TW202242002A - Resin composition, cured product, laminate, method for producing cured product, semiconductor device, and resin - Google Patents

Abstract

Provided are: a resin composition that yields a cured product having exceptional elongation at break; a cured product obtained by curing the resin composition; a laminate containing the cured product; a method for producing the cured product; and a semiconductor device containing the cured product or the laminate, or a novel resin. The resin composition has repeating units represented by formula (1-1) and/or repeating units represented by formula (1-2).

Description

Resin composition, cured product, laminate, method for producing cured product, semiconductor element, and resin

The present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a semiconductor device, and a resin.

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.

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 polyimide. 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.

For example, in Patent Document 1, a polyamide ester resin composition is described, which includes a polyimide precursor of a specific structure, a carboxylic acid compound of a specific structure or an anhydride thereof, and optionally includes A polymer compound other than the polyimide precursor, and the above-mentioned carboxylic acid compound or its anhydride may be chemically bonded to the above-mentioned polyimide precursor and/or a polymer compound other than the above-mentioned polyimide precursor. Patent Document 2 describes a resin composition containing a polyimide precursor having a specific repeating unit.

[Patent Document 1] International Publication No. 2020/080206 [Patent Document 2] Japanese Unexamined Patent Publication No. 2012-224755

In a resin composition containing a resin such as a polyimide precursor, the obtained cured product is required to have an excellent elongation at break. An object of the present invention is to provide a resin composition capable of obtaining a cured product excellent in elongation at break, 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 cured product including the above cured product. A semiconductor device or a new type of resin for a product or the above-mentioned laminate.

式（1-1）或式（1-2）中，W ¹表示2價的有機基團，X ¹表示4價的有機基團，R ¹～R ³分別獨立地表示下述式（3-1）所表示之基團或式（3-2）所表示之基團，W ²表示2價的有機基團，X ²表示3價的有機基團，上述樹脂包含選自包括由式（1-1）表示且R ¹及R ²中的至少1個係式（3-1）所表示之基團之重複單元、以及由式（1-2）表示且R ³係式（3-1）所表示之基團之重複單元之群組中之至少1種重複單元。 [化學式2]

式（3-1）、式（3-2）中，Z ¹及Z ²分別獨立地表示有機基團，Z ¹和Z ²可以鍵結而形成環結構，A ²表示氧原子或-NH-，R ¹¹³表示氫原子或一價的有機基團，*表示與其他結構的鍵結部位。 ＜2＞如＜1＞所述之樹脂組成物，其中，式（3-1）所表示之基團係下述式（3-1-1）或式（3-1-2）所表示之基團。 [化學式3]

式（3-1-1）中，Cy表示脂肪族環結構或芳香族環結構，*表示與其他結構的鍵結部位。 式（3-1-2）中，Z ³及Z ⁴分別獨立地表示烷基，*表示與其他結構的鍵結部位。 ＜3＞如＜1＞或＜2＞所述之樹脂組成物，其中，相對於上述樹脂中所包含之式（3-1）所表示之基團及式（3-2）所表示之基團的總莫耳量之、式（3-1）所表示之基團的莫耳量的比例為0.1莫耳%以上。 ＜4＞如＜1＞至＜3＞之任一項所述之樹脂組成物，其中，相對於上述樹脂中所包含之式（3-1）所表示之基團及式（3-2）所表示之基團的總莫耳量之、式（3-1）所表示之基團的莫耳量的比例為99.9莫耳%以下。 ＜5＞如＜1＞至＜4＞之任一項所述之樹脂組成物，其中，相對於上述樹脂中所包含之式（3-1）所表示之基團及式（3-2）所表示之基團的總莫耳量之、式（3-1）所表示之基團的莫耳量的比例為80莫耳%以上。 ＜6＞如＜1＞至＜5＞之任一項所述之樹脂組成物，其中，式（3-2）中的R ¹¹³係具有聚合性基之基團。 ＜7＞如＜1＞至＜6＞之任一項所述之樹脂組成物，其中，式（1-1）中的W ¹及式（1-2）中的W ²包含式（5）～式（7）中的任一個所表示之基團。 [化學式4]

式（5）中，Y ¹表示單鍵或2價的連結基，*分別表示與其他結構的鍵結部位，式（6）中，Y ²表示單鍵或2價的連結基，*分別表示與其他結構的鍵結部位，式（7）中，*分別表示與其他結構的鍵結部位。 ＜8＞如＜1＞至＜7＞之任一項所述之樹脂組成物，其中，上述樹脂的重量平均分子量為10,000以上。 ＜9＞如＜1＞至＜8＞之任一項所述之樹脂組成物，其中，上述樹脂的酸值為0～1mmol/g。 ＜10＞如＜1＞至＜9＞之任一項所述之樹脂組成物，其還包含聚合起始劑。 ＜11＞如＜1＞至＜10＞之任一項所述之樹脂組成物，其還包含聚合性化合物。 ＜12＞如＜11＞所述之樹脂組成物，其中，上述聚合性化合物具有選自包括醯亞胺基、脲基及胺基甲酸酯基之群組中之至少1種基團。 ＜13＞如＜1＞至＜12＞之任一項所述之樹脂組成物，其還包含：化合物B，該化合物B係選自包括具有順丁烯二醯亞胺結構之化合物及具有順丁烯二醯亞胺結構之化合物的前驅物之群組中之至少1個化合物。 ＜14＞如＜13＞所述之樹脂組成物，其還包含：化合物C，該化合物C係具有能夠與順丁烯二醯亞胺結構反應之基團之化合物。 ＜15＞如＜14＞所述之樹脂組成物，其中，上述化合物C中的能夠與順丁烯二醯亞胺結構反應之基團係選自包括乙烯性不飽和基、羥基、環氧基及胺基之群組中之至少1種基團。 ＜16＞如＜1＞至＜15＞之任一項所述之樹脂組成物，其用於形成再配線層用層間絕緣膜。 ＜17＞一種硬化物，其硬化＜1＞至＜16＞之任一項所述之樹脂組成物而成。 ＜18＞一種積層體，其包含2層以上由＜17＞所述之硬化物構成之層，在由上述硬化物構成之層之間至少包含1層金屬層。 ＜19＞一種硬化物的製造方法，其包括在基板上適用＜1＞至＜16＞之任一項所述之樹脂組成物來形成膜之膜形成步驟。 ＜20＞如＜19＞所述之硬化膜之製造方法，其包括： 曝光步驟，對上述膜進行曝光；及顯影步驟，對上述膜進行顯影。 ＜21＞如＜19＞或＜20＞所述之硬化物的製造方法，其包括在50～450℃下加熱上述膜之加熱步驟。 ＜22＞一種半導體裝置，其包含＜17＞所述之硬化物或＜18＞所述之積層體。 ＜23＞一種樹脂，其具有式（1-1）所表示之重複單元及式（1-2）所表示之重複單元中的至少1個。 [化學式5]

式（1-1）或式（1-2）中，W ¹表示2價的有機基團，X ¹表示4價的有機基團，R ¹～R ³分別獨立地表示下述式（3-1）所表示之基團或式（3-2）所表示之基團，W ²表示2價的有機基團，X ²表示3價的有機基團，樹脂包含選自包括由式（1-1）表示且R ¹及R ²中的至少1個係式（3-1）所表示之基團之重複單元、以及由式（1-2）表示且R ³係式（3-1）所表示之基團之重複單元之群組中之至少1種重複單元。 [化學式6]

式（3-1）、式（3-2）中，Z ¹及Z ²分別獨立地表示有機基團，Z ¹和Z ²可以鍵結而形成環結構，A ²表示氧原子或-NH-，R ¹¹³表示氫原子或一價的有機基團，*表示與其他結構的鍵結部位。 ＜24＞如＜23＞所述之樹脂，其中，式（3-2）中的R ¹¹³係具有聚合性基之基團。 ＜25＞如＜23＞或＜24＞之任一項所述之樹脂，其中，式（1-1）中的W ¹及式（1-2）中的W ²包含下述式（4）所表示之基團。 [化學式7]

式（4）中，*分別表示與其他結構的鍵結部位。 [發明效果] Examples of representative embodiments of the present invention are shown below. <1> A resin composition comprising: a resin having at least one of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (1-2); and a solvent. [chemical formula 1]

In formula (1-1) or formula (1-2), W ¹ represents a divalent organic group, X ¹ represents a tetravalent organic group, and R ¹ to R ³ independently represent the following formula (3- 1) The group represented by or the group represented by formula (3-2), W ² represents a divalent organic group, X ² represents a trivalent organic group, the above-mentioned resins are selected from the group consisting of formula (1 -1) A repeating unit represented by at least one of R ¹ and R ² is a group represented by formula (3-1), and represented by formula (1-2) and R ³ is a group represented by formula (3-1) At least one repeating unit in the group of repeating units of the group represented. [chemical formula 2]

In formula (3-1) and formula (3-2), Z ¹ and Z ² independently represent an organic group, Z ¹ and Z ² can be bonded to form a ring structure, A ² represents an oxygen atom or -NH- , R ¹¹³ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures. <2> The resin composition as described in <1>, wherein the group represented by the formula (3-1) is represented by the following formula (3-1-1) or formula (3-1-2) group. [chemical formula 3]

In formula (3-1-1), Cy represents an aliphatic ring structure or an aromatic ring structure, and * represents a bonding site with another structure. In formula (3-1-2), Z ³ and Z ⁴ each independently represent an alkyl group, and * represents a bonding site with another structure. <3> The resin composition according to <1> or <2>, wherein the group represented by the formula (3-1) and the group represented by the formula (3-2) contained in the resin The ratio of the molar amount of the group represented by the formula (3-1) to the total molar amount of the group is 0.1 mol% or more. <4> The resin composition according to any one of <1> to <3>, wherein, with respect to the group represented by formula (3-1) and formula (3-2) contained in the above resin The ratio of the molar amount of the group represented by the formula (3-1) to the total molar amount of the represented groups is 99.9 mol% or less. <5> The resin composition according to any one of <1> to <4>, wherein, with respect to the group represented by formula (3-1) and formula (3-2) contained in the above resin The ratio of the molar amount of the group represented by the formula (3-1) to the total molar amount of the represented groups is 80 mol% or more. <6> The resin composition according to any one of <1> to <5>, wherein R ¹¹³ in formula (3-2) is a group having a polymerizable group. <7> The resin composition according to any one of <1> to <6>, wherein W ¹ in formula (1-1) and W ² in formula (1-2) include formula (5) ~ A group represented by any one of the formula (7). [chemical formula 4]

In formula (5), Y ¹ represents a single bond or a divalent linking group, and * respectively represent the bonding sites with other structures; in formula (6), Y ² represents a single bond or a divalent linking group, and * represent respectively Bonding sites with other structures, in formula (7), * represent bonding sites with other structures, respectively. <8> The resin composition according to any one of <1> to <7>, wherein the resin has a weight average molecular weight of 10,000 or more. <9> The resin composition according to any one of <1> to <8>, wherein the resin has an acid value of 0 to 1 mmol/g. <10> The resin composition according to any one of <1> to <9>, further comprising a polymerization initiator. <11> The resin composition according to any one of <1> to <10>, further comprising a polymerizable compound. <12> The resin composition according to <11>, wherein the polymerizable compound has at least one group selected from the group consisting of an imide group, a urea group, and a urethane group. <13> The resin composition according to any one of <1> to <12>, further comprising: a compound B selected from compounds having a maleimide structure and compounds having a maleimide structure; At least one compound in the group of precursors of compounds having a butenediimide structure. <14> The resin composition according to <13>, further comprising: compound C, which is a compound having a group capable of reacting with a maleimide structure. <15> The resin composition as described in <14>, wherein the group in compound C that can react with the maleimide structure is selected from the group consisting of ethylenically unsaturated groups, hydroxyl groups, epoxy groups, and at least one group in the group of amine groups. <16> The resin composition according to any one of <1> to <15>, which is used for forming an interlayer insulating film for a rewiring layer. <17> A cured product obtained by curing the resin composition described in any one of <1> to <16>. <18> A laminate comprising two or more layers composed of the cured product described in <17>, and at least one metal layer between the layers composed of the cured product. <19> A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of <1> to <16> to form a film on a substrate. <20> The method for producing a cured film according to <19>, including: an exposure step of exposing the above-mentioned film; and a developing step of developing the above-mentioned film. <21> The method for producing a cured product according to <19> or <20>, which includes a heating step of heating the film at 50 to 450°C. <22> A semiconductor device comprising the cured product described in <17> or the laminate described in <18>. <23> A resin having at least one of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (1-2). [chemical formula 5]

In formula (1-1) or formula (1-2), W ¹ represents a divalent organic group, X ¹ represents a tetravalent organic group, and R ¹ to R ³ independently represent the following formula (3- 1) The group represented by or the group represented by formula (3-2), W ² represents a divalent organic group, X ² represents a trivalent organic group, and the resin contains a group selected from the group consisting of formula (1- 1) Represents and at least one of R ¹ and R ² is a repeating unit of the group represented by formula (3-1), and is represented by formula (1-2) and R ³ is represented by formula (3-1) At least one repeating unit in the group of repeating units of the group represented. [chemical formula 6]

In formula (3-1) and formula (3-2), Z ¹ and Z ² independently represent an organic group, Z ¹ and Z ² can be bonded to form a ring structure, A ² represents an oxygen atom or -NH- , R ¹¹³ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures. <24> The resin according to <23>, wherein R ¹¹³ in the formula (3-2) is a group having a polymerizable group. <25> The resin according to any one of <23> or <24>, wherein W ¹ in formula (1-1) and W ² in formula (1-2) include the following formula (4) The group represented. [chemical formula 7]

In formula (4), * represent the bonding sites with other structures, respectively. [Invention effect]

According to the present invention, there are provided a resin composition capable of obtaining a cured product excellent in elongation at break, a cured product obtained by curing the above resin composition, a laminate comprising the above cured product, a method for producing the above cured product, and a cured product comprising the above cured product. Or the semiconductor device or resin of the above-mentioned laminate.

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.

