferably 3-8), alkenyl (preferably 2-12 carbons, more preferably 2-10, 3-8 is more preferred), aryl group (6-22 carbon number is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl group (7-23 carbon number is preferred, 7-19 is more preferred, and 7-12 is further preferred), among which aryl is preferred.

[化學式45]

Figure 02_image086
[chemical formula 45]
Figure 02_image086

在式（B3）中，L為在連結相鄰之氧原子與碳原子之連結鏈的路徑上具有飽和烴基之2價烴基，表示連結鏈的路徑上的原子數為3以上的烴基。又，R N1及R N2分別獨立地表示1價有機基團。 In the formula (B3), L is a divalent hydrocarbon group having a saturated hydrocarbon group on the path connecting adjacent oxygen atoms and carbon atoms, and represents a hydrocarbon group having 3 or more atoms on the path of the connecting chain. Also, R N1 and R N2 each independently represent a monovalent organic group.

在本說明書中，“連結鏈”係指在連接連結對象的2個原子或原子群之間的路徑上的原子鏈中，以最短（最小原子數）的距離連接該等連結對象者。例如，在下述式所表示之化合物中，L由伸苯乙烯構成，作為飽和烴基具有乙烯基，連結鏈由4個碳原子構成，連結鏈的路徑上的原子數（亦即，構成連結鏈之原子的數量，以下，亦稱為“連結鏈長度”或“連結鏈的長度”。）為4。 [化學式46]

Figure 02_image088
In this specification, "connecting chain" refers to the chain of atoms on the path between two atoms or atomic groups connecting the connecting objects, which connects the connecting objects at the shortest (minimum number of atoms) distance. For example, in the compound represented by the following formula, L is composed of styrene, has a vinyl group as a saturated hydrocarbon group, the connecting chain is composed of 4 carbon atoms, and the number of atoms on the path of the connecting chain (that is, the number of atoms constituting the connecting chain The number, hereinafter, also referred to as "the length of the link chain" or "the length of the link chain".) is 4. [chemical formula 46]
Figure 02_image088

式（B3）的L中的碳數（亦包括除了連結鏈中的碳原子以外的碳原子）係3～24為較佳。上限係12以下為更佳，10以下為進一步較佳，8以下為特佳。下限為4以上為更佳。從使上述分子內環化反應快速進行的觀點考慮，L的連結鏈長度的上限係12以下為較佳，8以下為更佳，6以下為進一步較佳，5以下為特佳。尤其，L的連結鏈長度為4或5為較佳，4為最佳。作為鹼產生劑的較佳化合物的具體例，例如，亦可以舉出國際公開第2020/066416號的0102～0168段中所記載之化合物、國際公開第2018/038002號的0143～0177段中所記載之化合物。The number of carbons in L in the formula (B3) (including carbon atoms other than the carbon atoms in the linking chain) is preferably 3-24. The upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. The upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 5 or less, from the viewpoint of rapidly advancing the intramolecular cyclization reaction. In particular, the linking chain length of L is preferably 4 or 5, and 4 is the most optimal. Specific examples of preferred compounds as base generators include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/066416, and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018/038002. listed compounds.

又，鹼產生劑包含下述式（N1）所表示之化合物亦為較佳。 [化學式47]

Figure 02_image090
Moreover, it is also preferable that a base generating agent contains the compound represented by following formula (N1). [chemical formula 47]
Figure 02_image090

在式（N1）中，R N1及R N2分別獨立地表示1價有機基團，R C1表示氫原子或保護基，L表示2價連結基。 In formula (N1), R N1 and R N2 each independently represent a monovalent organic group, R C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L為2價連結基，2價有機基團為較佳。連結基的連結鏈長度為1個以上為較佳，2以上為更佳。作為上限，12以下為較佳，8以下為更佳，5以下為進一步較佳。連結鏈長度係指在式中的2個羰基之間成為最短路徑之原子排列中存在之原子數。L is a divalent linking group, preferably a divalent organic group. The length of the linking chain of the linking group is preferably 1 or more, more preferably 2 or more. As an upper limit, 12 or less is preferable, 8 or less is more preferable, and 5 or less is still more preferable. The linking chain length refers to the number of atoms present in the arrangement of atoms that forms the shortest path between two carbonyl groups in the formula.

在式（N1）中，R N1及R N2分別獨立地表示1價有機基團（碳數1～24為較佳，2～18為更佳，3～12為進一步較佳），烴基（碳數1～24為較佳，1～12為更佳，1～10為進一步較佳）為較佳，具體而言，能夠舉出脂肪族烴基（碳數1～24為較佳，1～12為更佳，1～10為進一步較佳）或芳香族烴基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳），脂肪族烴基為較佳。作為R N1及R N2，若使用脂肪族烴基，則所產生之鹼的鹼性高而較佳。此外，脂肪族烴基及芳香族烴基可以具有取代基，又，脂肪族烴基及芳香族烴基亦可以在脂肪族烴鏈中或芳香環中、取代基中具有氧原子。尤其，可以例示出脂肪族烴基在烴鏈中具有氧原子之態樣。 In formula (N1), R N1 and R N2 independently represent a monovalent organic group (preferably 1-24 carbons, more preferably 2-18, more preferably 3-12), hydrocarbon group (carbon 1 to 24 is preferred, 1 to 12 is more preferred, and 1 to 10 is further preferred), and specifically, aliphatic hydrocarbon groups can be mentioned (preferably 1 to 24 carbons, 1 to 12 more preferably, 1 to 10 are further preferred) or aromatic hydrocarbon groups (6 to 22 carbons are preferred, 6 to 18 are more preferred, 6 to 10 are further preferred), and aliphatic hydrocarbon groups are preferred. When an aliphatic hydrocarbon group is used as R N1 and R N2 , the resulting base has a high basicity, which is preferable. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain, in the aromatic ring, or in the substituent. In particular, an aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain can be exemplified.

作為構成R N1及R N2之脂肪族烴基，可以舉出直鏈或支鏈的鏈狀烷基、環狀烷基、有關鏈狀烷基與環狀烷基的組合之基團、鏈中具有氧原子之烷基。直鏈或支鏈的鏈狀烷基的碳數係1～24為較佳，2～18為更佳，3～12為進一步較佳。例如，直鏈或支鏈的鏈狀烷基可以舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基、異丙基、異丁基、二級丁基、三級丁基、異戊基、新戊基、三級戊基、異己基等。 環狀烷基的碳數係3～12為較佳，3～6為更佳。環狀烷基例如可以舉出環丙基、環丁基、環戊基、環己基、環辛基等。 有關鏈狀烷基與環狀烷基的組合之基團的碳數係4～24為較佳，4～18為更佳，4～12為進一步較佳。有關鏈狀烷基與環狀烷基的組合之基團，例如可以舉出環己基甲基、環己基乙基、環己基丙基、甲基環己基甲基、乙基環己基乙基等。 鏈中具有氧原子之烷基的碳數係2～12為較佳，2～6為更佳，2～4為進一步較佳。鏈中具有氧原子之烷基可以為鏈狀或環狀，亦可以為直鏈或支鏈。 其中，從提高後述分解生成鹼的沸點的觀點考慮，R N1及R N2係碳數5～12的烷基為較佳。其中，在重視與金屬（例如銅）層積層時的密接性的配方中，具有環狀烷基之基團、碳數1～8的烷基為較佳。 Examples of the aliphatic hydrocarbon groups constituting R N1 and R N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain alkyl groups and cyclic alkyl groups, groups having Alkyl group of oxygen atom. The carbon number of the linear or branched chain alkyl group is preferably 1-24, more preferably 2-18, and still more preferably 3-12. Examples of linear or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Base, isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, isohexyl, etc. The carbon number of the cyclic alkyl group is preferably 3-12, more preferably 3-6. As a cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned, for example. The carbon number of the combined chain alkyl group and cyclic alkyl group is preferably 4-24, more preferably 4-18, and still more preferably 4-12. As for the combination of a chain alkyl group and a cyclic alkyl group, for example, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, methylcyclohexylmethyl group, ethylcyclohexylethyl group, etc. are mentioned. The carbon number of the alkyl group having an oxygen atom in the chain is preferably 2-12, more preferably 2-6, and still more preferably 2-4. The alkyl group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched. Among them, R N1 and R N2 are preferably alkyl groups having 5 to 12 carbon atoms from the viewpoint of increasing the boiling point of the base decomposed to be produced later. Among them, a group having a cyclic alkyl group and an alkyl group having 1 to 8 carbon atoms are preferable in formulations where adhesion to a metal (such as copper) is emphasized.

R N1及R N2可以彼此連結而形成環狀結構。形成環狀結構時，可以在鏈中具有氧原子等。又，R N1及R N2所形成之環狀結構可以為單環，亦可以為縮合環，單環為較佳。作為所形成之環狀結構，含有式（N1）中的氮原子之5員環或6員環為較佳，例如可以舉出吡咯環、咪唑環、吡唑環、吡咯啉環、吡咯啶環、咪唑啶環、吡唑啶環、哌啶環、哌口井環、口末啉環等，可較佳地舉出吡咯啉環、吡咯啶環、哌啶環、哌口井環、口末啉環。 R N1 and R N2 may be connected to each other to form a ring structure. When forming a ring structure, an oxygen atom etc. may be contained in a chain. Also, the ring structure formed by R N1 and R N2 may be a single ring or a condensed ring, and a single ring is preferred. As the formed ring structure, a 5-membered ring or a 6-membered ring containing a nitrogen atom in formula (N1) is preferable, for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, and a pyrrolidine ring , imidazolidine ring, pyrazolidine ring, piperidine ring, piperidine ring, portoline ring, etc., preferably pyrroline ring, pyrrolidine ring, piperidine ring, piperridine ring, portoline ring, etc. phylloline ring.

R C1表示氫原子或保護基，氫原子為較佳。 R C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

作為保護基，藉由酸或鹼的作用而分解之保護基為較佳，可較佳地舉出藉由酸而分解之保護基。As the protecting group, a protecting group decomposed by the action of an acid or a base is preferable, and a protecting group decomposed by an acid is preferable.

作為保護基的具體例，可以舉出鏈狀或環狀烷基或鏈中具有氧原子之鏈狀或環狀烷基。作為鏈狀或環狀烷基，可以舉出甲基、乙基、異丙基、三級丁基、環己基等。作為鏈中具有氧原子之鏈狀烷基，具體而言，可以舉出烷氧基烷基，更具體而言，可以舉出甲氧基甲基（MOM）、乙氧基乙基（EE）等。作為鏈中具有氧原子之環狀烷基，可以舉出環氧基、環氧丙基、氧雜環丁基、四氫呋喃基、四氫哌喃（THP）基等。Specific examples of the protecting group include chain or cyclic alkyl groups or chain or cyclic alkyl groups having an oxygen atom in the chain. Examples of chain or cyclic alkyl groups include methyl, ethyl, isopropyl, tertiary butyl, cyclohexyl and the like. The chain alkyl group having an oxygen atom in the chain specifically includes an alkoxyalkyl group, more specifically a methoxymethyl group (MOM), an ethoxyethyl group (EE) Wait. Examples of the cyclic alkyl group having an oxygen atom in the chain include epoxy group, glycidyl group, oxetanyl group, tetrahydrofuryl group, tetrahydropyranyl (THP) group and the like.

作為構成L之2價連結基，並沒有特別限定，烴基為較佳，脂肪族烴基為更佳。烴基可以具有取代基，又，亦可以在烴鏈中具有碳原子以外的種類的原子。更具體而言，可以在鏈中具有氧原子之2價烴連結基為較佳，可以在鏈中具有氧原子之2價脂肪族烴基、2價芳香族烴基、或有關可以在鏈中具有氧原子之2價脂肪族烴基與2價芳香族烴基的組合之基團為更佳，可以在鏈中具有氧原子之2價脂肪族烴基為進一步較佳。該等基團不具有氧原子為較佳。 2價烴連結基的碳數為1～24為較佳，2～12為更佳，2～6為進一步較佳。2價脂肪族烴基的碳數為1～12為較佳，2～6為更佳，2～4為進一步較佳。2價芳香族烴基的碳數為6～22為較佳，6～18為更佳，6～10為進一步較佳。有關2價脂肪族烴基與2價芳香族烴基的組合之基團（例如，伸芳基烷基）的碳數係7～22為較佳，7～18為更佳，7～10為進一步較佳。 Although it does not specifically limit as a divalent linking group which comprises L, Hydrocarbon group is preferable, and aliphatic hydrocarbon group is more preferable. The hydrocarbon group may have a substituent, and may have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linking group that may have an oxygen atom in the chain is preferable, a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a related group that may have an oxygen atom in the chain. A combination of an atomic divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group is more preferable, and a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is still more preferable. These groups preferably do not have an oxygen atom. The number of carbon atoms in the divalent hydrocarbon linking group is preferably 1-24, more preferably 2-12, and still more preferably 2-6. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1-12, more preferably 2-6, and still more preferably 2-4. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably from 6 to 22, more preferably from 6 to 18, and still more preferably from 6 to 10. The carbon number of the group (for example, arylalkyl group) related to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group is preferably 7 to 22, more preferably 7 to 18, and further more preferably 7 to 10. good.

作為連結基L，具體而言，直鏈或支鏈的鏈狀伸烷基、環狀伸烷基、與鏈狀伸烷基與環狀伸烷基的組合相關之基團、鏈中具有氧原子之伸烷基、直鏈或支鏈的鏈狀伸烯基、環狀伸烯基、伸芳基、伸芳基伸烷基為較佳。 直鏈或支鏈的鏈狀伸烷基的碳數係1～12為較佳，2～6為更佳，2～4為進一步較佳。 環狀伸烷基的碳數係3～12為較佳，3～6為更佳。 有關鏈狀伸烷基與環狀伸烷基的組合之基團的碳數為4～24為較佳，4～12為更佳，4～6為進一步較佳。 鏈中具有氧原子之伸烷基可以為鏈狀或環狀，亦可以為直鏈或支鏈。鏈中具有氧原子之伸烷基的碳數係1～12為較佳，1～6為更佳，1～3為進一步較佳。 As the linking group L, specifically, a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and a group having oxygen in the chain. Atomic alkylene groups, linear or branched chain alkenylene groups, cyclic alkenylene groups, arylylene groups, and arylylenealkylene groups are preferred. The carbon number of the linear or branched chain alkylene group is preferably 1-12, more preferably 2-6, and still more preferably 2-4. The carbon number of the cyclic alkylene group is preferably 3-12, more preferably 3-6. The carbon number of the group related to the combination of a chain alkylene group and a cyclic alkylene group is preferably 4-24, more preferably 4-12, and still more preferably 4-6. The alkylene group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched. The carbon number of the alkylene group having an oxygen atom in the chain is preferably 1-12, more preferably 1-6, and still more preferably 1-3.

直鏈或支鏈的鏈狀伸烯基的碳數係2～12為較佳，2～6為更佳，2～3為進一步較佳。直鏈或支鏈的鏈狀伸烯基的C=C鍵數係1～10為較佳，1～6為更佳，1～3為進一步較佳。 環狀伸烯基的碳數係3～12為較佳，3～6為更佳。環狀伸烯基的C=C鍵數係1～6為較佳，1～4為更佳，1～2為進一步較佳。 伸芳基的碳數係6～22為較佳，6～18為更佳，6～10為進一步較佳。 伸芳基伸烷基的碳數係7～23為較佳，7～19為更佳，7～11為進一步較佳。 其中，鏈狀伸烷基、環狀伸烷基、鏈中具有氧原子之伸烷基、鏈狀伸烯基、伸芳基、伸芳基伸烷基為較佳，1,2-乙烯基、丙烷二基（尤其1,3-丙烷二基）、環己烷二基（尤其1,2-環己烷二基）、伸乙烯基（尤其順式伸乙烯基）、伸苯基（1,2-伸苯基）、伸苯基亞甲基（尤其1,2-伸苯基亞甲基）、乙烯氧基乙烯基（尤其1,2-乙烯氧基-1,2-乙烯基）為更佳。 The carbon number of the linear or branched alkenylene group is preferably 2-12, more preferably 2-6, and still more preferably 2-3. The number of C=C bonds in the linear or branched alkenylene group is preferably 1-10, more preferably 1-6, and still more preferably 1-3. The carbon number of the cyclic alkenylene group is preferably 3-12, more preferably 3-6. The number of C=C bonds in the cyclic alkenylene group is preferably 1-6, more preferably 1-4, and still more preferably 1-2. The carbon number of the aryl group is preferably 6-22, more preferably 6-18, and still more preferably 6-10. The carbon number of the arylalkylene group is preferably 7-23, more preferably 7-19, and still more preferably 7-11. Among them, chain alkylene, cyclic alkylene, alkylene with oxygen atoms in the chain, chain alkenylene, aryl, arylalkylene are preferred, 1,2-vinyl, Propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis-vinylene), phenylene (1, 2-phenylene), phenylene methylene (especially 1,2-phenylene methylene), vinyloxyvinyl (especially 1,2-vinyloxy-1,2-vinyl) are better.

作為鹼產生劑，可以舉出下述例子，但本發明不應被此作限定性解釋。As the base generating agent, the following examples can be mentioned, but the present invention should not be construed as limited thereto.

[化學式48]

Figure 02_image092
[chemical formula 48]
Figure 02_image092

非離子型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 base generator is preferably at most 800, more preferably at most 600, and still more preferably at most 500. The lower limit is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.

作為離子型鹼產生劑的較佳化合物的具體例，例如，亦可以舉出國際公開第2018/038002號的0148～0163段中所記載之化合物。Specific examples of preferable compounds of the ionic base generator include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.

作為銨鹽的具體例，能夠舉出以下化合物，但本發明並不限定於此。 [化學式49]

Figure 02_image094
Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto. [chemical formula 49]
Figure 02_image094

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50]

Figure 02_image096
Specific examples of imide salts include the following compounds, but the present invention is not limited thereto. [chemical formula 50]
Figure 02_image096

在本發明的樹脂組成物包含鹼產生劑的情況下，鹼產生劑的含量相對於本發明的樹脂組成物中的樹脂100質量份係0.1～50質量份為較佳。下限為0.3質量份以上為更佳，0.5質量份以上為進一步較佳。上限係30質量份以下為更佳，20質量份以下為進一步較佳，10質量份以下為更進一步較佳，可以為5質量份以下，亦可以為4質量份以下。 鹼產生劑能夠使用1種或2種以上。在使用2種以上的情況下，合計量在上述範圍內為較佳。 When the resin composition of this invention contains a base generator, it is preferable that content of a base generator is 0.1-50 mass parts with respect to 100 mass parts of resins in the resin composition of this invention. The lower limit is more preferably at least 0.3 parts by mass, and more preferably at least 0.5 parts by mass. The upper limit is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, may be 5 parts by mass or less, and may be 4 parts by mass or less. The base generator can be used 1 type or 2 or more types. When using 2 or more types, it is preferable that a total amount exists in the said range.

＜溶劑＞ 本發明的樹脂組成物包含溶劑為較佳。 溶劑能夠任意使用公知者。溶劑較佳為有機溶劑。作為有機溶劑，可以舉出酯類、醚類、酮類、環狀烴類、亞碸類、醯胺類、脲類、醇類等化合物。 <Solvent> It is preferable that the resin composition of the present invention contains a solvent. As a solvent, a known one can be used arbitrarily. The solvent is preferably an organic solvent. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfides, amides, ureas, and alcohols.

作為酯類，例如可以舉出乙酸乙酯、乙酸正丁酯、乙酸異丁酯、乙酸己酯、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、己酸乙酯、庚酸乙酯、丙二酸二甲酯、丙二酸二乙酯等作為較佳者。Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate , butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (e.g., methyl alkoxyacetate, alkanes Ethyl oxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., 2-alkoxy Methyl oxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkane Ethyl oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate , ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate , dimethyl malonate, diethyl malonate, etc. are preferred.

作為醚類，例如，可以舉出乙二醇二甲醚、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇乙基甲醚、二乙二醇丁基甲醚、三乙二醇二甲醚、四乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單乙醚、甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇二甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、乙二醇單丁醚、乙二醇單丁醚乙酸酯、二乙二醇乙基甲醚、丙二醇單丙醚乙酸酯、二丙二醇二甲醚等作為較佳者。Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol Alcohol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celuxo acetate, ethyl celuxo acetate, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether , ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, etc. are preferred.

作為酮類，例如，可以舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮、3-甲基環己酮、左旋葡萄糖酮（levoglucosenone）、二氫左旋葡萄糖酮等作為較佳者。As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone (levoglucosenone), dihydro Levoglucosone and the like are preferred.

作為環狀烴類，例如，可以舉出甲苯、二甲苯、大茴香醚等芳香族烴類、檸檬烯等環式萜烯類作為較佳者。As the cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferred.

作為亞碸類，例如可以舉出二甲基亞碸作為較佳者。As the arsonites, for example, dimethyl arsonite is preferred.

作為醯胺類，可以舉出N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-環己基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N,N-二甲基異丁醯胺、3-甲氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺、N-甲醯基口末啉、N-乙醯基口末啉等作為較佳者。Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetyl Amine, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N, N-dimethylacrylamide, N-formyl porperoline, N-acetyl porperoline, etc. are preferred.

作為脲類，可以舉出N,N,N’,N’-四甲基脲、1,3-二甲基-2-咪唑啶酮等作為較佳者。Ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like as preferred ones.

作為醇類，可以舉出甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、1-戊醇、1-己醇、苯甲醇、乙二醇單甲醚、1-甲氧基-2-丙醇、2-乙氧基乙醇、二乙二醇單乙醚、二乙二醇單己醚、三乙二醇單甲醚、丙二醇單乙醚、丙二醇單甲醚、聚乙二醇單甲醚、聚丙二醇、四乙二醇、乙二醇單丁醚、乙二醇單苄醚、乙二醇單苯醚、甲基苯甲醇、正戊醇、甲基戊醇及二丙酮醇等。Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy 2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol Monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methyl benzyl alcohol, n-pentanol, methyl pentanol and diacetone alcohol Wait.

關於溶劑，從塗佈面性狀的改良等觀點考慮，混合2種以上之形態亦為較佳。Regarding the solvent, it is also preferable to mix two or more types from the viewpoint of improving the properties of the coated surface.

在本發明中，選自3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙基賽路蘇乙酸酯、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、丙二醇甲醚乙酸酯、左旋葡萄糖酮及二氫左旋葡萄糖酮中之1種溶劑或由2種以上構成之混合溶劑為較佳。並用二甲基亞碸和γ-丁內酯或並用N-甲基-2-吡咯啶酮和乳酸乙酯為特佳。In the present invention, selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celuxoacetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Esters, Methyl 3-Methoxypropionate, 2-Heptanone, Cyclohexanone, Cyclopentanone, γ-Butyrolactone, Dimethylsulfene, Ethyl Carbitol Acetate, Butyl Carbitol One solvent among alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosone, and dihydrolevoglucosone, or a mixed solvent consisting of two or more is better. The combined use of dimethylsulfene and γ-butyrolactone or the combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

關於溶劑的含量，從塗佈性的觀點考慮，設為本發明的樹脂組成物的總固體成分濃度成為5～80質量%之量為較佳，設為總固體成分濃度成為5～75質量%之量為更佳，設為總固體成分濃度成為10～70質量%之量為進一步較佳，設為總固體成分濃度成為20～70質量%為更進一步較佳。溶劑含量根據塗膜所期望的厚度和塗佈方法調整即可。The content of the solvent is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass from the viewpoint of coatability, and the total solid content concentration is 5 to 75% by mass. The quantity is more preferable, and the quantity which makes total solid content concentration 10-70 mass % is still more preferable, and the total solid content concentration is 20-70 mass %, and it is still more preferable. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

本發明的樹脂組成物可以僅含有1種溶劑，亦可以含有2種以上。在包含2種以上溶劑的情況下，其合計在上述範圍內為較佳。The resin composition of this invention may contain only 1 type of solvent, and may contain 2 or more types. When two or more solvents are included, the total is preferably within the above range.

＜金屬接著性改良劑＞ 本發明的樹脂組成物包含用於提高與在電極或配線等中所使用之金屬材料的接著性之金屬接著性改良劑為較佳。作為金屬接著性改良劑，可以舉出具有烷氧基矽基之矽烷偶合劑、鋁系接著助劑、鈦系接著助劑、具有磺醯胺結構之化合物及具有硫脲結構之化合物、磷酸衍生物化合物、β酮酸酯化合物、胺基化合物等。 ＜Metal Adhesion Improver＞ It is preferable that the resin composition of the present invention contains a metal adhesion improving agent for improving adhesion with metal materials used for electrodes, wiring, and the like. Examples of metal adhesion improvers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesive additives, titanium-based adhesive additives, compounds with a sulfonamide structure and compounds with a thiourea structure, phosphoric acid-derived Compounds, β-ketoester compounds, amino compounds, etc.

〔矽烷偶合劑〕 作為矽烷偶合劑，例如，可以舉出國際公開第2015/199219號0167段中所記載之化合物、日本特開2014-191002號公報0062～0073段中所記載之化合物、國際公開第2011/080992號0063～0071段中所記載之化合物、日本特開2014-191252號公報0060～0061段中所記載之化合物、日本特開2014-041264號公報0045～0052段中所記載之化合物、國際公開第2014/097594號0055段中所記載之化合物、日本特開2018-173573的0067～0078段中所記載之化合物，該等內容編入本說明書中。又，如日本特開2011-128358號公報的0050～0058段中所記載，使用不同之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，Me表示甲基，Et表示乙基。 〔Silane coupling agent〕 Examples of the silane coupling agent include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, compounds described in International Publication No. 2011/080992 Compounds described in paragraphs 0063-0071, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014 The compounds described in paragraph 0055 of No. 097594 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Laid-Open No. 2018-173573 are incorporated in this specification. In addition, as described in paragraphs 0050 to 0058 of JP 2011-128358 A, it is also preferable to use two or more different silane coupling agents. Moreover, it is also preferable to use the following compounds as a silane coupling agent. In the following formulae, Me represents a methyl group, and Et represents an ethyl group.

