TW202219092A - Curable resin composition, cured object, layered product, method for producing cured object, semiconductor device, and photobase generator - Google Patents

Abstract

A curable resin composition comprising at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors and a photobase generator having an alkoxysilyl group; a cured object obtained by curing the curable resin composition; a layered product including the cured object; a method for producing the cured object; a semiconductor device including the cured object or the layered product; and a photobase generator.

Description

Curable resin composition, cured product, laminate, and method for producing cured product, semiconductor element, and photobase generator

The present invention relates to a curable resin composition, a cured product, a laminate, and a method for producing the cured product, a semiconductor element, and a photobase generator.

Resins such as polyimide, polybenzoxazole, and polyimide imide are suitable for various applications because of their excellent heat resistance and insulating properties. Although it does not specifically limit as said use, If the semiconductor element for actual mounting is mentioned as an example, the use as a material of an insulating film or a sealing 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-mentioned applications, resins such as polyimide, polybenzoxazole, polyimide imide, etc., are selected from the group consisting of polyimide precursor, polybenzoxazole precursor or polyimide imide. It is used in the form of a curable resin composition of at least one resin in the group of imine precursors. Such a curable resin composition can be applied to a substrate by, for example, coating to form a resin film, and thereafter, if necessary, exposure, development, heating, and the like can be performed to form a cured product on the substrate. The above-mentioned polyimide precursors, polybenzoxazole precursors or polyimide imide precursors are cyclized, for example, by the action of alkali and heating, and the cured products become polyimide, polybenzyl, respectively. Azole or polyamide imide. Since the curable resin composition can be applied by a known coating method, etc., it can be said that it is excellent in suitability for production, such as freedom of design of the shape, size, and application position of the curable resin composition to be applied at the time of application. high degree. In addition to the high performance of polyimide, polybenzoxazole, and polyimide imide, the above-mentioned curable resin composition is expected to be used in the industry from the viewpoint of its excellent suitability for production. application development on .

For example, Patent Document 1 describes a resin composition for an insulating film or a surface protection film of an electronic component comprising (A) a polymer of a specific structure, (B) a solvent, and (C) a compound of a specific structure. Patent Document 2 describes a negative photosensitive resin composition containing (A) a polyimide precursor having a specific structure and (B) a photopolymerization initiator: 0.1 to 20 parts by mass.

[Patent Document 1] Japanese Patent Laid-Open No. 2011-46918 [Patent Document 2] Japanese Patent Laid-Open No. 2020-24374

Among the curable resin compositions, the obtained cured product is required to be excellent in adhesion to metal.

An object of the present invention is to provide a curable resin composition from which a cured product excellent in adhesion to metal can be obtained, a cured product obtained by curing the aforementioned curable resin composition, a laminate comprising the aforementioned cured product, and the aforementioned cured product A manufacturing method of the product, and a semiconductor element including the above-mentioned cured product or the above-mentioned laminated body. Another object of the present invention is to provide a novel photobase generator.

式（1-1）中，X ¹表示具有羥基或羧基之芳基，R ¹、R ²表示氫原子或碳數1～12的烴基，R ¹及R ²可以鍵結而形成環結構，Y ¹表示2價的連接基，Z ¹表示烷氧基甲矽烷基； 式（1-2）中，X ²表示經取代或未經取代的蒽結構或具有硝基之芳基，R ³及R ⁴分別獨立地表示氫原子或碳數1～12的烴基，R ³及R ⁴可以鍵結而形成環結構，Y ²表示2價的連接基，Z ²表示烷氧基甲矽烷基； 式（1-3）中，X ³及X ⁴分別獨立地表示經取代或未經取代的芳基，R ⁵表示1價的有機基，R ⁶～R ⁹分別獨立地表示氫原子、碳數1～12的烴基或具有烷氧基甲矽烷基之基團，R ⁶～R ⁹中的至少2個可以鍵結而形成環結構，R ⁶～R ⁹中的至少1個為具有烷氧基甲矽烷基之基團。 ＜4＞如＜1＞至＜3＞之任一項所述之硬化性樹脂組成物，其中，上述光鹼產生劑為分子量2,000以下的化合物。 ＜5＞如＜1＞至＜4＞之任一項所述之硬化性樹脂組成物，其係進一步包含具有烷氧基甲矽烷基而不具有光鹼產生能的化合物。 ＜6＞如＜1＞至＜5＞之任一項所述之硬化性樹脂組成物，其係進一步包含不具有烷氧基甲矽烷基的光鹼產生劑。 ＜7＞如＜1＞至＜6＞之任一項所述之硬化性樹脂組成物，其係包含作為具有聚合性基及唑基之化合物之化合物B。 ＜8＞如＜1＞至＜7＞之任一項所述之硬化性樹脂組成物，其係包含作為不具有聚合性基而具有唑基之化合物之化合物C。 ＜9＞如＜8＞所述之硬化性樹脂組成物，其中，化合物C由式（C-1）或式（C-2）表示。 [化學式2]

式（C-1）中，Z ¹～Z ⁴分別獨立地表示=CR ⁷-或氮原子，R ¹表示氫原子或1價的有機基，R ⁷表示氫原子或1價的有機基，在式（C-1）所表示之結構中不包含聚合性基； 式（C-2）中，Z ⁵～Z ⁶分別獨立地表示=CR ⁸-或氮原子，R ²～R ⁶分別獨立地表示氫原子或1價的有機基，R ⁸表示氫原子或1價的有機基，在式（C-2）所表示之結構中不包含聚合性基。 ＜10＞如＜1＞至＜9＞之任一項所述之硬化性樹脂組成物，其係用於形成再配線層用層間絕緣膜。 ＜11＞一種硬化物，其係將＜1＞至＜10＞之任一項所述之硬化性樹脂組成物硬化而成。 ＜12＞一種積層體，其係包括2層以上的由＜11＞所述之硬化物形成之層，並且在由上述硬化物形成之層之間的任一個之間包括金屬層。 ＜13＞一種硬化物之製造方法，其係包括將＜1＞至＜10＞之任一項所述之硬化性樹脂組成物適用於基板上而形成膜之膜形成步驟。 ＜14＞如＜13＞所述之硬化物之製造方法，其係包括選擇性地曝光上述膜之曝光步驟及使用顯影液對上述膜進行顯影而形成圖案之顯影步驟。 ＜15＞如＜14＞所述之硬化物之製造方法，其在上述顯影步驟之後，進一步包括對藉由上述顯影而獲得之圖案進行曝光之顯影後曝光步驟。 ＜16＞如＜13＞至＜15＞之任一項所述之硬化物之製造方法，其係包括在50～450℃下對上述膜進行加熱之加熱步驟。 ＜17＞一種半導體元件，其係包含＜11＞所述之硬化物或＜12＞所述之積層體。 ＜18＞一種光鹼產生劑，其係由下述式（1-1）～式（1-3）中的任一個表示。 [化學式3]

式（1-1）中，X ¹表示具有羥基或羧基之芳基，R ¹及R ²表示氫原子或碳數1～12的烴基，R ¹及R ²可以鍵結而形成環結構，Y ¹表示2價的連接基，Z ¹表示烷氧基甲矽烷基； 式（1-2）中，X ²表示經取代或未經取代的蒽結構或具有硝基之芳基，R ³及R ⁴分別獨立地表示氫原子或碳數1～12的烴基，R ³及R ⁴可以鍵結而形成環結構，Y ²表示2價的連接基，Z ²表示烷氧基甲矽烷基； 式（1-3）中，X ³及X ⁴分別獨立地表示經取代或未經取代的芳基，R ⁵表示1價的有機基，R ⁶～R ⁹分別獨立地表示氫原子、碳數1～12的烴基或具有烷氧基甲矽烷基之基團，R ⁶～R ⁹可以鍵結而形成環結構，R ⁶～R ⁹中的至少1個為具有烷氧基甲矽烷基之基團。 [發明效果] Examples of typical embodiments of the present invention are shown below. <1> A curable resin composition comprising at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyimide precursor and having Photobase generator for alkoxysilyl groups. <2> The curable resin composition according to <1>, wherein the photobase generator is a compound that generates a base by the action of light having a wavelength of 100 to 600 nm. <3> The curable resin composition according to <1> or <2>, wherein the photobase generator is represented by any one of the following formulae (1-1) to (1-3) compound; [chemical formula 1]

In formula (1-1), X ¹ represents an aryl group having a hydroxyl group or a carboxyl group, R ¹ and R ² represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ¹ and R ² can be bonded to form a ring structure, Y ¹ represents a divalent linking group, Z ¹ represents an alkoxysilyl group; in formula (1-2), X ² represents a substituted or unsubstituted anthracene structure or an aryl group with a nitro group, R ³ and R ⁴ independently represents a hydrogen atom or a hydrocarbon group with 1 to 12 carbon atoms, R ³ and R ⁴ can be bonded to form a ring structure, Y ² represents a divalent linking group, and Z ² represents an alkoxysilyl group; formula ( In 1-3), X ³ and X ⁴ each independently represent a substituted or unsubstituted aryl group, R ⁵ represents a monovalent organic group, and R ⁶ to R ⁹ each independently represent a hydrogen atom and a carbon number of 1 to 1. A hydrocarbon group of 12 or a group having an alkoxysilyl group, at least two of R ⁶ to R ⁹ can be bonded to form a ring structure, and at least one of R ⁶ to R ⁹ is an alkoxysilyl group base group. <4> The curable resin composition according to any one of <1> to <3>, wherein the photobase generator is a compound having a molecular weight of 2,000 or less. <5> The curable resin composition according to any one of <1> to <4>, further comprising a compound having an alkoxysilyl group and not having photobase generating energy. <6> The curable resin composition according to any one of <1> to <5>, further comprising a photobase generator not having an alkoxysilyl group. <7> The curable resin composition according to any one of <1> to <6>, which contains Compound B as a compound having a polymerizable group and an azole group. <8> The curable resin composition according to any one of <1> to <7>, which contains Compound C as a compound having an azole group without a polymerizable group. <9> The curable resin composition according to <8>, wherein the compound C is represented by the formula (C-1) or the formula (C-2). [Chemical formula 2]

In formula (C-1), Z ¹ to Z ⁴ each independently represent =CR ⁷ - or a nitrogen atom, R ¹ represents a hydrogen atom or a monovalent organic group, and R ⁷ represents a hydrogen atom or a monovalent organic group. The structure represented by the formula (C-1) does not contain a polymerizable group; in the formula (C-2), Z ⁵ to Z ⁶ each independently represent =CR ⁸ - or a nitrogen atom, and R ² to R ⁶ each independently Represents a hydrogen atom or a monovalent organic group, R ⁸ represents a hydrogen atom or a monovalent organic group, and does not contain a polymerizable group in the structure represented by the formula (C-2). <10> The curable resin composition according to any one of <1> to <9>, which is used for forming an interlayer insulating film for a rewiring layer. <11> A cured product obtained by curing the curable resin composition according to any one of <1> to <10>. <12> A laminate comprising two or more layers formed of the cured product described in <11>, and including a metal layer between any of the layers formed of the cured product. <13> A method for producing a cured product including a film forming step of applying the curable resin composition according to any one of <1> to <10> on a substrate to form a film. <14> The manufacturing method of the hardened|cured material as described in <13> which comprises the exposure process of selectively exposing the said film, and the developing process of developing the said film using a developing solution, and forming a pattern. <15> The method for producing a cured product according to <14>, which further includes a post-development exposure step of exposing the pattern obtained by the above-mentioned development after the above-mentioned development step. <16> The manufacturing method of the hardened|cured material of any one of <13>-<15> which comprises the heating process of heating the said film at 50-450 degreeC. <17> A semiconductor element comprising the cured product described in <11> or the laminated body described in <12>. <18> A photobase generator represented by any one of the following formulae (1-1) to (1-3). [Chemical formula 3]

In formula (1-1), X ¹ represents an aryl group having a hydroxyl or carboxyl group, R ¹ and R ² represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ¹ and R ² can be bonded to form a ring structure, Y ¹ represents a divalent linking group, Z ¹ represents an alkoxysilyl group; in formula (1-2), X ² represents a substituted or unsubstituted anthracene structure or an aryl group with a nitro group, R ³ and R ⁴ independently represents a hydrogen atom or a hydrocarbon group with 1 to 12 carbon atoms, R ³ and R ⁴ can be bonded to form a ring structure, Y ² represents a divalent linking group, and Z ² represents an alkoxysilyl group; formula ( In 1-3), X ³ and X ⁴ each independently represent a substituted or unsubstituted aryl group, R ⁵ represents a monovalent organic group, and R ⁶ to R ⁹ each independently represent a hydrogen atom and a carbon number of 1 to 1. The hydrocarbon group of 12 or a group having an alkoxysilyl group, R ⁶ to R ⁹ may be bonded to form a ring structure, and at least one of R ⁶ to R ⁹ is a group having an alkoxysilyl group. [Inventive effect]

According to the present invention, there are provided a curable resin composition which can obtain a cured product having excellent adhesion to metals, a cured product obtained by curing the aforementioned curable resin composition, a laminate comprising the aforementioned cured product, and one of the aforementioned cured products. A manufacturing method and a semiconductor element including the above-mentioned cured product or the above-mentioned laminated body. Moreover, according to this invention, a novel photobase generator is provided.

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 shown by "-" symbol shows the range which includes the numerical value described before and after "-" as a lower limit value and an upper limit value, respectively. In this specification, the term "step" not only refers to an independent step, but also refers to a step that cannot be clearly distinguished from other steps as long as the intended function of the step can be achieved. With regard to the labels of groups (atomic groups) in this specification, the labels of unsubstituted and unsubstituted groups include both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure with light but also exposure with particle beams such as electron beams, ion beams, and the like. Moreover, as light used for exposure, the bright-line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams and other actinic rays and radiation can be mentioned. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" "Both or either, "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In the present specification, the total solid content refers to the total mass of the 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 with respect to the total mass of a composition of other components except a solvent. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. In this specification, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be obtained, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION), and combining guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (the above are manufactured by TOSOH CORPORATION) were connected in series and used as a column to obtain the determination. Unless otherwise stated, the molecular weights are determined using THF (tetrahydrofuran) as the 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, the detection in the GPC measurement was performed using a detector with a wavelength of 254 nm of UV rays (ultraviolet rays). In this specification, when the positional relationship of each layer constituting the layered product is described as "upper" or "lower", other layers may be present on the upper side or lower side of the reference layer among the plurality of layers concerned. That is, a third layer or element may be further interposed between the layer serving as the reference and the other layers described above, and the layer serving as the reference and the other layers described above do not need to be in contact. Also, unless otherwise specified, the direction in which the layers are gradually stacked with respect to the base material is referred to as "up", or, in the case of a resin composition layer, the direction from the base material toward the resin composition layer is referred to as "up" , and the opposite direction is called "down". Furthermore, the setting of the up-down direction is for the convenience of explaining this specification, and in an actual aspect, the "up" direction in this specification can also be different from the vertical upward direction. In this specification, unless otherwise stated, as each component contained in a composition, a composition may contain 2 or more types of compounds corresponding to this component. In addition, unless otherwise specified, the content of each component in the composition represents the total content of all the compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 air pressure), and the relative humidity is 50% RH. In this specification, the combination of the preferred aspects is the more preferred aspect.

(curable resin composition) The curable resin composition of the present invention contains at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyimide imide precursor (hereinafter, also referred to as "Specific resin".) and a photobase generator having an alkoxysilyl group (hereinafter, also referred to as "specific photobase generator").

The curable resin composition of the present invention may be a negative-type curable resin composition or a positive-type curable resin composition, but a negative-type curable resin composition is preferable. The negative-type curable resin composition refers to a composition in which an unexposed portion (non-exposed portion) is removed by a developing solution when the layer formed of the curable resin composition is exposed to light. The positive-type curable resin composition refers to a composition in which an exposed portion (exposed portion) is removed by a developing solution when the layer formed of the curable resin composition is exposed to light.

According to the curable resin composition of the present invention, a cured product excellent in adhesion to metal can be obtained. Although the mechanism by which the above-mentioned effects can be obtained is not clear, it is presumed as follows.

The curable resin composition of this invention contains the photobase generator (specific photobase generator) which has an alkoxysilyl group. It is presumed that the specific photobase generator is likely to exist unevenly in the deep part of the film due to the inclusion of the above-mentioned alkoxysilyl group. It is presumed that when a film formed of such a curable resin composition is exposed to light, an alkali is likely to be generated in the deep part of the film, so that the volatilization of the alkali is easily suppressed, and the cyclization of the specific resin is efficiently performed. Therefore, it is presumed that the hardening property of the deep part of the hardened substance is improved, and the adhesiveness is excellent. Moreover, since the cyclization in the resin after hardening fully progresses, it is presumed that the elongation at break also increases.

However, in patent document 1 or patent document 2, the curable resin composition containing a specific resin and a specific photobase generator is neither described nor suggested.

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

＜Specific resin＞ The curable resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyimide precursor. It is preferable that the curable resin composition of this invention contains a polyimide precursor as a specific resin.

Moreover, it is preferable that a specific resin has a polymerizable group. As a polymerizable group in a specific resin, well-known polymerizable groups, such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group, and an alkoxymethyl group, are mentioned. As the above-mentioned radically polymerizable group, a group having an ethylenically unsaturated bond is preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, and the like, which are directly bonded to an aromatic ring and have a vinyl group which may be substituted, and (meth)acryloyl group. An amine group, a (meth)acryloyloxy group, etc., a (meth)acryloyloxy group is preferable. It is preferable that a specific resin has a polymerizable group which can polymerize with the polymerizable group in the compound B mentioned later as a polymerizable group. As a combination of polymerizable groups that can be polymerized, a specific resin has a radically polymerizable group and the compound B has a radically polymerizable group, or a specific resin has an epoxy group, and the compound B has an epoxy group, or the like. According to the above aspect, it is considered that the polymerizable groups in the specific resin and the polymerizable groups in the compound B are polymerized in the cured product, and the bond between the specific resin and the compound B becomes strong, thereby improving the obtained cured product. Metal adhesion.

Moreover, it is preferable that a specific resin contains a radically polymerizable group. When the specific resin has a radically polymerizable group, the curable resin composition preferably contains a photoradical polymerization initiator described later as a polymerization initiator, and a photoradical polymerization initiator described later is included as a polymerization initiator In addition, it is more preferable to contain a radical polymerizable compound described later, and it is further more preferable to contain a radical polymerizable compound described later as a polymerization initiator, a radical polymerizable compound described later, and a sensitizer described later. For example, a negative photosensitive layer is formed from such a curable resin composition. In addition, the specific resin may have a polarity conversion group such as an acid-decomposable group. When a specific resin has an acid-decomposable group, it is preferable that a curable resin composition contains the photoacid generator mentioned later as a photosensitizer. From such a curable resin composition, for example, a positive-type photosensitive layer or a negative-type photosensitive layer, which is a chemically amplified type, is formed.

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價的有機基，R ¹¹⁵表示4價的有機基，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價的有機基。 [Polyimide Precursor] The type and the like of the polyimide precursor used in the present invention are not particularly limited, but it is preferable to include a repeating unit represented by the following formula (2). [Chemical formula 4]

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

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. As the divalent organic group, there can be exemplified groups including linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, including linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. The straight-chain or branched aliphatic group may be substituted with a hydrocarbon group in the chain containing a heteroatom, and the cyclic aliphatic and aromatic groups may be substituted with a ring-membered hydrocarbon group containing a heteroatom. As a preferable embodiment of this invention, the group represented by -Ar- and -Ar-L-Ar- can be illustrated, and the group represented by -Ar-L-Ar- is especially preferable. Wherein, Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms including a single bond and may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO- or a combination of two or more of the above. These preferred ranges are as described above.

Preferably R ¹¹¹ is derived from a diamine. As a diamine used for manufacture of a polyimide precursor, a linear or branched aliphatic, cyclic aliphatic, or aromatic diamine etc. are mentioned. Only one type of diamine may be used, or two or more types may be used. Specifically, the group includes a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof. The diamine is preferable, and the diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The straight-chain or branched aliphatic group may be substituted with a hydrocarbon group in the chain containing a heteroatom, and the cyclic aliphatic and aromatic groups may be substituted with a ring-membered hydrocarbon group containing a heteroatom. As an example of the group containing an aromatic group, the following are mentioned.

式中，A表示單鍵或2價的連接基，選自單鍵或可以經氟原子取代的碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-SO ₂-、-NHCO-或該等組合中之基團為較佳，選自單鍵、可以經氟原子取代的碳數1～3的伸烷基、-O-、-C（=O）-、-S-或-SO ₂-中之基團為更佳，-CH ₂-、-O-、-S-、-SO ₂-、-C（CF ₃） ₂-或-C（CH ₃） ₂-為進一步較佳。 式中，*表示與其他結構的鍵結部位。 [Chemical formula 5]

In the formula, A represents a single bond or a divalent linking group, and is selected from a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -C(=O)-, and -S- which may be substituted by a fluorine atom. , -SO ₂ -, -NHCO- or groups in these combinations are preferably selected from single bonds, alkylene groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -C (= The group in O)-, -S- or -SO ₂ - is more preferred, -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - or -C ( CH ₃ ) ₂ - is further preferred. In the formula, * represents a bonding site with other structures.

Specific examples of the diamine include those selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, and 1,4-diaminobutane and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diamine cyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4- Bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-di Methylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-Diaminodiphenylene and 3,3-diaminodiphenylene, 4,4'-diaminodiphenyl ether and 3,3'-diaminodiphenyl ether, 4 ,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane , 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-amine) phenyl) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)hexafluoropropane 3-amino-4-hydroxyphenyl) bismuth, bis(4-amino-3-hydroxyphenyl) bismuth, 4,4'-diamino-terphenyl, 4,4'-bis(4-amine bis[4-(4-aminophenoxy)phenyl]bis[4-(3-aminophenoxy)phenyl]bis[4-(3-aminophenoxy)phenyl]bis[4-(2 -Aminophenoxy)phenyl] bismuth, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene -Bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diamine diphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-( 4-Aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diamine Amino biphenyl, 9,9'-bis(4-amino) Phenyl) phenyl, 4,4'-dimethyl-3,3'-diaminodiphenyl, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenyl Phenylmethane, 2,4-diaminocumene 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)octa Methylpentasiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, bis Ester of aminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminobenzene) base) 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(trifluoropropane) Methyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) base) biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) base) diphenyl bismuth, 4,4'-bis(3-amino-5-trifluoromethylphenoxy) diphenyl bismuth, 2,2-bis[4-(4-amino-3- Trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2 At least 1 of ,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobenzidine and 4,4'-diaminotetraphenyl a diamine.

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

Moreover, the diamine which has two or more alkylene glycol units described in the paragraphs 0032 to 0034 of International Publication No. 2017/038598 in the main chain can also be preferably used.

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

式（51）中，R ⁵⁰～R ⁵⁷分別獨立地為氫原子、氟原子或1價的有機基，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價的有機基，可以舉出碳數1～10（較佳為碳數1～6）的未經取代的烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式7]

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。 作為提供式（51）或式（61）的結構之二胺，可以舉出2,2’-二甲基聯苯胺、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。該等可以使用1種或組合使用2種以上。 In addition, from the viewpoint of i-ray transmittance, it is preferable that R ¹¹¹ is a divalent organic group represented by the following formula (51) or formula (61). In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability. Formula (51) [Chemical Formula 6]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoromethyl group, * Each independently represents the bonding site to the nitrogen atom in the formula (2). Examples of the monovalent organic groups of R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably carbon atoms of 1 to 6), and unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably carbon atoms of 1 to 10). 1-6) fluorinated alkyl groups, etc. [Chemical formula 7]

In the formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in the formula (2). As the diamine which provides the structure of formula (51) or formula (61), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diamine can be mentioned Aminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used alone or in combination of two or more.

式（5）中，R ¹¹²為單鍵或2價的連接基，選自單鍵或可以經氟原子取代的碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO ₂-及-NHCO-以及該等組合中之基團為較佳，選自單鍵、可以經氟原子取代的碳數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-之群組中的2價的基團為進一步較佳。 R ¹¹⁵ in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group including an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), * each independently represents a bonding site with another structure. [Chemical formula 8]

In formula (5), R ¹¹² is a single bond or a divalent linking group, selected from a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, which may be substituted by a fluorine atom , -SO ₂ - and -NHCO- and the groups in these combinations are preferably selected from single bonds, alkylene groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -CO-, The groups in -S- and -SO ₂ - are more preferably selected from the group consisting of -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（O）中，R ¹¹⁵表示4價的有機基。R ¹¹⁵的較佳範圍與式（2）中之R ¹¹⁵的含義相同，較佳範圍亦相同。 Specific examples of R ¹¹⁵ include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride. As a structure corresponding to R ¹¹⁵ , the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue, or may contain two or more types. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical formula 9]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as that of R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic 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' - Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7 -Naphthalenetetracarboxylic dianhydride, 1,4,5,7-Naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 3-Dicarboxyphenyl) propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4 -Tetracarboxylic dianhydride, 1,4,5,6-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, the tetracarboxylic dianhydride (DAA-1) - (DAA-5) described in the 0038 paragraph of International Publication No. WO 2017/038598 can also be mentioned as a preferable example.

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

R ¹¹³ and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkoxy group. Moreover, 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. As the polymerizable group, a group capable of performing a crosslinking reaction by the action of heat, radicals, or the like, a radically polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, an acyloxymethyl group, an epoxy group, an oxetanyl group, and a benzoxyl group. azole group, blocked isocyanate group, amine group. As the radically polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, 2-methallyl group, and a group having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl, etc.), (meth)acrylamido, (meth)acryloyloxy, groups represented by the following formula (III), etc., the group represented by the following formula (III) is better.

[Chemical formula 10]

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and a hydrogen atom or a methyl group is preferred. 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 polyalkeneoxy group. Preferred examples of R ²⁰¹ include ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecane and the like. base, 1,2-butanediyl, 1,3-butanediyl, -CH ₂ CH(OH) CH ₂ -, polyalkyleneoxy, ethylidene, propylidene and other alkylene groups, -CH ₂ CH(OH)CH ₂ -, cyclohexyl, and polyalkeneoxy groups are more preferred, and alkylene groups such as ethylidene and propylidene groups or polyalkeneoxy groups are further preferred. In the present invention, the polyalkeneoxy group refers to a group in which two or more alkeneoxy groups are directly bonded. The alkylene groups in the plural alkyleneoxy groups contained in the polyalkeneoxy group may be the same or different, respectively. In the case where the polyalkeneoxy group contains a plurality of alkeneoxy groups with different alkylene groups, the arrangement of the alkeneoxy groups in the polyalkeneoxy group may be random, or may be a block arrangement, Arrangements with alternating patterns are also possible. The number of carbon atoms in the alkylene group (in the case where the alkylene group has a substituent, the number of carbon atoms including the substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, and 2 to 5 2 to 4 are still more preferable, 2 or 3 are particularly preferable, and 2 is the most preferable. Moreover, the said alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. are mentioned. Moreover, it is preferable that the number of alkeneoxy groups contained in the polyalkeneoxy group (the number of repetitions of the polyalkeneoxy group) is 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoints of solvent solubility and solvent resistance, the polyalkeneoxy group includes polyvinyloxy group, polypropeneoxy group, polytrimethyleneoxy group, polytetramethyleneoxy group, a plurality of vinyloxy groups and a plurality of A group obtained by bonding two propeneoxy groups is preferred, polyvinyloxy or polypropeneoxy is more preferred, and polyvinyloxy is further preferred. In the above-mentioned groups obtained by bonding a plurality of vinyloxy groups and a plurality of propeneoxy groups, the vinyloxy groups and the propeneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged alternately, etc. patterned. Several preferred aspects such as vinyloxy in these groups are repeated as described above.

In formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor can form a conjugate base with a tertiary amine compound having an ethylenically unsaturated bond. As an example of the tertiary amine compound which has such an ethylenically unsaturated bond, N,N- dimethylamino propyl methacrylate is mentioned.

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group and a carboxyl group, but an acetal group, a ketal group, a silyl group, and a silyl ether A group, a tertiary alkyl ester group, etc. are 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 tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, and ethoxymethyl. group, trimethylsilyl group, tertiary butoxycarbonyl methyl group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is 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 10% by mass or more, and preferably 20% by mass or less.

Moreover, in order to improve the adhesiveness with a board|substrate, a polyimide precursor may be copolymerized with the aliphatic group which has a siloxane structure. Specifically, as the diamine, an aspect in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like are used can be mentioned.

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價的有機基，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價的有機基，R ¹¹³及R ¹¹⁴中的至少一者為包含聚合性基之基團，兩者為包含聚合性基之基團為較佳。 Preferably, the repeating unit represented by the formula (2) is the repeating unit represented by the formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By making the polyimide precursor contain the repeating unit represented by the formula (2-A), the width of the exposure latitude can be increased. Formula (2-A) [Chemical Formula 11]

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

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each 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. In addition, structural isomers of the repeating unit represented by the formula (2) may also be included. In addition, it goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of the above formula (2).