式（1-1）或式（1-2）中，W ¹表示2價的有機基團，X ¹表示4價的有機基團，R ¹～R ³分別獨立地表示下述式（3-1）所表示之基團或式（3-2）所表示之基團，W ²表示2價的有機基團，X ²表示3價的有機基團，樹脂包含選自包括由式（1-1）表示且R ¹及R ²中的至少1個係式（3-1）所表示之基團之重複單元、以及由式（1-2）表示且R ³係式（3-1）所表示之基團之重複單元之群組中之至少1種重複單元。 [化學式9]

式（3-1）、式（3-2）中，Z ¹及Z ²分別獨立地表示有機基團，Z ¹和Z ²可以鍵結而形成環結構，A ²表示氧原子或-NH-，R ¹¹³表示氫原子或一價的有機基團，*表示與其他結構的鍵結部位。 亦即，前述式（1-1）中，W ¹表示2價的有機基團，X ¹表示4價的有機基團，R ¹及R ²分別獨立地表示下述式（3-1）所表示之基團或式（3-2）所表示之基團，R ¹及R ²中的至少1個係式（3-1）所表示之基團， 前述式（1-2）中，W ²表示2價的有機基團，X ²表示3價的有機基團，R ³表示式（3-1）所表示之基團。 (Resin composition) The resin composition of this invention contains the resin which has at least 1 of the repeating unit represented by following formula (1-1) and the repeating unit represented by formula (1-2), and a solvent. Hereinafter, a resin having at least one of the repeating unit represented by the following formula (1-1) and the repeating unit represented by the formula (1-2) is also described as "specific resin". [chemical formula 8]

In formula (1-1) or formula (1-2), W ¹ represents a divalent organic group, X ¹ represents a tetravalent organic group, and R ¹ to R ³ independently represent the following formula (3- 1) The group represented by or the group represented by formula (3-2), W ² represents a divalent organic group, X ² represents a trivalent organic group, and the resin contains a group selected from the group consisting of formula (1- 1) Represents and at least one of R ¹ and R ² is a repeating unit of the group represented by formula (3-1), and is represented by formula (1-2) and R ³ is represented by formula (3-1) At least one repeating unit in the group of repeating units of the group represented. [chemical formula 9]

In formula (3-1) and formula (3-2), Z ¹ and Z ² independently represent an organic group, Z ¹ and Z ² can be bonded to form a ring structure, A ² represents an oxygen atom or -NH- , R ¹¹³ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures. That is, in the aforementioned formula (1-1), W ¹ represents a divalent organic group, X ¹ represents a tetravalent organic group, R ¹ and R ² independently represent the following formula (3-1) The group represented by or the group represented by formula (3-2), at least one of R ¹ and R ² is the group represented by formula (3-1), in the aforementioned formula (1-2), W ² represents a divalent organic group, X ² represents a trivalent organic group, and R ³ represents a group represented by formula (3-1).

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. Furthermore, the resin composition of the present invention can be used to form a photosensitive film for positive development, and can also be used for forming a photosensitive film for negative development, but it is preferably used for forming a photosensitive film for negative 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. .

According to the resin composition of the present invention, a cured product having excellent elongation at break can be obtained. The mechanism by which counter-dyeing achieves the above effect is not clear, but it is speculated as follows.

Conventionally, a cured product has been obtained using a resin composition containing a polyimide precursor resin or a polyamideimide precursor resin. Also, research is under way to promote the formation of polyimide precursor resins or polyamide imide precursor resins by using a photobase generator or a thermal base generator in the above resin composition to generate a base when exposed or heated. Cyclization, thereby lowering the temperature during hardening. In the present invention, by using a resin having a repeating unit represented by formula (1-1) or formula (1-2), a secondary amine can be generated from the resin during heat hardening. In this way, the secondary amine can be generated along with the ring closure of the resin which is the main component, and thereby the amount of the secondary amine to be generated can be increased more than in the case of using a thermal base generator. As a result, compared with the case of using only a thermal base generator in the resin composition, it is considered that by using the resin composition of the present invention, even if it is heated at a low temperature (for example, 180° C., etc.), the ring closure of the resin is sufficient. In this way, a hardened product with excellent elongation at break can be obtained. Moreover, even if it heats at low temperature like this, since the ring closure of resin progresses sufficiently, it is considered that the chemical resistance of the obtained cured film is also excellent. In addition, in the base generating mechanism of the present invention, residues (carboxylic acid, salt, etc.) of the photo or thermal base generator after base generation and the photo or thermal base generator itself (undecomposed product) are less likely to remain in the composition , so the moisture resistance is also improved.

Here, Patent Document 1 and Patent Document 2 do not describe the use of a resin having at least one of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (1-2). .

Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

式（1-1）或式（1-2）中，W ¹表示2價的有機基團，X ¹表示4價的有機基團，R ¹～R ³分別獨立地表示下述式（3-1）所表示之基團或式（3-2）所表示之基團，W ²表示2價的有機基團，X ²表示3價的有機基團，樹脂包含選自包括由式（1-1）表示且R ¹及R ²中的至少1個係式（3-1）所表示之基團之重複單元、以及由式（1-2）表示且R ³係式（3-1）所表示之基團之重複單元之群組中之至少1種重複單元。 [化學式11]

式（3-1）、式（3-2）中，Z ¹及Z ²分別獨立地表示有機基團，Z ¹和Z ²可以鍵結而形成環結構，A ²表示氧原子或-NH-，R ¹¹³表示氫原子或一價的有機基團，*表示與其他結構的鍵結部位。 又，式（1-1）中，在R ¹及R ²均為式（3-1）所表示之基團的情況下，R ¹和R ²分別係對應於式（3-1）所表示之基團之基團即可，R ¹及R ²可以為相同的基團，亦可以為不同之基團。 式（1-1）中，在R ¹及R ²均為式（3-2）所表示之基團的情況下，R ¹和R ²分別係對應於式（3-2）所表示之基團之基團即可，R ¹及R ²可以為相同的基團，亦可以為不同之基團。 <Specific Resin> The resin composition of the present invention contains a resin (specific resin) having at least one of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (1-2). It is preferable that the specific resin contains at least a repeating unit represented by formula (1-1). Also, a specific resin-based polyimide precursor or a polyimide precursor is preferred, and a specific resin-based polyimide precursor is more preferred. [chemical formula 10]

In formula (1-1) or formula (1-2), W ¹ represents a divalent organic group, X ¹ represents a tetravalent organic group, and R ¹ to R ³ independently represent the following formula (3- 1) The group represented by or the group represented by formula (3-2), W ² represents a divalent organic group, X ² represents a trivalent organic group, and the resin contains a group selected from the group consisting of formula (1- 1) Represents and at least one of R ¹ and R ² is a repeating unit of the group represented by formula (3-1), and is represented by formula (1-2) and R ³ is represented by formula (3-1) At least one repeating unit in the group of repeating units of the group represented. [chemical formula 11]

In formula (3-1) and formula (3-2), Z ¹ and Z ² independently represent an organic group, Z ¹ and Z ² can be bonded to form a ring structure, A ² represents an oxygen atom or -NH- , R ¹¹³ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures. Also, in formula (1-1), when both R ¹ and R ² are groups represented by formula (3-1), R ¹ and R ² correspond to the groups represented by formula (3-1), respectively. ^The group of the group is ^sufficient , and R1 and R2 may be the same group or different groups. In formula (1-1), when both R ¹ and R ² are groups represented by formula (3-2), R ¹ and R ² are respectively corresponding to groups represented by formula (3-2) ^The group of the group is ^sufficient , and R1 and R2 may be the same group or different groups.

In formula (1-1), W ¹ 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, 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.

W ¹ is preferably derived from diamine. Examples of the diamine used in the production of the specific resin 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.

式中，A表示單鍵或2價基團，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、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 12]

In the formula, A represents a single bond or a divalent 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 a combination of these groups are preferred, single bonds, selected from alkylene groups with 1 to 3 carbons that may be substituted by fluorine atoms, -O-, -C(=O )-, -S- or -SO ₂ - is more preferred, -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - or -C(CH ₃ ) ₂ - as further preferred. In the formula, * represents a bonding site with other structures.

As the diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 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' -Diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4 ,4'- and 3,3'-diaminodiphenylsulfide, 4,4'- and 3,3'-diaminodiphenylsulfide, 4,4'- or 3,3'-diamine benzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3' -Dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2 ,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino- 4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino -3-Hydroxyphenyl) p-terphenyl, 4,4'-diamino-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy base) phenyl] phenyl], bis[4-(3-aminophenoxy)phenyl] phenyl, bis[4-(2-aminophenoxy)phenyl] -Aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl anthracene, 1,3- Bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)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) Terme, 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, Acetylguanamine, 2,3,5,6-Tetramethyl-p-phenylenediamine, 2,4,6-Trimethyl-m-phenylenediamine, Bis(3-Aminopropyl)tetramethyldisiloxane, Bis(p-Aminophenyl)Octamethylpentasiloxane, 2,7-Diaminopropyl, 2,5-Diaminopyridine , 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, 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 alkane, 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-aminophenoxy)-2-trifluoromethane phenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethyl Phenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylphenoxide, 4,4'-bis(3-amino-5-trifluoro Methylphenoxy)diphenylphenone, 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' , at least one diamine selected from 6,6'-hexafluorobenzidine and 4,4'-diaminoquaterphenyl.

Moreover, the diamines (DA-1)-(DA-18) described in paragraph 0030-0031 of International Publication No. 2017/038598 are also preferable.

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.

W ¹ is preferably represented by -Ar-L-Ar- from the viewpoint of the flexibility of the obtained organic film. 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 represented by L is preferably an alkylene group.

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（1-1）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14]

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（1-1）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, W ¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by the formula (61) is more preferable. Formula (51) [Chemical Formula 13]

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 (1-1). 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 14]

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 (1-1). 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（5）～式（7）中，Y ¹表示單鍵或2價的連結基，Y ²表示單鍵或2價的連結基，*分別表示與其他結構的鍵結部位。 In addition, from the viewpoint of moisture resistance and chemical resistance of the obtained cured film, it is preferable that W1 contains a group represented by any ^one of the following formulas (5) to (7), and the following The group represented by any one of formula (5) to formula (7) is more preferable. Among them, W ¹ is preferably a group represented by the following formula (5) from the viewpoint of suppressing film shrinkage during curing. [chemical formula 15]

In formulas (5) to (7), Y ¹ represents a single bond or a divalent linking group, Y ² represents a single bond or a divalent linking group, and * each represent a bonding site with another structure.

In formula (5), Y ¹ is a single bond or selected from aliphatic hydrocarbon groups with 1 to 10 carbons that may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO ₂ - , -NR ^N -, or a combination thereof are preferred, and a single bond is more preferred. The aforementioned R ^N each independently represent a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, further preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

In formula (6), Y ² is a single bond or selected from aliphatic hydrocarbon groups with 1 to 10 carbons that may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO ₂ - , -NR ^N -, or a combination thereof are preferred, and a single bond is more preferred. The above R ^N is as described above.

The group represented by the formula (7) is preferably a group represented by the following formula (7-1). [chemical formula 16]

式（4）中，*分別表示與其他結構的鍵結部位。 Among them, W ¹ preferably includes a group represented by the following formula (4), and more preferably a group represented by the formula (4), from the viewpoint of suppressing hardening shrinkage. [chemical formula 17]

In formula (4), * represent the bonding sites with other structures, respectively.

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。 X ¹ in formula (1-1) 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 18]

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.

在式（O）中，R ¹¹⁵表示4價有機基團。R ¹¹⁵的較佳範圍與式（1-1）中的X ¹的含義相同，較佳範圍亦相同。 Specific examples of X1 include ^a tetracarboxylic acid residue remaining after removing the acid anhydride group from the tetracarboxylic dianhydride. As ^a structure corresponding to X1, a specific resin may contain only 1 type of tetracarboxylic dianhydride residue, and may contain 2 or more types. It is preferable that tetracarboxylic dianhydride is represented by following formula (O). [chemical formula 19]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ has the same meaning as that of X ¹ in the formula (1-1), and the preferred range is also the same.

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.

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.

式（3-1）、式（3-2）中，Z ¹及Z ²分別獨立地表示有機基團，Z ¹和Z ²可以鍵結而形成環結構，A ²表示氧原子或-NH-，R ¹¹³表示氫原子或一價的有機基團，*表示與其他結構的鍵結部位。 In formula (1-1), R ¹ and R ² each independently represent a group represented by the following formula (3-1) or a group represented by formula (3-2). [chemical formula 20]

In formula (3-1) and formula (3-2), Z ¹ and Z ² independently represent an organic group, Z ¹ and Z ² can be bonded to form a ring structure, A ² represents an oxygen atom or -NH- , R ¹¹³ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures.

In formula (3-1), Z ¹ and Z ² independently represent an organic group, a hydrocarbon group or a hydrocarbon group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) A group represented by a combination of at least one of the groups of ₂ - and -NR ^N - is preferable, and a group represented by a hydrocarbon group or a combination of a hydrocarbon group and -O- is more preferable. R ^N is as described above. The above-mentioned hydrocarbon group may be any of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group. The carbon number of the above-mentioned aliphatic hydrocarbon group is preferably 1-20, more preferably 1-10, and still more preferably 1-8. In addition, the above-mentioned aliphatic hydrocarbon group may have any one of linear, branched, or cyclic structures, or may have structures represented by combinations of these. The carbon number of the above-mentioned aromatic hydrocarbon group is preferably 6-20, more preferably 6-10, and even more preferably 6. The above-mentioned hydrocarbon group may have a known substituent within the range in which the effect of the present invention can be obtained.

Moreover, the aspect in which at least ^one of Z1 and ^Z2 has a polymerizable group is also one of the preferable aspects of the present invention. Examples of the polymerizable group include radical polymerizable groups, epoxy groups, oxetanyl groups, methylol groups, and alkoxymethyl groups, among which radical polymerizable groups are preferred. As the free radical polymerizable group, a group having an ethylenically unsaturated group is preferable, and examples include (meth)acryloxy, (meth)acrylamide, vinylphenyl, maleic di Imide group, styryl group, vinyl group, (meth)allyl group, etc. Among them, a (meth)acryloxy group is preferable from the viewpoint of reactivity. These polymerizable groups may be directly bonded to the nitrogen atom in formula (3-1), or may be bonded via a linking group such as a hydrocarbon group (for example, an alkylene group).

In addition, in formula (3-1), Z ¹ and Z ² may form a ring structure. The formed ring structure may be an aromatic ring structure or an aliphatic ring structure, an aliphatic ring structure is preferable, and a saturated alicyclic ring structure is more preferable. As the above-mentioned ring structure, a cyclic amine having 2 to 10 carbon atoms is preferable, for example, a pyrrolidine ring, a piperidine ring, a morpholine ring, an octahydrone ring, a pyrrole ring, a pyridine ring, etc. ring, piperidine ring or morpholine ring are preferred. In addition, the above-mentioned ring structure may have a substituent within the range in which the effect of the present invention can be obtained. As a substituent, a hydrocarbon group, a halogen atom, etc. are mentioned. As a ring structure substituted by a substituent, a dimethylpiperidine ring etc. are mentioned, for example.

式（3-1-1）中，Cy表示脂肪族環結構或芳香族環結構，*表示與其他結構的鍵結部位。 式（3-1-2）中，Z ³及Z ⁴分別獨立地表示烷基，*表示與其他結構的鍵結部位。 The group represented by the formula (3-1) is preferably a group represented by the following formula (3-1-1) or formula (3-1-2). [chemical formula 21]

In formula (3-1-1), Cy represents an aliphatic ring structure or an aromatic ring structure, and * represents a bonding site with another structure. In formula (3-1-2), Z ³ and Z ⁴ each independently represent an alkyl group, and * represents a bonding site with another structure.

In formula (3-1-1), the ring structure represented by Cy is preferably an aliphatic ring structure, and more preferably a saturated aliphatic ring structure. Examples of the ring structure represented by Cy above include pyrrolidine ring, piperidine ring, morpholine ring, octahydroindole ring, pyrrole ring, pyridine ring, etc., pyrrolidine ring, piperidine ring, or morpholine ring is better. In addition, the ring structure represented by Cy above may have a substituent within the range in which the effect of the present invention can be obtained. As a substituent, a hydrocarbon group, a halogen atom, etc. are mentioned. As a ring structure substituted by a substituent, a dimethylpiperidine ring etc. are mentioned, for example.

