TW202244129A - Resin composition, cured product, laminated body, cured product manufacturing method, semiconductor device, and cyclization resin precursor - Google Patents

Abstract

Provided are: a resin composition which contains a cyclization resin precursor that generates a base when heated to 250 DEG C; a cured product which is obtained by curing the resin composition; a laminated body which contains the cured product; a semiconductor device which contains the cured product or the laminated body; a cured product manufacturing method by which a cured product with excellent rectangularity can be obtained; and a novel cyclization resin precursor.

Description

Resin composition, cured product, laminate, method for producing cured product, semiconductor device, and precursor of cyclized 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 precursor of a cyclized 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, but 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, a cyclized resin such as polyimide is used in the form of a resin composition containing a precursor of the cyclized resin. For example, by applying such a resin composition to a substrate 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 substrate. 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, they are also excellent in manufacturing adaptability, and the expansion of industrial applications of the above-mentioned resin compositions has been expected.

For example, Patent Document 1 describes a photosensitive resin composition having a polymer precursor and a specific structure that promotes the reaction to the final product by a basic substance or by heating in the presence of a basic substance, and Contains a base generator that generates a base by irradiation with electromagnetic waves and heating. Patent Document 2 describes a resin composition containing the following components (a) to (d). (a) Polyimide precursors with specific structural units (b) Compounds that generate free radicals by irradiation with active light (c) Compounds with specific structures (d) solvent

[Patent Document 1] Japanese Patent Laid-Open No. 2011-121962 [Patent Document 2] Japanese Patent Laid-Open No. 2014-201695

In the resin composition containing the precursor of the cyclized resin, after forming a pattern by exposure, development, etc., the precursor of the cyclized resin is cyclized to obtain the pattern of the cured product. Here, the pattern of the above-mentioned cured product is required to have excellent rectangularity. The excellent rectangularity of the pattern of the cured product means that the taper angle between the substrate on which the cured product is formed and the side of the cured product does not exceed 90° and the cross-sectional shape of the pattern is not an hourglass shape, and the taper angle is close to 90°. Hereinafter, the case where the pattern of the cured product is excellent in rectangularity is also simply referred to as “the cured product has excellent rectangularity”. An object of the present invention is to provide a resin composition obtained by obtaining a cured product excellent in rectangularity, a cured product obtained by curing the above resin composition, a laminate containing the above cured product, and a semiconductor containing the above cured product or the above laminate. A device and a method for producing a cured product capable of obtaining a cured product with excellent rectangularity, and a precursor of a novel cyclized resin.

式（1-1）中，R ¹分別獨立地為氫原子或1價有機基團，2個R ¹可以連結而形成環結構，L ¹表示3價有機基團，*表示與其他結構的鍵結部位。 ＜7＞如＜1＞至＜6＞之任一項所述之樹脂組成物，其進一步包含光聚合起始劑。 ＜8＞如＜1＞至＜7＞之任一項所述之樹脂組成物，其進一步包含聚合性化合物。 ＜9＞如＜1＞至＜8＞之任一項所述之樹脂組成物，其進一步包含鹼產生劑。 ＜10＞如＜1＞至＜9＞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。 ＜11＞一種硬化物，其藉由硬化＜1＞至＜10＞之任一項所述之樹脂組成物而成。 ＜12＞一種積層體，其包含2層以上由＜11＞所述之硬化物構成之層，在由上述硬化物構成之任意層彼此之間包含金屬層。 ＜13＞一種半導體裝置，其包含＜11＞所述之硬化物或＜12＞所述之積層體。 ＜14＞一種硬化物的製造方法，其包括： 膜形成步驟，在基材上適用包含環化樹脂的前驅物之樹脂組成物來形成膜； 曝光步驟，對上述膜進行選擇性曝光； 顯影步驟，使用顯影液對上述膜進行顯影來形成圖案；及 加熱步驟，在50℃以上且250℃以下的溫度下加熱上述圖案， 上述環化樹脂的前驅物為在上述加熱步驟中產生鹼之化合物。 ＜15＞如＜14＞所述之硬化物的製造方法，其中 在作為曝光步驟後、顯影步驟前的膜且顯影步驟後作為上述圖案殘留之膜中存在之鹼產生基的莫耳數E與在上述顯影步驟後的上述圖案中存在之鹼產生基的莫耳數F之比F/E超過0.9。 ＜16＞如＜14＞或＜15＞所述之硬化物的製造方法，其中 在上述膜形成步驟中形成之上述膜中，膜的厚度方向的上部50%內的鹼產生基的濃度X與下部50%內的鹼產生基的濃度Y之比X/Y為0.90＜X/Y＜1.10。 ＜17＞如＜14＞至＜16＞之任一項所述之硬化物的製造方法，其中 所獲得之硬化物的與上述基材接觸的一側相反的一側表面上的閉環率A和與上述基材接觸的一側表面上的閉環率B之比A/B為0.90＜A/B＜1.10。 ＜18＞如＜14＞至＜17＞之任一項所述之硬化物的製造方法，其中 在顯影步驟中形成膜厚20μm、間距10μm的1:1線與空間圖案，在加熱步驟中以230℃加熱180分鐘時，線圖案上端的寬度收縮率C與下端的寬度收縮率D之比C/D為0.90＜C/D＜1.10。 ＜19＞一種環化樹脂的前驅物，其包含選自包括由下述式（2）表示之重複單元、由式（3）表示之重複單元及由式（PAI-2）表示之重複單元之群組中之至少1種重複單元。 [化學式2]

式（2）中，A ¹及A ²分別獨立地表示氧原子或-NH-，R ¹¹¹表示2價有機基團，R ¹¹⁵表示4價有機基團，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價有機基團，R ¹¹¹、R ¹¹⁵、R ¹¹³及R ¹¹⁴中的至少1個包含由下述式（1-1）表示之結構。 [化學式3]

式（3）中，R ¹²¹表示2價有機基團，R ¹²²表示4價有機基團，R ¹²³及R ¹²⁴分別獨立地表示氫原子或1價有機基團，R ¹²¹、R ¹²²、R ¹²³及R ¹²⁴中的至少1個包含由下述式（1-1）表示之結構。 [化學式4]

式（PAI-2）中，R ¹¹⁷表示3價有機基團，R ¹¹¹表示2價有機基團，A ²表示氧原子或-NH-，R ¹¹³表示氫原子或1價有機基團，R ¹¹⁷、R ¹¹¹及R ¹¹³中的至少1個包含由下述式（1-1）表示之結構。 [化學式5]

式（1-1）中，R ¹分別獨立地為氫原子或1價有機基團，2個R ¹可以連結而形成環結構，L ¹表示3價有機基團，*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 including a precursor of a cyclized resin that generates a base when heated to 250°C. <2> The resin composition according to <1>, wherein the base is released from the precursor of the cyclization resin during the heating. <3> The resin composition according to <1> or <2>, wherein the structure exhibiting the property of generating a base contained in the precursor of the cyclized resin is a nonionic structure. <4> The resin composition according to any one of <1> to <3>, wherein the structure exhibiting base-generating properties contained in the precursor of the cyclized resin includes an amide bond. <5> The resin composition according to <4>, wherein the amide bond is bonded to the main chain of the precursor of the cyclized resin at the carbonyl side. <6> The resin composition according to any one of <1> to <5>, wherein the precursor of the cyclized resin contains a structure represented by the following formula (1-1). [chemical formula 1]

In the formula (1-1), R ¹ is independently a hydrogen atom or a monovalent organic group, two R ¹ can be connected to form a ring structure, L ¹ represents a trivalent organic group, and * represents a bond with other structures Knot part. <7> The resin composition according to any one of <1> to <6>, further comprising a photopolymerization initiator. <8> The resin composition according to any one of <1> to <7>, further comprising a polymerizable compound. <9> The resin composition according to any one of <1> to <8>, further comprising a base generator. <10> The resin composition according to any one of <1> to <9>, which is used for forming an interlayer insulating film for a rewiring layer. <11> A cured product obtained by curing the resin composition described in any one of <1> to <10>. <12> A laminate comprising two or more layers composed of the cured product described in <11>, wherein a metal layer is included between arbitrary layers composed of the cured product. <13> A semiconductor device comprising the cured product described in <11> or the laminate described in <12>. <14> A method for producing a cured product, comprising: a film forming step of applying a resin composition containing a precursor of a cyclized resin to a substrate to form a film; an exposing step of selectively exposing the film; a developing step , using a developer to develop the above film to form a pattern; and a heating step, heating the above pattern at a temperature above 50°C and below 250°C, the precursor of the cyclized resin is a compound that generates a base in the above heating step. <15> The method for producing a cured product as described in <14>, wherein the molar number E of the base-generating group present in the film after the exposure step and before the development step and remaining as the pattern after the development step and The ratio F/E of the molar number F of base-generating groups present in the above-mentioned pattern after the above-mentioned developing step exceeds 0.9. <16> The method for producing a cured product as described in <14> or <15>, wherein in the film formed in the film forming step, the concentration X of the base-generating group in the upper 50% in the thickness direction of the film and The ratio X/Y of the base-generating group concentration Y in the lower 50% is 0.90<X/Y<1.10. <17> The method for producing a cured product according to any one of <14> to <16>, wherein the loop closure rate A and The ratio A/B of the loop closure ratio B on the surface of the side in contact with the above substrate is 0.90<A/B<1.10. <18> The method for producing a cured product according to any one of <14> to <17>, wherein a 1:1 line-and-space pattern with a film thickness of 20 μm and a pitch of 10 μm is formed in the developing step, and a 1:1 line-and-space pattern is formed in the heating step with When heated at 230°C for 180 minutes, the ratio C/D of the width shrinkage rate C of the upper end of the line pattern to the width shrinkage rate D of the lower end of the line pattern is 0.90<C/D<1.10. <19> A precursor of a cyclized resin comprising a compound selected from the group consisting of the repeating unit represented by the following formula (2), the repeating unit represented by the formula (3) and the repeating unit represented by the formula (PAI-2). At least one repeating unit in the group. [chemical formula 2]

In formula (2), A ¹ and A ² independently represent an oxygen atom or -NH-, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and R ¹¹⁴ independently represent hydrogen As an atom or a monovalent organic group, at least one of R ¹¹¹ , R ¹¹⁵ , R ¹¹³ and R ¹¹⁴ includes a structure represented by the following formula (1-1). [chemical formula 3]

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group, R ¹²¹ , R ¹²² , R ¹²³ and at least one of R ¹²⁴ includes a structure represented by the following formula (1-1). [chemical formula 4]

In the formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or -NH-, R ¹¹³ represents a hydrogen atom or a monovalent organic group, R ¹¹⁷ At least one of , R ¹¹¹ and R ¹¹³ includes a structure represented by the following formula (1-1). [chemical formula 5]

In the formula (1-1), R ¹ is independently a hydrogen atom or a monovalent organic group, two R ¹ can be connected to form a ring structure, L ¹ represents a trivalent organic group, and * represents a bond with other structures Knot site. [Invention effect]

According to the present invention, there are provided a resin composition obtained by obtaining a cured product excellent in rectangularity, a cured product obtained by curing the above resin composition, a laminate including the above cured product, and a semiconductor device including the above cured product or the above laminate A method for producing a cured product capable of obtaining a cured product having excellent rectangularity, and a precursor of a novel cyclized resin.

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" not only includes an independent step, but also includes a step that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved. Among the notations of groups (atomic groups) in this specification, notation of substituted and unsubstituted includes groups (atomic groups) without substituents as well as groups (atomic groups) with substituents. 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 mercury lamps, 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 any of these, "(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 other than a solvent with respect to the total mass of a composition. In this specification, unless otherwise specified, weight average molecular weight (Mw) and 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 manual, for example, using HLC-8220GPC (manufactured by TOSOH CORPORATION), guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) are used in series As a column, weight average molecular weight (Mw) and number average molecular weight (Mn) can be calculated|required by this. 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 the opposite direction is referred to as "upper". Called "down". In addition, the setting of these up and down directions is for the convenience of this specification, and 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 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.

(resin composition) The resin composition of the present invention includes a precursor of a cyclized resin, and the precursor of the cyclized resin is a precursor of a cyclized resin that generates a base when heated to 250°C. Hereinafter, a resin which is a precursor of a cyclized resin and generates a base when heated to 250° C. is also referred to as a “specific resin”. Also, it is preferable that the specific resin generate a base by heating at 220°C, it is more preferable to show the property of generating a base by heating at 200°C, it is further preferable to generate a base by heating at 190°C, and it is more preferable to generate a base by heating at 180°C. Heating to generate base is especially preferred. The lower limit of the temperature at which the base is generated is not particularly limited, but is preferably 100° C. or higher, for example, from the viewpoint of storage stability of the composition.

The resin composition of the present invention is preferably used for forming a photosensitive film for exposure and development, and is preferably used for forming a film for exposure and development using a developing solution containing an organic solvent. The resin composition of the present invention can be used, for example, to form an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used for forming an interlayer insulating film for a rewiring layer. Moreover, the resin composition of this invention can be used for formation of the photosensitive film for positive tone development, and can also be used for formation of the photosensitive film for negative tone development. In the present invention, in exposure and development, negative tone development refers to development in which non-exposed areas are removed by development, and positive tone development refers to development in which exposed areas are removed by development. As the above-mentioned exposure method, the above-mentioned developer solution, and the above-mentioned development method, for example, the exposure method described in the exposure step in the description of the production method of the cured product described later, the developer solution and the development method described in the development step can be used.

The cured product obtained by the resin composition of the present invention has excellent rectangularity. The mechanism for obtaining the above effects is not clear, but it is presumed as follows.

Conventionally, by including a base generator in a resin composition containing a precursor of a cyclized resin, the rate of ring closure during heating is increased, and the elongation at break of the obtained cured product is increased. Here, as a result of intensive studies by the present inventors, it has been found that when a conventional base generator is used, the base generator may not be uniformly distributed in the film, and the obtained cured product pattern may have poor rectangularity. Generally, it is considered that since the molecular weight of the base generating agent is smaller than resins such as precursors of cyclized resins, for example, it may be distributed in a large amount on the surface of the film on the side opposite to the substrate. The cyclization is easy to proceed near the surface of one side of the film, but not easy to proceed near the substrate side of the film (ie, the deep side of the film). Here, film shrinkage occurs when the precursor of the cyclization resin is cyclized. Film shrinkage means that the volume of the cured product obtained after curing (for example, a cured film) decreases (shrinks) compared to the composition before curing (for example, a composition film before heating). For example, as mentioned above, when cyclization is easy to occur near the surface of the film opposite to the substrate, and cyclization is not easily carried out near the substrate of the film, the side of the film opposite to the substrate is prone to cyclization. Shrinkage, the shape of the obtained hardened product sometimes becomes a positive cone. In the present invention, as the precursor of the cyclized resin, a precursor of the cyclized resin (specific resin) that generates a base when heated to 250° C. is used. From this, it is believed that in the present invention, the structure showing the property of generating alkali is distributed in a nearly uniform state in the entire film, so that the degree of shrinkage of the film due to position is less likely to occur, and the rectangularity of the pattern is improved.

In addition, it is presumed that by using the above-mentioned specific resin, the elution of the base generator due to development can be suppressed during development, so the amount of base generated during subsequent heating is relatively large, and the elongation at break of the obtained cured product is also increased. . Furthermore, when the base generator with a molecular weight lower than that of the resin partially aggregates in the film, the solubility in the developing solution around the aggregate and the non-agglomerated site (for example, a resin-rich site such as a precursor of a cyclized resin) are different in the developing solution. Due to the difference in solubility, the roughness of the pattern (for example, line edge roughness, line width roughness) may increase when forming a pattern by development. According to the present invention, it is presumed that the structure exhibiting an alkali-generating property is distributed in a nearly uniform state in the entire film, so that the aforementioned roughness can also be reduced.

Here, Patent Documents 1 and 2 do not describe the use of a specific resin.

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

＜Specific resin＞ The resin composition of the present invention includes a precursor of a cyclized resin, and the precursor of the cyclized resin is a precursor of a cyclized resin that generates a base when heated to 250°C. The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure. In the present invention, the main chain refers to the relatively longest bonded chain in the resin molecule. Examples of the cyclized resin include polyimide, polybenzoxazole, polyamideimide, and the like. The precursor of the cyclized resin refers to the resin whose chemical structure is changed by external stimuli to become a cyclized resin. The resin whose chemical structure is changed by heat to become a cyclized resin is better, by (using heat to produce a ring-closing reaction ) It is more preferable to form a ring structure to become a cyclized resin. Examples of the precursor of the cyclized resin include polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, and the like. That is, the resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors as Certain resins are preferred. It is preferable that the resin composition of the present invention contains a polyimide precursor as a specific resin.

〔Alkaline production〕 Certain resins generate a base when heated to 250°C. Put 1 mole of resin alone into a sealed container, and in the sealed container, after heating at 250°C for 3 hours under 1 atmosphere, use HPLC (high-speed liquid chromatography) to quantify the amount of base produced. It can be judged as "alkali production" when the base is above the ears. Regardless of whether the above 1 mole resin is liquid or solid, it is placed in a sealed container so as to have a thickness of 0.50 cm or less. The above-mentioned production amount is preferably 0.1 mole or more, more preferably 1 mole or more. The upper limit of the amount of generation is not particularly limited, and can be set to, for example, 1000 mol or less. From the viewpoint of elongation at break of the cured product obtained, the base generated from the specific resin is preferably an amine, more preferably a secondary amine or a tertiary amine, and even more preferably a secondary amine. Also, when the amine is generated from a specific resin, the amine may be an aliphatic amine or an aromatic amine, but an amine having an aromatic ring structure is preferable from the viewpoint of suppressing shrinkage of the cured product. Although it does not specifically limit as said aromatic ring structure, An aromatic hydrocarbon ring structure is preferable, and a benzene ring structure is more preferable. The base to be produced is preferably a base with a pKa of 0 or more of the conjugate acid, more preferably a base of 3 or more, and more preferably a base of 6 or more. The upper limit of the pKa of the above-mentioned conjugate acid is not particularly limited, but 30 or less is preferable. pKa considers the dissociation reaction of releasing hydrogen ions from an acid and expresses its equilibrium constant Ka by its negative common logarithm pKa. 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 above-mentioned conjugate acid, at least one of them is preferably within the above-mentioned range.

From the viewpoint of elongation at break, it is preferable that the base generated from the specific resin is released from the precursor of the cyclized resin during the heating. The above-mentioned base may be released from the precursor of the cyclized resin by cleaving the site where the base is generated during heating, or may be released from the precursor of the cyclized resin as the precursor of the cyclized resin is ring-closed. When the above-mentioned base is freed from the precursor of the cyclization resin, the molecular weight of the produced base is preferably 70-500, more preferably 80-300, and even more preferably 90-220. Also, when the base is freed from the precursor of the cyclization resin, the resulting base has a boiling point of preferably 50-450°C at 1 atmosphere, more preferably 60-400°C, and still more preferably 80-350°C. Moreover, what remains alkali in the specific resin at the time of said heating can also be used as the specific resin of this invention.

Specific examples of the base to be generated include, for example, the following bases, but are not limited thereto. The bases may exist freely in the state of the bases, or may exist in a structure formed by removing a part of the hydrogen atoms of the bases and bonded to a specific resin after the bases are generated. [chemical formula 6]

[Structure showing base-generating properties] It is preferred that the particular resin comprises a structure exhibiting base-generating properties. The structure exhibiting the property of generating an alkali may be either an ionic structure or a nonionic structure, and a nonionic structure is preferable from the viewpoint of the rectangularity of the obtained cured product. As an ionic structure, a quaternary ammonium cation structure is mentioned. As a nonionic structure, the structure containing an amide bond or a urethane bond is mentioned. In the specific resin, with respect to 1 mole of the specific resin, it is preferable to include 1 to 1,000 moles of the structure exhibiting the property of generating a base, more preferably to include 2 to 800 moles, and to be further more preferably to include 5 to 500 moles. good.

Among these, from the viewpoint of the rectangularity of the obtained cured product, it is preferable that the structure exhibiting the property of generating a base contains an amide bond. In addition to the amide bond represented by the so-called (*-C(=O)NH-#), the amide bond in the specific resin also includes the amide bond represented by the so-called (*-C(=O)NR-#). replace the amide bond. The above-mentioned * and # represent bonding sites with other structures, respectively. In particular, it is preferable that both * and # are bonding sites with carbon atoms. The substituent (the above-mentioned R) in the substituted amide bond is not particularly limited, and known substituents can be used, and examples thereof include hydrocarbon groups such as alkyl groups, aromatic hydrocarbon groups, and groups represented by combinations thereof. The above-mentioned hydrocarbon groups may be further substituted with halogen atoms, alkoxy groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, hydroxyl groups, and the like. In addition, the above-mentioned hydrocarbon group may be bonded to at least one of the nitrogen atom in the above-mentioned substituted amide bond and the structure bonded to the # site to form a ring structure. Examples of the formed ring structure include a piperidine ring and a perperoline ring having nitrogen atoms included in the above-mentioned amide bond as ring members. These ring structures may further have a substituent. As a substituent, the thing similar to the substituent in the said hydrocarbon group is mentioned. Among them, from the standpoint of high basicity of the generated base and easy increase in elongation at break, the amide bond in the specific resin is preferably a substituted amide bond, and a substituted amide bond having a hydrocarbon group as a substituent is more preferable. good.

It is preferable that the amide bond is bonded to the main chain of the precursor of the cyclization resin at the carbonyl side. Thus, the generated base can be freed from the specific resin by cleavage of the amide bond. The carbonyl side of the amide bond in a specific resin refers to the * side in the above (*-C(=O)NH-#) or (*-C(=O)NR-#).

式（1-1）中，R ¹分別獨立地為氫原子或1價有機基團，2個R ¹可以連結而形成環結構，L ¹表示3價有機基團，*表示與其他結構的鍵結部位。 [Structure Represented by Formula (1-1)] It is preferable that the specific resin contains a structure represented by the following formula (1-1). Also, it is preferable that the amide group in the formula (1-1) is cleaved to generate a base during the above-mentioned heating. [chemical formula 7]

In the formula (1-1), R ¹ is independently a hydrogen atom or a monovalent organic group, two R ¹ can be connected to form a ring structure, L ¹ represents a trivalent organic group, and * represents a bond with other structures Knot site.