As an embodiment of the polyimide precursor in the present invention, the content of the repeating unit represented by the formula (2) is 50 mol % or more of all 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 total content is not particularly limited, and all the repeating units in the polyimide precursor other than the terminal may be repeating units represented by formula (2).

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

式（3）中，R ¹²¹表示2價的有機基，R ¹²²表示4價的有機基，R ¹²³及R ¹²⁴分別獨立地表示氫原子或1價的有機基。 [Polybenzoxazole Precursor] The structure and the like of the polybenzoxazole precursor used in the present invention are not particularly limited, but it is preferable to include a repeating unit represented by the following formula (3). [Chemical formula 12]

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.

In formula (3), R ¹²³ and R ¹²⁴ have the same meanings as R ¹¹³ in formula (2), respectively, and the 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. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a straight-chain aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable. As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferred, including a linear or branched (preferably linear) aliphatic group and 2 -COOH dicarboxylic acids are more preferred. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, and further preferably 4 to 15, 5 to 10 is particularly good. The straight-chain aliphatic group is preferably an alkylene group. Examples of the dicarboxylic acid containing a straight-chain aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, and succinic acid. acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexanoic acid Fluoroglutaric 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, dodecafluoroic acid Suberic 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, tridecanedioic acid acid, tetracosanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacosanedioic acid, Tridecanedioic acid, tridecanedioic acid, diglycolic acid, dicarboxylic acid represented by the following formula, and the like.

（式中，Z為碳數1～6的烴基，n為1～6的整數。） [Chemical formula 13]

(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, the following dicarboxylic acid having an aromatic group is preferred, and the following dicarboxylic acid including only a group having an aromatic group and two -COOH is more preferred.

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-之群組中的2價的基團，*分別獨立地表示與其他結構的鍵結部位。 [Chemical formula 14]

In the formula, A represents selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ - and -C(CH ₃ ) ₂ For a divalent group in the group of -, * each independently represents a bonding site with other structures.

Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and phthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as that of R ¹¹⁵ in the above formula (2), and the preferred range is also the same. R ¹²² is also preferably a group derived from a bisaminophenol derivative. Examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-diaminophenol. Hydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl, 4,4'-diamine bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane 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'-dihydroxybenzophenone, 3 ,3'-Diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4 ,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino- 4,6-Dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferable.

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價的取代基，氫原子或烴基為較佳，氫原子或烷基為更佳。又，R ¹²²為上述式所表示之結構亦較佳。在R ¹²²為上述式所表示之結構之情況下，在共計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其他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，或者2個*為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位為更佳，2個*為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位為進一步較佳。 [Chemical formula 15]

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

It is also preferable that the bisaminophenol derivative is a compound represented by the formula (As). [Chemical formula 16]

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 formula Organic groups in the group of (A-sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, and a cyclic alkyl group, which may be the same or different. R ₃ is any one of a hydrogen atom, a straight-chain or branched-chain alkyl group, an alkoxy group, an aryloxy group, and a cyclic alkyl group, which may be the same or different.

（式（A-sc）中，*表示與上述式（A-s）所表示之雙胺基苯酚衍生物的胺基苯酚基的芳香環鍵結。） [Chemical formula 17]

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

In the above formula (As), it is considered that having a substituent at the ortho position of the phenolic hydroxyl group, that is, also on R ₃ will make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and it will be higher when hardening at a low temperature is further improved. It is particularly preferable in terms of the effect of the cyclization rate.

In addition, in the above formula (As), when R ₂ is an alkyl group and R ₃ is an alkyl group, the effect of maintaining high transparency to i-rays and high cyclization rate during curing at low temperature is preferable.

In addition, in the above formula (As), it is more preferable that R ₁ is an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group for R ₁ include straight-chain or branched alkyl groups having 1 to 8 carbon atoms, wherein high transparency to i-rays and low temperature are maintained while maintaining high transparency. -CH 2 -, -CH(CH 3 )-, - -CH 2 -, -CH(CH 3 )-, - -CH ₂ -, -CH(CH ₃ )-, - C(CH ₃ ) ₂ - is better.

As a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A No. 2013-256506, and these The contents are 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 Japanese Patent Laid-Open No. 2013-256506, which are incorporated into the present specification. middle. Of course, it is not limited to these, it goes without saying.

In addition to the repeating unit of the above formula (3), the polybenzoxazole precursor may 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 in terms of suppressing the occurrence of warpage accompanying ring closure.

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，其餘為氫原子或碳數1～30的有機基，其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，亦可以為無規聚合。關於Z部分的莫耳%，a結構為5～95莫耳%、b結構為95～5莫耳%，a+b為100莫耳%。 [Chemical formula 18]

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

In the formula (SL), as preferable Z, those in which R ^5s and R ^6s in the structure b are phenyl groups can be mentioned. Moreover, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the above molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be more effectively reduced, 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 the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride as the repeating unit. Examples of such tetracarboxylic acid residues include R ¹¹⁵ in the formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and still more preferably 22,000 to 28,000. Moreover, as for the number average molecular weight (Mn), 7,200-14,000 are preferable, 8,000-12,000 are more preferable, 9,200-11,200 are still more preferable. The dispersity of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly specified, 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 further preferred, and 2.2 or less is preferred. for further better. Also, in the case where the resin composition contains a plurality of polybenzoxazole precursors as the specific resin, the weight average molecular weight, number average molecular weight and dispersion degree of at least one polybenzoxazole precursor are within the above-mentioned ranges. good. 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 types of polybenzoxazole precursors as one resin are respectively within the above-mentioned ranges.

式（PAI-2）中，R ¹¹⁷表示3價的有機基，R ¹¹¹表示2價的有機基，A ²表示氧原子或-NH-，R ¹¹³表示氫原子或1價的有機基。 [Polyamide imide precursor] It is preferable that the polyamide imide precursor contains a repeating unit represented by the following formula (PAI-2). [Chemical formula 19]

In 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.

In the formula (PAI-2), R ¹¹⁷ can be exemplified by linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, heteroaromatic groups or single bonds or through linking groups. A group obtained by linking two or more groups, such as a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, Preferably, an aromatic group having 6 to 20 carbon atoms or a single bond or a group obtained by combining two or more of these through a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms or a single bond or a linking group is preferred. A group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms is more preferred. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) ₂ -, alkylene, halogenated alkylene, arylidene, or two or more of these bonds The linking group formed is preferably, -O-, -S-, alkylene, halogenated alkylene, arylidene, or the linking group formed by bonding two or more of these 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 further preferable. As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Moreover, as a halogen atom in the said halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted with halogen atoms, but it is preferable that all hydrogen atoms be substituted with halogen atoms. As an example of a preferable halogenated alkylene group, a (ditrifluoromethyl)methylene group etc. are mentioned. As the above-mentioned arylidene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.

Further, 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 referred to as a tricarboxylic acid compound. Two carboxyl groups among the three carboxyl groups of the above-mentioned tricarboxylic acid compound may be acid anhydrided. As the tricarboxylic acid compound which may be halogenated to be used in the production of the polyamide imide precursor, a branched aliphatic, cyclic, or aromatic tricarboxylic acid compound, etc. can be mentioned. Only one type of these tricarboxylic acid compounds may be used, or two or more types may be used.

Specifically, the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, A tricarboxylic acid compound of an aromatic group having 6 to 20 carbon atoms, a single bond, or a group obtained by combining two or more of these through a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or a single bond is preferable. A bond or a tricarboxylic acid compound of a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a linking group is more preferable.

In addition, specific examples of the tricarboxylic acid compound include single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ - Or phenylene to connect 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalene tricarboxylic acid, phthalate Compounds of formic acid (or, phthalic anhydride) and benzoic acid, 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 ammonium chloride).

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

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

In formula (PAI-1), R ¹¹⁶ represents a divalent organic group, and R ¹¹¹ represents a divalent organic group. In formula (PAI-1), R ¹¹⁶ can be exemplified by linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, heteroaromatic groups, or single bonds or through linking groups. A group obtained by linking two or more groups, such as a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, Preferably, an aromatic group having 6 to 20 carbon atoms or a single bond or a group obtained by combining two or more of these through a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms or a single bond or a linking group is preferred. A group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms is more preferred. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) ₂ -, alkylene, halogenated alkylene, arylidene, or two or more of these bonds The linking group formed is preferably, -O-, -S-, alkylene, halogenated alkylene, arylidene, or the linking group formed by bonding two or more of these 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 further preferable. As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Moreover, as a halogen atom in the said halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted with halogen atoms, but it is preferable that all hydrogen atoms be substituted with halogen atoms. As an example of a preferable halogenated alkylene group, a (ditrifluoromethyl)methylene group etc. are mentioned. As the above-mentioned arylidene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.

Further, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide. In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide. The carboxyl group in the dicarboxylic acid dihalide may be halogenated, for example, it is preferably chlorinated. That is, it is preferable that the dicarboxylic acid dihalide is a dicarboxylic acid dichloride compound. Examples of dicarboxylic acid compounds or dicarboxylic acid dihalides that may be halogenated to be used in the production of polyamide imide precursors include linear or branched aliphatic and cyclic aliphatic Or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides, etc. Only one type of these dicarboxylic acid compounds or dicarboxylic acid dihalides may be used, or two or more types may be used.

Specifically, the dicarboxylic acid compound or the dicarboxylic acid dihalide includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a A cyclic aliphatic group, an aromatic group having 6 to 20 carbon atoms, a single bond, or a dicarboxylic acid compound or a dicarboxylic acid dihalide of a group obtained by combining two or more of these groups by a linking group is relatively Preferably, a dicarboxylic acid compound or dicarboxylic acid dihalogenation containing an aromatic group having 6 to 20 carbon atoms or a single bond or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a linking group Things are better.

Further, specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetra Fluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylsuccinic acid Glutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, hexanedioic acid acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, tenanedioic acid Heptanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid, behenanedioic acid, tetracosanedioic acid, tetracosanedioic acid , Pentadecanedioic acid, Hexadecanedioic acid, Heptacosanedioic acid, Hecosanedioic acid, Nonacosanedioic acid, Triacosanedioic acid, Triacosanedioic acid, Triacosanedioic acid Dodecanedioic 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 a dicarboxylic acid dihalide, the compound of the structure formed by halogenating two carboxyl groups in the specific example of the said dicarboxylic acid compound is mentioned.

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

Moreover, it is also preferable that the polyamide imide precursor has a fluorine atom in the structure. The content of fluorine atoms in the polyimide imide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

Moreover, in order to improve the adhesiveness with a board|substrate, the aliphatic group which has a siloxane structure may be copolymerized with a polyamide imide precursor. Specifically, as the diamine component, an aspect in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like are used can be mentioned.

As one 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 indicated repeating units is 50 mol % or more of all 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 repeating units in the polyamide imide precursor except the terminal may be repeating units represented by formula (PAI-2), and formula (PAI-1). Any one of the repeating unit and the repeating unit represented by formula (2). Moreover, as another embodiment of the polyamide imide 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 In the form of more than 50 mol% of all 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 polyamide imide precursor except the terminal may be the repeating units represented by the formula (PAI-2) or the formula (PAI-1). Any of the repeating units.

The weight average molecular weight (Mw) of the polyamide imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, further preferably 10,000 to 50,000. Moreover, as for the number average molecular weight (Mn), 800-250,000 are preferable, 2,000-50,000 are more preferable, 4,000-25,000 are still more preferable. The molecular weight of the polyamide imide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the dispersion degree of the molecular weight of the polyamide imide precursor is not particularly limited, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. Moreover, in the case where the resin composition contains a plurality of polyamide imide precursors as a specific resin, the weight average molecular weight, number average molecular weight and degree of dispersion of at least one polyamide imide precursor are within the above-mentioned ranges is better. 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 types of polyamide imide precursors as one resin are respectively within the above ranges.

[Method for producing polyimide precursor, etc.] The polyimide precursor and the like can be obtained, for example, by a method of reacting tetracarboxylic dianhydride and diamine at low temperature, and by reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamide A method of esterifying an amine acid with a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting it in the presence of a diamine and a condensing agent, by A method in which tetracarboxylic dianhydride and alcohol are used to obtain a diester, and the remaining dicarboxylic acid is halogenated using a halogenating agent, followed by a method of reacting it with a diamine. In the above-mentioned production method, a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is halogenated using a halogenating agent and reacted with a diamine is more preferable. As the above-mentioned condensing agent, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-Carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, etc. As said alkylating agent, N,N- dimethylformamide dimethyl acetal, N,N- dimethylformamide diethyl acetal, N,N-dialkylformamide can be mentioned Amine dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, etc. As said halogenating agent, thionyl chloride, oxalyl chloride, phosphorus oxychloride, etc. are mentioned. In the production method of a polyimide precursor or the like, it is preferable to use an organic solvent when the reaction is carried out. The organic solvent may be one type or two or more types. The organic solvent can be appropriately set depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, and ethyl propionate. , dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the production method of a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types. The basic compound can be appropriately set depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N- Dimethyl-4-aminopyridine and the like.

-Capping agent- In the production method of the polyimide precursor or the like, in order to further improve the storage stability, it is preferable to seal the carboxylic acid anhydride, acid anhydride derivative or amine group remaining at the resin end of the polyimide precursor or the like. When sealing carboxylic acid anhydrides and acid anhydride derivatives remaining at the resin end, examples of the blocking agent include monohydric alcohols, phenols, thiols, thiophenols, monoamines, and the like, from the viewpoint of reactivity and film stability. , it is better to use monohydric alcohols, phenols or monoamines. Preferable compounds of monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloroethanol Primary alcohols such as methanol and furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, and tertiary alcohols such as tertiary butanol and adamantanol alcohol. Preferable compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Moreover, as preferable compound of monoamine, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7- aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6- aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7- aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminowater Sylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these can be used, and a plurality of different terminal groups can be introduced by reacting a plurality of terminal blocking agents. Moreover, when sealing the amine group of a resin terminal, it can seal with the compound which has a functional group which can react with an amine group. The preferred sealants for amine groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, etc., carboxylic acid anhydrides, carboxylic acid chlorides are more preferred . Preferable compounds of the carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-di Carboxylic acid anhydride, etc. In addition, as a preferable compound of the carboxylic acid chloride, acetyl chloride, acryl chloride, acryl chloride, methacryloyl chloride, trimethyl acetyl chloride, cyclohexane methyl chloride, 2-ethyl chloride can be mentioned. Hexyl chloride, cinnamon chloride, 1-adamantanecarboxy chloride, heptafluorobutane chloride, stearate chloride, benzyl chloride, etc.

-Solid Precipitation- When producing a polyimide precursor or the like, a step of precipitating a solid may be included. Specifically, after filtering out the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction liquid as necessary, the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol, or a mixed solution thereof to make the polymer into a It is possible to obtain a polyimide precursor or the like by precipitation as a solid by analysis and drying. In order to improve the degree of purification, operations such as redissolving, reprecipitating, and drying the polyimide precursor and the like may be repeated. Further, a step of removing ionic impurities using an ion exchange resin may be included.

〔content〕 The content of the specific resin in the resin composition of the present invention is preferably 20 mass % or more, more preferably 30 mass % or more, more preferably 40 mass % or more, and 50 mass % with respect to the total solid content of the resin composition. The above is further preferred. Moreover, the content of the resin in the resin composition of the present invention is preferably 99.5 mass % or less, more preferably 99 mass % or less, more preferably 98 mass % or less, and 97 mass % or less with respect 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 two or more kinds are included, the total amount is preferably within the above range.

Moreover, it is also preferable that the resin composition of this invention contains at least 2 types of resin. 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 kinds of specific resins, for example, it contains 2 different from the structure (R ¹¹⁵ described in the above formula (2)) derived from the dianhydride which is a polyimide precursor. More than one polyimide precursor is preferred.

<Other resins> The resin composition of the present invention may contain the above-mentioned specific resins and other resins different from the specific resins (hereinafter, also simply referred to as “other resins”). Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylic acid amide resins, and urethane resins , butyraldehyde resin, styrene resin, polyether resin, polyester resin, etc. For example, by further adding a (meth)acrylic resin, a resin composition excellent in coatability can be obtained, and a pattern (hardened product) excellent in solvent resistance can be obtained. For example, in place of or in addition to the polymerizable compound described later, a polymerizable group having a weight average molecular weight of 20,000 or less with a high value of polymerizable groups (for example, the molar content of the polymerizable group in 1 g of resin is 1×10 ^-3 ) molar/g or more) (meth)acrylic resin is added to the resin composition to improve the coatability of the resin composition, the solvent resistance of the pattern (hardened product), and the like.

When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 1% by mass or more with respect to the total solid content of the resin composition. Preferably, 2 mass % or more is still more preferable, 5 mass % or more is still more preferable, and 10 mass % or more is still further preferable. In addition, the content of other resins in the resin composition of the present invention is preferably 80 mass % or less, more preferably 75 mass % or less, more preferably 70 mass % or less, and 60 mass % or less with respect to the total solid content of the resin composition. It is still more preferable that it is not more than 50 mass %, and it is still more preferable that it is not more than 50 mass %. Moreover, as a preferable aspect of the resin composition of this invention, the aspect in which content of another resin is a low content can also be used. In the above aspect, the content of other resins is preferably 20 mass % or less, more preferably 15 mass % or less, more preferably 10 mass % or less, and 5 mass % or less with respect to the total solid content of the resin composition. It is still more preferable, and 1 mass % or less is still more preferable. The lower limit of the content is not particularly limited, as long as it is 0 mass % or more. The resin composition of this invention may contain only 1 type of other resin, and may contain 2 or more types. When two or more kinds are included, the total amount is preferably within the above range.

<Specific photobase generator> The curable resin composition of this invention contains the photobase generator (specific photobase generator) which has an alkoxysilyl group. The photobase generator having an alkoxysilyl group is preferably a structure that generates a base having both a silicon atom derived from an alkoxysilyl group and a basic site. The alkoxysilyl group may be any of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group, but a trialkoxysilyl group is preferable . As the alkoxy group in the above-mentioned alkoxysilyl group, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and an ethoxy group is further preferable. The number of the alkoxysilyl groups in the specific photobase generator is not particularly limited, but 1 to 4 are preferable, 1 or 2 are more preferable, and 1 is even more preferable.

The specific photobase generator may be a compound that generates a base by irradiation with light, but a compound that generates a base by the action of light with a wavelength of 100 to 600 nm is preferable, and the action of light with a wavelength of 200 to 450 nm is preferable. Compounds that generate bases are more preferred.

In addition, as the base generated from the specific photobase generator, the pKa in DMSO (dimethylsulfite) of the conjugated acid is preferably 9 to 30, more preferably 10 to 25, and even more preferably 10 to 20 . pKa represents the logarithm of the reciprocal of the first dissociation constant for an acid and can be found in Determination of Organic Structures by Physical Methods (Authors: Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; Edited: Braude, E. A., Nachod , F. C.; Academic Press, New York, 1955) or Data for Biochemical Research (Author: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using the software of ACD/pKa (manufactured by ACD/Labs) was used as pKa.

A specific photobase generator may not contain a salt structure in a structure, and may contain a salt structure. In the case where a specific base generator does not contain a salt structure in its structure, it is preferable to latentize the generated base using a covalent bond, and use an amide bond, a urethane bond, or an oxime bond to make the generated base Potentially better. When a specific base generator contains a salt structure in a structure, as a salt structure, an amine salt structure or a quaternary ammonium salt structure is preferable.

The specific photobase generator is preferably a compound represented by any one of the following formulae (1-1) to (1-3). Among these, the compound represented by formula (1-1) is preferable from the viewpoint of storage stability and insulating properties. From the viewpoints of storage stability and chemical resistance, the compound represented by the formula (1-2) is preferable. From the viewpoint of elongation at break, the compound represented by the formula (1-3) is preferable. [Chemical formula 21]

In formula (1-1), X ¹ represents an aryl group having a hydroxyl or carboxyl group, R ¹ and R ² represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ¹ and R ² can be bonded to form a ring structure, Y ¹ represents a divalent linking group, and Z ¹ represents an alkoxysilyl group. In formula (1-2), X ² represents a substituted or unsubstituted anthracene structure or an aryl group having a nitro group, R ³ and R ⁴ independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ³ and R ⁴ can be bonded to form a ring structure, Y ² represents a divalent linking group, Z ² represents an alkoxysilyl group; In formula (1-3), X ³ and X ⁴ independently represent substituted or Unsubstituted aryl group, R ⁵ represents a monovalent organic group, R ⁶ to R ⁹ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a group having an alkoxysilyl group, R ⁶ to At least two of R ⁹ may be bonded to form a ring structure, and at least one of R ⁶ to R ⁹ is a group having an alkoxysilyl group.

In formula (1-1), X ¹ represents an aryl group having a hydroxyl group or a carboxyl group, preferably an aryl group having a hydroxyl group. As the above-mentioned aryl group, an aromatic hydrocarbon group is preferable, and a phenyl group is more preferable. The position of the hydroxyl group or carboxyl group in the above-mentioned aryl group is not particularly limited, but the above-mentioned aryl group is a bonding site to the carbon atom contained in the vinyl group to which X ¹ described in the formula (1-1) is bonded. It is preferable that the bonding site with the above-mentioned hydroxyl group or carboxyl group is an adjacent position. In the present invention, the adjacent position refers to a ring member having a certain bonding site in the ring structure and a ring member having a different bonding site adjacent to the ring member, and if the aryl group is a phenyl group, it means ortho. In formula (1-1), R ¹ and R ² represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms are more suitable. Preferably, a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms is more preferable. R ¹ and R ² may be bonded to form a ring structure, and as the formed ring structure, a 5-membered ring structure or a 6-membered ring structure is preferable, and a 6-membered ring structure is more preferable. As an example of the ring structure formed, a piperidine ring structure is mentioned. In formula (1-1), Y ¹ represents a divalent linking group, a hydrocarbon group or two or more selected from the group consisting of a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group and -NR ^N - Groups obtained by structural bonding are preferred, and hydrocarbon groups are more preferred. The above-mentioned hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aliphatic hydrocarbon group is preferable, and a saturated aliphatic hydrocarbon group is more preferable. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 2 to 6. The above R ^N represents a hydrogen atom or a hydrocarbon group, a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable. In the formula (1-1), Z ¹ represents an alkoxysilyl group, and preferable aspects of the alkoxysilyl group are as described above.

In formula (1-2), X ² represents a substituted or unsubstituted anthracene structure or an aryl group with a nitro group, and an unsubstituted anthracene structure or an aromatic hydrocarbon group with a nitro group is preferred, and unsubstituted An anthracene structure or a phenyl group having a nitro group is preferable. The number of nitro groups in the aryl group having a nitro group may be two or more, but one is preferable. Preferably, the bonding site to the carbon atom bonded to X ² described in the formula (1-2) and the bonding site to at least one of the nitro groups are adjacent positions in the aryl group. In formula (1-2), R ³ , R ⁴ , Y ² and Z ² have the same meanings as R ¹ , R ² , Y ¹ and Z ¹ in formula (1-1), respectively, and the preferred embodiments are also the same .

式（AS-1）中，L ¹表示2價的連接基，Z ³表示烷氧基甲矽烷基。 L ¹為烴基或選自包括烴基、醚鍵、羰基、硫醚鍵、磺醯基及-NR ^N-之群組中的2個以上的結構鍵結而獲得之基團為較佳，烴基為更佳。 上述烴基的碳數為1～10為較佳，2～6為更佳。 上述R ^N如上所述。 Z ³的較佳態樣如上述烷氧基甲矽烷基的較佳態樣。 In formula (1-3), X ³ and X ⁴ each independently represent a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted aromatic hydrocarbon group. In particular, X ³ is preferably a phenyl group and X ⁴ is a phenylene group. It does not specifically limit as a substituent in ^X3 and ^X4 , A well-known substituent can be provided in the range which can obtain the effect of this invention. In formula (1-3), R ⁵ represents a monovalent organic group, preferably a hydrocarbon group, and more preferably an alkyl group. The carbon number of the hydrocarbon group in R ⁵ is preferably 1-10, more preferably 1-4, and particularly preferably 1. Among these, it is particularly preferred that R ⁵ is methyl. In formula (1-3), R ⁶ to R ⁹ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a group having an alkoxysilyl group. At least one of R ⁶ to R ⁹ is a group having an alkoxysilyl group. As a group which has an alkoxysilyl group among R6 ^{- R9} , the group represented by following formula (AS-1) is mentioned. [Chemical formula 22]

In formula (AS-1), L ¹ represents a divalent linking group, and Z ³ represents an alkoxysilyl group. L ¹ is preferably a hydrocarbon group or a group obtained from two or more structural bonds selected from the group consisting of a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group and -NR ^N -, and the hydrocarbon group is better. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 2 to 6. The above R ^N is as described above. The preferred embodiment of Z ³ is the preferred embodiment of the above-mentioned alkoxysilyl group.

At least one of R ⁶ to R ⁹ is a group having an alkoxysilyl group, and one or two are preferably a group having an alkoxysilyl group. Among R ⁶ to R ⁹ , a group different from a group having an alkoxysilyl group is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms is Preferably, a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable.

At least two of R ⁶ to R ⁹ may be bonded to form a ring structure, and as the formed ring structure, a 5-membered ring structure or a 6-membered ring structure is preferable, and a 6-membered ring structure is more preferable. As an example of the ring structure formed, a piperidine ring structure is mentioned.

The molecular weight of the specific photobase generator is not particularly limited, but is preferably 2,000 or less, more preferably 1,000 or less, and even more preferably 500 or less.

[化學式24]

As a specific example of a specific photobase generator, the compound of the following structure is mentioned. [Chemical formula 23]

[Chemical formula 24]

The content of the specific photobase generator in the curable resin composition of the present invention is preferably 0.01 to 5 mass %, more preferably 0.02 to 3 mass % with respect to the total solid content of the curable resin composition of the present invention, 0.05-2.5 mass % is more preferable. Only 1 type of specific photobase generator may be sufficient as it, and 2 or more types may be sufficient as it. When containing 2 or more types of specific photobase generators, it is preferable that the sum total is in the said range.

It is preferable that the curable resin composition of the present invention further contains a compound having an alkoxysilyl group and not having photobase generating energy. As such a compound, the compound which has an alkoxysilyl group as a polymerizable group in the compound B mentioned later, and the compound corresponding to another silane coupling agent mentioned later can be mentioned.

<Compound B> It is preferable that the curable resin composition of this invention contains the compound B which is a compound which has a polymerizable group and an azole group.

[Polymerizable group] Examples of the polymerizable group in compound B include radically polymerizable groups, alkoxysilyl groups, epoxy groups, oxetanyl groups, methylol groups, alkoxymethyl groups, and (blocked) isocyanates known polymerizable groups such as radicals. Among these, from the viewpoint of the adhesiveness between the cured product and the metal, the compound B contains, as a polymerizable group, at least one group selected from the group consisting of a radical polymerizable group and an alkoxysilyl group is better.

The above-mentioned alkoxysilyl group may be any of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group, but from the viewpoint of the adhesiveness between the cured product and the metal, Trialkoxysilyl groups are preferred. As the alkoxy group in the above-mentioned alkoxysilyl group, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and an ethoxy group is further preferable.

As the above-mentioned radically polymerizable group, a group having an ethylenically unsaturated bond is preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, and the like, which are directly bonded to an aromatic ring and have a vinyl group which may be substituted, and (meth)acryloyl group. An amine group, a (meth)acryloyloxy group, etc., a (meth)acryloyloxy group is preferable. Compound B may have only one polymerizable group, or may have two or more. Moreover, compound B may have only 1 type of polymerizable group, and may have 2 or more types. For example, it may have a radical polymerizable group and an alkoxysilyl group.

[azolyl] The oxazolyl group in compound B should be a group having a structure obtained by removing one or more hydrogen atoms from a hetero 5-membered ring compound containing one or more nitrogen atoms as ring members and which may have a substituent or a condensed ring structure A group is sufficient, but a group having a structure obtained by removing one or more hydrogen atoms from a hetero 5-membered ring compound containing only one or more nitrogen atoms and one or more carbon atoms as ring members and which may have substituents is better. From the viewpoint of the adhesiveness between the cured product and the metal, the azole group includes a pyrrole ring, a pyrazole ring, an indazole ring, an imidazole ring, a benzimidazole ring, a 1,2,3-triazole ring, a 1,2 , 4-triazole ring, benzotriazole ring or tetrazole ring has a structure obtained by removing one or more hydrogen atoms. The group of the structure obtained by removing one or more hydrogen atoms from the triazole ring or the benzotriazole ring is more preferable.