In formula (3-1-2), Z ³ and Z ⁴ independently represent an alkyl group, preferably an alkyl group with 1 to 20 carbons, more preferably an alkyl group with 1 to 10 carbons, and an alkyl group with 1 to 10 carbons The alkyl group of 8 is further preferred. The above-mentioned alkyl group may have any structure of straight chain, branched chain or cyclic structure, or a structure represented by a combination of these.

Specific examples of the group represented by the formula (3-1) include the following, but are not limited thereto. [chemical formula 22]

The specific resin is preferably a resin that generates a base by heating at 250°C, a resin that generates a base by heating at 230°C is more preferable, and a resin that generates a base by heating at 200°C is even more preferable. It is particularly preferable to generate alkali at any temperature in the range of 120-180°C. Use the following method to judge whether a specific resin generates alkali at a certain temperature X°C. After heating 1 mole of a specific resin in a closed container at 1 atmosphere and at the above-mentioned X°C for 3 hours, the amount of decomposition can be quantified by methods such as HPLC (high-speed liquid chromatography), so that it can be determined whether alkali is generated . 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 molecular weight of the base generated from the specific resin is preferably from 40 to 1,000, more preferably from 40 to 500, and still more preferably from 50 to 400. The base having the above pyridine structure preferably has a boiling point of 50-600°C at 1 atmosphere, more preferably 50-500°C, still more preferably 50-450°C.

The resulting base-based conjugate acid has a pKa of 0 or higher, more preferably 3 or higher, and more preferably 6 or higher. The upper limit of the pKa of the above-mentioned conjugate acid is not particularly limited, but 30 or less is preferable. pKa is the one that expresses its equilibrium constant Ka by its negative common logarithm pKa considering the dissociation reaction of releasing hydrogen ions from an acid. In this specification, unless otherwise specified, pKa is a calculated value based on ACD/ChemSketch (registered trademark). When there are plural pKa's of the conjugate acid, at least one of them is preferably within the above range.

In formula (3-2), A ² is preferably an oxygen atom.

R ¹¹³ in formula (3-2) represents 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. In addition, it is preferable that R ¹¹³ contains a polymerizable group, and it is more preferable that both of them contain a polymerizable group. It is also preferable that R ¹¹³ 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 a radical polymerizable group which a specific resin has, the group which has 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.

[chemical formula 23]

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.

In formula (1-1), when R ¹¹³ is a hydrogen atom, the specific resin can form a conjugate base 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.

In formula (1-1), R ¹¹³ 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.

When the specific resin contains the repeating unit represented by formula (1-1), the specific resin may further contain other repeating units. In the case where the specific resin contains the repeating unit represented by the formula (1-1), the content of the repeating unit represented by the formula (1-1) relative to all the repeating units contained in the specific resin is 50 mole % The above aspect is also one of the preferred aspects of the present invention. Also, the above-mentioned content is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and still more preferably 95 mol% or more. The upper limit of the content is not particularly limited, and may be 100 mol%.

In formula (1-2), W ² and R ³ have the same meanings as W ¹ and R ² in formula (1-1), respectively, and preferred embodiments are also the same.

In the formula (1-2), X ² exemplifies a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or these are linked by a single bond or a linking group A group consisting of 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 to 20 carbons An aromatic group of 20 or a group formed by combining two or more of these through a single bond or a linking group is preferable, and an aromatic group with 6 to 20 carbons or a group having 6 carbons through a single bond or a linking group is preferred. A combination of two or more aromatic groups having ~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.

In addition, X2 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 which may be halogenated for the production of the specific resin include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used only by 1 type, and may use 2 or more types.

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.

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).

Certain resins may also contain other repeat units. Examples of other repeating units include repeating units represented by the above formula (1-1), repeating units represented by the following formula (PAI-1), and the like. [chemical formula 24]

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 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.

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 dicarboxylic acid compounds or dicarboxylic acid dihalide compounds that can be halogenated for the production of specific resins include linear or branched aliphatic, cyclic aliphatic, or aromatic dicarboxylic acid compounds or dicarboxylic acid compounds or dicarboxylic acid dihalide compounds. Carboxylic acid dihalide compounds, etc. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used only by 1 type, and may use 2 or more types.

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.

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.

In the formula (PAI-1), R ¹¹¹ has the same meaning as W ¹ in the above formula (1-1), and preferred embodiments are also the same.

When the specific resin contains the repeating unit represented by the formula (1-2), the repeating unit represented by the formula (1-2), the repeating unit represented by the formula (1-1) relative to all the repeating units contained in the specific resin The aspect in which the content of the repeating unit represented by the formula (PAI-1) and the repeating unit represented by the formula (PAI-1) is 50 mol% or more is also one of the preferable aspects of the present invention. Also, the above-mentioned content is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and still more preferably 95 mol% or more. Also, when the specific resin contains the repeating unit represented by the formula (1-2), the content of the repeating unit represented by (1-2) is 50 moles relative to all the repeating units contained in the specific resin The aspect above % is also one of the preferred aspects of the present invention. Also, the above-mentioned content is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and still more preferably 95 mol% or more. The upper limit of the content is not particularly limited, and may be 100 mol%.

The amount of the group represented by the formula (3-1) relative to the total molar amount of the group represented by the formula (3-1) and the group represented by the formula (3-2) contained in the specific resin The ratio of the total molar amount is preferably 0.1 mol% or more, more preferably 5 mol% or more, and further preferably 10 mol% or more. The total molar amount of the groups represented by the above (3-2) and the total molar amount of the groups represented by the formula (3-1) can be calculated by, for example, NMR (nuclear magnetic resonance apparatus). Also, for the reason of improving chemical resistance and pattern formation, relative to the total mole of the group represented by the formula (3-1) and the group represented by the formula (3-2) contained in the specific resin In terms of amount, the molar ratio of the group represented by formula (3-1) is preferably below 99.9 mole %, more preferably below 95 mole %, further preferably below 90 mole %, 80 Mole% and below are special prices. Also, from the viewpoint of accelerating the cyclization of polyimide precursor resins and polyamideimide precursor resins, lowering the temperature during curing, and increasing the elongation at break, relative to the specific resin contained in The ratio of the molar amount of the group represented by the formula (3-1) to the total molar amount of the group represented by the formula (3-2) is 80 More than 90 mol% is more preferable, 95 mol% or more is more preferable, and 98 mol% or more is especially preferable. The amount of the group represented by the formula (3-1) relative to the total molar amount of the group represented by the formula (3-1) and the group represented by the formula (3-2) contained in the specific resin The aspect that the ratio of the molar amount is 100 mol% is also one of the preferred aspects of the present invention.

Also, the molar content of the formula (3-1) contained in the specific resin relative to the total mass of the specific resin is preferably 0.001-10 mmol/g, more preferably 0.01-5 mmol/g, 0.1-3 mmol/g g is further preferred. Also, the content of the formula (3-1) contained in the specific resin is preferably 0.1 to 70%, more preferably 0.5 to 40%, and still more preferably 1 to 20%, based on the total mass of the specific resin. .

The weight average molecular weight (Mw) of the specific resin is preferably at least 2,000, more preferably at least 10,000, and still more preferably at least 15,000. Moreover, it is preferable that the said weight average molecular weight is 200,000 or less, More preferably, it is 50,000 or less, More preferably, it is 40,000 or less. The number average molecular weight (Mn) is preferably at least 1,000, more preferably at least 3,000, and still more preferably at least 4,000. In addition, the above-mentioned number average molecular weight is preferably at most 100,000, more preferably at most 30,000, and still more preferably at most 20,000. The molecular weight dispersion of the specific resin is preferably 1.5 or higher, more preferably 1.8 or higher, and still more preferably 2.0 or higher. The upper limit of the dispersion degree of molecular weight of a specific resin is not specifically limited, For example, 7.0 or less is preferable, 6.5 or less is more preferable, 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. Also, when the resin composition contains a plurality of specific resins as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one specific resin are within the above-mentioned ranges. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated using the above-mentioned plural kinds of specific resins as one type of resin are within the above-mentioned ranges, respectively.

The acid value of the specific resin is preferably 0 to 1 mmol/g or less, more preferably 0 to 0.8 mmol/g, and still more preferably 0 to 0.6 mmol/g. The said acid value is measured based on description of JIS(Japanese Industrial Standards) K 0070:1992. The cured film using the resin whose acid value is within the above range is less likely to be damaged by alkaline chemical solutions (for example, tetramethylammonium hydroxide, etc.).

Specific examples of the specific resin include SA-1 to SA-18 described in Examples described later, but are not limited thereto.

〔Manufacturing method of specific resin〕 For example, the specific resin can be obtained by the following methods: a method of reacting tetracarboxylic dianhydride and diamine at low temperature; reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamic acid, and using a condensing agent or A method of esterifying an alkylating agent; a method of reacting a diester obtained by tetracarboxylic dianhydride and alcohol in the presence of a diamine and a condensation agent; A method of halogenating the remaining dicarboxylic acid with a halogenating agent after the 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 the specific resin, it is preferable to use an organic solvent when performing the reaction. The organic solvent may be one type, or two or more types. The organic solvent can be appropriately determined according to the raw material, and examples include pyridine, diglyme (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate Esters, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the production method of the specific resin, it is preferable to add a basic compound during the 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.

-Encapping agent- In the production method of the specific resin, in order to further improve the storage stability, it is preferable to seal the carboxylic anhydride, acid anhydride derivative or amine group remaining at the resin terminal of the specific resin. 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.

式（T-1）中，L ^T表示2價的有機基團，Z ¹及Z ²分別獨立地表示有機基團，Z ¹和Z ²可以鍵結而形成環結構。 Moreover, the compound represented by formula (T-1) can also be used as a terminal blocking agent. It is considered that by sealing the ends with these compounds, a structure that easily generates bases can be introduced into the ends, whereby the elongation at break is also likely to increase when hardened at a low temperature. [chemical formula 25]

In the formula (T-1), L ^T represents a divalent organic group, Z ¹ and Z ² each independently represent an organic group, and Z ¹ and Z ² may be bonded to form a ring structure.

In formula (T-1), the L ^T series hydrocarbon group is preferred, and it can also be any of aromatic hydrocarbon group and aliphatic hydrocarbon group, but any of aromatic hydrocarbon group, unsaturated aliphatic hydrocarbon group, and cyclic aliphatic hydrocarbon group One is preferred. The linking chain length in ^LT (that is, the minimum number of atoms among the number of atoms linking the two carbonyl groups bonded to ^LT ) is preferably 2 to 4, and 2 is more preferred. In formula (T-1), Z ¹ and Z ² have the same meaning as Z ¹ and Z ² in formula (3-1), and preferred embodiments are also the same. In particular, an aspect in which at least one of Z ¹ and Z ² has a polymerizable group is also one of the preferred aspects of the present invention. Examples of the polymerizable group include radical polymerizable groups, epoxy groups, oxetanyl groups, methylol groups, and alkoxymethyl groups, among which radical polymerizable groups are preferred. As the free radical polymerizable group, a group having an ethylenically unsaturated group is preferable, and examples include (meth)acryloxy, (meth)acrylamide, vinylphenyl, maleic di Imide group, styryl group, vinyl group, (meth)allyl group, etc. Among them, a (meth)acryloxy group is preferable from the viewpoint of reactivity. These polymerizable groups may be directly bonded to the nitrogen atom in formula (T-1), or may be bonded via a linking group such as a hydrocarbon group (for example, an alkylene group).

Specific examples of the compound represented by the formula (T-1) include CSA-1 to CSA-7 in Examples described later, but are not limited thereto.

-Solid precipitation- When producing specific resins, a step of precipitating solids may also 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 specific resin etc. can be obtained by depositing and drying as a solid. In order to increase the degree of purification, operations such as redissolution, reprecipitation, and drying can also be repeatedly performed on a specific resin. It may further include the step of removing ionic impurities using an ion exchange resin.

〔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.

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 specific resins, that is, different structures derived from dianhydrides (X ¹ described in the above-mentioned formula (1-1)) are included. The above specific resins are preferred.

<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”). As other resins, there are repeating units that do not have the group represented by formula (1-1) and at least one of R ¹ and R ² is represented by formula (3-1), and those represented by formula (1-2) ) and R ³ is a polyimide precursor that is a repeating unit of the group represented by formula (3-1), does not have a polyimide precursor represented by formula (1-1) and at least one of R ¹ and R ² is The polyamide imide precursor of the repeating unit of the group represented by formula (3-1) and the repeating unit of the group represented by formula (1-2) and ^R3 is formula (3-1) , phenol resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane resin, butyraldehyde 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.

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.

<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. In addition, it is preferable that the polymerizable compound has at least one group selected from the group consisting of imide group, urea group, and urethane group. At least one group in the group of is further preferred. In the present invention, the imide group refers to the group represented by -C(=O) ^NR NC( ⁼ O)-, the urea group refers to the group represented by -NR NC(=O)NR ^N- , aminomethyl Ester group refers to -OC(=O)NR ^N- . The above R ^N is as described above. In addition, the orientation of these groups is not particularly limited. It is considered that by including these groups, the interaction between the specific resins or the specific resins and other components increases to resist Humidity is further improved.

〔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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

As a free radical crosslinking 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; Nippon Kayaku Co., Ltd.), diperythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.), and the structure in which the (meth)acryl groups are bonded via ethylene glycol residues or propylene glycol residues is preferred. These oligomer types can also be used.

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 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), etc.

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.

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.

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.

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.

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.

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.

〔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 the above-mentioned photoacid generator or photobase generator and the like in the composition. The compound that forms a covalent bond reaction group between other compounds or their reaction products is preferred, and has a plurality of compounds in the molecule that are promoted by the action of acid or base with other compounds or their reaction products in the composition Compounds of reactive groups forming covalent bonds between them are more preferred. 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.

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.

[chemical formula 26]

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.

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.

[chemical formula 27]

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 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.

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.

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.

[chemical formula 28]

[chemical formula 29]

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.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, and the like.

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.

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 and guanamine, monoethoxymethylated benzoguanamine; Diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropyl Oxymethylated Benzoguanamine, Tripropoxymethylated Benzoguanamine, Tetrapropoxymethylated Benzoguanamine, Monobutoxymethylated Benzoguanamine, Dibutoxymethylated Benzoguanamine, Dibutoxymethylated Benzoguanamine Methylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc.

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.

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.

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.

-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.

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.

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, 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.

[chemical formula 30]

In the formula, n is an integer of 1-5, and m is an integer of 1-20.

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.

-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.

-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.

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.

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.

-Compound B- Also, the resin composition of the present invention contains at least one compound selected from the group consisting of a compound having a maleimide structure and a precursor of a compound having a maleimide structure (hereinafter , also referred to as "compound B".) It is also preferable as a polymerizable compound. Hereinafter, the compound having a maleimide structure is described as "compound B-1", and the precursor of the compound having a maleimide structure is described as "compound B-2". Certain resins of the present invention produce secondary amines from the resin upon heat hardening. Here, it is considered that the polymerization of the maleimide structure is promoted by the secondary amine. Therefore, it is considered that by using the specific resin of the present invention and compound B-1 or compound B-2 in combination, the unpolymerized compound B-1 or the compound B-1 produced by compound B-2 has a maleimide structure and is not polymerized. It is difficult for the compound to remain in the film. It is considered that these unpolymerized compounds are easy to volatilize, and thus it is considered that a film with a large content of unpolymerized compounds has a large curing shrinkage before and after the film is cured. That is, it is considered that by using the specific resin of the present invention and the compound B together, the residue of the unpolymerized compound in the film is suppressed, and as a result, the cure shrinkage before and after the film is cured is suppressed.