-R ¹ - In the formula (1-1), each of R ¹ is preferably a monovalent organic group independently from the viewpoint of elongation at break. R ¹ is preferably a hydrocarbon group, an alkyl group, an aromatic hydrocarbon group, or a group represented by a combination thereof, an alkyl group with 1 to 10 carbons, an aromatic hydrocarbon group with 6 to 20 carbons, or a group represented by a combination of these The group represented by the combination of is further preferred, and an alkyl group having 1 to 10 carbon atoms is particularly preferred. As the above-mentioned alkyl group, any of linear, branched, and cyclic may be used. From the viewpoint of improving elongation at break, branched-chain alkyl groups (for example, isopropyl, isobutyl, 2-ethyl ylhexyl, etc.) or cyclic alkyl groups (eg, cyclohexyl, etc.) are preferred. R ¹ may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, and a hydroxyl group. Examples of the ring structure formed by linking two ^R1s include piperidine rings and perperoline rings having nitrogen atoms included in the above-mentioned amide bonds as ring members. These ring structures may further have a substituent. As a substituent, the thing similar to the substituent in the said hydrocarbon group is mentioned.

Examples of preferred aspects of R ¹ include the following structures. The nitrogen atoms included in the structures of the following specific examples refer to the nitrogen atoms included in the amide bond in formula (1-1). In the following specific examples, * represents a bonding site with a carbonyl group. [chemical formula 8]

-L ¹ - In the formula (1-1), L ¹ is not particularly limited, a hydrocarbon group or more than one hydrocarbon group selected from the group consisting of -O-, -S-, -C(=O)-, -S( A group represented by a bond of at least one structure in the group of =O) ₂ - and -NR ^N - is preferable. R ^N represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond of these is preferable. As the above-mentioned saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferable. Examples of the above-mentioned aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms. Groups obtained by removing a plurality of hydrogen atoms from a benzene ring or a naphthalene ring are preferred, and those obtained by removing a plurality of hydrogen atoms from a benzene ring Group is better. As the above-mentioned aliphatic hydrocarbon group, an aliphatic hydrocarbon ring group can be used. The aliphatic hydrocarbon ring group is not particularly limited, and a group obtained by removing a plurality of hydrogen atoms from a dicyclopentane ring, a camphene ring, an isocamphene ring, or an adamantane ring, etc. may be mentioned. Examples of the above-mentioned aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms. Groups obtained by removing a plurality of hydrogen atoms from a benzene ring or a naphthalene ring are preferred, and those obtained by removing a plurality of hydrogen atoms from a benzene ring Group is better. In addition, the above-mentioned aromatic hydrocarbon group or the above-mentioned aliphatic hydrocarbon ring group may be condensed with another ring. Examples of such aspects include groups obtained by removing a plurality of hydrogen atoms from a phthalimide ring, and the like. From the viewpoint of elongation at break and chemical resistance of the obtained cured product, as the above-mentioned hydrocarbon group, L ¹ preferably includes an aromatic hydrocarbon group, and more preferably includes a group obtained by removing a plurality of hydrogen atoms from a benzene ring. Also, from the viewpoint of base generation efficiency, when L ¹ contains an aromatic hydrocarbon group, it is also preferable that the aromatic hydrocarbon group in L ¹ is directly bonded to the hydroxyl group in formula (1-1). When the aromatic hydrocarbon group in L1 is directly bonded to the hydroxyl group in formula ( ^1-1 ), the above ^- mentioned hydroxyl group and the aromatic hydrocarbon group in L1 are directly or via ^a linking group and the amide bond. The ortho position in the aromatic hydrocarbon group is preferred. The ortho position means that the ring member bonded by a certain substituent in the aromatic hydrocarbon group and the ring member bonded by another substituent are adjacent ring members in the aromatic hydrocarbon group. When the aromatic hydrocarbon group is a benzene ring, it is Refers to the ortho. Moreover, OH in formula (1-1) may be a part of carboxyl group. In this case, it is also preferable that the aromatic hydrocarbon group in L1 is directly bonded to the above ^- mentioned carboxyl group. In addition, when the aromatic hydrocarbon group in L1 is directly bonded to the above ^- mentioned carboxyl group, the position where the above-mentioned hydroxyl group and the aromatic hydrocarbon group in L1 are directly or via ^a linking group and ^an amide bond is present in the aromatic hydrocarbon group in L1. The ortho position is preferred.

Examples ^of preferable aspects of L1 include the following structures. In the following specific examples, # represents the bonding site with the carbonyl group in formula (1-1), and * has the same meaning as * in formula (1-1). In addition, OH in the following specific examples is OH in formula (1-1). [chemical formula 9]

式（1-2）中，R ¹分別獨立地表示氫原子或1價有機基團，2個R ¹可以連結而形成環結構，L ²表示單鍵或2價連結基，Cy表示環結構，*表示與其他結構的鍵結部位。 [Structure Represented by Formula (1-2)] It is also preferable that the specific resin contains a structure represented by the following formula (1-2) as a structure exhibiting a property of generating a base. [chemical formula 10]

In the formula (1-2), R ¹ independently represents a hydrogen atom or a monovalent organic group, two R ¹ can be connected to form a ring structure, L ² represents a single bond or a divalent linking group, Cy represents a ring structure, * Indicates the bonding site with other structures.

-R ¹ - In formula (1-2), R ¹ has the same meaning as R ¹ in formula (1-1), and a preferred embodiment is also the same.

-L ² - In the formula (1-2), L ² represents a single bond or a divalent linking group, a single bond or a hydrocarbon group, or one or more hydrocarbon groups selected from the group consisting of -O-, -S-, -C ( =O)-, -S(=O) ₂ - and -NR ^N - groups are preferably groups represented by bonds of at least one structure, single bond or hydrocarbon group, or one or more hydrocarbon groups A group represented by a bond with at least one structure selected from the group consisting of -O- and -C(=O)- is more preferable. ^RN is as described above. As the above-mentioned hydrocarbon group, an alkylene group, a divalent aromatic hydrocarbon group, or a group represented by a bond of these is preferable. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable. Examples of the divalent aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms, preferably a phenylene group or a naphthylene group, and more preferably a phenylene group.

-Cy- In the formula (1-2), Cy represents a ring structure. The ring structure may be any of an aliphatic ring structure and an aromatic ring structure, and an aromatic ring structure is preferable. Moreover, any of a hydrocarbon ring structure and a heterocyclic structure may be used, and a hydrocarbon ring structure is preferable. Examples of the heteroatom contained in the above-mentioned heterocyclic structure include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. Moreover, as said heterocyclic structure, an aromatic heterocyclic structure is mentioned preferably, and pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, etc. are mentioned preferably. Among these, Cy is preferably an aliphatic hydrocarbon ring structure or an aromatic hydrocarbon ring structure from the viewpoint of base generation efficiency. Examples of the aliphatic hydrocarbon ring structure include a dicyclopentane ring, a camphene ring, an isocampene ring, an adamantane ring, and the like, and a dicyclopentane ring is preferable. As the aromatic hydrocarbon ring structure, an aromatic hydrocarbon ring structure having 6 to 20 carbon atoms is preferable, a benzene ring structure or a naphthalene ring structure is more preferable, and a benzene ring structure is still more preferable. In addition, the above-mentioned aromatic hydrocarbon ring structure or the above-mentioned aliphatic hydrocarbon ring structure may be condensed with another ring. Examples of such aspects include a phthalimide ring structure and the like. Among these, Cy is preferably a dicyclopentane ring structure or a benzene ring structure, and more preferably a benzene ring structure, from the viewpoint of base generation efficiency. Also, Cy may have a substituent. When Cy is an aromatic ring (preferably an aromatic hydrocarbon ring), from the viewpoint of base production efficiency, the bonding position of Cy in Cy to the hydroxyl group in formula ( ^1-2 ) is adjacent to L in Cy. bit is better. For example, when Cy is a benzene ring, it is preferable to have a hydroxyl group in formula (1-2) at the ortho position to L ² . Moreover, OH in formula (1-2) may be a part of carboxyl group. When the aromatic hydrocarbon group in Cy is directly bonded to the carboxyl group, it is preferable that the bonding position with the carboxyl group in Cy is an ortho position with respect to L2 in ^Cy .

式（1-3）中，R ¹為氫原子或1價有機基團，R ³為2價有機基團，L ³為2價有機基團，R ¹與L ³可以連結而形成環結構，*表示與其他結構的鍵結部位。 [Structure Represented by Formula (1-3)] It is also preferable that the specific resin contains a structure represented by the following formula (1-3) as a structure exhibiting a property of generating a base. [chemical formula 11]

In the ^formula ( ^1-3 ), R1 is a hydrogen atom or a monovalent organic group, ^R3 is a divalent organic group, L3 is ^a divalent organic group, R1 and ^L3 can be connected to form a ring structure, * Indicates the bonding site with other structures.

-R ¹ - In the formula (1-3), R ¹ has the same meaning as R ¹ in the above formula (1-1), and preferred embodiments are also the same.

-R ³ - In formula (1-3), R ³ is not particularly limited, hydrocarbon group or more than one hydrocarbon group selected from the group consisting of -O-, -S-, -C(=O)-, -S( A group represented by a bond of at least one structure in the group of =O) ₂ - and -NR ^N - is preferable. ^RN is as described above. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond of these is preferable. As the above-mentioned saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferable. Examples of the above-mentioned aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms. Groups obtained by removing a plurality of hydrogen atoms from a benzene ring or a naphthalene ring are preferred, and those obtained by removing a plurality of hydrogen atoms from a benzene ring Group is better. As the above-mentioned aliphatic hydrocarbon group, an aliphatic hydrocarbon ring group can be used. The aliphatic hydrocarbon ring group is not particularly limited, and a group obtained by removing a plurality of hydrogen atoms from a dicyclopentane ring, a camphene ring, an isocamphene ring, or an adamantane ring, etc. may be mentioned. Examples of the above-mentioned aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms. Groups obtained by removing a plurality of hydrogen atoms from a benzene ring or a naphthalene ring are preferred, and those obtained by removing a plurality of hydrogen atoms from a benzene ring Group is better. In addition, the above-mentioned aromatic hydrocarbon group or the above-mentioned aliphatic hydrocarbon ring group may be condensed with another ring. Examples of such aspects include groups obtained by removing a plurality of hydrogen atoms from a phthalimide ring, and the like. From the viewpoint of elongation at break and chemical resistance of the obtained cured product, as the hydrocarbon group, ^R3 preferably includes an aromatic hydrocarbon group, and more preferably includes a group obtained by removing a plurality of hydrogen atoms from a benzene ring. Also, from the viewpoint of base generation efficiency, when R ³ contains an aromatic hydrocarbon group, it is also preferable that the aromatic hydrocarbon group in R ³ is directly bonded to the hydroxyl group in formula (1-3). When the aromatic hydrocarbon group in ^R3 is directly bonded to the hydroxyl group in formula ( ^1-3 ), the above-mentioned hydroxyl group and the aromatic hydrocarbon group in ^R3 are directly or via a linking group and the amide bond. The ortho position in the aromatic hydrocarbon group is preferred. The ortho position means that the ring member bonded by a certain substituent in the aromatic hydrocarbon group and the ring member bonded by another substituent are adjacent ring members in the aromatic hydrocarbon group. When the aromatic hydrocarbon group is a benzene ring, it is Refers to the ortho. Moreover, OH in formula (1-3) may be a part of carboxyl group. In this case, it is also preferable that the aromatic hydrocarbon group in ^R3 is directly bonded to the above-mentioned carboxyl group. In addition, when the aromatic hydrocarbon group in ^R3 is directly bonded to the above-mentioned carboxyl group, the position where the above-mentioned hydroxyl group and the aromatic hydrocarbon group in ^R3 are directly or via a linking group and an amide bond is present in the aromatic hydrocarbon group in ^R3 . The ortho position is preferred.

-L ³ - In the formula (1-3), L ³ is not particularly limited, preferably a hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof, with a carbon number of 1 to A saturated aliphatic hydrocarbon group having 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof are further preferred, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is particularly preferred. L3 may have a substituent, and examples ^of the substituent include a halogen atom, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, and a hydroxyl group. ^The ring structure formed by linking R1 and L3 includes, for example, ^a piperidine ring and a perperoline ring having the nitrogen atom contained in the above-mentioned amide bond as a ring member. These ring structures may further have a substituent. As a substituent, the thing similar to the substituent in the said hydrocarbon group is mentioned.

式（1-4）中，R ¹表示氫原子或1價有機基團，R ⁴分別獨立地表示氫原子或1價有機基團，不存在R ⁴均為氫原子的情況，R ¹及R ⁴中的任一個上包含與其他結構的鍵結部位。 式（1-4）中，R ¹不包含與其他結構的鍵結部位時，R ¹與式（1-1）中的R ¹的含義相同，較佳態樣亦相同。 式（1-4）中，R ¹包含與其他結構的鍵結部位時，R ¹與式（1-3）中的L ³及鍵結部位（*）的含義相同，較佳態樣亦相同。 式（1-4）中，R ⁴不包含與其他結構的鍵結部位時，R ⁴可較佳地舉出氫原子、烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、烯基（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、芳基烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳），氫原子或甲基為更佳。 式（1-4）中，R ⁴包含與其他結構的鍵結部位時，R ⁴可較佳地舉出伸烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、伸烯基（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）、伸芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）或由該等的鍵結表示之基團，伸烷基為更佳。 式（1-5）中，R ⁵分別獨立地表示1價有機基團，R ⁵中的任一個上包含與其他結構的鍵結部位，A表示1價以上的相對陰離子。 式（1-5）中，R ⁵中未包含與其他結構的鍵結部位者分別獨立地表示烴基為較佳。作為烴基，可較佳地舉出烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、烯基（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、芳基烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳），烷基為更佳，甲基為進一步較佳。 式（1-5）中，R ⁵中包含與其他結構的鍵結部位者與式（1-3）中的L ³及鍵結部位（*）的含義相同，較佳態樣亦相同。 式（1-5）中，A表示相對陰離子。A係pKa1為0～4的陰離子為較佳。又，A為羧酸陰離子、苯酚陰離子、磷酸陰離子或硫酸陰離子為較佳，從兼顧鹽的穩定性及熱分解性的理由考慮，羧酸陰離子為更佳。 上述羧酸陰離子為具有2個以上的羧基之2價以上羧酸的陰離子為較佳，2價羧酸的陰離子為更佳。 上述羧酸陰離子係pKa1為4以下的羧酸的陰離子為較佳。pKa1為3.5以下為更佳，3.2以下為進一步較佳。根據該態樣，能夠進一步提高樹脂組成物的穩定性。 其中，pKa1表示酸的第一解離常數的逆數的對數，能夠參考Determination of Organic Structures by Physical Methods（著者:Brown,H.C.,McDaniel,D.H.,Hafliger,O.,Nachod,F.C.；編著:Braude,E.A.,Nachod, F.C.；Academic Press,New York,1955）或Data for Biochemical Research（著者:Dawson,R.M.C.et al；Oxford,Clarendon Press,1959）中記載之值。關於未記載於該等文獻之化合物，使用利用ACD/pKa（ACD/Labs製）軟體並藉由結構式算出之值。 Moreover, as a structure which shows the property which produces a base, the structure represented by following formula (1-4) - a formula (1-5) is mentioned. [chemical formula 12]

In the formula (1-4), R ¹ represents a hydrogen atom or a monovalent organic group, R ⁴ independently represents a hydrogen atom or a monovalent organic group, and there is no case where R ⁴ is a hydrogen atom, R ¹ and R Any one of ⁴ contains bonding sites with other structures. In formula (1-4), when R ¹ does not include a bonding site with other structures, R ¹ has the same meaning as R ¹ in formula (1-1), and the preferred aspects are also the same. In formula (1-4), when R ¹ includes a bonding site with other structures, R ¹ has the same meaning as L ³ and the bonding site (*) in formula (1-3), and the preferred aspects are also the same . In formula (1-4), when R ⁴ does not include a bonding site with other structures, R ⁴ can preferably include a hydrogen atom, an alkyl group (preferably 1-12 carbons, more preferably 1-6 , 1 to 3 is more preferred), alkenyl (2 to 12 carbons is preferred, 2 to 6 is more preferred, 2 to 3 is further preferred), aryl (6 to 22 carbons is preferred, 6-18 is more preferred, 6-10 is further preferred), arylalkyl (7-23 carbons is preferred, 7-19 is preferred, 7-11 is further preferred), hydrogen atom or methyl base is better. In formula (1-4), when R ⁴ includes a bonding site with other structures, R ⁴ can preferably include an alkylene group (preferably having 1 to 12 carbons, more preferably 1 to 6, and 1 to 6 3 is further preferred), alkenylene (preferably 2-12 carbons, more preferably 2-6, further preferably 2-3), arylylene (preferably 6-22 carbons, 6 ～18 is more preferred, 6～10 is still more preferred) or the group represented by these bonds, alkylene is more preferred. In formula (1-5), R ⁵ each independently represents a monovalent organic group, any of R ⁵ includes a bonding site with other structures, and A represents a relative anion with a valence or higher. In the formula (1-5), R ⁵ which does not contain a bonding site with other structures is preferably independently representing a hydrocarbon group. As the hydrocarbon group, preferably an alkyl group (preferably 1 to 12 carbons, more preferably 1 to 6, further preferably 1 to 3), alkenyl (preferably 2 to 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), arylalkyl group (carbon number 7-23 is preferable, 7-19 is more preferable, 7-11 is still more preferable), an alkyl group is more preferable, and a methyl group is still more preferable. In formula (1-5), R ⁵ including a bonding site with other structures has the same meaning as L ³ and the bonding site (*) in formula (1-3), and preferred embodiments are also the same. In the formula (1-5), A represents a relative anion. The anions of the A series with a pKa1 of 0-4 are preferred. In addition, A is preferably a carboxylic acid anion, a phenol anion, a phosphate anion, or a sulfate anion, and a carboxylic acid anion is more preferable in terms of both stability and thermal decomposability of the salt. The above-mentioned carboxylic acid anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, more preferably an anion of a divalent carboxylic acid. The above-mentioned carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. It is more preferable that pKa1 is 3.5 or less, and it is still more preferable that it is 3.2 or less. According to this aspect, the stability of the resin composition can be further improved. Wherein, pKa1 represents the logarithm of the inverse number of the first dissociation constant of the acid, which can refer to Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Editor: Braude, EA , Nachod, FC; Academic Press, New York, 1955) or Data for Biochemical Research (author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from structural formulas using ACD/pKa (manufactured by ACD/Labs) software were used.

Moreover, it is preferable that a specific resin has a polymerizable group, and it is more preferable that it contains a radical polymerizable group. When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably includes the radical polymerization initiator described later, more preferably includes the radical polymerization initiator described later and the radical crosslinking agent described later. The sensitizer mentioned later can be contained further as needed. For example, a negative photosensitive film is formed from such a resin composition of the present invention. In addition, the specific resin may have a polarity conversion group such as an acid decomposable group. When the specific resin has an acid-decomposable group, it is preferable that the resin composition of the present invention contains a photoacid generator described later. For example, a chemically amplified positive photosensitive film or a negative photosensitive film is formed from such a resin composition of the present invention.

式（2）中，A ¹及A ²分別獨立地表示氧原子或-NH-，R ¹¹¹表示2價有機基團，R ¹¹⁵表示4價有機基團，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價有機基團。 [Polyimide Precursor] The polyimide precursor used in the present invention is not particularly limited in its type, but preferably contains a repeating unit represented by the following formula (2). [chemical formula 13]

In formula (2), A ¹ and A ² independently represent an oxygen atom or -NH-, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and R ¹¹⁴ independently represent hydrogen atom or a monovalent organic group.

When the specific resin contains a repeating unit represented by formula (2), it is preferable that the specific resin contains a structure showing the property of generating a base in the repeating unit represented by formula (2), and in the repeating unit represented by formula (2) It is more preferable to include the structure represented by the above formula (1-1). For example, at least one structure selected from the group consisting of R ¹¹¹ , R ¹¹³ , R ¹¹⁴ and R ¹¹⁵ in formula (2) includes the above-mentioned structure showing the property of generating a base (preferably represented by the formula ( 1-1) The structure represented by) is preferably, at least one structure selected from the group including R ¹¹³ and R ¹¹⁴ in formula (2) includes the above-mentioned structure showing the property of generating a base (preferably is a structure represented by formula (1-1)) is more preferable. Also, when the specific resin contains a repeating unit represented by formula (2), the specific resin may contain a structure exhibiting a property of generating a base at a site different from the repeating unit represented by formula (2). For example, an aspect in which a structure exhibiting a property of generating a base is included at the end of a specific resin, and a specific resin further includes a repetition of a structure exhibiting a property of generating a base which is different from the repeating unit represented by formula (2) The shape of the unit, etc.