式（B-1）中，R ^B1表示與具有聚合性基之結構的鍵結部位、氫原子或不具有聚合性基的1價的有機基，Z ^B1～Z ^B4分別獨立地表示=CR ^B7-或氮原子，R ^B7表示與具有聚合性基之結構的鍵結部位、氫原子或不具有聚合性基的1價的有機基，式（B-1）中所包含之R ^B1及R ^B7中的至少1個表示與具有聚合性基之結構的鍵結部位； 式（B-2）中，R ^B2～R ^B6分別獨立地表示與具有聚合性基之結構的鍵結部位、氫原子或不具有聚合性基的1價的有機基，Z ^B5及Z ^B6分別獨立地表示=CR ^B8-或氮原子，R ^B8表示與具有聚合性基之結構的鍵結部位、氫原子或不具有聚合性基的1價的有機基，式（B-2）中所包含之R ^B2～R ^B6及R ^B8中的至少1個表示與具有聚合性基之結構的鍵結部位。 Moreover, it is preferable that the azole group in compound B is a group represented by following formula (B-1) or following formula (B-2). [Chemical formula 25]

In formula (B-1), R ^B1 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group, and Z ^B1 to Z ^B4 each independently represent =CR ^B7 - or a nitrogen atom, R ^B7 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group, R ^B1 and R ^B7 included in the formula (B-1) At least one of them represents a bonding site with a structure having a polymerizable group; In formula (B-2), R ^B2 to R ^B6 each independently represent a bonding site with a structure having a polymerizable group, a hydrogen atom or A monovalent organic group without a polymerizable group, Z ^B5 and Z ^B6 each independently represent =CR ^B8 - or a nitrogen atom, R ^B8 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a non-polymerizable group In the monovalent organic group of the polymerizable group, at least one of R ^B2 to R ^B6 and R ^B8 included in the formula (B-2) represents a bonding site with a structure having a polymerizable group.

In formula (B-1), R ^B1 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group, and the bonding site with a structure having a polymerizable group is: better. The monovalent organic group in R ^B1 is not particularly limited, and known organic groups can be used as long as the effects of the present invention can be obtained, but hydrocarbon groups or amino groups are preferable, and alkyl groups or amino groups are more preferable . Although the carbon number of the said hydrocarbon group or alkyl group is not specifically limited, 1-10 are preferable, and 1-4 are more preferable. The above-mentioned amino group may be a substituted amino group or an unsubstituted amino group.

In formula (B-1), Z ^B1 to Z ^B4 each independently represent =CR ^B7 - or a nitrogen atom. Among them, two of Z ^B1 to Z ^B4 are nitrogen atoms and two of them are =CR ^B7 -, and one of Z ^B1 to Z ^B4 is a nitrogen atom and three of them are =CR ^B7 -, or The aspect in which three of Z ^B1 to Z ^B4 are nitrogen atoms and one is =CR ^B7 - is preferable. Also, among these, Z ^B1 and Z ^B3 are nitrogen atoms and Z ^B2 and Z ^B4 are =CR ^B7 -, Z ^B1 and Z ^B2 are nitrogen atoms, and Z ^B3 and Z ^B4 are =CR ^B7 - In the case where Z ^B2 is a nitrogen atom and Z ^B1 , Z ^B3 and Z ^B4 are =CR ^B7 - or Z ^B1 , Z ^B2 and Z ^B3 are nitrogen atoms and Z ^B4 is =CR ^B7 - More preferably, Z ^B1 and Z ^B3 are nitrogen atoms and Z ^B2 and Z ^B4 are =CR ^B7 -. The above R ^B7 is preferably a hydrogen atom or a monovalent organic group. Moreover, when Z ^B1 , Z ^B2 and Z ^B3 are nitrogen atoms and Z ^B4 is =CR ^B7 -, it is preferable that R ^B7 is a bonding site with a structure having a polymerizable group. The preferable aspect of the monovalent organic group in R ^B7 is the same as the preferable aspect of the monovalent organic group in R ^B1 described above.

At least one of R ^B1 and R ^B7 included in the formula (B-1) represents a bonding site with a structure having a polymerizable group, and at least R ^B1 represents a bonding site with a structure having a polymerizable group. good. In addition, in the formula (B-1), only R ^B1 represents a bonding site with a structure having a polymerizable group, and R ^B7 independently represents a hydrogen atom or a monovalent organic group, which is also preferable in the present invention. One of the forms.

In formula (B-2), Z ^B5 and Z ^B6 each independently represent =CR ^B8 - or a nitrogen atom. Among them, the aspect in which both Z ^B5 and Z ^B6 represent a nitrogen atom or the aspect in which Z ^B5 represents a nitrogen atom and Z ^B6 represents =CR ^B8 - is preferable. In formula (B-2), when both Z ^B5 and Z ^B6 represent a nitrogen atom, it is preferable that R ^B6 represents a bonding site with a structure having a polymerizable group. Moreover, in formula (B-2), the aspect in which both Z ^B5 and Z ^B6 represent a nitrogen atom and only R ^B6 represents a bonding site with a structure having a polymerizable group is also one of the preferred aspects of the present invention. In formula (B-2), when Z ^B5 represents a nitrogen atom and Z ^B6 represents =CR ^B8 -, it is preferable that R ^B8 represents a bonding site with a structure having a polymerizable group. In addition, in the formula (B-2), Z ^B5 represents a nitrogen atom, Z ^B6 represents =CR ^B8 -, and only R ^B8 represents a bonding site with a structure having a polymerizable group is also preferred in the present invention. One of the forms.

In formula (B-2), it is preferable that R ^B2 to R ^B5 each independently represent a hydrogen atom or a monovalent organic group which does not have a polymerizable group. The preferable aspect of the monovalent organic group in R ^B2 to R ^B5 is the same as the preferable aspect of the monovalent organic group in R ^B1 described above. In formula (B-2), when Z ^B5 represents a nitrogen atom and Z ^B6 represents =CR ^B8 -, it is preferable that R ^B6 represents a hydrogen atom or a monovalent organic group having no polymerizable group. The preferable aspect of the monovalent organic group in R ^B6 is the same as the preferable aspect of the monovalent organic group in R ^B1 described above. In other cases, it is preferable that R ^B6 represents a bonding site with a structure having a polymerizable group. In particular, when Z ^B5 represents a nitrogen atom and Z ^B6 represents =CR ^B8 -, it is preferable that R ^B8 represents a bonding site with a structure having a polymerizable group. In the formula (B-2), R ^B8 preferably represents a bonding site with a structure having a polymerizable group. When both Z ^B5 and Z ^B6 represent =CR ^B8 -, one of R ^B8 represents a bonding site with a structure having a polymerizable group, and the other represents a hydrogen atom or a monovalent organic group. The preferable aspect of the monovalent organic group in R ^B8 is the same as the preferable aspect of the monovalent organic group in R ^B1 described above.

At least one of R ^B2 to R ^B6 and R ^B8 contained in the formula (B-2) represents a bonding site with a structure having a polymerizable group, and at least R ^B6 or R ^B8 represents a structure with a polymerizable group. The bonding site is better. Moreover, in formula (B-2), only one of R ^B6 and R ^B8 represents a bonding site with a structure having a polymerizable group, and the other of R ^B6 and R ^B8 and R ^B2 to R ^B5 are respectively An aspect that independently represents a hydrogen atom or a monovalent organic group is also one of the preferred aspects of the present invention.

Among these, the azolyl group is preferably a group represented by any one of the following formulae (B-3) to (B-6). [Chemical formula 26]

In formula (B-3) to formula (B-6), R ^B9 to R ^B20 each independently represent a hydrogen atom or a monovalent organic group without a polymerizable group, and * represents a bond with a structure having a polymerizable group knot site. In formula (B-3) to formula (B-6), the preferable aspect of the monovalent organic group in R ^B9 to R ^B20 is the same as the preferable aspect of the monovalent organic group in R ^B1 described above.

式（B-7）中，X ¹表示唑基，L ¹表示單鍵或2價的連接基，R ^B21表示氫原子或1價的有機基，*表示與具有聚合性基之結構的鍵結部位。 式（B-8）中，X ²表示唑基，L ²表示單鍵或2價的連接基，R ^B22表示氫原子或1價的有機基，*表示與具有聚合性基之結構的鍵結部位。 式（B-9）中，X ³表示唑基，L ³表示單鍵或2價的連接基，R ^B23及R ^B24分別獨立地表示氫原子或1價的有機基，*表示與具有聚合性基之結構的鍵結部位。 式（B-7）中，X ¹中之唑基的較佳態樣如上所述。上述唑基中之與具有聚合性基之結構的鍵結部位和與式（B-7）中的L ¹的鍵結部位對應。 式（B-7）中，作為L ¹中之2價的連接基，烴基或由烴基與選自包括-O-、-S-、-C（=O）-、-S（=O） ₂-及-NR ^N-之群組中的至少1個基團的鍵結表示之基團為較佳，烴基為更佳。 上述R ^N如上所述。 作為上述烴基，飽和脂肪族烴基為較佳，伸烷基為更佳。 上述烴基或伸烷基的碳數為2～20為較佳，2～10為更佳。 式（B-7）中，R ^B21表示氫原子或1價的有機基，氫原子為較佳。R ^B21中之1價的有機基的較佳態樣與上述R ^B1相同。 式（B-8）中，X ²與式（B-7）中的X ¹的含義相同，L ²與式（B-7）中的L ¹的含義相同，R ^B22與式（B-7）中的R ^B21的含義相同，較佳態樣亦相同。 式（B-9）中，X ³與式（B-7）中的X ¹的含義相同，L ³與式（B-7）中的L ¹的含義相同，R ^B23及R ^B24分別獨立地與式（B-7）中的R ^B21的含義相同，較佳態樣亦相同。 From the viewpoint of the adhesiveness between the cured product obtained and the metal, it is preferable that the compound B has at least one group selected from the group consisting of an amide group, a urethane group, and a urea group. It is presumed that the interaction between the compound B and the specific resin is promoted by making the compound B have at least one group selected from the group consisting of an amide group, a urethane group, and a urea group, thereby improving the cured product and the metal. of tightness. The above-mentioned amide group, urethane group and urea group may be directly bonded to the azole group, or may be bonded via a linking group. As the above-mentioned linking group, a hydrocarbon group or a hydrocarbon group and at least one selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) ₂ - and -NR ^N - The group represented by the bond of the group is preferable, and the hydrocarbon group is more preferable. The above R ^N represents a hydrogen atom or a hydrocarbon group, a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable. The carbon number of the above-mentioned hydrocarbon group or alkylene group is preferably 2-20, more preferably 2-10. In the case where the compound B has an amide group, a urethane group or a urea group, the compound B has a structure represented by the following formula (B-7), (B-8) or formula (B-9) as a compound containing the above-mentioned azole The structure of amide group and amide group, urethane group or urea group is preferred. [Chemical formula 27]

In formula (B-7), X ¹ represents an azole group, L ¹ represents a single bond or a divalent linking group, R ^B21 represents a hydrogen atom or a monovalent organic group, and * represents a bond with a structure having a polymerizable group. part. In formula (B-8), X ² represents an azole group, L ² represents a single bond or a divalent linking group, R ^B22 represents a hydrogen atom or a monovalent organic group, and * represents a bond with a structure having a polymerizable group part. In formula (B-9), X ³ represents an azole group, L ³ represents a single bond or a divalent linking group, R ^B23 and R ^B24 each independently represent a hydrogen atom or a monovalent organic group, and * represents a polymerizable group with The bonding site of the base structure. In formula (B-7), the preferable aspect of the azole group in X ¹ is as described above. Among the above-mentioned azole groups, the bonding site with the structure having a polymerizable group corresponds to the bonding site with L ¹ in the formula (B-7). In formula (B-7), as the divalent linking group in L ¹ , a hydrocarbon group or a hydrocarbon group and a group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) ₂ A group represented by a bond of at least one group in the group of - and -NR ^N - is preferable, and a hydrocarbon group is more preferable. The above R ^N is as described above. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable. The carbon number of the above-mentioned hydrocarbon group or alkylene group is preferably 2-20, more preferably 2-10. In formula (B-7), R ^B21 represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom. The preferable aspect of the monovalent organic group in R ^B21 is the same as the above-mentioned R ^B1 . In formula (B-8), X ² has the same meaning as X ¹ in formula (B-7), L ² has the same meaning as L ¹ in formula (B-7), R ^B22 has the same meaning as formula (B-7) ) in R ^B21 has the same meaning, and the preferred aspect is also the same. In formula (B-9), X ³ has the same meaning as X ¹ in formula (B-7), L ³ has the same meaning as L ¹ in formula (B-7), and R ^B23 and R ^B24 are independently The meaning is the same as that of R ^B21 in formula (B-7), and the preferred aspects are also the same.

The compound B may be a compound having a molecular weight of less than 2,000 (hereinafter, also referred to as "low molecular weight compound B"), or may be a resin (hereinafter, also referred to as "resin B"). Moreover, it is also preferable that the curable resin composition contains both the low molecular weight compound B and the resin B from the viewpoint of the adhesiveness between the cured product and the metal.

[Low molecular compound B] The molecular weight of the low molecular weight compound B is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less. The number of polymerizable groups in the low molecular weight compound B is not particularly limited, but 1 to 10 are preferable, 1 to 4 are more preferable, and 1 or 2 are more preferable. The number of the azole groups in the low molecular weight compound B is not particularly limited, but 1 to 10 are preferable, 1 to 4 are more preferable, 1 or 2 are more preferable, and 1 is further preferable.

The low molecular weight compound B is preferably a compound represented by the following formula (BL-1). [Chemical formula 28]

式（L-1）中，L ¹表示單鍵或2價的連接基，R ^B21表示氫原子或1價的有機基，L ³表示n1+1價的連接基，n1表示1以上的整數，#表示與唑基的鍵結部位，*表示與聚合性基的鍵結部位。 式（L-2）中，L ²表示單鍵或2價的連接基，R ^B22及R ^B23分別獨立地表示氫原子或1價的有機基，L ⁴表示n2+1價的連接基，n2表示1以上的整數，#表示與唑基的鍵結部位，*表示與聚合性基的鍵結部位。 式（L-1）中，L ¹及R ^B21分別與式（B-7）中的L ¹及R ^B21的含義相同，較佳態樣亦相同。 式（L-1）中，L ³為烴基或由烴基與選自包括-O-、-S-、-C（=O）-、-S（=O） ₂-及-NR ^N-之群組中的至少1個基團的鍵結表示之基團為較佳。 上述R ^N如上所述。 作為上述烴基，飽和脂肪族烴基為較佳，伸烷基為更佳。 上述烴基或伸烷基的碳數為2～20為較佳，2～10為更佳。 式（L-1）中，n1為1～10的整數為較佳，1～4的整數為更佳，1或2為進一步較佳，1為特佳。 式（L-2）中，L ²、R ^B22及R ^B23分別與式（B-8）中的L ²、R ^B22及R ^B23的含義相同，較佳態樣亦相同。 式（L-2）中，L ⁴與式（L-1）中的L ³的含義相同，較佳態樣亦相同。 式（L-2）中，n2為1～10的整數為較佳，1～4的整數為更佳，1或2為進一步較佳，1為特佳。 式（BL-1）中，X ^LB中之聚合性基的較佳態樣如上所述。 式（BL-1）中，n為1～10的整數為較佳，1～4的整數為更佳，1或2為進一步較佳，1為特佳。 在n為2以上之情況下，式（BL-1）中包含複數個之L ^LA及X ^LB分別可以相同，亦可以不同。 式（BL-1）中，m為1～10的整數為較佳，1～4的整數為更佳，1或2為進一步較佳，1為特佳。 在m為2以上之情況下，式（BL-1）中包含複數個之X ^LB分別可以相同，亦可以不同。 In formula (BL-1), X ^LA represents an azole group, L ^LA represents a single bond or an m+1-valent linking group, X ^LB represents a polymerizable group, n represents an integer of 1 or more, and m represents an integer of 1 or more. In formula (BL-1), the preferable aspect of the azole group in ^XLA is as described above. In formula (BL-1), L ^LA is a single bond, a hydrocarbon group or a hydrocarbon group and is selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) ₂ - and -NR ^N The group represented by the bond of at least one group in the group of - is preferable. The above R ^N is as described above. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable. The carbon number of the above-mentioned hydrocarbon group or alkylene group is preferably 2-20, more preferably 2-10. In addition, in the formula (BL-1), the aspect in which L ^LA is a group represented by the following formula (L-1) or formula (L-2) is also one of the preferred aspects of the present invention. [Chemical formula 29]

In formula (L-1), L ¹ represents a single bond or a divalent linking group, R ^B21 represents a hydrogen atom or a monovalent organic group, L ³ represents an n1+1 valent linking group, and n1 represents an integer of 1 or more, # represents a bonding site with an azole group, and * represents a bonding site with a polymerizable group. In formula (L-2), L ² represents a single bond or a divalent linking group, R ^B22 and R ^B23 each independently represent a hydrogen atom or a monovalent organic group, L ⁴ represents an n2+1 valent linking group, and n2 represents an integer of 1 or more, # represents a bonding site with an azole group, and * represents a bonding site with a polymerizable group. In formula (L-1), L ¹ and R ^B21 have the same meanings as L ¹ and R ^B21 in formula (B-7), respectively, and the preferred embodiments are also the same. In formula (L-1), L ³ is a hydrocarbon group or a hydrocarbon group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) ₂ - and -NR ^N - The group represented by the bond of at least one group in the group is preferred. The above R ^N is as described above. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable. The carbon number of the above-mentioned hydrocarbon group or alkylene group is preferably 2-20, more preferably 2-10. In formula (L-1), n1 is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, more preferably 1 or 2, and particularly preferably 1. In formula (L-2), L ² , R ^B22 and R ^B23 have the same meanings as L ² , R ^B22 and R ^B23 in formula (B-8), respectively, and the preferred aspects are also the same. In the formula (L-2), L ⁴ has the same meaning as L ³ in the formula (L-1), and the preferred aspects are also the same. In formula (L-2), n2 is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, more preferably 1 or 2, and particularly preferably 1. In formula (BL-1), the preferable aspect of the polymerizable group in ^XLB is as described above. In formula (BL-1), n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, more preferably 1 or 2, and particularly preferably 1. When n is 2 or more, L ^LA and X ^LB including plural numbers in the formula (BL-1) may be the same or different, respectively. In formula (BL-1), m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, more preferably 1 or 2, and particularly preferably 1. When m is 2 or more, the plural X ^LBs included in the formula (BL-1) may be the same or different, respectively.

[Resin B] Resin B is preferably a resin having a repeating unit including an azole group and a repeating unit including a polymerizable group, or a resin having a repeating unit including an azole group and a polymerizable group, and has a repeating unit including an azole group and a polymerizable group. The resin of the repeating unit is better. The weight average molecular weight of the resin B is preferably 2,000 to 100,000, more preferably 3,000 to 70,000, and even more preferably 5,000 to 50,000. Moreover, it is preferable that resin B is an acrylic resin.

式（BA-1）中，L ³表示單鍵或2價的連接基，X ³表示唑基，R表示氫原子或甲基。 式（BA-1）中，L ³表示單鍵或2價的連接基。 作為上述2價的連接基，烴基或由烴基與選自包括-O-、-S-、-C（=O）-、-S（=O） ₂-及-NR ^N-之群組中的至少1個基團的鍵結表示之基團為較佳，烴基為更佳。 上述R ^N如上所述。 作為上述烴基，飽和脂肪族烴基為較佳，伸烷基為更佳。 上述烴基或伸烷基的碳數為2～20為較佳，2～10為更佳。 在該等之中，L ³為單鍵、下述式（BA-1-1）所表示之基團或下述式（BA-1-2）所表示之基團為較佳。 [化學式31]

式（BA-1-1）或式（BA-1-2）中，L ⁴表示2價的連接基，L ⁵表示單鍵或2價的連接基，L ⁶表示2價的連接基，L ⁷表示單鍵或2價的連接基，*表示與式（BA-1）中的羰基的鍵結部位，A ¹及A ²表示-O-或-NR ^N-，#表示與（BA-1）中的X ³的鍵結部位。 Resin B preferably contains a repeating unit represented by the following formula (BA-1) as a repeating unit containing an azole group. [Chemical formula 30]

In formula (BA-1), L ³ represents a single bond or a divalent linking group, X ³ represents an azole group, and R represents a hydrogen atom or a methyl group. In formula (BA-1), L ³ represents a single bond or a divalent linking group. As the above-mentioned divalent linking group, a hydrocarbon group or a hydrocarbon group and a hydrocarbon group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) ₂ - and -NR ^N - A group represented by a bond of at least one group is preferable, and a hydrocarbon group is more preferable. The above R ^N is as described above. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable. The carbon number of the above-mentioned hydrocarbon group or alkylene group is preferably 2-20, more preferably 2-10. Among these, L ³ is preferably a single bond, a group represented by the following formula (BA-1-1), or a group represented by the following formula (BA-1-2). [Chemical formula 31]

In formula (BA-1-1) or formula (BA-1-2), L ⁴ represents a divalent linking group, L ⁵ represents a single bond or a divalent linking group, L ⁶ represents a divalent linking group, L ⁷ represents a single bond or a divalent linking group, * represents a bonding site with a carbonyl group in the formula (BA-1), A ¹ and A ² represent -O- or -NR ^N- , and # represents a bond with (BA-1 ) in the bonding site of X ³ .

In formula (BA-1-1), L ⁴ is a hydrocarbon group or a hydrocarbon group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) ₂ - and -NR ^N - The group represented by the bond of at least one group in the group is preferable, and the hydrocarbon group is more preferable. The above R ^N is as described above. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable. The carbon number of the above-mentioned hydrocarbon group or alkylene group is preferably 2-20, more preferably 2-10.

In formula (BA-1-1), L ⁵ is preferably a single bond. When L ⁵ is a divalent linking group, the preferred aspect of L ⁵ is the same as the preferred aspect when L ¹ is a divalent linking group in the above formula (B-7).

In the formula (BA-1-2), L ⁶ has the same meaning as L ⁴ in the formula (BA-1-1), and the preferred aspects are also the same.

In formula (BA-1-2), it is preferable that L ⁷ is a divalent linking group. When L ⁷ is a divalent linking group, the preferred aspect of L ⁷ is the same as the preferred aspect when L ² is a divalent linking group in the above formula (B-8).

In formula (BA-1-1) or formula (BA-1-2), A ¹ and A ² represent -O- or -NR ^N -, and -O- is preferred. R ^N is as described above.

In formula (BA-1), the preferable aspect of the azole group in X ³ is as described above. Among the above-mentioned azole groups, the bonding site with the structure having a polymerizable group corresponds to the bonding site with L ³ in the formula (BA-1).

Resin B may contain only 1 type of repeating unit represented by Formula (BA-1), and may contain 2 or more types.

式（BA-2）中，A ³表示-O-或-NR ^N-，L ^P1表示2價的連接基，X ^P1表示聚合性基，R表示氫原子或甲基。 Resin B preferably contains a repeating unit represented by the following formula (BA-2) as a repeating unit containing a polymerizable group. [Chemical formula 32]

In formula (BA-2), A ³ represents -O- or -NR ^N -, L ^P1 represents a divalent linking group, X ^P1 represents a polymerizable group, and R represents a hydrogen atom or a methyl group.

In formula (BA-2), A ³ represents -O- or -NR ^N -, and -O- is preferable. R ^N is as described above.

In formula (BA-2), L ^P1 represents a 2-valent linking group, a hydrocarbon group or a hydrocarbon group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) ₂ - and The group represented by the bond of at least one group in the group of -NR ^N- is preferable, and the hydrocarbon group is more preferable. The above R ^N is as described above. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable. The carbon number of the above-mentioned hydrocarbon group or alkylene group is preferably 2-20, more preferably 2-10.

X ^P1 represents a polymerizable group, preferably an alkoxysilyl group, an epoxy group, an oxetanyl group or a radically polymerizable group, and more preferably an alkoxysilyl group. Preferred embodiments of the alkoxysilyl group and the radically polymerizable group are as described above.

Resin B may contain only 1 type of repeating unit represented by formula (BA-2), and may contain 2 or more types. In particular, it is also one of the preferred aspects of the present invention that the resin B contains a plurality of repeating units represented by formula (BA-2) having different polymerizable groups. In the above aspect, resin B has a repeating unit represented by formula (BA-2) containing an alkoxysilyl group as a polymerizable group, and a group containing a group different from an alkoxysilyl group as a polymerizable group The repeating unit represented by formula (BA-2) is preferable.

Moreover, resin B may have another repeating unit different from the repeating unit represented by said formula (BA-1) or formula (BA-2).

[Specific example] As a specific example of compound B, the compound used in an Example can be mentioned, but it is not limited to these.

〔content〕 The content of Compound B is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, and even more preferably 0.15 to 2% by mass relative to the total solid content of the curable resin composition of the present invention. The curable resin composition of this invention may contain only 1 type of compound B, and may contain 2 or more types. When two or more types of compound B are contained, it is preferable that the total amount is within the above-mentioned range.

<Compound C> From the viewpoint of the adhesiveness between the cured product obtained and the metal, it is preferable that the curable resin composition of the present invention further contains Compound C which is a compound having an azole group without a polymerizable group. The preferred aspects of the azole group in compound C are the same as the preferred aspects of the azole group in compound B described above. In addition, although the compound C is a compound which does not have a polymerizable group, the detail of a polymerizable group is the same as the meaning of the polymerizable group in the said compound B.

式（C-1）中，Z ¹～Z ⁴分別獨立地表示=CR ⁷-或氮原子，R ¹表示氫原子或1價的有機基，R ⁷表示氫原子或1價的有機基，在式（C-1）所表示之結構中不包含聚合性基； 式（C-2）中，Z ⁵～Z ⁶分別獨立地表示=CR ⁸-或氮原子，R ²～R ⁶分別獨立地表示氫原子或1價的有機基，R ⁸表示氫原子或1價的有機基，在式（C-2）所表示之結構中不包含聚合性基。 Compound C is preferably a compound represented by the following formula (C-1) or the following formula (C-2). [Chemical formula 33]

In formula (C-1), Z ¹ to Z ⁴ each independently represent =CR ⁷ - or a nitrogen atom, R ¹ represents a hydrogen atom or a monovalent organic group, and R ⁷ represents a hydrogen atom or a monovalent organic group. The structure represented by the formula (C-1) does not contain a polymerizable group; in the formula (C-2), Z ⁵ to Z ⁶ each independently represent =CR ⁸ - or a nitrogen atom, and R ² to R ⁶ each independently Represents a hydrogen atom or a monovalent organic group, R ⁸ represents a hydrogen atom or a monovalent organic group, and does not contain a polymerizable group in the structure represented by the formula (C-2).

In formula (C-1), Z ¹ to Z ⁴ each independently represent =CR ⁷ - or a nitrogen atom. Among them, one of Z ¹ to Z ⁴ is a nitrogen atom and three of them are =CR ⁷ -, and two of Z ¹ to Z ⁴ are nitrogen atoms and two of them are =CR ⁷ -, or The aspect in which three of Z ¹ to Z ⁴ are nitrogen atoms and one is =CR ⁷ - is preferable. Also, among these, Z ¹ and Z ³ are nitrogen atoms and Z ² and Z ⁴ are =CR ⁷ -, Z ¹ and Z ² are nitrogen atoms, and Z ³ and Z ⁴ are =CR ⁷ - The aspect or the aspect in which Z ¹ , Z ² and Z ³ are nitrogen atoms and Z ⁴ is =CR ⁷ - is preferable, Z ¹ and Z ³ are nitrogen atoms, and Z ² and Z ⁴ are =CR ^B7 -. The aspect or the aspect in which Z ¹ , Z ² and Z ³ are nitrogen atoms and Z ⁴ is =CR ⁷ - is more preferable.

In formula (C-1), R ¹ is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. The carbon number of the above-mentioned hydrocarbon group or alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4.

In formula (C-1), the preferable aspect of R ⁷ is the same as that of R ¹ .

In formula (C-2), Z ⁵ and Z ⁶ each independently represent =CR ⁸ - or a nitrogen atom. Among them, the aspect in which both Z ⁵ and Z ⁶ represent a nitrogen atom or the aspect in which Z ⁵ represents a nitrogen atom and Z ⁶ represents =CR ⁸ - is preferable.

In formula (C-2), R ² to R ⁶ and R ⁸ are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

[Molecular weight] The molecular weight of compound C is preferably 67-500, more preferably 68-300.

[Specific example] As a specific example of compound C, the compound used in an Example can be mentioned, but it is not limited to these.

〔content〕 The content of compound C is preferably 0.05 to 10 mass %, more preferably 0.10 to 5 mass %, and even more preferably 0.15 to 2 mass % with respect to the total solid content of the curable resin composition of the present invention. The curable resin composition may contain only one compound C, or may contain two or more types. When two or more kinds of compounds C are contained, the total amount is preferably within the above-mentioned range.

