TW202309117A - Resin composition, cured product, multilayer body, method for producing cured product, method for producing multilayer body, method for producing semiconductor device, and semiconductor device - Google Patents

Abstract

The present invention provides: a resin composition which enables the achievement of a cured product having excellent pattern rectangularity; a cured product which is obtained by curing the resin composition; a multilayer body which comprises the cured product; a method for producing the cured product; a method for producing the multilayer body; a method for producing a semiconductor device, the method comprising the method for producing the multilayer body; and a semiconductor device which comprises the cured product or the multilayer body. The present invention provides: a resin composition that contains a resin and a base generator which has an [alpha],[beta]-unsaturated ketone group at a site where a base is to be generated, and which generates a base that is cyclized within the molecule, thereby forming a tertiary amine; a cured product which is obtained by curing the resin composition; a multilayer body which comprises the cured product; a method for producing the cured product; a method for producing the multilayer body; a method for producing a semiconductor device, the method comprising the method for producing the multilayer body; and a semiconductor device which comprises the cured product or the multilayer body.

Description

Resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, and semiconductor device

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

Nowadays, in various fields, resin materials are applied using resin compositions containing resins. For example, cyclized resins such as polyimides are used in various applications because they are excellent in heat resistance, insulation, and the like. The above application is not particularly limited, but if a semiconductor device for actual mounting is taken as an example, use as an insulating film, a sealing material material, or a protective film can be mentioned. Moreover, it can also be used as a base film, a cover film, etc. of a flexible substrate.

For example, in the above application, the cyclized resin such as polyimide is used in the form of a resin composition containing a precursor of the cyclized resin such as a polyimide precursor. For example, by applying such a resin composition to a substrate to form a photosensitive film by coating or the like, and then performing exposure, development, heating, etc. as necessary, a cured product can be formed on the substrate. Precursors of the above-mentioned cyclized resins such as polyimide precursors are cyclized by heating, for example, and become cyclized resins such as polyimides in cured products. Since the resin composition can be applied by known coating methods and the like, it can be said that, for example, the applicable resin composition has a high degree of design freedom in the application of the shape, size, application position, etc., and has excellent manufacturing adaptability. In addition to the high performance of cyclized resins such as polyimides, they are also excellent in manufacturing adaptability, and the expansion of industrial applications of the above-mentioned resin compositions has been expected.

For example, Patent Document 1 describes a resin composition characterized by containing a polymer precursor and a base generator. The reaction of the substance is promoted. The above-mentioned base generator is characterized by generating a base with a specific structure by electromagnetic wave irradiation and/or heating. The generated base undergoes Michael addition (Michael addition) in the same molecule by heating.

[Patent Document 1] Japanese Patent Laid-Open No. 2010-254982

In the resin composition used to obtain a cured product, it is required that the obtained cured product has excellent pattern squareness.

An object of the present invention is to provide a resin composition capable of obtaining a cured product excellent in pattern rectangularity, a cured product obtained by curing the above resin composition, a laminate including the above cured product, a method for producing the above cured product, and the above laminate A method for manufacturing a semiconductor device, a method for manufacturing a semiconductor device including the method for manufacturing the above-mentioned laminate, and a semiconductor device including the above-mentioned cured product or the above-mentioned laminate.