A ¹ and A ² in the formula (2) each independently represent an oxygen atom or -NH-, preferably an oxygen atom. R ¹¹¹ in formula (2) represents a divalent organic group. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups, and groups containing aromatic groups, linear or branched aliphatic groups having 2 to 20 carbon atoms, carbon A cycloaliphatic 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 is more preferred . 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 ring-membered hydrocarbon group of the above-mentioned cyclic aliphatic group and aromatic group may be substituted by a group containing a heteroatom. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, and groups represented by -Ar-L-Ar- are particularly preferable. Among them, Ar is independently an aromatic group, L is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or - NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Diamine may use only 1 type, and may use 2 or more types. Specifically, a straight-chain or branched aliphatic group with 2 to 20 carbons, a cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 3 to 20 carbons, or a combination thereof The diamine of the group is preferable, and the diamine containing an aromatic group with 6-20 carbon atoms is more preferable. 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 ring-membered hydrocarbon group of the above-mentioned cyclic aliphatic group and aromatic group may be substituted by a group containing a heteroatom. 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，單鍵或選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-或-SO ₂-之基團為更佳，-CH ₂-、-O-、-S-、-SO ₂-、-C（CF ₃） ₂-或-C（CH ₃） ₂-為進一步較佳。 式中，*表示與其他結構的鍵結部位。 [chemical formula 14]

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 the combination of these groups are preferred, single bond or selected from C1-3 alkylene groups, -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, or 1,6-Diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2 , 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'- Diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diamine Aminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4 '- or 3,3'-diaminodiphenylsulfide, 4,4'- or 3,3'-diaminodiphenylsulfide, 4,4'- or 3,3'-diaminodiphenylsulfide Benzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl Methoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2 -Bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4- hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)pyridine, bis(4-amino-3 -Hydroxyphenyl) p-terphenyl, 4,4'-diamino-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy) Phenyl]pyridine, bis[4-(3-aminophenoxy)phenyl]pyridine, bis[4-(2-aminophenoxy)phenyl]pyridine, 1,4-bis(4-amine phenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylphenene, 1,3-bis( 4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl- 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2, 2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis( 4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4- Diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl) terpine, 4,4'-Dimethyl-3,3'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2 ,4- and 2,5-diaminocumene, 2,5 -Dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3 -Aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminostilbene, 2,5-diaminopyridine, 1, 2-Bis(4-aminophenyl)ethane, diaminobenzaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3- Bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1 ,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4- (2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2, 2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy base) benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy) ) biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylene, 4,4'-bis(3-amino-5-trifluoromethylbenzene oxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetrafluoropropane Methyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6, At least one diamine selected from 6'-hexafluorobenzidine and 4,4'-diaminoquaterphenyl.

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 two 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.

From the viewpoint of the flexibility of the obtained organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Among them, Ar is independently an aromatic group, L is an aliphatic hydrocarbon group with 1 to 10 carbons which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, Or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group with 1 or 2 carbons which may be substituted by a fluorine atom, -O-, -CO-, -S- or -SO ₂ -. The aliphatic hydrocarbon group here is preferably an alkylene group.

在式（51）中，R ⁵⁰～R ⁵⁷分別獨立地為氫原子、氟原子或1價有機基團，R ⁵⁰～R ⁵⁷中的至少1個為氟原子、甲基或三氟甲基，*分別獨立地表示與式（2）中的氮原子的鍵結部位。 作為R ⁵⁰～R ⁵⁷的1價有機基團，可舉出碳數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16]

式（61）中，R ⁵⁸及R ⁵⁹分別獨立地為氟原子、甲基或三氟甲基，*分別獨立地表示與式（2）中的氮原子的鍵結部位。 作為賦予式（51）或（61）的結構之二胺，可舉出2,2'-二甲基對聯苯胺、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。該等可以使用1種或組合使用2種以上。 Also, from the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, a divalent organic group represented by formula (61) is more preferable from the viewpoint of i-ray transmittance and availability. Formula (51) [Chemical Formula 15]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoromethyl group, * Each independently represents a bonding site with a nitrogen atom in formula (2). Examples of monovalent organic groups for R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), 1 to 6) fluorinated alkyl groups, etc. [chemical formula 16]

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represent a bonding site with a nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or (61) include 2,2'-dimethyl-p-benzidine, 2,2'-bis(trifluoromethyl)-4,4'-diamine Biphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used 1 type or in combination of 2 or more types.

式（5）中，R ¹¹²為單鍵或2價連結基，單鍵或選自可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO ₂-及-NHCO-、以及該等的組合之基團為較佳，單鍵、選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-CO-、-S-及-SO ₂-中之基團為更佳，選自包括-CH ₂-、-C（CF ₃） ₂-、-C（CH ₃） ₂-、-O-、-CO-、-S-及-SO ₂-之群組中之2價基團為進一步較佳。 R ¹¹⁵ in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group including an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), * each independently represents a bonding site with another structure. [chemical formula 17]

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.

式（LD-1）中，Y ^D1表示n+2價有機基團，P ^D1表示包含顯示出產生鹼的性質之結構之基團，n表示1以上的整數，*分別表示與式（2）中的R ¹¹¹所鍵結之氮原子的鍵結部位。 In addition, R ¹¹¹ may also include a structure exhibiting base-generating properties. When R ¹¹¹ includes a structure showing a property of generating a base, for example, R ¹¹¹ is preferably a structure represented by the following formula (LD-1). [chemical formula 18]

In the formula (LD-1), Y ^D1 represents an n+2-valent organic group, ^PD1 represents a group including a structure showing the property of generating a base, n represents an integer greater than 1, and * represents the formula (2) The bonding site of the nitrogen atom to which R ¹¹¹ is bonded.

-Y ^D1 - In the formula (LD-1), Y ^D1 is preferably an n+2-valent organic group, more preferably an n+2-valent organic group including an aromatic hydrocarbon group. The aromatic hydrocarbon group in Y ^D1 is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group with 6 to 20 carbon atoms, and a group obtained by removing 2 or more hydrogen atoms from the benzene ring is further preferred. Preferably, a group obtained by removing 3 or more hydrogen atoms from a benzene ring is particularly preferred. In formula (LD-1), those directly bonded to the two bonding sites in formula (LD-1), that is, the bonding sites of * in Y ^D1 are preferably aromatic hydrocarbon groups. That is, it is preferable that the two * described in the formula (LD-1) are directly bonded to the aromatic hydrocarbon ring structure contained in Y ^D1 . Also, in the formula (LD-1), it is preferable that all bonding sites of Y ^D1 and ^PD1 are aromatic hydrocarbon groups. That is, it is preferable that ^PD1 is directly bonded to the aromatic hydrocarbon ring structure contained in ^YD1 .

式（A2-1）～（A2-5）中，R ^A211～R ^A214、R ^A221～R ^A224、R ^A231～R ^A238、R ^A241～R ^A248及R ^A251～R ^A258分別獨立地表示氫原子、烷基、環狀烷基、烷氧基、羥基、氰基、鹵化烷基或鹵素原子，L ^A231及L ^A241分別獨立地表示單鍵、羰基、磺醯基、2價飽和烴基、2價不飽和烴基、雜原子、雜環基或鹵化伸烷基，R ^A211～R ^A214中的至少1個、R ^A221～R ^A224中的至少1個、R ^A231～R ^A238中的至少1個、R ^A241～R ^A248中的至少1個及R ^A251～R ^A258中的至少1個可以為上述顯示出產生鹼的性質之結構，*分別獨立地表示與其他結構的鍵結部位。 It is preferred that Y ^D1 comprises at least one structure selected from the group consisting of structures represented by the following formula (A2-1) to formula (A2-5), and Y ^D1 is selected from the group consisting of the structures represented by the above formula (A2-5). 1) At least one structure in the group of structures represented by formula (A2-5) is more preferable. [chemical formula 19]

In formulas (A2-1) to (A2-5), R ^A211 to R ^A214 , R ^A221 to R ^A224 , R ^A231 to R ^A238 , R ^A241 to R ^A248 and R ^A251 to R ^A258 independently represent a hydrogen atom, Alkyl, cyclic alkyl, alkoxy, hydroxyl, cyano, halogenated alkyl or halogen atom, L ^A231 and L ^A241 independently represent a single bond, carbonyl, sulfonyl, divalent saturated hydrocarbon group, divalent non- Saturated hydrocarbon group, heteroatom, heterocyclic group or alkylene halide, at least one of R ^A211 to R ^A214 , at least one of R ^A221 to R ^A224 , at least one of R ^A231 to R ^A238 , R ^A241 At least one of R ^A248 and at least one of R ^A251 to R ^A258 may be the structure exhibiting the above-mentioned base-generating property, and * each independently represents a bonding site with another structure.

Among these, from the viewpoint of solvent solubility, it is preferable that ^Y1 includes a structure represented by any one of formula (A2-1) to formula (A2-4), including the structure represented by formula (A2-1) or formula The structure represented by any one of (A2-4) is better.

At least one of R ^A211 to R ^A214 , at least one of R ^A221 to R ^A224 , at least one of R ^A231 to R ^A238 , at least one of R ^A241 to R ^A248 , and at least one of R ^A251 to R ^A258 It is preferable that at least one of them is a bonding site with ^PD1 in the above formula (LD-1). In formula (A2-1), when R ^A211 ~ R ^A214 are not the bonding sites with ^{PD1, R A211 ~} R ^A214 independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, an alkyl group with 3 to 12 carbons A cyclic alkyl group, an alkoxy group having 1 to 6 carbons, a hydroxyl group, a cyano group, a halogenated alkyl group having 1 to 3 carbons, or a halogen atom are preferred. From the viewpoint of solvent solubility, a hydrogen atom, a carbon number 1 An alkyl group with 6 to 6 carbons, an alkoxy group with 1 to 6 carbons, a halogenated alkyl group with 1 to 3 carbons are more preferable, and a hydrogen atom or an alkyl group with 1 to 6 carbons is more preferable. Examples of the halogen atom in the halogenated alkyl group in the above-mentioned R ^A211 to R ^A214 or the above-mentioned halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom or a bromine atom is preferable. In formula (A2-2), R ^A221 to R ^A224 have the same meanings as R ^A211 to R ^A214 in formula (A2-1), respectively, and preferred embodiments are also the same. In formula (A2-3), R ^A231 to R ^A238 independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, a cyclic alkyl group with 3 to 12 carbons, an alkoxy group with 1 to 6 carbons, A hydroxyl group, a cyano group, a halogenated alkyl group having 1 to 3 carbons, or a halogen atom are preferred. From the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbons, and an alkoxy group having 1 to 6 carbons are preferred. Or a halogenated alkyl group having 1 to 3 carbons is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbons is more preferable. ^{Examples of the halogen atom in the halogenated alkyl group in the above-mentioned R A231 to R A238 or} the above-mentioned halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom or a bromine atom is preferable. In the formula (A2-3), L ^A231 represents a single bond, a divalent saturated hydrocarbon group with 1 to 6 carbons, a divalent unsaturated hydrocarbon group with 5 to 24 carbons, -O-, -S-, -NR ^N -, A heterocyclic group or a halogenated alkylene group with 1 to 6 carbons is preferred, which means a single bond, a saturated hydrocarbon group with 1 to 6 carbons, -O- or a heterocyclic group is more preferred, which means a single bond or -O- is Further better. The aforementioned ^RN is as described above. The aforementioned divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group, or a divalent aromatic hydrocarbon group, preferably a divalent aromatic hydrocarbon group. As the above-mentioned heterocyclic group, for example, a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocyclic ring is preferable, and a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocyclic ring is more preferable. Good, remove 2 hydrogen atoms from the ring structure of pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, pyrrole ring, furan ring, thiophene ring, piperidine ring, tetrahydropyran ring, pyridine ring, portoline ring, etc. The formed group is even better. These heterocycles may further form condensed rings with other heterocycles or hydrocarbon rings. The number of ring members of the heterocyclic ring is preferably 5-10, more preferably 5 or 6. Also, as the hetero atom in the above-mentioned heterocyclic group, an oxygen atom, a nitrogen atom or a sulfur atom is preferable. 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 chlorine atom or bromine atom is preferable. In formula (A2-4), R ^A241 to R ^A248 and L ^A241 have the same meanings as R ^A231 to R ^A238 and L A231 in formula (A2-3), respectively, and preferred ^embodiments are also the same. In formula (A2-5), R ^A251 to R ^A258 have the same meanings as R ^A211 to R ^A214 in formula (A2-1), respectively, and preferred embodiments are also the same.

In formula (A2-1), at least one of R ^A211 to R ^A214 is preferably a bonding site with ^PD1 in formula (LD-1), and one of R ^A211 to R ^A214 is the bonding site with the above-mentioned The bonding site of ^PD1 is more preferable, and the bonding site of ^RA213 with the aforementioned ^PD1 is more preferable. In formula (A2-2), at least one of R ^A221 to R ^A224 is preferably a bonding site with ^PD1 in formula (LD-1), and one of R ^A221 to R ^A224 is the bonding site with the above-mentioned The bonding site of ^PD1 is more preferable, and the bonding site of ^RA223 with the aforementioned ^PD1 is more preferable. In formula (A2-3), at least one of R A231 to R ^A238 is preferably a bonding site with ^PD1 in formula (LD-1), and two of R ^A231 to R ^A238 are ^bonded to the above-mentioned The bonding site of PD1 is more preferable, and a total of 2 of ^{RA231 to RA234 and 1 of RA235 to RA238 are the bonding sites} to the above-mentioned ^{PD1, and further preferably, RA231 and} R These two of ^{A238 are especially preferable} as the bonding sites with the aforementioned ^PD1 . In formula (A2-4), at least one of R ^A241 to R ^A248 is preferably a bonding site with ^PD1 in formula (LD-1), and two of R ^A241 to R ^A248 are the bonding site with the above-mentioned The bonding site of ^PD1 is more preferable, and one of R ^A241 to R ^A244 and one of R ^A245 to R ^A248 , a total of two are the bonding sites to the above PD1, and R ^A241 and R ^A241 are more preferable. These two of ^{A248 are particularly preferable} as the bonding sites with the aforementioned ^PD1 . In formula (A2-5), at least one of R ^A251 to R ^A258 is preferably a bonding site with ^PD1 in formula (LD-1), and two of R ^A251 to R ^A258 are the bonding site with the above-mentioned The bonding site of ^PD1 is more preferable, and one of R ^A251 to R ^A254 and one of R ^A255 to R ^A258 are a total of two bonding sites to the above PD1, and R ^A253 and R ^A253 are more preferable. These two of ^A257 are especially preferable as the bonding sites with the aforementioned ^PD1 .

In formula (A2-1) to formula (A2-5), it is preferable that two * are each * in formula (LD-1). That is, it is preferable that the two nitrogen atoms bonded by R ¹¹¹ in the formula (2) are directly bonded to the positions represented by the two * in the formula (A2-1) to the formula (A2-5).

式（Y-1）中，R ^Y11、R ^Y12、R ^Y13分別與式（A2-1）中的R ^A211、R ^A212及R ^A214的含義相同，較佳態樣亦相同。 式（Y-2）中，R ^Y21～R ^Y26、L ^X21分別與式（A2-4）中的R ^A242～R ^A247、L ^A241的含義相同，較佳態樣亦相同。 式（Y-1）或式（Y-2）中，*分別表示與式（2）中的R ¹¹¹所鍵結之2個氮原子的鍵結部位，#分別表示與式（LD-1）中的P ^D1的鍵結部位。 Among them, Y ^D1 is preferably a group represented by the following formula (Y-1) or (Y-2). [chemical formula 20]

In formula (Y-1), R ^Y11 , R ^Y12 , and R ^Y13 have the same meanings as R ^A211 , R ^A212 , and R ^A214 in formula (A2-1), respectively, and preferred embodiments are also the same. In formula (Y-2), R ^Y21 to R ^Y26 and L ^X21 have the same meanings as R ^A242 to R ^A247 and L ^A241 in formula (A2-4), respectively, and preferred embodiments are also the same. In formula (Y-1) or formula (Y-2), * respectively represent the bonding sites of the two nitrogen atoms bonded to R ¹¹¹ in formula (2), and # respectively represent the bonding sites of the two nitrogen atoms in formula (LD-1) The binding site of ^PD1 in.

式（PD-1）中，R ^P表示上述顯示出產生鹼的性質之結構，*表示與Y ^D1的鍵結部位，L ^P表示2價連結基。 作為L ^P，可舉出-OC（=O）-、-C（=O）O-、-C（=O）NR ^N-、-OC（=O）NR ^N-、-NR ^NC（=O）O-、-NR ^NC（=O）NR ^N-等，-O-或-C（=O）O-為較佳。上述R ^N為如上所述。 顯示出產生鹼的性質之結構的較佳態樣如上所述，例如能夠較佳地使用由式（1-1）表示之結構、由式（1-2）表示之結構等。 ^-PD1- In the formula (LD-1), ^PD1 represents a group including the above-mentioned structure showing a property of generating a base. For example, it is preferable that ^PD1 is the following formula (PD-1). [chemical formula 21]

In the formula (PD-1), R ^P represents the above-mentioned structure showing the property of generating a base, * represents a bonding site with Y ^D1 , and L ^P represents a divalent linking group. Examples of L ^P include -OC(=O)-, -C(=O)O-, -C(=O)NR ^N- , -OC(=O)NR ^N- , -NR ^N C(= O) O-, -NR ^N C (=O) NR ^N -, etc., -O- or -C (=O) O- is better. The aforementioned ^RN is as described above. Preferable aspects of the structure exhibiting the property of generating a base are as described above, for example, a structure represented by formula (1-1), a structure represented by formula (1-2), and the like can be preferably used.

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

上述式（LDA-1）中，Y ^D1、P ^D1、n分別與上述式（LD-1）中的Y ^D1、P ^D1、n的含義相同，較佳態樣亦相同。 又，例如，亦能夠藉由如下方法合成特定樹脂：使用具有羧基等反應性基之二胺合成樹脂，使具有與上述反應性基進行反應而形成共價鍵之結構（例如，羥基等）及顯示出產生鹼的性質之結構之化合物與上述樹脂進行反應，由此亦能夠合成特定樹脂。 -Synthesis method- For example, the structure represented by the above formula (LD-1) can be obtained as a structure derived from a diamine represented by the following formula (LDA-1). [chemical formula 22]

In the above formula (LDA-1), Y ^D1 , P ^D1 , and n have the same meanings as Y ^D1 , P ^D1 , and n in the above formula (LD-1), respectively, and preferred embodiments are also the same. Also, for example, a specific resin can also be synthesized by using a diamine synthetic resin having a reactive group such as a carboxyl group, and having a structure (for example, a hydroxyl group, etc.) that reacts with the reactive group to form a covalent bond and A specific resin can also be synthesized by reacting a compound having a structure that generates a base with the aforementioned resin.

在式（O）中，R ¹¹⁵表示4價有機基團。R ¹¹⁵與式（2）中的R ¹¹⁵的含義相同，較佳範圍亦相同。 Specifically, R ¹¹⁵ includes a tetracarboxylic acid residue remaining after removing an acid anhydride group from a tetracarboxylic dianhydride, and the like. As a structure corresponding to R ¹¹⁵ , the polyimide precursor may contain only one kind of tetracarboxylic dianhydride residues, or may contain two or more kinds. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [chemical formula 23]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as R ¹¹⁵ in formula (2), 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.

In formula (2), at least one of R ¹¹¹ and R ¹¹⁵ may have an OH group. More specifically, R ¹¹¹ includes a residue of a bisaminophenol derivative.

式（LD-2）中，Y ^D2表示n+4價有機基團，P ^D2表示包含顯示出產生鹼的性質之結構之基團，m表示1以上的整數，*分別表示與式（2）中的R ¹¹⁵所鍵結之羰基的鍵結部位。 In addition, R ¹¹⁵ can also include a structure showing a property of generating a base. When R ¹¹⁵ includes a structure showing a property of generating a base, for example, R ¹¹⁵ is preferably a structure represented by the following formula (LD-2). [chemical formula 24]

In the formula (LD-2), Y ^D2 represents an n+4-valent organic group, ^PD2 represents a group including a structure showing the property of generating a base, m represents an integer of 1 or more, and * represents the formula (2) The bonding site of the carbonyl group to which R ¹¹⁵ is bonded.

-Y ^D2 - In the formula (LD-2), Y ^D2 is preferably an n+4-valent organic group, more preferably an n+4-valent organic group including an aromatic hydrocarbon group. The aromatic hydrocarbon group in Y ^D4 is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group with 6 to 20 carbon atoms, and a group obtained by removing 2 or more hydrogen atoms from the benzene ring is further preferred. Preferably, a group obtained by removing 3 or more hydrogen atoms from a benzene ring is particularly preferable. In formula (LD-2), those in Y ^D2 that are directly bonded to the bonding site described in formula (LD-2), that is, *, are preferably aromatic hydrocarbon groups. That is, it is preferable that 4 * described in formula (LD-2) are directly bonded to the aromatic hydrocarbon ring structure contained in Y ^D2 . Also, in the formula (LD-2), it is preferable that the bonding sites of Y ^D2 and ^PD2 are all aromatic hydrocarbon groups. That is, it is preferable that ^PD2 is directly bonded to the aromatic hydrocarbon ring structure contained in ^YD2 .

式（A1-1）中，R ^A11～R ^A16分別獨立地表示氫原子、烷基、環狀烷基、烷氧基、羥基、氰基、鹵化烷基或鹵素原子，L ^A11表示單鍵、羰基、磺醯基、2價飽和烴基、2價不飽和烴基、雜原子、雜環基或鹵化伸烷基，R ^A11～R ^A16中的至少1個或L ^A11為與上述式（LD-2）中的P ^D2的鍵結部位，*分別獨立地表示與其他結構的鍵結部位。 It is preferable that Y ^D1 includes a structure represented by the following formula (A1-1), and it is more preferable that Y ^D1 is a structure represented by formula (A1-1). [chemical formula 25]

In the formula (A1-1), R ^A11 to R ^A16 independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group or a halogen atom, and L ^A11 represents a single bond, Carbonyl, sulfonyl, 2-valent saturated hydrocarbon group, 2-valent unsaturated hydrocarbon group, heteroatom, heterocyclic group or halogenated alkylene group, at least one of R ^A11 to R ^A16 or L ^A11 is the same as the above formula (LD-2 ), the bonding site of ^PD2 in ), and * independently represent the bonding sites with other structures.

In formula (A1-1), at least one of R ^A11 to R ^A16 or L ^A11 is a bonding site with ^{PD2 in the above formula (LD-2), and L A11 is} a bond with the above formula (LD The bonding site of ^PD2 in -2) is preferable. In the formula (A1-1), R ^A11 to R ^A16 independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, a cyclic alkyl group with 3 to 12 carbons, an alkoxy group with 1 to 6 carbons, A hydroxyl group, a cyano group, a halogenated alkyl group having 1 to 3 carbons, or a halogen atom are preferred. From the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbons, and an alkoxy group having 1 to 6 carbons are preferred. Or a halogenated alkyl group having 1 to 3 carbons is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbons is more preferable. Examples of the halogen atom in the halogenated alkyl group in the above-mentioned R ^A11 to R ^A16 or the above-mentioned halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom or a bromine atom is preferable.