式（M-1）中，R分別獨立地表示氫原子或取代基，*表示與其他結構的鍵結部位。R係氫原子為較佳。又，作為R中的取代基，沒有特別的限定，能夠具有公知的取代基，例如，可以舉出烴基等，烷基為較佳。 In the present invention, the maleimide structure means a structure represented by the following formula (M-1). [chemical formula 31]

In the formula (M-1), R each independently represent a hydrogen atom or a substituent, and * represents a bonding site with other structures. R is preferably a hydrogen atom. In addition, the substituent in R is not particularly limited, and known substituents can be included, for example, hydrocarbon groups and the like can be mentioned, and alkyl groups are preferred.

＜＜Compound with maleimide structure (compound B-1)＞＞ Compound B-1 preferably has two or more maleimide structures. The number of maleimide structures is preferably 2-10, more preferably 2-6, and even more preferably 2-4. Moreover, the aspect containing two maleimide structures is also one of the preferable aspects of this invention.

式（M-2）中，R分別獨立地表示氫原子或取代基，L表示n價的連結基，n表示1以上的整數。 式（M-2）中，R的較佳之態樣與上述的式（M-1）中的R的較佳之態樣相同。 式（M-2）中，L係烴基、或烴基與選自包括-O-、-C（=O）-、-S-、-S（=O） ₂-及-NR ^N-之群組中之至少1種基團的組合所表示之基團為較佳，烴基、或烴基與-O-的組合所表示之基團為更佳。 又，L中的與式（M-2）中的順丁烯二醯亞胺結構中的氮原子的鍵結部位係碳原子為較佳，烴基為更佳。 式（M-2）中，n係2以上的整數為較佳，2～10的整數為更佳，2～6的整數為進一步較佳，2～4的整數為特價。又，n為2之態樣亦為本發明的較佳之態樣之一。 Compound B-1 is not particularly limited, but a compound represented by the following formula (M-2) is preferred. [chemical formula 32]

In formula (M-2), R each independently represents a hydrogen atom or a substituent, L represents an n-valent linking group, and n represents an integer of 1 or more. In the formula (M-2), a preferable aspect of R is the same as a preferable aspect of R in the above-mentioned formula (M-1). In the formula (M-2), the L-based hydrocarbon group, or the hydrocarbon group is selected from the group including -O-, -C(=O)-, -S-, -S(=O) ₂ - and -NR ^N - A group represented by a combination of at least one of them is preferable, and a group represented by a hydrocarbon group or a combination of a hydrocarbon group and -O- is more preferable. Also, the bonding site in L to the nitrogen atom in the maleimide structure in formula (M-2) is preferably a carbon atom, and more preferably a hydrocarbon group. In the formula (M-2), n is preferably an integer of 2 or more, more preferably an integer of 2-10, more preferably an integer of 2-6, and an integer of 2-4 is a special price. Moreover, the aspect in which n is 2 is also one of the preferable aspects of this invention.

The molecular weight of compound B-1 is preferably from 90 to 2,000, more preferably from 100 to 1,000, and still more preferably from 150 to 800. Also, the content of the maleimide structure in Compound B-1 (the molar amount of the maleimide structure in 1 g of Compound B-1) is preferably 0.1 to 20 mmol/g , 1 to 15 mmol/g is more preferable.

Although it does not specifically limit as a specific example of compound B-1, BM-1-BM-3 in the Example mentioned later is mentioned.

＜＜Precursor of a compound having a maleimide structure (compound B-2)＞＞ A preferred aspect of the compound having a maleimide structure derived from compound B-2 is the same as that of compound B-1.

Compound B-2 is preferably a compound that generates a compound having a maleimide structure by heating. Specifically, compound B-2 is preferably a compound having a maleimide structure by heating at 230°C for 3 hours, and a compound having a maleimide structure by heating at 200°C for 3 hours is preferred. A compound having an imide structure is more preferable, and a compound having a maleimide structure produced by heating at 180° C. for 2 hours is still more preferable. The lower limit of the temperature at which the above-mentioned compound having a maleimide structure is produced is not particularly limited, but is preferably 100° C. or higher from the viewpoint of storage stability of the composition, for example. Whether a certain compound A exhibits the property of producing a compound having a maleimide structure 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 HPLC (high-speed liquid chromatography) or the like, and 0.01 mole or more of In the case of a compound having a maleimide structure, it was determined that Compound A produced a compound having a maleimide structure by heating at X°C. The structure of the compound having the produced maleimide structure is confirmed, for example, by using ¹ H-NMR. The production amount of the compound having the above-mentioned maleimide structure is preferably 0.1 mole or more, more preferably 0.5 mole or more. The upper limit of the production amount of the compound having a maleimide structure is not particularly limited, and can be set to, for example, 1,000 mol or less.

式（M-2）中，R分別獨立地表示氫原子或取代基，X表示-O-或-NR ^N2-，R ^N2表示氫原子或有機基團，R ^N1表示氫原子或有機基團，R ^N1和R ^N2可以鍵結而形成環結構，*表示與其他結構的鍵結部位。 Compound B-2 is preferably a compound having a structure represented by the following formula (M-2). The structure represented by formula (M-2) forms an imide ring by heating etc., and becomes the maleimide structure represented by formula (M-1). [chemical formula 33]

In formula (M-2), R independently represents a hydrogen atom or a substituent, X represents -O- or -NR ^N2 -, R ^N2 represents a hydrogen atom or an organic group, R ^N1 represents a hydrogen atom or an organic group, R ^N1 and R ^N2 can be bonded to form a ring structure, and * indicates a bonding site with other structures.

In the formula (M-2), R has the same meaning as that of R in the above formula (M-1), and preferred embodiments are also the same.

In the formula (M-2), X represents -O- or -NR ^N2 -, and -NR ^N2 - is preferred from the viewpoint of generating a base. Moreover, -O- is preferable from a viewpoint of easily forming a maleimide structure.

In formula (M-2), R ^N1 represents a hydrogen atom or an organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group.

In the formula (M-2), R ^N2 represents a hydrogen atom or an organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group.

In the formula (M-2), R ^N1 and R ^N2 may be bonded to form a ring structure, and as the formed ring structure, a 5-membered ring or a 6-membered ring is preferable. Also, the ring structure formed above may be an aliphatic ring structure or an aromatic ring structure, but an aliphatic ring structure is preferred. The ring structure formed above may contain heteroatoms other than the nitrogen atom bonded to ^{RN1, and the aspect that does not contain heteroatoms other than the nitrogen atom bonded to R N1 is} also a preferred state of the present invention one of the samples.

The molecular weight of compound B-2 is preferably 100-2,000, more preferably 100-1,500, and still more preferably 200-1,000.

Although it does not specifically limit as a specific example of compound B-2, BMB-1-BMB-2 in the Example mentioned later is mentioned.

The content of Compound B is preferably 0.1 to 60% by mass, more preferably 0.5 to 40% by mass, more preferably 1 to 20% by mass, and still more preferably 1 to 7% by mass, based on the total solid content of the resin composition of the present invention. It is better to go further.

-Compound C- Furthermore, when the resin composition contains the compound B, it is also preferable that the resin composition contains a compound having a group capable of reacting with the maleimide structure (also referred to as "compound C").

Examples of the group capable of reacting with the above-mentioned maleimide structure include at least one group selected from the group consisting of an ethylenically unsaturated group, a hydroxyl group, an epoxy group, and an amine group. Also, a group that generates an amine group by heating, a group that generates at least one group selected from the group consisting of an ethylenically unsaturated group, a hydroxyl group, an epoxy group, and an amine group by heating are also Included in groups capable of reacting with the maleimide structure.

As a specific example of the compound which has an ethylenically unsaturated group in compound C, the above-mentioned radical crosslinking agent is mentioned. Moreover, as a specific example of the compound which has an epoxy group in compound C, the above-mentioned epoxy compound is mentioned. Moreover, as a specific example of compound C, the compound etc. which are described in C-2-C-4 which are described in the Example mentioned later are mentioned.

It is also preferable that the compound C contains two or more groups capable of reacting with the maleimide structure in total. The number of the above-mentioned groups is preferably 2-10, more preferably 2-6, and even more preferably 2-4.

The content of Compound C is preferably 0.1-60% by mass, more preferably 0.5-40% by mass, and still more preferably 1-20% by mass, based on the total solid content of the resin composition of the present invention.

＜＜Compound D＞＞ Compound D, which is a compound having a ring-opening polymerizable group and a radical polymerizable group, is also preferable as the polymerizable compound. By including compound D, when imide cyclization of a specific resin by heating etc. starts, the group capable of ring-opening polymerization is not yet polymerized, and the precursor of the cyclization resin is suppressed by the crosslinked structure formed after polymerization The cyclization of the compound is hindered, and the polymerization of the group capable of ring-opening polymerization is also proceeding after heating, etc., so a high cyclization rate and a high cross-linking density can be taken into account. As a result, it is considered that the elongation at break and the chemical resistance are likely to be further improved.

As the group capable of ring-opening polymerization in compound D, a group capable of ring-opening polymerization by heating is preferred. The film formed by drying the resin composition of the present invention is opened at 250° C. for 3 hours. The ring-polymerized group is more preferable, and the ring-opening polymerized group is further preferably the above-mentioned film at 230°C for 3 hours, and the ring-opening polymerization of the above-mentioned film at 200°C for 3 hours A group is particularly preferred, and a group obtained by ring-opening polymerization of the above-mentioned film at 180° C. for 2 hours is particularly preferred.

As the group capable of ring-opening polymerization in compound D, it has at least A group with one structure is preferred. As a group which has an epoxy structure, an epoxy group, a glycidyl group, etc. are mentioned. As a group having an oxetane structure, oxetanyl, oxetanylmethyl, (3-methyloxetan-3-yl)methyl, (3-ethyloxetane butan-3-yl)methyl, oxetanylmethoxy, etc. Examples of the group having a lactone structure include β-propiolactone, γ-butyrolactone, ε-caprolactone, and the like. As a group having a cyclic carbonate structure, 2-oxo-1,3-dioxolan-4-yl, (2-oxo-1,3-dioxolan-4-yl ) Methyl etc. Examples of the group having a cyclic amido structure include 2-oxazepane-1-yl and the like.

It is also preferable that the compound D contains at least one structure selected from the group consisting of a urea bond, a urethane bond, and an amide bond not included in the ring structure. The above-mentioned urea bond in compound D is a structure represented by -NR ^N -C(=O)-NR ^N -. Both ends of the urea bond are preferably bonded to a carbon atom, more preferably bonded to a hydrocarbon. R ^N independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or benzene A group is further preferred, and a hydrogen atom is particularly preferred. In addition, R ^N may be bonded to each other or at least one of R ^N may be bonded to another structure bonded to a urea bond to form a ring structure. The above-mentioned urethane bond in compound D is a structure represented by -NR ^N -C(=O)-O-. Both ends of the urethane bond are preferably bonded to a carbon atom, and more preferably bonded to a hydrocarbon. R ^N is the same as R ^N in the above-mentioned urea bond. In addition, R ^N may be bonded to another structure bonded to a urethane bond to form a ring structure. The above-mentioned amide bond in compound D is a structure represented by -NR ^N -C(=O)-. Both ends of the amide bond are preferably bonded to a carbon atom, more preferably bonded to a hydrocarbon. In addition, the terminal on the carbonyl side of the amide bond may be directly bonded to the above-mentioned lactone structure, cyclic carbonate structure, and cyclic amide group structure. R ^N is the same as R ^N in the above-mentioned urea bond. Also, the above-mentioned amide bond in compound B is not included in the ring structure.

Examples of the radically polymerizable group in compound D include groups having an ethylenically unsaturated bond, such as vinyl, allyl, isoallyl, 2-methallyl, and groups having an ethylenic unsaturated bond. A group directly bonded to an aromatic ring (for example, vinylphenyl, etc.), (meth)acrylamide, (meth)acryloxy, maleimide, etc., have the same A group of an aromatic ring directly bonded to a vinyl group, a (meth)acrylamide group or a (meth)acryloxy group is preferable, and a (meth)acryloxy group is more preferable.

Examples of the radically polymerizable group in compound D include groups having an ethylenically unsaturated bond, such as vinyl, allyl, isoallyl, 2-methallyl, and groups having an ethylenic unsaturated bond. A group directly bonded to an aromatic ring (for example, vinylphenyl, etc.), (meth)acrylamide, (meth)acryloxy, maleimide, etc., have the same A group of an aromatic ring directly bonded to a vinyl group, a (meth)acrylamide group or a (meth)acryloxy group is preferable, and a (meth)acryloxy group is more preferable.

The number of ring-opening polymerizable groups in the compound D is not particularly limited, but 1-10 is preferable, 1-4 is more preferable, 1 or 2 is still more preferable, and 1 is special price. The number of radically polymerizable groups in compound D is not particularly limited, but 1-10 is preferable, 1-4 is more preferable, and 1 or 2 is still more preferable. Here, in compound D, an aspect in which only one ring-opening polymerizable group has one or two radical polymerizable groups is also one of the preferred aspects of the present invention. Also, when the compound D contains at least one structure selected from the group consisting of urea bonds, urethane bonds and amide bonds not included in the ring structure, the number is 1 to 10. Preferably, 1 to 4 are more preferred, 1 or 2 are further preferred, and 1 is a special price.

式（D-1）中，X分別獨立地表示具有選自包括環氧化物結構、氧環丁烷結構、內酯結構、環狀碳酸酯結構及環狀醯胺基結構之群組中之至少1種結構之基團，n表示1以上的整數，Z分別獨立地表示自由基聚合性基，m表示1以上的整數，L表示選自包括脲鍵、胺基甲酸酯鍵及不包含在環狀結構中之醯胺鍵之群組中之至少1種結構、烴基、或烴基與選自包括-O-、-C（=O）-、-S-、-S（=O） ₂-及-NR ^N-之群組中之至少1種結構的組合所表示之n+m價的連結基，R ^N表示氫原子或烴基。 Compound D is preferably a compound having a structure represented by the following formula (D-1). [chemical formula 34]

In formula (D-1), X each independently represent at least A group of one structure, n represents an integer of 1 or more, Z independently represents a free radical polymerizable group, m represents an integer of 1 or more, and L represents a group selected from the group consisting of urea bonds, urethane bonds, and not included in At least one structure, hydrocarbon group, or hydrocarbon group selected from the group of amide bonds in the ring structure, including -O-, -C(=O)-, -S-, -S(=O) ₂ - An n+m-valent linking group represented by a combination of at least one structure in the group of and -NR ^N -, where ^RN represents a hydrogen atom or a hydrocarbon group.

In formula (D-1), X is preferably a group having at least one structure selected from the group consisting of an epoxy structure and an oxetane structure. A preferred aspect of a group in X having at least one structure selected from the group consisting of an epoxy structure, an oxetane structure, a lactone structure, a cyclic carbonate structure, and a cyclic amide-based structure As above.

In formula (D-1), n represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1.