[化學式51]

Figure 02_image098
[chemical formula 51]
Figure 02_image098

作為其他矽烷偶合劑，例如，可以舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-（3,4-環氧基環己基）乙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽基-N-（1,3-二甲基-亞丁基）丙胺、N-苯基-3-胺基丙基三甲氧基矽烷、三-（三甲氧基矽基丙基）異氰脲酸酯、3-脲丙基三烷氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、3-三甲氧基矽基丙基琥珀酸酐。該等能夠單獨使用1種或組合使用2種以上。Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxy Propoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropoxy Propyltriethoxysilane, p-Styryltrimethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropyltrimethoxysilane , 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N- 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3- Aminopropyltrimethoxysilane, Tris-(trimethoxysilylpropyl)isocyanurate, 3-ureapropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-Mercaptopropyltrimethoxysilane, 3-Isocyanatepropyltriethoxysilane, 3-Trimethoxysilylpropylsuccinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

〔鋁系接著助劑〕 作為鋁系接著助劑，例如，能夠舉出三（乙醯乙酸乙酯）鋁、三（乙醯丙酮）鋁、乙醯乙酸乙酯二異丙酯鋁等。 〔Aluminum-based adhesive agent〕 Examples of the aluminum-based adhesive agent include tris(ethyl acetate)aluminum, tris(acetylacetonate)aluminum, ethyl acetate diisopropyl aluminum, and the like.

又，作為其他金屬接著性改良劑，亦能夠使用日本特開2014-186186號公報的0046～0049段中所記載之化合物、日本特開2013-072935號公報的0032～0043段中所記載之硫醚系化合物，該等內容編入本說明書中。In addition, as other metal adhesion improving agents, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfur described in paragraphs 0032-0043 of JP-A-2013-072935 can also be used. Ether-based compounds, the contents of which are included in this specification.

金屬接著性改良劑的含量相對於特定樹脂100質量份，較佳為0.01～30質量份，更佳為0.1～10質量份的範圍，進一步較佳為0.5～5質量份的範圍。藉由設為上述下限值以上，圖案與金屬層的接著性變良好，藉由設為上述上限值以下，圖案的耐熱性、機械特性變良好。金屬接著性改良劑可以為僅1種，亦可以為2種以上。在使用2種以上的情況下，其合計在上述範圍內為較佳。The content of the metal adhesion improving agent is preferably in the range of 0.01 to 30 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and still more preferably in the range of 0.5 to 5 parts by mass, based on 100 parts by mass of the specific resin. The adhesiveness of a pattern and a metal layer becomes favorable by making it more than the said lower limit, and the heat resistance of a pattern and mechanical characteristics become favorable by being below the said upper limit. The metal adhesiveness improving agent may be only 1 type, and may be 2 or more types. When using 2 or more types, it is preferable that the sum total is in the said range.

＜遷移抑制劑＞ 本發明的樹脂組成物可以進一步包含遷移抑制劑為較佳。藉由包含遷移抑制劑，能夠有效地抑制源自金屬層（金屬配線）之金屬離子轉移到膜內。 ＜Migration Inhibitor＞ It is preferable that the resin composition of the present invention may further contain a migration inhibitor. By including a migration inhibitor, the transfer of metal ions originating in the metal layer (metal wiring) into the film can be effectively suppressed.

作為遷移抑制劑，並沒有特別限制，可以舉出具有雜環（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、嗒口井環、嘧啶環、吡口井環、哌啶環、哌口井環、口末啉環、2H-哌喃環及6H-哌喃環、三口井環）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1,2,4-三唑、苯并三唑、3-胺基-1,2,4-三唑、3,5-二胺基-1,2,4-三唑等三唑系化合物、1H-四唑、5-苯基四唑、5-胺基-1H-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, isoxazole ring, isothiazole ring, Azole ring, pyridine ring, Dakou well ring, pyrimidine ring, pyrimidine well ring, piperidine ring, piperidine well ring, portoline ring, 2H-pyran ring and 6H-piperan ring, three well rings) Compounds, compounds with thioureas and mercapto groups, hindered phenolic compounds, salicylic acid derivatives, hydrazide derivatives. In particular, 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole can be preferably used Triazole-based compounds such as azoles, tetrazole-based compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole.

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 trapping agent that traps anions such as halogen ions can also be used.

作為其他遷移抑制劑，能夠使用日本特開2013-015701號公報的0094段中所記載之防鏽劑、日本特開2009-283711號公報的0073～0076段中所記載之化合物、日本特開2011-059656號公報的0052段中所記載之化合物、日本特開2012-194520號公報的0114、0116及0118段中所記載之化合物、國際公開第2015/199219號的0166段中所記載之化合物等，該等內容編入本說明書中。As other migration inhibitors, rust inhibitors described in paragraph 0094 of JP 2013-015701 A, compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, JP 2011 - Compounds described in Paragraph 0052 of Publication No. 059656, compounds described in Paragraphs 0114, 0116 and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, compounds described in Paragraph 0166 of International Publication No. 2015/199219, etc. , and these contents are incorporated into this manual.

作為遷移抑制劑的具體例，可以舉出下述化合物。Specific examples of migration inhibitors include the following compounds.

[化學式52]

Figure 02_image100
[chemical formula 52]
Figure 02_image100

在本發明的樹脂組成物具有遷移抑制劑的情況下，遷移抑制劑的含量相對於本發明的樹脂組成物的總固體成分係0.01～5.0質量%為較佳，0.05～2.0質量%為更佳，0.1～1.0質量%為進一步較佳。When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, based on the total solid content of the resin composition of the present invention. , 0.1 to 1.0% by mass is still more preferable.

遷移抑制劑可以為僅1種，亦可以為2種以上。在遷移抑制劑為2種以上的情況下，其合計在上述範圍內為較佳。The migration inhibitor may be only 1 type, or may be 2 or more types. When there are two or more kinds of migration inhibitors, the total of them is preferably within the above range.

＜聚合抑制劑＞ 本發明的樹脂組成物包含聚合抑制劑為較佳。作為聚合抑制劑，可以舉出酚系化合物、醌系化合物、胺基系化合物、N-氧自由基化合物系化合物、硝基系化合物、亞硝基系化合物、雜芳香環系化合物、金屬化合物等。 ＜Polymerization inhibitor＞ It is preferable that the resin composition of this invention contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone-based compounds, amino-based compounds, N-oxyl radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, metal compounds, etc. .

作為聚合抑制劑的具體化合物，可較佳地使用對氫醌、鄰氫醌、鄰甲氧基苯酚、對甲氧基苯酚、二-三級丁基-對甲酚、五倍子酚、對三級丁基兒茶酚、1,4-苯醌、二苯基-對苯醌、4,4’-硫代雙（3-甲基-6-三級丁基苯酚）、2,2’-亞甲基雙（4-甲基-6-三級丁基苯酚）、N-亞硝基苯基羥基胺基第一鈰鹽、N-亞硝基-N-苯基羥基胺基鋁鹽、N-亞硝基二苯胺、N-苯基萘胺、乙二胺四乙酸、1,2-環己二胺四乙酸、乙二醇醚二胺四乙酸、2,6-二-三級丁基-4-甲基苯酚、5-亞硝基-8-羥喹啉、1-亞硝基-2-萘酚、2-亞硝基-1-萘酚、2-亞硝基-5-（N-乙基-N-磺丙胺基）苯酚、N-亞硝基-N-（1-萘）羥基胺基銨鹽、雙（4-羥基-3,5-三級丁基）苯基甲烷、1,3,5-三（4-三級丁基-3-羥基-2,6-二甲基苄基）-1,3,5-三口井-2,4,6-（1H,3H,5H）-三酮、4‐羥基-2,2,6,6-四甲基哌啶1-氧自由基、2,2,6,6-四甲基哌啶1-氧自由基、啡噻口井、啡㗁口井、1,1-二苯基-2-苦肼基、二丁基二硫碳酸酯銅（II）、硝基苯、N-亞硝基-N-苯基羥基胺鋁鹽、N-亞硝基-N-苯基羥基胺銨鹽等。又，亦能夠使用日本特開2015-127817號公報的0060段中所記載之聚合抑制劑及國際公開第2015/125469號0031～0046段中所記載之化合物，該內容編入本說明書中。As specific compounds of polymerization inhibitors, p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tertiary butyl-p-cresol, gallicol, p-tertiary Butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'- Methylbis(4-methyl-6-tertiary butylphenol), N-nitrosophenylhydroxylamine first cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N -Nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tertiary butyl -4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-( N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthalene)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane , 1,3,5-tris(4-tertiary butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three wells-2,4,6-(1H,3H ,5H)-triketone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 2,2,6,6-tetramethylpiperidine 1-oxyl radical, Thiophthalic acid, morphine, 1,1-diphenyl-2-picrylhydrazyl, dibutyl dithiocarbonate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxyl Amine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. Also, the polymerization inhibitors described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used, and these contents are incorporated in the present specification.

在本發明的樹脂組成物具有聚合抑制劑的情況下，聚合抑制劑的含量相對於本發明的樹脂組成物的總固體成分係0.01～20質量%為較佳，0.02～15質量%為更佳，0.05～10質量%為進一步較佳。When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, based on the total solid content of the resin composition of the present invention. , 0.05 to 10% by mass is still more preferable.

聚合抑制劑可以為僅1種，亦可以為2種以上。在聚合抑制劑為2種以上的情況下，其合計在上述範圍內為較佳。The polymerization inhibitor may be only 1 type, or may be 2 or more types. When there are two or more kinds of polymerization inhibitors, the total is preferably within the above range.

＜其他添加劑＞ 本發明的樹脂組成物在可以獲得本發明的效果之範圍內，能夠根據需要配合各種的添加物，例如界面活性劑、高級脂肪酸衍生物、熱聚合起始劑、無機粒子、紫外線吸收劑、有機鈦化合物、抗氧化劑、抗凝聚劑、酚系化合物、其他高分子化合物、可塑劑及其他助劑類（例如，消泡劑、阻燃劑等）等。藉由適當地含有該等成分，能夠調整膜物理性質等性質。關於該等成分，例如，能夠參考日本特開2012-003225號公報的0183段以後（對應之美國專利申請公開第2013/0034812號說明書的0237段）的記載、日本特開2008-250074號公報的0101～0104、0107～0109段等的記載，該等內容編入本說明書中。在配合該等添加劑的情況下，將其合計配合量設為本發明的樹脂組成物的固體成分的3質量%以下為較佳。 ＜Other additives＞ The resin composition of the present invention can contain various additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic Titanium compounds, antioxidants, anti-coagulation agents, phenolic compounds, other polymer compounds, plasticizers and other additives (such as defoamers, flame retardants, etc.), etc. Properties such as film physical properties can be adjusted by appropriately containing these components. For these components, for example, reference can be made to the descriptions in paragraphs 0183 and later of Japanese Patent Application Laid-Open No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013/0034812 specification), and the descriptions in Japanese Patent Laid-Open No. 2008-250074. 0101-0104, 0107-0109, etc., these contents are incorporated into this specification. When compounding these additives, it is preferable to make the total compounding quantity into 3 mass % or less of the solid content of the resin composition of this invention.

〔界面活性劑〕 作為界面活性劑，能夠使用氟系界面活性劑、聚矽氧系界面活性劑、烴系界面活性劑等各種界面活性劑。界面活性劑可以為非離子型界面活性劑，可以為陽離子型界面活性劑，亦可以為陰離子型界面活性劑。 〔Surfactant〕 As the surfactant, various surfactants such as fluorine-based surfactants, polysiloxane-based surfactants, and hydrocarbon-based surfactants can be used. The surfactant can be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

藉由在本發明的感光性樹脂組成物中含有界面活性劑，能夠進一步提高製成塗佈液時的液體特性（尤其流動性），並進一步改善塗佈厚度的均勻性或省液性。亦即，在利用適用了含有界面活性劑之組成物之塗佈液形成膜的情況下，被塗佈面與塗佈液之間的界面張力下降，藉此改善對被塗佈面的潤濕性，並提高對被塗佈面的塗佈性。因此，能夠進一步較佳地形成厚度不均少的均勻厚度的膜。By including a surfactant in the photosensitive resin composition of the present invention, it is possible to further improve the liquid properties (especially fluidity) when it is made into a coating liquid, and further improve the uniformity of the coating thickness or the liquid-saving property. That is, in the case of forming a film using a coating liquid to which a surfactant-containing composition is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, thereby improving the wetting of the surface to be coated and improve the coatability of the surface to be coated. Therefore, it is possible to more preferably form a film having a uniform thickness with less thickness unevenness.

作為氟系界面活性劑，例如，可以舉出MEGAFACE F171、MEGAFACE F172、MEGAFACE F173、MEGAFACE F176、MEGAFACE F177、MEGAFACE F141、MEGAFACE F142、MEGAFACE F143、MEGAFACE F144、MEGAFACE R30、MEGAFACE F437、MEGAFACE F475、MEGAFACE F479、MEGAFACE F482、MEGAFACE F554、MEGAFACE F780、RS-72-K（以上為DIC Corporation製）、Fluorad FC430、Fluorad FC431、Fluorad FC171、Novec FC4430、Novec FC4432（以上為3M Japan Limited製）、Surflon S-382、Surflon SC-101、Surflon SC-103、Surflon SC-104、Surflon SC-105、Surflon SC1068、Surflon SC-381、Surflon SC-383、Surflon S393、Surflon KH-40（以上為ASAHI GLASS CO.,LTD.製）、PF636、PF656、PF6320、PF6520、PF7002（OMNOVA Solutions Inc.製）等。氟系界面活性劑亦能夠使用日本特開2015-117327號公報的0015～0158段中所記載之化合物、日本特開2011-132503號公報0117～0132段中所記載之化合物，該等內容編入本說明書中。作為氟系界面活性劑，亦能夠使用嵌段聚合物，作為具體例，例如可以舉出日本特開2011-89090號公報中所記載之化合物，該等內容編入本說明書中。 氟系界面活性劑亦能夠較佳地使用含氟高分子化合物（包含源自具有氟原子之（甲基）丙烯酸酯化合物之重複單元和源自具有2個以上（較佳為5個以上）的伸烷氧基（較佳為乙烯氧基、丙烯氧基）之（甲基）丙烯酸酯化合物之重複單元），亦可以例示下述化合物作為在本發明中所使用之氟系界面活性劑。 [化學式53]

Figure 02_image102
Examples of fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479 , MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (the above are manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, Novec FC4432 (the above are manufactured by 3M Japan Limited), Surflon S-382 , Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (the above are ASAHI GLASS CO.,LTD .), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and the compounds described in paragraphs 0117-0132 of JP-A-2011-132503 can also be used, and these contents are incorporated herein. in the manual. A block polymer can also be used as a fluorine-type surfactant, and as a specific example, the compound described in Unexamined-Japanese-Patent No. 2011-89090 is mentioned, The content is incorporated in this specification. Fluorine-based surfactants can also preferably use fluorine-containing polymer compounds (including repeating units derived from (meth)acrylate compounds with fluorine atoms and derived from 2 or more (preferably 5 or more) As the repeating unit of (meth)acrylate compound of alkyleneoxy group (preferably ethyleneoxy group, propyleneoxy group), the following compounds can also be exemplified as the fluorine-based surfactant used in the present invention. [chemical formula 53]
Figure 02_image102

上述化合物的重量平均分子量較佳為3,000～50,000，5,000～30,000為更佳。 關於氟系界面活性劑，亦能夠將在側鏈具有乙烯性不飽和基之含氟聚合物用作氟系界面活性劑。作為具體例，可以舉出日本特開2010-164965號公報的0050～0090段及0289～0295段中所記載之化合物，該內容編入本說明書中。又，作為市售品，例如可以舉出DIC Corporation製MEGAFACE RS-101、RS-102、RS-718K等。 The weight average molecular weight of the above compound is preferably from 3,000 to 50,000, more preferably from 5,000 to 30,000. Regarding the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as the fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, and the contents thereof are incorporated in the present specification. Moreover, as a commercial item, DIC Corporation Megaface RS-101, RS-102, RS-718K etc. are mentioned, for example.

氟系界面活性劑中的含氟率係3～40質量%為較佳，更佳為5～30質量%，特佳為7～25質量%。含氟率在該範圍內之氟系界面活性劑在塗佈膜的厚度均勻性或省液性方面有效，在組成物中的溶解性亦良好。The fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, and particularly preferably from 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.

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

作為烴系界面活性劑，例如，可以舉出PIONIN A-76、NEWKALGEN FS-3PG、PIONIN B-709、PIONIN B-811-N、PIONIN D-1004、PIONIN D-3104、PIONIN D-3605、PIONIN D-6112、PIONIN D-2104-D、PIONIN D-212、PIONIN D-931、PIONIN D-941、PIONIN D-951、PIONIN E-5310、PIONIN P-1050-B、PIONIN P-1028-P、PIONIN P-4050-T等（以上為TAKEMOTO OIL & FAT CO.,LTD製）等。Examples of hydrocarbon-based surfactants include PIONIN A-76, NEWKALGEN FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, PIONIN P-4050-T, etc. (the above are manufactured by TAKEMOTO OIL & FAT CO.,LTD), etc.

作為非離子型界面活性劑，可以例示出甘油、三羥甲基丙烷、三羥甲基乙烷以及該等的乙氧基化物及丙氧基化物（例如，甘油丙氧基化物、甘油乙氧基化物等）、聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、山梨糖醇酐脂肪酸酯等。作為市售品，可以舉出PLURONIC（註冊商標）L10、L31、L61、L62、10R5、17R2、25R2（BASF公司製）、Tetronic 304、701、704、901、904、150R1（BASF公司製）、Solsperse 20000（Lubrizol Japan Ltd.製）、NCW-101、NCW-1001、NCW-1002（FUJIFILM Wako Pure Chemical Corporation製）、PIONIN D-6112、D-6112-W、D-6315（TAKEMOTO OIL & FAT CO.,LTD製）、OLFIN E1010、Surfynol 104、400、440（Nissin Chemical Industry CO.,Ltd.製）等。Examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerin propoxylate, glycerin ethoxylate base compounds, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol di Laurate, macrogol distearate, sorbitan fatty acid ester, etc. Commercially available products include PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF Corporation), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF Corporation), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT CO ., LTD), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry CO., Ltd.), etc.

作為陽離子型界面活性劑，具體而言，可以舉出有機矽氧烷聚合物KP-341（Shin-Etsu Chemical Co.,Ltd.製）、（甲基）丙烯酸系（共）聚合物POLYFLOW No.75、No.77、No.90、No.95（Kyoeisha chemical Co.,Ltd.製）、W001（Yusho Co.,Ltd.製）等。Specific examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer POLYFLOW No. 75, No.77, No.90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), etc.

作為陰離子型界面活性劑，具體而言，可以舉出W004、W005、W017（Yusho Co.,Ltd.）、SANDET BL（SANYO KASEI Co.Ltd.製）等。Specific examples of the anionic surfactant include W004, W005, W017 (Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Kasei Co. Ltd.), and the like.

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

〔高級脂肪酸衍生物〕 為了防止由氧導致的聚合阻礙，本發明的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使其在塗佈後的乾燥過程中偏在於本發明的樹脂組成物的表面。 〔Higher fatty acid derivatives〕 In order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide can be added to the resin composition of the present invention so that it is biased in the natural state during the drying process after coating. The surface of the inventive 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段中所記載之化合物，該內容編入本說明書中。Moreover, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used as a higher fatty acid derivative, and the content is incorporated in this specification.

在本發明的樹脂組成物含有高級脂肪酸衍生物的情況下，高級脂肪酸衍生物的含量相對於本發明的樹脂組成物的總固體成分，0.1～10質量%為較佳。高級脂肪酸衍生物可以僅為1種，亦可以為2種以上。在高級脂肪酸衍生物為2種以上的情況下，其合計在上述範圍內為較佳。When the 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 resin composition of the present invention. The higher fatty acid derivative may be only one kind, or may be two or more kinds. When there are two or more kinds of higher fatty acid derivatives, it is preferable that the total thereof is within the above-mentioned range.

〔熱聚合起始劑〕 本發明的樹脂組成物可以包含熱聚合起始劑，尤其可以包含熱自由基聚合起始劑。熱自由基聚合起始劑係藉由熱能而產生自由基，並開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，亦能夠使樹脂及聚合性化合物進行聚合反應，因此能夠進一步提高耐溶劑性。又，有時上述光聚合起始劑亦具有藉由熱而開始聚合之作用，有時能夠作為熱聚合起始劑添加。 〔Thermal polymerization initiator〕 The resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator. Thermal free radical polymerization initiators are compounds that generate free radicals by thermal energy and initiate or accelerate the polymerization reaction of polymerizable compounds. By adding the thermal radical polymerization initiator, the resin and the polymerizable compound can also be polymerized, so that the solvent resistance can be further improved. Moreover, the said photoinitiator may also have the effect of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

作為熱自由基聚合起始劑，具體而言，可以舉出日本特開2008-063554號公報的0074～0118段中所記載之化合物，該內容編入本說明書中。Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, and the contents are incorporated in this specification.

在包含熱聚合起始劑的情況下，其含量相對於本發明的樹脂組成物的總固體成分係0.1～30質量%為較佳，更佳為0.1～20質量%，進一步較佳為0.5～15質量%。熱聚合起始劑可以僅含有1種，亦可以含有2種以上。在含有2種以上熱聚合起始劑的情況下，合計量在上述範圍內為較佳。When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 30% by mass relative to the total solid content of the resin composition of the present invention. 15% by mass. A thermal-polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.

〔無機粒子〕 本發明的樹脂組成物可以包含無機微粒子。作為無機粒子，具體而言，能夠包含碳酸鈣、磷酸鈣、二氧化矽、高嶺土、滑石、二氧化鈦、氧化鋁、硫酸鋇、氟化鈣、氟化鋰、沸石、硫化鉬、玻璃等。 〔Inorganic particles〕 The resin composition of the present invention may contain inorganic fine particles. Specifically, the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.

作為上述無機粒子的平均粒徑，0.01～2.0μm為較佳，0.02～1.5μm為更佳，0.03～1.0μm為進一步較佳，0.04～0.5μm為特佳。 微粒子的上述平均粒徑為一次粒徑，又，為體積平均粒徑。體積平均粒徑能夠藉由基於Nanotrac WAVE II EX-150（NIKKISO CO.,LTD.製）之動態光散射法測定。 在難以進行上述測定的情況下，亦能夠藉由離心沉降透光法、X射線透射法、雷射衍射/散射法測定。 The average particle diameter of the inorganic particles is preferably from 0.01 to 2.0 μm, more preferably from 0.02 to 1.5 μm, still more preferably from 0.03 to 1.0 μm, and particularly preferably from 0.04 to 0.5 μm. The above average particle diameter of the fine particles is the primary particle diameter, and also the volume average particle diameter. The volume average particle diameter can be measured by the dynamic light scattering method based on Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO., LTD.). When it is difficult to perform the measurement, it can also be measured by the centrifugal sedimentation light transmission method, the X-ray transmission method, and the laser diffraction/scattering method.

〔紫外線吸收劑〕 本發明的組成物可以包含紫外線吸收劑。作為紫外線吸收劑，能夠使用水楊酸酯系、二苯甲酮系、苯并三唑系、取代丙烯腈系、三口井系等紫外線吸收劑。 作為水楊酸酯系紫外線吸收劑的例子，可以舉出水楊酸苯酯、水楊酸對辛基苯酯、水楊酸對三級丁基苯酯等，作為二苯甲酮系紫外線吸收劑的例子，可以舉出2,2’-二羥基-4-甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2,4-二羥基二苯甲酮、2-羥基-4-辛氧基二苯甲酮等。又，作為苯并三唑系紫外線吸收劑的例子，可以舉出2-（2’-羥基-3’,5’-二-三級丁基苯基）-5-氯苯并三唑、2-（2’-羥基-3’-三級丁基-5’-甲基苯基）-5-氯苯并三唑、2-（2’-羥基-3’-三級戊基-5’-異丁基苯基）-5-氯苯并三唑、2-（2’-羥基-3’-異丁基-5’-甲基苯基）-5-氯苯并三唑、2-（2’-羥基-3’-異丁基-5’-丙基苯基）-5-氯苯并三唑、2-（2’-羥基-3’,5’-二-三級丁基苯基）苯并三唑、2-（2’-羥基-5’-甲基苯基）苯并三唑、2-[2’-羥基-5’-（1,1,3,3-四甲基）苯基]苯并三唑等。 〔UV absorber〕 The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and Sanguchi-based ultraviolet absorbers can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-tertiary butylphenyl salicylate, etc., as benzophenone-based ultraviolet absorbers. Examples of agents include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxydiphenyl Methanone etc. Also, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxyl-3',5'-di-tertiary butylphenyl)-5-chlorobenzotriazole, 2 -(2'-Hydroxy-3'-tertiary butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-Hydroxy-3'-tertiary pentyl-5' -isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2- (2'-Hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-Hydroxy-3',5'-di-tertiary butyl Phenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetra Methyl) phenyl] benzotriazole, etc.