In the formula (A1-1), it is preferable that L ^A1 is a bonding site with ^PD2 in the above formula (LD-2). Here, when L ^A1 is a bonding site with ^PD2 in the above formula (LD-2), it is preferable that L ^A1 is a divalent hydrocarbon group, such as an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof A group is more preferred, and an aliphatic hydrocarbon group is particularly preferred. As the above-mentioned aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferable, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 10 carbon atoms is preferable, and an aromatic hydrocarbon group having 6 carbon atoms is more preferable. When L ^A1 is not a bonding site with ^PD2 in the formula (LD-2), L ^A1 represents a single bond, a divalent saturated hydrocarbon group with 1 to 6 carbons, a divalent unsaturated hydrocarbon group with 5 to 24 carbons, - O-, -S-, -NR ^N -, heterocyclic group or a halogenated alkylene group with 1 to 6 carbons is preferred, representing a single bond, a saturated hydrocarbon group with 1 to 6 carbons, -O- or a heterocyclic group More preferably, it represents a single bond or -O- is further more preferable. The aforementioned ^RN is as described above.

^-PD2 - ^PD2 is preferably a group represented by the above formula (PD-1).

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

上述式（LDB-1）中，Y ^D2、P ^D2、m分別與上述式（LD-2）中的Y ^D2、P ^D2、m的含義相同，較佳態樣亦相同。 又，例如，亦能夠藉由如下方法合成特定樹脂：使用具有烷氧基等反應性基之羧酸二酐合成樹脂，使具有與上述反應性基進行反應而形成共價鍵之結構（例如，鹵化烷基等）及顯示出產生鹼的性質之結構之化合物與上述樹脂進行反應。 特定樹脂的合成方法能夠考慮欲獲得之特定樹脂的結構、特定樹脂的產率、合成的容易度、與原料或反應條件相關的成本等來選擇。 -Synthesis method- For example, the structure represented by said formula (LD-1) can be obtained as a structure derived from the carboxylic dianhydride represented by following formula (LDB-1). [chemical formula 26]

In the above formula (LDB-1), Y ^D2 , P ^D2 , and m have the same meanings as Y ^D2 , P ^D2 , and m in the above formula (LD-2), respectively, and preferred embodiments are also the same. Also, for example, a specific resin can also be synthesized by using a carboxylic dianhydride synthetic resin having a reactive group such as an alkoxy group, and having a structure that reacts with the reactive group to form a covalent bond (for example, Alkyl halide, etc.) and a compound showing a structure that generates a base are reacted with the above-mentioned resin. The synthesis method of the specific resin can be selected in consideration of the structure of the specific resin to be obtained, the yield of the specific resin, the ease of synthesis, the cost related to raw materials or reaction conditions, and the like.

R ¹¹³ and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferable to contain a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. Also, it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferable that both of them contain a polymerizable group. It is also preferable that at least one of R ¹¹³ and R ¹¹⁴ contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, free radicals, etc., and a radical polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, and a benzoyl group. Azolyl, blocked isocyanate, amine. As the radical polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable. As the group having an ethylenically unsaturated bond, vinyl, allyl, isoallyl, 2-methallyl, and a group having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl, etc.), (meth)acrylamide, (meth)acryloxy, groups represented by the following formula (III), etc., the group represented by the following formula (III) is better.

[chemical formula 27]

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 plurality of alkyleneoxy groups included in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group can be randomly arranged, can be arranged with blocks, or can be arranged alternately. Arrangement of other 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 still more preferably 2-5. Excellent, 2 to 4 are more preferred, 2 or 3 are particularly preferred, and 2 is the best. 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 (the number of repetitions 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 (2), when R ¹¹³ is a hydrogen atom or R ¹¹⁴ is a hydrogen atom, the polyimide precursor can form a conjugated salt with a tertiary amine compound having an ethylenically unsaturated bond. N,N- dimethylaminopropyl methacrylate is mentioned as an example of the tertiary amine compound which has such an ethylenically unsaturated bond.

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polarity switching group such as an acid decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group. An ester group or the like is preferable, and an acetal group or a ketal group is more preferable from the viewpoint of exposure sensitivity. Specific examples of acid-decomposable groups include tertiary butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuryl, ethoxyethyl, methoxyethyl, ethoxymethyl group, trimethylsilyl group, tertiary butoxycarbonylmethyl group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuryl group is preferable.

In addition, it is also one of the preferred aspects of the present invention that at least one of R ¹¹³ and R ¹¹⁴ includes the above-mentioned structure showing the property of generating a base. For example, an aspect in which at least one of R ¹¹³ and R ¹¹⁴ is a structure represented by the above formula (1-1) or a structure represented by the above formula (1-2) is preferably mentioned. When at least one of R ¹¹³ and R ¹¹⁴ contains the above-mentioned structure showing the property of generating a base, R ¹¹³ and R ¹¹⁴ including a structure showing a property of generating a base relative to all R ¹¹³ and R ¹¹⁴ in the specific resin The content of 0.1-100 mol% is preferable, 0.5-50 mol% is more preferable, and 1-20 mol% is still more preferable.

Moreover, it is also preferable that the polyimide precursor has a fluorine atom in the structure. The content of fluorine atoms in the polyimide precursor is preferably at least 10% by mass, more preferably at most 20% by mass.

Also, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving the adhesion to the substrate. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

式（2-A）中，A ¹及A ²表示氧原子，R ¹¹¹及R ¹¹²分別獨立地表示2價有機基團，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價有機基團，R ¹¹³及R ¹¹⁴中的至少1個為包含聚合性基之基團，兩者均為包含聚合性基之基團為較佳。 The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, the width of the exposure latitude can be further increased. Formula (2-A) [Chemical Formula 28]

In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or a monovalent organic group, At least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ independently have the same meanings as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and the preferred ranges are also the same. R ¹¹² has the same meaning as R ¹¹² in formula (5), and the preferred range is also the same.

The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. Also, structural isomers of the repeating unit represented by formula (2) may be included. Moreover, besides the repeating unit of the above-mentioned formula (2), the polyimide precursor may obviously also contain other types of repeating units.

As one embodiment of the polyimide precursor in the present invention, an aspect in which the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units is mentioned. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above-mentioned total content is not particularly limited, and all the repeating units in the polyimide precursor except the terminal may be the repeating unit represented by formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably from 5,000 to 100,000, more preferably from 10,000 to 50,000, even more preferably from 15,000 to 40,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 2,000-40,000, More preferably, it is 3,000-30,000, More preferably, it is 4,000-20,000. The molecular weight dispersion of the polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and still more preferably 2.0 or higher. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited. For example, 7.0 or less is preferable, 6.5 or less is more preferable, and 6.0 or less is still more preferable. In the present specification, the degree of dispersion of molecular weight is a value calculated from weight average molecular weight/number average molecular weight. In addition, when the resin composition contains a plurality of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyimide precursor 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 by using the above-mentioned plural polyimide precursors as one resin are within the above-mentioned ranges, respectively.

在式（3）中，R ¹²¹表示2價有機基團，R ¹²²表示4價有機基團，R ¹²³及R ¹²⁴分別獨立地表示氫原子或1價有機基團。 [Polybenzoxazole precursor] The structure of the polybenzoxazole precursor used in the present invention is not particularly limited, but preferably includes a repeating unit represented by the following formula (3). [chemical formula 29]

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

When the specific resin contains a repeating unit represented by formula (3), it is preferable that the specific resin contains a structure showing the property of generating a base in the repeating unit represented by formula (3), and in the repeating unit represented by formula (3) It is more preferable to include the structure represented by the above formula (1-1). For example, at least one structure selected from the group consisting of R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ in formula (3) includes the above-mentioned structure showing the property of generating a base (preferably represented by the formula ( 1-1) The structure represented by) is preferably, at least one structure selected from the group including R ¹²³ and R ¹²⁴ in formula (3) includes the above-mentioned structure showing the property of generating a base (preferably is a structure represented by formula (1-1)) is more preferable. Also, when the specific resin contains a repeating unit represented by formula (3), the specific resin may contain a structure exhibiting a property of generating a base at a site different from the repeating unit represented by formula (3). For example, an aspect in which a structure exhibiting a property of generating a base is included at the end of a specific resin, and a specific resin further includes a repetition of a structure exhibiting a property of generating a base which is different from the repeating unit represented by formula (3) The shape of the unit, etc.

In formula (3), R ¹²³ and R ¹²⁴ have the same meanings as R ¹¹³ in formula (2), and their preferred ranges are also the same. That is, at least one of them is preferably a polymerizable group. In formula (3), R ¹²¹ represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a straight-chain aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. As for dicarboxylic acid residues, only 1 type may be used, and 2 or more types may be used.

As the dicarboxylic acid residue, an aliphatic group-containing dicarboxylic acid residue and an aromatic group-containing dicarboxylic acid residue are preferable, and an aromatic group-containing dicarboxylic acid residue is more preferable. As the dicarboxylic acid containing aliphatic group, dicarboxylic acid containing straight chain or branched (preferably straight chain) aliphatic group is preferred, from straight chain or branched (preferably straight chain) fatty A dicarboxylic acid composed of a group group and two -COOH is more preferable. The carbon number of the straight-chain or branched (preferably straight-chain) aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, and still more preferably 4 to 15 , 5-10 is particularly good. The linear aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing straight-chain aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, and succinic acid. , tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2 -Methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, Adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid Acid, Sebacic Acid, Hexadecanedioic Acid, 1,9-Azelaic Acid, Dodecanedioic Acid, Tridecanedioic Acid, Tetradecanedioic Acid, Pentadecanedioic Acid, Hexadecandioic Acid , heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, docosanedioic acid, tricosanedioic acid, tetradecanedioic acid Diacid, pentadecanedioic acid, hexacanedioic acid, heptacanedioic acid, octacosanedioic acid, nonacanedioic acid, triacanedioic acid, triundecanedioic acid , docosanedioic acid, diglycolic acid, dicarboxylic acid represented by the following formula, etc.

（式中，Z為碳數1～6的烴基，n為1～6的整數。） [chemical formula 30]

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic group is preferable, and a dicarboxylic acid consisting only of a group having the following aromatic group and two -COOH is more preferable.

式中，A表示選自包括-CH ₂-、-O-、-S-、-SO ₂-、-CO-、-NHCO-、-C（CF ₃） ₂-及-C（CH ₃） ₂-之群組中之2價基團，*分別獨立地表示與其他結構的鍵結部位。 [chemical formula 31]

In the formula, A represents the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ - and -C(CH ₃ ) ₂ The divalent groups in the group of -, * each independently represent a bonding site with another structure.

Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the above formula (2), and the preferred range is also the same. Also, R ¹²² is preferably a group derived from a bisaminophenol derivative. As a group derived from a bisaminophenol derivative, for example, 3,3'-diamino-4,4 '-Dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl, 4 ,4'-Diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxy phenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis -(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-di Hydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3 '-Diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1 , 3-diamino-4,6-dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

Among the bisaminophenol derivatives, those having the following aromatic groups are preferred.

式中，X ₁表示-O-、-S-、-C（CF ₃） ₂-、-CH ₂-、-SO ₂-、-NHCO-，*及#分別表示與其他結構的鍵結部位。R表示氫原子或1價取代基，氫原子或烴基為較佳，氫原子或烷基為更佳。又，R ¹²²為由上述式表示之結構亦較佳。R ¹²²為由上述式表示之結構時，共計4個*及#中，任意2個為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位且另2個為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位為較佳，2個*為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位或2個*為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位為更佳，2個*為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位為進一步較佳。 [chemical formula 32]

In the formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, -NHCO-, and * and # represent bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. In addition, it is also preferable that R ¹²² is a structure represented by the above formula. When R ¹²² is a structure represented by the above formula, among a total of 4 * and #, any 2 are bonded to the nitrogen atom bonded to R ¹²² in formula (3) and the other 2 are bonded to the formula ( 3) The bonding site of the oxygen atom bonded by R ¹²² is preferred, the 2 * are the bonding sites of the oxygen atom bonded with R ¹²² in formula (3) and the 2 #s are the bonding sites of the formula (3) (3) The bonding site of the nitrogen atom to which R ¹²² is bonded or 2 * are the bonding sites to the nitrogen atom bonded to R ¹²² in formula (3) and the 2 #s are the bonding sites to the nitrogen atom bonded to formula (3) ) in the bonded position of the oxygen atom bonded by R ¹²² is more preferable, and 2 * are bonded sites with the oxygen atom bonded to R ¹²² in formula (3) and 2 # are the bonded position with the formula ( 3) The bonding site of the nitrogen atom to which R ¹²² is bonded is further preferred.

It is also preferable that the bisaminophenol derivative is a compound represented by the formula (As). [chemical formula 33]

In formula (As), R ₁ is selected from hydrogen atom, alkylene group, substituted alkylene group, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, single bond or the following The organic group in the group of formula (A-sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R ₃ is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

（在式（A-sc）中，*表示與由上述式（A-s）表示之雙胺基苯酚衍生物的胺基苯酚基的芳香環鍵結。） [chemical formula 34]

(In formula (A-sc), * represents bonding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

It is believed that in the above formula (As), having a substituent at the ortho position of the phenolic hydroxyl group, that is, at _R3 will make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and further improve the cyclization during hardening at low temperature. Considering the effect of increasing the rate, it is especially good.

In addition, in the above-mentioned _formula (As), when R2 is an alkyl group and _R3 is an alkyl group, high transparency to i-rays and the effect of high cyclization rate during curing at low temperature can be maintained, which is preferable.

Also, in the above formula (As), R ₁ is further preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and substituted alkylene group related to R1 include straight-chain or branched-chain alkyl groups having ₁ to 8 carbon atoms. -CH 2 -, -CH(CH 3 )-, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ - is more preferred.

As a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A-2013-256506 can be referred to. incorporated into this manual.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of JP-A-2013-256506, which are incorporated herein. Of course it is not limited to these.

In addition to the repeating units of the above formula (3), the polybenzoxazole precursor may also contain other types of repeating units. It is preferable that the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another type of repeating unit from the viewpoint of being able to suppress warpage accompanying ring closure.

在式（SL）中，Z具有a結構和b結構，R ^1s為氫原子或碳數1～10的烴基，R ^2s為碳數1～10的烴基，R ^3s、R ^4s、R ^5s、R ^6s中的至少1個為芳香族基，剩餘部分為氫原子或碳數1～30的有機基團且分別可以相同，亦可以不同。a結構及b結構的聚合可以為嵌段聚合或隨機聚合。關於Z部分的莫耳%，a結構為5～95莫耳%，b結構為95～5莫耳%，a+b為100莫耳%。 [chemical formula 35]

In formula (SL), Z has structure a and structure b, R ^1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbons, R ^2s is a hydrocarbon group with 1 to 10 carbons, R ^3s , R ^4s , R ^5s , R At least one of ^6s is an aromatic group, and the rest is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and they may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. The molar % of the Z moiety is 5 to 95 molar % for the a structure, 95 to 5 molar % for the b structure, and 100 molar % for a+b.

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the structure b are phenyl groups. Moreover, the molecular weight of the structure represented by formula (SL) is preferably 400-4,000, more preferably 500-3,000. By setting the above-mentioned molecular weight within the above-mentioned range, the elastic modulus after dehydration and ring-closure of the polybenzoxazole precursor can be lowered more effectively, and both the effect of suppressing warpage and the effect of improving solvent solubility can be achieved.

When the diamine residue represented by formula (SL) is included as another type of repeating unit, it is also preferable to further include, as the repeating unit, a tetracarboxylic acid residue remaining after removing the acid anhydride group from the tetracarboxylic dianhydride. Examples of such tetracarboxylic acid residues include the example of R ¹¹⁵ in formula (2).

For example, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000-30,000, more preferably 20,000-29,000, further preferably 22,000-28,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 7,200-14,000, More preferably, it is 8,000-12,000, More preferably, it is 9,200-11,200. The molecular weight dispersion of the polybenzoxazole precursor is preferably at least 1.4, more preferably at least 1.5, and still more preferably at least 1.6. The upper limit of the molecular weight dispersion of the polybenzoxazole precursor is not particularly limited, for example, 2.6 or less is preferred, 2.5 or less is more preferred, 2.4 or less is further preferred, 2.3 or less is still more preferred, Below 2.2 is further preferred. Also, when the resin composition contains plural polybenzoxazole precursors as the specific resin, it is preferable that the weight average molecular weight, number average molecular weight and dispersion of at least one polybenzoxazole precursor are within the above ranges. Furthermore, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of polybenzoxazole precursors mentioned above as one resin fall within the above ranges, respectively.

在式（PAI-2）中，R ¹¹⁷表示3價有機基團，R ¹¹¹表示2價有機基團，A ²表示氧原子或-NH-，R ¹¹³表示氫原子或1價有機基團。 [Polyamideimide Precursor] The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2). [chemical formula 36]

In the formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or -NH-, and R ¹¹³ represents a hydrogen atom or a monovalent organic group.

When the specific resin contains the repeating unit represented by the formula (PAI-2), it is preferable that the specific resin contains a structure showing the property of generating a base in the repeating unit represented by the formula (PAI-2). 2) It is more preferable that the structure represented by the above-mentioned formula (1-1) is included in the repeating unit represented. For example, at least one structure selected from the group consisting of R ¹¹¹ , R ¹¹³ and R ¹¹⁷ in formula (PAI-2) includes the above-mentioned structure showing the property of generating a base (preferably represented by formula (1 The structure represented by -1) is preferable, and it is more preferable to include the above-mentioned structure (preferably the structure represented by formula (1-1)) that shows the property of generating a base in R ¹¹³ in the formula (PAI-2). good. Also, when the specific resin contains a repeating unit represented by formula (PAI-2), the specific resin may contain a structure exhibiting a base-generating property at a site different from the repeating unit represented by formula (PAI-2). For example, an aspect in which a structure showing a property of generating a base is included at the end of a specific resin, and a specific resin further includes a structure showing a property of generating a base which is different from the repeating unit represented by formula (PAI-2) The form of the repeating unit, etc.

In the formula (PAI-2), R ¹¹⁷ can be exemplified by a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or these are linked by a single bond or a linking group 2 A group consisting of more than one, 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, and aliphatic group with 6 to 20 carbons An aromatic group or a group formed by combining two or more of these through a single bond or a linking group is preferred. An aromatic group with 6 to 20 carbons or a group with 6 to 20 carbons connected through a single bond or a linking group is preferred. A combination of two or more aromatic groups 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 preferred 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 ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As the above-mentioned halogenation, chlorination is preferable. In the present invention, a compound having three carboxyl groups is called a tricarboxylic acid compound. Among the three carboxyl groups of the tricarboxylic acid compound, two carboxyl groups may be anhydrided. Examples of the tricarboxylic acid compound that may be halogenated for the production of the polyamideimide precursor include branched aliphatic, cycloaliphatic, or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used only by 1 type, and may use 2 or more types.

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 cyclic aliphatic group having 6 to 20 carbons, A tricarboxylic acid compound having an aromatic group of ~20 or a group formed by combining two or more of them through a single bond or a linking group is preferred, including an aromatic group with a carbon number of 6 to 20 or through a single bond Or a tricarboxylic acid compound in which two or more aromatic groups having 6 to 20 carbon atoms are combined as a linking group is more preferable.

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).

In formula (PAI-2), R ¹¹¹ , A ² , and R ¹¹³ have the same meanings as R ¹¹¹ , A ² , and R ¹¹³ in formula (2), respectively, and preferred embodiments are also the same.

The polyamideimide precursor may further comprise other repeating units. As another repeating unit, the repeating unit represented by said formula (2), the repeating unit represented by following formula (PAI-1), etc. are mentioned. [chemical formula 37]

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 these are linked by a single bond or a linking group 2 A group consisting of more than one, 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, and aliphatic group with 6 to 20 carbons An aromatic group or a group formed by combining two or more of these through a single bond or a linking group is preferred. An aromatic group with 6 to 20 carbons or a group with 6 to 20 carbons connected through a single bond or a linking group is preferred. A combination of two or more aromatic groups 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 preferred 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 halogenated dicarboxylic acid compounds or dicarboxylic acid dihalide compounds used in the production of polyamideimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic Dicarboxylic acid compound or dicarboxylic acid dihalide compound, etc. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used only by 1 type, and may use 2 or more types.

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, Aliphatic groups, aromatic groups with 6 to 20 carbon atoms, or dicarboxylic acid compounds or dicarboxylic acid dihalide compounds in which two or more of these are combined through a single bond or a linking group are preferred. A dicarboxylic acid compound or a dihalogenated dicarboxylic acid 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 Compounds are better.

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. As a specific example of the dicarboxylic acid dihalide compound, the compound of the structure which halogenated two carboxyl groups in the said specific example of a dicarboxylic acid compound is mentioned.

In the formula (PAI-1), R ¹¹¹ has the same meaning as R ¹¹¹ in the above formula (2), and preferred embodiments are also the same.

Also, it is preferable that the polyamideimide precursor has a fluorine atom in its structure. The content of fluorine atoms in the polyamideimide precursor is preferably at least 10% by mass, and more preferably at most 20% by mass.

Also, for the purpose of improving the adhesion to the substrate, the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as a diamine component, the aspect which used bis(3-aminopropyl) tetramethyldisiloxane, bis(p-aminophenyl) octamethylpentasiloxane, etc. is mentioned.

As an embodiment of the polyamide imide precursor in the present invention, the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1) and the repeating unit represented by the formula (2) can be mentioned. The total content of the repeating units represented is 50 mol% or more of the total repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above-mentioned total content is not particularly limited, and all the repeating units in the polyamideimide precursor except the terminal can be the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1) Any one of repeating units and repeating units represented by formula (2). In addition, as another embodiment of the polyamideimide precursor in the present invention, the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) can be mentioned. It is an aspect of more than 50 mol% of the total repeating unit. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above-mentioned total content is not particularly limited, and all the repeating units in the polyamideimide precursor except the terminal can be the repeating unit represented by formula (PAI-2) or the repeating unit represented by formula (PAI-1). any of the repeating units.