In formula (D-1), L is at least one structure, hydrocarbon group, or hydrocarbon group selected from the group consisting of urea bond, urethane bond and amide bond not included in the ring structure. An n+m-valent linking group represented by a combination of at least one structure from the group consisting of -O- and -C(=O)- is preferable. As the hydrocarbon group in L, it can be any of the groups represented by aromatic hydrocarbon groups, aliphatic hydrocarbon groups or their bonds, and the groups represented by aromatic hydrocarbon groups, aliphatic saturated hydrocarbon groups or their bonds are relatively good. In addition, it is preferable that L contains an aromatic hydrocarbon group. When L contains an aromatic hydrocarbon group, L is selected from the group including urea bonds, urethane bonds, and amide bonds not included in the ring structure. It is preferable that at least one structure in the group is directly bonded to an aromatic hydrocarbon group. As the aromatic hydrocarbon group in L, 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. As the aliphatic hydrocarbon group in L, an aliphatic saturated hydrocarbon group is preferred, an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms is more preferred, and an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms is still more preferred.

式（L-1）中，R ¹及R ²分別獨立地表示單鍵、-NR ^N-或-O-，R ¹及R ²中的至少1個為-NR ^N-，R ^N分別獨立地表示氫原子或1價的有機基團，Ar表示芳香族烴基，*及#分別表示與其他結構的鍵結部位。 Among them, L preferably contains a group represented by the following formula (L-1). [chemical formula 35]

In formula (L-1), R ¹ and R ² each independently represent a single bond, -NR ^N - or -O-, at least one of R ¹ and R ² is -NR ^N -, and R ^N each independently Represents a hydrogen atom or a monovalent organic group, Ar represents an aromatic hydrocarbon group, and * and # represent bonding sites with other structures, respectively.

When L includes a group represented by formula (L-1), R ¹ and R ² are both -NR ^N - or R ¹ is -NR ^N -, and R ² is -O-, which is preferable.

In formula (L-1), preferred aspects of R ^N are as described above.

In the formula (L-1), an Ar-based aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, and a phenylene group is more preferable.

In the case where L includes a group represented by formula (L-1), * in formula (L-1) can be one side of the bond with X in formula (B-1), or it can be with Z On one side of the bond, the orientation of the structure represented by the formula (L-1) in the formula (B-1) is not particularly limited, and the side where * is bonded to X is preferable.

〔Molecular weight〕 The molecular weight of compound D is preferably from 200 to 1,000, more preferably from 220 to 800, and still more preferably from 240 to 500.

[Specific examples] Specific examples of the compound D are not particularly limited, and examples include compounds having the following structures. In addition, glycidyl (meth)acrylate, (3-ethyloxycyclobutan-3-yl)methyl (meth)acrylate, and the like can also be used as the compound D. [chemical formula 36]

The content of compound D with respect to the total solid content of the resin composition of this invention is 0.1-60 mass %, 1-40 mass % is more preferable, 3-30 mass % is still more preferable.

〔polymerization initiator〕 The resin composition of the present invention preferably includes a polymerization initiator, more preferably includes a radical polymerization initiator. The radical polymerization initiator preferably includes a radical polymerization initiator capable of initiating polymerization by light and/or heat. It is particularly preferable to include 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. In addition, it may be an active agent that interacts with a sensitizer excited by light to generate active radicals.

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).

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.

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.

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.

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).

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. ).

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.

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.

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.

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.

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.

As preferred oxime compounds, for example, compounds of the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetyloxyiminobutan-2-one, 3 -Propionyloxyiminobutan-2-one, 2-Acetyloxyiminopentan-3-one, 2-Acetyloxyimino-1-phenylpropan-1-one , 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-tosyloxy)iminobutan-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.

[chemical formula 37]

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]

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.

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.

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.

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.

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.

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.

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.

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]

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 A sulfonyl group, an arylsulfonyl group, an acyloxy group or an amino group, and R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent. Among them, at least one of R ^X10 to R ^X14 is an electron withdrawing group.

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.

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.

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.

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.

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.

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.

[chemical formula 40]

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.

[chemical formula 41]

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 in the above formula (I).

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.

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.

When a photoradical polymerization 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% by mass relative to the total solid content of the resin composition of the present invention. -15 mass %, More preferably, it is 1.0-10 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.

〔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.

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.

[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.

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.

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.

<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. The base generator mentioned here does not include the above-mentioned specific resins. A thermal base generator and a photobase generator are mentioned as a base generator suitable for the resin composition of this invention. 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]

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.

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.

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 exerted. 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 .

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.

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]

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 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 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.

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

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.

[chemical formula 45]

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.

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]

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.

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

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 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.

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.

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 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 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

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.

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.

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.

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.

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.

As the base generating agent, the following examples can be mentioned, but the present invention should not be construed as limited thereto.

[chemical formula 48]

式（B-1）中，R ^B1及R ^B2分別獨立地表示有機基團，R ^B1及R ^B2可以鍵結而形成環結構，具有虛線部分之鍵表示單鍵或雙鍵，*分別表示與其他結構的鍵結部位。 Moreover, the compound which has the structure represented by following formula (B-1) is also preferable as a nonionic base generator. [chemical formula 49]

In the formula (B-1), R ^B1 and R ^B2 independently represent an organic group, and R ^B1 and R ^B2 can be bonded to form a ring structure. A bond with a dotted line represents a single bond or a double bond, and * represents the Bonding sites of other structures.

In formula (B-1), preferred aspects of R ^B1 and R ^B2 are the same as those of R ¹ and R ² in formula (3-1) above. In the formula (B-1), it is preferable that the bond having a dotted line part is a double bond. Also, when the bond having a dotted line portion is a single bond, it is preferable that the two carbon atoms included in the single bond be a member ring of one ring structure.

The molecular weight of the compound represented by formula (B-1) is preferably at most 10,000, more preferably at most 8,000, and still more preferably at most 5,000. Moreover, it is preferable that the said molecular weight is 2,000 or less, and it is still more preferable that it is 1,000 or less. The lower limit of the above-mentioned molecular weight is not particularly limited, for example, 100 or more is preferable.

Examples of the compound represented by the formula (B-1) include the following compounds, but are not limited thereto. [chemical formula 50]

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.

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.

Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto. [chemical formula 51]

Specific examples of imide salts include the following compounds, but the present invention is not limited thereto. [chemical formula 52]

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. Also, in the present invention, since a base can also be generated from a specific resin, it can be designed to reduce the content of the base generator compared to a conventional resin composition containing a base generator and a cyclized resin or its precursor. As a result, it is considered that the residue of the base generator after base generation, the undecomposed base generator itself, and the like are less likely to remain in the composition, thereby improving the moisture resistance. Among these aspects, an aspect in which the content of the base generating agent is 2% by mass or less with respect to 100 parts by mass of the resin is also preferable. Furthermore, the aspect which makes content of a base generating agent 1 mass % or less with respect to 100 mass parts of resins is also preferable, and the aspect which is 0.5 mass % or less is more preferable. Moreover, the aspect which makes content of a base generator into 1 mass % or less with respect to 100 mass parts of resins is also preferable. In these aspects, the lower limit of the content of the base generator may be 0% by mass. The content of the base generator can be determined in consideration of the amount of base generated from a specific resin, heating conditions, and the like.

<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.

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.

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.

As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone (levoglucosenone), dihydro Levoglucosone and the like are preferred.

As the cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferred.

As the arsonites, for example, dimethyl arsonite is preferred.

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.

Ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like as preferred ones.

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.

Regarding the solvent, it is also preferable to mix two or more types from the viewpoint of improving the properties of the coated surface.

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.

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.

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.

＜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.

〔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.

[chemical formula 53]

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.

〔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.

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.

The content of the metal adhesion improving agent is preferably in the range of 0.1 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.

＜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.

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.

Alternatively, an ion trapping agent that traps anions such as halogen ions can also be used.

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.

Specific examples of migration inhibitors include the following compounds.

[chemical formula 54]

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.

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.

＜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. .

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.

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.

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.

＜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.

〔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.

By including a surfactant in the resin composition of the present invention, the liquid properties (especially fluidity) when it is made into a coating liquid can be further improved, and the uniformity of coating thickness and liquid-saving property can be further improved. 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.

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 SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, 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 55]

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.

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.

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), KP-341, KF6001, KF6002 (manufactured by Shin- Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie GmbH), etc.

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.

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.

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.

Specific examples of the anionic surfactant include W004, W005, W017 (Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Kasei Co. Ltd.), and the like.

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.

〔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.

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.

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.

〔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.

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.

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.

〔Inorganic particles〕 The resin composition of the present invention may contain inorganic 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.

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 said average particle diameter of an inorganic particle is a primary particle diameter, and is a 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.

〔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.

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.

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.

〔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.

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.

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.

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.

〔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 preferable. 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.

[chemical formula 56]

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.

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.

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.

The compound represented by the general formula (3) may be exemplified by the following compounds, but is not limited to the following structures.

[chemical formula 57]

[chemical formula 58]

[chemical formula 59]

[chemical formula 60]

The amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the resin system. 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.

〔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.

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 %.

〔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.

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 %.

〔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.

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.

<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.

<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.

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.

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.

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.

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.

＜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

<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.

＜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.

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.

(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.

＜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.

〔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).

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.

Coating is preferred as a method for applying the resin composition of the present invention to a substrate.

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.

＜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.

<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.

The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, preferably 240 to 550 nm.

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), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser Radiated 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. .

＜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.

＜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.

〔developer〕 As a developing solution used in an image development process, the developing solution containing alkali aqueous solution or an organic solvent is mentioned.

When the developing solution is an alkaline aqueous solution, the alkaline 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, formazan Diethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylamine hydroxide, tetrabutylamine hydroxide, tetrapentylamine hydroxide, tetrahexylamine hydroxide, tetrahydroxide Octylamine, Ethyltrimethylammonium Hydroxide, Butyltrimethylammonium Hydroxide, Methyltripentylammonium Hydroxide, Dibutyldipentylammonium Hydroxide, Dimethylbis(2- 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.

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.

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.

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 %.

The developer may further contain other components. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

[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.

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.

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.

〔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).

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.

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.

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.

The rinse solution may further contain other ingredients. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

[How to supply the rinse solution] The method of supplying the rinsing liquid is not particularly limited as long as the desired pattern can be formed, and there are the following methods: a method of immersing the substrate in the rinsing liquid, a method of supplying the rinsing liquid on the substrate by spin coating, spraying A method of supplying a rinse liquid on a substrate by a shower head, and 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.

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.

＜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, the specific resin is cyclized into a resin 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. Also, since the resin composition of the present invention can obtain a cured film having excellent elongation at break even at low temperatures, it is also preferable to set the heating temperature to 200° C. or lower, and further to 180° C. or lower. Mentioned one by one.

The heating step is preferably a step of promoting the cyclization reaction of the above-mentioned specific resin within the above-mentioned pattern by the action of the base or the like generated from the above-mentioned base generator by heating.

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.

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) is, for example, 30° lower than the boiling point of the solvent contained in the resin composition of the present invention. A temperature of ~200°C is preferred for starting the temperature rise.

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.

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.

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.

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.

<Exposure step after development> The pattern obtained by the development step (in the case of the rinse step, the pattern after rinse) may be used instead of or in addition to the above heating step to expose the pattern after the development step. Post-development exposure step. 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, a reaction of cyclization of a specific resin by exposure of a photobase generator, a reaction of detachment of an acid-decomposable group by exposure of a photoacid generator, and the like 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.

＜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.

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.

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.

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.

＜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 semiconductor 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, Japan Polyimide Aromatic Polymer Research Society/edited "Basic and Application of Latest Polyimide" NTS, August 2010, etc.

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.

(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.

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.

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.

＜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.

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.

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.

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.

(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 .

(Semiconductor device and manufacturing method thereof) The present invention also discloses a semiconductor device including the cured product of the present invention or the laminate of the present invention. Furthermore, 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.

式（1-1）或式（1-2）中，W ¹表示2價的有機基團，X ¹表示4價的有機基團，R ¹～R ³分別獨立地表示下述式（3-1）所表示之基團或式（3-2）所表示之基團，W ²表示2價的有機基團，X ²表示3價的有機基團，樹脂包含選自包括由式（1-1）表示且R ¹及R ²中的至少1個係式（3-1）所表示之基團之重複單元、以及由式（1-2）表示且R ³係式（3-1）所表示之基團之重複單元之群組中之至少1種重複單元。 [化學式62]

式（3-1）、式（3-2）中，Z ¹及Z ²分別獨立地表示有機基團，Z ¹和Z ²可以鍵結而形成環結構，A ²表示氧原子或-NH-，R ¹¹³表示氫原子或一價的有機基團，*表示與其他結構的鍵結部位。 本發明的樹脂的較佳之態樣與上述的本發明的樹脂組成物中所包含之特定樹脂的較佳之態樣相同。 [實施例] (Resin) The resin of the present invention has at least one of the repeating unit represented by the following formula (1-1) and the repeating unit represented by the formula (1-2). [chemical formula 61]

In formula (1-1) or formula (1-2), W ¹ represents a divalent organic group, X ¹ represents a tetravalent organic group, and R ¹ to R ³ independently represent the following formula (3- 1) The group represented by or the group represented by formula (3-2), W ² represents a divalent organic group, X ² represents a trivalent organic group, and the resin contains a group selected from the group consisting of formula (1- 1) Represents and at least one of R ¹ and R ² is a repeating unit of the group represented by formula (3-1), and is represented by formula (1-2) and R ³ is represented by formula (3-1) At least one repeating unit in the group of repeating units of the group represented. [chemical formula 62]

In formula (3-1) and formula (3-2), Z ¹ and Z ² independently represent an organic group, Z ¹ and Z ² can be bonded to form a ring structure, A ² represents an oxygen atom or -NH- , R ¹¹³ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures. The preferable aspect of the resin of this invention is the same as the preferable aspect of the specific resin contained in the above-mentioned resin composition of this invention. [Example]

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.

<Synthesis of polyimide precursor resin (SA-1)> 19.1 g (61.2 mmol) of 4,4'-oxydiphthalic dianhydride, 12.3 g (94 mmol) of 2-Hydroxyethyl methacrylate, 0.05 g of hydroquinone, 21.5 g (272 mmol) of pyridine, and 80 g of diglyme were mixed and stirred at 25°C. Next, 2.18 g (30.6 millimoles) of pyrrolidine was dissolved in 10 g of diglyme and added dropwise over 30 minutes, then stirred at 60° C. for 4 hours, and cooled to 25° C. . Next, after cooling the said reaction liquid to -10 degreeC, 15.3 g (127 mmoles) of thionyl chlorides were dripped over 90 minutes, and it stirred for 2 hours. Next, what dissolved 18.8 g (51 millimoles) of 4,4'-bis (4-aminophenoxy) biphenyl in 100 mL of NMP was dripped over 1, and it stirred for 2 hours. Then, add ethanol 9.0g (195 mmoles), stir the mixture for 2 hours, make the polyimide precursor resin precipitate in 4 liters of water, and the water-polyimide precursor resin mixture is heated at a speed of 500rpm Stirred for 15 minutes. The polyimide precursor resin was collected by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor resin was dried at 45 degreeC under reduced pressure for 2 days, and the polyimide precursor (SA-1) was obtained. The obtained polyimide precursor SA-1 had a weight average molecular weight (Mw) of 23,100 and a number average molecular weight (Mn) of 8,900. The structure of SA-1 is presumed to be a structure represented by the following formula (SA-1). [chemical formula 63]

＜Synthesis of polyimide precursor resin (SA-2～SA-5)＞ The types of amine (pyrrolidine in the synthesis of SA-1) and alcohol (2-hydroxyethyl methacrylate in the synthesis of SA-1) and the molar ratios were changed as described in the following table, and Carboxylic anhydride (4,4'-oxydiphthalic dianhydride in the synthesis of SA-1) and diamine (4,4'-bis(4-amino group in the synthesis of SA-1) were appropriately changed phenoxy)biphenyl), and SA-2 to SA-5 were synthesized in the same manner as SA-1. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of these resins are described in the columns of Mw and Mn in the table below, respectively. The structures of SA-2 to SA-5 are presumed to be structures represented by the following formulas (SA-2) to (SA-5), respectively. In the following formulae, subscripts in parentheses representing repeating units represent the molar ratio of each repeating unit.