作為取代丙烯腈系紫外線吸收劑的例子，可以舉出2-氰基-3,3-二苯基丙烯酸乙酯、2-氰基-3,3-二苯基丙烯酸2-乙基己酯等。進而，作為三口井系紫外線吸收劑的例子，可以舉出2-[4-[（2-羥基-3-十二氧基丙基）氧基]-2-羥基苯基]-4,6-雙（2,4-二甲基苯基）-1,3,5-三口井、2-[4-[（2-羥基-3-三癸氧基丙基）氧基]-2-羥基苯基]-4,6-雙（2,4-二甲基苯基）-1,3,5-三口井、2-（2,4-二羥基苯基）-4,6-雙（2,4-二甲基苯基）-1,3,5-三口井等單（羥基苯基）三口井化合物；2,4-雙（2-羥基-4-丙氧基苯基）-6-（2,4-二甲基苯基）-1,3,5-三口井、2,4-雙（2-羥基-3-甲基-4-丙氧基苯基）-6-（4-甲基苯基）-1,3,5-三口井、2,4-雙（2-羥基-3-甲基-4-己氧基苯基）-6-（2,4-二甲基苯基）-1,3,5-三口井等雙（羥基苯基）三口井化合物；2,4-雙（2-羥基-4-丁氧基苯基）-6-（2,4-二丁氧基苯基）-1,3,5-三口井、2,4,6-三（2-羥基-4-辛氧基苯基）-1,3,5-三口井、2,4,6-三[2-羥基-4-（3-丁氧基-2-羥基丙氧基）苯基]-1,3,5-三口井等三（羥基苯基）三口井化合物等。Examples of substituted acrylonitrile UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, etc. . Furthermore, as an example of the three well-type ultraviolet absorbers, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6- Bis(2,4-dimethylphenyl)-1,3,5-three wells, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxybenzene base]-4,6-bis(2,4-dimethylphenyl)-1,3,5-three wells, 2-(2,4-dihydroxyphenyl)-4,6-bis(2, 4-dimethylphenyl)-1,3,5-mono(hydroxyphenyl)three well compounds; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-( 2,4-dimethylphenyl)-1,3,5-three wells, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methyl phenyl)-1,3,5-three wells, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl )-1,3,5-bis(hydroxyphenyl)three well compounds; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxy phenyl)-1,3,5-three wells, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-three wells, 2,4,6- Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-three wells and other tris(hydroxyphenyl) three wells compounds, etc.

在本發明中，上述各種紫外線吸收劑可以單獨使用1種，亦可以組合使用2種以上。 本發明的組成物可以包含紫外線吸收劑，亦可以不包含紫外線吸收劑，但包含的情況下，紫外線吸收劑的含量相對於本發明的組成物的總固體成分質量，0.001質量%以上且1質量%以下為較佳，0.01質量%以上且0.1質量%以下為更佳。 In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more. The composition of the present invention may or may not contain an ultraviolet absorber, but when it is included, the content of the ultraviolet absorber is 0.001% by mass or more and 1% by mass relative to the total solid content of the composition of the present invention. % or less is preferable, and 0.01 mass % or more and 0.1 mass % or less are more preferable.

〔有機鈦化合物〕 本實施形態的樹脂組成物可以含有有機鈦化合物。藉由樹脂組成物含有有機鈦化合物，在低溫下硬化的情況下亦能夠形成耐藥品性優異之樹脂層。 〔Organotitanium compound〕 The resin composition of this embodiment may contain an organic titanium compound. By containing the organotitanium compound in the resin composition, a resin layer excellent in chemical resistance can be formed even when cured at a low temperature.

作為能夠使用的有機鈦化合物，可以舉出有機基團經由共價鍵或離子鍵與鈦原子鍵結者。 在以下I）～VII）中示出有機鈦化合物的具體例： I）螯合鈦化合物：其中，從樹脂組成物的保存穩定性良好且可以獲得良好的硬化圖案的方面考慮，具有2個以上烷氧基之螯合鈦化合物為更佳。具體例為雙（三乙醇胺）二異丙氧基鈦、二（正丁氧基）雙（2,4-戊二酸酯）鈦、二異丙氧基雙（2,4-戊二酸酯）鈦、二異丙氧基雙（四甲基庚二酸酯）鈦、二異丙氧基雙（乙醯乙酸乙酯）鈦等。 II）四烷氧基鈦化合物：例如為四（正丁氧基）鈦、四乙氧基鈦、四（2-乙基己氧基）鈦、四異丁氧基鈦、四異丙氧基鈦、四甲氧基鈦、四甲氧基丙氧基鈦、四甲基苯氧基鈦、四（正壬氧基）鈦、四（正丙氧基）鈦、四硬脂氧基鈦、四[雙｛2,2-（烯丙氧基甲基）丙氧基｝]鈦等。 III）二茂鈦化合物：例如為五甲基環戊二烯三甲氧基鈦、雙（η5-2,4-環戊二烯-1-基）雙（2,6-二氟苯基）鈦、雙（η5-2,4-環戊二烯-1-基）雙（2,6-二氟-3-（1H-吡咯-1-基）苯基）鈦等。 IV）單烷氧基鈦化合物：例如為三（磷酸二辛酯）異丙氧基鈦、三（苯磺酸十二酯）異丙氧基鈦等。 V）氧化鈦化合物：例如為雙（戊二酸酯）氧化鈦、雙（四甲基庚二酸酯）氧化鈦、酞菁氧化鈦等。 VI）四乙醯丙酮鈦化合物：例如為四乙醯丙酮鈦等。 VII）鈦酸酯偶合劑：例如為異丙基三十二基苯磺醯基鈦酸酯等。 Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organic titanium compounds are shown in the following I) to VII): I) Chelate titanium compound: Among them, a chelate titanium compound having two or more alkoxy groups is more preferable from the standpoints that the resin composition has good storage stability and can obtain a good hardening pattern. Specific examples are bis(triethanolamine)diisopropoxytitanium, bis(n-butoxy)bis(2,4-glutarate)titanium, diisopropoxybis(2,4-glutarate) ) titanium, diisopropoxy bis (tetramethylpimelate) titanium, diisopropoxy bis (ethyl acetylacetate) titanium, etc. II) Tetraalkoxytitanium compounds: such as tetra(n-butoxy)titanium, tetraethoxytitanium, tetrakis(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium Titanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonyloxy)titanium, tetra(n-propoxy)titanium, tetrastearyloxytitanium, Tetra[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc. III) Titanocene compounds: e.g. pentamethylcyclopentadienetrimethoxytitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium , bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Monoalkoxytitanium compound: For example, tris(dioctyl phosphate) isopropoxytitanium, tris(dodecylbenzenesulfonate)isopropoxytitanium, and the like. V) Titanium oxide compound: For example, bis(glutarate)titanium oxide, bis(tetramethylpimelate)titanium oxide, titanium phthalocyanine oxide, and the like. VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetonate and the like. VII) Titanate coupling agent: for example, isopropyl docosylbenzenesulfonyl titanate and the like.

其中，作為有機鈦化合物，從發揮更良好的耐藥品性的觀點考慮，選自包括上述I）螯合鈦化合物、II）四烷氧基鈦化合物及III）二茂鈦化合物之群組中之至少1種化合物為較佳。尤其，二異丙氧基雙（乙醯乙酸乙酯）鈦、四（正丁氧基）鈦及雙（η5-2,4-環戊二烯-1-基）雙（2,6-二氟-3-（1H-吡咯-1-基）苯基）鈦為較佳。Among them, the organotitanium compound is selected from the group consisting of the above-mentioned I) chelated titanium compound, II) tetraalkoxytitanium compound and III) titanocene compound from the viewpoint of exhibiting better chemical resistance. At least one compound is preferred. In particular, diisopropoxybis(ethyl acetate)titanium, tetrakis(n-butoxy)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-bis Fluoro-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

在配合有機鈦化合物的情況下，其配合量相對於100質量份的特定樹脂，0.05～10質量份為較佳，更佳為0.1～2質量份。在配合量為0.05質量份以上的情況下，所獲得之硬化圖案更有效地顯示出良好的耐熱性及耐藥品性，另一方面，10質量份以下的情況下，組成物的保存穩定性更優異。When blending an organic titanium compound, the compounding amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the compounding amount is 0.05 parts by mass or more, the obtained hardened pattern more effectively exhibits good heat resistance and chemical resistance, while on the other hand, when the amount is 10 parts by mass or less, the storage stability of the composition is improved. excellent.

〔抗氧化劑〕 本發明的組成物可以包含抗氧化劑。藉由含有抗氧化劑作為添加劑，能夠提高硬化後的膜的拉伸特性、與金屬材料的密接性。作為抗氧化劑，可以舉出酚化合物、亞磷酸酯化合物、硫醚化合物等。作為酚化合物，能夠使用以往為酚系抗氧化劑之任意酚化合物。作為較佳之酚化合物，可以舉出受阻酚化合物。在與酚性羥基相鄰之部位（鄰位）具有取代基之化合物為較佳。作為上述取代基，碳數1～22的經取代或未經取代之烷基為較佳。又，關於抗氧化劑，在同一分子內具有苯酚基和亞磷酸酯基之化合物亦為較佳。又，抗氧化劑亦能夠較佳地使用磷系抗氧化劑。作為磷系抗氧化劑，可以舉出三[2-[[2,4,8,10-四（1,1-二甲基乙基）二苯并[d,f][1,3,2]二氧雜膦雜環庚二烯-6-基]氧基]乙基]胺、三[2-[（4,6,9,11-四-三級丁基二苯并[d,f][1,3,2]二氧雜膦雜環庚二烯-2-基）氧基]乙基]胺、亞磷酸雙（2,4-二-三級丁基-6-甲基苯基）乙酯等。作為抗氧化劑的市售品，例如，可以舉出ADEKA STAB AO-20、ADEKA STAB AO-30、ADEKA STAB AO-40、ADEKA STAB AO-50、ADEKA STAB AO-50F、ADEKA STAB AO-60、ADEKA STAB AO-60G、ADEKA STAB AO-80、ADEKA STAB AO-330（以上為ADEKA CORPORATION製）等。又，抗氧化劑亦能夠使用日本專利第6268967號公報的0023～0048段中所記載之化合物，該內容編入本說明書中。又，本發明的組成物可根據需要含有潛在抗氧化劑。作為潛在抗氧化劑，可以舉出作為抗氧化劑發揮作用之部位被保護基保護之化合物，在該化合物中，保護基藉由在100～250℃下加熱或在酸/鹼觸媒的存在下以80～200℃加熱而脫離，藉此作為抗氧化劑發揮作用。作為潛在抗氧化劑，可以舉出國際公開第2014/021023號、國際公開第2017/030005號、日本特開2017-008219號公報中所記載之化合物，該內容編入本說明書中。作為潛在抗氧化劑的市售品，可以舉出ADEKA ARKLS GPA-5001（ADEKA CORPORATION製）等。 作為較佳之抗氧化劑的例子，可以舉出2,2-硫代雙（4-甲基-6-三級丁基苯酚）、2,6-二-三級丁基苯酚及式（3）所表示之化合物。 〔Antioxidants〕 The compositions of the present invention may contain antioxidants. By containing an antioxidant as an additive, the tensile properties of the film after hardening and the adhesiveness with a metal material can be improved. As an antioxidant, a phenolic compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound conventionally used as a phenolic antioxidant can be used. A hindered phenol compound is mentioned as a preferable phenol compound. A compound having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) is preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Moreover, as for an antioxidant, the compound which has a phenol group and a phosphite group in the same molecule is also preferable. Moreover, phosphorus antioxidant can also be used preferably as an antioxidant. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2] Dioxaphosphine-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tertiary butyldibenzo[d,f] [1,3,2]dioxaphosphine-2-yl)oxy]ethyl]amine, bis(2,4-di-tertiary-butyl-6-methylphenylphosphite ) ethyl ester etc. Examples of commercially available antioxidants include ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60, and ADEKA STAB AO-60. STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (the above are manufactured by ADEKA CORPORATION), etc. In addition, as an antioxidant, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, and the content is incorporated in this specification. Moreover, the composition of this invention may contain a latent antioxidant as needed. As a potential antioxidant, there can be mentioned a compound in which the part acting as an antioxidant is protected by a protecting group. In this compound, the protecting group is heated at 100-250° C. ~200°C is heated to detach, thereby functioning as an antioxidant. Examples of potential antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Application Laid-Open No. 2017-008219, the contents of which are incorporated in this specification. As a commercial item of a latent antioxidant, ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION) etc. are mentioned. Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-tertiary butylphenol), 2,6-two-tertiary butylphenol and formula (3) indicated compound.

[化學式54]

Figure 02_image104
[chemical formula 54]
Figure 02_image104

在通式（3）中，R 5表示氫原子或碳數2以上（較佳為碳數2～10）的烷基，R 6表示碳數2以上（較佳為碳數2～10）的伸烷基。R 7表示包含碳數2以上（較佳為碳數2～10）的伸烷基、氧原子及氮原子中的至少任一個之1～4價有機基團。k表示1～4的整數。 In the general formula (3), R 5 represents a hydrogen atom or an alkyl group with 2 or more carbons (preferably 2 to 10 carbons), and R 6 represents an alkyl group with 2 or more carbons (preferably 2 to 10 carbons). Alkylene. R 7 represents a 1-4 valent organic group including at least any one of an alkylene group having 2 or more carbons (preferably 2-10 carbons), an oxygen atom, and a nitrogen atom. k represents an integer of 1-4.

式（3）所表示之化合物抑制樹脂所具有之脂肪族基、酚性羥基的氧化劣化。又，藉由對金屬材料的防鏽作用，能夠抑制金屬氧化。The compound represented by formula (3) suppresses oxidation degradation of the aliphatic group and phenolic hydroxyl group which resin has. In addition, metal oxidation can be suppressed by the antirust effect on metal materials.

為了能夠對樹脂和金屬材料同時起作用，k為2～4的整數為更佳。作為R 7，可以舉出烷基、環烷基、烷氧基、烷基醚基、烷基矽基、烷氧基矽基、芳基、芳基醚基、羧基、羰基、烯丙基、乙烯基、雜環基、-O-、-NH-、-NHNH-、組合該等而成者等，可以進一步具有取代基。其中，從在顯影液中的溶解性、金屬密接性的觀點考慮，具有烷基醚、-NH-為較佳，從與樹脂的相互作用和基於金屬錯合物形成之金屬密接性的觀點考慮，-NH-為更佳。 In order to act simultaneously on the resin and the metal material, k is more preferably an integer of 2-4. Examples of R 7 include alkyl, cycloalkyl, alkoxy, alkyl ether, alkyl silyl, alkoxy silyl, aryl, aryl ether, carboxyl, carbonyl, allyl, A vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, a combination thereof, and the like may further have a substituent. Among them, it is preferable to have an alkyl ether or -NH- from the viewpoint of solubility in a developer and metal adhesion, and from the viewpoint of interaction with a resin and metal adhesion by formation of a metal complex , -NH- is more preferred.

通式（3）所表示之化合物可以舉出以下化合物作為例子，但並不限於下述結構。The compound represented by the general formula (3) may be exemplified by the following compounds, but is not limited to the following structures.

[化學式55]

Figure 02_image106
[chemical formula 55]
Figure 02_image106

[化學式56]

Figure 02_image108
[chemical formula 56]
Figure 02_image108

[化學式57]

Figure 02_image110
[chemical formula 57]
Figure 02_image110

[化學式58]

Figure 02_image112
[chemical formula 58]
Figure 02_image112

抗氧化劑的添加量相對於特定樹脂100質量份，0.1～10質量份為較佳，0.5～5質量份為更佳。藉由將添加量設為0.1質量份以上，即使在高溫高濕環境下，亦容易獲得拉伸特性、提高對金屬材料的密接性的效果，又，藉由設為10質量份以下，例如利用與感光劑的相互作用，樹脂組成物的靈敏度提高。抗氧化劑可以僅使用1種，亦可以使用2種以上。使用2種以上的情況下，該等的合計量在上述範圍內為較佳。The addition amount of an antioxidant is preferably 0.1-10 mass parts with respect to 100 mass parts of specific resins, More preferably, it is 0.5-5 mass parts. By setting the addition amount to 0.1 parts by mass or more, even in a high-temperature and high-humidity environment, it is easy to obtain the effects of tensile properties and improved adhesion to metal materials, and by setting it to 10 parts by mass or less, for example, using The interaction with the photosensitizer improves the sensitivity of the resin composition. Antioxidant may use only 1 type, and may use 2 or more types. When using 2 or more types, it is preferable that these total amounts are in the said range.

〔抗凝聚劑〕 本實施形態的樹脂組成物可根據需要含有抗凝聚劑。作為抗凝聚劑，可以舉出聚丙烯酸鈉等。 〔Anti-coagulation agent〕 The resin composition of this embodiment may contain an anti-agglomeration agent as needed. Sodium polyacrylate etc. are mentioned as an anti-agglomeration agent.

本發明中，可以單獨使用1種抗凝聚劑，亦可以組合使用2種以上。 本發明的組成物可以包含抗凝聚劑，亦可以不包含抗凝聚劑，但在包含的情況下，抗凝聚劑的含量相對於本發明的組成物的總固體成分質量，0.01質量%以上且10質量%以下為較佳，0.02質量%以上且5質量%以下為更佳。 In the present invention, one type of anti-aggregation agent may be used alone, or two or more types may be used in combination. The composition of the present invention may or may not contain an anti-aggregating agent, but when included, the content of the anti-aggregating agent is 0.01% by mass or more and 10% by mass relative to the total solid content of the composition of the present invention. It is preferably at most mass %, more preferably at least 0.02 mass % and at most 5 mass %.

〔酚系化合物〕 本實施形態的樹脂組成物可以根據需要含有酚系化合物。作為酚系化合物，可以舉出Bis-Z、BisP-EZ、TekP-4HBPA、TrisP-HAP、TrisP-PA、BisOCHP-Z、BisP-MZ、BisP-PZ、BisP-IPZ、BisOCP-IPZ、BisP-CP、BisRS-2P、BisRS-3P、BisP-OCHP、Methylene Tris-FR-CR、BisRS-26X（以上為商品名，Honshu Chemical Industry Co.,Ltd.製）、BIP-PC、BIR-PC、BIR-PTBP、BIR-BIPC-F（以上為商品名，ASAHI YUKIZAI CORPORATION製）等。 〔Phenolic compounds〕 The resin composition of this embodiment may contain a phenolic compound as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP- CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR -PTBP, BIR-BIPC-F (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), etc.

在本發明中，酚系化合物可以單獨使用1種，亦可以組合使用2種以上。 本發明的組成物可以包含酚系化合物，亦可以不包含酚系化合物，但在包含的情況下，酚系化合物的含量相對於本發明的組成物的總固體成分質量，0.01質量%以上且30質量%以下為較佳，0.02質量%以上且20質量%以下為更佳。 In the present invention, the phenolic compound may be used alone or in combination of two or more. The composition of the present invention may or may not contain a phenolic compound, but when included, the content of the phenolic compound is 0.01% by mass or more and 30% or more relative to the total solid content of the composition of the present invention. It is preferably at most mass %, more preferably at least 0.02 mass % and at most 20 mass %.

〔其他高分子化合物〕 作為其他高分子化合物，可以舉出矽氧烷樹脂、與（甲基）丙烯酸共聚的（甲基）丙烯酸聚合物、酚醛清漆樹脂、甲階酚醛樹脂、多羥基苯乙烯樹脂及該等的共聚物等。其他高分子化合物可以為導入了羥甲基、烷氧基甲基、環氧基等交聯基之改質體。 〔Other polymer compounds〕 Examples of other polymer compounds include siloxane resins, (meth)acrylic acid polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. Wait. Other high molecular compounds may be modified bodies introduced with cross-linking groups such as methylol, alkoxymethyl, and epoxy groups.

本發明中，其他高分子化合物可以單獨使用1種，亦可以組合使用2種以上。 本發明的組成物可以包含其他高分子化合物，亦可以不包含其他高分子化合物，但在包含的情況下，其他高分子化合物的含量相對於本發明的組成物的總固體成分質量，0.01質量%以上且30質量%以下為較佳，0.02質量%以上且20質量%以下為更佳。 In the present invention, other polymer compounds may be used alone or in combination of two or more. The composition of the present invention may or may not contain other high molecular compounds, but when contained, the content of other high molecular compounds is 0.01% by mass relative to the total solid content of the composition of the present invention More than 30 mass % is more preferable, and 0.02 mass % or more and 20 mass % or less are more preferable.

＜樹脂組成物的特性＞ 本發明的樹脂組成物的黏度能夠根據樹脂組成物的固體成分濃度調整。從塗佈膜厚的觀點考慮，1,000mm 2/s～12,000mm 2/s為較佳，2,000mm 2/s～10,000mm 2/s為更佳，2,500mm 2/s～8,000mm 2/s為進一步較佳。只要在上述範圍內，則容易獲得均勻性高的塗佈膜。例如，若為1,000mm 2/s以上，則容易以作為再配線用絕緣膜所需的膜厚塗佈，若為12,000mm 2/s以下，則可以獲得塗佈面狀優異之塗膜。 <Characteristics of the resin composition> The viscosity of the resin composition of the present invention can be adjusted according to the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000mm 2 /s to 12,000mm 2 /s is preferable, 2,000mm 2 /s to 10,000mm 2 /s is more preferable, and 2,500mm 2 /s to 8,000mm 2 /s is more preferable for further improvement. As long as it is within the above range, it is easy to obtain a coating film with high uniformity. For example, if it is 1,000 mm 2 /s or more, it is easy to coat with a film thickness required as an insulating film for rewiring, and if it is 12,000 mm 2 /s or less, a coating film with excellent coating surface shape can be obtained.

＜對樹脂組成物含有物質的限制＞ 本發明的樹脂組成物的含水率小於2.0質量%為較佳，小於1.5質量%為更佳，小於1.0質量%為進一步較佳。若小於2.0%，則樹脂組成物的保存穩定性提高。 作為維持含水量的方法，可以舉出保管條件下的濕度調整、保管時的收容容器的孔隙率降低等。 <Restrictions on Substances Contained in Resin Composition> The moisture content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and still more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition will improve. As a method for maintaining the water content, humidity adjustment under storage conditions, porosity reduction of storage containers during storage, and the like can be mentioned.

從絕緣性的觀點考慮，本發明的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，可以舉出鈉、鉀、鎂、鈣、鐵、銅、鉻、鎳等，但作為有機化合物與金屬的錯合物來包含之金屬除外。包含複數種金屬的情況下，該等金屬的合計在上述範圍內為較佳。From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million (parts per million)), more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. good. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel and the like, but metals contained as complexes of organic compounds and metals are excluded. When a plurality of metals are included, the total of these metals is preferably within the above range.

又，作為減少意外包含在本發明的樹脂組成物中的金屬雜質之方法，能夠舉出如下方法：選擇金屬含量少的原料作為構成本發明的樹脂組成物之原料，對構成本發明的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。In addition, as a method of reducing metal impurities accidentally included in the resin composition of the present invention, the following method can be mentioned: selecting a raw material with a small metal content as the raw material constituting the resin composition of the present invention, and improving the composition of the resin composition of the present invention. The raw material of the product is filtered through a filter, and the inside of the device is lined with polytetrafluoroethylene, etc., and the distillation is carried out under the condition of suppressing pollution as much as possible.

關於本發明的樹脂組成物，若考慮作為半導體材料的用途，則從配線腐蝕性的觀點考慮，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，可以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在上述範圍內為較佳。 作為調整鹵素原子的含量的方法，可較佳地舉出離子交換處理等。 Regarding the resin composition of the present invention, considering its use as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosion. Further better. Among them, those present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is preferably within the above-mentioned ranges. As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.

作為本發明的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本發明的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，可以舉出日本特開2015-123351號公報中所記載之容器。As a container for the resin composition of the present invention, a conventionally known container can be used. In addition, as the storage container, for the purpose of suppressing the mixing of impurities into the raw material or the resin composition of the present invention, it is also possible to use a multi-layer bottle whose inner wall is composed of 6 kinds of 6-layer resins, or a bottle in which 6 kinds of resins are formed into a 7-layer structure. better. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

＜樹脂組成物的硬化物＞ 藉由硬化本發明的樹脂組成物，能夠獲得該樹脂組成物的硬化物， 本發明的硬化物為硬化本發明的樹脂組成物而成之硬化物。 樹脂組成物的硬化藉由加熱進行為較佳，加熱溫度在120℃～400℃的範圍內為更佳，在140℃～380℃的範圍內為進一步較佳，在170℃～350℃的範圍內為特佳。樹脂組成物的硬化物的形態並沒有特別限定，能夠根據用途選擇膜狀、棒狀、球狀、顆粒狀等。本發明中，該硬化物為膜狀為較佳。又，藉由樹脂組成物的圖案加工，亦能夠根據在壁面形成保護膜、形成導通用通孔、調整阻抗、靜電電容或內部應力、賦予散熱功能等用途選擇該硬化物的形狀。該硬化物（由硬化物構成之膜）的膜厚為0.5μm以上且150μm以下為較佳。 本發明的樹脂組成物硬化時的收縮率為50%以下為較佳，45%以下為更佳，40%以下為進一步較佳。在此，收縮率係指樹脂組成物的硬化前後的體積變化的百分率，能夠根據下述式算出。 收縮率[%]=100-（硬化後的體積÷硬化前的體積）×100 ＜Cured product of resin composition＞ By curing the resin composition of the present invention, a hardened product of the resin composition can be obtained, The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. The hardening of the resin composition is preferably performed by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, more preferably in the range of 140°C to 380°C, and in the range of 170°C to 350°C The inside is especially good. The form of the cured product of the resin composition is not particularly limited, and film, rod, spherical, granular, etc. can be selected according to the application. In the present invention, it is preferable that the cured product is in the form of a film. In addition, by patterning the resin composition, the shape of the cured product can also be selected according to purposes such as forming a protective film on the wall surface, forming a via hole for conduction, adjusting impedance, capacitance, or internal stress, and imparting a heat dissipation function. The film thickness of the cured product (film composed of the cured product) is preferably not less than 0.5 μm and not more than 150 μm. The shrinkage rate of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less. Here, the shrinkage rate refers to the percentage of volume change before and after curing of the resin composition, and can be calculated according to the following formula. Shrinkage [%]=100-(volume after hardening ÷ volume before hardening)×100

＜樹脂組成物的硬化物的特性＞ 本發明的樹脂組成物的硬化物的醯亞胺化反應率為70%以上為較佳，80%以上為更佳，90%以上為進一步較佳。若為70%以上，則有時會成為機械特性優異之硬化物。 本發明的樹脂組成物的硬化物的斷裂伸長率為30%以上為較佳，40%以上為更佳，50%以上為進一步較佳。 本發明的樹脂組成物的硬化物的玻璃轉移溫度（Tg）為180℃以上為較佳，210℃以上為更佳，230℃以上為進一步較佳。 <Characteristics of hardened resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or higher, more preferably 80% or higher, and still more preferably 90% or higher. If it is 70% or more, it may become a cured product excellent in mechanical properties. The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and still more preferably 230°C or higher.