The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000-500,000, more preferably 5,000-100,000, further preferably 10,000-50,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 800-250,000, More preferably, it is 2,000-50,000, More preferably, it is 4,000-25,000. The molecular weight dispersion of the polyamideimide precursor is preferably at least 1.5, more preferably at least 1.8, and still more preferably at least 2.0. The upper limit of the molecular weight dispersion of the polyamideimide precursor is not particularly limited, for example, 7.0 or less is preferable, 6.5 or less is more preferable, 6.0 or less is still more preferable. Also, when the resin composition contains a plurality of polyamide imide precursors as the specific resin, it is preferable that the weight average molecular weight, number average molecular weight and dispersity of at least one polyamide imide precursor are within the above range . Furthermore, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the above-mentioned plural polyimide precursors as one resin are within the above-mentioned ranges, respectively.

[Methods for producing polyimide precursors, etc.] For example, a polyimide precursor etc. can be obtained by the method of making tetracarboxylic dianhydride and diamine react at low temperature, making tetracarboxylic dianhydride and diamine react at low temperature to obtain polyamic acid The method of esterifying with a condensing agent or an alkylating agent, the method of obtaining a diester by tetracarboxylic dianhydride and alcohol, and then reacting it in the presence of diamine and condensing agent, using tetracarboxylic dianhydride and alcohol A method of halogenating the remaining dicarboxylic acid with a halogenating agent after obtaining a diester and reacting it with a diamine, etc. Among the above production methods, the method of obtaining a diester from tetracarboxylic dianhydride and alcohol, and then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine is more preferable. Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1, 1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, etc. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide Amide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, etc. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, and the like. In the production method of a polyimide precursor etc., it is preferable to use an organic solvent when carrying out a reaction. The organic solvent may be one type, or two or more types. As the organic solvent, it can be appropriately determined according to the raw material, and pyridine, diglyme (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, Dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the production method of a polyimide precursor etc., it is preferable to add a basic compound at the time of reaction. The basic compound may be one type, or two or more types. The basic compound can be appropriately determined according to the raw material, and triethylamine, diisopropylethylamine, pyridine, 1,8-diazibicyclo[5.4.0]undec-7-ene, N,N-dimethyl -4-aminopyridine, etc.

-Encapping agent- When producing polyimide precursors, etc., in order to further improve storage stability, it is better to block carboxylic anhydrides, acid anhydride derivatives, or amine groups remaining at the ends of resins such as polyimide precursors. When blocking the carboxylic acid anhydride and acid anhydride derivatives remaining at the end of the resin, examples of the blocking agent include monoalcohols, phenols, mercaptans, thiophenols, monoamines, etc. Alcohols, phenols, and monoamines are more preferable. Preferred compounds of the 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 end groups can be introduced by reacting a plurality of end-capping agents. Also, when blocking the amine group at the terminal of the resin, it can be blocked with a compound having a functional group capable of reacting with the amine group. Preferred end-capping agents for amino groups are 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.

Also, by using a compound having a structure showing a base-generating property as a capping agent, it is also possible to introduce a structure showing a base-generating property at the terminal of a specific resin. As such an end-blocking agent, for example, a hydroxyl group, a thiol group, an amino group, a carboxyl group, a carboxylic acid anhydride group, a carboxylic acid halide group, a sulfonic acid anhydride group, a sulfonic acid halide group, etc. Compounds with reactive groups such as sulfonic acid carboxylic acid anhydride groups. As an end-blocking agent, for example, a compound having a structure showing a property of generating one or more bases and one of the above-mentioned reactive groups can be used. Preferable aspects of the structure exhibiting base-generating properties are as described above.

-Solid precipitation- When producing a polyimide precursor and the like, a solid precipitation step may be included. Specifically, after the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction liquid is collected by filtration as required, the obtained polymer component is put into a poor solvent such as water, aliphatic lower alcohol or a mixture thereof, and the polymer component is precipitated. Thereby, a polyimide precursor etc. can be obtained by depositing and drying as a solid. In order to improve the degree of purification, operations such as redissolution, reprecipitation, and drying can be repeated on the polyimide precursor. It may further include the step of removing ionic impurities using an ion exchange resin.

〔Specific example〕 Although it does not specifically limit as a specific example of a specific resin, The specific resin used in the Example mentioned later is mentioned preferably.

〔content〕 The content of the specific resin in the resin composition of the present invention is preferably at least 20% by mass, more preferably at least 30% by mass, more preferably at least 40% by mass, and even more preferably at least 50% by mass, based on 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 the total amount is 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, it preferably contains two or more polyimide precursors having different structures derived from dianhydrides (R ¹¹⁵ in the above formula (2)).

<Other resins> The resin composition of the present invention may contain the above-mentioned specific resins and other resins different from the specific resins (hereinafter also simply referred to as “other resins”). Examples of other resins include polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, polyamideimides, phenol Resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane resin, butyral resin, styrene resin , polyether resin, polyester resin, etc. As the above-mentioned polyimide precursor, polybenzoxazole precursor, and polyamidoimide precursor, resins similar to those of the above-mentioned specific resins can be used except that they do not have a structure showing the property of generating a base. In addition, as the above-mentioned polyimide, polybenzoxazole, and polyamideimide, those obtained by ring-closing the above-mentioned specific resin or those obtained by ring-closing the following resins: Except for the structure, the same resin as the above-mentioned specific resin. In this case, the partial structure may be changed in consideration of solubility in a solvent. 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 adding a (meth)acrylic resin to the resin composition instead of the polymerizable compound described later or adding a (meth)acrylic resin in addition to the polymerizable compound described later, the coatability and pattern of the resin composition can be improved. (hardened product) solvent resistance, etc., the weight average molecular weight of the (meth)acrylic resin is 20,000 or less and the polymerizable group value is high (for example, the molar amount of the polymerizable group contained in 1 g of the resin is 1×10 ^-3 mol ears/g or more).

When the resin composition of the present invention contains other resins, the content of the other resins is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, and still more preferably at least 1% by mass, based on the total solid content of the resin composition. It is more preferably 2 mass % or more, 5 mass % or more is still more preferable, and 10 mass % or more is still more preferable. 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 a preferable aspect of the resin composition of this invention, it can also set it as the aspect with low content of another resin. In the above-mentioned aspect, the content of other resins is preferably not more than 20% by mass, more preferably not more than 15% by mass, still more preferably not more than 10% by mass, and not more than 5% by mass, based on 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 the total amount is in the said range.

＜Organometallic complexes＞ From the viewpoint of chemical resistance, the resin composition of the present invention may contain an organometallic complex. As long as the organometallic complex is an organic complex compound containing a metal atom, a complex compound containing a metal atom and an organic group is preferred, and a compound in which an organic group coordinates with a metal atom is more preferred. Metal compounds are further preferred. In the present invention, the metallocene compound refers to an organometallic complex comprising two cyclopentadienyl anion derivatives which may have substituents as η5-ligands. Although it does not specifically limit as said organic group, The group which consists of a hydrocarbon group or a combination of a hydrocarbon group and a heteroatom is preferable. As the hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferable. In the present invention, at least one of the organic groups is preferably a cyclic group, and at least two are more preferably a cyclic group. The above-mentioned cyclic group is preferably selected from a cyclic group of a 5-membered ring and a cyclic group of a 6-membered ring, more preferably a cyclic group of a 5-membered ring. The above-mentioned cyclic group may be a hydrocarbon ring or a heterocycle, preferably a hydrocarbon ring. A cyclopentadienyl group is preferable as the cyclic group of a 5-membered ring. Also, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

The metal contained in the organometallic complex is not particularly limited, and metals conforming to group 4 elements are preferred, and at least one metal selected from the group consisting of titanium, zirconium, and hafnium is more preferred, selected from At least one metal of the group consisting of titanium and zirconium is further preferred, and titanium is particularly preferred.

The organometallic complex may contain two or more metal atoms, or only one metal atom, but preferably only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one kind of metal atom, or may contain two or more kinds of metal atoms.

The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound or a hafnocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, and a titanocene compound Compounds or zirconocene compounds are further preferred, and titanocene compounds are particularly preferred.

The aspect in which the organometallic complex has the ability to initiate photoradical polymerization is also one of the preferred aspects of the present invention. In the present invention, having the ability to initiate photoradical polymerization refers to being able to generate radicals capable of initiating radical polymerization by irradiation of light. For example, when a composition containing a radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region in which the organometallic complex absorbs light and a wavelength region in which the radical crosslinking agent does not absorb light, by confirming that the free Whether the radical cross-linking agent disappears can confirm the ability to initiate photoradical polymerization. When confirming disappearance, an appropriate method can be selected according to the type of radical crosslinking agent, for example, IR measurement (infrared spectroscopy measurement) or HPLC measurement (high performance liquid chromatography) may be used for confirmation. When the organometallic complex has the ability to initiate photoradical polymerization, the organometallic complex metallocene compound is preferred, the titanocene compound, zirconocene compound or hafnocene compound is more preferred, and the titanocene compound Or a zirconocene compound is more preferred, and a titanocene compound is particularly preferred. When the organometallic complex does not have the ability to initiate photoradical polymerization, the organometallic complex is selected from the group consisting of titanocene compound, tetraalkoxytitanium compound, titanium acylate compound, chelated titanium compound, zirconocene At least one compound selected from the group consisting of a compound and a hafnocene compound is preferred, and at least one compound selected from the group consisting of a titanocene compound, a zirconocene compound, and a hafnocene compound is more preferred. At least one compound selected from the group consisting of titanocene compounds and zirconocene compounds is further preferred, and titanocene compounds are particularly preferred.

The molecular weight of the organometallic complex is preferably from 50 to 2,000, more preferably from 100 to 1,000.

式（P）中，M為金屬原子，R分別獨立地為取代基。 上述R分別獨立地選自芳香族基、烷基、鹵素原子及烷基磺醯氧基為較佳。 As an organometallic complex, the compound represented by following formula (P) is mentioned preferably. [chemical formula 38]

In the formula (P), M is a metal atom, and R are each independently a substituent. The above-mentioned Rs are preferably independently selected from aromatic groups, alkyl groups, halogen atoms and alkylsulfonyloxy groups.

In formula (P), as the metal atom represented by M, iron atom, titanium atom, zirconium atom or hafnium atom is preferable, titanium atom, zirconium atom or hafnium atom is more preferable, titanium atom or zirconium atom is still more preferable , titanium atoms are particularly preferred. As the aromatic group in R in the formula (P), an aromatic group having 6 to 20 carbon atoms is mentioned, preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, such as phenyl, 1-naphthyl Or 2-naphthyl etc. As the alkyl group in R in the formula (P), an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable, such as methyl, ethyl, propyl, octane, etc. Base, isopropyl, tertiary butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. Examples of the halogen atom in the above R include F, Cl, Br, and I. As the alkyl group constituting the alkylsulfonyloxy group in the above-mentioned R, an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable, such as methyl, ethyl, propyl, etc. Base, octyl, isopropyl, tertiary butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. Said R may further have a substituent. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, amino, cyano, aryl, alkoxy, aryloxy, acyl, alkoxycarbonyl, Aryloxycarbonyl, acyloxy, monoalkylamino, dialkylamino, monoarylamino and diarylamino, etc.

Specific examples of organometallic complexes are not particularly limited, and tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, and diisopropoxybis(ethylacetate)titanium can be exemplified. , Diisopropoxybis(acetylacetonate)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl) ) phenyl) titanium, pentamethylcyclopentadienetrimethoxytitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium and the following compound. [chemical formula 39]

In addition, compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 can also be used, but are not limited thereto.

The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 1.0 mass % or more, still more preferably 1.5 mass % or more, and particularly preferably 3.0 mass % or more. The upper limit is more preferably 25% by mass or less. One type or two or more types of organometallic complexes can be used. When using 2 or more types, it is preferable that a total amount exists in the said range.

＜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.

〔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 above-mentioned ethylenically unsaturated bond. From the viewpoint of reactivity, (meth)acryl base) acryl group 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. 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 radically polymerizable compounds 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, it is also preferable to use unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfhydryl groups, and monofunctional or polyfunctional isocyanates or epoxy compounds. , 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. Moreover, as another example, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds 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, polyester acrylates described in the gazettes of JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490 polyfunctional acrylates or methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid; and mixtures thereof. Also, compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also preferred. 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 preferred radical crosslinking agents other than those mentioned above, those having an oxene ring and having an oxene ring described in JP-A-2010-160418, JP-A-2010-129825, and JP-A-4364216 can also be used. Compounds having two or more ethylenically unsaturated bond groups, cardo resins.

Furthermore, as other examples, Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, specific unsaturated compounds described in Japanese Patent Publication No. 01-040336, Japanese Patent Laid-Open No. 02-025493 Vinylphosphonic acid-based compounds described in the Publication No. 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, and these contents are incorporated herein. in the manual.

Also, 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 radical crosslinking agents, and these contents are incorporated in this specification.

As a free radical cross-linking agent, diperythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.), dipiperythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), diperythritol penta(meth)acrylate (commercially available as KAYARAD) D-310 (manufactured by Nippon Kayaku Co., Ltd.), diperythritol hexa(meth)acrylate (commercially available is KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)), A-DPH ( Shin-Nakamura Chemical Co., Ltd.) and a structure in which (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues is preferable. These oligomer types can also be used.

Commercially available 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 the radical crosslinking agent, carbamic acid described in JP-A-48-041708, JP-A-51-037193, JP-02-032293, JP-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 an oxirane-based skeleton The urethane compounds are also preferred. Furthermore, as a radical crosslinking agent, it is also possible to use those having an amino group structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-01-105238. , Compounds with 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, polyacid-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% by mass and not more than 60% by mass relative to the total solid content of the resin composition of the present 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 simultaneously, it is preferable that the total amount is 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 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 (in the composition). The compound that forms a covalent bond between other compounds or their reaction products) is preferably a compound that has a plurality of reaction groups in the molecule that are promoted by the action of an acid or base (with other compounds in the composition or A compound that is a reactive group that forms a covalent bond between its reaction products is more preferable. It is preferable that the above-mentioned acid or base is an acid or base generated from a photoacid generator or a photobase generator in the exposure step. As other crosslinking agents, compounds having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl and alkoxymethyl groups are preferred, and compounds having groups selected from the group consisting of acyloxymethyl A compound having a structure in which at least one group of the group of hydroxymethyl, alkoxymethyl, and alkoxymethyl is directly bonded to a nitrogen atom is more preferable. Examples of other crosslinking agents include compounds having a structure in which formaldehyde is reacted with an amino group-containing compound such as melamine, acetylene urea, urea, alkylene urea, or benzoguanamine, or formaldehyde is used in combination with an alcohol. A structure in which the hydrogen atom of the above-mentioned amine group is replaced by an acyloxymethyl group, a hydroxymethyl group or an alkoxymethyl group. The production method of these compounds is not particularly limited, as long as it is a compound having the same structure as the compound produced by the above-mentioned method. Moreover, it may be an oligomer obtained by self-condensing the methylol groups of these compounds. As the above-mentioned amine group-containing compound, the cross-linking agent using melamine is called melamine-based cross-linking agent, the cross-linking agent using acetylene carbamide, urea or alkylene urea is called urea-based cross-linking agent, and the cross-linking agent using alkylene urea A urea crosslinking agent is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. Among them, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of urea-based cross-linking agents and melamine-based cross-linking agents, including acetylene carbamide-based cross-linking agents and At least one compound of the group of melamine-based crosslinking agents is more preferable.

As a compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention, those having an alkoxymethyl group or an acyloxymethyl group directly on an aromatic group, the following urea structure Compounds substituted on a nitrogen atom or on a trichodium atom are examples of structures. 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 compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6. The molecular weight of the above compound is preferably 1500 or less, more preferably 180-1200.

[chemical formula 40]

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 41]

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. Regarding 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 that is decomposed by the action of an acid to form an alkali-soluble group or a group that is 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 the compound 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 42]

[chemical formula 43]

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 trioxane 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, monomethylolated acetylene carbamide, dimethylolated acetylene carbamide, trimethylolated acetylene carbamide, tetramethylolated 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, Monomethylolated ethylene urea or dimethylolated 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, Monomethylolated propylene urea, dimethylolated 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 monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, tetramethylolated benzoguanamine, and tetramethylolated benzoguanamine. Methylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine Benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine Guanamine, Monopropoxymethylated Benzoguanamine, Dipropoxymethylated Benzoguanamine, Tripropoxymethylated Benzoguanamine, Tetrapropoxymethylated Benzoguanamine , Monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc.

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(methylol)cresol, bis(methylol)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(methylol) base) benzophenone, hydroxymethylbenzene, hydroxymethylbenzoate, 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.

Commercially available products can be used as other crosslinking agents, and preferred commercially available products include 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION above), 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.

Also, it is 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, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700 , EPOLEAD (registered trademark) PB3600 (the above are trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000- L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER- 1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. Moreover, the following compounds can also be preferably used.

[chemical formula 44]

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

In the above-mentioned structure, it is preferable that n is 1-2 and m is 3-7 from the viewpoint of achieving both heat resistance and elongation improvement.

-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.

-Benzozoline compounds (compounds having a benzoxazolyl group)- The benzo 㗁 𠯤 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 benzophenone compounds include P-d type benzophenone, F-a type benzophenone (the above are trade names, manufactured by Shikoku Chemicals Corporation), polyhydroxystyrene resin benzophenone As a product, novolac type dihydrobenzo 㗁 𠯤 compound. 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, still more 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 other thermal crosslinking agents are contained, it is preferable that the total is within the above-mentioned range.

〔polymerization initiator〕 The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it is preferable to include a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited, and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to rays from an ultraviolet region to a visible region is preferable. Also, it may be an active agent that interacts with a sensitizer excited by light to generate active radicals.

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 trioxadiazole 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, organoboron 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. In addition, examples include paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in JP-A-6301489, and peroxides described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019. Material-based photopolymerization initiator, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, and the photopolymerization initiator described in Japanese Patent Laid-Open No. 2019-043864 The photopolymerization initiator, the photopolymerization initiator described in Japanese Patent Application Laid-Open No. 2019-044030, the peroxide-based initiator described in Japanese Patent Application Laid-Open No. 2019-167313, these contents are incorporated into this specification .

As the ketone compound, for example, compounds described in paragraph 0087 of JP-A-2015-087611 can be exemplified, and the content thereof is incorporated in the present 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. in 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 an oxime compound has wide exposure latitude (exposure margin) and also functions as a photocuring accelerator, it is especially preferable.

Specific examples of oxime compounds include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, the compounds described in JP-A-2006-342166, J.C.S. Compounds described in 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) ), compounds described in JP-A-2000-066385, compounds described in JP-A-2004-534797, compounds described in JP-A-2017-019766, JP-A-6065596 Compounds described in the gazette, compounds described in International Publication No. 2015/152153, compounds described in International Publication No. 2017/051680, compounds described in Japanese Patent Laid-Open No. 2017-198865, International Publication No. 2017/164127 The compounds described in paragraphs 0025 to 0038 of , and the compounds described in International Publication No. 2013/167515, etc., are incorporated in this specification.

Examples of preferred oxime compounds include compounds of the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetyloxy(imino))butyl -2-keto, 3-(propionyloxy(imino))butan-2-one, 2-(acetyloxy(imino))pentan-3-one, 2-(acetyloxy (imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonate Acyloxy)imino)butan-2-one and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, etc. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based radical photopolymerization initiator) as the radical photopolymerization initiator. The oxime-based photoradical polymerization initiator has a linking group>C=N-O-C(=O)- in the molecule.

[chemical formula 45]

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, JP 2012-014052 The photoradical polymerization initiator 2 described in the Publication No. 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 46]

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-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, JP-A-2013 - Compound (C-3) and the like described in Paragraph 0101 of Publication No. 164471 are incorporated in this specification.

As a photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable 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 , compounds described 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 are 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 contents are 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), more preferably the compound represented by the formula (OX2). [chemical formula 47]

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 specific substituents 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 trisulfone 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 photo-radical polymerization initiators are trihalomethyl trisulfone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salts Compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyl tristannium compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, and 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 48]

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 having 2 to 18 carbon atoms and an alkyl group having 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 49]

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 decreases, the solubility in a solvent or the like increases, and precipitation becomes difficult over time, thereby improving the temporal stability of the resin composition. Specific examples of difunctional or trifunctional or more photoradical polymerization initiators include JP 2010-527339, JP 2011-524436, International Publication No. 2015/004565, JP Paragraphs 0407 to 0412 of Table No. 2016-532675, dimers of oxime compounds described in paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E) described in Japanese Patent Publication No. 2013-522445, and Compound (G), Cmpd 1-7 described in International Publication No. 2016/034963, oxime ester photoinitiator described in paragraph 0007 of JP 2017-523465 A, JP 2017-167399 A Photoinitiators described in paragraphs 0020 to 0033, photopolymerization initiators (A) described in paragraphs 0017 to 0026 of Japanese Patent Application Laid-Open No. 2017-151342, oxime ester photoinitiators described in Japanese Patent No. 6469669 Initiators, etc., are included in this manual.

When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15% by mass, based on the total solid content of the resin composition of the present invention. , and still more preferably 1.0 to 10% by mass. A photoinitiator may contain only 1 type, and may contain 2 or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above 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, a thermal radical polymerization initiator and a photoradical polymerization initiator cause a chemical change and decompose to generate a radical, an acid, or a base. As sensitizers that can be used, benzophenone series, Michelerone series, coumarin series, pyrazole azo series, anilino azo series, triphenylmethane series, anthraquinone series, anthracene series, Anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenanthrene series, pyrrolopyrazole azomethine series , 𠮿kou galaxy, phthalocyanine, benzopyran, indigo and other compounds. 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 even more preferably 0.5 to 10% by mass, relative to the total solid content of the resin composition. good. 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 low-activity free radicals to generate free radicals, or can generate free radicals by deprotonation after being oxidized. 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, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. , 0.5 to 5 parts by mass 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 types of chain transfer agents, the total is preferably within the above 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. A thermal base generator and a photobase generator are mentioned as a base generator suitable for the resin composition of this invention. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. When the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be accelerated by heating, and the mechanical properties and chemical resistance of the cured product will be improved. For example, it can be used as an interlayer insulating film for rewiring layers included in semiconductor packages. performance 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 generator, the compound represented by formula (B1), formula (B2), or formula (B3) is mentioned. [chemical formula 50]

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. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, more preferably a cyclohexane ring.