[化學式65]

[Table 1] Resin name Amines used Alcohol used Amine/alcohol molar ratio mw mn SA-2 cis octahydroisoindole 2-Hydroxyethyl methacrylate 10/90 25200 11000 SA-3 Pyrrolidine/Methylcyclohexylamine=80/20mol% 2-Hydroxyethyl methacrylate 50/50 19500 7900 SA-4 Pyrrolidine 2-Hydroxyethyl methacrylate 30/70 20500 8400 SA-5 Pyrrolidine 2-Hydroxyethyl methacrylate 25/75 22000 8900 [chemical formula 64]

[chemical formula 65]

<Synthesis of CSAH-1> In a flask equipped with a stirrer and a condenser, 22.1 g (105 millimoles) of trimellitic anhydride chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), pyridine (Tokyo Chemical Industry Co., Ltd.) 8.70 g was dissolved in 150 mL of tetrahydrofuran, and cooled to below 0 to 10°C. Next, 13.0 g (100 millimoles) of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour, and after stirring at 0 to 10°C for 1 hour, the temperature was raised to 25°C. and stirred for 3 hours. Next, the reaction solution was diluted with 700 mL of ethyl acetate, and transferred to a separatory funnel. Next, this was washed with 200 mL of water, 300 mL of saturated sodium bicarbonate (baking soda), 300 mL of dilute hydrochloric acid, and 300 mL of saturated saline, and the organic layer was dried with magnesium sulfate and filtered, and the organic solvent was removed by a distiller. , thus obtaining 25g of CSAH-1. It was confirmed to be CSAH-1 by ¹ H-NMR spectrum. [chemical formula 66]

<Synthesis of CSA-1> In a flask equipped with a stirrer and a condenser, 20.0 g (135 mmol) of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 200 mL of ethyl acetate , and cooled to below 0-10°C. Next, 8.64 g (122 mmol) of pyrrolidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour, stirred at 0 to 10°C for 1 hour, then heated to 25°C and stirred for 3 hours. . Next, the precipitated crystals were filtered, washed with 100 mL of ethyl acetate, and filtered. This was dried at 25° C. for 24 hours to obtain 19 g of CSA-1. It was confirmed to be CSA-1 by ¹ H-NMR spectrum. [chemical formula 67]

<Synthesis of CSA-2 to CSA-8> CSA-2 to CSA-8 were synthesized in the same manner as the synthesis of CSA-1 above, except that the raw materials were appropriately changed. [chemical formula 68]

<Synthesis of CS-1> In a flask equipped with a stirrer and a condenser, 11.0 g (50 millimoles) of CSA-1, 4-methoxyaniline (Tokyo Chemical Industry Co., Ltd.) 6.16 g (50 mmol), 4-methylaminopyridine (Tokyo Chemical Industry Co., Ltd.) 7.41 g (60 mmol), tetrahydrofuran 100 g, and cooled to 0 to 10 below ℃. Next, 11.5 g (60 millimoles) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at 0 After stirring at ~10°C for 1 hour, the temperature was raised to 25°C and stirred for 3 hours. Next, the above reaction solution was poured into 500 mL of ethyl acetate, transferred to a separatory funnel, washed with 300 mL of water, 300 mL of saturated sodium bicarbonate (baking soda), and 300 mL of 1N hydrochloric acid water in this order, and dried with magnesium sulfate. Ethyl acetate was removed using a distiller. After adding and dissolving 70 g of tetrahydrofuran there, 700 g of hexane precipitated, and the mixture was stirred for 30 minutes and filtered. This was dried at 25° C. for 24 hours to obtain 19 g of CS-1. It was confirmed to be CS-1 by ¹ H-NMR spectrum. [chemical formula 69]

<Synthesis of BS-1> In a flask equipped with a stirrer and a condenser, 27.44 g (200 mmoles) of 2-(4-aminophenyl) ethyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd. ), 0.03 g of p-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 250 mL of tetrahydrofuran, and cooled to 0°C. Next, 29.48 g (190 millimoles) of Karenz MOI (manufactured by Showa Denko KK) was added dropwise over 1 hour, and after stirring at 0° C. to 10° C. for 1 hour, the mixture was heated up to 25° C. and stirred for 2 hours. Next, this was precipitated in a solution of 800 mL of ethyl acetate/200 mL of hexane, and filtered. Next, the filtrate was stirred in 500 mL of ethyl acetate for 1 hour, and filtered. This was dried at 45° C. for 24 hours to obtain 45 g of BS-1. It was confirmed to be BS-1 by ¹ H-NMR spectrum. [chemical formula 70]

<Synthesis of BS-2> In a flask equipped with a stirrer and a condenser, 13.0 g (100 mmol) of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), p-methoxy 0.001 g of phenylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.01 g of Neostan U-600 (manufactured by NITTO KASEI CO,. LTD.) were dissolved in 60 mL of tetrahydrofuran, and stirred at 25°C. Next, 11.9 g (100 millimoles) of phenylisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour, and then the temperature was raised to 50° C., followed by stirring for 4 hours. Next, this was dissolved in 800 mL of ethyl acetate, and transferred to a separatory funnel. Next, washing was performed in this order with dilute hydrochloric acid, sodium bicarbonate, and saturated saline, and the solvent was removed by a distiller to obtain 18 g of BS-2. It was confirmed to be BS-2 by ¹ H-NMR spectrum. [chemical formula 71]

<Synthesis of SA-6> 19.1 g (61.2 mmol) of 4,4'-oxydiphthalic dianhydride, 13.9 g (105 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 21.5 g (272 mmol) of pyridine, and 80 g of diglyme were mixed and stirred at 25°C. Next, 1.31 g (18.4 millimoles) of pyrrolidine was dissolved in 10 g of diglyme and added dropwise over 30 minutes, followed by stirring at 60°C for 4 hours and cooling to 25°C . Next, after adding 2.42 g of CSA-1 and cooling the said reaction liquid to -10 degreeC, 18.1 g (150 millimoles) of thionyl chlorides were dripped over 90 minutes, and it stirred for 2 hours. Next, what dissolved 22.4 g (60.6 millimoles) of 4,4'-bis(4-aminophenoxy)biphenyl in 100 mL of NMP was dripped over 1 hour, and it stirred for 3 hours. Next, 100 mL of tetrahydrofuran was added, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again, and the obtained polyimide precursor resin was dried under reduced pressure at 45° C. for 24 hours. Next, the dried polyimide precursor resin was dissolved in 300 mL of tetrahydrofuran, 50 g of ion exchange resin was added and stirred for 6 hours, and then the polyimide precursor resin was precipitated in 4 liters of water, and the water-polymer The imide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, and dried at 45° C. for 2 days to obtain a polyimide precursor (SA-6). The obtained polyimide precursor SA-6 had a weight average molecular weight of 19,700 and a number average molecular weight of 7,900. The structure of SA-6 is presumed to be a structure represented by the following formula (SA-6). [chemical formula 72]

＜Synthesis of polyimide precursor resin (SA-7～SA-12)＞ The types of amines (pyrrolidine in the synthesis of SA-6) and alcohols (2-hydroxyethyl methacrylate in the synthesis of SA-6), the molar ratios, and the blocking agent (synthesis of SA-6 CSA-1) in the table was changed as described in the following table, and the carboxylic anhydride (4,4'-oxydiphthalic dianhydride in the synthesis of SA-6) and diamine (4, 4'-bis(4-aminophenoxy)biphenyl) and SA-7 to SA-12 were synthesized in the same manner as SA-6. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of these resins are described in the columns of Mw and Mn in the table below, respectively. The structures of SA-7 to SA-12 are presumed to be structures represented by the following formulas (SA-7) to (SA-12), respectively.

[Table 2] Resin name Amines used Alcohol used Amine/alcohol molar ratio Capping agent mw mn SA-7 Pyrrolidine 2-Hydroxyethyl methacrylate 10/90 CSA-7 16900 6500 SA-8 Pyrrolidine 2-Hydroxyethyl methacrylate 0.5/99.5 CSA-5 18900 7200 SA-9 3,5-Dimethylpiperidine 2-Hydroxyethyl methacrylate 30/70 CSA-1 21800 8600 SA-10 Morpholine 2-Hydroxyethyl methacrylate 25/75 CSA-1 20000 8100 SA-11 Pyrrolidine Glycerin Dimethacrylate 25/75 CSA-2 26400 9800 SA-12 Pyrrolidine BS-1 25/75 CSA-6 35200 12600

[化學式74]

[chemical formula 73]

[chemical formula 74]

<Synthesis of SA-13> 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a separate flask, and 97.6 g of 2-hydroxyethyl methacrylate (HEMA) was added , 17.8g of pyrrolidine and 400ml of γ-butyrolactone. While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After the heat generation due to the reaction ended, it was naturally cooled to room temperature, and then left still for 16 hours. Next, after adding CSA-3 to 15.2 g of the reaction solution under ice cooling, a solution obtained by dissolving 243 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was stirred, and passed through Added to the reaction mixture for 40 minutes. Next, a suspension obtained by suspending 99.1 g of 4,4'-diaminodiphenyl ether in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethanol was added, followed by stirring for 1 hour. Then, 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was collected by filtration to obtain a reaction liquid. The obtained reaction solution was added to 3 liters of ethanol to form a precipitate consisting of a crude polymer. The resulting crude polymer was collected by filtration, and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and vacuum-dried to obtain powdery polymer SA-13. The weight average molecular weight (Mw) of this polymer SA-13 was measured to be 20,100, and the number average molecular weight (Mn) was 8,000. The structure of SA-13 is presumed to be a structure represented by the following formula (SA-13). [chemical formula 75]

<Synthesis of SA-14> 19.1 g (61.2 mmol) of 4,4'-oxydiphthalic dianhydride, 0.05 g of hydroquinone, 21.5 g (272 mmol) of pyridine, 80 g The diglyme was mixed and stirred at 25 °C. Next, 2.45 g (40 mmol) of pyrrolidine, 5.01 g (40 mmol) of cis-octahydroisoindole, 7.97 g (43 mmol) of 2-(tert-butyl The amino)ethyl group was dissolved in 20 g of diglyme and added dropwise over 1 hour, then stirred at a temperature of 60°C for 4 hours, and cooled to 25°C. Next, after adding 2.52 g of CSA-7 and cooling the said reaction liquid to -10 degreeC, 15.5 g (129 millimoles) of thionyl chlorides were dripped over 90 minutes, and it stirred for 2 hours. Next, what dissolved 12.1 g (60.6 millimoles) of 4,4'- diaminodiphenyl ether in 100 mL of NMP was dripped over 1 hour, and it stirred for 3 hours. Next, 100 mL of tetrahydrofuran was added, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again, and the obtained polyimide precursor resin was dried under reduced pressure at 45° C. for 24 hours. Next, the dried polyimide precursor resin was dissolved in 300 mL of tetrahydrofuran, 50 g of ion exchange resin was added and stirred for 6 hours, and then the polyimide precursor resin was precipitated in 4 liters of water, and the water-polymer The imide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, and dried at 45° C. for 2 days to obtain a polyimide precursor (SA-14). The obtained polyimide precursor SA-14 had a weight average molecular weight of 22,000 and a number average molecular weight of 8.600. The structure of SA-14 is presumed to be a structure represented by the following formula (SA-14). [chemical formula 76]

＜Synthesis of SA-15～SA-18＞ The types of amines (pyrrolidine, cis-octahydroisoindole, 2-(tertiary butylamino) ethyl methacrylate in the synthesis of SA-14) and alcohols, the molar ratios and the capping The agent (CSA-7 in the synthesis of SA-6) was changed as described in the following table, and the carboxylic anhydride (4,4'-oxydiphthalic dianhydride in the synthesis of SA-14 was changed appropriately) ) and diamine (4,4'-diaminodiphenyl ether), and SA-15 to SA-18 were synthesized in the same manner as SA-14. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of these resins are described in the columns of Mw and Mn in the table below, respectively. The structures of SA-15 to SA-18 are presumed to be structures represented by the following formulas (SA-15) to (SA-18), respectively.

[table 3] Resin name Amines used or Alcohols used A/B/C (mol ratio) Capping agent MW mn A B C SA-15 Pyrrolidine cis octahydroisoindole 2-(tert-butylamino)ethyl methacrylate 30/20/50 CSA-7 16900 6500 SA-16 Pyrrolidine 2-(tert-butylamino)ethyl methacrylate - 30/70 CSA-4 18900 7200 SA-17 Pyrrolidine - - 100 CSA-l 21800 8600 SA 18 Pyrrolidine 2-Hydroxyethyl methacrylate - 45/55 CSA 1 20000 8100

[chemical formula 77]

Here, the ratio (%) of the total molar amount of the group represented by the formula (3-1) in each resin, and the ratio (% ) as shown in the table below. In addition, in the following tables, the description in the column of "ratio 1" represents the total mole of the group represented by the formula (3-1) and the group represented by the formula (3-2) contained in the resin The proportion (%) of the total molar amount of the group represented by the formula (3-1).