＜樹脂組成物的製備＞ 本發明的樹脂組成物能夠藉由混合上述各成分來製備。混合方法並沒有特別限定，能夠藉由以往公知的方法來進行。 混合能夠採用基於攪拌葉片之混合、基於球磨機之混合、使罐本身旋轉的混合等。 混合中的溫度為10～30℃為較佳，15～25℃為更佳。 ＜Preparation of resin composition＞ The 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. For mixing, mixing by a stirring blade, mixing by a ball mill, mixing by rotating the tank itself, etc. can be used. The temperature during mixing is preferably from 10 to 30°C, more preferably from 15 to 25°C.

又，以去除本發明的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。關於過濾器孔徑，例如可以舉出5μm以下之態樣，1μm以下為較佳，0.5μm以下為更佳，0.1μm以下為進一步較佳。過濾器的材質為聚四氟乙烯、聚乙烯或尼龍為較佳。過濾器的材質為聚乙烯的情況下，HDPE（高密度聚乙烯）為更佳。過濾器可以使用用有機溶劑預先清洗者。過濾器的過濾步驟中，複數種過濾器可以串聯或並聯連接使用。使用複數種過濾器的情況下，可以組合使用孔徑或材質不同之過濾器。作為連接態樣，例如，可以舉出如下態樣：將孔徑1μm的HDPE過濾器作為第一段，將孔徑0.2μm的HDPE過濾器作為第二段，將兩者串聯連接。又，可以將各種材料過濾複數次。過濾複數次的情況下，可以為循環過濾。又，可以進行加壓過濾。進行加壓過濾的情況下，例如可以舉出所施加的壓力為0.01MPa以上且1.0MPa以下之態樣，0.03MPa以上且0.9MPa以下為較佳，0.05MPa以上且0.7MPa以下為更佳，0.05MPa以上且0.5MPa以下為進一步較佳。 除了使用過濾器之過濾以外，亦可以進行使用吸附材料之雜質去除處理。亦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，可以舉出矽膠、沸石等無機系吸附材料、活性碳等有機系吸附材料。 可以在用過濾器進行過濾之後，進一步實施將填充於瓶中的樹脂組成物放置於減壓下進行脫氣之步驟。 Moreover, for the purpose of removing foreign substances such as dust and fine particles in the resin composition of the present invention, it is preferable to perform filtration using a filter. Regarding the filter pore size, for example, an aspect of 5 μm or less is mentioned, preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, HDPE (high density polyethylene) is more preferable. Filters can be used pre-cleaned with organic solvents. In the filtration step of the filter, a plurality of types of filters may be used in series or parallel connection. When using multiple types of filters, filters with different pore diameters or materials can be used in combination. As a connection aspect, for example, an aspect in which an HDPE filter with a pore diameter of 1 μm is used as the first stage, an HDPE filter with a pore diameter of 0.2 μm is used as the second stage, and both are connected in series. Also, various materials may be filtered multiple times. In the case of filtering multiple times, loop filtering can be used. In addition, pressure filtration may be performed. In the case of pressure filtration, for example, the applied pressure is 0.01 MPa to 1.0 MPa, preferably 0.03 MPa to 0.9 MPa, more preferably 0.05 MPa to 0.7 MPa, More preferably, it is 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, known adsorbents can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtering with a filter, a step of degassing the resin composition filled in the bottle under reduced pressure may be further performed.

（硬化物的製造方法） 本發明的硬化物的製造方法包括在基材上適用樹脂組成物來形成膜之膜形成步驟為較佳。 又，本發明的硬化物的製造方法包括上述膜形成步驟、對藉由膜形成步驟形成之膜進行選擇性曝光之曝光步驟及使用顯影液對藉由曝光步驟被曝光的膜進行顯影來形成圖案之顯影步驟為更佳。 本發明的硬化物的製造方法包括上述膜形成步驟、上述曝光步驟、上述顯影步驟、以及對藉由顯影步驟獲得之圖案進行加熱之加熱步驟及對藉由顯影步驟獲得之圖案進行曝光之顯影後曝光步驟中的至少1個為特佳。 又，本發明的製造方法包括上述膜形成步驟及加熱上述膜之步驟亦為較佳。 以下，對各步驟的詳細內容進行說明。 (Manufacturing method of hardened product) The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film. In addition, the method for producing a cured product of the present invention includes the above-mentioned film forming step, an exposure step of selectively exposing the film formed in the film forming step, and developing the film exposed in the exposing step using a developer to form a pattern. The development step is better. The method for producing a cured product of the present invention includes the above-mentioned film forming step, the above-mentioned exposure step, the above-mentioned developing step, a heating step of heating the pattern obtained in the developing step, and a post-development step of exposing the pattern obtained in the developing step. At least one of the exposure steps is particularly preferred. Moreover, it is also preferable that the production method of the present invention includes the above-mentioned film forming step and the step of heating the above-mentioned film. The details of each step will be described below.

＜膜形成步驟＞ 本發明的樹脂組成物能夠在適用於基材上來形成膜之膜形成步驟中使用。 本發明的硬化物的製造方法包括在基材上適用樹脂組成物來形成膜之膜形成步驟為較佳。 ＜Film formation process＞ The resin composition of the present invention can be used in a film forming step for forming a film on a base material. The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film.

〔基材〕 基材的種類能夠根據用途適當確定，可以舉出矽、氮化矽、聚矽、氧化矽、非晶矽等半導體製作用基材、石英、玻璃、光學膜、陶瓷材料、沉積膜、磁性膜、反射膜、Ni、Cu、Cr、Fe等金屬基材（例如，由金屬形成之基材及金屬層例如可以為藉由鍍覆、沉積等形成之基材中的任一種）、紙、SOG（Spin On Glass：旋塗式玻璃）、TFT（薄膜電晶體）陣列基材、鑄模基材、電漿顯示面板（PDP）的電極板等，並沒有特別限制。本發明中，尤其，半導體製作用基材為較佳，矽基材、Cu基材、鑄模基材為更佳。 又，可以在該等基材的表面設置有由六甲基二矽氮烷（HMDS）等形成之密接層、氧化層等層。 又，基材的形狀並沒有特別限定，可以為圓形形狀，亦可以為矩形形狀。 作為基材的尺寸，若為圓形形狀，則例如直徑為100～450mm，較佳為200～450mm。若為矩形形狀，則例如短邊的長度為100～1000mm，較佳為200～700mm。 又，作為基材，例如可以使用板狀，較佳為使用面板狀基材（基板）。 〔Substrate〕 The type of substrate can be appropriately determined according to the application, and examples include substrates for semiconductor production such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, deposited films, and magnetic films. , reflective film, metal substrates such as Ni, Cu, Cr, Fe (for example, the substrate and metal layer formed of metal can be any of the substrates formed by plating, deposition, etc.), paper, SOG (Spin On Glass: spin-on glass), TFT (Thin Film Transistor) array substrate, mold substrate, electrode plate of plasma display panel (PDP), etc., are not particularly limited. In the present invention, especially, a base material for semiconductor production is preferable, and a silicon base material, a Cu base material, and a mold base material are more preferred. In addition, layers such as an adhesive layer and an oxide layer formed of hexamethyldisilazane (HMDS) or the like may be provided on the surface of these substrates. Moreover, the shape of a base material is not specifically limited, It may be a circular shape, or may be a rectangular shape. As a dimension of a base material, if it is a circular shape, it is 100-450 mm in diameter, for example, Preferably it is 200-450 mm. If it is a rectangular shape, the length of a short side is 100-1000 mm, for example, Preferably it is 200-700 mm. Also, as the base material, for example, a plate-shaped base material (substrate) can be used, and it is preferable to use a panel-shaped base material (substrate).

又，在樹脂層（例如，由硬化物構成之層）的表面、金屬層的表面適用樹脂組成物來形成膜的情況下，樹脂層、金屬層成為基材。Also, when a resin composition is applied to the surface of a resin layer (for example, a layer made of a cured product) or a metal layer to form a film, the resin layer and the metal layer serve as base materials.

作為將本發明的樹脂組成物適用於基材上之方法，塗佈為較佳。Coating is preferred as a method for applying the resin composition of the present invention to a substrate.

作為適用方法，具體而言，可以例示出浸塗法、氣刀塗佈法、簾塗法、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。從膜的厚度均勻性的觀點考慮，更佳為旋塗法、狹縫塗佈法、噴塗法或噴墨法，從膜的厚度均勻性的觀點及生產性的觀點考慮，旋塗法及狹縫塗佈法為較佳。根據方法調整樹脂組成物的固體成分濃度、塗佈條件，藉此能夠獲得所期望厚度的膜。又，能夠根據基材的形狀適當選擇塗佈方法，若為晶圓等圓形基材，則旋塗法或噴塗法、噴墨法等為較佳，若為矩形基材，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500～3,500rpm的轉速適用10秒～3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段中所記載之製作方法。 又，亦可以進行在基材的端部去除多餘膜之步驟。關於該種步驟的例子，可以舉出邊珠沖洗（edge bead rinse：EBR）、背面沖洗等。 又，亦可以採用如下預濕步驟：將樹脂組成物塗佈於基材之前，對基材塗佈各種溶劑以提高基材的潤濕性之後，塗佈樹脂組成物。 Specific examples of the applicable method include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, narrow coating, etc. Slot coating method and inkjet method, etc. From the viewpoint of film thickness uniformity, spin coating method, slit coating method, spray coating method, or inkjet method are more preferable. From the viewpoint of film thickness uniformity and productivity, spin coating method and slit coating method Slot coating is preferred. A film having a desired thickness can be obtained by adjusting the solid content concentration of the resin composition and coating conditions according to the method. In addition, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, and inkjet methods are preferred. For rectangular substrates, slit coating is preferred. Cloth method or spraying method, inkjet method, etc. are preferred. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. In addition, a method of transferring a coating film formed on a dummy support in advance by the above-mentioned application method to a base material can also be applied. Regarding the transfer method, in the present invention, it is also possible to preferably utilize the methods described in paragraphs 0023, 0036-0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096-0108 of Japanese Patent Application Laid-Open No. 2006-047592. method. Moreover, you may perform the process of removing an excess film at the edge part of a base material. Examples of such steps include edge bead rinse (EBR), backside rinse, and the like. In addition, a pre-wetting step may also be adopted: before applying the resin composition to the substrate, after applying various solvents to the substrate to improve the wettability of the substrate, and then applying the resin composition.

＜乾燥步驟＞ 上述膜可以在膜形成步驟（層形成步驟）之後，對所形成之膜（層）進行乾燥之步驟（乾燥步驟）以去除溶劑。 亦即，本發明的硬化物的製造方法可以包括對藉由膜形成步驟形成之膜進行乾燥之乾燥步驟。 又，上述乾燥步驟在膜形成步驟之後且曝光步驟之前進行為較佳。 乾燥步驟中的膜的乾燥溫度為50～150℃為較佳，70℃～130℃為更佳，90℃～110℃為進一步較佳。又，可以藉由減壓進行乾燥。作為乾燥時間，可以例示出30秒～20分鐘，1分鐘～10分鐘為較佳，2分鐘～7分鐘為更佳。 ＜Drying procedure＞ The above-mentioned film may be subjected to a step (drying step) of drying the formed film (layer) to remove the solvent after the film forming step (layer forming step). That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step. Moreover, it is preferable to perform the said drying process after a film formation process and before an exposure process. The drying temperature of the film in the drying step is preferably from 50°C to 150°C, more preferably from 70°C to 130°C, and still more preferably from 90°C to 110°C. Moreover, drying can be performed by reducing pressure. As a drying time, 30 seconds - 20 minutes can be illustrated, Preferably it is 1 minute - 10 minutes, More preferably, it is 2 minutes - 7 minutes.

＜曝光步驟＞ 上述膜可以用於對膜進行選擇性曝光之曝光步驟。 亦即，本發明的硬化物的製造方法可以包括對藉由膜形成步驟形成之膜進行選擇性曝光之曝光步驟。 選擇性曝光係指對膜的一部分進行曝光。又，藉由選擇性曝光，在膜上形成經曝光之區域（曝光部）及未曝光之區域（非曝光部）。 曝光量只要能夠硬化本發明的樹脂組成物，則並沒有特別限定，例如，以波長365nm處的曝光能量換算計，50～10,000mJ/cm 2為較佳，200～8,000mJ/cm 2為更佳。 <Exposure step> The above-mentioned film can be used in the exposure step of selectively exposing the film. That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed in the film formation step. Selective exposure refers to exposing a portion of the film. Moreover, by selective exposure, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film. The amount of exposure is not particularly limited as long as it can harden the resin composition of the present invention. For example, in terms of exposure energy at a wavelength of 365 nm, it is preferably 50-10,000 mJ/cm 2 , more preferably 200-8,000 mJ/cm 2 good.

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

關於曝光波長，若以與光源的關係來說，則可以舉出（1）半導體雷射（波長830nm、532nm、488nm、405nm、375nm、355nm等）、（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種波長）、（4）準分子雷射、KrF準分子雷射（波長248nm）、ArF準分子雷射（波長193nm）、F 2準分子雷射（波長157nm）、（5）極紫外線；EUV（波長13.6nm）、（6）電子束、（7）YAG雷射的二次諧波532nm、三次諧波355nm等。關於本發明的樹脂組成物，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，尤其可獲得高曝光靈敏度。 又，曝光的方式並沒有特別限定，只要為由本發明的樹脂組成物構成之膜的至少一部分被曝光之方式即可，可以舉出使用了光罩之曝光、基於雷射直接成像法之曝光等。 Regarding the exposure wavelength, in terms of the relationship with the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamp, (3) High-pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (three wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser Radiation (wavelength 248nm), ArF excimer laser (wavelength 193nm), F 2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG Laser second harmonic 532nm, third harmonic 355nm, etc. Regarding the resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferable, and among them, exposure by i-rays is preferable. Thereby, especially high exposure sensitivity can be obtained. In addition, the method of exposure is not particularly limited, as long as at least a part of the film composed of the resin composition of the present invention is exposed, exposure using a photomask, exposure by laser direct imaging, etc. .

＜曝光後加熱步驟＞ 上述膜可以在曝光後用於加熱步驟（曝光後加熱步驟）。 亦即，本發明的硬化物的製造方法可以包括對藉由曝光步驟被曝光的膜進行加熱之曝光後加熱步驟。 曝光後加熱步驟能夠在曝光步驟後、顯影步驟前進行。 曝光後加熱步驟中的加熱溫度為50℃～140℃為較佳，60℃～120℃為更佳。 曝光後加熱步驟中的加熱時間為30秒～300分鐘為較佳，1分鐘～10分鐘為更佳。 關於曝光後加熱步驟中的升溫速度，從加熱開始時的溫度至最高加熱溫度為止為1～12℃/分鐘為較佳，2～10℃/分鐘為更佳，3～10℃/分鐘為進一步較佳。 又，升溫速度可以在加熱過程中適當變更。 作為曝光後加熱步驟中的加熱方法，並沒有特別限定，能夠使用公知的加熱板、烘箱、紅外線加熱器等。 又，加熱時，藉由流通氮、氦、氬等惰性氣體，在低氧濃度的環境下進行亦為較佳。 ＜Heating step after exposure＞ The above film may be used in a heating step after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposing step. The post-exposure heating step can be performed after the exposure step and before the image development step. The heating temperature in the post-exposure heating step is preferably from 50°C to 140°C, more preferably from 60°C to 120°C. The heating time in the post-exposure heating step is preferably from 30 seconds to 300 minutes, more preferably from 1 minute to 10 minutes. Regarding the rate of temperature increase in the post-exposure heating step, from the temperature at the start of heating to the maximum heating temperature, it is preferably 1 to 12°C/minute, more preferably 2 to 10°C/minute, and further preferably 3 to 10°C/minute. better. In addition, the rate of temperature increase can be appropriately changed during the heating process. The heating method in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters, and the like can be used. Moreover, when heating, it is also preferable to carry out under the environment of low oxygen concentration by passing inert gas, such as nitrogen, helium, and argon.

＜顯影步驟＞ 曝光後的上述膜可以在用顯影液進行顯影來形成圖案之顯影步驟中使用。 亦即，本發明的硬化物的製造方法可以包括使用顯影液對藉由曝光步驟被曝光的膜進行顯影來形成圖案之顯影步驟。 藉由進行顯影，膜的曝光部及非曝光部中的一個被去除，形成圖案。 在此，將藉由顯影步驟去除膜的非曝光部之顯影稱為負型顯影，將藉由顯影步驟影去除膜的曝光部之顯影稱為正型顯影。 ＜Development step＞ The said film after exposure can be used in the image development process which develops with a developing solution and forms a pattern. That is, the method for producing a cured product of the present invention may include a developing step of developing a film exposed in the exposing step using a developer to form a pattern. By developing, one of the exposed part and the non-exposed part of a film is removed, and a pattern is formed. Here, the development of removing the non-exposed portion of the film by the development step is called negative image development, and the image development of removing the exposed portion of the film by the image development step is called positive image development.

〔顯影液〕 作為在顯影步驟中所使用之顯影液，可以舉出鹼水溶液或包含有機溶劑之顯影液。 〔developer〕 As a developing solution used in an image development process, the developing solution containing alkali aqueous solution or an organic solvent is mentioned.

在顯影液為鹼水溶液的情況下，作為鹼水溶液能夠包含之鹼性化合物，可以舉出無機鹼類、一級胺類、二級胺類、三級胺類、四級銨鹽，較佳為TMAH（氫氧化四甲基銨）、氫氧化鉀、碳酸鈉、氫氧化鈉、矽酸鈉、偏矽酸鈉、氨、乙胺、正丙胺、二乙胺、二正丁胺、三乙胺、甲基二乙胺、二甲基乙醇胺、三乙醇胺、氫氧化四乙基銨、氫氧化四丙基胺、氫氧化四丁基胺、氫氧化四戊基胺、氫氧化四己基胺、氫氧化四辛基胺、氫氧化乙基三甲基銨、氫氧化丁基三甲基銨、氫氧化甲基三戊基銨、氫氧化二丁基二戊基銨、氫氧化二甲基雙（2-羥基乙基）銨、氫氧化三甲基苯基銨、氫氧化三甲基苄基銨、氫氧化三乙基苄基銨、吡咯、哌啶，更佳為TMAH。例如使用TMAH的情況下，顯影液中鹼性化合物的含量在顯影液總質量中為0.01～10質量%為較佳，0.1～5質量%為更佳，0.3～3質量%為進一步較佳。When the developing solution is an alkaline aqueous solution, the basic compound that can be included in the alkaline aqueous solution includes inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, Methyldiethylamine, Dimethylethanolamine, Triethanolamine, Tetraethylammonium Hydroxide, Tetrapropylamine Hydroxide, Tetrabutylamine Hydroxide, Tetrapentylamine Hydroxide, Tetrahexylamine Hydroxide, Hydroxide Tetraoctylamine, Ethyltrimethylammonium Hydroxide, Butyltrimethylammonium Hydroxide, Methyltripentylammonium Hydroxide, Dibutyldipentylammonium Hydroxide, Dimethylbis(2) Hydroxide - hydroxyethyl)ammonium, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, piperidine, more preferably TMAH. For example, when TMAH is used, the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.3 to 3% by mass, based on the total mass of the developer.

在顯影液包含有機溶劑的情況下，關於有機溶劑，作為酯類，例如可較佳地舉出乙酸乙酯、乙酸正丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁內酯、ε-己內酯、δ-戊內酯、烷氧基乙酸烷基酯（例如：烷氧基乙酸甲酯、烷氧基乙酸乙酯、烷氧基乙酸丁酯（例如，甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯等））、3-烷氧基丙酸烷基酯類（例如：3-烷氧基丙酸甲酯、3-烷氧基丙酸乙酯等（例如，3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯等））、2-烷氧基丙酸烷基酯類（例如：2-烷氧基丙酸甲酯、2-烷氧基丙酸乙酯、2-烷氧基丙酸丙酯等（例如，2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯））、2-烷氧基-2-甲基丙酸甲酯及2-烷氧基-2-甲基丙酸乙酯（例如，2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯等）、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸甲酯、2-氧代丁酸乙酯等，以及作為醚類，例如可較佳地舉出二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單乙醚、甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚（PGME）、丙二醇單甲醚乙酸酯（PGMEA）、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯等，以及作為酮類，例如可較佳地舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮、N-甲基-2-吡咯啶酮等，以及作為環狀烴類，例如可較佳地舉出甲苯、二甲苯、大茴香醚等芳香族烴類、檸檬烯等環式萜烯類，以及作為亞碸類，可較佳地舉出二甲基亞碸，以及作為醇類，可較佳地舉出甲醇、乙醇、丙醇、異丙醇、丁醇、戊醇、辛醇、二乙二醇、丙二醇、甲基異丁基甲醇、三乙二醇等，以及作為醯胺類，可較佳地舉出N-甲基吡咯啶酮、N-乙基吡咯啶酮、二甲基甲醯胺等。When the developer contains an organic solvent, examples of the organic solvent preferably include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, propionic acid, and Butyl ester, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkoxy acetate base esters (e.g. methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl methyl oxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionates (for example: methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g. methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxy Alkyl propionate (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, 2-methoxypropionate methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy - Methyl 2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2- Ethyl methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, 2-oxobutyl Acetate ethyl ester, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celuxo acetate, ethyl Basecelusu acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone Ketones, N-methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene, And as the oxenes, preferably dimethyl phenylene, and as the alcohols, preferably methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, dimethanol, Ethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and as amides, preferably N-methylpyrrolidone, N-ethylpyrrolidone, dimethyl Formamide, etc.

又，在顯影液包含有機溶劑的情況下，有機溶劑能夠使用1種或混合使用2種以上。本發明中，尤其包含選自包括環戊酮、γ-丁內酯、二甲基亞碸、N-甲基-2-吡咯啶酮及環己酮之群組中之至少1種之顯影液為較佳，包含選自包括環戊酮、γ-丁內酯及二甲基亞碸之群組中之至少1種之顯影液為更佳，包括環戊酮之顯影液為最佳。Moreover, when a developing solution contains an organic solvent, organic solvent can be used 1 type or in mixture of 2 or more types. In the present invention, especially, at least one developer selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone and cyclohexanone is included More preferably, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethylsulfide is more preferred, and a developer containing cyclopentanone is most preferred.

在顯影液包含有機溶劑的情況下，相對於顯影液的總質量之有機溶劑的含量為50質量%以上為較佳，70質量%以上為更佳，80質量%以上為進一步較佳，90質量%以上為特佳。又，上述含量亦可以為100質量%。When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% by mass. More than % is especially good. Moreover, the said content may be 100 mass %.

顯影液可以進一步包含其他成分。 作為其他成分，例如，可以舉出公知的界面活性劑和公知的消泡劑等。 The developer may further contain other components. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

〔顯影液的供給方法〕 只要能夠形成所期望圖案，則顯影液的供給方法並沒有特別限制，有如下方法：將形成有膜之基材浸漬於顯影液中之方法、用噴嘴對形成於基材上之膜供給顯影液之旋覆浸沒顯影或連續供給顯影液之方法。噴嘴的種類並沒有特別限制，可以舉出直流噴嘴、噴淋噴嘴、噴霧噴嘴等。 從顯影液的滲透性、非圖像部的去除性、製造上的效率的觀點考慮，將顯影液用直流噴嘴供給之方法、或用噴霧噴嘴連續供給之方法為較佳，從顯影液對圖像部的滲透性的觀點考慮，用噴霧噴嘴供給之方法為更佳。 又，可以採用如下步驟：用直流噴嘴連續供給顯影液之後，旋轉基材以從基材上去除顯影液，旋轉乾燥後再次用直流噴嘴連續供給之後，旋轉基材以從基材上去除顯影液，亦可以將該步驟重複複數次。 又，作為顯影步驟中的顯影液的供給方法，能夠採用在基材上連續供給顯影液之步驟、顯影液以大致靜止狀態保持在基材上之步驟、利用超音波等使顯影液在基材上振動之步驟及將該等組合之步驟等。 [How to supply the developer] The method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and there are methods such as immersing the substrate on which the film is formed in the developer, and supplying the developer with a nozzle to the film formed on the substrate. The method of spin immersion development or continuous supply of developer. The type of nozzle is not particularly limited, and examples thereof include straight-line nozzles, shower nozzles, spray nozzles, and the like. From the perspective of the permeability of the developer, the removability of the non-image area, and the efficiency of production, the method of supplying the developer with a straight-line nozzle or the method of continuously supplying the developer with a spray nozzle is preferable. From the viewpoint of the permeability of the image area, the method of supplying with a spray nozzle is more preferable. In addition, the following steps may be adopted: after continuously supplying the developing solution through the DC nozzle, rotating the base material to remove the developing solution from the base material, and after spinning drying and continuously supplying the developing solution through the DC nozzle again, rotating the base material to remove the developing solution from the base material , and this step can also be repeated multiple times. Also, as a method for supplying the developing solution in the developing step, a step of continuously supplying the developing solution on the substrate, a step of maintaining the developing solution on the substrate in a substantially static state, or using ultrasonic wave or the like to apply the developing solution on the substrate can be adopted. The steps of vibrating and the steps of combining them, etc.