More specifically, Rb ¹ and Rb ² are a hydrogen atom, an alkyl group (preferably 1-24 carbons, more preferably 2-18, more preferably 3-12), alkenyl (2-24 carbons is preferred, 2-18 is more preferred, 3-12 is further preferred), aryl (6-22 carbons is preferred, 6-18 is more preferred, 6-10 is further preferred) or arane A group (preferably 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms) is preferred. These groups may have substituents within the range in which the effects of the present invention are exhibited. Rb ¹ and Rb ² may be bonded to each other to form a ring. As the formed ring, a nitrogen-containing heterocyclic ring with 4 to 7 members is preferable. In particular, Rb ¹ and Rb ² are linear, branched or cyclic alkyl groups that may have substituents (preferably 1 to 24 carbons, more preferably 2 to 18, and further preferably 3 to 12) Preferably, a cycloalkyl group that may have a substituent (preferably 3 to 24 carbons, more preferably 3 to 18, and even more preferably 3 to 12) is more preferred, and a cyclohexyl group that may have a substituent is even more preferred .

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 exhibited.

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 51]

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ³² have the same meanings as Rb ¹ and Rb ² in the formula (B1), respectively. Rb ¹³ is 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 52]

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 53]

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 a compound represented by the following formula, L consists of styrene, has a vinyl group as a saturated hydrocarbon group, the linking chain is composed of 4 carbon atoms, and the number of atoms on the path of the linking chain (that is, the number of atoms constituting the linking chain The number of atoms, hereinafter, also referred to as "linkage chain length" or "linkage chain length".) is 4. [chemical formula 54]

It is preferable that the number of carbons (carbon atoms other than the carbon atoms in the linking chain) in L in the formula (B3) is 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 linkage 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 linkage 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, compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/066416, and compounds described in paragraphs 0143 to 0177 of International Publication No. 2018/038002. compound.

Moreover, it is also preferable that a base generator contains the compound represented by following formula (N1). [chemical formula 55]

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 linking chain length 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 linkage 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 number of carbon atoms in 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 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 group related to the combination of a chain alkyl group and a 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 carbons from the viewpoint of increasing the boiling point of a base decomposed to be described 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 (for example, copper) laminate is important.

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, porperoline ring, etc., preferably pyrroline ring, pyrrolidine ring, piperidine ring, piperridine ring, and perperoline 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. Specific examples of chain alkyl groups having an oxygen atom in the chain include alkoxyalkyl groups, and more specific examples include methoxymethyl (MOM) and ethoxyethyl (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 7-22, more preferably 7-18, and even more preferably 7-10. 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 number of carbon atoms in the linear or branched chain alkylene group is preferably 1-12, more preferably 2-6, and still more preferably 2-4. The number of carbon atoms in 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 number of carbon atoms in the linear or branched chain 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 chain 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 number of carbon atoms in the arylylene group is preferably 6-22, more preferably 6-18, and still more preferably 6-10. The number of carbon atoms in 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 56]

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 57]

Specific examples of imide salts include the following compounds, but the present invention is not limited thereto. [chemical formula 58]

When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present 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, further 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.

<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 the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, phenylenes, 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.

Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, 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.

As ureas, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, etc. are mentioned as preferable.

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 improvement of the properties of the coated surface.

In the present invention, it is selected from methyl 3-ethoxy propionate, ethyl 3-ethoxy propionate, ethyl celusoacetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate , Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfide, ethyl carbitol acetate, butyl carbitol One solvent among acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosone, and dihydrolevuroglucone, or a mixed solvent consisting of two or more of them is better. It is particularly preferable to use dimethylsulfoxide and γ-butyrolactone or N-methyl-2-pyrrolidone and ethyl lactate simultaneously.

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 can be adjusted according to the required 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 paragraphs 0063 to 0073 of Japanese Patent Application Laid-Open No. 2011/080992, and Compounds described in Paragraph 0071, Compounds described in Paragraphs 0060 to 0061 of JP-A-2014-191252, Compounds described in Paragraphs 0045-0052 of JP-A-2014-041264, Paragraph 0055 of International Publication No. 2014/097594 The compounds described in , and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Laid-Open No. 2018-173573 are incorporated into this specification. Moreover, 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 compound as a silane coupling agent. In the following formulae, Me represents a methyl group, and Et represents an ethyl group.

[chemical formula 59]

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 thioether-based compounds described in paragraphs 0032-0043 of JP-A-2013-072935 can also be used. Compounds, the contents of which are incorporated into this specification.

The content of the metal adhesion improving agent is preferably in the range of 0.01 to 30 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and still more preferably in the range of 0.5 to 5 parts by mass, based on 100 parts by mass of the specific resin. The adhesiveness of a pattern and a metal layer becomes favorable by making it more than the said lower limit, and the heat resistance of a pattern and mechanical characteristics become favorable by being below the said upper limit. The metal adhesiveness improving agent may be only 1 type, and may be 2 or more types. When using 2 or more types, it is preferable that the sum total is in the said range.

＜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, oxazole ring, pyridine ring, pyridine ring, pyrimidine ring, pyrimidine ring, piperidine ring, piperyl ring, portoline ring, 2H-pyranyl ring and 6H-pyranyl ring, three pyranyl ring) compounds, with Thiourea and mercapto compounds, 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, the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073-0076 of JP-A-2009-283711, and the compounds described in JP-A-2011-059656 can be used. The compounds described in Paragraph 0052 of Japanese Patent Publication No. 2012-194520, the compounds described in Paragraphs 0114, 0116 and 0118 of Japanese Patent Laid-Open No. 2012-194520, the compounds described in Paragraph 0166 of International Publication No. 2015/199219, etc. incorporated into this manual.

Specific examples of migration inhibitors include the following compounds.

[chemical formula 60]

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, and 0.1 to 2.0% by mass relative to the total solid content of the resin composition of the present invention. 1.0 mass % is 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, it is preferable that the total thereof is within the above-mentioned 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-tris-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, Thiophylline, phenanthrene, 1,1-diphenyl-2-picrylhydrazinyl, copper(II) dibutyldithiocarbonate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. Also, the polymerization inhibitor 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 the content is incorporated in this 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, and 0.05 to 10% by mass relative to the total solid content of the resin composition of the present invention. 10 mass % is 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, it is preferable that the total is within the above-mentioned range.

＜Other additives＞ The resin composition of the present invention can contain various additives as needed within the range of obtaining the effects of the present invention, for example, photoacid generators, surfactants, higher fatty acid derivatives, thermal polymerization initiators known in the art , 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, the total compounding amount thereof is preferably 3% by mass or less of the solid content of the resin composition of the present 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, when a film is formed by applying a composition containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, thereby improving the wettability to the surface to be coated, and improving the wettability of the surface to be coated. Coatability of cloth surface. 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, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and compounds described in paragraphs 0117-0132 of JP-A-2011-132503 can also be used, and these contents are incorporated in this specification. . 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 61]

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 (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.

Glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerin propoxylate, glycerol ethoxylate, etc.) can be exemplified as nonionic surfactants. compounds, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilauryl ether esters, macrogol distearate, sorbitan fatty acid esters, 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. The thermal radical polymerization initiator is a compound that generates free radicals by thermal energy, and initiates or accelerates the polymerization reaction of polymerizable compounds. Since the polymerization reaction of resin and a polymeric compound can also be advanced by adding a thermal radical polymerization initiator, solvent resistance can be improved further. In addition, the above-mentioned photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

As a thermal radical polymerization initiator, the compound described in paragraph 0074-0118 of Unexamined-Japanese-Patent No. 2008-063554 is mentioned specifically, The content is 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 still more preferably 0.5 to 15% by mass, relative to the total solid content of the resin composition of the present invention. . 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 dynamic light scattering method based on Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO., LTD.). When it is difficult to perform the above 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 trisulfone-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'-hydroxy-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-based UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, etc. . Furthermore, as an example of a trioxane-based ultraviolet absorber, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6- Bis(2,4-Dimethylphenyl)-1,3,5-trimethanone, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxybenzene base]-4,6-bis(2,4-dimethylphenyl)-1,3,5-trimethylphenyl, 2-(2,4-dihydroxyphenyl)-4,6-bis(2, 4-Dimethylphenyl)-1,3,5-trimethanone and other mono(hydroxyphenyl)trimethanium compounds; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-( 2,4-Dimethylphenyl)-1,3,5-trimethanone, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methyl phenyl)-1,3,5-trimethanone, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl )-1,3,5-tris(hydroxyphenyl)tris(hydroxyphenyl)tris(2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxy) phenyl)-1,3,5-trimethanone, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-trimethanium, 2,4,6- Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-trisanthene and other tris(hydroxyphenyl)trisanthene 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 included, the content of the ultraviolet absorber is 0.001% by mass to 1% by mass relative to the total solid content of the composition of the present invention Below 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. When the resin composition contains the organotitanium compound, it is possible to form a resin layer having excellent chemical resistance even when cured at a low temperature.

Examples of organic titanium compounds that can be used 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 in terms of excellent storage stability of the resin composition and 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 an organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the specific resin. When the compounding amount is 0.05 parts by mass or more, the obtained cured 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 more 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 known 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. Also, as an antioxidant, a compound having 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 compounds in which the part that acts as an antioxidant is protected by a protecting group. In this compound, the protecting group is heated at 100 to 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 (made by ADEKA CORPORATION) etc. are mentioned. As examples of preferred antioxidants, 2,2-thiobis(4-methyl-6-tertiary butylphenol), 2,6-two-tertiary butylphenol and formula (3) indicated compound.

[chemical formula 62]

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 the oxidation degradation of the aliphatic group and phenolic hydroxyl group which the 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, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, A vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, a combination of these, 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 compounds represented by the general formula (3) are exemplified by the following compounds, but are not limited to the following structures.

[chemical formula 63]

[chemical formula 64]

[chemical formula 65]

[chemical formula 66]

The amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. 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. Below is preferable, and 0.02 mass % or more and 5 mass % or less are more preferable.

〔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 it contains a phenolic compound, the content of the phenolic compound is 0.01% by mass or more with respect to the total solid content of the composition of the present invention. 30 mass % or less is preferable, and 0.02 mass % or more and 20 mass % or less are more preferable.

〔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 included, the content of other high molecular compounds relative to the total solid content of the composition of the present invention is 0.01% by mass or more and 30 mass % or less is 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 preferred, 2,000mm ² /s to 10,000mm ² /s is more preferred, and 2,500mm ² /s to 8,000mm ² /s is preferred 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 will be 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 the storage container 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. Also, as a 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 better to use a multi-layer bottle whose inner wall is composed of 6 kinds of 6-layer resins, or a bottle with 6 kinds of resins formed into a 7-layer structure. good. 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 can be filtered multiple times. When filtering multiple times, it can be cyclic filtering. 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, and 0.05 MPa It is more preferably above and below 0.5 MPa. 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 production method of the cured product of the present invention includes: a film forming step of applying a resin composition containing a precursor of a cyclized resin to a substrate to form a film; an exposing step of selectively exposing the above film; a developing step of using a developing developing the above-mentioned film to form a pattern; and a heating step, heating the above-mentioned pattern at a temperature of not less than 50°C and not more than 250°C, and the precursor of the above-mentioned cyclized resin is a compound that generates a base in the above-mentioned heating step. Preferable examples of the precursor of the cyclized resin used in the production method of the cured product of the present invention include the specific resins contained in the above-mentioned resin composition of the present invention. Moreover, it is preferable that the resin composition used in the film formation process of the manufacturing method of the hardened|cured material of this invention is the above-mentioned resin composition of this invention.

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 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.

As the applicable method, specifically, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slot coating method, etc. 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, the production method described in paragraphs 0023, 0036-0051 of JP-A-2006-023696 or paragraphs 0096-0108 of JP-A-2006-047592 can also be preferably used. . 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 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.

From the viewpoint of the rectangularity of the cured product, in the film formed in the film forming step, the concentration X of base generating groups in the upper 50% and the concentration Y of base generating groups in the lower 50% of the film in the thickness direction The ratio X/Y is preferably 0.90<X/Y<1.10. From such aspects, it is presumed that the alkali is likely to be generated in a nearly uniform state in the film, for example, a pattern of a cured product excellent in rectangularity can be obtained. The above-mentioned base generating group includes both the structure showing the property of generating a base contained in the specific resin and the structure showing the property of generating a base contained in the above-mentioned base generating agent. Also, when there is a compound including a structure exhibiting a base-generating property as another compound, the structure exhibiting a base-generating property is also included in the base-generating group. From the viewpoint of the rectangularity of the cured product, the aforementioned X/Y is preferably 0.92<X/Y<1.08, more preferably 0.94<X/Y<1.06. Said X/Y can be measured by the method described in the Example mentioned later.

<Exposure step> The above-mentioned film is used in the exposure step of selectively exposing the film. That is, the method for producing a cured product of the present invention includes 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 (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer Laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ₂ excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) The second harmonic of YAG laser is 532nm, the third harmonic is 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. Accordingly, particularly 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 is 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 includes 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 image development that removes the non-exposed portion of the film by the image development step is called negative image development, and the image image that removes the exposed portion of the film by the image image development step is called positive image 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 basic compounds that can be included in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably TMAH (hydroxide Tetramethylammonium), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyl di Ethylamine, Dimethylethanolamine, Triethanolamine, Tetraethylammonium Hydroxide, Tetrapropylamine Hydroxide, Tetrabutylamine Hydroxide, Tetrapentylamine Hydroxide, Tetrahexylamine Hydroxide, Tetraoctylamine Hydroxide Amine, Ethyltrimethylammonium Hydroxide, Butyltrimethylammonium Hydroxide, Methyltripentylammonium Hydroxide, Dibutyldipentylammonium Hydroxide, Dimethylbis(2-Hydroxyethylammonium Hydroxide) base) 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 amount of the developer.

When the developing solution contains an organic solvent, regarding the organic solvent, examples of the esters preferably include ethyl acetate, n-butyl acetate, amyl 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.

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 or more. Excellent. 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 the following methods: a method of 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, and spray nozzles. 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. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse solution.

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] As long as the desired pattern can be formed, the method of supplying the rinsing liquid is not particularly limited, and there are the following methods: the method of immersing the substrate in the rinsing liquid, the method of supplying the substrate by spin immersion, and the method of using a shower head. A method of supplying a rinsing liquid on a substrate, a method of continuously supplying a rinsing 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, and spray nozzles. 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.

From the viewpoint of the elongation at break of the cured product, the molar number E of the base-generating group present in the film after the exposure step and before the development step and the film remaining as the above-mentioned pattern after the development step is different from that after the above-mentioned development step. It is preferable that the ratio F/E of the molar number F of the base generating groups present in the above pattern exceeds 0.9. According to such an aspect, it is considered that a cured product excellent in elongation at break can be easily obtained while suppressing the decrease of base-generating groups by image development. Here, the film that is the film after the exposure step and before the above-mentioned development step and remains as the above-mentioned pattern after the development step refers to the part of the film that remains after development. In the case of negative development, the exposed part corresponds to this part. If For positive tone development, the unexposed portion corresponds to this portion. The above-mentioned base generating group includes both the structure showing the property of generating a base contained in the specific resin and the structure showing the property of generating a base contained in the above-mentioned base generating agent. Also, when there is a compound including a structure exhibiting a base-generating property as another compound, the structure exhibiting a base-generating property is also included in the base-generating group. From the viewpoint of the elongation at break of the cured product, the above-mentioned F/E is preferably 0.92 or more, more preferably 0.94 or more. The upper limit of F/E is not particularly limited, for example, it can be set to 5.0 or less. For example, it is also possible to increase the alkali after the developing step or after the rinsing step by making at least one of the developing solution and the rinsing solution contain an alkali generating agent, and contacting the pattern with a treatment solution containing an alkali generating agent after developing or after rinsing. Generate the content of the base. The said F/E can be measured by the method described in the Example mentioned later.

＜Heating step＞ The pattern obtained by the developing step (the pattern after washing when the washing step is performed) is used in the heating step of heating the pattern obtained by the above-mentioned developing at a temperature of 50° C. or higher and 250° C. or lower. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the developing step. In addition, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing the developing step or a film obtained by the film forming step. In the heating step, resins such as polyimide precursors are cyclized into resins such as polyimide. In addition, crosslinking of unreacted crosslinkable groups in a specific resin or a crosslinking agent other than the specific resin is also performed. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 250°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. The heating temperature can be appropriately set to a temperature at which a base is generated from a specific resin.

The heating step is preferably a step of accelerating the cyclization reaction of the polyimide precursor in the pattern by utilizing the action of the base or the like generated from the specific resin or the 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, lower than the boiling point of the solvent contained in the resin composition of the present invention It is preferable to start heating up at a temperature of 30 to 200°C.

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 temperature is preferably 250°C or lower, more preferably 240°C or lower, and still more preferably 230°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 membrane can be improved by such 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.

<Post-development exposure step> The pattern obtained in the development step (in the case of a rinse step, the pattern after rinse) may be used in post-development exposure for exposing the pattern after the development step in addition to the above-mentioned heating step. step. That is, the manufacturing method of the hardened|cured material of this invention may include the post-development exposure process which exposes the pattern obtained by the development process. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include any of the heating step and the post-development exposure step. In the post-development exposure step, for example, the reaction of cyclization of polyimide precursors and the like by exposure to photobase generators, the reaction of detachment of acid-decomposable groups by exposure to photoacid generators, etc. can be promoted. . In the post-development exposure step, at least a part of the pattern obtained in the development step may be exposed, but it is preferable that the entire pattern is exposed. In terms of exposure energy conversion at the wavelength at which the photosensitive compound has sensitivity, the exposure amount in the post-development exposure step is preferably 50-20,000 mJ/cm ² , more preferably 100-15,000 mJ/cm ² . The post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, and it is preferable to use broadband light.

＜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 metals can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, copper and aluminum. Copper is more preferred, and copper is further preferred.

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 of recording. 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.

From the viewpoint of the rectangularity of the cured product, the difference between the loop closure rate A on the surface of the obtained cured product opposite to the side in contact with the substrate and the loop closure rate B on the surface of the substrate in contact with the obtained cured product is The ratio A/B is preferably 0.90<A/B<1.10. According to the above aspect, the degree of shrinkage of the film is the same near the side in contact with the base material and in the vicinity of the side opposite to the side in contact with the base material, so it is presumed that the rectangularity of the cured product is improved. The ring-closing rate refers to the imidization rate when the specific resin is a polyimide precursor or polyamideimide precursor, and refers to the oxazole conversion rate when the specific resin is a polybenzoxazole precursor. From the viewpoint of the rectangularity of the cured product, the above-mentioned A/B is preferably 0.92<A/B<1.08, more preferably 0.94<A/B<1.06. The said A/B can be measured by the method described in the Example mentioned later.

From the viewpoint of the rectangularity of the cured product, a 1:1 line and space pattern with a film thickness of 20 μm and a pitch of 10 μm is formed in the developing step, and the width shrinkage ratio C of the upper end of the line pattern is obtained when heating at 230°C for 180 minutes in the heating step The ratio C/D to the width shrinkage ratio D at the lower end is preferably 0.90<C/D<1.10. According to the above aspect, the degree of shrinkage of the film before and after heating is the same in the vicinity of the side in contact with the base material and in the vicinity of the side opposite to the side in contact with the base material. Therefore, it is presumed that the rectangularity of the cured product is improved. From the viewpoint of the rectangularity of the cured product, the above-mentioned C/D is preferably 0.92<C/D<1.08, more preferably 0.94<C/D<1.06. The said C/D can be measured by the method described in the Example mentioned later.

＜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, cover film, and interlayer insulating film for flexible printed circuit boards), or cases where patterns are formed on insulating films for actual mounting applications such as those described above by etching. Regarding such uses, for example, Science & Technology Co., Ltd. "Highly functionalized and applied technology of polyimide" April 2008, Masakimoto Kakimoto/Supervisor, CMC Technical Library "Polyimide materials "Basic and Development of Polyimide" published in November 2011, edited by the Japan Polyimide and Aromatic Polymer Research Society/edited "Basic and Application of the Latest Polyimide" NTS, August 2010, etc.

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. It is also preferable that all the layers composed of the cured product included in the above 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 form different compositions. 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 the (a) film forming step, (d) heating step, and post-development exposure step 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 the layering step is further performed 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. 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 is preferably a structure in which the resin layer is 2 or more and 20 or less, and it is more than 2 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 performing surface activation treatment on the surface of the resin composition layer, the adhesiveness with the metal layer and 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 ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ etching treatment, surface treatment by ultraviolet (UV) ozone method, dipping in hydrochloric acid aqueous solution to remove oxide film, dipping Treatment in an organic surface treatment agent of at least one compound of amine group and thiol group, mechanical roughening treatment using a brush, plasma treatment is preferable, especially oxygen plasma treatment using oxygen as a raw material gas 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（2）中，A ¹及A ²分別獨立地表示氧原子或-NH-，R ¹¹¹表示2價有機基團，R ¹¹⁵表示4價有機基團，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價有機基團，R ¹¹¹、R ¹¹⁵、R ¹¹³及R ¹¹⁴中的至少1個包含由下述式（1-1）表示之結構。 [化學式68]

式（3）中，R ¹²¹表示2價有機基團，R ¹²²表示4價有機基團，R ¹²³及R ¹²⁴分別獨立地表示氫原子或1價有機基團，R ¹²¹、R ¹²²、R ¹²³及R ¹²⁴中的至少1個包含由下述式（1-1）表示之結構。 [化學式69]

式（PAI-2）中，R ¹¹⁷表示3價有機基團，R ¹¹¹表示2價有機基團，A ²表示氧原子或-NH-，R ¹¹³表示氫原子或1價有機基團，R ¹¹⁷、R ¹¹¹及R ¹¹³中的至少1個包含由下述式（1-1）表示之結構。 [化學式70]

式（1-1）中，R ¹分別獨立地為氫原子或1價有機基團，2個R ¹可以連結而形成環結構，L ¹表示3價有機基團，*表示與其他結構的鍵結部位。 (Precursor of Cyclized Resin) The precursor of the cyclized resin of the present invention comprises a repeating unit represented by the following formula (2), a repeating unit represented by the formula (3), and a repeating unit represented by the formula (PAI-2) At least one repeating unit in the group of the represented repeating units. [chemical formula 67]

In formula (2), A ¹ and A ² independently represent an oxygen atom or -NH-, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and R ¹¹⁴ independently represent hydrogen As an atom or a monovalent organic group, at least one of R ¹¹¹ , R ¹¹⁵ , R ¹¹³ and R ¹¹⁴ includes a structure represented by the following formula (1-1). [chemical formula 68]

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group, R ¹²¹ , R ¹²² , R ¹²³ and at least one of R ¹²⁴ includes a structure represented by the following formula (1-1). [chemical formula 69]

In the formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or -NH-, R ¹¹³ represents a hydrogen atom or a monovalent organic group, R ¹¹⁷ At least one of , R ¹¹¹ and R ¹¹³ includes a structure represented by the following formula (1-1). [chemical formula 70]

In formula (1-1), R ¹ is independently a hydrogen atom or a monovalent organic group, two R ¹ can be connected to form a ring structure, L ¹ represents a trivalent organic group, and * represents a bond with other structures Knot part.