[Table 4] Resin name The ratio of the total molar amount of the group represented by formula (3-1) The ratio of the total molar amount of the group represented by formula (3-2) Scale 1 SA-1 15 85 15 SA-2 10 90 10 SA-3 50 50 50 SA-4 30 70 30 SA-5 25 75 25 SA-6 15 85 15 SA-7 10 90 10 SA-8 0.5 99.5 0.5 SA-9 30 70 30 SA-10 25 75 25 SA-11 25 75 25 SA-12 25 75 25 SA-13 25 75 25 SA-14 100 0 100 SA-15 100 0 100 SA-16 100 0 100 SA-17 100 0 100 SA-18 45 55 45

<Synthesis of C-1> In a flask equipped with a stirrer and a condenser, 27.44 g (200 mmoles) of 2-(4-aminophenyl) ethyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd. ), 0.03 g of p-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 250 mL of tetrahydrofuran, and cooled to 0°C. Next, 29.48 g (190 millimoles) of Karenz MOI (manufactured by Showa Denko KK) was added dropwise over 1 hour, and after stirring at 0° C. to 10° C. for 1 hour, the mixture was heated up to 25° C. and stirred for 2 hours. Next, this was precipitated in a solution of 800 mL of ethyl acetate/200 mL of hexane, and filtered. Next, the filtrate was stirred in 500 mL of ethyl acetate for 1 hour, and filtered. This was dried at 45° C. for 24 hours to obtain 45 g of C-1. It was confirmed to be C-1 by ¹ H-NMR spectrum. [chemical formula 78]

<Synthesis of BMB-1> Add 8.88g (52.5mmol) of CSA-3, 2,2-bis[4-(4-amino group) synthesized above to a flask equipped with a stirrer and a condenser phenoxy)phenyl]propane 10.26g (25mmol), 4-methylaminopyridine 1.22g (10mmol), 1-(3-dimethylaminopropyl)-3-ethane 10.54 g (55 mmol) of carbodiimide hydrochloride and 60 g of tetrahydrofuran were stirred at 25° C. for 6 hours. Next, the reaction solution was transferred to a separatory funnel while diluting it with 500 mL of ethyl acetate, washed with 300 mL of water, 300 mL of dilute hydrochloric acid, 300 mL of saturated sodium bicarbonate (baking soda), and 300 mL of saturated saline, and washed with magnesium sulfate. 50 g was dried. After filtering this with filter paper, the solvent was removed in a distiller to obtain 11 g of BMB-1. It was confirmed to be BMB-1 by ¹ H-NMR spectrum. [chemical formula 79]

<Synthesis of BMB-2> Except having changed CSA-1 of BMB-1 to CSA-8, it synthesize|combined by the method similar to BMB-1. [chemical formula 80]

<Synthesis of Comparative Example Cmp-1> 〔Cmp-1: Polyimide precursor synthesized from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (Cmp- 1: Polyimide precursor with radical polymerizable group)] Put 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) into a separate flask, and add 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone . While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After the heat generation due to the reaction ended, it was naturally cooled to room temperature, and then left still for 16 hours. Next, under ice cooling, stirring a solution in which 206.3 g of dicyclohexylcarbodiimide (DCC) was dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes. Next, a suspension obtained by suspending 93.0 g of 4,4'-diaminodiphenyl ether in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethanol was added, followed by stirring for 1 hour. Then, 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was collected by filtration to obtain a reaction liquid. The obtained reaction solution was added to 3 liters of ethanol to form a precipitate consisting of a crude polymer. The resulting crude polymer was collected by filtration, and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and vacuum-dried to obtain powdery polymer Cmp-1. As a result of measuring the weight average molecular weight (Mw) of this polymer Cmp-1, it was 24,000.

＜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 of each component described in the table was set to the amount (parts by mass) described in the column of "addition amount" in each column of the table. The obtained resin composition and the composition for comparison were subjected to pressure filtration using a polytetrafluoroethylene filter having a pore width of 0.5 μm. In addition, in the table, description of "-" shows that a composition does not contain a corresponding component.

[table 5] resin polymeric compound polymerization initiator base generator migration inhibitor metal adhesion improver polymerization inhibitor other additives solvent hardening condition Developing method (developing solution) elongation at break Drug resistance Moisture resistance type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added temperature Example 1 SA-1 32 SR-209 5.9 OXE-01 1.2 - 0 E-1 0.12 F-1 0.7 G-2 0.08 one one DMSO/GBL 60 180°C Solvent (cyclopentanone) A B A Example 2 SA-2 31 BS-2 6.8 OXE-02 1.2 D-2 0.1 E-2 0.12 F-2 0.7 G-2 0.08 one one NMP 60 180°C Solvent (cyclopentanone) A A B Example 3 SA-3 32 SR-209/BS-1 7.9 OXE-01 1.2 - 0 E-3 0.12 F-1 0.7 G-1 0.08 one one DMSO/GBL 58 180°C Solvent (cyclopentanone) B A B Example 4 SA-4 32 SR-209 6.0 OXE-02 0.8 - 0 E-4 0.1 F-1 1.0 G-2 0.1 one one DMSO/GBL 60 180°C Solvent (cyclopentanone) A B B Example 5 SA-5 30.5 SR-209 7.4 OXE-01 1.2 - 0 E-5 0.12 F-2 0.7 G-2 0.08 one one DMSO/GBL 60 180°C Solvent (cyclopentanone) B B B Example 6 SA-1 31.8 SR-209/BS-2 6.0 OXE-01 1.2 D-1 0.1 E-6 0.12 F-3 0.7 G-2 0.08 one one DMSO/GBL 60 180°C Solvent (cyclopentanone) A A A Example 7 SA-2 31.5 BS-1 5.0 OXE-01 1.4 CS-1 1.5 - 0 F-1 0.5 G-2 0.1 one one DMSO/GBL 60 180°C Solvent (cyclopentanone) A A A Example 8 SA-1 33 SR-231 4.9 OXE-01 1.3 - 0 E-3 0.2 - 0 G-3 0.1 H-1 0.5 DMSO/GBL 60 180°C Solvent (cyclopentanone) A B A Example 9 SA-16 40 - 0.0 - 0 - 0 - 0 - 0 - 0 one 0 NMP 60 180°C - A - - Example 10 SA-6 32 SR-209 5.9 OXE-01 1.2 - 0 E-1 0.12 F-1 0.7 G-2 0.08 one one DMSO/GBL 60 180°C Solvent (cyclopentanone) A B A Example 11 SA-7 32.2 BS-2 4.7 OXE-02 1.2 CS-1 1.0 E-2 0.12 F-2 0.7 G-2 0.08 one one DMSO/GBL 60 180°C Solvent (cyclopentanone) A A A Example 12 SA-8 32 SR-209/BS-1 5.7 OXE-01 1.2 D-2 2.2 E-3 0.12 F-1 0.7 G-1 0.08 one one DMSO/GBL 58 180°C Solvent (cyclopentanone) B B B Example 13 SA-9 32 SR-209 6.0 OXE-02 0.8 - 0 E-4 0.1 F-1 1.0 G-2 0.1 one one NMP 60 180°C Solvent (cyclopentanone) B B A Example 14 SA-10 30.5 BS-1 5.4 OXE-01 1.2 D-3 2 E-5 0.12 F-2 0.7 G-2 0.08 one one NMP 60 180°C Solvent (cyclopentanone) A A A Example 15 SA-11 32 BS-2 5.9 OXE-01 1.2 - 0 E-1 0.12 F-1 0.7 G-2 0.08 one one DMSO/GBL 60 180°C Solvent (cyclopentanone) B A A

[Table 6] resin polymeric compound polymerization initiator base generator migration inhibitor metal adhesion improver polymerization inhibitor other additives solvent hardening condition Developing method (developing solution) elongation at break Drug resistance Moisture resistance type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added temperature Example 16 SA-12 32 SR-209 5.9 OXE-01 1.2 - 0 E-1 0.12 F-1 0.7 G-2 0.08 one one DMSO/GBL 60 180°C Solvent (cyclopentanone) B A B Example 17 SA-13 32 BS-1 5.9 OXE-01 1.2 - 0 E-1 0.12 F-1 0.7 G-2 0.08 one one NMP 60 180°C Solvent (cyclopentanone) A A B Example 18 SA-14 32 BS-2 5.9 OXE-01 1.2 - 0 E-1 0.12 F-1 0.7 G-2 0.08 one one NMP 60 180°C Solvent (cyclopentanone) A B A Example 19 SA-15 31.2 BS-1 4.5 OXE-01 1.2 CS-1 2.2 E-1 0.12 F-1 0.7 G-2 0.08 one one DMSO/GBL 60 180°C Solvent (cyclopentanone) A A A Example 20 SA-16/Cmp-1 22 /10 SR-209 5.9 OXE-01 1.2 - 0 E-1 0.12 F-1 0.7 G-4 0.08 one one DMSO/GBL 60 180°C Solvent (cyclopentanone) B B A Example 21 SA-17 32 BS-1 5.9 OXE-01 1.2 - 0 E-1 0.12 F-1 0.7 G-2 0.08 one one DMSO/GBL 60 180°C Solvent (cyclopentanone) B A A Example 22 SA-18 32 BS-1 5.9 OXE-01 1.2 - 0 E-1 0.12 F-1 0.7 G-2 0.08 one one DMSO/GBL 60 200℃ Solvent (cyclopentanone) B A B Example 23 SA-1 32 SR-209 5.9 OXE-01 1.2 - 0 E-1 0.12 F-1 0.7 G-2 0.08 one one DMSO/GBL 60 200℃ Solvent (cyclopentanone) A A A Example 24 SA-1 32 SR-209 5.9 OXE-01 1.2 - 0 E-1 0.12 F-1 0.7 G-2 0.08 one one DMSO/GBL 60 230°C Solvent (cyclopentanone) A A A Example 25 SA-15 31.2 BS-1 4.5 OXE-01 1.2 CS-1 2.2 E-1 0.12 F-1 0.7 G-2 0.08 one one NMP 60 200℃ Solvent (cyclopentanone) A A A Example 26 SA-16 31.2 BS-1 4.5 OXE-01 1.2 CS-1 2.2 E-1 0.12 F-1 0.7 G-2 0.08 one one DMSO/GBL 60 230°C Solvent (cyclopentanone) A A A Comparative example 1 Cmp-1 32 SR-209 5.9 OXE-01 1.2 - 0 E-1 0.12 F-3 0.7 G-4 0.08 one one DMSO/GBL 60 180°C Solvent (cyclopentanone) C D. C Comparative example 2 Cmp-1 30 SR-209 4.5 OXE-01 1.2 D-3 3.4 E-1 0.12 F-1 0.7 G-2 0.08 one one DMSO/GBL 60 180°C Solvent (cyclopentanone) C C D.

[Table 7] resin Compound B polymeric compound polymerization initiator base generator migration inhibitor metal adhesion improver polymerization inhibitor other additives solvent hardening condition elongation at break Drug resistance hardening shrinkage Moisture resistance type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added temperature Example 27 SA-1 31.5 BM-1 2.0 C-1 4.4 OXE-01 1.2 - - E-1 0.12 F-1 0.7 G-3 0.08 - - DMSO/GBL 60 230°C A A A A Example 28 SA-2 30.5 BM-2 2.4 SR-209 5.0 OXE-01 1.2 - - E-2 0.12 F-1 0.7 G-2 0.08 - - DMSO/GBL 60 230°C A A A B Example 29 SA-3 30.4 BM-3 5.0 A-DPH 2.5 OXE-01 1.2 - - E-3 0.12 F-1 0.7 G-1 0.08 - - DMSO/GBL 60 180°C A B A A Example 30 SA-4 32 BMB-1 2.4 SR-209 3.5 OXE-01 1.2 - - E-4 0.12 F-1 0.7 G-2 0.08 - - DMSO/GBL 60 200℃ A A A A Example 31 SA-5 30 BMB-1 2.4 C-1 /C-3 3.5 /2 OXE-02 1.2 - - E-5 0.12 F-1 0.7 G-3 0.08 - - DMSO/GBL 60 230°C A A A A Example 32 SA-6 31 BMB-2 2.3 SR-209/C-4 3.5 /1.5 OXE-01 1.5 - - E-6 0.15 - - G-2 0.05 - - DMSO/GBL 60 230°C A A A A Example 33 SA-7 31.7 BM-1 2.0 A-DPH/C-4 3.0 /2.0 OXE-01 1.2 - - E-1 0.1 - - - - - - DMSO/GBL 60 180°C B A A A Example 34 SA-8 31 BM-3 1.9 SR-209/C-3 3.0 2.0/ OXE-01 1.2 - - E-1 0.12 F-1 0.7 G-2 0.08 - - DMSO/GBL 60 200℃ A A B A Example 35 SA-9 29.4 BM-2 2.5 C-1/ SR-209 3.0/ 3.0 OXE-02 1.2 - - E-1 0.12 F-2 0.7 G-2 0.08 - - DMSO/GBL 60 230°C A A A A Example 36 SA-10 31.4 BM-3 1.5 A-DPH/C-2 4.0 /1.0 OXE-01 1.2 - - E-1 0.12 F-3 0.7 G-4 0.08 - - DMSO/GBL 60 230°C A A A A Example 37 SA-11 30.2 BM-3 3.5 C-1 /C-4 3.0 /2.0 OXE-01 1.3 - - - - - - - - - - DMSO/GBL 60 230°C A A A A Example 38 SA-12 31.5 BM-3/BMB-1 1.2/ 1.2 C-1 4.0 OXE-01 1.2 - - E-2 0.12 F-1 0.7 G-2 0.08 - - DMSO/GBL 60 230°C A A A A Example 39 SA-13 31.5 BM-3 2.4 SR-209 4.0 OXE-01 1.2 - - E-1 0.12 F-2 0.7 G-2 0.08 - - DMSO/GBL 60 230°C A A B B Example 40 SA-14 31.5 BM-3 2.4 A-DPH 4.0 OXE-01 1.2 - - E-1 0.12 F-1 0.7 G-2 0.08 - - NMP 60 230°C A A B B

[Table 8] resin Compound B polymeric compound polymerization initiator base generator migration inhibitor metal adhesion improver polymerization inhibitor other additives solvent hardening condition elongation at break Drug resistance hardening shrinkage Moisture resistance type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added type Amount added temperature Example 41 SA-15 31.4 BM-3 1.5 C-1/C-3 3.0/1.0 OXE-01 1.2 D-2 1.0 E-1 0.12 F-3 0.7 G-1 0.08 - - DMSO/GBL 60 180°C A B B A Example 42 SA-16 30.5 BM-3 1.4 SR-209/C-4 3.5 /1.5 OXE-01 1.2 - - E-1 0.12 F-3 0.7 G-2 0.08 H-1 1.0 DMSO/GBL 60 180°C A B B A Example 43 SA-17 30.5 BM-3 2.4 A-DPH/C-4 3.0 /2.0 OXE-01 1.2 - - E-1 0.12 F-3 0.7 G-3 0.08 - - DMSO/GBL 60 200℃ A A A B Example 44 SA-18 30.9 BM-3 2.0 C-1/ SR-209 3.0 /2.0 OXE-02 1.2 - - E-1 0.12 F-3 0.7 G-4 0.08 - - DMSO/GBL 60 230°C A A A B Example 45 SA-1 30 BM-2/BM-3 3.0/ 3.9 - - OXE-01 1.2 D-1 1.0 E-1 0.12 F-3 0.7 G-4 0.08 - - DMSO/GBL 60 230°C A A B B Example 46 SA-1 30 BM-1 2.0 C-1 4.4 OXE-01 1.2 - - E-1 0.12 F-1 0.7 G-3 0.08 BS-3 1.5 DMSO/GBL 60 230°C A A A A Example 47 SA-2 30.5 BM-2 2.4 SR-209 3.0 OXE-01 1.2 - - E-2 0.12 F-1 0.7 G-2 0.08 BS-2 2.0 DMSO/GBL 60 200℃ A A A B Example 48 SA-3 30.4 BM-3 3.0 A-DPH 1.5 OXE-01 1.2 - - E-3 0.12 F-1 0.7 G-1 0.08 BS-1 3.0 DMSO/GBL 60 180°C A A A B

The details of each component described in the table are as follows.

[resin] •SA-1~SA-18: SA-1~SA-18 synthesized above • Cmp-1: The above synthetic product (comparative example)

[Compound B] • BM-1: N,N'-Ethylene bismaleimide (manufactured by Tokyo Chemical Industry Co., Ltd.) • BM-2: 1,8-bis(maleimide) diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) • BM-3: 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane (manufactured by Tokyo Chemical Industry Co., Ltd.) •BMB-1～BMB-2: Synthesis of the above

[Polymeric compounds (both are trade names)] • SR-209: SR-209 (manufactured by Sartomer Company, Inc) • SR-231: SR-231 (manufactured by Sartomer Company, Inc) • A-DPH: A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., diperythritol hexaacrylate) • BS-1～BS-2: Synthetic products of the above • C-1: Synthesis of the above • C-2: 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether (manufactured by Tokyo Chemical Industry Co.,Ltd.) • C-3: Diglycidyl 4-cyclohexene-1,2-dicarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.) • C-4: Karenz BEI (SHOWA DENKO K.K.)