<Other silane coupling agents> The curable resin composition of the present invention preferably contains a silane coupling agent (also referred to as "other silane coupling agent") which is different from the above-mentioned photobase generator having an alkoxysilyl group and does not have an azole group. Examples of the above-mentioned silane coupling agent include Compound D which is a silane coupling agent having a polymerizable group different from that of an alkoxysilyl group and no azole group, or a compound D which is a silane coupling agent that does not have a polymerizable group different from that of an alkoxysilyl group. Compound E of a silane coupling agent of either a group or an azole group.

[Compound D] The curable resin composition of the present invention may further contain Compound D as a silane coupling agent having a polymerizable group different from the alkoxysilyl group and not having an azole group.

Compound D is preferably a compound containing an alkoxysilyl group and a polymerizable group different from the alkoxysilyl group. The preferred aspect of the alkoxysilyl group in compound D is the same as the preferred aspect of the alkoxysilyl group in compound B described above. In addition, although the compound D is a compound which does not have an azole group, the details of the azole group are the same as the meaning of the azole group in the compound B mentioned above.

As a polymerizable group different from the alkoxysilyl group in the compound D, a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group, a (block ) known polymerizable groups such as isocyanate groups, radical polymerizable groups or epoxy groups are preferred. The preferable aspect of the radically polymerizable group in the compound D is the same as the preferable aspect of the radically polymerizable group in the compound B described above.

式（DA-1）中，R ^D1～R ^D3分別獨立地表示烷基，L ^D1表示2價的連接基，X ^D1表示聚合性基。 As the compound D, a compound having a structure represented by the following formula (DA-1) is preferable. [Chemical formula 34]

In formula (DA-1), R ^D1 to R ^D3 each independently represent an alkyl group, L ^D1 represents a divalent linking group, and X ^D1 represents a polymerizable group.

In the formula (DA-1), R ^D1 to R ^D3 are each independently preferably an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group, and more preferably an ethyl group.

In the formula (DA-1), L ^D1 represents a divalent linking group, a hydrocarbon group or a hydrocarbon group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) ₂ - and The group represented by the bond of at least one group in the group of -NR ^N- is preferable, and the hydrocarbon group is more preferable. The above R ^N is as described above. Moreover, the aspect which has at least 1 type of group chosen from the group which consists of an amide group and a urea group in L ^D1 is also one of preferable aspects of this invention.

In formula (DA-1), X ^D1 represents a polymerizable group, and preferable aspects of the polymerizable group are as described above.

The compound D may be a compound having a molecular weight of less than 2,000 (hereinafter, also referred to as "low molecular weight compound D"), or may be a resin (hereinafter, also referred to as "resin D"). Moreover, it is also preferable that the curable resin composition contains both the low molecular weight compound D and the resin D from the viewpoint of the adhesiveness between the cured product and the metal.

[Low molecular compound D] The molecular weight of the low molecular weight compound D is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less. The number of polymerizable groups different from the alkoxysilyl group in the low molecular compound D is not particularly limited, but 1 to 10 are preferable, 1 to 4 are more preferable, and 1 or 2 are more preferable. The low molecular weight compound D is preferably a compound represented by the above formula (DA-1) and having a molecular weight within the above range.

[Resin D] Resin D is a resin having a repeating unit including an alkoxysilyl group and a repeating unit including a polymerizable group different from an alkoxysilyl group, or a resin having an alkoxysilyl group and a repeating unit including an alkoxysilyl group and an alkoxysilyl group Resins having repeating units of different polymerizable groups are preferred, and resins having repeating units including alkoxysilyl groups and repeating units including polymerizable groups different from alkoxysilyl groups are more preferred. The weight average molecular weight of the resin D is preferably 2,000 to 100,000, more preferably 3,000 to 70,000, and even more preferably 5,000 to 50,000. Moreover, it is preferable that resin D is an acrylic resin.

As the repeating unit including an alkoxysilyl group and the repeating unit including a polymerizable group different from the alkoxysilyl group in the resin D, the repeating unit represented by the above formula (BA-2) can be preferably mentioned. unit.

Moreover, resin D may have another repeating unit different from the repeating unit represented by the said formula (BA-2).

[Specific example] As a specific example of compound D, the compound used in an Example can be mentioned, but it is not limited to these.

〔content〕 The content of Compound D is preferably 0.05 to 10 mass %, more preferably 0.10 to 5 mass %, and even more preferably 0.15 to 2 mass % with respect to the total solid content of the curable resin composition of the present invention. The curable resin composition may contain only one compound D, or may contain two or more types. When two or more kinds of compounds D are contained, the total amount is preferably within the above range.

<Compound E> It is preferable that the curable resin composition of this invention further contains compound E which is a silane coupling agent which does not have either a polymerizable group different from an alkoxysilyl group, and an azole group. As the compound E, a compound having an alkoxysilyl group and not having a polymerizable group and an azole group different from the alkoxysilyl group is preferable. The compound E is a compound that does not have a polymerizable group different from the alkoxysilyl group, but the details of the polymerizable group different from the alkoxysilyl group are different from the alkoxysilyl group in the above-mentioned compound D The polymerizable group has the same meaning as the polymerizable group. The compound E is a compound without an azole group, but the details of the azole group are the same as those of the azole group in the above-mentioned compound B.

Examples of compound E include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, and the compounds described in International Publication No. 2011/080992 The compounds described in paragraphs 0063 to 0071 of JP 2014-191252 A, the compounds described in paragraphs 0060 to 0061 of JP 2014-191252 A, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264 A, The compounds described in paragraph 0055 of International Publication No. 2014/097594 and the compounds described in paragraphs 0067 to 0078 of JP-A No. 2018-173573 are incorporated herein by reference. 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 compounds as a silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group.

[Chemical formula 35]

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxysilane. 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl triethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 - Methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, N-2- (Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane Oxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-amine propyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane , 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

〔content〕 The content of Compound E is preferably 0.05 to 10 mass %, more preferably 0.10 to 5 mass %, and even more preferably 0.15 to 2 mass % with respect to the total solid content of the curable resin composition of the present invention. The curable resin composition may contain only one compound E, or may contain two or more types. When two or more kinds of compounds E are contained, the total amount is preferably within the above range.

<Alkali generator> The resin composition of this invention may contain the alkali generator which does not have an alkoxysilyl group. Among them, the base generator is a compound capable of generating a base by physical or chemical action. As a preferable alkali generator for the resin composition of this invention, a thermal alkali generator and a photobase generator are mentioned. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains an alkali generator. By including a thermal alkali generator in the resin composition, for example, the cyclization reaction of the precursor can be accelerated by heating, and the cured product has good mechanical properties and chemical resistance, for example, as a rewiring layer included in a semiconductor package The performance with the interlayer insulating film becomes good. As an alkali generator, an ionic alkali generator may be sufficient, and a nonionic alkali generator may be sufficient. Examples of the base generated from the base generator include secondary amines and tertiary amines. The alkali generator of the present invention is not particularly limited, and known alkali generators can be used. As known base generators, for example, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, carbamoyl amine compounds, acetamide compounds, urethane compounds, and benzyl carbamic acid can be used. Ester Compounds, Nitrobenzyl Carbamate Compounds, Sulfonamide Compounds, Imidazole Derivative Compounds, Aminoimide Compounds, Pyridine Derivative Compounds, α-Aminoacetophenone Derivative Compounds, Quaternary Ammonium Salts Derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amide imide compounds, phthalimide derivative compounds, acyloxyimide-based compounds, and the like. As a specific compound of a nonionic base generator, the compound represented by a formula (B1), a formula (B2), or a formula (B3) is mentioned. [Chemical formula 36]

In formula (B1) and formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group, a halogen atom or a hydrogen atom which does not have a tertiary amine structure. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. In addition, 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-based carbon atom. Therefore, when the carbon atom to be bonded is a carbon atom forming a carbonyl group, that is, when forming an amide group together with a nitrogen atom, it is not limited to this.

In formula (B1) and formula (B2), at least one of Rb ¹ , Rb ² and Rb ³ preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a condensed ring formed by condensing a monocyclic ring or 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 single ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.

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

Examples of Rb ³ include alkyl (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), and aryl (preferably having 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms). 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 (carbon number 7-23) is better, 7-19 is better, 7-12 is further better), aralkenyl (carbon number 8-24 is better, 8-20 is better, 8-16 is further better), alkane Oxy group (preferably carbon number 1-24, more preferably 2-18, more preferably 3-12), aryloxy (preferably carbon number 6-22, more preferably 6-18, 6- 12 is more preferred) or aralkoxy (the number of carbon atoms is preferably 7-23, more preferably 7-19, and more preferably 7-12). Among them, cycloalkyl (preferably carbon number of 3 to 24, more preferably 3 to 18, and even more preferably 3 to 12), aralkenyl and aralkoxy are preferred. Rb ³ may 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 37]

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 carbon number 1-24, more preferably 2-18, further preferably 3-12), alkenyl (preferably carbon number 2-24, more preferably 2-18, 3-12 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 are more preferable, and 7-12 are 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 having 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3), an alkenyl group (preferably having a carbon number of 2 to 12). preferably, 2-8 are more preferred, 2-3 are further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred), aralkyl ( The number of carbon atoms is preferably 7 to 23, more preferably 7 to 19, and further preferably 7 to 11), and hydrogen atom is more preferred.

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

Moreover, it is also preferable that the compound represented by formula (B1-1) is a compound represented by formula (B1-1a). [Chemical formula 38]

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 atoms, alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), alkenyl (preferably having 2 to 12 carbon atoms, and 2 ～6 is better, 2-3 is further better), aryl (carbon number is 6-22 is better, 6-18 is better, 6-10 is further better), aralkyl (carbon number is 7 ～23 is preferable, 7～19 is more preferable, 7～11 is further preferable), hydrogen atom or methyl group is preferable. Rb ¹⁷ is alkyl (preferably carbon number 1-24, more preferably 1-12, and further preferably 3-8), alkenyl (preferably carbon number 2-12, more preferably 2-10, 3-8 are further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 are more preferable, 7-12 are further preferable), among them, aryl group is preferable.

[Chemical formula 39]

In the formula (B3), L represents a hydrocarbon group, which is a hydrocarbon group having a divalent valence of a saturated hydrocarbon group on the path of the connecting chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the connecting chain is 3 more than one. In addition, R ^N1 and R ^N2 each independently represent a monovalent organic group.

In this specification, the "connection chain" refers to the one that connects the connection objects in the shortest (minimum number of atoms) manner among the atomic chains on the path between the two atoms of the connection object or the connection atom group. For example, in a compound represented by the following formula, L is composed of phenylene ethylidene, and has ethylidene as a saturated hydrocarbon group, the connecting chain is composed of 4 carbon atoms, and the number of atoms on the path of the connecting chain (that is, is The number of atoms constituting the connecting chain, hereinafter also referred to as "connecting chain length" or "connecting chain length") is four. [Chemical formula 40]

The number of carbon atoms in L in the formula (B3) (including carbon atoms other than the carbon atoms in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly advancing the above-mentioned intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less. In particular, it is preferable that the linking chain length of L is 4 or 5, and 4 is the most optimal. Specific preferred compounds of the base generator 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 the base generator contains a compound represented by the following formula (N1). [Chemical formula 41]

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, and a divalent organic group is preferable. 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 more preferable. The linking chain length is the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group (preferably carbon number 1-24, more preferably 2-18, further preferably 3-12), hydrocarbon group (carbon number 1 to 24 are preferred, 1 to 12 are more preferred, and 1 to 10 are further preferred), and specifically, aliphatic hydrocarbon groups (1 to 24 carbon atoms are preferred, 1 to 12 are preferred) More preferably, 1-10 is further preferred) or aromatic hydrocarbon group (preferably carbon number 6-22, 6-18 is more preferred, 6-10 is further preferred), aliphatic hydrocarbon group is preferred. When an aliphatic hydrocarbon group is used as R ^N1 and R ^N2 , since the basicity of the generated base is high, it 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 substituent in the aliphatic hydrocarbon chain or in the aromatic ring. In particular, the 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 the combination of chain alkyl groups and cyclic alkyl groups, and chain alkyl groups. An alkyl group with an oxygen atom in it. The linear or branched chain alkyl group having 1 to 24 carbon atoms is preferable, 2 to 18 are more preferable, and 3 to 12 are further preferable. Examples of linear or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, deca Dialkyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, and the like. The cyclic alkyl group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. 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 group related to the combination of the chain alkyl group and the cyclic alkyl group is preferably one having 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. Groups related to the combination of a chain alkyl group and a cyclic alkyl group include, for example, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl Wait. The alkyl group having an oxygen atom in the chain is preferably one having 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. Among them, it is preferable that R ^N1 and R ^N2 are alkyl groups having 5 to 12 carbon atoms from the viewpoint of increasing the boiling point of the bases generated by decomposition described later. Among them, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable in a formulation that places importance on the adhesion at the time of lamination with a metal (for example, copper).

R ^N1 and R ^N2 may be connected to each other to form a ring structure. When forming a cyclic structure, an oxygen atom or the like may be included in the chain. In addition, the cyclic structure formed by R ^N1 and R ^N2 may be a single ring or a condensed ring, but a single ring is preferable. The cyclic structure to be formed is preferably a 5-membered or 6-membered ring containing a nitrogen atom in the formula (N1), and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, and a pyrrolidine ring. , an imidazoline ring, a pyrazolidine ring, a piperidine ring, a piperidine ring, a morpholine ring, and the like, preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperidine ring, and a morpholine ring.

R ^C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

As the protecting group, a protecting group that decomposes by the action of an acid or a base is preferable, and a protecting group that decomposes with an acid is preferably used.

Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. As a chain or cyclic alkyl group, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group, etc. are mentioned. Specific examples of the chain-like alkyl group having an oxygen atom in the chain include alkyloxyalkyl groups, and more specifically, methoxymethyl (MOM) groups, ethoxyethyl ( EE) base et al. As a cyclic alkyl group which has an oxygen atom in a chain, an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyran (THP) group, etc. are mentioned.

The divalent linking group constituting L is not particularly limited, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable. The hydrocarbon group may have a substituent, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a bivalent hydrocarbon linking group which may have an oxygen atom in the chain is preferable, and a bivalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a bivalent aromatic hydrocarbon group, or a bivalent aromatic hydrocarbon group which may have an oxygen atom in the chain. A group related to a combination of a divalent aliphatic hydrocarbon group having an oxygen atom 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 further preferable. Preferably, these groups do not have oxygen atoms. The divalent hydrocarbon linking group is preferably one having 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group is preferably one having 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group is preferably one having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group related to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an aryl-extended alkyl group) is preferably one having 7 to 22 carbon atoms, more preferably 7 to 18, and 7 to 10 for further better.

As the linking group L, specifically, a linear or branched chain-like alkylene group, a cyclic alkylene group, a group related to a combination of a chain-like alkylene group and a cyclic alkylene group, a group having in the chain An alkylene group of an oxygen atom, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylidene group, and an arylidene group are preferred. The linear or branched chain alkylene group having 1 to 12 carbon atoms is preferred, 2 to 6 are more preferred, and 2 to 4 are further preferred. The cyclic alkylene group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The group related to the combination of the chain alkylene group and the cyclic alkylene group is preferably one having 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. The alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain is preferably one having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3.

The linear or branched chain alkenylene group is preferably one having 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The number of C=C bonds of the linear or branched chain alkenylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The number of C=C bonds of the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. The aryl extended group is preferably one having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The arylidene alkylene group is preferably one having 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among them, chain alkylene, cyclic alkylene, alkylene having oxygen atoms in the chain, chain alkenylene, aryl, aryl, and alkylene are preferred, 1,2 -ethylidene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylidene (especially cis-vinylidene), vinylidene Phenyl (1,2-phenylene), phenylmethylene (especially 1,2-phenylene), oxyethylidene (especially 1,2-vinyloxy-1,2- ethylidene) is better.

As the base generator, the following examples can be given, but the present invention is not limited to these.

[Chemical formula 42]

The molecular weight of the nonionic thermal alkali generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Specific preferred 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 to these. [Chemical formula 43]

Specific examples of the imide salt include the following compounds, but the present invention is not limited to these. [Chemical formula 44]

When the resin composition of the present invention contains an alkali generator, the content of the alkali 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 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less. Alkali generators can be used 1 type or 2 or more types. When using 2 or more types, it is preferable that the total amount is in the said range.

＜Solvent＞ The resin composition of the present invention preferably contains a solvent. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfites, amides, ureas, and alcohols.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. , butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, Ethoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), alkyl 3-alkoxypropanoates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionate alkyl esters (for example, 2-alkane 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)), methyl 2-alkoxy-2-methyl propionate and 2-alkane Ethyl oxy-2-methylpropionate (eg, 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, and triethyl ether. Glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Alcohol 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 Ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether and the like are preferred.

Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levodextran ketone, and dihydrodextran Sugar ketones and the like are preferred.

As cyclic hydrocarbons, aromatic hydrocarbons, such as toluene, xylene, and anisole, and cyclic terpenes, such as limonene, are mentioned as preferable ones, for example.

As the sulfites, for example, dimethyl sulfite can be mentioned as a preferable one.

Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexylester-2-pyrrolidone, N,N-dimethylethyl acetate amide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N , N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine, etc. are preferred.

Preferable examples of the urea include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methyl alcohol Oxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monodiethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monopropylene glycol monoethyl ether, Propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethylene glycol monobenzyl ether, ethylene glycol monoethylene glycol monophenyl ether, methyl benzyl alcohol, n-amyl alcohol, methyl amyl alcohol and diacetone alcohol, etc.

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

In the present invention, selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, gamma-butyrolactone, dimethylsulfoxide, ethyl carbitol acetate, butyl carbitol Alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, levoglucan ketone, dihydroglucan ketone, one kind of solvent or two or more kinds of solvents The mixed solvent is preferred. It is particularly preferred to use dimethylsulfoxide and γ-butyrolactone together or N-methyl-2-pyrrolidone and ethyl lactate together.

From the viewpoint of coatability, the content of the solvent is preferably set to an amount of 5 to 80% by mass, more preferably 5 to 75% by mass of the total solid concentration of the resin composition of the present invention , it is more preferable to set it as an amount of 10-70 mass %, and it is still more preferable to set it as 20-70 mass %. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

The resin composition of this invention may contain only 1 type of solvent, and may contain 2 or more types. When two or more kinds of solvents are contained, the total is preferably within the above-mentioned range.

[Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator capable of starting polymerization by light and/or heat. In particular, it is preferable to contain a photopolymerization initiator. Preferably, the photopolymerization initiator is 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 light in the ultraviolet region to the visible region is preferred. Moreover, it can also be an activator which produces|generates active radicals by some action with the sensitizer of photoexcitation.

Preferably, 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 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferable to measure at a concentration of 0.01 g/L by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) using an ethyl acetate solvent.

As the photoradical polymerization initiator, any known compounds can be used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazole skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, and hexaarylbis Oxime compounds such as imidazoles and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxyl groups such as hydroxyacetophenone Ketone compounds, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron aromatic complexes, etc. For such details, reference can be made to the descriptions of paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of International Publication No. 2015/199219, and the contents are incorporated into the present specification. In addition, the compounds described in paragraphs 0065 to 0111 of Japanese Patent Laid-Open No. 2014-130173, the compounds described in Japanese Patent No. 6301489, and the compounds described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019 can be mentioned. Peroxide-based photopolymerization initiator, Photopolymerization initiator described in International Publication No. 2018/221177, Photopolymerization initiator described in International Publication No. 2018/110179, JP 2019-043864 The photopolymerization initiator described in JP-A No. 2019-044030, the peracid-based initiator described in JP-A No. 2019-167313, These contents are also incorporated into this manual.

As the ketone compound, for example, the compound described in paragraph 0087 of JP-A No. 2015-087611 can be exemplified, and this content is incorporated in the present specification. Among the 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 the photo-radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969, the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and the This content is incorporated into this manual.

As the α-hydroxyketone-based initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (the above are manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE- 2959, IRGACURE 127 (product name: all made by BASF).

As the α-amino ketone-based starter, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (the above are manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all are BASF Corporation) can be used system).

As the aminoacetophenone-based initiator, the compounds described in Japanese Patent Laid-Open No. 2009-191179 whose absorption maximum wavelength matches a light source with a wavelength of 365 nm or 405 nm can also be used, and the contents are incorporated in the present specification.

As an acylphosphine oxide-based initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, etc. are mentioned. In addition, Omnirad 819, Omnirad TPO (the above are manufactured by IGM Resins B.V.), IRGACURE-819 or IRGACURE-TPO (product name: both manufactured by BASF Corporation) can be used.

Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF Corporation), Keycure VIS 813 (manufactured by King Brother Chem Corporation), and the like.

As a photoradical polymerization initiator, an oxime compound can be mentioned more preferably. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound has a wide exposure latitude (exposure margin) and also functions as a photohardening accelerator, so it is particularly preferable.

Specific examples of the oxime compound include compounds described in JP 2001-233842 A, compounds described in JP 2000-080068 A, and compounds described in JP 2006-342166 A. Compounds, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in JP 2000-066385 A, compounds described in JP 2004-534797 A, JP 2017-019766 A Compounds described, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015/152153, compounds described in International Publication No. 2017/051680, Japanese Patent Laid-Open No. 2017-198865 The compounds described in WO 2017/164127, the compounds described in paragraphs 0025 to 0038 of WO 2017/164127, the compounds described in WO 2013/167515, and the like are incorporated herein by reference.

Examples of preferable oxime compounds include compounds having the following structures, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-Propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1- Ketones, 2-Benzyloxyimino-1-phenylpropan-1-one, 3-(4-Tosyloxy)iminobutan-2-one and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, etc. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. The oxime-based photo-radical polymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

[Chemical formula 45]

Among the 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, Japanese Patent Laid-Open 2012- The photoradical polymerization initiator 2) described in Gazette 014052. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Trolly 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 Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Moreover, the oxime compound of the following structure can also be used. [Chemical formula 46]

As a photoradical polymerization initiator, an oxime compound having a perylene ring can also be used. Specific examples of the oxime compound having a perylene ring include the compounds described in Japanese Patent Laid-Open No. 2014-137466 and the compounds described in Japanese Patent No. 06636081, the contents of which are incorporated in the present specification.

As the photoradical polymerization initiator, an oxime compound having at least one benzene ring in a carbazole ring serving as a skeleton of a naphthalene ring can also be used. As a specific example of such an oxime compound, the compound described in International Publication No. 2013/083505 is mentioned, and the content is incorporated in this specification.

Moreover, the oxime compound which has a fluorine atom can also be used. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 24-500852 A. Compound (C-3) and the like described in paragraph 0101 of Unexamined Publication No. 2013-164471, and the contents thereof are incorporated into the present specification.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include those described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466 A. The compound is the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, and the contents thereof are incorporated into the present specification. Moreover, ADEKA ARKLS NCI-831 (made by ADEKA CORPORATION) is also mentioned as an oxime compound which has a nitro group.

As a photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

As the photoradical polymerization initiator, an oxime compound obtained by bonding a substituent having a hydroxyl group to a carbazole skeleton can also be used. As such a photopolymerization initiator, the compound described in International Publication No. 2019/088055, etc. are mentioned, and the content is incorporated in this specification.

As the photopolymerization initiator, an oxime compound (hereinafter, also referred to as an oxime compound OX) having an aromatic ring group Ar ^OX1 into which an electron withdrawing group is introduced can also be used. Examples of the electron withdrawing group possessed by the above-mentioned 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, and an acyl group is more preferable, and a benzyl group is still more preferable because of the ease of forming a film excellent in light resistance. The benzyl group may have a substituent. As a substituent, halogen atom, cyano group, nitro group, hydroxyl group, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkenyl group, alkylthio group, arylthio group , amide group or amine group is preferred, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclicoxy group, alkylthio group, arylthio group or amine group are more preferred, alkoxy group, alkyl group A thio 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、烷基硫基、芳基硫基、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、亞膦醯基、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、烷基硫基、芳基硫基、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 group consisting of the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and 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 alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an aryl group sulfinyl group, alkylsulfonyl group, arylsulfonyl group, yl group, yloxy group, amino group, phosphonide group, carbamoyl group or sulfamoyl group, R ^X2 represents alkyl, alkene alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl group, arylsulfonyl group, aryloxy group or amine 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 the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, which are incorporated in the present specification.

As the optimum oxime compound, the oxime compound having a specific substituent shown in JP-A No. 2007-269779 or the oxime compound having a thioaryl group shown in JP-A No. 2009-191061 can be mentioned. , and incorporate it into this manual.

From the viewpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyltrisium compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl groups Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl - Compounds in the group of benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

Further preferred photo-radical polymerization initiators are trihalomethyltriazole compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, Onium salt compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyltriazole compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, dibenzoyl It is still more preferable to use at least one compound in the group of ketone compounds, and it is still more preferable to use a metallocene compound or an oxime compound.

In addition, as the photoradical polymerization initiator, N, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. can also be used. ,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 , 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1 and other aromatic ketones, alkyl anthraquinones and other quinones formed by condensed 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, and the like. Moreover, the compound represented by following formula (I) can also be used.

[Chemical formula 48]

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms or a phenyl group or C1-20 alkyl, C1-12 alkoxy, halogen atom, cyclopentyl, cyclohexyl, C2-12 alkenyl, interrupted by one or more oxygen atoms A phenyl group or biphenyl group substituted with at least one of the alkyl group having 2 to 18 carbon atoms and the alkyl group having 1 to 4 carbon atoms, R ^I01 is a group represented by formula (II) or the same as R ^I00 R ^I02 to R ^I04 are each independently an alkyl group with 1 to 12 carbons, an alkoxy group with 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 of the above formula (I).

In addition, the compounds described in paragraphs 0048 to 0055 of International Publication No. WO 2015/125469 can also be used as the photo-radical polymerization initiator, and the contents are incorporated in the present specification.

As the photoradical polymerization initiator, a bifunctional or trifunctional or more photoradical polymerization initiator can be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation over time becomes difficult, so that the stability over time of the resin composition can be improved. Specific examples of the bifunctional or trifunctional or more than trifunctional photo-radical polymerization initiators include JP 2010-527339 A, JP 2011-524436 A, WO 2015/004565, JP 2011-524436 Dimers of oxime compounds described in paragraphs 0407 to 0412 of Table 2016-532675, paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E ) and compound (G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester-based photoinitiators described in paragraph 0007 of JP 2017-523465 A, JP 2017- The photoinitiator described in paragraphs 0020 to 0033 of Japanese Patent Publication No. 167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Unexamined Patent Application Publication No. 2017-151342, and Japanese Patent No. 6469669 The oxime ester photoinitiator and the like described, and the contents are incorporated into this specification.

When a photopolymerization initiator is contained, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 0.5 to 30 mass % with respect to the total solid content of the resin composition of the present invention. 15 mass %, more preferably 1.0 to 10 mass %. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above-mentioned range. In addition, since the photopolymerization initiator may function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further performed by heating in an oven, a hot plate, or the like.

[Sensitizer] The resin composition may include a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state contacts with the thermal radical polymerization initiator, the photoradical polymerization initiator, etc., thereby producing electron transfer, energy transfer, and heat generation. Thereby, the thermal radical polymerization initiator and the photoradical polymerization initiator are decomposed by chemical change, and a radical, an acid, or a base is generated. As sensitizers that can be used, benzophenone-based, micheler's ketone-based, coumarin-based, pyrazoleazo-based, anilinoazo-based, triphenylmethane-based, anthraquinone-based, and anthracene-based sensitizers can be used series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, Kouyamaguchi galaxy, phthalocyanine series, benzopyran series, indigo series and other compounds. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane Alkane, 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-diethylamine Methylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylidene)benzo Thiazole, 2-(p-dimethylaminophenylvinylidene)isonaphthothiazole, 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-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin , 3-ethoxycarbonyl-7-diethylamino coumarin (7-(diethylamino) coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Esters, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethyazole) Methylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminostyryl) Styrene, diphenylacetanilide, benzalanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. In addition, other sensitizing dyes can be used. For details of the sensitizing dye, the descriptions in paragraphs 0161 to 0163 of JP 2016-027357 A can be referred to, and the contents are incorporated in the present 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 more preferably 0.5 to 10% by mass relative to the total solid content of the resin composition. for further better. 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. Regarding the chain transfer agent, it is defined, for example, in pages 683-684 of the Polymer Dictionary, 3rd edition (edited by The Society of Polymer Science, Japan, 2005). As the chain transfer agent, for example, a group of compounds having -SS-, -SO ₂ -S-, -NO-, SH, PH, SiH, and GeH in the molecule, a compound having a compound used for RAFT (Reversible Addition Fragmentation chain Transfer: Reversible addition chain transfer polymerization) polymerized thiocarbonylthio dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds, etc. These can generate free radicals by supplying hydrogen to the less reactive radicals or can be deprotonated to generate free radicals after being oxidized. In particular, a thiol compound can be preferably used.