The precursor of the cyclized resin of the present invention comprises at least 1 kind of repeating unit including the structure represented by the above formula (1-1) in the repeating unit, other than the same meaning as the specific resin contained in the above-mentioned resin composition of the present invention, and a preferred embodiment is also same. Moreover, the preferable aspect of Formula (1-1) is the same as the preferable aspect of Formula (1-1) in the said specific resin. In addition, the preferred aspects of formula (2), formula (3) and formula (PAI-2) combine the structure represented by the above formula (1-1) in the structure, and the formula in the specific resin Preferred aspects of (2), formula (3) and formula (PAI-2) are the same. [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.

<Manufacturing method of precursor of cyclized resin> [Synthesis Example 1: Synthesis of Precursor of Cyclized Resin (Resin 1)] Put 46.96 g of 4,4'-oxydiphthalic anhydride (ODPA) into a separate flask, add 37.71 g of 2-hydroxyethyl methacrylate (HEMA), 3.80 g of (3-(2,5 -dihydroxyphenyl)-1-(piperidin-1-yl)propan-1-one), 136.83 g of tetrahydrofuran and stirring at room temperature (25° C.), adding 24.66 g of pyridine while stirring, thus obtaining the reaction mixture. After the heat generated by the reaction ended, it was naturally cooled to room temperature and left to stand for 16 hours. Next, under ice-cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes while stirring, and the 4,4'-diamino 27.42 g of diphenyl ether (DADPE) was added while suspending in 119.73 g of tetrahydrofuran over 60 minutes. After further stirring at room temperature for 2 hours, 7.17 g of ethanol was added and stirred for 1 hour, and then 136.83 g of tetrahydrofuran was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. The obtained reaction liquid was added to 716.21 g of ethanol, and a precipitate consisting of a crude polymer was generated. The generated crude polymer was collected by filtration, and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum-dried to obtain 80.3 g of powdery resin 1 . As a result of measuring the molecular weight of the resin 1 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000. Resin 1 is presumed to have a structure represented by the following formula (P-1), and R contains a repeating unit which is a structure represented by formula (R-1). The description of mol% in formula (R-1) represents the content molar ratio of each structure. Also, * in the formula represents the bonding site of the oxygen atom to which R is bonded.

[Synthesis Example 2: Synthesis of the Precursor of Cyclized Resin (Resin 2)] Mix 21.2 g of 4,4'-oxydiphthalic anhydride, 17.0 g of 2-hydroxyethyl methacrylate, 1.7 g of (3-(2,5-dihydroxyphenyl)-1-(piper pyridine-1-yl) propan-1-one), 23.9g of pyridine and 250mL of diglyme (diethylene glycol dimethyl ether), stirred at 60°C for 4 hours, and synthesized 4 , Diester of 4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10°C, and 17.0 g of thionyl chloride was added over 60 minutes while maintaining the temperature at -10±5°C. After diluting with 50mL of N-methylpyrrolidone, a solution of 12.6g of 4,4'-diaminodiphenyl ether dissolved in 100mL of N-methylpyrrolidone was heated at -10±5°C It was added dropwise to the reaction mixture over 60 minutes, and the mixture was stirred at room temperature for 2 hours. Thereafter, 10.0 g of ethanol (capping agent) was added, followed by stirring at room temperature for 1 hour. Next, it was added to 6000 g of water to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was collected by filtration and dissolved in 500 g of tetrahydrofuran. 6000 g of water (poor solvent) was added to the obtained solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (polyimide precursor solid) after stirring was filtered again, and it dried at 45 degreeC under reduced pressure for 3 days. After dissolving 46.6 g of the dried powder in 419.6 g of tetrahydrofuran, 2.3 g of triethylamine was added, followed by stirring at room temperature for 35 minutes. Then, it was added to ethanol 3000g, and the deposit was collected by filtration. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by Ambertech Limited) were added thereto, and stirred for 4 hours. Thereafter, the ion exchange resin was filtered off, and the obtained polymer solution was added to a mixed solution of 4500 g of heptane and 500 g of ethyl acetate to obtain a precipitate. The precipitate was collected by filtration and dried at 45° C. under reduced pressure for 24 hours to obtain 45.1 g of resin 2 . As a result of measuring the molecular weight of the resin 2 by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000. Also, by appropriately adjusting the equivalent of 4,4'-diaminodiphenyl ether, Resin 2 with Mw of 4,500, Resin 2 with Mw of 7,500, Resin 2 with Mw of 10,000, and Resin with Mw of 30,000 were also synthesized. 2. Resin 2 with a Mw of 50,000, and resin 2 with a Mw of 100,000. Resin 2 is presumed to have a structure represented by the following formula (P-1), and R contains a repeating unit which is a structure represented by formula (R-1). The description of mol% in formula (R-1) represents the content molar ratio of each structure. Also, * in the formula represents the bonding site of the oxygen atom to which R is bonded.

[Synthesis Examples 3 to 21: Synthesis of Precursors of Cyclized Resins (Resins 3 to 21)] Resins 3 to 20 were synthesized in the same manner as in Synthesis Example 2 except that the compounds used were appropriately changed. The raw materials used for the synthesis of each resin are described in the table below. The Mw of resins 3 to 20 were all 20,000. Resins 3 to 23 are presumed to have structures represented by formula (P-1), respectively, and R includes repeating units that are structures represented by formulas (R-2) to (R-22). The description of mol% in each formula represents the content molar ratio of each structure. Table 1 shows the structure of R in the formula (P-1) in resins 1 to 23. [Table 1] resin R Resin 1 (R-1) Resin 2 (R-1) Resin 3 (R-2) Resin 4 (R-3) Resin 5 (R-4) Resin 6 (R-5) Resin 7 (R-6) Resin 8 (R-7) Resin 9 (R-8) Resin 10 (R-9) Resin 11 (R-10) Resin 12 (R-11) Resin 13 (R-12) Resin 14 (R-13) Resin 15 (R-14) Resin 16 (R-15) Resin 17 (R-16) Resin 18 (R-17) Resin 19 (R-18) Resin 20 (R-19) Resin 21 (R-20) Resin 22 (R-21) Resin 23 (R-22) Resins 24 to 35 are presumed to be resins containing repeating units represented by formula (P-24) to formula (P-35), respectively. Subscripts in parentheses indicate the molar ratio of each repeating unit. The description of mol% in each formula represents the content molar ratio of each structure. In addition, resins 24 to 35 were synthesized using raw materials described in Table 2 or Table 3 described later.

[化學式72]

[化學式73]

[化學式74]

[化學式75]

[化學式76]

[化學式77]

[chemical formula 71]

[chemical formula 72]

[chemical formula 73]

[chemical formula 74]

[chemical formula 75]

[chemical formula 76]

[chemical formula 77]

乙醇 樹脂25

乙醇 樹脂26

乙醇 樹脂27

乙醇 樹脂28

乙醇 樹脂29

乙醇 樹脂30

樹脂31

乙醇 [Table 2] resin anhydride side chain diamine Quenching compound (capping agent) Resin 24

ethanol Resin 25

ethanol Resin 26

ethanol Resin 27

ethanol Resin 28

ethanol Resin 29

ethanol Resin 30

Resin 31

ethanol

乙醇 樹脂33

乙醇 樹脂34

無

乙醇 樹脂35

無

乙醇 [table 3] resin anhydride side chain diamine quenching compound Resin 32

ethanol Resin 33

ethanol Resin 34

none

ethanol Resin 35

none

ethanol

[Synthesis of precursor of cyclized resin (comparative resin 1)] Put 23.48 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.27 g of bisphthalic dianhydride (BPDA) into a separate flask, and add 2-hydroxyethyl methacrylate (HEMA) 39.69 g and 136.83 g of tetrahydrofuran were stirred at room temperature (25° C.), and 24.66 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction ended, it was naturally cooled to room temperature and left to stand for 16 hours. Next, under ice-cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes while stirring, and the 4,4'-diamino 27.42 g of diphenyl ether (DADPE) was added while suspending in 119.73 g of tetrahydrofuran over 60 minutes. After further stirring at room temperature for 2 hours, 7.17 g of ethanol was added and stirred for 1 hour, and then 136.83 g of tetrahydrofuran was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. The obtained reaction liquid was added to 716.21 g of ethanol, and a precipitate consisting of a crude polymer was generated. The generated crude polymer was collected by filtration, and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the obtained precipitate was collected by filtration, followed by vacuum drying to obtain 80.3 g of powdery comparative resin 1 . As a result of measuring the molecular weight of Comparative Resin 1 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000. The structure of comparative resin 1 is presumed to be a structure represented by the following formula (CP-1).

[chemical formula 78]

＜Example and Comparative Example＞ In each example, the components described in the following table were mixed, respectively, to obtain each resin composition. Moreover, in each comparative example, the components described in the following table|surface were mixed, respectively, and each comparative composition was obtained by this. Specifically, the content (compounding amount) of each component described in the table was defined as the amount (parts by mass) described in the column of “parts by mass” 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 0.8 μm. In addition, in the table, description of "-" shows that a composition does not contain a corresponding component.

[Table 4] Example comparative example Example Example Example Example Example Example 1 1 2 3 4 5 6 7 composition resin type Resin 1 Compare Resins 1 Resin 2 Resin 3 Resin 4 Resin 5 Resin 6 Resin 7 mw 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 type - - - - - - - - mw - - - - - - - - parts by mass - - - - - - - - monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 polymerization initiator type I-2 I-2 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 heat base generator type - AX-1 - - - - - - parts by mass - 2 - - - - - - polymerization inhibitor type B-2 B-2 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-2 C-2 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type E-2 E-2 - - - - - - parts by mass 2.4 2.4 - - - - - - type E-3 E-3 - - - - - - parts by mass 0.9 0.9 - - - - - - solvent type NMP NMP GBL GBL GBL GBL GBL GBL parts by mass 45 45 40 40 40 40 40 40 type EL EL DMSO DMSO DMSO DMSO DMSO DMSO parts by mass 10 10 10 10 10 10 10 10 Solid content concentration (mass%) 46 47 46 46 46 46 46 46 Process Film thickness (μm) 20 20 20 20 20 20 20 20 PB temperature (°C) 100 100 100 100 100 100 100 100 Pattern size (μm) 10 10 10 10 10 10 10 10 exposure method m m m m m m m m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Hardening temperature (°C) 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 Developing conditions burden burden burden burden burden burden burden burden Evaluation elongation at break B D. B A A A B B Pattern Rectangularity A D. A B A A B C Pattern roughness after development A D. A A A A A A F/E 1.00 0.85 1.00 1.00 1.00 1.00 1.00 1.00 X/Y 1.00 1.23 1.00 1.00 1.00 1.00 1.00 1.00 A/B 0.95 1.15 0.95 0.95 0.95 0.95 0.93 0.92 C/D 0.99 1.31 0.98 0.99 0.98 0.98 0.95 0.91

[table 5] Example Example Example Example Example Example Example Example 8 9 10 11 12 13 14 15 composition resin type Resin 8 Resin 9 Resin 10 Resin 11 Resin 12 Resin 13 Resin 14 Resin 15 mw 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 type - - - - - - - - mw - - - - - - - - parts by mass - - - - - - - - monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 polymerization initiator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 heat base generator type - - - - - - - - parts by mass - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - parts by mass - - - - - - - - type - - - - - - - - parts by mass - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL parts by mass 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO parts by mass 10 10 10 10 10 10 10 10 Solid content concentration (mass%) 46 46 46 46 46 46 46 46 Process Film thickness (μm) 20 20 20 20 20 20 20 20 PB temperature (°C) 100 100 100 100 100 100 100 100 Pattern size (μm) 10 10 10 10 10 10 10 10 exposure method m m m m m m m m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Hardening temperature (°C) 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 Developing conditions burden burden burden burden burden burden burden burden Evaluation elongation at break B C A A A C C B Pattern Rectangularity B C A B C C C A Pattern roughness after development A C A B C C C A F/E 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 X/Y 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 A/B 0.94 0.91 0.98 1.00 1.00 1.00 1.00 0.95 C/D 0.93 0.91 0.99 0.99 1.00 1.00 1.00 0.98

[Table 6] Example Example Example Example Example Example Example Example 16 17 18 19 20 twenty one twenty two twenty three composition resin type Resin 16 Resin 17 Resin 18 Resin 19 Resin 20 Resin 21 Resin 22 Resin 23 mw 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 type - - - - - - - - mw - - - - - - - - parts by mass - - - - - - - - monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 polymerization initiator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 heat base generator type - - - - - - - - parts by mass - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - parts by mass - - - - - - - - type - - - - - - - - parts by mass - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL parts by mass 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO parts by mass 10 10 10 10 10 10 10 10 Solid content concentration (mass%) 46 46 46 46 46 46 46 46 Process Film thickness (μm) 20 20 20 20 20 20 20 20 PB temperature (°C) 100 100 100 100 100 100 100 100 Pattern size (μm) 10 10 10 10 10 10 10 10 exposure method m m m m m m m m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Hardening temperature (°C) 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 Developing conditions burden burden burden burden burden burden burden burden Evaluation elongation at break A A A A A A A A Pattern Rectangularity A A A A A A A A Pattern roughness after development A A A A A A A A F/E 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 X/Y 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 A/B 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 C/D 0.98 0.98 0.98 0.98 0.98 0.98 0.98 0.98

[Table 7] Example Example Example Example Example Example Example Example twenty four 25 26 27 28 29 30 31 composition resin type Resin 24 Resin 25 Resin 26 Resin 27 Resin 28 Resin 29 Resin 30 Resin 31 mw 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 type - - - - - - - - mw - - - - - - - - parts by mass - - - - - - - - monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 - parts by mass 6 6 6 6 6 6 6 - polymerization initiator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-4 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1 heat base generator type - - - - - - - - parts by mass - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 - parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 - Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - parts by mass - - - - - - - - type - - - - - - - - parts by mass - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL parts by mass 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO parts by mass 10 10 10 10 10 10 10 10 Solid content concentration (mass%) 46 46 46 46 46 46 46 43 Process Film thickness (μm) 20 20 20 20 20 20 20 20 PB temperature (°C) 100 100 100 100 100 100 100 100 Pattern size (μm) 10 10 10 10 10 10 10 10 exposure method m m m m m m m m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone TMAH aqueous solution Hardening temperature (°C) 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 Developing conditions burden burden burden burden burden burden burden just Evaluation elongation at break A B C A A C C B Pattern Rectangularity A B A A A A A B Pattern roughness after development A A A A A A A B F/E 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 X/Y 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 A/B 0.96 0.96 0.95 0.95 0.96 0.92 0.92 0.94 C/D 0.98 0.98 0.96 0.94 0.95 0.93 0.92 0.94

[Table 8] Example Example Example Example Example Example Example Example 32 33 34 35 36 37 38 39 composition resin type 32 33 34 35 36 37 38 39 mw 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 25 15 50 35 type - - - - - - - - mw - - - - - - - - parts by mass - - - - - - - - monomer type M-1 M-1 - M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 - 6 6 6 6 12 polymerization initiator type I-4 I-1 I-4 I-1 I-1 I-1 I-1 I-1 parts by mass 1 1.1 1 1.1 1.1 1.1 1.1 1.1 heat base generator type - - - - - - - - parts by mass - - - - - - - - polymerization inhibitor type - B-1 - B-1 B-1 B-1 B-1 B-1 parts by mass - 0.1 - 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - parts by mass - - - - - - - - type - - - - - - - - parts by mass - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL parts by mass 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO parts by mass 10 10 10 10 10 10 10 10 Solid content concentration (mass%) 46 46 43 46 40 32 54 50 Process Film thickness (μm) 20 20 20 20 20 20 30 20 PB temperature (°C) 100 100 100 100 100 100 100 100 Pattern size (μm) 10 10 10 10 10 10 10 10 exposure method m m m m m m m m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 Developer Cyclopentanone Cyclopentanone TMAH aqueous solution Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Hardening temperature (°C) 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 Developing conditions burden burden just burden burden burden burden burden Evaluation elongation at break B B B B A A A A Pattern Rectangularity B A B A A A B A Pattern roughness after development B A B A A A A A F/E 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 X/Y 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 A/B 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 C/D 0.93 0.94 0.93 0.94 0.98 0.98 0.98 0.98

[Table 9] Example Example Example Example Example Example Example Example 40 41 42 43 44 45 46 47 composition resin type Resin 22 Resin 22 Resin 22 Resin 22 Resin 22 Resin 22 Resin 22 Resin 22 mw 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 type - - - - - - - - mw - - - - - - - - parts by mass - - - - - - - - monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 2 6 6 6 6 6 6 6 polymerization initiator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 2.2 3.5 0.5 1.1 1.1 1.1 1.1 heat base generator type - - - - - - - - parts by mass - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.05 0.3 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 0.5 2 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - parts by mass - - - - - - - - type - - - - - - - - parts by mass - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL parts by mass 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO parts by mass 10 10 10 10 10 10 10 10 Solid content concentration (mass%) 44 47 48 46 46 47 46 47 Process Film thickness (μm) 20 20 20 20 20 20 20 20 PB temperature (°C) 100 100 100 100 100 100 100 100 Pattern size (μm) 10 10 10 10 10 10 10 10 exposure method m m m m m m m m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Hardening temperature (°C) 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 Developing conditions burden burden burden burden burden burden burden burden Evaluation elongation at break A A B A A A A A Pattern Rectangularity B A A B A A A A Pattern roughness after development A A A A A A A A F/E 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 X/Y 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 A/B 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 C/D 0.98 0.98 0.98 0.98 0.98 0.98 0.98 0.98

[Table 10] Example Example Example Example Example Example Example Example 48 49 50 51 52 53 54 55 composition resin type Resin 22 Resin 22 Resin 22 Resin 22 Resin 22 Resin 22 Resin 22 Resin 2 mw 20000 20000 20000 20000 20000 20000 20000 100000 parts by mass 35 35 35 35 35 35 35 35 type - - - - - - - - mw - - - - - - - - parts by mass - - - - - - - - monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 polymerization initiator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 heat base generator type - - - - - - - - parts by mass - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.1 0.3 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - parts by mass - - - - - - - - type - - - - - - - - parts by mass - - - - - - - - solvent type GBL GBL GBL NMP NMP GBL NMP GBL parts by mass 40 40 10 45 10 40 40 40 type DMSO DMSO DMSO EL EL EL DMSO DMSO parts by mass 10 10 40 10 45 10 10 10 Solid content concentration (mass%) 46 47 46 44 44 46 46 46 Process Film thickness (μm) 20 20 20 20 20 20 20 20 PB temperature (°C) 100 100 100 100 100 100 100 100 Pattern size (μm) 10 10 10 10 10 10 10 10 exposure method m m m m m m m m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Hardening temperature (°C) 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 Developing conditions burden burden burden burden burden burden burden burden Evaluation elongation at break A A A A A A A B Pattern Rectangularity A A A A A A A B Pattern roughness after development A A A A A A A B F/E 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 X/Y 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 A/B 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 C/D 0.98 0.98 0.98 0.98 0.98 0.98 0.98 0.94

[Table 11] Example Example Example Example Example Example Example Example 56 57 58 59 60 61 62 63 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 mw 50000 30000 10000 7500 4500 20000 20000 20000 parts by mass 35 35 35 35 35 18 18 18 type - - - - - Resin 4 Compare Resins 1 Compare Resins 1 mw - - - - - 20000 20000 20000 parts by mass - - - - - 18 18 18 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 polymerization initiator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 heat base generator type - - - - - - - A-1 parts by mass - - - - - - - 1 polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - parts by mass - - - - - - - - type - - - - - - - - parts by mass - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL parts by mass 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO parts by mass 10 10 10 10 10 10 10 10 Solid content concentration (mass%) 46 46 46 46 46 47 47 48 Process Film thickness (μm) 20 20 20 20 20 20 20 20 PB temperature (°C) 100 100 100 100 100 100 100 100 Pattern size (μm) 10 10 10 10 10 10 10 10 exposure method m m m m m m m m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Hardening temperature (°C) 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 Developing conditions burden burden burden burden burden burden burden burden Evaluation elongation at break B B B B C A C B Pattern Rectangularity A A A A B A B C Pattern roughness after development A A A A B A A B F/E 1.00 1.00 1.00 1.00 1.00 1.00 1.00 0.95 X/Y 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.06 A/B 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 C/D 0.94 0.94 0.93 0.93 0.93 0.95 0.94 0.95