式（1-1）中，L ¹表示n+m價連結基，R ¹分別獨立地表示1價有機基團，R ¹中的至少1個包含α,β-不飽和酮基，X分別獨立地表示羥基或羧基，m表示1以上的整數，n表示1以上的整數。 ＜6＞如＜5＞所述之樹脂組成物，其中 上述式（1-1）中的L ¹包含芳香環結構。 ＜7＞如＜5＞或＜6＞所述之樹脂組成物，其中 上述式（1-1）中的L ¹包含聚合性基。 ＜8＞如＜1＞至＜7＞之任一項所述之樹脂組成物，其中 從上述鹼產生劑產生之三級胺的分子量為100～200。 ＜9＞如＜1＞至＜8＞之任一項所述之樹脂組成物，其中 從上述鹼產生劑產生之三級胺包含具有構成三級胺之氮原子作為環員之5員環結構或具有構成三級胺之氮原子作為環員之6員環結構。 ＜10＞如＜1＞至＜9＞之任一項所述之樹脂組成物，其中 上述鹼產生劑在波長365nm處的莫耳吸光係數為100mol ^-1・L・cm ^-1以下。 ＜11＞如＜1＞至＜10＞之任一項所述之樹脂組成物，其滿足下述條件1及條件2中的至少1個。 條件1：樹脂具有自由基聚合性基 條件2：進一步包含具有自由基聚合性基之聚合性化合物 ＜12＞如＜1＞至＜11＞之任一項所述之樹脂組成物，其包含光自由基聚合起始劑。 ＜13＞如＜1＞至＜12＞之任一項所述之樹脂組成物，其包含聚合性化合物。 ＜14＞如＜1＞至＜13＞之任一項所述之樹脂組成物，其中 上述樹脂為環化樹脂的前驅物。 ＜15＞如＜1＞至＜13＞之任一項所述之樹脂組成物，其包含環化樹脂或其前驅物作為上述樹脂且用於形成再配線層用層間絕緣膜。 ＜16＞一種硬化物，其藉由硬化＜1＞至＜15＞之任一項所述之樹脂組成物而成。 ＜17＞一種硬化物，其包含： 樹脂；以及 三級胺，具有酮基及環狀結構。 ＜18＞一種積層體，其包含2層以上由＜16＞或＜17＞所述之硬化物構成之層，在由上述硬化物構成之任意層彼此之間包含金屬層。 ＜19＞一種硬化物的製造方法，其包括在基材上適用＜1＞至＜15＞之任一項所述之樹脂組成物來形成膜之膜形成步驟。 ＜20＞如＜19＞所述之硬化物的製造方法，其包括對上述膜進行選擇性曝光之曝光步驟、及使用顯影液對上述膜進行顯影來形成圖案之顯影步驟。 ＜21＞如＜19＞或＜20＞所述之硬化物的製造方法，其包括在50～450℃下加熱上述膜之加熱步驟。 ＜22＞一種積層體的製造方法，其包括＜19＞至＜21＞之任一項所述之硬化物的製造方法。 ＜23＞一種半導體裝置的製造方法，其包括＜22＞所述之積層體的製造方法。 ＜24＞一種半導體裝置，其包含＜16＞或＜17＞所述之硬化物或＜18＞所述之積層體。 [發明效果] Examples of representative embodiments of the present invention are shown below. <1> A resin composition comprising: a resin; and a base generator having an α,β-unsaturated ketone group at a site to be a generated base and the generated base is cyclized into a tertiary amine in a molecule. <2> A resin composition comprising: a resin; and a base generator having an α,β-unsaturated ketone group, a group represented by -NR ¹ C(=O)-, and a group selected from the group consisting of carboxyl and hydroxyl At least one group in the group, at least one of the above-mentioned α,β-unsaturated keto groups exists on the side of the nitrogen atom of the group represented by the above-mentioned -NR ¹ C(=O)-, the above-mentioned group selected from the group consisting of At least one of at least one group of the carboxyl group and the hydroxyl group is present on the carbon atom side of the above-mentioned -NR ¹ C(=O)-, and the above-mentioned R ¹ is a monovalent organic group. <3> The resin composition according to <1> or <2>, wherein the base generator is a compound that generates a base by at least one of light and heat. <4> The resin composition according to any one of <1> to <3>, wherein the boiling point of the tertiary amine generated from the base generator is 180 to 280°C. <5> The resin composition according to any one of <1> to <4>, wherein the base generator includes a compound represented by the following formula (1-1). [chemical formula 1]