作為顯影時間，10秒～10分鐘為較佳，20秒～5分鐘為更佳。顯影時的顯影液的溫度並沒有特別限定，較佳為能夠在10～45℃下進行，更佳為能夠在18℃～30℃下進行。As developing time, 10 seconds - 10 minutes are preferable, and 20 seconds - 5 minutes are more preferable. The temperature of the developing solution at the time of image development is not specifically limited, Preferably it can carry out at 10-45 degreeC, More preferably, it can carry out at 18-30 degreeC.

在顯影步驟中，可以在使用顯影液進行處理之後進一步進行基於沖洗液之圖案的清洗（沖洗）。又，亦可以採用在與圖案接觸之顯影液未完全乾燥之前供給沖洗液等之方法。In the developing step, after processing with a developing solution, cleaning (rinsing) of the pattern with a rinse solution may be further performed. In addition, a method of supplying a rinse solution or the like before the developer in contact with the pattern is completely dried may also be employed.

〔沖洗液〕 在顯影液為鹼水溶液的情況下，作為沖洗液，例如能夠使用水。在顯影液為包含有機溶劑之顯影液的情況下，作為沖洗液，例如，能夠使用與顯影液中所包含之溶劑不同之溶劑（例如，水、與顯影液中所包含之有機溶劑不同之有機溶劑）。 〔rinsing fluid〕 When the developing solution is an alkaline aqueous solution, water, for example, can be used as a rinse solution. In the case where the developing solution is a developing solution containing an organic solvent, as the rinse solution, for example, a solvent different from the solvent contained in the developing solution (for example, water, an organic solvent different from the organic solvent contained in the developing solution) can be used. solvent).

作為沖洗液包含有機溶劑時的有機溶劑，作為酯類，例如可較佳地舉出乙酸乙酯、乙酸正丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁內酯、ε-己內酯、δ-戊內酯、烷氧基乙酸烷基酯（例如：烷氧基乙酸甲酯、烷氧基乙酸乙酯、烷氧基乙酸丁酯（例如，甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯等））、3-烷氧基丙酸烷基酯類（例如：3-烷氧基丙酸甲酯、3-烷氧基丙酸乙酯等（例如，3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯等））、2-烷氧基丙酸烷基酯類（例如：2-烷氧基丙酸甲酯、2-烷氧基丙酸乙酯、2-烷氧基丙酸丙酯等（例如，2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯））、2-烷氧基-2-甲基丙酸甲酯及2-烷氧基-2-甲基丙酸乙酯（例如，2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯等）、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸甲酯、2-氧代丁酸乙酯等，以及作為醚類，例如可較佳地舉出二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單乙醚、甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚（PGME）、丙二醇單甲醚乙酸酯（PGMEA）、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯等，以及作為酮類，例如可較佳地舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮、N-甲基-2-吡咯啶酮等，以及作為環狀烴類，例如可較佳地舉出甲苯、二甲苯、大茴香醚等芳香族烴類、檸檬烯等環式萜烯類，以及作為亞碸類，可較佳地舉出二甲基亞碸，以及作為醇類，可較佳地舉出甲醇、乙醇、丙醇、異丙醇、丁醇、戊醇、辛醇、二乙二醇、丙二醇、甲基異丁基甲醇、三乙二醇等，以及作為醯胺類，可較佳地舉出N-甲基吡咯啶酮、N-乙基吡咯啶酮、二甲基甲醯胺等。When the rinse solution contains an organic solvent, examples of esters include ethyl acetate, n-butyl acetate, pentyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, Isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate ( Examples: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid methyl ester, ethyl ethoxy acetate, etc.)), alkyl 3-alkoxypropionate (e.g. methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionate Alkyl esters (e.g. methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g. methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy-2- Methyl methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl acetate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate etc., and as the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cyrusuacetate, ethyl cyrus Threoacetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N -Methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene, and cyclic terpenes such as As the argon, preferably dimethyl argon, and as alcohols, preferably methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol , propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and as amides, preferably N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide Wait.

在沖洗液包含有機溶劑的情況下，有機溶劑能夠使用1種或混合使用2種以上。本發明中，尤其，環戊酮、γ-丁內酯、二甲基亞碸、N-甲基吡咯啶酮、環己酮、PGMEA、PGME為較佳，環戊酮、γ-丁內酯、二甲基亞碸、PGMEA、PGME為更佳，環己酮、PGMEA為進一步較佳。When the rinsing liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. Among the present invention, especially, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are preferred, and cyclopentanone, γ-butyrolactone , dimethylsulfoxide, PGMEA, and PGME are more preferable, and cyclohexanone and PGMEA are still more preferable.

在沖洗液包含有機溶劑的情況下，沖洗液中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，沖洗液可以為100質量%為有機溶劑。When the rinsing liquid contains an organic solvent, the rinsing liquid is preferably 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and still more preferably 90% by mass or more of the organic solvent. In addition, the rinsing liquid may be 100% by mass of an organic solvent.

沖洗液可以進一步包含其他成分。 作為其他成分，例如，可以舉出公知的界面活性劑和公知的消泡劑等。 The rinse solution may further contain other ingredients. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

〔沖洗液的供給方法〕 只要能夠形成所期望的圖案，則沖洗液的供給方法並沒有特別限制，有如下方法：將基材浸漬於沖洗液中之方法、藉由旋覆浸沒在基材上供給之方法、用噴淋頭在基材上供給沖洗液之方法、藉由直流噴嘴等方法在基材上連續供給沖洗液之方法。 從沖洗液的滲透性、非圖像部的去除性、製造上的效率的觀點考慮，有用噴淋噴嘴、直流噴嘴、噴霧噴嘴等供給沖洗液之方法，用噴霧噴嘴連續供給之方法為較佳，從沖洗液對圖像部的滲透性的觀點考慮，用噴霧噴嘴供給之方法為更佳。噴嘴的種類並沒有特別限制，可以舉出直流噴嘴、噴淋噴嘴、噴霧噴嘴等。 亦即，沖洗步驟為利用直流噴嘴對上述曝光後的膜供給或連續供給沖洗液之步驟為較佳，藉由噴霧噴嘴供給沖洗液之步驟為更佳。 又，作為沖洗步驟中的沖洗液的供給方法，能夠採用在基材上連續供給沖洗液之步驟、沖洗液以大致靜止狀態保持在基材上之步驟、利用超音波等使沖洗液在基材上振動之步驟及將該等組合而成之步驟等。 [How to supply the rinse solution] As long as the desired pattern can be formed, the method of supplying the rinsing liquid is not particularly limited, and there are the following methods: a method of immersing the substrate in the rinsing liquid, a method of supplying the substrate by spinning and immersion, using a spray A method of supplying a rinse liquid on a substrate by a head, a method of continuously supplying a rinse liquid on a substrate by means of a straight-line nozzle or the like. From the viewpoint of the permeability of the rinse liquid, the removability of the non-image area, and the efficiency of production, the method of supplying the rinse liquid with a shower nozzle, a straight-line nozzle, a spray nozzle, etc., and the method of continuously supplying it with a spray nozzle are preferable. , from the viewpoint of the permeability of the rinse liquid to the image portion, the method of supplying it with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples thereof include straight-line nozzles, shower nozzles, spray nozzles, and the like. That is, the rinsing step is preferably a step of supplying or continuously supplying a rinsing liquid to the above-mentioned exposed film using a straight-line nozzle, and more preferably a step of supplying a rinsing liquid through a spray nozzle. Also, as a method of supplying the rinse liquid in the rinse step, a step of continuously supplying the rinse liquid on the base material, a step of maintaining the rinse liquid on the base material in a substantially static state, and making the rinse liquid flow on the base material by ultrasonic wave or the like can be adopted. The steps of vibrating and the steps of combining them, etc.

作為沖洗時間，10秒～10分鐘為較佳，20秒～5分鐘為更佳。沖洗時的沖洗液的溫度並沒有特別限定，較佳為能夠在10～45℃下進行，更佳為能夠在18℃～30℃下進行。The rinsing time is preferably from 10 seconds to 10 minutes, more preferably from 20 seconds to 5 minutes. The temperature of the rinsing solution during rinsing is not particularly limited, but it is preferably 10 to 45°C, more preferably 18 to 30°C.

＜加熱步驟＞ 藉由顯影步驟獲得之圖案（進行沖洗步驟的情況下為沖洗後的圖案）可以用於對藉由上述顯影獲得之圖案進行加熱之加熱步驟。 亦即，本發明的硬化物的製造方法可以包括對藉由顯影步驟獲得之圖案進行加熱之加熱步驟。 又，本發明的硬化物的製造方法亦可以包括對未進行顯影步驟而藉由其另一方法來獲得之圖案或藉由膜形成步驟獲得之膜進行加熱之加熱步驟。 加熱步驟中，聚醯亞胺前驅物等樹脂環化成為聚醯亞胺等樹脂。 又，亦進行特定樹脂或除特定樹脂以外的交聯劑中的未反應的交聯性基的交聯等。 作為加熱步驟中的加熱溫度（最高加熱溫度），50～450℃為較佳，150～350℃為更佳，150～250℃為進一步較佳，160～250℃為更進一步較佳，160～230℃為特佳。 ＜Heating step＞ The pattern obtained by the developing step (the pattern after washing when the washing step is performed) can be used in the heating step of heating the pattern obtained by the above-mentioned developing. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the developing step. In addition, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing the developing step or a film obtained by the film forming step. In the heating step, resins such as polyimide precursors are cyclized into resins such as polyimide. In addition, crosslinking of unreacted crosslinkable groups in a specific resin or a crosslinking agent other than the specific resin is also performed. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, still more preferably 150 to 250°C, still more preferably 160 to 250°C, and more preferably 160 to 250°C. 230°C is particularly preferred.

加熱步驟為如下步驟為較佳：利用藉由加熱從上述鹼產生劑產生之鹼等的作用，在上述圖案內促進上述聚醯亞胺前驅物的環化反應。The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern using the action of the base or the like generated from the base generator by heating.

關於加熱步驟中的加熱，從加熱開始時的溫度至最高加熱溫度為止以1～12℃/分鐘的升溫速度進行為較佳。上述升溫速度為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酸或溶劑的過度揮發，藉由將升溫速度設為12℃/分鐘以下，能夠緩和硬化物的殘留應力。 此外，能夠進行快速加熱的烘箱的情況下，從加熱開始時的溫度至最高加熱溫度為止以1～8℃/秒的升溫速度進行為較佳，2～7℃/秒為更佳，3～6℃/秒為進一步較佳。 It is preferable to carry out the heating in the heating step at a temperature increase rate of 1 to 12° C./min from the temperature at the start of heating to the highest heating temperature. The temperature increase rate is more preferably 2 to 10° C./minute, more preferably 3 to 10° C./minute. By setting the temperature increase rate at 1° C./min or more, excessive volatilization of acid or solvent can be prevented while ensuring productivity, and by setting the temperature increase rate at 12° C./min or less, residual stress of the cured product can be relaxed. In addition, in the case of an oven capable of rapid heating, it is better to carry out the temperature increase rate from the temperature at the beginning of heating to the highest heating temperature at a rate of 1 to 8°C/sec, more preferably 2 to 7°C/sec, and 3 to 7°C/sec. 6° C./second is more preferable.

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加熱至最高加熱溫度之步驟開始時的溫度。例如，將本發明的樹脂組成物適用於基材上之後使其乾燥的情況下為其乾燥後的膜（層）的溫度，例如，從比本發明的樹脂組成物中所包含之溶劑的沸點低30～200℃的溫度開始升溫為較佳。The temperature at the start of heating is preferably from 20 to 150°C, more preferably from 20 to 130°C, and still more preferably from 25 to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the highest heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature of the dried film (layer), for example, is higher than the boiling point of the solvent contained in the resin composition of the present invention. It is better to start heating at a temperature lower than 30-200°C.

加熱時間（在最高加熱溫度下的加熱時間）為5～360分鐘為較佳，10～300分鐘為更佳，15～240分鐘為進一步較佳。The heating time (heating time at the highest heating temperature) is preferably from 5 to 360 minutes, more preferably from 10 to 300 minutes, and still more preferably from 15 to 240 minutes.

尤其，在形成多層積層體的情況下，從層間密接性的觀點考慮，加熱溫度為30℃以上為較佳，80℃以上為更佳，100℃以上為進一步較佳，120℃以上為特佳。 上述加熱溫度的上限為350℃以下為較佳，250℃以下為更佳，240℃以下為進一步較佳。 In particular, when forming a multilayer laminate, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, still more preferably 100°C or higher, and particularly preferably 120°C or higher from the viewpoint of interlayer adhesion. . The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and still more preferably 240°C or lower.

加熱可以分階段進行。作為例子，可以進行如下步驟：以3℃/分鐘從25℃升溫至120℃且在120℃下保持60分鐘，以2℃/分鐘從120℃升溫至180℃且在180℃下保持120分鐘。又，如美國專利第9159547號說明書中記載，照射紫外線的同時進行處理亦為較佳。藉由該等前處理步驟能夠提高膜的特性。前處理步驟在10秒～2小時左右的短時間內進行即可，15秒～30分鐘為更佳。前處理可以設為2階段以上的步驟，例如可以在100～150℃的範圍內進行第1階段的前處理步驟，然後在150～200℃的範圍內進行第2階段的前處理步驟。 進而，可以在加熱之後進行冷卻，作為此時的冷卻速度，1～5℃/分鐘為較佳。 Heating can be done in stages. As an example, the following steps can be performed: ramping from 25°C to 120°C at 3°C/min and holding at 120°C for 60 minutes, ramping from 120°C to 180°C at 2°C/min and holding at 180°C for 120 minutes. Moreover, as described in US Patent No. 9159547, it is also preferable to perform treatment while irradiating ultraviolet rays. The properties of the film can be improved by these pretreatment steps. The pretreatment step can be carried out within a short period of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more stages. For example, the first stage pretreatment step may be performed at 100°C to 150°C, and the second stage pretreatment step may be performed at 150°C to 200°C. Furthermore, cooling may be performed after heating, and the cooling rate at this time is preferably 1 to 5° C./min.

關於加熱步驟，從防止特定樹脂分解的方面考慮，藉由流通氮、氦、氬等惰性氣體之減壓下進行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。 作為加熱步驟中的加熱方法，並沒有特別限定，例如可以舉出加熱板、紅外爐、電熱式烘箱、熱風式烘箱、紅外線烘箱等。 Regarding the heating step, it is preferable to carry out under reduced pressure by flowing an inert gas such as nitrogen, helium, or argon in an environment with a low oxygen concentration from the viewpoint of preventing decomposition of a specific resin. The oxygen concentration is preferably not more than 50 ppm (volume ratio), more preferably not more than 20 ppm (volume ratio). It does not specifically limit as a heating method in a heating process, For example, a hot plate, an infrared oven, an electric oven, a hot-air oven, an infrared oven, etc. are mentioned.

＜顯影後曝光步驟＞ 藉由顯影步驟獲得（進行沖洗步驟的情況下為沖洗後的圖案）代替上述加熱步驟或者除了上述加熱步驟以外，亦可以用於對顯影步驟後的圖案進行曝光之顯影後曝光步驟。 亦即，本發明的硬化物的製造方法可以包括對藉由顯影步驟獲得之圖案進行曝光之顯影後曝光步驟。本發明的硬化物的製造方法可以包括加熱步驟及顯影後曝光步驟，亦可以包括加熱步驟及顯影後曝光步驟中的任一個。 顯影後曝光步驟中，例如，能夠促進藉由光鹼產生劑的感光進行聚醯亞胺前驅物等的環化之反應、藉由光酸產生劑的感光進行酸分解性基的脫離之反應等。 在顯影後曝光步驟中，在顯影步驟中獲得之圖案的至少一部分被曝光即可，但上述圖案的全部被曝光為較佳。 以感光性化合物具有靈敏度之波長處的曝光能量換算計，顯影後曝光步驟中的曝光量為50～20,000mJ/cm 2為較佳，100～15,000mJ/cm 2為更佳。 關於顯影後曝光步驟，例如能夠使用上述曝光步驟中的光源進行，使用寬頻光為較佳。 <Exposure step after development> Obtained by a development step (in the case of a rinse step, a pattern after rinse) can be used instead of the above heating step or in addition to the above heating step. exposure steps. That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing a pattern obtained in the development step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include any of the heating step and the post-development exposure step. In the post-development exposure step, for example, the reaction of cyclization of polyimide precursor and the like by exposure to photobase generator, the reaction of detachment of acid-decomposable groups by exposure to photoacid generator, etc. can be promoted. . In the post-development exposure step, at least a part of the pattern obtained in the development step may be exposed, but it is preferable that the entire pattern is exposed. In terms of exposure energy conversion at the wavelength at which the photosensitive compound has sensitivity, the exposure amount in the post-development exposure step is preferably 50-20,000 mJ/cm 2 , more preferably 100-15,000 mJ/cm 2 . The post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, and it is preferable to use broadband light.

＜金屬層形成步驟＞ 藉由顯影步驟獲得之圖案（在加熱步驟及顯影後曝光步驟中的至少1個中使用者為較佳）可以用於在圖案上形成金屬層之金屬層形成步驟。 亦即，本發明的硬化物的製造方法包括在藉由顯影步驟獲得之圖案（在加熱步驟及顯影後曝光步驟中的至少1種步驟中使用者為較佳）上形成金屬層之金屬層形成步驟為較佳。 ＜Metal layer formation process＞ The pattern obtained in the development step (preferably used in at least one of the heating step and post-development exposure step) can be used in the metal layer forming step of forming a metal layer on the pattern. That is, the method for producing the cured product of the present invention includes metal layer formation in which a metal layer is formed on the pattern obtained by the development step (at least one of the heating step and the post-development exposure step is preferably used) steps are better.

作為金屬層，並沒有特別限定，能夠使用現有的金屬種類，可以例示出銅、鋁、鎳、釩、鈦、鉻、鈷、金、鎢、錫、銀及包含該等金屬之合金，銅及鋁為更佳，銅為進一步較佳。The metal layer is not particularly limited, and existing metal types can be used, examples of which include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, copper and Aluminum is more preferable, and copper is still more preferable.

金屬層的形成方法並沒有特別限定，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、美國專利第7888181B2、美國專利第9177926B2中所記載之方法。例如，可考慮光微影、PVD（物理沉積法）、CVD（化學氣相沈積法）、剝離（lift off）、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，可以舉出組合濺射、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。作為電鍍的較佳態樣，可以舉出使用了硫酸銅電鍍液、氰化銅電鍍液之電解電鍍。The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. the method described. For example, photolithography, PVD (Physical Deposition), CVD (Chemical Vapor Deposition), lift off, electrolytic plating, electroless plating, etching, printing, methods combining these, and the like can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating are mentioned. As a preferable aspect of electroplating, electrolytic plating using a copper sulfate electroplating solution and a copper cyanide electroplating solution is mentioned.

作為金屬層的厚度，以最厚的部分計，0.01～50μm為較佳，1～10μm為更佳。The thickness of the metal layer is preferably from 0.01 to 50 μm, more preferably from 1 to 10 μm, in terms of the thickest part.

＜用途＞ 作為能夠適用本發明的硬化物的製造方法或本發明的硬化物的領域，可以舉出電子裝置的絕緣膜、再配線層用層間絕緣膜、應力緩衝膜等。除此以外，可以舉出密封膜、基板材料（柔性印刷電路板的基底膜或覆蓋膜、層間絕緣膜）或藉由蝕刻在上述之類的實際安裝用途的絕緣膜上形成圖案之情況等。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。 ＜Use＞ Examples of fields to which the method for producing a cured product of the present invention or the cured product of the present invention can be applied include insulating films of electronic devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. Other examples include sealing films, substrate materials (base film or cover film for flexible printed circuit boards, interlayer insulating films), or cases where patterns are formed on insulating films for actual mounting applications such as those described above by etching. Regarding such uses, for example, Science & Technology Co., Ltd. "Highly functionalized and applied technology of polyimide" April 2008, Masakimoto Kakimoto/Supervisor, CMC Technical Library "Polyimide materials "Basic and Development of Polyimide" published in November 2011, edited by the Japan Polyimide and Aromatic Polymer Research Society/edited "Basic and Application of the Latest Polyimide" NTS, August 2010, etc.

又，本發明的硬化物的製造方法或本發明的硬化物亦能夠用於膠印版面或網版版面等版面的製造、成形部件在蝕刻中的使用、電子、尤其微電子中的保護漆及介電層的製造等。In addition, the method for producing a cured product of the present invention or the cured product of the present invention can also be used in the production of offset printing plates or screen plates, the use of molded parts in etching, and protective varnishes and dielectrics in electronics, especially microelectronics. Fabrication of electrical layers, etc.

（積層體及積層體的製造方法） 本發明的積層體係指具有複數層由本發明的硬化物構成之層之結構體。 本發明的積層體係包含2層以上由硬化物構成之層之積層體，亦可以為積層3層以上而成之積層體。 上述積層體中所包含之2層以上的上述由硬化物構成之層中，至少1層為由本發明的硬化物構成之層，從抑制硬化物的收縮或伴隨上述收縮產生之硬化物的變形等觀點考慮，上述積層體中所包含之由硬化物構成之層全部為由本發明的硬化物構成之層亦為較佳。 (Laminated body and method for manufacturing the laminated body) The layered system of the present invention refers to a structure having a plurality of layers composed of the cured product of the present invention. The layered system of the present invention may be a layered body comprising two or more layers of hardened materials, or may be a layered body formed by layering three or more layers. Among the two or more layers composed of the above-mentioned cured product contained in the above-mentioned laminated body, at least one layer is a layer composed of the cured product of the present invention. From a viewpoint, it is also preferable that all the layers composed of the cured product contained in the above-mentioned laminate are layers composed of the cured product of the present invention.

亦即，本發明的積層體的製造方法包括本發明的硬化物的製造方法為較佳，包括重複複數次本發明的硬化物的製造方法之步驟為更佳。That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the steps of the method for producing a cured product of the present invention a plurality of times.

本發明的積層體包含2層以上由硬化物構成之層，由上述硬化物構成之任意層彼此之間包含金屬層之態樣為較佳。上述金屬層藉由上述金屬層形成步驟形成為較佳。 亦即，本發明的積層體的製造方法在進行複數次硬化物的製造方法之間進一步包括在由硬化物構成之層上形成金屬層之金屬層形成步驟為較佳。金屬層形成步驟的較佳態樣為如上所述。 作為上述積層體，例如，可以舉出至少包含依序積層有由第一硬化物構成之層、金屬層、由第二硬化物構成之層的3個層之層結構之積層體作為較佳者。 上述由第一硬化物構成之層及上述由第二硬化物構成之層均為由本發明的硬化物構成之層為較佳。用於形成由上述第一硬化物構成之層之本發明的樹脂組成物和用於形成由上述第二硬化物構成之層之本發明的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金屬配線。 The laminate of the present invention includes two or more layers made of cured products, and it is preferable that any layer made of the above-mentioned cured products contains a metal layer between each other. It is preferable that the above-mentioned metal layer is formed by the above-mentioned metal layer forming step. That is, it is preferable that the method for producing a laminate of the present invention further includes a metal layer forming step of forming a metal layer on a layer made of the cured product between performing the manufacturing method of the cured product a plurality of times. A preferred aspect of the metal layer forming step is as described above. As the above-mentioned laminate, for example, a laminate having a layer structure including at least three layers in which a layer composed of a first cured product, a metal layer, and a layer composed of a second cured product are sequentially laminated is preferred. . It is preferable that both the layer composed of the first cured product and the layer composed of the second cured product are layers composed of the cured product of the present invention. The resin composition of the present invention for forming the layer composed of the above-mentioned first cured product and the resin composition of the present invention for forming the layer composed of the above-mentioned second cured product may have the same composition or may be composed of different components. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a rewiring layer.

＜積層步驟＞ 本發明的積層體的製造方法包括積層步驟為較佳。 積層步驟為包括在圖案（樹脂層）或金屬層的表面，再次依序進行（a）膜形成步驟（層形成步驟）、（b）曝光步驟、（c）顯影步驟、（d）加熱步驟及顯影後曝光步驟中的至少1個之一系列步驟。其中，可以為重複（a）的膜形成步驟、（d）加熱步驟及顯影後曝光步驟中的至少1個之態樣。又，可以在（d）加熱步驟及顯影後曝光步驟的中的至少1個之後包括（e）金屬層形成步驟。積層步驟中顯然可以適當地進一步包括上述乾燥步驟等。 ＜Stacking procedure＞ It is preferable that the manufacturing method of the laminated body of this invention includes a lamination step. The lamination step includes (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step and A series of steps of at least one of post-development exposure steps. However, at least one of (a) film formation process, (d) heating process, and post-development exposure process may be repeated. Moreover, (e) metal layer formation process may be included after at least 1 of (d) heating process and post-development exposure process. Obviously, the above-mentioned drying step and the like may be further appropriately included in the lamination step.

在積層步驟之後進一步進行積層步驟的情況下，可以在上述曝光步驟後，上述加熱步驟後或上述金屬層形成步驟後進一步進行表面活性化處理步驟。作為表面活性化處理，例示電漿處理。關於表面活性化處理的詳細內容，在後面進行說明。When further performing a layering step after the layering step, a surface activation treatment step may be further performed after the above-mentioned exposure step, after the above-mentioned heating step, or after the above-mentioned metal layer forming step. As the surface activation treatment, plasma treatment is exemplified. The details of the surface activation treatment will be described later.