[Table 12] Example Example Example Example Example Example Example Example 64 65 66 67 68 69 70 71 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 4 mw 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 type - - - - - - - - mw - - - - - - - - parts by mass - - - - - - - - monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 polymerization initiator type I-1 I-1 I-1 I-2 I-3 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 heat base generator type A-1 A-2 A-3 - - - - - parts by mass 1 1 1 - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-2 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-2 C-1 parts by mass 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 - parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 - additive type - - - - - - - - parts by mass - - - - - - - - type - - - - - - - - parts by mass - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL parts by mass 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO parts by mass 10 10 10 10 10 10 10 10 Solid content concentration (mass%) 47 47 47 46 46 46 46 46 Process Film thickness (μm) 20 20 20 20 20 20 20 20 PB temperature (°C) 100 100 100 100 100 100 100 100 Pattern size (μm) 10 10 10 10 10 10 10 10 exposure method m m m m m m m m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Hardening temperature (°C) 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 Developing conditions burden burden burden burden burden burden burden burden Evaluation elongation at break A A A B B B B A Pattern Rectangularity B B C A A A A A Pattern roughness after development B B C A A A A A F/E 0.96 0.96 0.93 1.00 1.00 1.00 1.00 1.00 X/Y 1.05 1.05 1.02 1.00 1.00 1.00 1.00 1.00 A/B 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 C/D 0.95 0.94 0.94 0.96 0.94 0.96 0.96 0.98

[Table 13] Example Example Example Example Example Example Example Example 72 73 74 75 76 77 78 79 composition resin type Resin 5 Resin 13 Resin 16 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 mw 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 18 35 35 35 35 type - - - Resin 3 - - - - mw - - - 20000 - - - - parts by mass - - - 18 - - - - monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 polymerization initiator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 heat base generator type - - - - - - - - parts by mass - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 migration inhibitor type - - - - D-1 D-1 D-1 D-1 parts by mass - - - - 0.2 0.2 0.2 0.2 additive type - - - - - - - - parts by mass - - - - - - - - type - - - - - - - - parts by mass - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL parts by mass 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO parts by mass 10 10 10 10 10 10 10 10 Solid content concentration (mass%) 46 46 46 47 46 46 46 46 Process Film thickness (μm) 20 20 20 20 20 20 20 10 PB temperature (°C) 100 100 100 100 100 100 100 100 Pattern size (μm) 10 10 10 10 10 10 10 10 exposure method m m m m m m m m Exposure wavelength (nm) 365 365 365 365 365 365 365 365 Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Hardening temperature (°C) 230 230 230 230 200 180 IR 230 Hardening time (min) 180 180 180 180 120 120 180 180 Developing conditions burden burden burden burden burden burden burden burden Evaluation elongation at break A A A A B C B A Pattern Rectangularity A A A A A B A A Pattern roughness after development A A A A A B A A F/E 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 X/Y 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 A/B 0.95 0.96 0.96 0.95 0.95 0.95 0.95 1.00 C/D 0.98 0.98 0.95 0.95 0.96 0.96 0.94 0.99

[Table 14] Example Example Example Example 80 81 82 83 composition resin type Resin 2 Resin 4 Resin 13 Resin 16 mw 20000 20000 20000 20000 parts by mass 35 35 35 35 type - - - - mw - - - - parts by mass - - - - monomer type M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 polymerization initiator type I-1 I-5 I-5 I-5 parts by mass 1.1 2 2 2 heat base generator type - - - - parts by mass - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 additive type - - - - parts by mass - - - - type - - - - parts by mass - - - - solvent type GBL GBL GBL GBL parts by mass 40 40 40 40 type DMSO DMSO DMSO DMSO parts by mass 10 10 10 10 Solid content concentration (mass%) 46 47 47 47 Process Film thickness (μm) 30 20 20 20 PB temperature (°C) 100 100 100 100 Pattern size (μm) 10 10 10 10 exposure method m LDI LDI LDI Exposure wavelength (nm) 365 405 405 405 Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Hardening temperature (°C) 230 230 230 230 Hardening time (min) 180 180 180 180 Developing conditions burden burden burden burden Evaluation elongation at break B A A A Pattern Rectangularity B A A A Pattern roughness after development A A A A F/E 1.00 1.00 1.00 1.00 X/Y 1.00 1.00 1.00 1.00 A/B 0.93 0.95 0.96 0.96 C/D 1.04 0.98 0.98 0.95

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

[resin] ・Resin 1 to Resin 35: Resin 1 to Resin 35 obtained in the above synthesis example ・Comparative resin 1: Comparative resin 1 obtained by the above synthesis example

[Monomers (polymerizable compounds)] ・M-1: Compounds with the following structures, and the subscripts in parentheses indicate the number of repetitions. [chemical formula 79]

[Polymerization initiator] ・I-1 to I-4: Compounds of the following structure [Chemical formula 80]

[Thermal base generator] ・A-1 to A-3: Compounds with the following structures ・AX-1: Compounds with the following structures [Chemical formula 81]

[Polymerization inhibitors] ・B-1 to B-2: Compounds of the following structure [Chemical formula 82]

[Silane Coupling Agent (Metal Adhesion Improver)] ・C-1 to C-2: Compounds of the following structures In the following formulae, Et represents an ethyl group. [chemical formula 83]

[Migration Inhibitor] ・D-1: Compound of the following structure [Chemical Formula 84]

[Additives] ・E-1 to E-2: Compounds of the following structure [Chemical formula 85]

〔Solvent〕 ・NMP: N-methyl-2-pyrrolidone ・EL: ethyl lactate ・DMSO: Dimethylsulfone ・GBL: γ-butyrolactone

<Evaluation> [Measurement of F/E] The resin composition prepared in each of the Examples and each of the Comparative Examples or the composition for comparison was applied to a silicon wafer by a spin coating method to form a resin layer. The obtained silicon wafer formed with the resin layer was dried on a hot plate at 100° C. for 5 minutes, thereby obtaining a resin composition layer with a uniform thickness on the silicon wafer. Regarding the film thickness, the description (film thickness after curing) in the column of "film thickness (μm)" in the table is "approximately 26 μm" for an example of "20", and "approximately 13 μm" for an example of "10". An example of "30" is "about 40 μm". Regarding a part of the above-mentioned resin composition layer, in the example described as "negative" in the column of developing conditions in the table, the entire surface of the resin composition layer on the silicon wafer was subjected to exposure energy of 500mJ/ ^cm2 . exposure. The exposure wavelength is described in "Exposure wavelength (nm)" in the table. In the example described as "positive" in the column of the image development condition in a table|surface, exposure was not performed. After the above exposure, the film (pattern) after development was obtained by immersing the above resin composition layer in the developer described in the table. For each film before and after development, ¹ H-NMR measurement and HPLC measurement were performed using heavy DMSO to quantify the base generating component (molar amount of base generating group) remaining in the film before and after development. Calculate the ratio F/E of the molar amount E of the base-generating group present in the film before development to the molar amount F of the base-generating group present in the film after development, and record it in the table "F/E" column.

〔Measurement of X/Y〕 After forming a film having the film thickness described in the column of "film thickness (μm)" in the table, hollowing was performed along the thickness direction of the film by the gas cluster ion beam (GCIB) method. The concentration of the base-generating group in each site was calculated by performing FT-IR measurement on the hollow site. Specifically, the ratio X/Y of the concentration X of base-generating groups in the upper 50% of the thickness direction of the film to the concentration Y of base-generating groups in the lower 50% of the film is calculated and recorded in the column "X/Y" in the table. .

[Measurement of A/B] A cured resin composition layer (cured product) was produced by the same method as the evaluation of the elongation at break described later. The silicon wafer on which the hardened material was formed was immersed in a 4.9 mass % hydrofluoric acid aqueous solution, and the hardened material was peeled off from the silicon wafer. By performing FT-IR measurement on the surface side (the side opposite to the silicon wafer) of the obtained peeling film and the side in contact with the silicon wafer, the loop closure rate of each surface was calculated. FT-IR measurement was performed as follows. When resins 1 to 33 were used as the resins, the absorption peak derived from the imide structure in the infrared absorption spectrum measured by FT-IR was measured at 1377cm Peak intensity P1 around ^-1 . Next, after heat-treating the cured product at 350°C for 1 hour, FT-IR measurement was performed again, and the peak intensity P2 around 1377 cm ^-1 was obtained for each of the surface side in contact with the silicon wafer. Using the obtained peak intensities P1 and P2, the imidization rate (ring closure rate) of the polyimide was calculated from the following formula. Imidization ratio (%) = (peak intensity P1/peak intensity P2) × 100 When resins 34 and 35 are used as the resin, the peak intensity Q1 around 1650 cm ^-1 which is the absorption peak derived from the amide structure is obtained , and then normalized using the absorption intensity of the aromatic ring observed around 1490 cm ^-1 . After heat-treating the polybenzoxazole at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity Q2 around 1650 cm ^-1 was obtained, and normalized using the absorption intensity of the aromatic ring observed around 1490 cm ^-1 . One. Using the obtained standard values of the peak intensities Q1 and Q2, the oxazolization rate (ring closure rate) of polybenzoxazole was calculated from the following formula. Ozolization rate (%) = (standard value of peak intensity Q1/standard value of peak intensity Q2) × 100 Specifically, calculate the closed loop rate on the side surface of the hardened product opposite to the side in contact with the silicon wafer The ratio A/B of A to the closed-loop rate B on the side surface in contact with the silicon wafer is recorded in the column "A/B" in the table.

〔Measurement of C/D〕 Except for changing the film thickness and setting the heating time to 180 minutes, a 1:1 line and space pattern cured film with a film thickness of 20 μm and a pitch of 10 μm was obtained by the same method as the evaluation of pattern squareness described later. By measuring the cross-sectional SEM of the line and space pattern before and after the heating step (before and after curing), the width shrinkage ratio at the upper end and the width shrinkage ratio at the lower end of the line pattern were calculated. Specifically, the ratio C/D of the width shrinkage rate C at the upper end of the line pattern to the width shrinkage rate D at the lower end was calculated and described in the column "C/D" in the table.

[Evaluation of Elongation at Break] The resin compositions prepared in Examples and Comparative Examples or comparative compositions were applied to silicon wafers by spin coating to form resin layers. Dry the obtained silicon wafer with the resin layer formed thereon on a hot plate at 100°C for 5 minutes. An example of "20" is "about 26 μm", an example of "10" is "about 13 μm", and an example of "30" is "about 40 μm". A resin composition layer with a uniform thickness was obtained. In the example described as "negative" in the column of developing conditions in the table, the entire surface of the resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ/cm ² . The exposure wavelength is described in "Exposure wavelength (nm)" in the table. In the example described as "positive" in the column of the image development condition in a table|surface, exposure was not performed. In the example described as "M" in the column of exposure conditions, exposure was performed using a stepper as a light source. In the example described as "LDI" in the column of exposure conditions, exposure was performed using a direct exposure device (ADTEC DE-6UH III) as a light source. In the example where the numerical value is recorded in the column of "curing temperature (°C)", the temperature of the above-mentioned exposed resin composition layer was raised at a rate of 10°C/min under a nitrogen atmosphere using a hot plate to reach the temperature of " After the temperature recorded in the "curing temperature (°C)" column, the above temperature is maintained within the "hardening time (min)" in the table. In the example described as "IR" in the "curing temperature (°C)" column, an infrared lamp heating device (RTP-6 manufactured by ADVANCE RIKO, Inc.) was used in a nitrogen atmosphere at a heating rate of 10°C/min. The temperature of the resin film obtained in each example was raised to 230° C., and then the temperature was maintained for 180 minutes. The cured resin composition layer (cured product) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and the cured product was peeled off from the silicon wafer. The peeled cured product was punched out with a punching machine to prepare a test piece having a sample width of 3 mm and a sample length of 30 mm. The elongation in the longitudinal direction of the obtained test piece was measured in accordance with JIS-K6251 in an environment with a crosshead speed of 300 mm/min, 25° C., and 65% RH (relative humidity) using a tensile testing machine (TENSILON). The measurement was performed five times, and the arithmetic mean value of the elongation (elongation at break) of the test piece at breakage in the five measurements was used as an index value. Evaluation was performed according to the following evaluation criteria, and the evaluation results were described in the column of "elongation at break" in the table. It can be said that the larger the index value, the better the film strength of the cured product. -Evaluation criteria- A: The above index value is 65% or more. B: The above index value is above 60% and below 65%. C: The above index value is more than 55% and less than 60%. D: The above index value is lower than 55%.

[Evaluation of Pattern Rectangularity] In each of the examples and comparative examples, each resin composition or comparative composition was applied (coated) in a layer on a silicon wafer by a spin coating method, thereby forming resin composition film. In each of the Examples and Comparative Examples, the silicon wafer to which the obtained resin composition film was applied was dried on a hot plate at 100° C. for 5 minutes, thereby forming a resin composition film on the silicon wafer. The resin composition film on the silicon wafer was exposed at an exposure energy of 500 mJ/cm ² using the exposure wavelength described in the "Exposure wavelength (μm)" column in the table. Exposure was performed through a mask (a binary mask in which the pattern is 1:1 line and space, and the line width is the line width described in the "pattern size (μm)" column in the table). In the example described as "positive" in the column of "development conditions" in the table after the above exposure, development was carried out for 60 seconds with a 2.5 mass % tetramethylammonium hydroxide aqueous solution, and rinsed with pure water for 20 seconds, thereby obtaining exposure The line and space pattern of the final resin composition film. In the case where "Negative" is written in the "Development Conditions" column in the table, the resin composition was obtained by developing with cyclopentanone for 60 seconds and rinsing with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds. Line and space pattern of the film. Next, hardening was performed under specified hardening (hardening) conditions. Specifically, in the example where a numerical value is described in the column of "curing temperature (°C)", the temperature of the above-mentioned exposed resin composition layer was raised at a rate of 10°C/min in a nitrogen atmosphere using a hot plate, After reaching the temperature recorded in the column of "curing temperature (°C)" in the table, the above temperature is maintained for the time recorded in the column of "curing time (min)" in the table. In addition, in the example described as "IR" in the column of "curing temperature (°C)" in the table, an infrared lamp heating device (RTP-6 manufactured by ADVANCE RIKO, Inc.) was used in a nitrogen atmosphere at 10°C/ The temperature increase rate of 1 minute was used to raise the temperature of the developed resin composition film obtained in each example, and after reaching 230° C., the above temperature was maintained for 180 minutes. On the silicon wafer on which the obtained cured film was formed, the silicon wafer was diced perpendicular to the line-and-space pattern of the cured film to expose the cross section of the pattern. The pattern cross-section of the line and space pattern was observed at a magnification of 200 times with an optical microscope, and the cross-sectional shape of the pattern was evaluated. Specifically, in each of the Examples and Comparative Examples, the taper angle formed by the surface of the silicon wafer (substrate surface) and the side surface of the cured film was measured, and evaluated according to the following evaluation criteria. The evaluation results are described in the column of "pattern rectangularity" in the table. It can be said that the taper angle exceeds 90° and the cross-sectional shape of the pattern is not an hourglass shape, and the closer the taper angle is to 90°, the better the pattern shape is. -Evaluation Criteria- A: The taper angle is not less than 85° and not more than 90°. B: The taper angle is 80° or more and less than 85°. C: The taper angle is 75° or more and less than 80°. D: The taper angle is less than 75°, the cross-sectional shape of the pattern is an inverted cone shape forming a taper angle larger than 90°, or the cross-sectional shape of the pattern is an hourglass shape.

[Evaluation of pattern roughness after development] In each example and comparative example, each resin composition or comparative composition was applied (coated) in a layered form on a silicon wafer by the spin coating method. This forms a resin composition film. In each of the Examples and Comparative Examples, the silicon wafer to which the obtained resin composition film was applied was dried on a hot plate at 100° C. for 5 minutes, thereby forming a resin composition film on the silicon wafer. The resin composition film on the silicon wafer was exposed at an exposure energy of 500 mJ/cm ² using the exposure wavelength described in the column "Exposure wavelength (nm)" in the table. Exposure was performed through a mask (a binary mask in which the pattern is 1:1 line and space, and the line width is the line width described in the "pattern size (μm)" column in the table). In the example described as "positive" in the column of "development conditions" in the table after the above exposure, development was carried out for 60 seconds with a 2.5 mass % tetramethylammonium hydroxide aqueous solution, and rinsed with pure water for 20 seconds, thereby obtaining exposure The line and space pattern of the final resin composition film. In the example described as "negative" in the "Development Conditions" column in the table, the resin composition was obtained by developing with cyclopentanone for 60 seconds and rinsing with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds. Line and space pattern of the film. Using a critical dimension scanning electron microscope (SEM, Hitachi, Ltd., S-9380II), observe the obtained line and space pattern from the top of the pattern, and measure the line width within 2000 μm of the edge of the line pattern in the longitudinal direction. Wide measurement unevenness, standard deviation σ was obtained, and 3σ was calculated. Smaller values indicate better performance. The evaluation results are described in the column of "pattern roughness after development" in the table. - Evaluation Criteria - A: 3σ is less than 50 nm. B: 3σ is 50 nm or more and less than 75 nm. C: 3σ is 75 nm or more and less than 100 nm. D: 3σ is 100 nm or more.

From the above results, it can be seen that the rectangularity of the pattern in the obtained cured product is improved by using the resin composition of the present invention. The comparative composition in Comparative Example 1 does not contain the specific resin. It can be seen that in such an aspect, the rectangularity of the pattern in the obtained cured product is poor.

<Example 101> The resin composition used in Example 1 was applied in a layer form to the surface of the thin copper layer of the resin substrate on which the copper thin layer was formed by the spin coating method, and dried at 100°C for 5 minutes, thereby forming a film thickness After the photosensitive film of 20 μm, exposure was performed with a stepper (manufactured by Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a pattern of 1:1 line-space and a line width of 10 μm). After exposure, it heated at 100 degreeC for 4 minutes. After the above-mentioned heating, 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 120 minutes to form an interlayer insulating film for a rewiring layer. The interlayer insulating film for a rewiring layer is excellent in insulating properties. Furthermore, as a result of manufacturing semiconductor devices using these interlayer insulating films for rewiring layers, normal operation was confirmed.

none.

Claims (19)

A kind of resin composition, it comprises the precursor of cyclization resin, The precursor of the aforementioned cyclized resin generates a base when heated to 250°C. The resin composition as described in claim 1, wherein During the heating, the base is released from the precursor of the cyclization resin. The resin composition as described in claim 1 or claim 2, wherein The structure exhibiting the property of generating a base contained in the precursor of the aforementioned cyclized resin is a nonionic structure. The resin composition as described in claim 1 or claim 2, wherein The structure exhibiting base-generating properties contained in the precursor of the aforementioned cyclized resin includes an amide bond. The resin composition as described in claim 4, wherein The amide bond is bonded to the main chain of the precursor of the cyclization resin at the carbonyl side. The resin composition as described in Claim 1 or Claim 2, wherein the precursor of the aforementioned cyclized resin comprises a structure represented by the following formula (1-1), [Chemical Formula 1]

In formula (1-1), R ¹ is independently a hydrogen atom or a monovalent organic group, two R ¹ can be connected to form a ring structure, L ¹ represents a trivalent organic group, and * represents a bond with other structures Knot part. The resin composition according to claim 1 or claim 2, further comprising a photopolymerization initiator. The resin composition according to claim 1 or claim 2, further comprising a polymerizable compound. The resin composition according to claim 1 or claim 2, further comprising a base generator. 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 10. A laminate comprising two or more layers composed of the cured product described in claim 11, wherein a metal layer is included between any layers composed of the cured product. A semiconductor device comprising the cured product described in Claim 11. A method of manufacturing a cured product, comprising: A film forming step, applying a resin composition comprising a precursor of a cyclized resin to form a film on the substrate; an exposure step, selectively exposing the aforementioned film; A developing step, using a developing solution to develop the aforementioned film to form a pattern; and a heating step of heating the aforementioned pattern at a temperature of not less than 50°C and not more than 250°C, The precursor of the aforementioned cyclization resin is a compound that generates a base in the aforementioned heating step. The method for producing a hardened product as claimed in claim 14, wherein The molar number E of the base-generating group present in the film as the film before the exposure step and before the development step and remaining as the aforementioned pattern after the developing step and the molar number E of the base-generating group present in the aforementioned pattern after the aforementioned developing step The ratio F/E of the number F exceeds 0.9. The manufacturing method of the cured product as described in Claim 14 or Claim 15, wherein In the aforementioned film formed in the aforementioned film forming step, the ratio X/Y of the base-generating group concentration X in the upper 50% of the film to the base-generating group concentration Y in the lower 50% of the film is 0.90<X/ Y<1.10. The manufacturing method of the cured product as described in Claim 14 or Claim 15, wherein The ratio A/B of the loop closure rate A on the surface opposite to the substrate contacting side of the obtained hardened product to the loop closure ratio B on the substrate contacting surface is 0.90<A/B <1.10. The manufacturing method of the cured product as described in Claim 14 or Claim 15, wherein In the developing step, a 1:1 line and space pattern with a film thickness of 20 μm and a pitch of 10 μm is formed. When heating at 230°C for 180 minutes in the heating step, the ratio C of the width shrinkage rate C at the upper end of the line pattern to the width shrinkage rate D at the lower end /D is 0.90<C/D<1.10. A precursor of a cyclized resin, comprising a group selected from the group consisting of the repeating unit represented by the following formula (2), the repeating unit represented by the formula (3) and the repeating unit represented by the formula (PAI-2) of at least one repeating unit, [chemical formula 2]

In formula (2), A ¹ and A ² independently represent an oxygen atom or -NH-, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and R ¹¹⁴ independently represent hydrogen An atom or a monovalent organic group, at least one of R ¹¹¹ , R ¹¹⁵ , R ¹¹³ and R ¹¹⁴ contains a structure represented by the following formula (1-1), [Chemical formula 3]

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group, R ¹²¹ , R ¹²² , R ¹²³ and at least one of R ¹²⁴ comprises a structure represented by the following formula (1-1), [chemical formula 4]

In the formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or -NH-, R ¹¹³ represents a hydrogen atom or a monovalent organic group, R ¹¹⁷ At least one of R ¹¹¹ and R ¹¹³ includes a structure represented by the following formula (1-1), [Chemical formula 5]

In formula (1-1), R ¹ is independently a hydrogen atom or a monovalent organic group, two R ¹ can be connected to form a ring structure, L ¹ represents a trivalent organic group, and * represents a bond with other structures Knot part.