In addition, as a chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. WO 2015/199219 can also be used, and the contents are incorporated in the present specification.

When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the total solid content of the resin composition of the present invention More preferably, 0.5-5 mass parts is more preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more types of chain transfer agents, the total is preferably within the above range.

[Photoacid generator] It is preferable that the resin composition of this invention contains a photoacid generator. The photoacid generator represents a compound that generates at least one of a Brynster acid and a Lewis acid by irradiation with light of 200 nm to 900 nm. The light to be irradiated is preferably light having a wavelength of 300 nm to 450 nm, more preferably light having a wavelength of 330 nm to 420 nm. When a photoacid generator is used alone or in combination with a sensitizer, a photoacid generator capable of generating an acid by exposure to light is preferred. Preferable examples of the acid to be generated include hydrogen halide, carboxylic acid, sulfonic acid, sulfinic acid, thiosulfinic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, boron derivatives, and phosphorus derivatives. , Antimony derivatives, halogen peroxides, sulfonamides, etc.

Examples of the photoacid generator used in the resin composition of the present invention include quinonediazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfonic acid compounds, onium salt compounds, and the like. . From the viewpoints of sensitivity and storage stability, organohalogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the viewpoints of mechanical properties of the formed film, oxime esters are preferred.

Examples of the quinonediazide compound include a sulfonic acid ester bond of quinonediazide to a monovalent or polyvalent hydroxy compound, and a sulfonic acid sulfonamide bond of quinonediazide to a monovalent or polyvalent amine compound. On the other hand, those obtained are those obtained by the sulfonate bond of quinonediazide and/or the sulfonamide bond to the polyhydroxypolyamine compound. All functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxy polyamine compounds may not be substituted with quinonediazide, but on average, more than 40 mol% of the total functional groups are substituted with quinonediazide as better. By containing such a quinonediazide compound, it is possible to obtain a resin composition that is sensitive to i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) of a mercury lamp, which are normal ultraviolet rays.

Specific examples of the hydroxy compound include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, tert-butanol, cyclohexanol, naphthol, Bis-Z, and BisP. -EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P , BisRS-3P, BisP-OCHP, Methylenetri-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF , TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the product name above, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR -PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are the product names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethylacetate Oxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxydiol Benzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), novolak resin, etc., but It is not limited to these.

Specific examples of the amino compound include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'- Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, etc., but not limited on such.

In addition, specific examples of the polyhydroxypolyamine compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3′-dihydroxybenzidine, and the like, but It is not limited to these.

Among these, it is preferable to contain a phenol compound and an ester with a 4-naphthoquinonediazidesulfonyl group as the quinonediazide compound. Thereby, higher sensitivity and higher resolution to i-ray exposure can be obtained.

The content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the resin. By setting the content of the quinonediazide compound within this range, the contrast between the exposed portion and the unexposed portion can be obtained, and thus higher sensitivity can be achieved, which is preferable. Furthermore, a sensitizer etc. can be added as needed.

The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the following formula (OS-103), the formula (OS-104), or the formula (OS-105) The represented oxime sulfonate compounds are preferred.

[Chemical formula 50]

In formula (OS-1), X ³ represents an alkyl group, an alkoxy group or a halogen atom. When a plurality of X ³ exist, they may be the same or different. The alkyl group and the alkoxy group in the above-mentioned X ³ may have a substituent. As the alkyl group in the aforementioned X ³ , a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group in the above-mentioned X ³ , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom in the above-mentioned X ³ , a chlorine atom or a fluorine atom is preferable. In formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of ^X3 may be the same or different. In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. The halogenated alkoxy group of 5, the phenyl group which may be substituted with W, the naphthyl group which may be substituted with W, or the anthracenyl group which may be substituted with W are preferred. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms. , an aryl group with a carbon number of 6-20, a halogenated aryl group with a carbon number of 6-20.

In formula (OS-1), m3 is ³ , ^X3 is a methyl group, the substitution position of X3 is an ortho position, and ^R34 is a straight-chain alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- Compounds of 2-oxonorkanylmethyl or p-tolyl are particularly preferred.

Specific examples of the oxime sulfonate compound represented by formula (OS-1) include those in paragraphs 0064 to 0068 of JP 2011-209692 A and 0158 to 0167 in JP 2015-194674 A. The following compounds are described, and these contents are incorporated into this specification.

[Chemical formula 51]

In formula (OS-103) to formula (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, and sometimes there are plural R ^s2 which independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen. Atom, sometimes there are plural R ^s6 each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, and ns represents 1 Or 2, ms represents an integer from 0 to 6. In formulas (OS-103) to (OS-105), the alkyl group (preferably carbon number 1-30), aryl group (preferably carbon number 6-30) or heteroaryl group represented by R ^s1 ( It is preferable to have 4 to 30 carbon atoms) within a range in which the effects of the present invention can be obtained, and may have a known substituent.

In formulas (OS-103) to (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably with a carbon number of 1-12) or an aryl group (preferably with a carbon number of 6-30), A hydrogen atom or an alkyl group is more preferable. In the compound sometimes there are more than 2 R ^s2 , one or two is preferably an alkyl group, an aryl group or a halogen atom, one is an alkyl group, an aryl group or a halogen atom, more preferably, one is an alkyl group, an aryl group or a halogen atom Alkyl groups and the remainder are hydrogen atoms are particularly preferred. The alkyl group or aryl group represented by R ^s2 may have a known substituent within a range in which the effects of the present invention can be obtained. In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, and O is preferred. In the above formulae (OS-103) to (OS-105), the ring including Xs as a ring member is a 5-membered ring or a 6-membered ring.

In the formulas (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1, and when Xs is S, ns is 2. good. In formulas (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and alkoxy group (preferably having 1 to 30 carbon atoms) represented by R ^s6 may have a substituent . In formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

In addition, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), and the above formula (OS-104) ) represented by the compound represented by the following formula (OS-107) is particularly preferred, and the compound represented by the above formula (OS-105) is represented by the following formula (OS-108) or formula (OS-109) The compounds indicated are particularly preferred. [Chemical formula 52]

In formulas (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, and R ^t8 represents a hydrogen atom or an alkane having 1 to 8 carbon atoms group, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl or chlorophenyl, R ^t9 represents hydrogen atom, halogen atom, methyl or methoxy group, R ^t2 represents hydrogen atom or methyl group. In the formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

In formulas (OS-106) to (OS-111), R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, and a methoxymethyl group , phenyl or chlorophenyl, preferably an alkyl group with 1 to 8 carbon atoms, a halogen atom or a phenyl group, preferably an alkyl group with 1 to 8 carbon atoms, and even more preferably an alkyl group with 1 to 6 carbon atoms , methyl is particularly good.

In formulas (OS-106) to (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and a hydrogen atom is preferable. R ^t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In addition, among the above-mentioned oxime sulfonate compounds, the three-dimensional structure (E, Z) of the oxime may be any of them, or a mixture may be used. Specific examples of the oxime sulfonate compounds represented by the above formulae (OS-103) to (OS-105) include paragraphs 0088 to 0095 of Japanese Patent Laid-Open No. 2011-209692 and Japanese Patent Laid-Open No. 2015-194674. Compounds described in paragraphs 0168 to 0194 of the gazette, and these contents are incorporated into the present specification.

As another preferable aspect of the oxime sulfonate compound containing at least one oxime sulfonate group, the compound represented by following formula (OS-101) and formula (OS-102) is mentioned.

[Chemical formula 53]

In formula (OS-101) or formula (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group , cyano, aryl or heteroaryl. The aspect in which R ^u9 is a cyano group or an aryl group is more preferable, and the aspect in which R ^u9 is a cyano group, a phenyl group or a naphthyl group is further preferable. In formula (OS-101) or formula (OS-102), R ^u2a represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, ^{-CR u6} H- or CR ^u6 R ^u7 - , R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, and an alkylcarbonyl group , arylcarbonyl, amido, sulfo, cyano or aryl. Two of R ^u1 to R ^u4 may each be bonded to each other to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring. As R ^u1 to R ^u4 , a hydrogen atom, a halogen atom or an alkyl group is preferable, and an aspect in which at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group is also preferable. Among them, the aspect in which all of R ^u1 to R ^u4 are hydrogen atoms is preferable. All of the above-mentioned substituents may further have a substituent.

作為市售品，可以舉出WPAG-336（FUJIFILM Wako Pure Chemical Corporation製）、WPAG-443（FUJIFILM Wako Pure Chemical Corporation製）、MBZ-101（Midori Kagaku Co.,Ltd.製）等。 More preferably, the compound represented by the above formula (OS-101) is the compound represented by the formula (OS-102). In addition, among the above-mentioned oxime sulfonate compounds, the three-dimensional structure (E, Z, etc.) of the oxime or benzothiazole ring may be any of them, respectively, or a mixture may be used. As specific examples of the compound represented by the formula (OS-101), the compounds described in paragraphs 0102 to 0106 of JP-A No. 2011-209692 and paragraphs 0195-0207 of JP-A No. 2015-194674 can be exemplified. These contents are incorporated into this manual. Among the above-mentioned compounds, the following b-9, b-16, b-31, and b-33 are preferable. [Chemical formula 54]

As a commercial item, WPAG-336 (made by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (made by FUJIFILM Wako Pure Chemical Corporation), MBZ-101 (made by Midori Kagaku Co., Ltd.), etc. are mentioned.

Moreover, the compound represented by the following structural formula can also be mentioned as a preferable example. [Chemical formula 55]

Specific examples of the organic halogenated compound include Wakabayashi et al. "Bull Chem. Soc Japan" 42, 2924 (1969), the specification of U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Laid-Open Japanese Patent Laid-Open No. 48-36281, Japanese Patent Laid-Open No. 55-32070, Japanese Patent Laid-Open No. 60-239736, Japanese Patent Laid-Open No. 61-169835, Japanese Patent Laid-Open No. 61-169837, Japanese Patent Laid-Open No. 61-169837 Sho 62-58241, JP 62-212401, JP 63-70243, JP 63-298339, M.P.Hutt "Jurnal of Heterocyclic Chemistry" 1 (No3), (1970) and the like, and these contents are incorporated into the present specification. In particular, a trihalomethyl-substituted oxazole compound: S-triazole compound can be mentioned as a preferable example. More preferably, at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-tris-s-tris-s-s-s-s-s-s-s-s-s-s-s-s-s-s-s-derivatives, for example, 2,4,6 -Tris(monochloromethyl)-s-tris-tris, 2,4,6-tris(dichloromethyl)-s-tris-tris, 2,4,6-tris(trichloromethyl)-s-tris 𠯤, 2-methyl-4,6-bis(trichloromethyl)-s-tris𠯤, 2-n-propyl-4,6-bis(trichloromethyl)-s-tris𠯤, 2-( α,α,β-Trichloroethyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-phenyl-4,6-bis(trichloromethyl)-s-tris , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl) methyl)-s-tris-tris, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-[1-(p-methoxyphenyl)-2 ,4-butadienyl]-4,6-bis(trichloromethyl)-s-tris-tris, 2-styryl-4,6-bis(trichloromethyl)-s-s-tris, 2 -(p-Methoxystyryl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl) base)-s-tris-tris, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-(4-naphthyloxynaphthyl)-4,6-bis (Trichloromethyl)-s-tris-tris, 2-phenylsulfanyl-4,6-bis(trichloromethyl)-s-tris-tris, 2-benzylsulfanyl-4,6-bis(trichloromethyl) base)-s-tris-tris, 2,4,6-tris (dibromomethyl)-s-tris, 2,4,6-tris (tribromomethyl)-s-tris, 2-methyl -4,6-bis(tribromomethyl)-s-tris-tris, 2-methoxy-4,6-bis(tribromomethyl)-s-s-tris, etc.

As the organoborate compound, for example, Japanese Patent Laid-Open No. 62-143044, Japanese Patent Laid-Open No. 62-150242, Japanese Patent Laid-Open No. 9-188685, Japanese Patent Laid-Open No. 9-188686, Japanese Patent Laid-Open No. 9-188686, Japanese Patent Application Laid-Open No. 9-188710, Japanese Patent Laid-Open No. 2000-131837, Japanese Patent Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Laid-Open No. 2002-116539, etc. and Kunz, Martin "Rad Tech'98" .Proceeding April 19-22, 1998, the organic borate described in "Chicago", etc., Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, Japanese Patent Laid-Open No. 6-175561 Organoboronium complexes or organoboroxonium complexes, Organoboronium complexes described in Japanese Patent Laid-Open No. 6-175554, Japanese Patent Laid-Open No. 6-175553, Japanese Patent Laid-Open No. 9-188710 The organoboron phosphonium complexes described in Gazette No. 6-348011, JP 7-128785, JP 7-140589, JP 7-306527, JP 7-306527 Organoboron transition metal complex complexes, such as Unexamined-Japanese-Patent No. 7-292014, etc. are taken as specific examples, and these content are incorporated in this specification.

As the dioxane compound, the compounds and the diazodioxane compounds described in Japanese Patent Application Laid-Open No. 61-166544, Japanese Patent Application No. 2001-132318 and the like can be mentioned.

Examples of the above-mentioned onium salt compounds include the diazonium salts described in S.I.Schlesinger, Photogr.Sci.Eng., 18, 387 (1974), T.S. Bal et al, Polymer, 21,423 (1980), and U.S. Patent No. 4,069,055 No. specification, ammonium salts described in Japanese Patent Laid-Open No. 4-365049, etc., phosphonium salts described in each specification of US Pat. No. 4,069,055, US Pat. No. 4,069,056, European Patent No. 104,143, US Pat. No., each specification of U.S. Patent No. 410,201, the iodonium salt described in Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 390,214, European Patent No. 233,567 No., European Patent No. 297,443, European Patent No. 297,442, US Patent No. 4,933,377, US Patent No. 161,811, US Patent No. 410,201, US Patent No. 339,049, US Patent No. 4,760,013, US Patent No. 4,734,444, The permalate salts described in the respective specifications of US Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, and German Patent No. 3,604,581, J.V.Crivello et al, Macromolecules, 10(6), 1307(1977), Selenium salts, C.S.Wen et al, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, Oct. (1988), arsenic salts, onium salts such as pyridinium salts, etc., and these contents are incorporated into the present specification.

式（RI-I）中，Ar ₁₁表示可以具有1～6個取代基之碳數20以下的芳基，作為較佳的取代基，可以舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數6～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的烷基胺基、碳數2～12的二烷基胺基、烷基的碳數為1～12的烷基醯胺基或芳基的碳數為6～20的芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z ₁₁ ^-表示1價的陰離子，其為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性的方面考慮，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子為較佳。式（RI-II）中，Ar ₂₁、Ar ₂₂各自獨立地表示可以具有1～6個取代基的碳數1～20的芳基，作為較佳的取代基，可以舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的單烷基胺基、烷基的碳數分別獨立地為1～12的二烷基胺基、烷基的碳數為碳數1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z21 ^-表示1價的陰離子，其為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性、反應性的方面考慮，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。式（RI-III）中，R ₃₁、R ₃₂、R ₃₃各自獨立地表示可以具有1～6個取代基之碳數6～20的芳基或烷基、烯基、炔基，較佳地，從反應性、穩定性的方面考慮，芳基為較佳。作為較佳的取代基，可以舉出碳數1～12的烷基、碳數2～12的烯基、碳數2～12的炔基、碳數1～12的芳基、碳數1～12的烷氧基、碳數1～12的芳氧基、鹵素原子、碳數1～12的單烷基胺基、烷基的碳數分別獨立地為碳數1～12的二烷基胺基、烷基的碳數為碳數1～12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1～12的硫代烷基、碳數1～12的硫代芳基。Z ₃₁ ^-表示1價的陰離子，其為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子，從穩定性、反應性的方面考慮，過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。 Examples of the onium salt include those represented by the following general formulae (RI-I) to (RI-III). [Chemical formula 56]

In formula (RI-I), Ar ₁₁ represents an aryl group with 20 or less carbon atoms which may have 1 to 6 substituents, and preferable substituents include an alkyl group with 1 to 12 carbons, an alkyl group with 2 carbons Alkenyl group of to 12, alkynyl of carbon number of 2 to 12, aryl group of carbon number of 6 to 12, alkoxy of carbon number of 1 to 12, aryloxy group of carbon number of 1 to 12, halogen atom, carbon number of 1 Alkylamine group of ~12, dialkylamine group of carbon number of 2 to 12, alkylamide of alkyl group of carbon number of 1 to 12, or arylamide of aryl group of carbon number of 6 to 20 group, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, and thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, from From the viewpoint of stability, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, and sulfinic acid ion are preferable. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferable substituents include 1 to 12 carbon atoms. alkyl, alkenyl with 2-12 carbons, alkynyl with 2-12 carbons, aryl with 1-12 carbons, alkoxy with 1-12 carbons, aryloxy with 1-12 carbons , halogen atom, monoalkylamine group with 1 to 12 carbon atoms, dialkylamine group with 1 to 12 carbon atoms in the alkyl group, and alkyl amide group with 1 to 12 carbon atoms in the alkyl group An amino group or an aryl amido group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z21 ^- represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, stable from stable From the viewpoint of properties and reactivity, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylate ion are preferable. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ each independently represent an aryl group, an alkyl group, an alkenyl group, and an alkynyl group having 1 to 6 substituents having 6 to 20 carbon atoms, preferably , from the viewpoint of reactivity and stability, aryl groups are preferred. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an aryl group having 1 to 12 carbon atoms. Alkoxy group of 12, aryloxy group of carbon number of 1 to 12, halogen atom, monoalkylamine group of carbon number of 1 to 12, dialkylamine of carbon number of alkyl group each independently being carbon number of 1 to 12 The carbon number of the group and the alkyl group is an alkyl amido group or an aryl amido group with a carbon number of 1 to 12, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group with a carbon number of 1 to 12, a carbon number 1-12 thioaryl groups. Z ₃₁ ^- represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, from From the viewpoint of stability and reactivity, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylate ion are preferable.

[化學式58]

[化學式59]

[化學式60]

Specific examples of preferable photoacid generators include the following. [Chemical formula 57]

[Chemical formula 58]

[Chemical formula 59]

[Chemical formula 60]

The photoacid generator is preferably used in 0.1 to 20 mass %, more preferably 0.5 to 18 mass %, more preferably 0.5 to 10 mass %, and 0.5 to 3 mass % with respect to the total solid content of the resin composition. It is even more preferable to use 0.5 to 1.2 mass %. A photoacid generator may be used individually by 1 type, and may be used in combination of a plurality of types. When using a plurality of types in combination, it is preferable that these total amounts are within the above-mentioned range. Moreover, in order to provide photosensitivity to a desired light source, it is also preferable to use together with a sensitizer.

<Thermal acid generator> The composition of the present invention may contain a thermal acid generator. The thermal acid generator has the effect of generating an acid by heating to promote a compound selected from the group consisting of a methylol group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound, and a benzoyl group A polymerization reaction of at least one of the 𠯤 compounds.

The thermal decomposition initiation temperature of the thermal acid generator is preferably 50°C to 270°C, more preferably 50°C to 250°C. In addition, if one is selected, no acid is generated during drying (pre-baking: about 70 to 140° C.) after applying the composition on the substrate, and final heating (curing) is performed after patterning during subsequent exposure and development. : about 100 to 400° C.), which generates an acid as a thermal acid generator can suppress the decrease in sensitivity at the time of development, so it is preferable. The thermal decomposition initiation temperature was obtained as the peak temperature of the exothermic peak with the lowest temperature when the thermal acid generator was heated to 500° C. in a pressure-resistant capsule at 5° C./min. A Q2000 (manufactured by TA Instruments.) etc. is mentioned as an apparatus used when measuring the thermal decomposition start temperature.

The acid generated from the thermal acid generator is preferably a strong acid, such as arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, alkanesulfonic acid such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or trifluoromethanesulfonic acid, etc. Haloalkanesulfonic acid and the like are preferred. Examples of such thermal acid generators include those described in paragraph 0055 of Japanese Patent Laid-Open No. 2013-072935.

Among them, from the viewpoint of less residual in the organic film and less likely to degrade the physical properties of the organic film, those that generate alkanesulfonic acids having 1 to 4 carbon atoms or haloalkane sulfonic acids having 1 to 4 carbon atoms are more preferable as thermal acids. Generating agent, methanesulfonic acid (4-hydroxyphenyl) dimethyl sulfamate, methanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl) dimethyl sulfamate, methanesulfonic acid benzyl ( 4-Hydroxyphenyl) methyl sulfamate, benzyl methanesulfonate (4-((methoxycarbonyl)oxy)phenyl)methyl sulfamate, methanesulfonate (4-hydroxyphenyl)methyl ( (2-Methylphenyl)methyl)perylium salt, (4-hydroxyphenyl)dimethylperylium trifluoromethanesulfonate, (4-((methoxycarbonyl)oxy) trifluoromethanesulfonic acid phenyl) dimethyl perionate salt, benzyl (4-hydroxyphenyl) methyl perylium trifluoromethanesulfonate, benzyl (4-((methoxycarbonyl)oxy)phenyl trifluoromethanesulfonate ) methyl sulfamate, (4-hydroxyphenyl) methyl ((2-methylphenyl)methyl) sulfamate trifluoromethanesulfonate, 3-(5-(((propanesulfonyl)oxy) )imino)thiophene-2(5H)-idene)-2-(o-tolyl)propionitrile, 2,2-bis(3-(methylsulfonamido)-4-hydroxyphenyl)hexa Fluoropropane is preferred.

Moreover, as a thermal acid generator, the compound described in the 0059 paragraph of Unexamined-Japanese-Patent No. 2013-167742 is also preferable.

The content of the thermal acid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, with respect to 100 parts by mass of the specific resin. Since a polymerization reaction is accelerated|stimulated by containing 0.01 mass part or more, the mechanical property and solvent resistance of an organic film can be improved further. In addition, from the viewpoint of the electrical insulating properties of the organic film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is still more preferable.

<Polymerizable compound> It is preferable that the resin composition of this invention contains a polymerizable compound. As a polymerizable compound, a radical crosslinking agent or another crosslinking agent is mentioned.

[Radical crosslinking agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radically polymerizable group. The radically polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing the above-mentioned ethylenically unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acryloyl. Groups with ethylenically unsaturated bonds such as amine groups. Among these, as the above-mentioned group containing an ethylenically unsaturated bond, a (meth)acrylamide group, a (meth)acrylamido group, and a vinylphenyl group are preferable, and from the viewpoint of reactivity, (Meth)acryloyl groups are more preferred.

The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. As the above-mentioned compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 15 ethylenically unsaturated bonds is more preferable. The compound of 6 is more preferable. In addition, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention may also include a compound having two ethylenically unsaturated bonds and a compound having three or more 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 even 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 the radical crosslinking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, amides The amines are preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, the addition reaction products of unsaturated carboxylic acid esters or amides with affinity substituents such as hydroxyl groups, amine groups, and hydrogen thiol groups and monofunctional or polyfunctional isocyanates or epoxides can also be preferably used, Dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. In addition, 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 halogen groups or Substitution reaction products of unsaturated carboxylic acid esters or amides with releasable substituents such as tosyloxy and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, a compound group substituted with vinylbenzene derivatives such as unsaturated phosphonic acid, styrene, vinyl ether, and allyl ether can also be used instead of the above-mentioned unsaturated carboxylic acid. As a specific example, the description of paragraphs 0113 to 0122 of JP 2016-027357 A can be referred to, and these contents are incorporated into the present specification.

Moreover, it is also preferable that the 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, and neopentaerythritol tri(meth)acrylate. (Meth)acrylate, Neotaerythritol Tetra (meth)acrylate, Dipivalerythritol Penta (meth)acrylate, Dipivalerythritol Hexa (meth)acrylate, Hexylene Glycol Di( meth)acrylate, trimethylolpropane tris(acryloyloxypropyl) ether, tris(acryloyloxyethyl) isocyanurate, glycerol or trimethylolethane, etc. Compounds obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols and then (meth)acrylated Amino (meth)acrylates described in each publication of Sho 51-037193, Japanese Patent Publication No. Sho 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. Sho 52-030490 Polyester acrylates, polyfunctional acrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid, or methacrylates, and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also preferred. Moreover, polyfunctional (meth)acrylate etc. obtained by making the compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, react with a polyfunctional carboxylic acid are also mentioned.

Moreover, as preferable radical crosslinking agent substances other than the above, those described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216 and the like can also be used. A compound having a perylene ring and having two or more ethylenically unsaturated bond-containing groups or a cardo resin.

Furthermore, as other examples, the specific unsaturated compounds described in JP 46-043946 A, JP 01-040337 A, JP 01-040336 A, or JP 02 - Vinylphosphonic acid-based compounds and the like described in Gazette 025493. Moreover, the compound containing a perfluoroalkyl group described in Unexamined-Japanese-Patent No. 61-022048 can also be used. Furthermore, those described as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP 2015-034964 A and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the etc. are incorporated into this manual.

In addition, in Japanese Patent Application Laid-Open No. 10-062986, the following compounds, which are described as formula (1) and formula (2) together with specific examples thereof, can also be used as a radical crosslinking agent in a polyfunctional alcohol. A compound obtained by adding ethylene oxide or propylene oxide and then (meth)acrylated.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as the radical crosslinking agent, and these contents are incorporated in the present specification.

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

Commercially available products of the radical crosslinking agent include, for example, SR-494 produced by Sartomer Company, Inc. as a tetrafunctional acrylate having four ethoxy-extending chains, and SR-494 as a tetrafunctional acrylate having four vinyloxy chains Functional methyl acrylate SR-209, 231, 239 manufactured by Sartomer Company, Inc., DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, as DPCA-60 having 3 TPA-330 of trifunctional acrylate of isobutyloxy 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, for example, the amine esters described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765 Acrylates, those described in 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 having an ethylene oxide-based skeleton The amine ester compounds are also preferred. Furthermore, as the radical crosslinking agent, those described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. Hei 01-105238 having an amino group in the molecule can also be used. Compounds of structure or sulfide structure.

The free-radical cross-linking agent may be a free-radical cross-linking agent having an acid group such as a carboxyl group and a phosphoric acid group. The free-radical crosslinking agent with an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride reacts with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. Free radical crosslinking agents are more preferred. Particularly preferred is a free-radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, and the aliphatic polyhydroxy compound is neopentylerythritol or dipivostriol Alcohol compounds. As a commercial item, M-510, M-520 etc. are mentioned as a polybasic acid-modified acrylic oligomer by TOAGOSEI CO., Ltd., for example.

The preferred acid value of the radical crosslinking agent having an acid group is 0.1-300 mgKOH/g, and particularly preferably 1-100 mgKOH/g. As long as the acid value of the radical crosslinking agent is within the above-mentioned range, the workability in production is excellent, and furthermore, the developability is excellent. In addition, the polymerizability was good. The said acid value is measured based on the description of JISK0070:1992.

From the viewpoints of pattern resolution and film stretchability, it is preferable to use a 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) can be used 200 Diacrylate, PEG200 Dimethacrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate Esters, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6hexanediol dimethacrylate , dimethylol tricyclodecane diacrylate, dimethylol tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO of bisphenol A Adduct dimethacrylate, PO (propylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, 2hydroxy-3-propenyloxypropane methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, bifunctional acrylate with other urethane bond, bifunctional methyl with urethane bond based acrylate. These can be mixed and used 2 or more types as needed. In addition, for example, PEG200 diacrylate refers to a polyethylene glycol diacrylate and the formula weight of the polyethylene glycol chain is about 200. Regarding the resin composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the pattern (hardened product). As the monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy Ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-Methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, alkenyl glycidyl ether, and the like. 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. In addition, as a bifunctional or more radical crosslinking agent, allyl compounds, such as diallyl phthalate and triallyl trimellitate, are mentioned.

When a radical crosslinking agent is contained, it is preferable that the content exceeds 0 mass % and 60 mass % or less with respect to the total solid content of the resin composition of this invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.

A radical crosslinking agent may be used individually by 1 type, and may be used in mixture of 2 or more types. When using 2 or more types simultaneously, it is preferable that the total amount is in the said range.