In formula (1-1), L ¹ represents an n+m valent linking group, R ¹ independently represents a monovalent organic group, at least one of R ¹ contains an α, β-unsaturated ketone group, and X are independently ground represents a hydroxyl group or a carboxyl group, m represents an integer of 1 or more, and n represents an integer of 1 or more. <6> The resin composition according to <5>, wherein L ¹ in the above formula (1-1) contains an aromatic ring structure. <7> The resin composition according to <5> or <6>, wherein L ¹ in the above formula (1-1) contains a polymerizable group. <8> The resin composition according to any one of <1> to <7>, wherein the molecular weight of the tertiary amine generated from the base generator is 100-200. <9> The resin composition according to any one of <1> to <8>, wherein the tertiary amine generated from the above-mentioned base generator has a 5-membered ring structure having a nitrogen atom constituting the tertiary amine as a ring member Or a 6-membered ring structure having a nitrogen atom constituting a tertiary amine as a ring member. <10> The resin composition according to any one of <1> to <9>, wherein the base generator has a molar absorption coefficient at a wavelength of 365 nm of 100 mol ⁻¹ ·L·cm ⁻¹ or less. <11> The resin composition according to any one of <1> to <10>, which satisfies at least one of the following conditions 1 and 2. Condition 1: The resin has a radically polymerizable group Condition 2: Further comprising a polymerizable compound having a radically polymerizable group <12> The resin composition according to any one of <1> to <11>, which contains photo Free radical polymerization initiator. <13> The resin composition according to any one of <1> to <12>, which contains a polymerizable compound. <14> The resin composition according to any one of <1> to <13>, wherein the resin is a precursor of a cyclized resin. <15> The resin composition according to any one of <1> to <13>, which contains a cyclized resin or a precursor thereof as the resin and is used for forming an interlayer insulating film for a rewiring layer. <16> A cured product obtained by curing the resin composition described in any one of <1> to <15>. <17> A cured product comprising: a resin; and a tertiary amine having a ketone group and a cyclic structure. <18> A laminate comprising two or more layers composed of the cured product described in <16> or <17>, wherein any layers composed of the cured product include a metal layer. <19> A method for producing a cured product, comprising a film forming step of applying the resin composition described in any one of <1> to <15> to form a film on a substrate. <20> The method for producing a cured product according to <19>, comprising an exposure step of selectively exposing the film, and a developing step of developing the film using a developer to form a pattern. <21> The method for producing a cured product according to <19> or <20>, which includes a heating step of heating the film at 50 to 450°C. <22> A method for producing a laminate including the method for producing a cured product according to any one of <19> to <21>. <23> A method of manufacturing a semiconductor device including the method of manufacturing the laminate described in <22>. <24> A semiconductor device comprising the cured product described in <16> or <17> or the laminate described in <18>. [Invention effect]

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

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the illustrated embodiments. In this specification, the numerical range represented by the symbol "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit, respectively. In this specification, the term "step" not only includes an independent step, but also includes a step that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved. Among the notations of groups (atomic groups) in this specification, notation of substituted and unsubstituted includes groups (atomic groups) without substituents as well as groups (atomic groups) with substituents. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group), but also an alkyl group having a substituent (substituted alkyl group). In this specification, unless otherwise specified, "exposure" includes not only exposure by light but also exposure by particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include bright line spectrum of mercury lamps, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams and other active rays or radiation. In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate" or either, and "(meth)acrylic" means "acrylic" and "methacrylic". Both or any of these, "(meth)acryl" means both or either of "acryl" and "methacryl". In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of components other than the solvent among all the components of the composition. In addition, in this specification, solid content concentration is mass percentage of other components other than a solvent with respect to the total mass of a composition. In this specification, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are the values measured by the gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. In this manual, for example, using HLC-8220GPC (manufactured by TOSOH CORPORATION), guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) are used in series As a column, weight average molecular weight (Mw) and number average molecular weight (Mn) can be calculated|required by this. Unless otherwise specified, these molecular weights were measured using THF (tetrahydrofuran) as an eluent. Among them, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as an eluent, such as when the solubility is low. In addition, unless otherwise specified, a UV ray (ultraviolet) detector with a wavelength of 254 nm was used for detection in the GPC measurement. In this specification, when "upper" or "lower" is described as "upper" or "lower" regarding the positional relationship of the layers constituting the laminate, other layers may exist above or below the reference layer among the plurality of layers concerned. That is, a third layer or a third element may be further interposed between the reference layer and the above-mentioned other layers, and the reference layer and the above-mentioned other layers do not need to be in contact. In addition, unless otherwise specified, the direction of stacking layers on the substrate is referred to as "upper", or when there is a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper", and the opposite direction is referred to as "upper". Called "down". In addition, the setting of these up and down directions is for the convenience of this specification, and in an actual situation, the "up" direction in this specification may also be different from the vertical direction. In this specification, unless otherwise specified, as each component contained in the composition, the composition may contain two or more compounds belonging to the component. In addition, unless otherwise specified, the content of each component in the composition means the total content of all the compounds belonging to the component. In this specification, unless otherwise specified, the temperature is 23° C., the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, the combination of preferable aspects is a more preferable aspect.