上述積層步驟進行2～20次為較佳，進行2～9次為更佳。 例如，可以舉出樹脂層/金屬層/樹脂層/金屬層/樹脂層/金屬層之類的將樹脂層設為2層以上且20層以下的結構為較佳，設為2層以上且9層以下的結構為進一步較佳。 上述各層的組成、形狀、膜厚等可以相同，亦可以不同。 It is better to carry out the above lamination step 2 to 20 times, more preferably 2 to 9 times. For example, a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer or the like can be cited as a structure in which the resin layer is more than 2 layers and 20 layers or less, and it is better to set it as more than 2 layers and 9 layers. The structure below the layer is further preferable. The composition, shape, film thickness, etc. of each of the above-mentioned layers may be the same or different.

本發明中，尤其在設置金屬層之後，進一步形成上述本發明的樹脂組成物的硬化物（樹脂層）以覆蓋上述金屬層之態樣為較佳。具體而言，可以舉出以（a）膜形成步驟、（b）曝光步驟、（c）顯影步驟、（d）加熱步驟及顯影後曝光步驟中的至少1個、（e）金屬層形成步驟的順序重複之態樣或以（a）膜形成步驟、（d）加熱步驟及顯影後曝光步驟中的至少1個、（e）金屬層形成步驟的順序重複之態樣。藉由交替進行積層本發明的樹脂組成物層（樹脂層）之積層步驟與金屬層形成步驟，能夠交替積層本發明的樹脂組成物層（樹脂層）與金屬層。In the present invention, after providing the metal layer, it is preferable to further form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer. Specifically, at least one of (a) film formation step, (b) exposure step, (c) development step, (d) heating step, and post-development exposure step, (e) metal layer formation step or an aspect in which the order of (a) film forming step, (d) at least one of heating step and post-development exposure step, and (e) metal layer forming step is repeated. By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer forming step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately laminated.

（表面活性化處理步驟） 本發明的積層體的製造方法包括對上述金屬層及樹脂組成物層的至少一部分進行表面活性化處理之表面活性化處理步驟為較佳。 表面活性化處理步驟通常在金屬層形成步驟之後進行，但亦可以在上述顯影步驟之後（較佳為加熱步驟及顯影後曝光步驟中的至少1個之後）、對樹脂組成物層進行表面活性化處理步驟之後進行金屬層形成步驟。 表面活性化處理可以僅對金屬層的至少一部分進行，亦可以僅對曝光後的樹脂組成物層的至少一部分進行，亦可以對金屬層及曝光後的樹脂組成物層這兩者的至少一部分進行。表面活性化處理對金屬層的至少一部分進行為較佳，對金屬層中表面形成樹脂組成物層之區域的一部分或全部進行表面活性化處理為較佳。如此，藉由對金屬層的表面進行表面活性化處理，能夠提高與設置於其表面之樹脂組成物層（膜）的密接性。 又，表面活性化處理亦對曝光後的樹脂組成物層（樹脂層）的一部分或全部進行為較佳。如此，藉由對樹脂組成物層的表面進行表面活性化處理，能夠提高與設置於表面活性化處理過之表面之金屬層或樹脂層的密接性。尤其，在進行負型顯影的情況等，樹脂組成物層被硬化的情況下，不易因表面處理而受損，容易提高密接性。 作為表面活性化處理，具體而言，可以選自各種原料氣體（氧、氫、氬、氮、氮/氫混合氣體、氬/氧混合氣體等）的電漿處理、電暈放電處理、基於CF 4/O 2、NF 3/O 2、SF 6、NF 3、NF 3/O 2之蝕刻處理、基於紫外線（UV）臭氧法之表面處理、浸漬於鹽酸水溶液來去除氧化覆膜之後浸漬於包含具有胺基和硫醇基中的至少1種之化合物之有機表面處理劑中的處理、使用刷子之機械性粗面化處理，電漿處理為較佳，尤其將氧作為原料氣體之氧電漿處理為較佳。電暈放電處理的情況下，能量為500～200,000J/m 2為較佳，1000～100,000J/m 2為更佳，10,000～50,000J/m 2為最佳。 (Surface activation treatment step) The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a part of the metal layer and the resin composition layer to a surface activation treatment. The surface activation treatment step is usually performed after the metal layer formation step, but it may also be performed after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) to surface activate the resin composition layer. The processing step is followed by a metal layer forming step. The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the exposed resin composition layer, or may be performed on at least a part of both the metal layer and the exposed resin composition layer. . The surface activation treatment is preferably performed on at least a part of the metal layer, and it is more preferred to perform the surface activation treatment on a part or all of the region of the metal layer on which the resin composition layer is formed. Thus, by surface-activating the surface of a metal layer, the adhesiveness with the resin composition layer (film) provided on the surface can be improved. In addition, it is also preferable to perform the surface activation treatment on a part or all of the exposed resin composition layer (resin layer). Thus, by surface-activating the surface of the resin composition layer, the adhesiveness with the metal layer or resin layer provided in the surface-activation-treated surface can be improved. In particular, when the resin composition layer is hardened, such as when performing negative tone development, it is less likely to be damaged by surface treatment, and it is easier to improve the adhesiveness. As the surface activation treatment, specifically, it can be selected from plasma treatment, corona discharge treatment, CF-based Etching treatment of 4 /O 2 , NF 3 /O 2 , SF 6 , NF 3 , NF 3 /O 2 , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, and then immersion in containing Treatment in an organic surface treatment agent of a compound having at least one of an amine group and a thiol group, mechanical roughening treatment using a brush, and plasma treatment are preferred, especially oxygen plasma using oxygen as a raw material gas Treatment is better. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J/m 2 , more preferably 1,000 to 100,000 J/m 2 , and most preferably 10,000 to 50,000 J/m 2 .

（半導體裝置的製造方法） 本發明亦公開一種包含本發明的硬化物或本發明的積層體之半導體裝置。 本發明亦公開包括本發明的硬化物的製造方法或本發明的積層體的製造方法之半導體裝置的製造方法。作為將本發明的樹脂組成物用於形成再配線層用層間絕緣膜之半導體裝置的具體例，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，該等內容編入本說明書中。 (Manufacturing method of semiconductor device) The present invention also discloses a semiconductor device including the cured product of the present invention or the laminate of the present invention. The present invention also discloses a method of manufacturing a semiconductor device including the method of manufacturing a cured product of the present invention or the method of manufacturing a laminate of the present invention. As a specific example of a semiconductor device in which the resin composition of the present invention is used to form an interlayer insulating film for a rewiring layer, reference can be made to the description in paragraphs 0213 to 0218 of JP-A-2016-027357 and the description in FIG. 1 . The content is incorporated into this manual.

（鹼產生劑） 關於本發明的第一態樣之鹼產生劑，係所產生之鹼係在同一分子內環化而成為三級胺之鹼，所產生之鹼不是α、β-不飽和羰基化合物及α、β不飽和亞胺化合物中的任一種。 本發明的第一態樣之鹼產生劑與上述的本發明的第一態樣之樹脂組成物中所使用之特定鹼產生劑的含義相同，較佳之態樣亦同樣。 本發明的第二態樣之鹼產生劑係上述式（1-1）所表示之鹼產生劑。 本發明的第二態樣之鹼產生劑與上述的本發明的第二態樣之樹脂組成物中所使用之特定鹼產生劑的含義相同，較佳之態樣亦同樣。 [實施例] (base generator) Regarding the base generator of the first aspect of the present invention, the base generated is a base that is cyclized in the same molecule to become a tertiary amine, and the base generated is not an α, β-unsaturated carbonyl compound and α, β Any of unsaturated imine compounds. The base generator of the first aspect of the present invention has the same meaning as the specific base generator used in the above-mentioned resin composition of the first aspect of the present invention, and the same applies to preferred aspects. The base generator of the second aspect of the present invention is a base generator represented by the above formula (1-1). The base generator of the second aspect of the present invention has the same meaning as the specific base generator used in the above-mentioned resin composition of the second aspect of the present invention, and the same applies to preferred aspects. [Example]

以下，舉出實施例對本發明進行進一步詳細的說明。以下實施例所示之材料、使用量、比例、處理內容、處理順序等，只要不脫離本發明的主旨，則能夠適當變更。因此，本發明的範圍並不限定於以下所示之具體例。只要沒有特別說明，則“份”、“%”為質量基準。Hereinafter, the present invention will be described in more detail with reference to examples. Materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed unless departing from the gist 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 based on mass.

＜環化樹脂的前驅物的製造方法＞ 〔合成例1：環化樹脂的前驅物（樹脂2）的合成〕 將4,4’-氧雙鄰苯二甲酸二酐（ODPA）23.48g及雙鄰苯二甲酸二酐（BPDA）22.27g放入分離型燒瓶，添加甲基丙烯酸2-羥乙酯（HEMA）39.69g及四氫呋喃136.83g並在室溫（25℃）下攪拌，攪拌的同時添加吡啶24.66g，藉此獲得了反應混合物。基於反應之發熱結束後自然冷卻至室溫，並放置了16小時。 接著，在冰冷下，攪拌將二環己碳二亞胺（DCC）62.46g溶解於四氫呋喃61.57g中的溶液的同時經40分鐘添加至反應混合物中，接著攪拌將4,4’-二胺基二苯醚（DADPE）27.42g懸浮在四氫呋喃119.73g中者的同時經60分鐘添加。進一步在室溫下攪拌2小時之後，添加乙醇7.17g並攪拌1小時，接著，添加了四氫呋喃136.83g。藉由過濾去除反應混合物中生成之沉澱物，藉此獲得了反應液。 將所獲得之反應液添加至716.21g的乙醇中，生成了由粗聚合物構成之沉澱物。過濾出所生成之粗聚合物，溶解於四氫呋喃403.49g中獲得了粗聚合物溶液。將所獲得之粗聚合物溶液滴加至8470.26g的水中使聚合物沉澱，過濾出所獲得之沉澱物之後，進行真空乾燥，藉此獲得了80.3g的粉末狀的樹脂2。利用凝膠滲透層析法（標準聚苯乙烯換算）測定樹脂2的分子量之結果，重量平均分子量（Mw）為20,000。推測樹脂2的結構為下述式（P-1）所表示之結構。 <Manufacturing method of precursor of cyclized resin> [Synthesis Example 1: Synthesis of the Precursor of Cyclized Resin (Resin 2)] Put 23.48 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.27 g of bisphthalic dianhydride (BPDA) into a separate flask, and add 2-hydroxyethyl methacrylate (HEMA) 39.69 g and 136.83 g of tetrahydrofuran were stirred at room temperature (25° C.), and 24.66 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction ended, it was naturally cooled to room temperature and left to stand for 16 hours. Next, under ice-cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes while stirring, and the 4,4'-diamino 27.42 g of diphenyl ether (DADPE) was added while suspending in 119.73 g of tetrahydrofuran over 60 minutes. After further stirring at room temperature for 2 hours, 7.17 g of ethanol was added and stirred for 1 hour, and then 136.83 g of tetrahydrofuran was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. The obtained reaction liquid was added to 716.21 g of ethanol, and a precipitate consisting of a crude polymer was formed. The generated crude polymer was filtered off, and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the obtained precipitate was filtered and vacuum-dried to obtain 80.3 g of powdery resin 2 . As a result of measuring the molecular weight of the resin 2 by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000. The structure of the resin 2 is presumed to be a structure represented by the following formula (P-1).

〔合成例2：環化樹脂的前驅物（樹脂1）的合成〕 混合21.2g的4,4’-氧雙鄰苯二甲酸酐、18.0g的甲基丙烯酸2-羥乙酯、23.9g的吡啶及250mL的二甘二甲醚（diglyme，二乙二醇二甲醚），在60℃的溫度下攪拌4小時，合成了4,4’-氧雙鄰苯二甲酸與甲基丙烯酸2-羥乙酯的二酯。接著，將反應混合物冷卻至-10℃，將溫度保持在-10±5℃的同時經60分鐘添加了17.0g的亞硫醯氯。用50mL的N-甲基吡咯啶酮稀釋之後，將100mL的N-甲基吡咯啶酮中溶解有12.6g的4,4’-二胺基二苯醚之溶液在-10±5℃下經60分鐘滴加至反應混合物中，並將混合物在室溫下攪拌了2小時。之後，添加乙醇10.0g，在室溫下攪拌了1小時。 接著，添加6000g的水使聚醯亞胺前驅物沉澱，將沉澱物（水-聚醯亞胺前驅物混合物）攪拌了15分鐘。過濾收集攪拌後的沉澱物（聚醯亞胺前驅物的固體），使其溶解於四氫呋喃500g中。在所獲得之溶液中添加6000g的水（不良溶劑），使聚醯亞胺前驅物沉澱，將沉澱物（水-聚醯亞胺前驅物混合物）攪拌了15分鐘。再次過濾攪拌後的沉澱物（聚醯亞胺前驅物的固體），並在減壓下、45℃下乾燥了3天。 將乾燥後的粉體46.6g溶解於四氫呋喃419.6g中之後，添加2.3g的三乙胺並在室溫下攪拌了35分鐘。之後，添加乙醇3000g，過濾收集了沉澱物。將所獲得之沉澱物溶解於四氫呋喃281.8g中。對其添加水17.1g及離子交換樹脂UP6040（Ambertech Limited製）46.6g，並攪拌了4小時。之後，藉由過濾濾除離子交換樹脂，將所獲得之聚合物溶液添加到庚烷4500g與乙酸乙酯500g的混合溶液中獲得了沉澱物。過濾收集沉澱物，在減壓下45℃使其乾燥24小時，藉此獲得了45.1g的樹脂1。 推測樹脂1的結構為下述式（P-2）所表示之結構。利用凝膠滲透層析法（標準聚苯乙烯換算）測定樹脂1的分子量之結果，重量平均分子量（Mw）為20,000。 [Synthesis Example 2: Synthesis of Precursor of Cyclized Resin (Resin 1)] Mix 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme (diethylene glycol dimethyl Ether) was stirred at 60°C for 4 hours to synthesize the diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10°C, and 17.0 g of thionyl chloride was added over 60 minutes while maintaining the temperature at -10±5°C. After diluting with 50mL of N-methylpyrrolidone, a solution of 12.6g of 4,4'-diaminodiphenyl ether dissolved in 100mL of N-methylpyrrolidone was heated at -10±5°C It was added dropwise to the reaction mixture over 60 minutes, and the mixture was stirred at room temperature for 2 hours. Thereafter, 10.0 g of ethanol was added, followed by stirring at room temperature for 1 hour. Next, 6000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was collected by filtration and dissolved in 500 g of tetrahydrofuran. 6000 g of water (poor solvent) was added to the obtained solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (polyimide precursor solid) after stirring was filtered again, and it dried at 45 degreeC under reduced pressure for 3 days. After dissolving 46.6 g of the dried powder in 419.6 g of tetrahydrofuran, 2.3 g of triethylamine was added, followed by stirring at room temperature for 35 minutes. Thereafter, 3000 g of ethanol was added, and the precipitate was collected by filtration. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by Ambertech Limited) were added thereto, and stirred for 4 hours. Thereafter, the ion exchange resin was filtered off, and the obtained polymer solution was added to a mixed solution of 4500 g of heptane and 500 g of ethyl acetate to obtain a precipitate. The precipitate was collected by filtration and dried at 45° C. under reduced pressure for 24 hours to obtain 45.1 g of resin 1 . The structure of the resin 1 is presumed to be a structure represented by the following formula (P-2). As a result of measuring the molecular weight of the resin 1 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000.

〔合成例3～8：環化樹脂的前驅物（樹脂3～樹脂8）的合成〕 適當變更所所使用之化合物，除此以外，以與合成例2相同的方法合成了由下述式（P-3）～式（P-8）中的任一個表示之結構的樹脂3～樹脂8。 樹脂3的Mw為20,000、樹脂4的Mw為20,000、樹脂5的Mw為20,000、樹脂6的Mw為20,000、樹脂7的Mw為20,000、樹脂8的Mw為20,000。 [Synthesis examples 3-8: Synthesis of precursors of cyclized resins (resin 3-resin 8)] Resin 3 to Resin having a structure represented by any of the following formulas (P-3) to (P-8) were synthesized in the same manner as in Synthesis Example 2 except that the compounds used were appropriately changed. 8. The Mw of resin 3 is 20,000, the Mw of resin 4 is 20,000, the Mw of resin 5 is 20,000, the Mw of resin 6 is 20,000, the Mw of resin 7 is 20,000, and the Mw of resin 8 is 20,000.

[化學式59]

Figure 02_image114
[化學式60]
Figure 02_image116
[chemical formula 59]
Figure 02_image114
[chemical formula 60]
Figure 02_image116

〔合成例9：樹脂9的合成〕 在安裝有冷凝器及攪拌機之燒瓶中，去除水分的同時將4,4’-（六氟亞異丙基）二鄰苯二甲酸酐（Tokyo Chemical Industry Co.,Ltd.製）18.0g（40.5毫莫耳）溶解於N-甲基吡咯啶酮（NMP）80.0g中。接著，添加4,4’-二胺基二苯醚（Tokyo Chemical Industry Co.,Ltd.製）7.95g（39.7毫莫耳），在25℃下攪拌3小時，進一步在45℃下攪拌了3小時。接著，添加吡啶12.8g（160毫莫耳）、乙酸酐10.3g（101毫莫耳）、N-甲基吡咯啶酮（NMP）40.0g，在80℃下攪拌3小時，添加N-甲基吡咯啶酮（NMP）50g進行了稀釋。 使該反應液在1升的甲醇中沉澱，以3000rpm的速度攪拌了15分鐘。過濾獲取樹脂，在1升的甲醇中再次攪拌30分鐘並再次進行了過濾。將所獲得之樹脂在減壓下、40℃下乾燥1天而獲得了樹脂9。利用凝膠滲透層析法（標準聚苯乙烯換算）測定樹脂9的分子量之結果，重量平均分子量（Mw）為20,000。推測樹脂9的結構為下述式（P-9）所表示之結構。 [化學式61]

Figure 02_image118
[Synthesis Example 9: Synthesis of Resin 9] In a flask equipped with a condenser and a stirrer, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (Tokyo Chemical Industry Co. ., Ltd.) 18.0 g (40.5 millimoles) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Next, 7.95 g (39.7 mmol) of 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, stirred at 25°C for 3 hours, and further stirred at 45°C for 3 hours. Hour. Next, 12.8 g (160 mmol) of pyridine, 10.3 g (101 mmol) of acetic anhydride, and 40.0 g of N-methylpyrrolidone (NMP) were added, stirred at 80°C for 3 hours, and N-methyl Pyrrolidone (NMP) 50g was diluted. This reaction solution was precipitated in 1 liter of methanol, and stirred at 3000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried under reduced pressure at 40° C. for 1 day to obtain resin 9 . As a result of measuring the molecular weight of the resin 9 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000. The structure of resin 9 is presumed to be represented by the following formula (P-9). [chemical formula 61]
Figure 02_image118

〔合成例10：樹脂10的合成〕 在合成例9中，將4,4’-（六氟亞異丙基）二鄰苯二甲酸酐變更為等莫耳量的4,4’-氧雙鄰苯二甲酸二酐（ODPA），將4,4’-二胺基二苯醚變更為等莫耳量的2,2’-雙（三氟甲基）聯苯胺，除此以外，以與合成例9相同的方法獲得了樹脂10。利用凝膠滲透層析法（標準聚苯乙烯換算）測定樹脂10的分子量之結果，重量平均分子量（Mw）為20,000。推測樹脂10的結構為下述式（P-10）所表示之結構。 [化學式62]

Figure 02_image120
[Synthesis Example 10: Synthesis of Resin 10] In Synthesis Example 9, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride was changed to an equimolar amount of 4,4'-oxybis Phthalic dianhydride (ODPA), by changing 4,4'-diaminodiphenyl ether to an equimolar amount of 2,2'-bis(trifluoromethyl)benzidine, in addition to Resin 10 was obtained in the same manner as in Synthesis Example 9. As a result of measuring the molecular weight of the resin 10 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000. The structure of the resin 10 is presumed to be a structure represented by the following formula (P-10). [chemical formula 62]
Figure 02_image120

＜實施例及比較例＞ 在各實施例中，分別混合下述表中所記載之成分，藉此獲得了各樹脂組成物。又，在各比較例中，分別混合下述表中所記載之成分，藉此獲得了各比較用組成物。 具體而言，將溶劑以外的表中所記載之各成分的含量（配合量）設為表的各欄的“質量份”的欄中所記載之量（質量份）。 溶劑的含量（配合量）使組成物的固體成分濃度成為表中的“固體成分濃度”的值（質量%），各溶劑的含量相對於溶劑的總質量的比率（質量比）成為表中的“比率”的欄中所記載的比率。 利用細孔寬度為0.8μm的聚四氟乙烯製過濾器，對所獲得之樹脂組成物及比較用組成物進行了加壓過濾。 又，在表中，“-”的記載表示組成物不含有相應成分。 ＜Example and Comparative Example＞ In each example, each resin composition was obtained by mixing the components described in the following table|surface, respectively. Moreover, in each comparative example, the components described in the following table|surface were mixed, respectively, and each comparative composition was obtained by this. Specifically, the content (compounding amount) of each component described in the table other than the solvent was the amount (parts by mass) described in the column of "parts by mass" in each column of the table. The solvent content (mixing amount) is such that the solid content concentration of the composition becomes the value (mass %) of the "solid content concentration" in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvent becomes the value (mass %) in the table. The ratio described in the column of "ratio". The obtained resin composition and the composition for comparison were subjected to pressure filtration using a polytetrafluoroethylene filter having a pore width of 0.8 μm. In addition, in the table, description of "-" shows that a composition does not contain a corresponding component.

[表1]    實施例 比較例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 組成 樹脂 種類 樹脂2 樹脂2 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 質量份 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 單體 種類 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 質量份 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 聚合起始劑或 光酸產生劑 種類 I-2 I-2 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 質量份 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 鹼產生劑 種類 A-1 AR-1 A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 A-13 A-14 質量份 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 種類 ― ― ― ― ― ― ― ― ― ― ― ― ― ― ―    質量份 ― ― ― ― ― ― ― ― ― ― ― ― ― ― ―    聚合 抑制劑 種類 B-2 B-2 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 質量份 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 矽烷 偶合劑 種類 C-2 C-2 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 質量份 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 遷移抑制劑 種類 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 質量份 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 添加劑 種類 E-1 E-1    - - - - - - - - - - - -    質量份 2.4 2.4    - - - - - - - - - - - -    種類 E-2 E-2    - - - - - - - - - - - -    質量份 0.9 0.9    - - - - - - - - - - - -    溶劑1 種類 NMP NMP GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL 比率 45 45 40 40 40 40 40 40 40 40 40 40 40 40 40 40 溶劑2 種類 EL EL DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO 比率 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 固體成分濃度 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 過濾器材質 PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE 過濾器孔徑（μm） 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 製程 膜厚（μm） 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB溫度（℃） 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 曝光條件 M M M M M M M M M M M M M M M M 曝光波長（nm） 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 顯影液 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 顯影條件 負 負 負 負 負 負 負 負 負 負 負 負 負 負 負 負 硬化溫度（℃） 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 硬化時間（min） 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 評價 圖案矩形性評價 B D B B B B B C B A A B B B B B 斷裂伸長率評價 B D B B C C C C B A A B B B B B 耐藥品性評價 B D B B C C C C B B B A A B B B [Table 1] Example comparative example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 composition resin type Resin 2 Resin 2 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator type I-2 I-2 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 base generator type A-1 AR-1 A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 A-13 A-14 parts by mass 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - polymerization inhibitor type B-2 B-2 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-2 C-2 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type E-1 E-1 - - - - - - - - - - - - parts by mass 2.4 2.4 - - - - - - - - - - - - type E-2 E-2 - - - - - - - - - - - - parts by mass 0.9 0.9 - - - - - - - - - - - - Solvent 1 type NMP NMP GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 45 45 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Solvent 2 type EL EL DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 filter material PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE Filter Pore Size (μm) 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB temperature (°C) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 exposure conditions m m m m m m m m m m m m m m m m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Developing conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 Evaluation Evaluation of Pattern Rectangularity B D. B B B B B C B A A B B B B B Elongation at break evaluation B D. B B C C C C B A A B B B B B Drug Resistance Evaluation B D. B B C C C C B B B A A B B B

[表2]    實施例 比較例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 組成 樹脂 種類 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 質量份 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 單體 種類 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 質量份 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 聚合起始劑或 光酸產生劑 種類 I-2 I-2 I-2 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 質量份 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 鹼產生劑 種類 A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 A-29 A-30 質量份 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 種類 ― ― ― ― ― ― ― ― ― ― ― ― ― ― ―    質量份 ― ― ― ― ― ― ― ― ― ― ― ― ― ― ―    聚合 抑制劑 種類 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 質量份 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 矽烷 偶合劑 種類 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 質量份 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 遷移抑制劑 種類 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 質量份 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 添加劑 種類 - - - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - - - 種類 - - - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - - - 溶劑1 種類 GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL 比率 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 溶劑2 種類 DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO 比率 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 固體成分濃度 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 過濾器材質 PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE 過濾器孔徑（μm） 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 製程 膜厚（μm） 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB溫度（℃） 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 曝光條件 M M M M M M M M M M M M M M M M 曝光波長（nm） 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 顯影液 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 顯影條件 負 負 負 負 負 負 負 負 負 負 負 負 負 負 負 負 硬化溫度（℃） 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 硬化時間（min） 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 評價 圖案矩形性評價 B B C B B C B B A B B B B B B B 斷裂伸長率評價 B B C B B B B A A B A B B B B B 耐藥品性評價 B C C B B B A A A C B B B B B B [Table 2] Example comparative example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 16 17 18 19 20 twenty one twenty two twenty three twenty four 25 26 27 28 29 30 31 composition resin type Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator type I-2 I-2 I-2 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 base generator type A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 A-29 A-30 parts by mass 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - - type - - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - - Solvent 1 type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Solvent 2 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 filter material PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE Filter Pore Size (μm) 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB temperature (°C) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 exposure conditions m m m m m m m m m m m m m m m m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Developing conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 Evaluation Evaluation of Pattern Rectangularity B B C B B C B B A B B B B B B B Elongation at break evaluation B B C B B B B A A B A B B B B B Drug Resistance Evaluation B C C B B B A A A C B B B B B B