[Other cross-linking agents] It is also preferable that the resin composition of the present invention contains other cross-linking agents different from the above-mentioned radical cross-linking agents. In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and has a plurality of crosslinking agents in the molecule, which are promoted by the above-mentioned photoacid generator or photobase generator to facilitate interaction with the composition. The other compounds in the compound or the reaction products of the other compounds or the reaction products thereof are preferably the compounds of the group that form a covalent bond, and have a plurality of compounds in the molecule that are promoted by the action of acids or bases in the composition with the other compounds or their compounds. Compounds of reactive groups that form covalent bonds between the reaction products are preferred. The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step. As other cross-linking agents, compounds having at least one group selected from the group consisting of oxymethyl, methylol and alkoxymethyl are preferred, and compounds having at least one group selected from the group consisting of oxymethyl, hydroxymethyl and alkoxymethyl are preferred. A compound having a structure in which at least one group in the group of hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom is more preferable. Examples of other cross-linking agents include compounds having an amine group-containing compound such as formaldehyde or formaldehyde and alcohols, such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, to be reacted with an oxymethyl group, A compound in which a hydroxymethyl group or an alkoxymethyl group is substituted for the hydrogen atom of the above-mentioned amine 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, the oligomer which the hydroxymethyl group of these compounds self-condenses may be sufficient. The cross-linking agent using melamine as the above-mentioned amine group-containing compound is called a melamine-based cross-linking agent, and the cross-linking agent using glycoluril, urea, or alkylene urea is called a urea-based cross-linking agent. The crosslinking agent using alkylene urea is called alkylene urea crosslinking agent, and the crosslinking agent using benzoguanamine is called benzoguanamine crosslinking agent. Among these, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent, and contains a compound selected from the group consisting of glycoluril-based crosslinking agents described below. At least one compound in the group of the agent and the melamine-based crosslinking agent is more preferable.

As a compound containing at least one of the alkoxymethyl group and the alkoxymethyl group in the present invention, the alkoxymethyl group or the alkoxymethyl group directly in the aromatic group or the following urea structure can be mentioned. Compounds substituted on a nitrogen atom or on a trisium are taken as structural examples. Preferably, the alkoxymethyl or alkoxymethyl group of the above compound has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of the alkoxymethyl group and the alkoxymethyl group contained in the above-mentioned compound is preferably 1-10, more preferably 2-8, particularly preferably 3-6. The molecular weight of the above-mentioned compound is preferably 1500 or less, more preferably 180-1200.

[Chemical formula 61]

R ₁₀₀ represents an alkyl group or an acyl group. R ₁₀₁ and R ₁₀₂ each independently represent a monovalent organic group, and 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 with an aromatic group include various compounds of the following general formula.

[Chemical formula 62]

In the formula, X represents a single bond or a divalent organic group, each R ₁₀₄ independently represents an alkyl group or an acyl group, and R ₁₀₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or an acid A group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that is released by the action of an acid, a group represented by -C(R ⁴ ) ₂ COOR ⁵ (R ⁴ independently represents a hydrogen atom or An alkyl group having 1 to 4 carbon atoms, R ⁵ represents a group that can be removed by the action of an acid.)). R ₁₀₅ each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1-3, d is 0-4, e is 0-3, f is 0-3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. Examples of R ⁵ in the group represented by -C(R ⁴ ) ₂ COOR ⁵ include a group that is decomposed by the action of an acid to generate an alkali-soluble group, a group that is released by the action of an acid, and a group represented by -C(R 4 ) 2 COOR 5 . Out-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 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 cycloalkyl group may have a monocyclic structure or 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, and more preferably a phenyl group. As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable. The above-mentioned aralkyl group refers to an aryl group substituted with an alkyl group, and the preferred aspects of the alkyl group and the aryl group are the same as the preferred aspects of the above-mentioned alkyl group and the aryl group. The above-mentioned alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Moreover, these groups may have a well-known substituent within the range which can obtain the effect of this invention.

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 which is decomposed by the action of an acid to generate an alkali-soluble group or a group which is released by the action of an acid, a tertiary alkyl ester group, an acetal group, a cumyl ester group, and an enol ester are preferred. Base et al. Further preferred are tertiary alkyl ester groups and acetal groups.

As a compound which has an alkoxymethyl group, the following structures are mentioned specifically,. As a compound which has an acyloxymethyl group, the compound which changed the alkoxymethyl group of the following compounds to an acyloxymethyl group is mentioned. As a compound which has an alkoxymethyl group or an acyloxymethyl group in a molecule|numerator, the following various compounds are mentioned, However, It is not limited to these.

[Chemical formula 63]

[Chemical formula 64]

As for the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available one 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 alkoxymethyl group is directly substituted on an aromatic ring or a tris-ring is preferable.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like.

Specific examples of the urea-based crosslinking agent include monomethylolated glycoluril, dimethylolated glycoluril, trimethylolated glycoluril, tetramethylolated glycoluril, and monomethoxyl glycoluril. Methylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethyl methylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethyl Glycoluril Glycoluril based cross-linking agents such as glycoluril; Urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea, etc., Monomethylolated ethyl urea or dimethylolated ethyl urea, monomethoxymethylated ethyl urea, dimethoxymethylated ethyl urea, monoethoxymethylated ethyl urea , diethoxymethylated ethyl urea, monopropoxymethylated ethyl urea, dipropoxymethylated ethyl urea, monobutoxymethylated ethyl urea or dibutoxymethyl ethyl urea Ethyl urea and other ethyl urea crosslinking agents, Monomethylolated Propylene Urea , diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethyl propylene urea Propylene urea based crosslinking agent such as propylene propylene urea, 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole pyridone etc.

Specific examples of the benzoguanamine-based crosslinking agent include, for example, monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, and tetramethylolated benzoguanamine. Methylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine Amine, 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 methylol and alkoxymethyl, a direct bond on an aromatic ring (preferably a benzene ring) can also be preferably used A compound having at least one group selected from the group consisting of methylol and alkoxymethyl. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl) base) benzophenone, hydroxymethyl phenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(hydroxymethyl)biphenyl (Methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methyl Methoxymethylphenyl oxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylene yltris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxyl -1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

Commercially available products can also be used as other crosslinking agents, and preferred commercialized products include 46DMOC, 46DMOEP (the above are manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML- OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML- BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, the same below) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (the above are Sanwa Chemical Co., Ltd.) and the like.

Moreover, it is also preferable that the resin composition of this invention contains at least 1 compound chosen from the group which consists of an epoxy compound, an oxetane compound, and a benzodiazepine compound as another crosslinking agent.

-Epoxy compounds (compounds with epoxy groups)- As an epoxy compound, the compound which has two or more epoxy groups in one molecule is preferable. The epoxy group undergoes a cross-linking reaction below 200°C, and does not produce a dehydration reaction caused by cross-linking, so it is difficult to cause film shrinkage. Therefore, containing an epoxy compound is effective in suppressing low-temperature hardening and warpage of the resin composition of the present invention.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus is further lowered, 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 to 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, butylene glycol Glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl Polyalkylene glycol type epoxy resins such as glycerol ethers; epoxy epoxy silicones such as polymethyl(glycidoxypropyl)siloxane, etc., but not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP- 4700, EPICLON (registered trademark) 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), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (product name, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (product names above, 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 product names above, 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. In addition, the following compounds can also be preferably used.

[Chemical formula 65]

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

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

-Oxetane compounds (compounds with an oxetane group)- Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxy oxetane, 1,4-bis{ [(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4- Benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, ARON OXETANE series (for example, OXT-121 and OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

-Benzoxazole compounds (compounds with a benzoxazolyl group)- Since the cross-linking reaction is caused by the ring-opening addition reaction, the benzodiazepine compound is preferred without degassing during curing, thereby further reducing thermal shrinkage and suppressing warpage.

Preferable examples of benzodiazepine compounds include P-d-type benzodiazepines, F-a-type benzodiazepines, (the above are product names, manufactured by Shikoku Chemicals Corporation), and benzodiazepines of polyhydroxystyrene resins. Adducts, novolac-type dihydrobenzos 㗁𠯤 compounds. These can be used individually or in mixture of 2 or more types.

The content of other crosslinking agents is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, more preferably 0.5 to 15 mass %, and 1.0 to 10 mass % relative to the total solid content of the resin composition of the present invention. Mass % is particularly good. The other crosslinking agent may be contained only by one type, or may contain two or more types. When two or more types of other crosslinking agents are contained, the total is preferably within the above range.

<Polymerization inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol-based 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, and the like .

As a specific compound of the polymerization inhibitor, for example, p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallic phenol, p- tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2' - Methylene bis(4-methyl-6-tert-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-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl) Phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5-tris𠯤-2,4,6- (1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 2,2,6,6-tetramethylpiperidine 1-oxygen Free radicals, phenothia, phenothia, 1,1-diphenyl-2-pyrrolehydrazine, copper(II) dibutyldithiocarbonate, nitrobenzene, N-nitroso-N-phenyl Hydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. In addition, the polymerization inhibitors described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of International Publication No. WO 2015/125469 can also be used, and the contents are incorporated into the present specification. .

When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, preferably 0.02 to 15% by mass, more preferably 0.02 to 15% by mass relative to the total solid content of the resin composition of the present invention. 0.05-10 mass % is more preferable.

Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more kinds of polymerization inhibitors, it is preferable that the total is within the above-mentioned range.

<Metal Adhesion Improver> It is preferable that the resin composition of this invention contains the metal adhesion improver for improving the adhesion with the metal material used for electrodes, wiring, etc.. Examples of the metal adhesion improver include aluminum-based adhesive agents, titanium-based adhesive agents, compounds having a sulfonamide structure, compounds having thiourea, phosphoric acid derivative compounds, β-ketoester compounds, and amine compounds. Wait.

[Aluminum-based Adhesives] Examples of the aluminum-based adhesive adjuvant include aluminum tris(ethylacetate)aluminum, tris(acetoacetate)aluminum, aluminum ethylacetate diisopropoxide, and the like.

In addition, as other metal adhesion improving agents, the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A, and the vulcanized compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A can also be used compounds, and these contents are incorporated into this specification.

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.01 to 10 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the specific resin . By setting it as the said lower limit or more, the adhesiveness of a pattern and a metal layer becomes favorable, and by setting it as the said upper limit or less, the heat resistance and mechanical properties of a pattern become favorable. Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is in the said range.

＜Acid scavenger＞ It is preferable that the resin composition of this invention contains an acid scavenger in order to reduce the change in performance with time from exposure to heating. Among them, the acid scavenger refers to a compound that can capture and generate an acid by being present in the system, and a compound having a low acidity and a high pKa is preferable. As the acid scavenger, compounds with amine groups are preferred, primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred, primary amines, secondary amines, tertiary amines, ammonium salts More preferably, secondary amine, tertiary amine and ammonium salt are more preferable. As the acid scavenger, compounds having an imidazole structure, a diazabicyclic structure, an onium structure, a trialkylamine structure, an aniline structure, or a pyridine structure, and alkylamine derivatives having a hydroxyl group and/or an ether bond can be preferably used. compounds, aniline derivatives with hydroxyl and/or ether bonds, etc. In the case of having an onium structure, the acid scavenger is an anion having a cation selected from the group consisting of ammonium, diazo, iodonium, perium, phosphonium, pyridinium and the like and an acid having a lower acidity than that generated by the acid generator. Salt is preferred.

As an acid scavenger having an imidazole structure, imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole, etc. are mentioned. As an acid scavenger having a diazabicyclic structure, 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]nonane- 5-ene, 1,8-diazabicyclo[5,4,0]undec-7-ene, etc. Examples of the acid scavenger having an onium structure include tetrabutylammonium hydroxide, triaryl perionium hydroxide, benzylmethyl perionium hydroxide, perium hydroxide having a 2-oxoalkyl group, and specifically Triphenyl perium hydroxide, tris(tert-butylphenyl) perium hydroxide, bis(tert-butylphenyl) iodonium hydroxide, benzalkonium methylthiophenium hydroxide, 2-oxopropane hydroxide base thiophenium, etc. Tri(n-butyl)amine, tri(n-octyl)amine, etc. are mentioned as an acid scavenger which has a trialkylamine structure. As an acid scavenger having an aniline structure, 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, N,N-dihexylaniline, etc. are mentioned. As an acid scavenger having a pyridine structure, pyridine, 4-picoline, etc. are mentioned. Examples of alkylamine derivatives having a hydroxyl group and/or ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris(methoxyethoxyethyl)amine, and the like. N,N-bis(hydroxyethyl)aniline etc. are mentioned as an aniline derivative which has a hydroxyl group and/or an ether bond.

Specific examples of preferable acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, Cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine , DBU (diazabicyclo undecyl), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylene glycol Amine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine Amine, N,N,N',N'-Tetrabutyl-1,6-hexanediamine, Spermine, Diaminocyclohexane, Bis(2-methoxyethyl)amine, Piperidine , methylpiperidine, piperidine, tropane, N-phenylbenzylamine, 1,2-diphenylaminoethane (dianilinoethane), 2-aminoethanol, toluidine, aminophenol, hexylaniline, benzene diamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrroleidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylamine, etc.

These acid scavengers may be used alone or in combination of two or more. The composition of the present invention may contain an acid scavenger or may not contain an acid scavenger, but when it does contain an acid scavenger, the content of the acid scavenger is usually 0.001 to 10% by mass based on the total solid content of the composition. Preferably it is 0.01-5 mass %.

The usage ratio of the acid generator and the acid scavenger is preferably acid generator/acid scavenger (molar ratio)=2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing the reduction of the resolution caused by the increase in thickness of the relief pattern with time from exposure to heat treatment. , 300 or less is better. The acid generator/acid scavenger (molar ratio) is more preferably 5.0 to 200, further preferably 7.0 to 150.

＜Other additives＞ The resin composition of the present invention can contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium, as needed, within the range in which the effects of the present invention can be obtained. Compounds, antioxidants, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (eg, defoaming agents, flame retardants, etc.), etc. By appropriately containing these components, properties such as film physical properties can be adjusted. For these components, for example, refer to the descriptions in paragraph 0183 and subsequent paragraphs of Japanese Patent Application Laid-Open No. 2012-003225 (paragraph 0237 of the corresponding specification of US Patent Application Publication No. 2013/0034812) and the descriptions in Japanese Patent Application Laid-Open No. 2008-250074 paragraphs 0101 to 0104, paragraphs 0107 to 0109, etc., and these contents are incorporated into this specification. When these additives are blended, the total blending amount is preferably 3 mass % or less of the solid content of the resin composition of the present invention.

[Surfactant] As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (especially, fluidity) when prepared as a coating liquid can be further improved, and the uniformity of the coating thickness and the liquid saving property can be further improved. . That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved, thereby improving the wettability of the surface to be coated. Improves coatability to the coated surface. Therefore, it is possible to more preferably form a film with a uniform thickness with little 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, Novell FC4430, Novell 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 (ASAHI GLASS CO above ., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A and the compounds described in paragraphs 0117 to 0132 of JP 2011-132503 A can also be used, and these The contents are incorporated into this manual. A block polymer can also be used as a fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090, which are incorporated into the present specification. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, which contains a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably A repeating unit of a (meth)acrylate compound of an alkaneoxy group (preferably vinyloxy group, propyleneoxy group) having 5 or more), the following compounds can also be exemplified as the fluorine-based interface used in the present invention active agent. [Chemical formula 66]

The weight average molecular weight of the above-mentioned compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000. Fluorine-based Surfactant A fluoropolymer having an ethylenically unsaturated group on a side chain can also be used as a fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, which are incorporated into the present specification. Moreover, as a commercial item, MEGAFACE RS-101 by DIC CORPORATION, RS-102, RS-718K etc. are mentioned, for example.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of the uniformity of the thickness of the coating film and the liquid-saving property, and the solubility in the composition is also good.

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are Dow Corning Toray Co. ., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive performance Materials Inc.), KP-341, KF6001, KF6002 (the above are Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie GmbH), and the like.

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.

As the nonionic surfactant, glycerin, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate) can be exemplified etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilauric acid ester, polyethylene glycol distearate, sorbitan fatty acid ester, etc. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), 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 (TAKEMOTO OIL & FAT CO ., manufactured by LTD), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), and the like.

Specific examples of the cationic surfactant 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.), and the like.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), SANDET BL (manufactured by SANYO KASEI Co., Ltd.), and the like.

Only one type of surfactant may be used, or two or more types may be used in combination. The content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition.

[Higher fatty acid derivatives] In order to prevent polymerization inhibition due to oxygen, higher fatty acid derivatives such as behenic acid or behenamide may be added to the resin composition of the present invention to make it non-uniform in the drying process after coating exist on the surface of the resin composition of the present invention.

In addition, the compound described in the paragraph 0155 of International Publication No. WO 2015/199219 can also be used as the higher fatty acid derivative, and the content is incorporated in the present specification.

When the resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. Only one type of higher fatty acid derivatives may be used, or two or more types may be used. When there are two or more kinds of higher fatty acid derivatives, it is preferable that the total is within the above-mentioned range.

[Thermal polymerization initiator] The resin composition of the present invention may contain a thermal polymerization initiator, especially a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates a radical by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed, so that the solvent resistance can be further improved. 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.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554, and the contents thereof are incorporated in the present specification.

When a thermal polymerization initiator is contained, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 30% by mass relative to the total solid content of the resin composition of the present invention. 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. 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, as inorganic particles, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc. can be included.

The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 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 a dynamic light scattering method based on Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). In the case where it is difficult to perform the above-mentioned measurement, the measurement can also be performed by the centrifugal sedimentation light transmission method, the X-ray transmission method, and the laser diffraction/scattering method.

[Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and trisulfuric acid-based absorbers can be used. Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like. Examples of the benzophenone-based ultraviolet absorber include Examples of the agent 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 ketone etc. Moreover, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2- -(2'-Hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-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-tert-butyl Phenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetrakis Methyl)phenyl]benzotriazole, etc.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like . Furthermore, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 is mentioned as an example of a tris-based ultraviolet absorber -Bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2- Hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-(2,4-dihydroxyphenyl)-4,6-bis( 2,4-Dimethylphenyl)-1,3,5-tris(hydroxyphenyl)tris-compounds such as 2,4-bis(2-hydroxy-4-propoxyphenyl)-6 -(2,4-Dimethylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4 -Methylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethyl Phenyl)-1,3,5-tris(bis(hydroxyphenyl)tris) compounds such as bis(hydroxyphenyl)tris; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis) Butoxyphenyl)-1,3,5-tris𠯤, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris𠯤, 2,4, 6-Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris-tris(hydroxyphenyl)tris-compounds, etc.

In this invention, the said various ultraviolet absorbers may be used individually by 1 type, and may be used in combination of 2 or more types. 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 or more and 1% by mass relative to the total solid mass of the composition of the present invention. Mass % or less is preferable, and 0.01 mass % or more and 0.1 mass % or less are more preferable.

[Organo-titanium compound] The resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organotitanium compound, a resin layer excellent in chemical resistance can be formed even when it is cured at a low temperature.

As the organotitanium compound that can be used, an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organotitanium compounds are shown in the following I) to VII): I) Titanium chelate compound: Among them, the resin composition has excellent storage stability and a good hardened pattern can be obtained, so the titanium chelate compound having two or more alkoxy groups is more preferable. Specific examples are diisopropoxide bis(triethanolamine) titanium, di(n-butanol) bis(2,4-pentanedione) titanium, diisopropoxide bis(2,4-pentanedione) titanium, diisopropoxide bis(2,4-pentanedione) titanium, Isopropanol bis (tetramethylheptanedione) titanium, diisopropanol bis (ethyl acetate) titanium, etc. II) Titanium tetraalkoxide compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetrakis(2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, Titanium Tetramethoxypropoxide, Titanium Tetramethylphenoxide, Titanium Tetra(n-nonanol), Titanium Tetra(n-propoxide), Titanium Tetrastearyloxide, Tetrakis[bis{2,2-(allyloxy) Methyl) butanol}] titanium and so on. III) Titanocene compounds: for example, titanium pentamethylcyclopentadienyltrimethoxide, 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 compounds: for example, tris(dioctyl phosphate) titanium isopropoxide, tris(dodecylphenyl sulfonate) titanium isopropoxide, and the like. V) Titanium oxide compound: for example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agent: for example, isopropyl tridodecylbenzenesulfonic acid titanate and the like.

Among them, as the organotitanium compound, from the viewpoint of exhibiting better chemical resistance, those selected from the group consisting of the above-mentioned I) titanium chelate compounds, II) tetraalkoxytitanium compounds and III) titanocene compounds At least one compound is preferred. In particular, bis(ethylacetate)titanium diisopropoxide, tetrakis(n-butoxide)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro- 3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

When the 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, with respect to 100 parts by mass of the specific resin. When the compounding amount is 0.05 parts by mass or more, the obtained cured pattern exhibits good heat resistance and chemical resistance more effectively. On the other hand, when the compounding amount is 10 parts by mass or less, the The storage stability is more excellent.

〔Antioxidants〕 The composition of the present invention may contain antioxidants. By containing an antioxidant as an additive, the elongation property of the film after hardening and the adhesiveness with a metal material can be improved. As an antioxidant, a phenol 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. Moreover, it is also preferable that the antioxidant is a compound having a phenol group and a phosphite group in the same molecule. In addition, phosphorus-based antioxidants can also be preferably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2] Dioxaphosphin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f] [1,3,2]Dioxaphosphin-2-yl)oxy]ethyl]amine and phosphite ethylbis(2,4-di-tert-butyl-6-methyl) phenyl) etc. Commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO- 80 and Adekastab AO-330 (the above are made by ADEKA CORPORATION), etc. In addition, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as antioxidants, and the contents are incorporated in the present specification. Moreover, the composition of this invention may contain a latent antioxidant as needed. As potential antioxidants, compounds whose sites that act as antioxidants are protected by protective groups can be exemplified by heating at 100 to 250°C or at 80 to 200°C in the presence of an acid/base catalyst. A compound that acts as an antioxidant when heated to remove the protecting group. Examples of potential antioxidants include compounds described in International Publication No. WO 2014/021023, International Publication No. 2017/030005, and JP 2017-008219 A, the contents of which are incorporated into the present specification. As a commercial item of a potential antioxidant, ADEKA ARKLS GPA-5001 (made by ADEKA CORPORATION) etc. are mentioned. Examples of preferable antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and formula (3) the indicated compound.

[Chemical formula 67]

In the general formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably carbon number 2 to 10), and R ⁶ represents an extension of carbon number 2 or more (preferably carbon number 2 to 10). alkyl. R ⁷ represents an alkylene group having 2 or more carbon atoms (preferably, a carbon number of 2 to 10), and a 1- to 4-valent organic group containing at least any one of an oxygen atom and a nitrogen atom. k represents an integer of 1-4.

The compound represented by the formula (3) suppresses the oxidative deterioration of the aliphatic group and the phenolic hydroxyl group contained in the resin. Moreover, metal oxidation can be suppressed by the rust preventive effect on the metal material.

Since it can act on a resin and a metal material at the same time, it is more preferable that k is an integer of 2 to 4. Examples of R ⁷ include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, and an allyl group. group, vinyl group, heterocyclic group, -O-, -NH-, -NHNH-, a combination of these, etc., and may have a substituent. Among them, those having an alkyl ether group and -NH- are preferred from the viewpoints of solubility in a developer and metal adhesion, and from the viewpoints of interaction with resins and metal adhesion at the time of metal complex formation Consider, -NH- is better.

The compounds represented by the general formula (3) include the following as examples, but are not limited to the following structures.

[Chemical formula 68]

[Chemical formula 69]

[Chemical formula 70]

[Chemical formula 71]

The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, with respect 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 effect of improving elongation properties and adhesion to metal materials, and by setting the addition amount to 10 parts by mass or less, for example The sensitivity of the resin composition is improved by the interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When using 2 or more types, it is preferable that these total amounts are in the said range.

[Anti-agglomeration agent] The resin composition of this embodiment may contain an anti-agglomeration agent as needed. As an anti-agglomeration agent, sodium polyacrylate etc. are mentioned.

In this invention, an anti-agglomeration agent may be used individually by 1 type, and may be used in combination of 2 or more types. The composition of the present invention may or may not contain an anti-agglomeration agent, but when included, the content of the anti-agglomeration agent is 0.01% by mass or more and 10% by mass relative to the total solid mass of the composition of the present invention. Mass % or less 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, Methylenetris-FR-CR, BisRS-26X (the product names above, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC , BIR-PTBP, BIR-BIPC-F (the product name above, 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 the phenolic compound, but when included, the content of the phenolic compound is 0.01% by mass or more and 30% by mass relative to the total solid mass of the composition of the present invention. 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 polymers obtained by copolymerizing (meth)acrylic acid, novolak resins, cresol resins, polyhydroxystyrene resins, and copolymers thereof. things etc. The other polymer compound may be a modified product into which a cross-linking group such as a methylol group, an alkoxymethyl group, and an epoxy group is introduced.

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 polymer compounds, but when included, the content of the other polymer compounds is 0.01% by mass relative to the total solid mass of the composition of the present invention More than 30 mass % 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 by the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm ² /s to 12,000 mm ² /s is preferable, 2,000 mm ² /s to 10,000 mm ² /s is more preferable, and 3,000 mm ² /s to 8,000 mm ² /s for further better. As long as it is in the said range, it becomes easy to obtain the coating film with high uniformity. When it is 1,000 mm ² /s or less, for example, it is difficult to coat with a film thickness required as an insulating film for rewiring, and when it is 12,000 mm ² /s or more, the coating surface morphology may be deteriorated.

<Restrictions on Substances Contained in Resin Compositions> The water 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 even more preferably less than 1.0% by mass. When it is 2.0% or more, the storage stability of the resin composition may be impaired. As a method of maintaining the moisture content, adjustment of the humidity in the storage conditions, reduction of the porosity of the storage container during storage, and the like are exemplified.

From the viewpoint of insulating properties, 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 even more preferably less than 0.5 mass ppm good. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, and the like, with the exception of metals included as complexes of organic compounds and metals. When a plurality of metals are contained, it is preferable that the sum of these metals is within the above-mentioned range.

Further, as a method for reducing the metal impurities accidentally contained in the resin composition of the present invention, there can be mentioned a method of selecting a raw material having a small metal content as a raw material constituting the resin composition of the present invention; The raw material of the product is filtered through a filter; the polytetrafluoroethylene and the like are lined in the device to conduct distillation under the condition that the pollution is suppressed as much as possible.

Considering the use of the resin composition of the present invention as a semiconductor material, from the viewpoint of wiring corrosion, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm good. Among them, it is preferable that it is less than 5 mass ppm in the state of halide ions, it is more preferable that it is less than 1 mass ppm, and it is more preferable that it is less than 0.5 mass ppm. As a halogen atom, a chlorine atom and a bromine atom are mentioned. The total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is preferably within the above ranges, respectively. As a method for adjusting the content of halogen atoms, ion exchange treatment and the like can be preferably used.

As a container of the resin composition of the present invention, a conventionally known container can be used. Further, as the container, in order to suppress the contamination of impurities into the raw material or the resin composition of the present invention, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 kinds of 6-layer resins, or a bottle in which 6 kinds of resins are formed into a 7-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<The cured product of the resin composition> By curing the resin composition of the present invention, a cured 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 carried out 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 Excellent inside. The form of the cured product of the resin composition is not particularly limited, and a film form, a rod form, a spherical form, a granular form, and the like can be selected according to the application. In the present invention, the cured product is preferably in the form of a film. Furthermore, by patterning the resin composition, the cured product can also be selected for purposes such as forming a protective film on the wall surface, forming a beer hall for conduction, adjusting impedance, capacitance or internal stress, and imparting a heat release function. shape. The film thickness of the cured product (film formed from the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage ratio when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage ratio refers to the percentage of volume change before and after curing of the resin composition, and can be calculated by the following formula. Shrinkage rate [%]=100-(volume after hardening÷volume before hardening)×100

<Characteristics of cured product of resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When it is less than 70%, the mechanical properties of the cured product may be poor. 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 even 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 even 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 can be performed by a conventionally known method. For the mixing, mixing by a stirring blade, mixing by a ball mill, mixing by rotating a tank itself, and the like can be employed. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

In addition, in order to remove foreign matter, such as dust and fine particles, in the resin composition of the present invention, it is preferable to perform filtration using a filter. The filter pore diameter is, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, HDPE (High Density Polyethylene) is better. Filters can be pre-cleaned with organic solvents. In the filtering step of the filter, a plurality of filters may be connected in series or in parallel and used. In the case of using a plurality of filters, filters with different pore sizes or materials can be used in combination. As a connection aspect, for example, an HDPE filter having a pore diameter of 1 μm as the first stage and an HDPE filter having a pore diameter of 0.2 μm as the second stage are connected in series. Also, various materials can be filtered multiple times. In the case of filtering multiple times, it can be a loop filtering. Moreover, you may filter after pressurization. In the case of pressurizing and filtering, the pressurizing pressure can be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. Preferably, it is more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be mentioned. Furthermore, after the filtration using a filter, the step of leaving the resin composition filled in the bottle in a reduced pressure state and deaerating may be carried out.