(Resin Composition) The resin composition according to the first aspect of the present invention includes a resin and a base generator having an α,β-unsaturated ketone group at the site of the base to be generated and the base to be generated is Intramolecular cyclization into tertiary amines. The resin composition of the second aspect of the present invention includes a resin and a base generator having an α,β-unsaturated ketone group, a group represented by -NR ¹ C(=O)-, and a group selected from At least one of the group consisting of carboxyl and hydroxyl, wherein at least one of the above-mentioned α, β-unsaturated ketone groups is present on the side of the nitrogen atom of the group represented by the above-mentioned -NR ¹ C(=O)-, At least one of the above-mentioned carboxyl group and hydroxyl group exists on the carbon atom side of the above-mentioned -NR ¹ C(=O)-, and the above-mentioned R ¹ is a monovalent organic group. In the present invention, the resin composition of the first aspect and the resin composition of the second aspect are simply collectively referred to as "resin composition". In addition, any one of the above-mentioned base generators contained in the resin composition of the first aspect of the present invention and the above-mentioned base generators contained in the resin composition of the second aspect of the present invention is also used. It is called "specific base generator".

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

According to the resin composition of this invention, the cured film excellent in pattern rectangularity can be obtained. The mechanism for obtaining the above effects is not clear, but it is presumed as follows.

Conventionally, it is known that a base generator that generates a secondary amine is used as a base generator in a resin composition. Secondary amines sometimes undergo addition reactions with carbonyl groups, C=C groups, etc. contained in resins and other components in resin compositions, resulting in hindered diffusion of amines and uneven cyclization of resins, resulting in sometimes The pattern rectangularity of the cured product is reduced. Both the base generator of the first aspect of the present invention and the base generator of the second aspect are compounds that generate tertiary amines. These tertiary amines are considered to easily diffuse in the composition film because of their low reactivity with the above-mentioned resins. Also, since the ketone group is not easily soluble in a solvent due to its high polarity, it is considered that the solvent solubility of the produced amine is lowered. Therefore, for example, when it is used for image development using a solvent as a developing solution, it is thought that the solubility increase of a pattern can be suppressed, and pattern rectangularity is excellent. Patent Document 1 describes a resin composition including a base generator containing an imine (Myco acceptor) in an amine generated, for example, an α,β-unsaturated ester. In such aspects, the amines produced are cyclized by the addition of Myco, and as a result, tertiary amines can be produced. However, since α,β-unsaturated esters have high reactivity, polymerization of amines or polymerization of amines and resins, polymerizable compounds, etc. may occur, resulting in a reduction in the diffusibility of amines. In the base generating agent of the first aspect or the second aspect of the present invention, a secondary amine having an α,β-unsaturated ketone group is generated, and the secondary amine group in the secondary amine and the α,β- Unsaturated ketones react to form tertiary amines. It is considered that the α,β-unsaturated ketone group has lower polymerization reactivity than α,β-unsaturated esters, and thus inhibits the polymerization of amines or the polymerization of amines and resins, polymerizable compounds, etc., and further improves the diffusibility of amines. From the above, it is considered that the amine generated by the base generator of the present invention has excellent diffusivity, and thus the resin composition of the present invention containing the base generator has excellent pattern squareness. In particular, when the resin contains a precursor of a cyclization resin such as a polyimide precursor, it is considered that the cyclization of the resin tends to proceed uniformly in the film, and the pattern squareness is improved.