[表3]    實施例 比較例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例   32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47   組成 樹脂 種類 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 30000 10000 質量份 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 單體 種類 M-1 M-1 M-1 M-1 6 6 6 6 6 6 M-1 M-1 M-1 M-1 M-1 M-1 質量份 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 聚合起始劑或 光酸產生劑 種類 I-2 I-2 I-2 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 質量份 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 鹼產生劑 種類 A-31 A-32 AR-33 A-34 A-35 A-36 A-37 A-38 A-39 A-40 A-1 A-1 A-1 A-1 A-1 A-1 質量份 2 2 2 2 2 2 2 2 2 2 1 1 1 1 2 2 種類 ― ― ― ― ― ― ― ― ― ― A-21 AX-1 AX-2 AR-1 ― ― 質量份 ― ― ― ― ― ― ― ― ― ― 1 1 1 1 ― ― 聚合 抑制劑 種類 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 質量份 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 矽烷 偶合劑 種類 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 質量份 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 遷移抑制劑 種類 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 質量份 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 添加劑 種類          - - - - - - - - - - - -    質量份          - - - - - - - - - - - -    種類          - - - - - - - - - - - -    質量份          - - - - - - - - - - - -    溶劑1 種類 GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL 比率 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 溶劑2 種類 DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO 比率 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 固體成分濃度 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42   過濾器材質 PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE   過濾器孔徑（μm） 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8   製程 膜厚（μm） 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20   PB溫度（℃） 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100   曝光條件 M M M M M M M M M M M M M M M M   曝光波長（nm） 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365   顯影液 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮   顯影條件 負 負 負 負 負 負 負 負 負 負 負 負 負 負 負 負   硬化溫度（℃） 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230   硬化時間（min） 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180   評價 圖案矩形性評價 C C C C A A B B A A B C B C B B   斷裂伸長率評價 C C C C A A C C A A B B B C B B   耐藥品性評價 C C C C B B B B B B A B B C B B   [table 3] Example comparative example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 composition resin type Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 30000 10000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 6 6 6 6 6 6 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator type I-2 I-2 I-2 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 base generator type A-31 A-32 AR-33 A-34 A-35 A-36 A-37 A-38 A-39 A-40 A-1 A-1 A-1 A-1 A-1 A-1 parts by mass 2 2 2 2 2 2 2 2 2 2 1 1 1 1 2 2 type - - - - - - - - - - A-21 AX-1 AX-2 AR-1 - - parts by mass - - - - - - - - - - 1 1 1 1 - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - - parts by mass - - - - - - - - - - - - type - - - - - - - - - - - - parts by mass - - - - - - - - - - - - Solvent 1 type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Solvent 2 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 filter material PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE Filter Pore Size (μm) 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB temperature (°C) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 exposure conditions m m m m m m m m m m m m m m m m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Developing conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 Evaluation Evaluation of Pattern Rectangularity C C C C A A B B A A B C B C B B Elongation at break evaluation C C C C A A C C A A B B B C B B Drug Resistance Evaluation C C C C B B B B B B A B B C B B

[表4]    實施例 比較例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 組成 樹脂 種類 樹脂1 樹脂3 樹脂4 樹脂5 樹脂6 樹脂7 樹脂8 樹脂9 樹脂10 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 Mw 5000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 質量份 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 單體 種類 M-1 M-1 M-1 ― M-1 ― M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 質量份 6 6 6 ― 6 ― 6 6 6 6 6 6 12 2 6 6 聚合起始劑或 光酸產生劑 種類 I-1 I-1 I-1 I-3 I-1 I-4 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 質量份 1.1 1.1 1.1 2 1.1 2 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 2.2 3.5 鹼產生劑 種類 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-1 A-1 A-1 A-1 質量份 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 種類 ― ― ― ― ― ― ― ― ― ― ― ― ― ― ―    質量份 ― ― ― ― ― ― ― ― ― ― ― ― ― ― ―    聚合 抑制劑 種類 B-1 B-1 B-1 ― B-1 ― B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 質量份 0.1 0.1 0.1 ― 0.1 ― 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 矽烷 偶合劑 種類 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 質量份 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 遷移抑制劑 種類 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 質量份 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 添加劑 種類 - - - - - - - E-3 E-3 - - - - - -    質量份 - - - - - - - 6 6 - - - - - -    種類 - - - - - - - - - - - - - - -    質量份 - - - - - - - - - - - - - - -    溶劑1 種類 GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL 比率 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 溶劑2 種類 DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO 比率 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 固體成分濃度 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 過濾器材質 PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE 過濾器孔徑（μm） 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 製程 膜厚（μm） 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB溫度（℃） 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 曝光條件 M M M M M M M M M M M M M M M M 曝光波長（nm） 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 顯影液 環戊酮 環戊酮 環戊酮 TMAH 水溶液 環戊酮 TMAH 水溶液 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 顯影條件 負 負 負 正 負 正 負 負 負 負 負 負 負 負 負 負 硬化溫度（℃） 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 硬化時間（min） 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 評價 圖案矩形性評價 C B B C B C B A A B B B B B B B 斷裂伸長率評價 C B B C B C B A A B B B C A B C 耐藥品性評價 C B B C B C B A A B B B A C B A [Table 4] Example comparative example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 composition resin type Resin 1 Resin 3 Resin 4 Resin 5 Resin 6 Resin 7 Resin 8 Resin 9 Resin 10 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 mw 5000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 - M-1 - M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 - 6 - 6 6 6 6 6 6 12 2 6 6 Polymerization initiator or photoacid generator type I-1 I-1 I-1 I-3 I-1 I-4 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 2 1.1 2 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 2.2 3.5 base generator type 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-1 A-1 A-1 A-1 parts by mass 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 - B-1 - B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 - 0.1 - 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - E-3 E-3 - - - - - - parts by mass - - - - - - - 6 6 - - - - - - type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - Solvent 1 type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Solvent 2 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 filter material PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE Filter Pore Size (μm) 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB temperature (°C) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 exposure conditions m m m m m m m m m m m m m m m m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Developer Cyclopentanone Cyclopentanone Cyclopentanone TMAH aqueous solution Cyclopentanone TMAH aqueous solution Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Developing conditions burden burden burden just burden just burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 Evaluation Evaluation of Pattern Rectangularity C B B C B C B A A B B B B B B B Elongation at break evaluation C B B C B C B A A B B B C A B C Drug Resistance Evaluation C B B C B C B A A B B B A C B A

[表5]    實施例 比較例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 組成 樹脂 種類 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 質量份 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 單體 種類 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 質量份 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 聚合起始劑或 光酸產生劑 種類 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 質量份 0.5 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 鹼產生劑 種類 A-1 A-1 A-1 A-1 A-23 A-1 A-1 A-1 A-1 A-23 A-1 A-1 A-1 A-23 A-1 A-23 質量份 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 種類 ― ― ― ― ― ― ― ― ― ― ― ― ― ― ―    質量份 ― ― ― ― ― ― ― ― ― ― ― ― ― ― ―    聚合 抑制劑 種類 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 ― ― 質量份 0.1 0.05 0.3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 ― ― 矽烷 偶合劑 種類 C-1 C-1 C-1 ― ― C-1 C-1 C-3 C-1 C-1 C-1 C-1 ― ― ― ― 質量份 1 1 1 ― ― 0.5 2 1 1 1 1 1 ― ― ― ― 遷移抑制劑 種類 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 ― ― D-1 D-1 ― ― ― ― 質量份 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 ― ― 0.1 0.3 ― ― ― ― 添加劑 種類 - - - - - - - - - - - - - - -    質量份 - - - - - - - - - - - - - - -    種類 - - - - - - - - - - - - - - -    質量份 - - - - - - - - - - - - -aa - -    溶劑1 種類 GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL 比率 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 溶劑2 種類 DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO 比率 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 固體成分濃度 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 過濾器材質 PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE 過濾器孔徑（μm） 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 製程 膜厚（μm） 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB溫度（℃） 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 曝光條件 M M M M M M M M M M M M M M M M 曝光波長（nm） 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 顯影液 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 顯影條件 負 負 負 負 負 負 負 負 負 負 負 負 負 負 負 負 硬化溫度（℃） 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 硬化時間（min） 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 評價 圖案矩形性評價 B B B B A B B B B A B B B A B A 斷裂伸長率評價 A B B B A B B B B A B B B A B A 耐藥品性評價 C B B B A B B B B A B B B A B A [table 5] Example comparative example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 composition resin type Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 0.5 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 base generator type A-1 A-1 A-1 A-1 A-23 A-1 A-1 A-1 A-1 A-23 A-1 A-1 A-1 A-23 A-1 A-23 parts by mass 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 - - parts by mass 0.1 0.05 0.3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 - - Silane coupling agent type C-1 C-1 C-1 - - C-1 C-1 C-3 C-1 C-1 C-1 C-1 - - - - parts by mass 1 1 1 - - 0.5 2 1 1 1 1 1 - - - - migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 - - D-1 D-1 - - - - parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 - - 0.1 0.3 - - - - additive type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - -aa - - Solvent 1 type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Solvent 2 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 filter material PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE Filter Pore Size (μm) 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB temperature (°C) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 exposure conditions m m m m m m m m m m m m m m m m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Developing conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 Evaluation Evaluation of Pattern Rectangularity B B B B A B B B B A B B B A B A Elongation at break evaluation A B B B A B B B B A B B B A B A Drug Resistance Evaluation C B B B A B B B B A B B B A B A

[表6]    實施例 比較例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 80 81 82 83 84 85 86 87 88 89 90 91 92 組成 樹脂 種類 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 質量份 35 35 35 35 35 35 35 35 35 35 35 35 35 單體 種類 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 質量份 6 6 6 6 6 6 6 6 6 6 6 6 6 聚合起始劑或 光酸產生劑 種類 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-5 I-5 I-1 質量份 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 2 2 1.1 鹼產生劑 種類 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-23 A-1 質量份 2 2 2 2 2 2 2 2 2 2 2 2 2 種類 ― ― ― ― ― ― ― ― ― ― ― ― ― 質量份 ― ― ― ― ― ― ― ― ― ― ― ― ― 聚合 抑制劑 種類 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 質量份 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 矽烷 偶合劑 種類 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 質量份 1 1 1 1 1 1 1 1 1 1 1 1 1 遷移抑制劑 種類 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 質量份 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 添加劑 種類 - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - 種類 - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - 溶劑1 種類 GBL NMP NMP GBL NMP GBL GBL GBL GBL GBL GBL GBL GBL 比率 10 45 10 40 40 40 40 40 40 40 40 40 40 溶劑2 種類 DMSO EL EL EL DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO 比率 40 10 45 10 10 10 10 10 10 10 10 10 10 固體成分濃度 42 42 42 42 42 50 35 42 42 42 42 42 42 過濾器材質 PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE 過濾器孔徑（μm） 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 製程 膜厚（μm） 20 20 20 20 20 30 10 20 20 20 20 20 20 PB溫度（℃） 100 100 100 100 100 100 100 100 100 100 100 100 100 曝光條件 M M M M M M M M M M D D M 曝光波長（nm） 365 365 365 365 365 365 365 365 365 365 405 405 365 顯影液 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 顯影條件 負 負 負 負 負 負 負 負 負 負 負 負 負 硬化溫度（℃） 230 230 230 230 230 230 230 200 180 160 230 230 IR 硬化時間（min） 180 180 180 180 180 180 180 120 120 120 180 180 180 評價 圖案矩形性評價 B B B B B C A B B C B A B 斷裂伸長率評價 B B B B B B A B B C B A B 耐藥品性評價 B B B B B B A B B C B A B [Table 6] Example comparative example Example Example Example Example Example Example Example Example Example Example Example 80 81 82 83 84 85 86 87 88 89 90 91 92 composition resin type Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-5 I-5 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 2 2 1.1 base generator type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-23 A-1 parts by mass 2 2 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - type - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - Solvent 1 type GBL NMP NMP GBL NMP GBL GBL GBL GBL GBL GBL GBL GBL ratio 10 45 10 40 40 40 40 40 40 40 40 40 40 Solvent 2 type DMSO EL EL EL DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 40 10 45 10 10 10 10 10 10 10 10 10 10 Solid content concentration 42 42 42 42 42 50 35 42 42 42 42 42 42 filter material PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE Filter Pore Size (μm) 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Process Film thickness (μm) 20 20 20 20 20 30 10 20 20 20 20 20 20 PB temperature (°C) 100 100 100 100 100 100 100 100 100 100 100 100 100 exposure conditions m m m m m m m m m m D. D. m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 405 405 365 Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Developing conditions burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 200 180 160 230 230 IR Hardening time (min) 180 180 180 180 180 180 180 120 120 120 180 180 180 Evaluation Evaluation of Pattern Rectangularity B B B B B C A B B C B A B Elongation at break evaluation B B B B B B A B B C B A B Drug Resistance Evaluation B B B B B B A B B C B A B

表中所記載之各成分的詳細內容如下。The details of each component described in the table are as follows.

〔樹脂〕 ・樹脂1～樹脂10：藉由上述合成例獲得之樹脂1～樹脂10 [resin] ・Resin 1 to Resin 10: Resin 1 to Resin 10 obtained in the above synthesis example

〔單體（聚合性化合物）〕 ・M-1：下述結構的化合物、括號的角標表示重複數。 [化學式63]

Figure 02_image122
[Monomers (polymerizable compounds)] ・M-1: Compounds with the following structures, and the subscripts in parentheses indicate the number of repetitions. [chemical formula 63]
Figure 02_image122

〔聚合起始劑或光酸產生劑〕 ・I-1～I-5：下述結構的化合物 [化學式64]

Figure 02_image124
[Polymerization initiator or photoacid generator] ・I-1 to I-5: Compounds with the following structures [Chemical formula 64]
Figure 02_image124

〔鹼產生劑〕 ・A-1～A-34：下述結構的化合物。A-1～A-34均為對應於上述特定鹼產生劑之化合物。 ・AX-1～AX-2：下述結構的化合物。AX-1～AX-2為不與上述特定鹼產生劑對應的化合物。 ・AR-1：下述結構的化合物AR-1為不與上述特定鹼產生劑對應的化合物。 [化學式65]

Figure 02_image126
[化學式66]
Figure 02_image128
[化學式67]
Figure 02_image130
[Base generators] - A-1 to A-34: Compounds of the following structures. All of A-1 to A-34 are compounds corresponding to the above-mentioned specific base generator.・AX-1 to AX-2: Compounds of the following structures. AX-1 to AX-2 are compounds that do not correspond to the above-mentioned specific base generator.・AR-1: Compound AR-1 having the following structure is a compound that does not correspond to the above-mentioned specific base generator. [chemical formula 65]
Figure 02_image126
[chemical formula 66]
Figure 02_image128
[chemical formula 67]
Figure 02_image130

〔合成例〕 -A-35的合成- [化學式68]

Figure 02_image132
將肌胺酸18.0g在乙腈396g中進行了攪拌。向其中添加了三乙胺30.7g、3,4-二氫香豆素15.0g。將反應液在水浴中加熱至80℃，並攪拌了5個半小時。然後，將反應液進行濾過從而去除固體不溶物，並將濾液在加熱減壓下進行濃縮從而獲得了粗生成物。將粗生成物用二氯甲烷250g進行溶解之後，在1N（1mol/L）HCl水溶液120mL中清洗3次，然後在水150mL中清洗1次，用硫酸鈉進行乾燥，並將濾液在加熱減壓下進行濃縮，從而獲得了化合物A-35-I1 23.5g（產率98%）。以下示出 1H-NMR數據。 1H-NMR，400MHz，δ（（DMSO-d6）ppm：2.42-2.59（2H,m），2.69-2.75（2H,m），2.83（1H,s）,2.99（2H,s），3.99（1.3H,s）,4.11（0.7H,s），6.67-6.72（1H,m）,6.75-6.79（1H,m）,6.97-7.10（2H,m）,9.36（1H,bs）,12.68（1H,bs）。 將A-35-I1 7.2g在二氯甲烷202g中進行了攪拌。向其中添加4-甲基胺基吡啶（DMAP）0.7g、（S）-（-）-縮水甘油4.5g，並將溶液在水浴中冷卻至0～5℃。向其中緩慢添加1-（3-二甲基胺基丙基）-3-乙基碳二亞胺鹽酸鹽（WSC）6.4g，然後將反應液升溫至室溫。在室溫下攪拌6小時之後，添加水200mL並進一步攪拌15分鐘。取出有機層之後，在水200mL中清洗2次，在飽和碳酸氫鈉水溶液200mL中清洗1次，並在水200mL中清洗了1次。用硫酸鈉進行乾燥，並將濾液在加熱減壓下進行濃縮，從而獲得了粗生成物13.5g。矽膠層析（展開溶劑：己烷/乙酸乙酯=1/1（體積比）→1/2（體積比））。關於目標物，藉由用己烷/乙酸乙酯=1/1（Rf=0.13）純化，獲得了6.3g的目標物A-35（無色油狀）（產率70%）。以下示出 1H-NMR數據。 1H-NMR，400MHz，δ（（DMSO-d6）ppm：2.44-2.61（2H,m），2.62-2.66（1H,m），2.68-2.74（2H,m），2.77-2.80（1H,m）、2.83（1H,s）、3.02（2H,s）、3.18-3.22（1H,m）、3.87-3.93（1H,m）、4.12（1.4H,s）、4.30（0.6H,s）、4.42（0.7H,dd,J=12,4）、4.47（0.3H,dd,J=12,4）、6.67-6.72（1H,m）、6.74-6.78（1H,m）、6.97-7.10（2H,m）、9.33（0.3H,bs）、9.35（0.7H,bs）. [Synthesis Example] -Synthesis of A-35- [Chemical Formula 68]
Figure 02_image132
18.0 g of sarcosine was stirred in 396 g of acetonitrile. 30.7 g of triethylamine and 15.0 g of 3,4-dihydrocoumarin were added thereto. The reaction solution was heated to 80° C. in a water bath and stirred for 5.5 hours. Then, the reaction liquid was filtered to remove solid insoluble matter, and the filtrate was concentrated under heating and reduced pressure to obtain a crude product. The crude product was dissolved in 250 g of dichloromethane, washed three times in 120 mL of 1N (1 mol/L) HCl aqueous solution, then washed once in 150 mL of water, dried with sodium sulfate, and the filtrate was heated and reduced pressure Concentration was carried out under , thereby obtaining 23.5 g of compound A-35-I1 (yield 98%). 1 H-NMR data are shown below. 1 H-NMR, 400 MHz, δ((DMSO-d6) ppm: 2.42-2.59 (2H, m), 2.69-2.75 (2H, m), 2.83 (1H, s), 2.99 (2H, s), 3.99 ( 1.3H, s), 4.11 (0.7H, s), 6.67-6.72 (1H, m), 6.75-6.79 (1H, m), 6.97-7.10 (2H, m), 9.36 (1H, bs), 12.68 ( 1H, bs). 7.2 g of A-35-I1 was stirred in 202 g of methylene chloride. 0.7 g of 4-methylaminopyridine (DMAP), 4.5 g of (S)-(-)-glycidol g, and the solution was cooled to 0-5°C in a water bath. 6.4 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (WSC) was slowly added thereto, Then the reaction solution was warmed up to room temperature. After stirring at room temperature for 6 hours, 200 mL of water was added and further stirred for 15 minutes. After the organic layer was taken out, it was washed twice in 200 mL of water and washed for 1 time in 200 mL of saturated aqueous sodium bicarbonate solution. and washed once in 200 mL of water. Drying was carried out with sodium sulfate, and the filtrate was concentrated under reduced pressure under heating to obtain 13.5 g of a crude product. Silica gel chromatography (developing solvent: hexane/ethyl acetate Esters = 1/1 (volume ratio) → 1/2 (volume ratio)). Regarding the target substance, 6.3 g of the target substance was obtained by purification with hexane/ethyl acetate = 1/1 (Rf = 0.13) A-35 (colorless oil) (70% yield). 1 H-NMR data are shown below. 1 H-NMR, 400 MHz, δ((DMSO-d6)ppm: 2.44-2.61 (2H, m), 2.62 -2.66 (1H, m), 2.68-2.74 (2H, m), 2.77-2.80 (1H, m), 2.83 (1H, s), 3.02 (2H, s), 3.18-3.22 (1H, m), 3.87 -3.93 (1H, m), 4.12 (1.4H, s), 4.30 (0.6H, s), 4.42 (0.7H, dd, J=12,4), 4.47 (0.3H, dd, J=12,4 ), 6.67-6.72 (1H, m), 6.74-6.78 (1H, m), 6.97-7.10 (2H, m), 9.33 (0.3H, bs), 9.35 (0.7H, bs).

-A-36的合成- [化學式69]

Figure 02_image134
將L-脯胺酸23.3g在乙腈396g中進行了攪拌。向其中添加了三乙胺30.7g、3,4-二氫香豆素15.0g。將反應液在水浴中加熱至80℃，並攪拌了5個半小時。然後，將反應液進行濾過從而去除固體不溶物，並將濾液在加熱減壓下進行濃縮從而獲得了粗生成物。將粗生成物用二氯甲烷250g進行溶解之後，在1N（1mol/L）HCl水溶液120mL中清洗3次，然後在水150mL中清洗1次，用硫酸鈉進行乾燥，並將濾液在加熱減壓下進行濃縮，從而獲得了化合物A-36-I1 26.5g（產率99%）。以下示出 1H-NMR數據。 1H-NMR，400MHz，δ（（DMSO-d6）ppm：1.67-2.28（4H,m）,2.45-2.58（2H,m）,2.66-2.80（2H,m）,3.33-3.53（2H,m）,4.21-4.24（0.7H,m）,4.40-4.43（0.3H,m）,6.67-6.72（1H,m）,6.75-6.79（1H,m）,6.97-7.09（2H,m）,9.37（1H,bs）,12.53（1H,bs）。 將A-36-I1 19.7g在二氯甲烷252g中進行了攪拌。向其中添加4-甲基胺基吡啶0.9g、（S）-（-）-縮水甘油5.6g，並將溶液在水浴中冷卻至0～5℃。向其中緩慢添加1-（3-二甲基胺基丙基）-3-乙基碳二亞胺鹽酸鹽（WSC）8.0g，然後將反應液升溫至室溫。在室溫下攪拌3小時之後，添加水200mL並進一步攪拌15分鐘。取出有機層之後，在水200mL中清洗2次，在飽和碳酸氫鈉水溶液200mL中清洗1次，並在水200mL中清洗了1次。用硫酸鈉進行乾燥，並將濾液在加熱減壓下進行濃縮，從而獲得了粗生成物23.2g。矽膠層析（展開溶劑：己烷/乙酸乙酯=1/1（體積比）→1/2（體積比））。關於目標物，藉由用己烷/乙酸乙酯=1/1（Rf=0.13）純化，獲得了8.7g的目標物A-36（無色油狀）（產率72%）。以下示出 1H-NMR數據。 1H-NMR，400MHz，δ（（DMSO-d6）ppm：1.67-2.28（4H,m）、2.44-2.78（6H,m）、3.15-3.20（1H,m）、3.36-3.56（2H,m）、3.88-3.94（1H,m）、4.31（0.8H,dd,J=8,4）、4.40（0.8H,dd,J=12,4）、4.46（0.2H,dd,J=12,4）、4.61（0.2H,dd,J=8,4）、6.66-6.72（1H,m）、6.74-6.78（1H,m）、6.97-7.09（2H,m）、9.33（0.2H,bs）、9.35（0.8H,bs）。 -Synthesis of A-36- [Chemical Formula 69]
Figure 02_image134
23.3 g of L-proline was stirred in 396 g of acetonitrile. 30.7 g of triethylamine and 15.0 g of 3,4-dihydrocoumarin were added thereto. The reaction solution was heated to 80° C. in a water bath and stirred for 5.5 hours. Then, the reaction liquid was filtered to remove solid insoluble matter, and the filtrate was concentrated under heating and reduced pressure to obtain a crude product. The crude product was dissolved in 250 g of dichloromethane, washed three times in 120 mL of 1N (1 mol/L) HCl aqueous solution, then washed once in 150 mL of water, dried with sodium sulfate, and the filtrate was heated and reduced pressure Concentration was carried out under , thereby obtaining 26.5 g of compound A-36-I1 (yield 99%). 1 H-NMR data are shown below. 1 H-NMR, 400 MHz, δ((DMSO-d6) ppm: 1.67-2.28 (4H, m), 2.45-2.58 (2H, m), 2.66-2.80 (2H, m), 3.33-3.53 (2H, m ), 4.21-4.24 (0.7H, m), 4.40-4.43 (0.3H, m), 6.67-6.72 (1H, m), 6.75-6.79 (1H, m), 6.97-7.09 (2H, m), 9.37 (1H, bs), 12.53 (1H, bs). 19.7 g of A-36-I1 was stirred in 252 g of methylene chloride. 0.9 g of 4-methylaminopyridine, (S)-(- )-glycidol 5.6g, and the solution was cooled to 0~5°C in a water bath. Slowly added 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride ( WSC) 8.0g, and then the reaction solution was warmed to room temperature. After stirring at room temperature for 3 hours, 200mL of water was added and further stirred for 15 minutes. After the organic layer was taken out, it was washed twice in 200mL of water, and in saturated sodium bicarbonate Wash once in 200 mL of aqueous solution and once in 200 mL of water. Dry over sodium sulfate, and concentrate the filtrate under heating and reduced pressure to obtain 23.2 g of a crude product. Silica gel chromatography (developing solvent: Hexane/ethyl acetate=1/1 (volume ratio) → 1/2 (volume ratio)). Regarding the target substance, by purifying with hexane/ethyl acetate=1/1 (Rf=0.13), obtained 8.7 g of the target substance A-36 (colorless oil) (72% yield). 1 H-NMR data are shown below. 1 H-NMR, 400 MHz, δ((DMSO-d6)ppm: 1.67-2.28 (4H ,m), 2.44-2.78 (6H,m), 3.15-3.20 (1H,m), 3.36-3.56 (2H,m), 3.88-3.94 (1H,m), 4.31 (0.8H,dd,J=8 ,4), 4.40 (0.8H, dd, J=12,4), 4.46 (0.2H, dd, J=12,4), 4.61 (0.2H, dd, J=8,4), 6.66-6.72 ( 1H, m), 6.74-6.78 (1H, m), 6.97-7.09 (2H, m), 9.33 (0.2H, bs), 9.35 (0.8H, bs).