(Manufacturing method of hardened product) It is preferable that the manufacturing method of the hardened|cured material of this invention includes the film formation process of forming a film by applying a resin composition to a base material. Moreover, the manufacturing method of the hardened|cured material of this invention comprises the said film formation process, the exposure process of selectively exposing the film formed by the film formation process, and developing the film exposed by the exposure process using a developing solution to form a pattern The development step is better. Moreover, it is preferable that the manufacturing method of the hardened|cured material of this invention includes the said image development process, and further includes the post-development exposure step of exposing the pattern obtained by the said image development after the said image development process. The manufacturing method of the hardened|cured material of this invention includes the said film formation process, the said exposure process, the said development process, the heating process which heats the pattern obtained by the development process, and the exposure process of the pattern obtained by the development process. At least one of the post-development exposure steps is particularly preferred. In the case where the manufacturing method of the cured product of the present invention includes both the above-mentioned post-development exposure step and the above-mentioned heating step, the exposure in the post-development exposure step and the heating in the heating step may be performed simultaneously, or one of them may be started first. One may end first, and the order of execution and the repetition time are not particularly limited. Moreover, the aspect which does not include a heating process but an exposure process after image development can also be used. Moreover, it is also preferable that the manufacturing method of this invention includes the said film formation step and the step of heating the said film. Hereinafter, the details of each step will be described.

<Film formation step> The resin composition of the present invention can be used in a film forming step for forming a film by applying it to a substrate. It is preferable that the manufacturing method of the hardened|cured material of this invention includes the film formation process of forming a film by applying a resin composition to a base material.

[Substrate] The type of the substrate can be appropriately set according to the application, but is not particularly limited, and examples thereof include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor Metal substrates such as coating films, magnetic films, reflective films, Ni, Cu, Cr, Fe, etc. ), paper, SOG (Spin On Glass: spin-on glass), TFT (Thin Film Transistor) array substrates, mold substrates, electrode plates for plasma display panels (PDP), etc. In the present invention, especially semiconductor fabrication substrates are preferred, and silicon substrates, Cu substrates and mold substrates are even more preferred. In addition, layers such as an adhesion layer and an oxide layer made of hexamethyldisilazane (HMDS) or the like may be provided on the surfaces of these substrates. In addition, the shape of the base material is not particularly limited, and may be circular or rectangular. As a size of a base material, if it is a circle, a diameter is 100-450 mm, for example, Preferably it is 200-450 mm. In the case of a rectangle, the length of the short side is, for example, 100 to 1000 mm, preferably 200 to 700 mm. Moreover, as a base material, for example, a plate-shaped, preferably panel-shaped base material (substrate) can be used.

Moreover, when a resin composition is applied to the surface of a resin layer (for example, a layer formed of a cured product) or the surface of a metal layer to form a film, the resin layer or the metal layer becomes a base material.

As a method of applying the resin composition of the present invention to a substrate, coating is preferable.

Specific examples of the applicable method include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, and spin coating. method, slit coating method, inkjet method, etc. From the viewpoint of uniformity of film thickness, spin coating method, slit coating method, spray method or inkjet method are more preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating method and The slit coating method is preferred. A film having a desired thickness can be obtained by adjusting the solid content concentration or coating conditions of the resin composition according to the method. In addition, the coating method can also be appropriately selected according to the shape of the substrate. In the case of a circular substrate such as a wafer, spin coating, spray coating, inkjet method, etc. are preferred, and in the case of a rectangular substrate, slit A coating method, a spraying method, an ink jet method, etc. are preferable. In the case of the spin coating method, for example, it can be applied at a rotational speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Moreover, the method of transcribe|transferring the coating film formed by the said application method to a dummy support beforehand is also applicable to a base material. Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used in the present invention. . Also, a step of removing excess film in the end portion of the base material may be performed. Examples of such a step include edge bead rinse (EBR), back rinse (Back rinse), and the like. In addition, a pre-wetting step may be employed, in which the resin composition is applied after various solvents are applied to the substrate to improve the wettability of the substrate before the resin composition is applied to the substrate.

<Drying step> After the film forming step (layer forming step), the above-mentioned film may be used in a step (drying step) of drying the formed film (layer) in order to remove the solvent. That is, the manufacturing method of the hardened|cured material of this invention may include the drying process which dries the film formed by the film formation process. 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 50-150°C, more preferably 70-130°C, and further preferably 90-110°C. Moreover, drying can also be performed by reducing pressure. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

<Exposure step> The said film can be used for the exposure step of selectively exposing the film. That is, the manufacturing method of the hardened|cured material of this invention may include the exposure process which selectively exposes the film formed by the film formation process. Selectively exposing means exposing a portion of the film. Moreover, by selectively exposing, an exposed area (exposed part) and an unexposed area (non-exposed part) are formed on the film. The exposure amount is not particularly limited as long as the resin composition of the present invention can be cured. For example, the exposure energy at a wavelength of 365 nm is converted to 50 to 10,000 mJ/cm ² , preferably 200 to 8,000 mJ/cm ² . for better.

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

Regarding the exposure wavelength, if the relationship with the light source is explained, (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), broad (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser radiation (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser The second harmonic of the radiation is 532nm and 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-ray is preferable. Thereby, a particularly high exposure sensitivity can be obtained. In addition, the method of exposure is not particularly limited, as long as it is a method of exposing at least a part of the film formed of the resin composition of the present invention, and exposure using a mask, exposure by direct laser imaging, etc. .

<Heating step after exposure> The above-mentioned film may be used in a step of heating after exposure (post-exposure heating step). That is, the manufacturing method of the hardened|cured material of this invention may include the post-exposure heating process which heats the film exposed by the exposure process. The post-exposure heating step can be performed after the exposure step and before the developing step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. Regarding the heating rate in the post-exposure heating step, the temperature from the start of heating to the maximum heating temperature is preferably 1 to 12°C/min, more preferably 2 to 10°C/min, and still more preferably 3 to 10°C/min good. In addition, the temperature increase rate can be appropriately changed during the heating process. It does not specifically limit as a heating means in a post-exposure heating process, A well-known hot plate, oven, infrared heater, etc. can be used. Moreover, it is also preferable to carry out in the environment of a low oxygen concentration by flowing inert gas, such as nitrogen gas, helium gas, and argon gas, etc. at the time of heating.

<Development step> The above-mentioned film after exposure can be used in the developing step of forming a pattern by developing with a developing solution. That is, the manufacturing method of the hardened|cured material of this invention may include the developing process which develops the film exposed by the exposure process using a developing solution, and forms a pattern. By performing development, one of the exposed part and the non-exposed part of the film is removed, and a pattern is formed. Among them, the development of removing the non-exposed portion of the film by the development step is called negative development, and the development of removing the exposed portion of the film by the development step is called positive development.

[Developer] As the developing solution used in the developing step, an alkaline aqueous solution or a developing solution containing an organic solvent can be exemplified.

When the developing solution is an alkaline aqueous solution, examples of the alkaline compounds that the alkaline aqueous solution can contain include inorganic bases, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, TMAH ( Tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyl Diethylamine, Dimethylethanolamine, Triethanolamine, Tetraethylammonium Hydroxide, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide, Tetrapentylammonium Hydroxide, Tetrahexylammonium Hydroxide, Hydrogen Tetraoctylammonium oxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethyl bis(hydroxide) 2-hydroxyethyl)ammonium, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole and piperidine are preferred, and TMAH is more preferred. For example, in the case of using TMAH, the content of the alkaline compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass in the total mass of the developer. good.

When the developing solution contains an organic solvent, the organic solvent includes, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, propionic acid, etc., for example. Butyl, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkoxyacetate alkoxyacetate (e.g. methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl methoxyacetate) Methyl oxyacetate, ethyl ethoxyacetate, etc.), 3-alkoxy propionate alkyl esters (for example: 3-alkoxy propionate methyl ester, 3-alkoxy ethyl propionate, etc.) (For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxy Alkyl propionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., 2-methoxypropionic acid) methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy -Methyl 2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (eg, methyl 2-methoxy-2-methylpropanoate, 2-ethoxy-2- ethyl methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, 2-oxobutane Ethyl acid, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethylene glycol Cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone can be preferably used ketone, N-methyl-2-pyrrolidone, etc., and cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, cyclic terpenes such as limonene, Preferable examples of the sulfites include dimethylsulfoxide, and as the alcohols, preferred examples include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, and diethylenediol. Alcohol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., and as the amides, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide are preferably used. Wait.

When the developer contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, development of at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone and cyclohexanone is particularly included The solution is preferred, and the developing solution containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone and dimethylsulfoxide is more preferred, and the developing solution including cyclopentanone is the most preferred.

When the developing solution contains an organic solvent, the content of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more relative to the total mass of the developer solution. The above are 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 developer] The method for supplying the developer is not particularly limited as long as a desired pattern can be formed, and there are methods of immersing the substrate on which the film is formed in the developer, and supplying the developer to the film formed on the substrate using a nozzle In order to carry out spin-on immersion development or continuous supply of developer. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removal of the non-image area, and the production efficiency, the method of supplying the developer using a straight nozzle or the method of continuously supplying the developer using a spray nozzle is preferable. From the viewpoint of the permeability of the part, the method of supplying using a spray nozzle is more preferable. Also, after the developer is continuously supplied using the straight nozzle, the substrate is rotated to remove the developer from the substrate, and after the continuous supply using the straight nozzle again after spin drying, the substrate is rotated to remove the developer from the substrate The step of liquid solution can also be repeated several times. Further, as a method of supplying the developer in the developing step, a step of continuously supplying the developer to the substrate, a step of keeping the developer in a substantially stationary state on the substrate, and developing the substrate by ultrasonic waves or the like can be employed The steps of liquid vibration and the steps combining these, etc.

The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, but it can be preferably carried out at 10 to 45°C, and more preferably at 18 to 30°C.

In the developing step, after the treatment with the developing solution, cleaning (rinsing) of the pattern using the rinsing solution may be further performed. In addition, a method of supplying a rinsing liquid or the like may be employed before the developing liquid in contact with the pattern is completely dried.

[Rinse fluid] When the developing solution is an alkaline aqueous solution, for example, water can be used as the rinsing solution. In the case where the developing solution is a developing solution containing an organic solvent, as the rinsing solution, for example, a solvent different from the solvent contained in the developing solution (for example, water, an organic solvent different from the organic solvent contained in the developing solution) can be used ).

As the organic solvent when the rinsing liquid contains an organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, Isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate ( Example: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid methyl ester, ethyl ethoxyacetate, etc.), 3-alkoxypropionic acid alkyl esters (for example: methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid Alkyl esters (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, 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 acid ethyl ester, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve can be preferably mentioned. Agent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N -Methyl-2-pyrrolidone, etc., and cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, cyclic terpenes such as limonene, Examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, amyl alcohol, octanol, diethylene glycol, and propylene glycol. , methyl isobutyl methanol, triethylene glycol, etc., and as the amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are preferably mentioned.

When the rinsing liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, especially cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are preferred, cyclopentanone, γ-butyrolactone , dimethyl sulfoxide, PGMEA, PGME are more preferred, and cyclohexanone and PGMEA are further preferred.

When the rinsing liquid contains an organic solvent, preferably 50% by mass or more of the rinsing liquid is an organic solvent, more preferably 70% by mass or more is an organic solvent, and more preferably 90% by mass or more is an organic solvent. Moreover, 100 mass % of the rinse liquid may be an organic solvent.

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

[How to supply the rinse solution] The method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and there are a method of immersing the substrate in the rinsing liquid, a method of supplying the rinsing liquid to the substrate through a liquid pan, and a method of showering A method of supplying a rinsing liquid to the substrate in the form of a method of continuously supplying the rinsing liquid to the substrate through a mechanism such as a straight nozzle. From the viewpoints of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is: Preferably, from the viewpoint of the permeability of the rinse liquid to the image portion, the method of supplying it using a spray nozzle is more preferable. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. That is, the rinsing step is preferably a step of supplying or continuously supplying a rinsing liquid to the above-mentioned exposed film through a straight nozzle, and more preferably a step of supplying the rinsing liquid through a spray nozzle. In addition, as a method of supplying the rinsing liquid in the rinsing step, a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid in a substantially static state on the substrate, and rinsing the substrate with ultrasonic waves or the like can be used. The steps of liquid vibration and the steps combining these, etc.

The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid at the time of rinsing is not particularly limited, but it can be performed preferably at 10 to 45°C, and more preferably at 18 to 30°C.

<Heating step> The pattern obtained by the development step (the rinsed pattern in the case of the rinse step) may be used in the heating step of heating the pattern obtained by the above development. That is, the manufacturing method of the hardened|cured material of this invention may include the heating process which heats the pattern obtained by the developing process. Moreover, the manufacturing method of the hardened|cured material of this invention may include the heating process which heats the pattern obtained by another method or the film obtained by the film formation process in the state which did not carry out the developing process. In the heating step, resins such as polyimide precursors are cyclized into resins such as polyimide. Moreover, the crosslinking etc. of the unreacted crosslinkable group in a specific resin or a crosslinking agent other than a specific resin are also performed. As the heating temperature (maximum heating temperature) in the heating step, 50-450°C is preferable, 150-350°C is more preferable, 150-250°C is further preferable, 160-250°C is further preferable, 160- 230°C is particularly preferred.

The heating step is preferably a step of promoting the cyclization reaction of the above-mentioned polyimide precursor in the above-mentioned pattern by heating and utilizing the action of a base or the like generated from the above-mentioned alkali generator.

The heating in the heating step is preferably performed at a temperature increase rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature. The above-mentioned temperature increase rate is more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min. By setting the temperature increase rate to 1°C/min or more, excessive volatilization of the acid or solvent can be prevented while maintaining productivity, and by setting the temperature increase rate to 12°C/min or less, the residual stress of the cured product can be alleviated. In addition, in the case of an oven capable of rapid heating, it is preferable to carry out a heating rate of 1 to 8°C/sec, more preferably 2 to 7°C/sec, from the temperature at the start of heating to the maximum heating temperature. 3 to 6°C/sec is more preferable.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature of the film (layer) after drying is, for example, higher than the temperature of the solvent contained in the resin composition of the present invention. It is preferable to start the temperature rise at a temperature that is 30 to 200°C lower in the boiling point.

The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

In particular, when forming a multilayer laminate, from the viewpoint of the adhesion between layers, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, more preferably 100°C or higher, and particularly 120°C or higher. good. The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

Heating can be performed in stages. As an example, the following steps may be performed: ramp from 25°C to 120°C at 3°C/min and hold at 120°C for 60 minutes, and ramp from 120°C to 180°C at 2°C/min and hold at 180°C for 120 minutes . Moreover, as described in the specification of US Pat. No. 9,159,547, it is also preferable to perform treatment while irradiating ultraviolet rays. By such a pretreatment step, the characteristics of the film can be improved. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be two or more steps, for example, the pretreatment step of the first step may be performed in the range of 100 to 150°C, and then the pretreatment step of the second step may be performed in the range of 150 to 200°C. Furthermore, cooling may be performed after heating, and the cooling rate at this time is preferably 1 to 5°C/min.

From the viewpoint of preventing the decomposition of the specific resin, it is preferable to conduct the heating step in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, and argon under a reduced pressure state. . The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less. Although it does not specifically limit as a heating means in a heating process, For example, a hot plate, an infrared furnace, an electric oven, a hot air oven, an infrared oven etc. are mentioned.

<Exposure step after development> Instead of or in addition to the above heating step, the pattern obtained by the development step (in the case of performing the rinse step, the rinsed pattern) can also be used after the development of the pattern after the exposure and development step. in the exposure 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 manufacturing method of the cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. In the post-development exposure step, for example, a reaction of cyclization of a polyimide precursor or the like by exposure to a photobase generator can be accelerated, or a reaction of detachment of an acid-decomposable group by exposure to a photoacid generator can be accelerated. reaction etc. In the post-development exposure step, it is sufficient to expose at least a part of the pattern obtained in the development step, but it is preferable to expose all of the above-mentioned patterns. The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm ² , more preferably 100 to 15,000 mJ/cm ² , when the exposure energy at the wavelength at which the photosensitive compound has sensitivity is converted. The post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, preferably broadband light.

<Metal layer formation step> The pattern obtained by the developing step (preferably the pattern for at least one of the heating step and the post-development exposure step) can be used in the metal layer forming step of forming the metal layer on the pattern. That is, it is preferable that the manufacturing method of the cured product of the present invention includes a metal layer forming step in the pattern obtained by the developing step (for at least one of the heating step and the post-development exposure step). pattern is preferably formed on the metal layer.

The metal layer is not particularly limited, and existing metals can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, alloys containing these metals, copper and aluminum. More preferred, copper is further preferred.

The formation method of the metal layer is not particularly limited, and conventional methods can be applied. For example, Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Laid-Open No. 2004-214501, Japanese Patent Application Laid-Open No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. the method described. For example, photolithography, PVD (Physical Vapor 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 can be mentioned. As a preferable aspect of electroplating, electrolytic electroplating using a copper sulfate or copper cyanide electroplating solution can be mentioned.

The thickness of the metal layer is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm, in the thickest part.

＜Use＞ As the field to which the cured product of the present invention can be produced, or the cured product of the present invention, an insulating film of an electronic device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like can be mentioned. In addition, sealing films, substrate materials (base films or cover films of flexible printed wiring boards, interlayer insulating films), and patterns formed by etching insulating films for practical mounting as described above can also be used. For such uses, for example, you can refer to Science&Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Masaki Kakimoto/Supervisor, CMC Technical Library "Basics and Application of Polyimide Materials" "Development" published in November 2011, Japan Polyimide/Aromatic Polymer Research Association/Edited "Latest Polyimide Fundamentals and Applications" NTS, August 2010, etc.

In addition, the manufacturing method of the cured product of the present invention or the cured product of the present invention can also be used for the manufacture of layouts such as offset printing plates or screen plates, the use of etching forming components, and the protection of protective paint and dielectric layers in electronics, especially in microelectronics. manufacturing etc.

(Laminated body and method for manufacturing the laminated body) The layered product of the present invention refers to a structure having a plurality of layers formed of the cured product of the present invention. The layered body of the present invention is a layered body including two or more layers formed of a cured product, and may be a layered body formed by stacking three or more layers. At least one of the two or more layers formed of the above-mentioned cured product included in the above-mentioned layered body is a layer formed of the cured product of the present invention, and suppresses the shrinkage of the cured product or the deformation of the cured product accompanying the shrinkage, etc. From a viewpoint, it is also preferable that all the layers formed of the cured product included in the above-mentioned laminate are layers formed of the cured product of the present invention.

That is, it is preferable that the manufacturing method of the laminated body of this invention includes the manufacturing method of the hardened|cured material of this invention, and it is more preferable to include the steps of repeating the manufacturing method of the hardened|cured material of this invention several times.

The layered product of the present invention includes two or more layers formed of a cured product, and an aspect in which a metal layer is included between any of the layers formed of the cured product is preferred. The above-mentioned metal layer is preferably formed by the above-mentioned metal layer forming step. That is, it is preferable that the manufacturing method of the laminated body of this invention further includes the metal layer forming step of forming a metal layer on the layer formed of the hardened|cured material between the manufacturing methods of the hardened|cured material performed a plurality of times. The preferred aspect of the metal layer forming step is as described above. As the above-mentioned layered product, for example, a layered product having a layer structure in which at least three layers of a first layer made of a cured product, a metal layer, and a second layer of a cured product are laminated in this order can be mentioned as a preferred one. . It is preferable that the above-mentioned first layer formed from the hardened product and the above-mentioned second layer formed from the hardened product are both layers formed from the hardened product of the present invention. The resin composition of the present invention for forming the above-mentioned first layer formed of the hardened material and the resin composition of the present invention for forming the above-mentioned second layer formed of the hardened material may be compositions of the same composition, or Compositions with different compositions may be used. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a rewiring layer.

<Lamination step> It is preferable that the manufacturing method of the laminated body of this invention includes a lamination|stacking step. The lamination step includes again sequentially performing (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, (d) a heating step, on the surface of the pattern (resin layer) or metal layer. A series of steps of at least one of the post-development exposure steps. However, at least one of the film formation step of (a) and the (d) heating step and the post-development exposure step may be repeated. Moreover, after at least one of the (d) heating step and the post-development exposure step, the (e) metal layer forming step may be included. It goes without saying that 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, the 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 can be exemplified. Details of the surface activation treatment will be described later.

Preferably, the above-mentioned layering step is performed 2 to 20 times, more preferably 2 to 9 times. For example, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, it is preferable to set the resin layer to 2 or more and 20 or less layers, and to set it to 2 or more and 9 layers or less. The constitution is further preferable. The composition, shape, film thickness, etc. of the above-mentioned layers may be the same or different.

In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after the metal layer is provided. Specifically, at least one of (a) film formation step, (b) exposure step, (c) development step, (d) heating step, and post-development exposure step, and (e) metal layer are repeated in this order. In the form of the formation step, at least one of (a) the film forming step, (d) the heating step, and the post-development exposure step, and (e) the metal layer forming step are sequentially repeated. The resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated by alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer forming step.

(Surface activation treatment step) It is preferable that the manufacturing method of the laminated body of the present invention 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 the metal layer formation step may be performed after the surface activation treatment step for the resin composition layer after the above-described development 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 both the metal layer and the exposed resin composition layer, respectively. at least in part. Surface activation treatment is preferably performed on at least a part of the metal layer, and surface activation treatment is preferably performed on a part or all of a region of the metal layer where the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesiveness with the resin composition layer (film) provided on the surface can be improved. Moreover, it is preferable to also perform surface activation treatment on a part or all of the resin composition layer (resin layer) after exposure. In this way, by subjecting the surface of the resin composition layer to the surface activation treatment, the adhesiveness with the metal layer and the resin layer provided on the surface activated by the surface activation treatment can be improved. In particular, when the resin composition layer is hardened, such as in the case of performing negative development, it is difficult to be damaged by the surface treatment, and it is easy to improve the adhesiveness. Specifically, the surface activation treatment is selected from plasma treatment, corona discharge treatment, corona discharge treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.) Etching treatment of CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film and then immersion in Immersion treatment in organic surface treatment agents containing at least one amine group and thiol group compound, mechanical roughening treatment using a brush, plasma treatment is preferred, especially oxygen plasma using oxygen as a raw material gas Handling is better. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/m ² , more preferably 1000-100,000 J/m ² , and most preferably 10,000-50,000 J/m ² .

(Manufacturing method of electronic components) Furthermore, the present invention discloses a semiconductor element including the cured product of the present invention or the laminate of the present invention. Moreover, this invention also discloses the manufacturing method of the semiconductor element which includes the manufacturing method of the hardened|cured material of this invention or the manufacturing method of the laminated body of this invention. As a specific example of a semiconductor element in which the resin composition of the present invention is used in the formation of the interlayer insulating film for rewiring layers, the descriptions in paragraphs 0213 to 0218 of Japanese Patent Laid-Open No. 2016-027357 and the description in FIG. 1 can be referred to. These contents are incorporated into this manual.

(Photobase generator) The photobase generator of the present invention is preferably a photobase generator represented by any one of the above formulae (1-1) to (1-3). The photobase generator of the present invention is the same as the above-mentioned specific photobase generator except that it is represented by any one of the above formulas (1-1) to (1-3), and the preferred aspects are also the same. [Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

<Synthesis Example BS-1: Synthesis of BS-1> In a flask equipped with a stirrer and a capacitor, 16.4 g (100 mmol) of trans-2-hydroxycinnamic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) ) was dissolved in 100 mL of tetrahydrofuran and cooled to 0 °C. Next, 20.1 g (105 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. Next, 13.5 g (105 mmol) of 4-(2-hydroxyethyl)piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 50 mL of tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.). And it was dripped at 0 degreeC for 1 hour. Next, the temperature was raised to 25° C. and stirred for 2 hours. Then, the mixture was dissolved in 800 mL of ethyl acetate and transferred to a separatory funnel. Next, it was washed twice with 100 mL of water, twice with 100 mL of 0.1 mmol/L dilute hydrochloric acid, twice with 150 mL of saturated saline, and dried with sodium sulfate. This was transferred to a one-neck flask while being filtered with filter paper, and the solvent was removed using a distiller to obtain 19 g of intermediate BS-1A. In a flask equipped with a stirrer and a capacitor, 12.3 g (50 mmol) of 3-(triethoxysilyl)propyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), NEOSTAN U- 0.01 g of 600 (manufactured by NITTO KASEI CO., LTD.) was dissolved in 60 mL of tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 25°C. Next, 13.7 g (50 mmol) of the intermediate BS-1A synthesized as described above was dissolved in 100 mL of tetrahydrofuran at 25°C, added dropwise over 1 hour, and then stirred at 40°C for 2 hours to dissolve in 1000 mL of tetrahydrofuran. ethyl acetate and transferred to a separatory funnel. Next, it was washed twice with 100 mL of water, twice with 150 mL of saturated saline, and dried with sodium sulfate. This was transferred to a one-neck flask while being filtered with filter paper, and the solvent was removed using a distiller to obtain 18 g of BS-1. The structure of BS-1 is estimated to be the following structure. [Chemical formula 72]

<Synthesis example BS-3: Synthesis of BS-3> In a flask equipped with a stirrer and a capacitor, 3-(triethoxysilyl)propyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared. ) 12.3 g (50 mmol) and 0.01 g of NEOSTAN U-600 (manufactured by NITTO KASEI CO., LTD.) were dissolved in 150 mL of tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.), and the Stir. Next, 10.4 g of 9-(hydroxymethyl)anthracene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 40° C. for 3 hours. Next, this was dissolved in 1000 mL of ethyl acetate, transferred to a separatory funnel, washed twice with 100 mL of water, twice with 150 mL of saturated saline, and dried over sodium sulfate. This was transferred to a one-neck flask while being filtered with filter paper, and the solvent was removed using a distiller to obtain 20 g of BS-3. The structure of BS-3 is estimated to be the following structure. [Chemical formula 73]

<Synthesis Examples BS-4 to BS-6: Synthesis of BS-4 to BS-6> BS-4 to BS-6 were synthesized by the same method as the synthesis of BS-1. The structures of BS-4 to BS-6 are estimated to be the following structures, respectively. [Chemical formula 74]

<Synthesis Examples BS-8 to BS-9: Synthesis of BS-8 to BS-9> In a flask equipped with a stirrer and a capacitor, 2-(3-benzylphenyl)propionic acid (Tokyo Chemical Industry Co., Ltd.) 12.7 g (50 mmol) was dissolved in 130 mL of tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.), and stirred at 25°C. Next, 17.2 g of bis[3-(trimethoxysilyl)propyl]amine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 60 mL of tetrahydrofuran, which was added dropwise over 1 hour, and the mixture was heated at 25° C. Stir for 30 minutes. The reaction liquid was transferred to a one-neck flask while being filtered with filter paper, and the solvent was removed using a distiller to obtain 39 g of BS-8. The structure of BS-8 is presumed to be the following structure. About BS-9, it synthesize|combined by the same method. The structures of BS-8 to BS-9 are estimated to be the following structures, respectively. [Chemical formula 75]

<Synthesis example AA-1: Synthesis of diamine (AA-1)> In a flask equipped with a capacitor and a stirrer, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation) was prepared. ) and dehydrated pyridine (manufactured by FUJIFILM Wako Pure Chemical Corporation) 17.4 g (0.22 mol) were dissolved in 78 g of ethyl acetate, and cooled to 5° C. or lower. Next, 48.4 g (0.21 mol) of 3,5-dinitrobenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 145 g of ethyl acetate, and the solution was subjected to a dropping funnel. Added dropwise to the flask over 1 hour. After completion of the dropwise addition, the mixture was stirred at a temperature of 10°C or lower for 30 minutes, heated to 25°C, and stirred for 3 hours. Next, the reaction solution was diluted with 600 mL of ethyl acetate (CH ₃ COOEt), transferred to a separatory funnel, and washed with 300 mL of water, 300 mL of saturated sodium bicarbonate water, 300 mL of dilute hydrochloric acid, and 300 mL of saturated brine in this order. After liquid separation washing, drying with 30 g of magnesium sulfate, concentration and vacuum drying using a distiller, 61.0 g of a dinitro body (A-1) was obtained. Reduced iron (manufactured by FUJIFILM Wako Pure Chemical Corporation) 27.9 g (500 mmol), ammonium chloride (manufactured by FUJIFILM Wako Pure Chemical Corporation) 5.9 g (110 mmol), acetic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation) 3.0 g (50 mmol), 0.03 g of 2,2,6,6-tetramethylpiperidine 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) was weighed into a flask equipped with a capacitor and a stirrer , 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added and stirred. Next, 16.2 g of the dinitro form (A-1) was added little by little for 1 hour, followed by stirring for 30 minutes. Next, after raising the external temperature to 85° C., stirring for 2 hours, and cooling to 25° C. or lower, filtration was performed using CELITE (registered trademark). The filtrate was concentrated with a rotary still, and dissolved in 800 mL of ethyl acetate. This was transferred to a separatory funnel, washed twice with 300 mL of saturated sodium bicarbonate water, and washed with 300 mL of water and 300 mL of saturated saline in this order. After liquid separation washing, drying with 30 g of magnesium sulfate, concentration and vacuum drying using a distiller, 11.0 g of diamine (AA-1) was obtained. The outline of the above synthesis scheme is shown below. [Chemical formula 76]