In addition, it is considered that the alkali-based reaction in the resin layer such as cyclization of the resin as described above proceeds easily and uniformly, and as a result, the cured product is also excellent in elongation at break. Furthermore, it is considered that the reduction of polymerizable groups such as C=C groups contained in resins, polymerizable compounds, etc. due to the reaction with the above-mentioned base can be suppressed, so the crosslinking density in the cured film is easy to increase, and the chemical resistance is also excellent. In addition, it is considered that the obtained cured product is also excellent in adhesion to the metal because the base of the tertiary amine is higher than that of the secondary amine and the migration of metal ions from the metal to the cured product is easily suppressed.

Here, Patent Document 1 does not describe a resin composition containing a specific base generator.

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

＜Resin＞ The resin composition of this invention contains resin. The resin is not particularly limited, and examples thereof include resins used in conventional pattern-forming compositions, and it is preferable to include at least one resin (specific resin) selected from the group including cyclized resins and their precursors. Preferably, a precursor comprising a cyclized resin is more preferred. Moreover, it is preferable that the resin of this invention has a polymeric group. As the polymerizable group, a group capable of undergoing a crosslinking reaction by the action of heat, free radicals, etc. is preferable, and a radical polymerizable group is more 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 benzoxanyl group. An azole group, a blocked isocyanate group, an amine group, and a group having an ethylenically unsaturated bond are preferred. As the group having an ethylenically unsaturated bond, vinyl, allyl, isoallyl, 2-methallyl, and a group having an aromatic ring directly bonded to a vinyl group (for example, Vinylphenyl, etc.), (meth)acrylamide, (meth)acryloxy, etc., a group having an aromatic ring directly bonded to vinyl, (meth)acrylamide or ( Meth)acryloxy is preferred, and (meth)acryloxy is more preferred.

Here, it is preferable that the resin composition of the present invention satisfies at least one of the following conditions 1 and 2. Also, satisfying both of the following condition 1 and condition 2 is also one of the preferred aspects of the present invention. Condition 1: The resin has a free radical polymerizable group Condition 2: Further containing a polymerizable compound having a radically polymerizable group

The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure. In the present invention, the main chain refers to the relatively longest bonded chain in the resin molecule. Examples of the cyclized resin include polyimide, polybenzoxazole, polyamideimide, and the like. The precursor of the cyclized resin refers to the resin whose chemical structure is changed into a cyclized resin by external stimuli, and the resin whose chemical structure is changed by heat to become a cyclized resin is better. It is formed by using heat to generate a ring closure reaction. It is more preferable to use a ring structure to become a cyclized resin. Examples of the precursor of the cyclized resin include polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, and the like. That is, the resin composition of the present invention comprises polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide and polyamideimide It is preferable that at least one type of resin (specific resin) in the group of imine precursors is used as the specific resin. The resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin. Moreover, it is preferable that a specific resin has a polymerizable group, and it is more preferable that it contains a radical polymerizable group. When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably includes the radical polymerization initiator described later, more preferably includes the radical polymerization initiator described later and the radical crosslinking agent described later. The sensitizer mentioned later can be contained further as needed. For example, a negative photosensitive film is formed from such a resin composition of the present invention. In addition, the specific resin may have a polarity conversion group such as an acid decomposable group. When the specific resin has an acid-decomposable group, it is preferable that the resin composition of the present invention contains a photoacid generator described later. For example, a chemically amplified positive photosensitive film or a negative photosensitive film is formed from such a resin composition of the present invention.

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

In formula (2), A ¹ and A ² independently represent an oxygen atom or -NH-, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and R ¹¹⁴ independently represent hydrogen 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. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups, and groups containing aromatic groups, linear or branched aliphatic groups having 2 to 20 carbon atoms, carbon A cycloaliphatic group with 3 to 20 carbons, an aromatic group with 3 to 20 carbons, or a combination thereof is preferred, and a group including an aromatic group with 6 to 20 carbons is more preferred . The hydrocarbon group in the chain of the above-mentioned linear or branched aliphatic group may be substituted by a group containing a heteroatom, and the ring-membered hydrocarbon group of the above-mentioned cyclic aliphatic group and aromatic group may be substituted by a group containing a heteroatom. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, and groups represented by -Ar-L-Ar- are particularly preferable. Among them, Ar is independently an aromatic group, L is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or - NHCO-or a group consisting of a combination of two or more of the above. Such preferred ranges are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Diamine may use only 1 type, and may use 2 or more types. Specifically, a straight-chain or branched aliphatic group with 2 to 20 carbons, a cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 3 to 20 carbons, or a combination thereof The diamine of the group is preferable, and the diamine containing an aromatic group with 6-20 carbon atoms is more preferable. The hydrocarbon group in the chain of the above-mentioned linear or branched aliphatic group may be substituted by a group containing a heteroatom, and the ring-membered hydrocarbon group of the above-mentioned cyclic aliphatic group and aromatic group may be substituted by a group containing a heteroatom. Examples of the group containing an aromatic group include the following groups.