〔聚合抑制劑〕 ・B-1～B-2：下述結構的化合物 [化學式70]

Figure 02_image136
[Polymerization inhibitors] ・B-1 to B-2: Compounds of the following structure [Chemical formula 70]
Figure 02_image136

〔矽烷偶合劑（金屬接著性改良劑）〕 ・C-1～C-2：下述結構的化合物下述式中，Et表示乙基。 [化學式71]

Figure 02_image138
[Silane Coupling Agent (Metal Adhesion Improver)] ・C-1 to C-2: Compounds of the following structures In the following formulae, Et represents an ethyl group. [chemical formula 71]
Figure 02_image138

〔遷移抑制劑〕 ・D-1：下述結構的化合物 [化學式72]

Figure 02_image140
[Migration inhibitor] ・D-1: Compound of the following structure [Chemical formula 72]
Figure 02_image140

〔添加劑〕 ・E-1～E-3：下述結構的化合物 [化學式73]

Figure 02_image142
[Additives] ・E-1 to E-3: Compounds of the following structure [Chemical formula 73]
Figure 02_image142

〔溶劑〕 ・NMP：N-甲基-2-吡咯啶酮 ・EL：乳酸乙酯 ・DMSO：二甲基亞碸 ・GBL：γ-丁內酯 〔Solvent〕 ・NMP: N-methyl-2-pyrrolidone ・EL: ethyl lactate ・DMSO: Dimethylsulfone ・GBL: γ-butyrolactone

＜評價＞ 〔圖案矩形性評價〕 在各實施例及比較例中，藉由旋塗法，分別將各樹脂組成物或比較用組成物以層狀適用（塗佈）於矽晶圓上，藉此形成了樹脂組成物膜。 在各實施例及比較例中，將適用了所獲得之樹脂組成物膜之矽晶圓在加熱板上，以100℃乾燥3分鐘，藉此在矽晶圓上形成了表的“膜厚（μm）”的欄中所記載之厚度，且厚度均勻的樹脂膜。 在曝光條件中記載為“M”之例子中，使用表的“曝光波長（nm）”的欄中所記載之曝光波長，以500mJ/cm 2的曝光能量對矽晶圓上的樹脂膜進行了曝光。隔著遮罩（圖案為1:1線與空間，線寬為10μm的二元遮罩）進行了曝光。 在曝光條件中記載為“D”的例子中，使用直接曝光裝置（ADTEC DE-6UH III）進行了曝光。關於曝光，在波長405nm處，進行了雷射直接成像曝光，以使曝光部成為寬度10μm的1:1線與空間圖案中的線部。將曝光量設為500mJ/cm 2。 上述曝光後，在正顯影的例子（在“顯影條件”的欄中記載為“正”之例子）中，使用表的“顯影液”的欄中所記載之顯影液進行60秒顯影，用純水沖洗20秒，藉此獲得了曝光後的樹脂膜的線與空間圖案。表中的“TMAH水溶液”的記載係指2.5質量%氫氧化四甲基銨水溶液。在負顯影的例子（在“顯影條件”的欄中記載為“負”之例子）中，使用表的“顯影液”的欄中所記載之顯影液進行60秒顯影，用丙二醇單甲醚乙酸酯（PGMEA）沖洗20秒，藉此獲得了樹脂膜的線與空間圖案。 針對所獲得之形成有線與空間圖案之矽晶圓，以垂直於線與空間圖案的方式切割矽晶圓，使圖案剖面露出。利用光學顯微鏡，以200倍的倍率觀察上述線與空間圖案的圖案剖面，進行了圖案的剖面形狀的評價。 具體而言，在各實施例及比較例中，分別測定矽晶圓的表面（基板表面）與硬化膜的側面所成的錐角，按照下述評價基準進行了評價。評價結果記載於表中的“圖案矩形性評價”的欄中。可以說錐角不大於90°且圖案的剖面形狀不是沙漏形狀，錐角愈接近90°，圖案形狀愈優異。 -評價基準- A：錐角為85°以上且90°以下。 B：錐角為80°以上且小於85°。 C：錐角為75°以上且小於80°。 D：錐角小於75°、圖案的剖面形狀為形成大於90°的錐角之倒錐形狀或圖案的剖面形狀為沙漏形狀。 <Evaluation> [Evaluation of Pattern Rectangularity] In each example and comparative example, each resin composition or comparative composition was applied (coated) in a layer on a silicon wafer by the spin coating method. This forms a resin composition film. In each example and comparative example, the silicon wafer to which the obtained resin composition film was applied was dried on a hot plate at 100° C. for 3 minutes, thereby forming a “film thickness ( μm)” and a resin film with a uniform thickness. In the example described as "M" in the exposure condition, the resin film on the silicon wafer was exposed to the exposure energy of 500mJ/ cm2 using the exposure wavelength described in the "Exposure wavelength (nm)" column of the table. exposure. Exposure was performed through a mask (a binary mask with a pattern of 1:1 line-space and a line width of 10 μm). In the example described as "D" in the exposure condition, exposure was performed using a direct exposure device (ADTEC DE-6UH III). Regarding exposure, laser direct imaging exposure was performed at a wavelength of 405 nm so that the exposed portion became a line portion in a 1:1 line-and-space pattern with a width of 10 μm. The exposure amount was set to 500 mJ/cm 2 . After the above-mentioned exposure, in the case of positive development (the example described as "positive" in the column of "development conditions"), development was carried out for 60 seconds using the developer described in the column of "developing solution" in the table, with pure Water was rinsed for 20 seconds, whereby a line and space pattern of the exposed resin film was obtained. The description of "TMAH aqueous solution" in the table means a 2.5% by mass tetramethylammonium hydroxide aqueous solution. In the case of negative development (the example described as "Negative" in the "Development Conditions" column), develop for 60 seconds using the developer described in the "Developer" column of the table, and use propylene glycol monomethyl ether Ester (PGMEA) was rinsed for 20 seconds, whereby a line and space pattern of the resin film was obtained. For the obtained silicon wafer formed with the line and space pattern, the silicon wafer is cut perpendicular to the line and space pattern, so that the pattern section is exposed. The pattern cross-section of the line and space pattern was observed at a magnification of 200 times with an optical microscope, and the cross-sectional shape of the pattern was evaluated. Specifically, in each of the Examples and Comparative Examples, the taper angle formed by the surface of the silicon wafer (substrate surface) and the side surface of the cured film was measured, and evaluated according to the following evaluation criteria. The evaluation results are described in the column of "pattern squareness evaluation" in the table. It can be said that the taper angle is not greater than 90° and the cross-sectional shape of the pattern is not an hourglass shape, and the closer the taper angle is to 90°, the better the pattern shape. -Evaluation Criteria- A: The taper angle is not less than 85° and not more than 90°. B: The taper angle is 80° or more and less than 85°. C: The taper angle is 75° or more and less than 80°. D: The taper angle is less than 75°, the cross-sectional shape of the pattern is an inverted cone shape forming a taper angle larger than 90°, or the cross-sectional shape of the pattern is an hourglass shape.

〔斷裂伸長率的評價〕 藉由旋塗法，將在各實施例及各比較例中製備之樹脂組成物或比較用組成物分別適用於矽晶圓上，形成了樹脂層。 將所獲得之形成有樹脂層之矽晶圓在加熱板上以100℃乾燥5分鐘，在矽晶圓上獲得了表的“膜厚（μm）”的欄中所記載之厚度且厚度均勻的樹脂組成物層。 在下述表中的顯影條件的欄中記載為“負”的例子中，以500mJ/cm 2的曝光能量對矽晶圓上的樹脂組成物層的整面進行了曝光。曝光波長記載於表中的“曝光波長（nm）”。在表中的顯影條件的欄中記載為“正”的例子中，未進行曝光。 在曝光條件的欄中記載為“M”的例子中，作為光源，使用步進機進行了曝光。 曝光條件的欄中記載為“D”的例子中，作為光源，使用直接曝光裝置（ADTEC DE-6UH III）進行了曝光。 在“硬化溫度（℃）”的欄中記載有數值之例子中，使用加熱板，在氮氣環境下，以10℃/分鐘的升溫速度對上述曝光後的樹脂組成物層進行升溫，達到表的“硬化溫度（℃）”的欄中所記載之溫度之後，在表的“硬化時間（min）”內維持了上述溫度。 在“硬化溫度（℃）”的欄中記載為“IR”的例子中，使用紅外線燈加熱裝置（ADVANCE RIKO,Inc.製RTP-6），在氮氣環境下，以10℃/分鐘的升溫速度對各實施例中獲得之樹脂膜進行升溫，達到230℃之後，在表的“硬化時間（min）”內維持了上述溫度。 將硬化後的樹脂組成物層（硬化物）浸漬於4.9質量%氫氟酸水溶液中，從矽晶圓剝離了硬化物。用沖裁機沖裁所剝離的硬化物來製作了試樣寬度3mm、試樣長度30mm的試驗片。利用拉伸試驗機（TENSILON），在十字頭速度300mm/分鐘、25℃、65%RH（相對濕度）的環境下，遵照JIS-K6251，測定了所獲得之試驗片的長度方向的伸長率。測定各實施5次，並將5次測定中的試驗片斷裂時的伸長率（斷裂伸長率）的算術平均值用作指標值。 按照下述評價基準進行評價，將評價結果記載於表的“斷裂伸長率評價”的欄中。可以說指標值愈大，硬化物的膜強度愈優異。 -評價基準- A：上述指標值為65%以上。 B：上述指標值為60%以上且小於65%。 C：上述指標值為55%以上且小於60%。 D：上述指標值小於55%。 [Evaluation of Elongation at Break] The resin composition or comparative composition prepared in each of Examples and Comparative Examples was applied to a silicon wafer by spin coating, respectively, to form a resin layer. The obtained silicon wafer with the resin layer formed thereon was dried on a hot plate at 100°C for 5 minutes, and the thickness described in the column of "film thickness (μm)" in the table was obtained on the silicon wafer, and the thickness was uniform. resin composition layer. In the example described as "negative" in the column of developing conditions in the following table, the entire surface of the resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ/cm 2 . The exposure wavelength is described in "Exposure wavelength (nm)" in the table. In the example described as "positive" in the column of the image development condition in a table|surface, exposure was not performed. In the example described as "M" in the column of exposure conditions, exposure was performed using a stepper as a light source. In the example described as "D" in the column of exposure conditions, exposure was performed using a direct exposure device (ADTEC DE-6UH III) as a light source. In the example where the numerical value is described in the column of "curing temperature (°C)", the temperature of the above-mentioned exposed resin composition layer was raised at a rate of 10°C/min in a nitrogen atmosphere using a hot plate to reach the temperature indicated in the table. After the temperature described in the column of "curing temperature (°C)", the temperature was maintained for the "curing time (min)" in the table. In the example described as "IR" in the column of "curing temperature (°C)", an infrared lamp heating device (RTP-6 manufactured by ADVANCE RIKO, Inc.) was used in a nitrogen atmosphere at a heating rate of 10°C/min. The temperature of the resin film obtained in each example was raised to 230° C., and the above-mentioned temperature was maintained within the “hardening time (min)” in the table. The cured resin composition layer (cured product) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and the cured product was peeled off from the silicon wafer. The peeled cured product was punched out with a punching machine to prepare a test piece having a sample width of 3 mm and a sample length of 30 mm. The elongation in the longitudinal direction of the obtained test piece was measured in accordance with JIS-K6251 in an environment with a crosshead speed of 300 mm/min, 25° C., and 65% RH (relative humidity) using a tensile testing machine (TENSILON). The measurement was performed five times, and the arithmetic mean value of the elongation (elongation at break) of the test piece at breakage in the five measurements was used as an index value. Evaluation was performed according to the following evaluation criteria, and the evaluation results were described in the column of "elongation at break evaluation" in the table. It can be said that the larger the index value, the better the film strength of the cured product. -Evaluation criteria- A: The above index value is 65% or more. B: The above index value is more than 60% and less than 65%. C: The above index value is more than 55% and less than 60%. D: The above index value is less than 55%.

〔耐藥品性的評價〕 藉由旋塗法，將在各實施例或比較例中製備之樹脂組成物或比較用組成物塗佈於矽晶圓上。上述矽晶圓在加熱板上以100℃乾燥5分鐘，在矽晶圓上形成了表的“膜厚（μm）”的欄中所記載之均勻厚度的樹脂組成物層。 在顯影條件中記載為“負”且在曝光條件中記載為“M”的例子中，用步進機對矽晶圓上的樹脂組成物層進行了曝光。使用表中的“曝光波長（nm）”中所記載之波長的光，未使用光罩對感光膜的整面進行了曝光。將曝光量設為後述解析度評價中的最小線寬成為最小的曝光量。 在顯影條件中記載為“負”且在曝光條件中記載為“D”的例子中，使用直接曝光裝置（ADTEC DE-6UH III）進行了曝光。使用表中的“曝光波長（nm）”中所記載之波長的光，對感光膜的整面進行了曝光。將曝光量設為500mJ/cm 2。 在顯影條件中記載為“正”的例子中，未進行曝光 在“硬化溫度（℃）”的欄中記載有數值之例子中，使用加熱板，在氮氣環境下，以10℃/分鐘的升溫速度對各實施例或比較例中獲得之樹脂膜進行升溫，達到表的“硬化溫度（℃）”中所記載之溫度之後，在“硬化時間（min）”中所記載之時間內維持該溫度，藉此形成了硬化膜。 在“硬化溫度（℃）”的欄中記載為“IR”的例子中，使用紅外線燈加熱裝置（ADVANCE RIKO,Inc.製RTP-6），在氮氣環境下，以10℃/分鐘的升溫速度對各實施例中獲得之樹脂膜進行升溫，達到230℃之後，在“硬化時間（min）”中所記載之時間內維持該溫度，藉此形成了硬化膜。 將所獲得之硬化膜在下述條件下浸漬於下述藥品中，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：將上述硬化膜在上述藥品中，以75℃浸漬15分鐘，比較浸漬前後的硬化膜的膜厚而算出了溶解速度（nm/分鐘）。 關於所獲得之溶解速度的值，按照下述評價基準進行評價，記載於“耐藥品性評價”的欄中。可以說溶解速度愈慢，耐藥品性愈優異。 -評價基準- A：溶解速度小於250nm/分鐘。 B：溶解速度為250nm/分鐘以上且小於500nm/分鐘。 C：溶解速度為500nm/分鐘以上且小於750nm/分鐘。 D：溶解速度為750nm/分鐘以上。 [Evaluation of Chemical Resistance] The resin composition or comparative composition prepared in each Example or Comparative Example was coated on a silicon wafer by a spin coating method. The above-mentioned silicon wafer was dried on a hot plate at 100° C. for 5 minutes, and a resin composition layer having a uniform thickness described in the column of “film thickness (μm)” in the table was formed on the silicon wafer. In the example described as "negative" in the development conditions and "M" in the exposure conditions, the resin composition layer on the silicon wafer was exposed with a stepper. The entire surface of the photosensitive film was exposed without using a photomask using the light of the wavelength described in the "exposure wavelength (nm)" in the table. The exposure amount was set as the exposure amount at which the minimum line width becomes the minimum in the resolution evaluation described later. In the example described as "negative" in the development conditions and "D" in the exposure conditions, exposure was performed using a direct exposure device (ADTEC DE-6UH III). The entire surface of the photosensitive film was exposed using the light of the wavelength described in the "exposure wavelength (nm)" in the table. The exposure amount was set to 500 mJ/cm 2 . In the example described as "positive" in the developing condition, no exposure was performed. In the example described in the column of "curing temperature (°C)", the temperature was raised at a rate of 10°C/min in a nitrogen atmosphere using a hot plate. Speed Raise the temperature of the resin film obtained in each example or comparative example, and after reaching the temperature described in the "curing temperature (°C)" in the table, maintain the temperature for the time described in the "curing time (min)" , thereby forming a cured film. In the example described as "IR" in the column of "curing temperature (°C)", an infrared lamp heating device (RTP-6 manufactured by ADVANCE RIKO, Inc.) was used in a nitrogen atmosphere at a heating rate of 10°C/min. After the temperature of the resin film obtained in each Example was raised to 230° C., the temperature was maintained for the time described in “curing time (min)”, whereby a cured film was formed. The obtained cured film was immersed in the following chemicals under the following conditions, and the dissolution rate was calculated. Drug: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution After immersion for 15 minutes, the film thickness of the cured film before and after immersion was compared to calculate the dissolution rate (nm/min). The value of the obtained dissolution rate was evaluated according to the following evaluation criteria, and described in the column of "chemical resistance evaluation". It can be said that the slower the dissolution rate, the better the chemical resistance. -Evaluation Criteria- A: The dissolution rate is less than 250 nm/min. B: The dissolution rate is 250 nm/minute or more and less than 500 nm/minute. C: The dissolution rate is not less than 500 nm/min and less than 750 nm/min. D: The dissolution rate is 750 nm/minute or more.

從以上結果可知，藉由使用本發明的樹脂組成物，所獲得之硬化物的圖案的矩形性提高。 比較例1及比較例2中的比較用組成物不包含特定鹼產生劑。可知在該種態樣中，所獲得之硬化物的圖案的矩形性差。 From the above results, it can be seen that by using the resin composition of the present invention, the rectangularity of the pattern of the obtained cured product is improved. The comparative compositions in Comparative Example 1 and Comparative Example 2 did not contain the specific base generator. It can be seen that in such an aspect, the rectangularity of the pattern of the obtained cured product is poor.

＜實施例101＞ 藉由旋塗法將實施例1中所使用之樹脂組成物以層狀適用於表面形成有銅薄層之樹脂基材的銅薄層表面，在100℃下乾燥5分鐘，藉此形成了膜厚20μm的感光膜之後，用步進機（Nikon Corporation製，NSR1505 i6）進行了曝光。隔著遮罩（圖案為1:1線與空間，線寬為10μm的二元遮罩），在波長365nm處進行了曝光。上述曝光之後，用環己酮顯影2分鐘，用PGMEA沖洗30秒，藉此獲得了層的圖案。 接著，在氮氣環境下，以10℃/分鐘的升溫速度進行升溫，達到230℃之後，在230℃維持180分鐘，藉此形成了再配線層用層間絕緣膜。該再配線層用層間絕緣膜的絕緣性優異。 又，使用該等再配線層用層間絕緣膜製造半導體裝置之結果，確認到正常工作。 <Example 101> The resin composition used in Example 1 was applied in a layered form to the surface of the thin copper layer of the resin substrate on which the thin copper layer was formed by spin coating, and dried at 100°C for 5 minutes to form a film. After the photosensitive film with a thickness of 20 μm, exposure was performed with a stepper (manufactured by Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a pattern of 1:1 line-space and a line width of 10 μm). After the above exposure, it was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds, whereby a layer pattern was obtained. Next, in a nitrogen atmosphere, the temperature was raised at a rate of 10° C./minute to reach 230° C., and then maintained at 230° C. for 180 minutes to form an interlayer insulating film for a rewiring layer. The interlayer insulating film for a rewiring layer is excellent in insulating properties. Furthermore, as a result of manufacturing semiconductor devices using these interlayer insulating films for rewiring layers, normal operation was confirmed.

Claims (15)

一種樹脂組成物，其係包含： 環化樹脂的前驅物；及 鹼產生劑， 所述樹脂組成物中， 從前述鹼產生劑產生之鹼係在同一分子內環化而成為三級胺之鹼， 從前述鹼產生劑產生之鹼不是α、β-不飽和羰基化合物及α、β-不飽和亞胺化合物中的任一種。 A resin composition comprising: Precursors for cyclized resins; and base generator, In the resin composition, The base generated from the aforementioned base generator is cyclized in the same molecule to become a base of a tertiary amine, The base generated from the aforementioned base generator is not any of α, β-unsaturated carbonyl compounds and α, β-unsaturated imine compounds. 如請求項1所述之樹脂組成物，其中 從前述鹼產生劑產生之鹼係包含選自包括環氧化物、氧環丁烷、醛、酮及鹵素基之群組中之至少一種基團之胺。 The resin composition as described in claim 1, wherein The base generated from the aforementioned base generator is an amine containing at least one group selected from the group consisting of epoxides, oxetanes, aldehydes, ketones, and halogen groups. 如請求項1或請求項2所述之樹脂組成物，其中 前述鹼產生劑為非離子性的鹼產生劑。 The resin composition as described in claim 1 or claim 2, wherein The aforementioned base generator is a nonionic base generator. 一種樹脂組成物，其係包含： 環化樹脂的前驅物；及 式（1-1）所表示之鹼產生劑， [化學式1]
Figure 03_image144
式（1-1）中，L 1表示n+m價的連結基，R 1分別獨立地表示1價的有機基團，R 1中的至少一個包含環氧化物、氧環丁烷、醛、酮或鹵素基，X分別獨立地為羥基或羧基，m表示1以上的整數，n表示1以上的整數。 A resin composition comprising: a precursor of a cyclized resin; and a base generator represented by formula (1-1), [chemical formula 1]
Figure 03_image144
In formula (1-1), L 1 represents a linking group with n+m valence, R 1 each independently represents a monovalent organic group, and at least one of R 1 includes epoxy, oxetane, aldehyde, Ketone or halogen group, X each independently represents a hydroxyl group or a carboxyl group, m represents an integer of 1 or more, and n represents an integer of 1 or more. 如請求項1、請求項2及請求項4之任一項所述之樹脂組成物，其係包含光自由基聚合起始劑。The resin composition according to any one of claim 1, claim 2 and claim 4, which contains a photoradical polymerization initiator. 如請求項1、請求項2及請求項4之任一項所述之樹脂組成物，其係包含聚合性化合物。The resin composition according to any one of claim 1, claim 2, and claim 4, which contains a polymerizable compound. 如請求項1、請求項2及請求項4之任一項所述之樹脂組成物，其係用於形成再配線層用層間絕緣膜。The resin composition according to any one of claim 1, claim 2, and claim 4, which is used to form an interlayer insulating film for a rewiring layer. 一種硬化物，其係硬化請求項1至請求項7之任一項所述之樹脂組成物而成。A cured product obtained by curing the resin composition described in any one of claim 1 to claim 7. 一種積層體，其係包含2層以上由請求項8所述之硬化物構成之層，在由前述硬化物構成之任意層彼此之間包含金屬層。A laminate comprising two or more layers composed of the cured product described in claim 8, wherein any layers composed of the cured product include a metal layer. 一種硬化物的製造方法，其係包括在基材上適用請求項1至請求項7之任一項所述之樹脂組成物來形成膜之膜形成步驟。A method for producing a cured product, comprising a film forming step of applying the resin composition described in any one of claims 1 to 7 on a substrate to form a film. 如請求項10所述之硬化物的製造方法，其包括： 曝光步驟，對前述膜進行選擇性曝光；及 顯影步驟，使用顯影液對前述膜進行顯影來形成圖案。 The manufacturing method of the hardened object as described in Claim 10, which comprises: an exposing step of selectively exposing the aforementioned film; and In the development step, the film is developed using a developer to form a pattern. 如請求項10所述之硬化物的製造方法，其包括在50～450℃下加熱前述膜之加熱步驟。The method for producing a cured product according to claim 10, which includes a heating step of heating the film at 50 to 450°C. 一種半導體裝置，其包含請求項8所述之硬化物。A semiconductor device comprising the cured product described in Claim 8. 一種鹼產生劑，其中 所產生之鹼係在同一分子內環化而成為三級胺之鹼，所產生之鹼不是α、β-不飽和羰基化合物及α、β不飽和亞胺化合物中的任一種。 A base generator, wherein The generated base is cyclized in the same molecule to become a base of tertiary amine, and the generated base is not any of α, β-unsaturated carbonyl compound and α, β-unsaturated imine compound. 一種鹼產生劑，其由下述式（1-1）表示， [化學式2]
Figure 03_image144
式（1-1）中，L 1表示n+m價的連結基，R 1分別獨立地表示1價的有機基團，R 1中的至少一個包含環氧化物、氧環丁烷、醛、酮或鹵素基，X分別獨立地為羥基或羧基，m表示1以上的整數，n表示1以上的整數。 A base generator represented by the following formula (1-1), [Chemical formula 2]
Figure 03_image144
In formula (1-1), L 1 represents a linking group with n+m valence, R 1 each independently represents a monovalent organic group, and at least one of R 1 includes epoxy, oxetane, aldehyde, Ketone or halogen group, X each independently represents a hydroxyl group or a carboxyl group, m represents an integer of 1 or more, and n represents an integer of 1 or more.
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