<Synthesis example A-1: Synthesis of polybenzoxazole precursor (A-1)> [From 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4' - Synthesis of polybenzoxazole precursor (A-1) with oxodibenzoyl chloride] 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 28.0 g (76.4 ear) was stirred and dissolved in N-methylpyrrolidone 200 g. Next, 12.1 g (153 mmol) of pyridine was added, and 20.7 g (70.1 mmol) of 4,4'-oxodibenzyl chloride was added dropwise over 1 hour while maintaining the temperature at -10 to 0°C. ) was dissolved in 75 g of N-methylpyrrolidone. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and the mixture was further stirred for 60 minutes. Next, the polybenzoxazole precursor resin was precipitated in 6 liters of water, and the water-polybenzoxazole precursor resin mixture was stirred at 500 rpm for 15 minutes. The polybenzoxazole precursor resin was obtained by filtration, stirred again in 6 liters of water for 30 minutes, and filtered again. Next, in a reduced pressure state, the obtained polybenzoxazole precursor resin was dried at 45° C. for 3 days to obtain a polybenzoxazole precursor (A-1). The molecular weight of the polybenzoxazole precursor is Mw=21500 and Mn=9500. The structure of A-1 is presumed to be a structure represented by the following formula (A-1). [Chemical formula 77]

<Synthesis example A-2: Synthesis of polyimide precursor (A-2)> 14.06 g (64.5 mmol) of pyromellitic dianhydride (obtained by drying at 140° C. for 12 hours), 16.8 g (64.5 mmol) were mixed g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine and 100 g of diglyme (diglyme ), and stirred at a temperature of 60° C. for 18 hours, thereby producing a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, after chlorinating the obtained diester with SOCl ₂ , it was converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example A-5, and synthesized with The polyimide precursor (A-2) was obtained in the same manner as in Example A-5. The weight average molecular weight of the polyimide precursor was 21,000. The structure of A-2 is presumed to be a structure represented by the following formula (A-2). [Chemical formula 78]

<Synthesis example A-3: Synthesis of polyimide precursor (A-3)> [From 4,4'-oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether and methyl Synthesis of polyimide precursor based on 2-hydroxyethyl acrylate (A-3: polyimide precursor having a radically polymerizable group)] Mix 20.0 g (64.5 mmol) of 4,4'-oxygen Diphthalic dianhydride (obtained by drying at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) ) of pyridine and 100 g of diglyme, and stirred at a temperature of 60°C for 18 hours, thereby producing a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate . Next, after chlorinating the obtained diester with SOCl ₂ , it was converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example A-5, and synthesized with The polyimide precursor (A-3) was obtained in the same manner as in Example A-5. The weight average molecular weight of the polyimide precursor was 19,600. The structure of A-3 is presumed to be the structure represented by the following formula (A-3). [Chemical formula 79]

<Synthesis example A-4: Synthesis of polyimide precursor (A-4)> [From 4,4'-oxydiphthalic dianhydride, 4,4'-diamino-2,2' - Synthesis of polyimide precursor with dimethyl biphenyl (bitoluidine) and 2-hydroxyethyl methacrylate (A-4: polyimide precursor with radically polymerizable group)] Mixing 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (obtained by drying at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate , 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were stirred at 60°C for 18 hours to produce 4,4'-oxydiphthalene Diester of dicarboxylic acid and 2-hydroxyethyl methacrylate. Next, after chlorinating the obtained diester with SOCl ₂ , it was converted into polyamide with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example A-5. An imine precursor was obtained, and a polyimide precursor (A-4) was obtained in the same manner as in Synthesis Example A-5. The weight average molecular weight of the polyimide precursor was 23,500. The structure of A-4 is presumed to be a structure represented by the following formula (A-4). [Chemical formula 80]

<Synthesis example A-5: Synthesis of polyimide precursor (A-5)> [From A-5: oxydiphthalic dianhydride, 4,4'-biphenyltetracarboxylic dianhydride, methyl 2-Hydroxyethyl acrylate and 4,4'-diaminodiphenyl ether synthesis polyimide precursor resin A-5] In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a capacitor and an internal thermometer, while While removing water, 9.49 g (32.25 mmol) of 4,4'-biphenyltetracarboxylic dianhydride and 10.0 g (32.25 mmol) of oxydiphthalic dianhydride were suspended in 140 mL of diglyme. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water, and 10.7 g (135 mmol) of pyridine were further added, and the mixture was stirred at a temperature of 60° C. for 18 hours. . Next, after cooling the mixture to -20°C, 16.1 g (135.5 mmol) of thionium chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride can be obtained. Next, after warming the mixture to room temperature and stirring for 2 hours, 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a clear solution. Next, the obtained clear solution was added dropwise over 1 hour and obtained by dissolving 11.8 g (58.7 mmol) of 4,4′-diaminodiphenyl ether in 100 mL of NMP. Next, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor resin was dried at 45° C. for 3 days under reduced pressure to obtain a polyimide precursor (A-5). The weight average molecular weight of the obtained polyimide precursor A-5 was 23,800, and the number average molecular weight was 10,400. [Chemical formula 81]

<Synthesis example A-6> [From A-6: 4,4'-oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate synthesis of polyimide precursor 6: Polyimide precursor with radically polymerizable group)] Into the separable flask, 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA), 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After the heat generation by the reaction was completed, it was cooled to room temperature, and was further left to stand for 16 hours. Next, under ice-cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes. Next, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. Furthermore, after stirring at room temperature for 2 hours, 30 ml of ethanol was added and the mixture was stirred for 1 hour. After that, 400 ml of γ-butyrolactone was added. A reaction liquid was obtained by collecting the precipitate generated in the reaction mixture by filtration. The obtained reaction solution was added to 3 liters of ethanol, whereby a precipitate formed of a crude polymer was generated. The resulting crude polymer was collected by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate a polymer, and the obtained precipitate was collected by filtration and then vacuum-dried to obtain a powdery polymer A-6. The weight average molecular weight (Mw) of the polymer A-6 was measured and found to be 24,000.

<Synthesis example A-7> [Synthesis of polyimide precursor (A- 7: Polyimide precursor with radically polymerizable group)] In Synthesis Example 6, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride, the same The reaction was carried out in the same manner as the method described in Synthesis Example A-6 to obtain a polymer A-7. The weight average molecular weight (Mw) of the polymer A-7 was measured and found to be 22,900.

<Synthesis example M-1> In a flask equipped with a stirrer and a capacitor, 7.25 g (105 mmol) of 1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.), Karenz MOI (SHOWA) were prepared. DENKO KK) 15.52 g (100 mmol) and NEOSTAN U-600 (NITTO KASEI CO., LTD.) 0.01 g were dissolved in 70 mL of tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.), and heated at 25°C under stirring for 1 hour. Next, after stirring at 45°C for 2 hours, it was dissolved in 600 mL of ethyl acetate and transferred to a separatory funnel. Next, it was washed twice with 100 mL of water, twice with 150 mL of saturated saline, and dried with sodium sulfate. This was transferred to a one-neck flask while being filtered with filter paper, and the solvent was removed using a distiller to obtain 18 g of M-1. The structure of the obtained M-1 is presumed to be the following structure. [Chemical formula 82]

<Synthesis example M-2> In a flask equipped with a stirrer and a capacitor, 15.2 g (0.22 mol) of triazole and 150 mL of dichloromethane were mixed, and cooled to 10° C. or lower. Next, 10.5 g (0.1 mol) of methacryloyl chloride was added dropwise over 1 hour, and the temperature was raised to 20 to 25°C. After stirring at 20 to 25° C. for 3 hours, 200 mL of dichloromethane was added, the resulting salt was filtered with filter paper, and the filtrate was recovered. The filtrate was transferred to a separatory funnel, washed twice with 50 mL of water, twice with 150 mL of saturated brine, and dried over sodium sulfate. This was transferred to a one-neck flask while being filtered with filter paper, and the solvent was removed using a distiller to obtain 20 g of M-2. The structure of the obtained M-2 is presumed to be the following structure. [Chemical formula 83]

<Synthesis Examples M-3 to M-5> The following M-3 to M-5 were synthesized in the same manner as M-1 to M-2. The structures of the obtained M-3 to M-5 are presumed to be the following structures, respectively. [Chemical formula 84]

<Synthesis example DS-1> In a flask equipped with a stirrer and a capacitor, 7.25 g (105 mmol) of 1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 3 -(Triethoxysilyl)propyl (manufactured by Tokyo Chemical Industry Co., Ltd.) 24.7 g (100 mmol) and 0.02 g of NEOSTAN U-600 (manufactured by NITTO KASEI CO., LTD.) were dissolved in 100 mL of tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 25° C. for 1 hour. Next, after stirring at 45°C for 2 hours, it was dissolved in 800 mL of ethyl acetate and transferred to a separatory funnel. Next, it was washed twice with 100 mL of water, twice with 150 mL of saturated saline, and dried with sodium sulfate. This was transferred to a one-neck flask while being filtered with filter paper, and the solvent was removed using a distiller to obtain 26 g of DS-1. The case of DS-1 was confirmed from the ¹ H-NMR spectrum. The structure of the obtained DS-1 is presumed to be the following structure. [Chemical formula 85]

<Synthesis example DS-2> DS-2 was synthesized by the same method as DS-1. The structure of the obtained DS-2 is presumed to be the following structure. [Chemical formula 86]

<Synthesis example AP-1: Synthesis of resin AP-1 having an azole group and an alkoxysilyl group> 15 g of propylene glycol monomethyl ether was added to the flask 1, and the temperature was raised to 80°C while flowing nitrogen. Stir. Next, 14.52 g (50 mmol) of 3-(triethoxysilyl)propyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.16 g ( 50 mmol) of M-3, 50 g of propylene glycol monomethyl ether, and 0.46 g of a polymerization initiator V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) were dissolved and added dropwise to flask 1 over 3 hours. . Next, after heating up to 85 degreeC and stirring for 3 hours, it cooled to room temperature, and obtained AP-1 solution. The solid content concentration of the AP-1 solution (solid content/total mass of the solution×100) was 24.1 mass %, and the weight average molecular weight (Mw) of AP-1 was 12,500. The structure of the obtained AP-1 is presumed to be the following structure. [Chemical formula 87]

<Synthesis Examples AP-2 to AP-4: Synthesis of Compounds AP-2 to AP-4> Compounds AP-2 to AP-4 were synthesized in the same manner as in Synthesis Example AP-1. The estimated structures of AP-2 to AP-4 are shown in the following formulae (AP-2) to (AP-4), respectively. In each structure, the parenthesized subscript indicates the molar ratio of each repeating unit. The Mw of the AP-2 is 15,800, the Mw of the AP-3 is 25,000, and the Mw of the AP-4 is 8,500. [Chemical formula 88]

<Examples and Comparative Examples> In each Example, each curable resin composition was obtained by mixing the components described in the following table, respectively. In addition, in each comparative example, each composition for comparison was obtained by mixing the components described in the following table, respectively. Specifically, the content of the components other than the solvent described in the table is the amount (parts by mass) described in the column of each "addition amount" in the table. In addition, AP-1-AP-4 were added so that the solid content in a solution might become the quantity (mass part) described in each "addition amount" of a table|surface. The obtained curable resin composition and the composition for comparison were subjected to pressure filtration through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm. In addition, in the table|surface, the description of "-" shows that a composition does not contain the corresponding component.

[Table 1] resin specific photobase generator Other silane coupling agents Compound B Other alkali generators Compound C photopolymerization initiator polymeric compound polymerization inhibitor Other additives solvent Hardening temperature (℃) Hardening method Elongation at break Copper adhesion type added amount type added amount type added amount type added amount type added amount type added amount type added amount type added amount type added amount type added amount type added amount type added amount Example 1 A-2 32 BS-1 0.2 C-1 0.07 AP-1 0.05 M-1 0.05 D-2 0.05 E-1 0.2 OXE-01 1.2 SR-209 6.1 I-2 0.08 - 0 DMSO/GBL 60 230 A B A Example 2 A-3 32 BS-1 0.2 C-2 0.07 AP-2 0.05 M-2 0.05 D-4 0.05 E-2 0.1 OXE-01 1.2 SR-209 6.2 I-2 0.08 - 0 DMSO/GBL 60 230 A A A Example 3 A-4 32 BS-1 0.1 C-1 0.17 AP-3 0.05 AP-1 0.05 D-1 0.05 E-2 0.1 OXE-01 1.2 SR-209 6.2 I-3 0.08 - 0 DMSO/GBL 60 230 A A A Example 4 A-5 32 BS-1 0.15 C-1 0.12 AP-4 0.05 AP-2 0.05 D-2 0.05 E-2 0.1 OXE-01 1.2 A-DPH 6.2 I-1 0.08 - 0 DMSO/GBL 60 230 A A A Example 5 A-3 32 BS-1 0.2 C-1 0.07 AP-1 0.05 AP-3 0.05 D-3 0.05 E-3 0.1 OXE-01 1.2 SR-209 6.2 I-2 0.08 - 0 DMSO/GBL 60 230 A A A Example 6 A-3 32 BS-3 0.2 C-1 0.07 AP-2 0.05 AP-4 0.05 D-4 0.05 E-4 0.1 OXE-01 1.2 SR-209 6.2 I-2 0.08 - 0 DMSO/GBL 60 230 A A B Example 7 A-3 32 BS-4 0.2 C-1 0.07 AP-3 0.05 M-1 0.05 D-1 0.05 E-5 0.1 OXE-01 1.2 SR-209 6.2 I-2 0.08 - 0 DMSO/GBL 60 230 A B A Example 8 A-3 32 BS-5 0.2 C-2 0.07 AP-4 0.05 M-3 0.05 D-2 0.05 E-6 0.1 OXE-02 1.2 SR-239 6.2 I-1 0.08 - 0 DMSO/GBL 60 230 A B B Example 9 A-3 32 BS-6 0.2 C-1 0.07 AP-1 0.05 M-4 0.05 D-3 0.05 E-2 0.1 OXE-01 1.2 SR-239 6.2 I-2 0.08 - 0 NMP 60 230 A B A Example 10 A-3 32 BS-4 /BS-8 0.1 /0.1 C-2 0.07 AP-2 0.05 M-5 0.05 D-4 0.05 E-2 0.1 OXE-01 1.2 SR-239 6.2 I-2 0.08 - 0 DMSO/GBL 60 230 A A A Example 11 A-6/ A-7 16/16 BS-8 0.2 C-1 0.07 DS-1 0.05 M-1 0.05 D-1 0.05 E-1 0.2 OXE-01 1.2 SR-209 6.1 I-4 0.08 - 0 DMSO/GBL 60 230 A A B Example 12 A-3 32 BS-9 0.1 C-1 0.17 DS-2 0.05 AP-1 0.05 D-1 0.05 E-2 0.1 OXE-01 1.2 SR-209 6.2 I-3 0.08 - 0 DMSO/GBL 60 230 A B A Example 13 A-6 32 BS-1 0.2 C-2 0.07 AP-3 0.05 - 0 D-4 0.05 E-6 0.15 OXE-01 1.2 SR-209 6.2 I-2 0.08 - 0 DMSO/GBL 60 230 A A B Example 14 A-7 32 BS-1 0.2 C-2 0.10 - 0 - 0 - 0 E-2 0.12 OXE-02 1.2 SR-231 6.1 I-2 0.08 J-1 0.2 DMSO/GBL 60 230 A A B Example 15 A-1 32 BS-1 /BS-3 0.1 /0.1 C-2 0.07 AP-4 0.05 M-4 0.05 D-3 0.05 E-2 0.1 OXE-01 1.2 SR-209 6.2 I-2 0.08 - 0 DMSO/GBL 60 300 A B B Example 16 A-3 32 BS-1 /BS-6 0.1 /0.1 C-2 0.07 AP-2 0.05 M-2 0.05 D-4 0.05 E-2 0.1 OXE-01 1.2 SR-209 6.2 I-2 0.08 - 0 DMSO/GBL 60 200 B B A Example 17 A-2 32 BS-1 0.25 C-1 0.07 AP-1 0.05 M-1 0.05 - 0 E-1 0.2 OXE-01 1.2 SR-209 6.1 I-2 0.08 - 0 DMSO/GBL 60 230 A B A Comparative Example 1 A-7 32 - 0 C-2 0.2 - 0 - 0 D-4 0.07 E-3 0.15 OXE-02 1.2 SR-231 6.1 I-3 0.08 J-1 0.2 NMP 60 230 A C D Comparative Example 2 A-1 32 - 0 C-2 0.25 - 0 - 0 D-4 0.07 E-3 0.2 OXE-02 1.2 A-DPH 6.2 I-3 0.08 - 0 DMSO/GBL 60 230 A D C Comparative Example 3 A-6 32 - 0 C-2 0.07 AP-3 0.05 - 0 D-4 0.05 E-6 0.15 OXE-01 1.2 SR-209 6.2 I-2 0.08 - 0 DMSO/GBL 60 230 A C E

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

[resin] · A-1 to A-7: A-1 to A-7 synthesized in the above synthesis example

[Specific photobase generator] BS-1 to BS-9: BS-1 to BS-9 synthesized in the above synthesis example

[Other silane coupling agents] C-1 to C-2: compounds of the following structures [Chemical formula 89]

[Compound B] AP-1 to AP-4: AP-1 to AP-4 synthesized in the above synthesis example DS-1 to DS-2: DS-1 to DS-2 synthesized in the above synthesis example · M-1 to M-5: M-1 to M-5 synthesized in the above synthesis example

[Other base generators] D-1 to D-3: compounds of the following structures D-4: WPBG-27 (FUJIFILM Wako Pure Chemical Corporation) [Chemical formula 90]

[Compound C] E-1 to E-6: compounds of the following structures [Chemical formula 91]

[Photopolymerization initiators (all are product names)] OXE-01: IRGACURE OXE 01 (manufactured by BASF) OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[Polymerizable compounds (all are product names)] SR-209: SR-209 (manufactured by Sartomer Company, Inc.) SR-231: SR-231 (manufactured by Sartomer Company, Inc.) SR-239: SR-239 (manufactured by Sartomer Company, Inc.) · A-DPH: Dipivalerythritol hexaacrylate (Shin-Nakamura Chemical Co., Ltd.)

[Polymerization inhibitor] · I-1: 1,4-benzoquinone · I-2: 4-methoxyphenol · I-3: 1,4-dihydroxybenzene · I-4: the following compound [Chemical formula 92 ]

[Other additives] · J-1: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Solvent] DMSO: dimethyl sulfoxide GBL: gamma-butyrolactone NMP: N-methylpyrrolidone In the table, the description of "DMSO/GBL" indicates that a mixture obtained by mixing DMSO and GBL at a mixing ratio (mass ratio) of 80:20 was used.

<Evaluation> [Evaluation of Elongation at Break] In each of the Examples and Comparative Examples, the curable resin composition or the composition for comparison was applied to a silicon wafer by spin coating to form a curable resin composition. material layer. The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to obtain a curable resin composition layer with a uniform thickness of about 15 μm on the silicon wafer. In the example described as "A" in the column of "Curing method", using a stepper (Nikon NSR 2005 i9C), the entire surface of the obtained curable resin composition layer was subjected to exposure energy of 500 mJ/cm ² . i-ray exposure. In a nitrogen atmosphere, the curable resin composition layer (resin layer) after the exposure was heated at a temperature increase rate of 10° C./min until it reached the temperature described in the column of “hardening temperature (° C.)” in the table. , heated for 3 hours. In the example described as "B" in the column of "hardening method", the whole surface of the curable resin composition layer after the above-mentioned exposure was exposed to i-rays at an exposure energy of 500 mJ/cm ² . Heating was performed in the same manner as in the example described as "A". The cured resin layer (cured product) was immersed in a 4.9 mass % hydrofluoric acid aqueous solution, and the cured product was peeled off from the silicon wafer. The peeled hardened material was punched out using a punching machine to produce a test piece having a sample width of 3 mm and a sample length of 30 mm. The obtained test piece was measured in the longitudinal direction of the film according to JIS-K6251 at a crosshead speed of 300 mm/min in an environment of 25° C. and 65% RH (relative humidity) using a tensile tester (Tensilon). Elongation at break. The evaluation was performed five times, and the arithmetic mean of the elongation at break (elongation at break) of the film was used as an index value. The above-mentioned index values were evaluated according to the following evaluation criteria, and the evaluation results were described in the column of "elongation at break" in the table. It can be said that the larger the above-mentioned index value is, the more excellent the film strength (elongation at break) of the obtained cured product is. -Evaluation Criteria- A: The above-mentioned index value is 60% or more. B: The above-mentioned index value is 55% or more and less than 60%. C: The above-mentioned index value is 50% or more and less than 55%. D: The above index value is less than 50%.

[Evaluation of Copper Adhesion] Each of the above-filtered curable resin compositions or the composition for comparison was applied in layers on a copper substrate by spin coating to form a curable resin composition layer. The copper substrate to which the obtained curable resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to form a curable resin composition layer with a uniform thickness of 20 μm on the copper substrate. Using a stepper (Nikon NSR 2005 i9C), the curable resin composition layer on the copper substrate was exposed to light with an exposure energy of 500 mJ/cm ² using a mask having a 100 μm square non-masked portion formed thereon, and then By developing with cyclopentanone for 60 seconds, a resin layer having a square shape of 100 μm was obtained. In the example described as "A" in the column of "Curing method", i-rays (365 nm) were used as a light source, and after exposure at an exposure energy of 500 mJ/cm ² , in a nitrogen atmosphere, the The temperature was increased at a heating rate, and after reaching the temperature described in the column of "hardening temperature (° C.)" in the table, the temperature was maintained for 3 hours, and the resin film 2 was obtained. In the example described as "B" in the column of "Curing method", while using i-ray (365 nm) as a light source and exposing with an exposure energy of 500 mJ/cm ² , in a nitrogen atmosphere, at a temperature of 10 °C/min. The temperature was increased at a heating rate, and after reaching the temperature described in the column of "hardening temperature (° C.)" in the table, the temperature was maintained for 3 hours, and the resin film 2 was obtained. The shear force of the 100 μm square resin film 2 on the copper substrate was measured using an adhesive strength tester (manufactured by XYZTEC, CondorSigma) in an environment of 25° C. and 65% relative humidity (RH). It can be said that the greater the shear force, the greater the adhesion force, and the better the adhesion between the metal and the hardened material, and the better result. The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the column of "Copper Adhesion" in the table. -Evaluation Criteria- A: Shear force exceeds 40gf B: Shear force exceeds 35gf and is 40gf or less C: Shear force exceeds 30gf and is 35gf or less D: Shear force exceeds 25gf and is 30gf or less E: Shear force is 25gf or less 1gf is 9.80665× ^10-3N .

From the above results, it was found that the cured product formed of the curable resin composition of the present invention has excellent adhesion to metal. The compositions for comparison of Comparative Examples 1 to 2 did not contain a specific photobase generator. It turns out that the hardened|cured material and the metal which consist of such a composition for comparison are inferior.

<Example 101> The curable resin composition used in Example 1 was applied to the surface of the copper thin layer of the resin substrate with the copper thin layer formed on the surface by spin coating, and dried at 100° C. for 4 After forming a curable resin composition layer with a film thickness of 20 μm in minutes, exposure was performed using a stepper (Nikon Co., Ltd., NSR1505 i6). For exposure, via a mask (a binary mask with a pattern of 1:1 line-to-space, line width 10 μm) at a wavelength of 365 nm. After exposure, it was heated at 100°C for 4 minutes. After the above heating, development was performed with cyclohexanone for 2 minutes, and rinsed with PGMEA for 30 seconds, thereby obtaining a layer pattern. Next, the temperature was increased at a temperature increase rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 3 hours to form an interlayer insulating film for rewiring layers. This interlayer insulating film for rewiring layers is excellent in insulating properties. Moreover, a semiconductor element was manufactured using these interlayer insulating films for rewiring layers, and as a result, normal operation was confirmed.

Claims (18)

A curable resin composition comprising at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor and a polyimide precursor, and A photobase generator having an alkoxysilyl group. The curable resin composition according to claim 1, wherein The aforementioned photobase generator is a compound that generates a base by the action of light having a wavelength of 100 to 600 nm. The curable resin composition according to claim 1 or claim 2, wherein the photobase generator is a compound represented by any one of the following formulas (1-1) to (1-3); [chemical formula 1]

In formula (1-1), X ¹ represents an aryl group having a hydroxyl group or a carboxyl group, R ¹ and R ² represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ¹ and R ² can be bonded to form a ring structure, Y ¹ represents a divalent linking group, Z ¹ represents an alkoxysilyl group; in formula (1-2), X ² represents a substituted or unsubstituted anthracene structure or an aryl group with a nitro group, R ³ and R ⁴ independently represents a hydrogen atom or a hydrocarbon group with 1 to 12 carbon atoms, R ³ and R ⁴ can be bonded to form a ring structure, Y ² represents a divalent linking group, and Z ² represents an alkoxysilyl group; formula ( In 1-3), X ³ and X ⁴ each independently represent a substituted or unsubstituted aryl group, R ⁵ represents a monovalent organic group, and R ⁶ to R ⁹ each independently represent a hydrogen atom and a carbon number of 1 to 1. A hydrocarbon group of 12 or a group having an alkoxysilyl group, at least two of R ⁶ to R ⁹ can be bonded to form a ring structure, and at least one of R ⁶ to R ⁹ is an alkoxysilyl group base group. The curable resin composition according to claim 1 or claim 2, wherein The aforementioned photobase generator is a compound having a molecular weight of 2,000 or less. The curable resin composition according to claim 1 or claim 2, further comprising a compound having an alkoxysilyl group and not having photobase generating energy. The curable resin composition according to claim 1 or claim 2, further comprising a photobase generator not having an alkoxysilyl group. The curable resin composition according to claim 1 or claim 2, comprising compound B as a compound having a polymerizable group and an azole group. The curable resin composition according to claim 1 or claim 2, comprising compound C which is a compound having no polymerizable group but an azole group. The curable resin composition according to claim 8, wherein compound C is represented by formula (C-1) or formula (C-2), [chemical formula 2]

In formula (C-1), Z ¹ to Z ⁴ each independently represent =CR ⁷ - or a nitrogen atom, R ¹ represents a hydrogen atom or a monovalent organic group, and R ⁷ represents a hydrogen atom or a monovalent organic group. The structure represented by the formula (C-1) does not contain a polymerizable group; in the formula (C-2), Z ⁵ to Z ⁶ each independently represent =CR ⁸ - or a nitrogen atom, and R ² to R ⁶ each independently Represents a hydrogen atom or a monovalent organic group, R ⁸ represents a hydrogen atom or a monovalent organic group, and does not contain a polymerizable group in the structure represented by the formula (C-2). The curable 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 curable resin composition according to any one of claim 1 to claim 10. A layered body comprising two or more layers formed of the hardened product described in claim 11, and including a metal layer between any of the layers formed of the hardened product. A method for producing a cured product, comprising a film forming step of applying the curable resin composition according to any one of Claims 1 to 10 on a substrate to form a film. The method for producing a cured product according to claim 13, which comprises an exposure step of selectively exposing the film and a development step of developing the film with a developer to form a pattern. The method for producing a cured product according to claim 14, further comprising a post-development exposure step of exposing the pattern obtained by the aforementioned development after the aforementioned development step. The manufacturing method of the hardened|cured material of Claim 13 which comprises the heating process of heating the said film at 50-450 degreeC. A semiconductor element comprising the cured product of claim 11. A photobase generator represented by any one of the following formulas (1-1) to (1-3), [Chemical formula 3]

In formula (1-1), X ¹ represents an aryl group having a hydroxyl or carboxyl group, R ¹ and R ² represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ¹ and R ² can be bonded to form a ring structure, Y ¹ represents a divalent linking group, Z ¹ represents an alkoxysilyl group; in formula (1-2), X ² represents a substituted or unsubstituted anthracene structure or an aryl group with a nitro group, R ³ and R ⁴ independently represents a hydrogen atom or a hydrocarbon group with 1 to 12 carbon atoms, R ³ and R ⁴ can be bonded to form a ring structure, Y ² represents a divalent linking group, and Z ² represents an alkoxysilyl group; formula ( In 1-3), X ³ and X ⁴ each independently represent a substituted or unsubstituted aryl group, R ⁵ represents a monovalent organic group, and R ⁶ to R ⁹ each independently represent a hydrogen atom and a carbon number of 1 to 1. The hydrocarbon group of 12 or a group having an alkoxysilyl group, R ⁶ to R ⁹ may be bonded to form a ring structure, and at least one of R ⁶ to R ⁹ is a group having an alkoxysilyl group.