式中，A表示單鍵或2價連結基，單鍵或選自可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-SO ₂-、-NHCO-或該等的組合之基團為較佳，單鍵或選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-或-SO ₂-之基團為更佳，-CH ₂-、-O-、-S-、-SO ₂-、-C（CF ₃） ₂-或-C（CH ₃） ₂-為進一步較佳。 式中，*表示與其他結構的鍵結部位。 [chemical formula 3]

In the formula, A represents a single bond or a divalent linking group, a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -SO ₂ -, -NHCO- or the combination of these groups are preferred, single bond or selected from C1-3 alkylene groups, -O-, -C(=O )-, -S- or -SO ₂ - is more preferred, -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - or -C(CH ₃ ) ₂ - as further preferred. In the formula, * represents a bonding site with other structures.

Specific examples of diamines include those selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-Diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2 , 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'- Diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- and 3,3'-diamine Aminobiphenyl, 4,4'- and 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3 '-Diaminodiphenylsulfone, 4,4'- or 3,3'-diaminodiphenylsulfide, 4,4'- 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-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)pyridine, bis(4-amino-3-hydroxyphenyl)pyridine , 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]pyridine, bis [4-(3-aminophenoxy)phenyl]pyridine, bis[4-(2-aminophenoxy)phenyl]pyridine, 1,4-bis(4-aminophenoxy)benzene , 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl anthracene, 1,3-bis(4-aminophenoxy base) benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-di Aminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4- (4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl )-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl) fennel, 4,4'-bis Methyl-3,3'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2, 5-Diaminocumene, 2,5-Dimethyl-p-phenylenediamine, Acetylguanamine, 2,3,5,6-Tetramethyl-p-phenylenediamine, 2,4,6-tri Methyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminoterpene, 2,5-Diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, Diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4- Aminophenyl) decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexa Fluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis Methylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4- Amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amine base-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylphenylene, 4,4'-bis(3 -amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2 , at least one diamine selected from 2',5,5',6,6'-hexafluorobenzidine and 4,4'-diaminoquaterphenyl.

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

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

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

式（51）中，R ⁵⁰～R ⁵⁷分別獨立地為氫原子、氟原子或1價有機基團，R ⁵⁰～R ⁵⁷中的至少1個為氟原子、甲基或三氟甲基，*分別獨立地表示與式（2）中的氮原子的鍵結部位。 作為R ⁵⁰～R ⁵⁷的1價有機基團，可舉出碳數1～10（較佳為碳數1～6）的未經取代之烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式5]

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

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 a bonding site with a nitrogen atom in formula (2). Examples of monovalent organic groups for R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), 1 to 6) fluorinated alkyl groups, etc. [chemical formula 5]

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

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

In formula (5), R ¹¹² is a single bond or a divalent linking group, a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - and -NHCO-, and the combination of these groups are preferred, a single bond or a group selected from a C1-3 alkylene group that may be substituted by a fluorine atom, -O-, -CO-, The groups in -S- and -SO ₂ - are more preferred, selected from the group including -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, The divalent group in the group of -S- and -SO ₂ - is more preferable.