[Polymerization initiators (both are trade names)] • OXE-01: IRGACURE OXE 01 (manufactured by BASF Corporation) • OXE-02: IRGACURE OXE 02 (manufactured by BASF Corporation)

[Base Generator] • D-1 to D-2: compounds with the following structures • D-3: WPBG-027 (FUJIFILM Wako Pure Chemical Corporation) • CS-1: the above-mentioned synthetic product [Chemical Formula 81]

[Migration Inhibitor] • E-1 to E-6: Compounds with the following structures [Chemical Formula 82]

[Metal Adhesion Improver] • F-1 to F-3: Compounds with the following structures [Chemical Formula 83]

[Polymerization inhibitor] • G-1: 1,4-benzoquinone • G-2: 4-methoxyphenol • G-3: 1,4-dihydroxybenzene • G-4: a compound of the following structure [ Chemical formula 84]

[Other additives] • H-1: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.) • BS-1 to BS-3: Compounds with the following structures, corresponding to BS-1 to BS-3 A compound in the above-mentioned compound D. [chemical formula 85]

〔Solvent〕 • DMSO: Dimethylsulfone • GBL: gamma-butyrolactone • NMP: N-Methylpyrrolidone In the table, the description of "DMSO/GBL" indicates that DMSO and GBL were mixed at a mixing ratio (mass ratio) of DMSO:GBL=80:20.

<Evaluation> [Evaluation of elongation at break] In each of the Examples and Comparative Examples, a resin composition or a composition for comparison was applied to a silicon wafer by a spin coating method to form a resin layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes, thereby obtaining a uniform resin composition layer with a thickness of about 15 μm on the silicon wafer. The entire surface of the obtained resin composition layer was exposed to i-rays at an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). The above-mentioned exposed resin composition layer (resin layer) is heated at a rate of 10°C/min in a nitrogen atmosphere, and after reaching the temperature described in the "Temperature" column of "Curing Conditions" in the table, heat for 3 hours. The cured resin layer (cured film) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and the cured film was peeled off from the silicon wafer. The peeled cured film was punched out with a punching machine to produce a test piece having a sample width of 3 mm and a sample length of 30 mm. Using a tensile testing machine (TENSILON), the longitudinal direction of the obtained test piece was measured in accordance with JIS-K6251 in an environment with a crosshead speed of 300mm/min, 25°C, and 65%RH (relative humidity). elongation on. The evaluation was carried out five times in real time, and the arithmetic mean value of the elongation (elongation at break) of the test piece at breakage was used as an index value. The above-mentioned index values were evaluated according to the following evaluation criteria, and the evaluation results were described in the column of "elongation at break" in the table. It can be said that the larger the index value is, the more excellent the film strength (elongation at break) of the obtained cured film is. -Evaluation criteria- A: The above index value is 70% or more. B: The above index value is more than 60% and less than 70%. C: The above index value is more than 50% and less than 60%. D: The above index value is less than 50%.

[Evaluation of Chemical Resistance] Each of the resin compositions prepared in Examples and Comparative Examples or the composition for comparison was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes, whereby a uniform resin composition layer having a thickness of 15 μm was formed on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C), expose the entire surface of the resin composition layer on the silicon wafer with an exposure energy of 500mJ/ ^cm2 , and expose the exposed resin composition layer (resin layer) under a nitrogen atmosphere The temperature was raised at a rate of 10° C./min, and heated for 180 minutes at the temperature described in the “Temperature” column of “Curing Conditions” in the table to obtain a cured layer (resin layer) of the resin composition layer. The obtained resin layer was immersed in the following chemical solution under the following conditions, and its dissolution rate was calculated. Chemical solution: 90:10 (mass ratio) mixture of dimethylsulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution , dipped for 15 minutes, compared the film thickness before and after dipping, and calculated the dissolution rate (nm/min). The film thickness was measured at 10 places on the coating surface with an ellipsometer (KT-22 manufactured by Foothill Co., Ltd.), and the film thickness was determined as the arithmetic mean value. Evaluation was performed according to the following evaluation criteria, and the evaluation results were described in the "chemical resistance" column of the table. It can be said that the slower the dissolution rate, the better the chemical resistance. In the case where "-" was described in the column of "chemical resistance" of a table|surface, the evaluation of chemical resistance was not performed. -Evaluation Criteria- A: The dissolution rate is less than 200 nm/min. B: The dissolution rate is 200 nm/minute or more and less than 300 nm/minute. C: The dissolution rate is not less than 300 nm/min and less than 400 nm/min. D: The dissolution rate is 400 nm/minute or more.

[Evaluation of Moisture Resistance] Each of the resin compositions prepared in Examples and Comparative Examples or the composition for comparison was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes, whereby a uniform resin composition layer having a thickness of 15 μm was formed on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C), expose the entire surface of the resin composition layer on the silicon wafer with an exposure energy of 500mJ/ ^cm2 , and expose the exposed resin composition layer (resin layer) under a nitrogen atmosphere The temperature was raised at a rate of 10° C./min, and heated for 180 minutes at the temperature described in the “Temperature” column of “Curing Conditions” in the table to obtain a cured layer (resin layer) of the resin composition layer. The obtained hardened layer was placed in a high-temperature, high-humidity tank at a temperature of 121°C and a humidity of 100% for 250 hours. The hardened layer before and after the input was immersed in the following chemical solution under the following conditions, and the film was measured. decrease. Chemical solution: 90:10 (mass ratio) mixture of dimethylsulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution Evaluation conditions: Immerse the resin layer in the chemical solution at 75°C After 15 minutes, the film thickness before and after immersion was compared, and the film weight reduction (%) was calculated. The film thickness was measured at 10 places on the coating surface with an ellipsometer (KT-22 manufactured by Foothill Co., Ltd.), and the film thickness was determined as the arithmetic mean value. Evaluation was performed according to the following evaluation criteria, and the evaluation results were described in the column of "moisture resistance" in the table. The smaller the difference (%) in film weight loss before and after putting into a high-temperature, high-humidity tank, the better the moisture resistance. The difference in film weight loss before and after high temperature and high humidity input = AB A: film thickness after immersion in the above chemical solution under the above conditions in the hardened layer before input into high temperature and high humidity tank / film thickness before immersion × 100 B: input Film thickness after immersion in the above-mentioned chemical solution under the above-mentioned conditions in the hardened layer after entering the high-temperature and high-humidity tank/film thickness before immersion×100 -Evaluation criteria- A: The difference in film weight loss before and after high-temperature and high-humidity injection is less than 5 %. B: The difference in film weight loss before and after high-temperature and high-humidity injection is 5% or more and less than 10%. C: The difference in film weight loss before and after high-temperature and high-humidity injection is 10% or more and less than 20%. D: The difference in film weight loss before and after high-temperature and high-humidity injection is 20% or more.

[Evaluation of Curing Shrinkage] In each of the Examples and Comparative Examples, a resin composition or a comparative composition was applied to a silicon wafer by a spin coating method to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes, and a uniform curable resin composition layer with a thickness of about 15 μm was obtained on the silicon wafer. The film thickness of the said curable resin composition layer was measured with the reflection spectroscopic film thickness meter (FE-3000 manufactured by OTSUKA ELECTRONICS CO., LTD), and this value was made into "film thickness A". Next, the entire surface of the obtained curable resin composition layer was exposed to i-rays at an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). The temperature of the curable resin composition layer (resin layer) after the above-mentioned exposure is raised at a rate of 10°C/min in a nitrogen atmosphere, and after reaching the temperature described in the "Temperature" column of "Curing Conditions" in the table , heated for 3 hours, and cooled to 25° C. to obtain a hardened product. The film thickness of the above-mentioned cured product was measured with a reflection spectroscopic film thickness meter (FE-3000 manufactured by OTSUKA ELECTRONICS CO., LTD), and this value was set as "film thickness B". The shrinkage rate of the film was calculated by the following calculation formula. Calculation formula: Shrinkage rate (%)=100-(film thickness B÷film thickness A×100) Evaluation was performed according to the following evaluation criteria, and the evaluation results were described in the column of "hardening shrinkage" in the table. The smaller the value of the aforementioned shrinkage ratio is, the more excellent the hardening shrinkage property of the obtained composition layer is. In addition, in the Example or the comparative example which does not have the column of "hardening shrinkage" in a table, the evaluation of hardening shrinkage was not performed. -Evaluation Criteria- A: The shrinkage rate of the film is less than 20%. B: The shrinkage rate of the film is 20% or more and less than 25%. C: The shrinkage rate of the film is 25% or more and less than 30%. D: The shrinkage rate of the film is 30% or more.

From the above results, it can be seen that the cured film composed of the resin composition of the present invention is excellent in elongation at break. The resin contained in the comparative composition of Comparative Examples 1-2 does not contain the repetition of the group represented by formula (1-1) and at least one of R ¹ and R ² is represented by formula (3-1) unit, and any of the repeating units represented by formula (1-2) and R ³ is a group represented by formula (3-1). It can be seen that the elongation at break of the cured films composed of these comparative compositions is poor. <Example 101> Apply the resin composition used in Example 1 in a layered form to the surface of the copper thin layer of the resin substrate with the copper thin layer formed on the surface by spin coating, and dry it at 100°C for 4 minutes. After forming a resin composition layer with a film thickness of 20 μm, exposure was performed using 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 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 3 hours 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 (25)

A resin composition comprising: a resin having at least one of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (1-2); and a solvent, [chemical formula 1]

In formula (1-1) or formula (1-2), W ¹ represents a divalent organic group, X ¹ represents a tetravalent organic group, and R ¹ to R ³ independently represent the following formula (3- 1) The group represented by or the group represented by formula (3-2), W ² represents a divalent organic group, X ² represents a trivalent organic group, the aforementioned resins are selected from the group consisting of formula (1 -1) A repeating unit represented by at least one of R ¹ and R ² is a group represented by formula (3-1), and represented by formula (1-2) and R ³ is a group represented by formula (3-1) At least one repeating unit in the group of repeating units of the represented group, [Chemical Formula 2]

In formula (3-1) and formula (3-2), Z ¹ and Z ² independently represent an organic group, Z ¹ and Z ² can be bonded to form a ring structure, A ² represents an oxygen atom or -NH- , R ¹¹³ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures. The resin composition as described in Claim 1, wherein the group represented by formula (3-1) is the group represented by formula (3-1-1) or formula (3-1-2), [chemical formula 3 ]

In formula (3-1-1), Cy represents an aliphatic ring structure or an aromatic ring structure, * represents a bonding site with other structures, and in formula (3-1-2), Z ³ and Z ⁴ are independently Indicates an alkyl group, and * indicates a bonding site with other structures. The resin composition as described in claim 1 or claim 2, wherein The amount of the group represented by the formula (3-1) relative to the total molar amount of the group represented by the formula (3-1) and the group represented by the formula (3-2) contained in the aforementioned resin The ratio of the molar amount is 0.1 mole % or more. The resin composition as described in claim 1 or claim 2, wherein The amount of the group represented by the formula (3-1) relative to the total molar amount of the group represented by the formula (3-1) and the group represented by the formula (3-2) contained in the aforementioned resin The ratio of the molar amount is 99.9 mol% or less. The resin composition as described in claim 1 or claim 2, wherein The amount of the group represented by the formula (3-1) relative to the total molar amount of the group represented by the formula (3-1) and the group represented by the formula (3-2) contained in the aforementioned resin The ratio of the molar amount is 80 mole% or more. The resin composition according to claim 1 or claim 2, wherein R ¹¹³ in formula (3-2) is a group having a polymerizable group. The resin composition as described in Claim 1 or Claim 2, wherein W ¹ in formula (1-1) or W ² in formula (1-2) includes the following formulas (5) to (7) Any one of the groups represented, [chemical formula 4]

In formula (5), Y ¹ represents a single bond or a divalent linking group, and * respectively represent the bonding sites with other structures. In formula (6), Y ² represents a single bond or a divalent linking group, and * represent respectively Bonding sites with other structures In the formula (7), * represent bonding sites with other structures, respectively. The resin composition as described in claim 1 or claim 2, wherein The weight average molecular weight of the said resin is 10,000 or more. The resin composition as described in claim 1 or claim 2, wherein The acid value of the said resin is 0-1 mmol/g. The resin composition according to claim 1 or claim 2, further comprising a polymerization initiator. The resin composition according to claim 1 or claim 2, further comprising a polymerizable compound. The resin composition as described in claim 11, wherein The aforementioned polymerizable compound has at least one group selected from the group consisting of an imide group, a urea group, and a urethane group. The resin composition as described in claim 1 or claim 2, which also includes: Compound B, which is at least one compound selected from the group consisting of compounds having a maleimide structure and precursors of compounds having a maleimide structure. The resin composition as described in claim 13, which also includes: Compound C, the compound C is a compound having a group capable of reacting with a maleimide structure. The resin composition as described in claim 14, wherein The group capable of reacting with the maleimide structure in the aforementioned compound C is at least one group selected from the group consisting of ethylenically unsaturated groups, hydroxyl groups, epoxy groups, and amine groups. The resin composition according to Claim 1 or Claim 2, which is used for forming an interlayer insulating film for a rewiring layer. A cured product obtained by curing the resin composition described in any one of claim 1 to claim 16. A laminate comprising two or more layers made of the hardened product described in claim 17, and at least one metal layer between the layers made of the hardened product. A method for producing a cured product, comprising a film forming step of applying the resin composition described in any one of claim 1 to claim 16 to form a film on a substrate. The manufacturing method of the hardened object as described in Claim 19, which comprises: an exposing step of exposing the aforementioned film; and a developing step of developing the aforementioned film. The method for producing a cured product according to claim 19 or claim 20, which includes a heating step of heating the film at 50 to 450°C. A semiconductor device comprising the cured product described in Claim 17 or the laminate described in Claim 18. A resin having at least one of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (1-2), [chemical formula 5]

In formula (1-1) or formula (1-2), W ¹ represents a divalent organic group, X ¹ represents a tetravalent organic group, and R ¹ to R ³ independently represent the following formula (3- 1) The group represented by or the group represented by formula (3-2), W ² represents a divalent organic group, X ² represents a trivalent organic group, the aforementioned resins are selected from the group consisting of formula (1 -1) A repeating unit represented by at least one of R ¹ and R ² is a group represented by formula (3-1), and represented by formula (1-2) and R ³ is a group represented by formula (3-1) At least one repeating unit in the group of repeating units of the represented group, [Chemical Formula 6]

In formula (3-1) and formula (3-2), Z ¹ and Z ² independently represent an organic group, Z ¹ and Z ² can be bonded to form a ring structure, A ² represents an oxygen atom or -NH- , R ¹¹³ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with other structures. The resin according to claim 23, wherein R ¹¹³ in formula (3-2) is a group having a polymerizable group. The resin as described in any one of claim 23 or claim 24, wherein W ¹ in formula (1-1) and W ² in formula (1-2) include a group represented by the following formula (4): group, [chemical formula 7]

In formula (4), * represent the bonding sites with other structures, respectively.