式（O）中，R ¹¹⁵表示4價有機基團。R ¹¹⁵與式（2）中的R ¹¹⁵的含義相同，較佳範圍亦相同。 Specifically, R ¹¹⁵ includes a tetracarboxylic acid residue remaining after removing an acid anhydride group from a tetracarboxylic dianhydride, and the like. As the structure belonging to ^R115 , 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 7]

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

Specific examples of tetracarboxylic dianhydride include pyromelite dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride , 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4' -Biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7 -naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4 -tetracarboxylic dianhydride, 1,4,5,6-naphthalene tetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylene Tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride , 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,2,3,4-benzene Tetracarboxylic dianhydride and these alkyl groups having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Moreover, tetracarboxylic dianhydride (DAA-1) - (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can also be mentioned as a preferable example.

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

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

[chemical formula 8]

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site with other structures. In the formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, a cycloalkylene group, or a polyalkylene group. Preferred examples of ^R201 include alkylene groups such as vinyl, propenyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH ₂ CH(OH)CH ₂ -, polyalkyleneoxy, vinyl, propenyl and other alkylene, -CH ₂ CH( OH) CH ₂ -, cyclohexyl, and polyalkyleneoxy are more preferred, and alkylene or polyalkylene such as vinyl and propenyl are still more preferred. In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups included in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group can be a random arrangement, an arrangement with blocks, or an arrangement with Arrangement of alternating patterns. The carbon number of the above-mentioned alkylene group (when the alkylene group has a substituent, including the carbon number of the substituent) is preferably 2 or more, more preferably 2-10, more preferably 2-6, and still more preferably 2-5. Excellent, 2 to 4 are more preferred, 2 or 3 are particularly preferred, and 2 is the best. Moreover, the said alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. are mentioned. Moreover, the number of the alkyleneoxy groups contained in a polyalkyleneoxy group (the number of repetitions of a polyalkyleneoxy group) is 2-20 preferably, 2-10 are more preferable, 2-6 are still more preferable. As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy, or a plurality of ethyleneoxy groups and a plurality of A group bonded with propyleneoxy group is preferable, polyethyleneoxy group or polypropyleneoxy group is more preferable, and polyethyleneoxy group is still more preferable. In the above-mentioned groups in which a plurality of ethyleneoxy groups are bonded to a plurality of propyleneoxy groups, the ethyleneoxy groups and the propyleneoxy groups can be arranged randomly, arranged in blocks, or arranged in alternate patterns. Desirable aspects of the repeating numbers of ethyleneoxy groups and the like in these groups are as described above.

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

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

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

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

式（2-A）中，A ¹及A ²表示氧原子，R ¹¹¹及R ¹¹²分別獨立地表示2價有機基團，R ¹¹³及R ¹¹⁴分別獨立地表示氫原子或1價有機基團，R ¹¹³及R ¹¹⁴中的至少1個為包含聚合性基之基團，兩者均為包含聚合性基之基團為較佳。 The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, the width of the exposure latitude can be further increased. Formula (2-A) [Chemical Formula 9]

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

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

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

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

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

〔Polyimide〕 The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developing solution mainly composed of an organic solvent. In this specification, an alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more in 100 g of a 2.38 mass % tetramethylammonium aqueous solution at 23° C., and dissolves 0.5 g from the viewpoint of pattern formation. The above polyimides are preferred, and it is still more preferred to dissolve 1.0 g or more of the polyimides. The upper limit of the above-mentioned dissolved amount is not particularly limited, but is preferably 100 g or less. Moreover, from the viewpoint of film strength and insulating properties of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain. In the present specification, the "main chain" means the relatively longest bonded chain among the molecules of the polymer compound constituting the resin, and the "side chain" means the bonded chains other than it.

-Fluorine atom- It is also preferable that polyimide has a fluorine atom from the viewpoint of the film strength of the obtained organic film. A fluorine atom, for example, contained in R ¹³² in the repeating unit represented by the following formula (4) or R ¹³¹ in the repeating unit represented by the following formula (4) is preferred, as a fluorinated alkyl group contained in the following formula ( R ¹³² in the repeating unit represented by 4) or R ¹³¹ in the repeating unit represented by the following formula (4) is more preferable. The amount of fluorine atoms relative to the total mass of polyimide is preferably at least 5% by mass, and more preferably at most 20% by mass.

-Silicon atom- It is also preferable that the polyimide has a silicon atom from the viewpoint of the film strength of the obtained organic film. A silicon atom such as R 131 contained in the repeating unit represented by the following formula (4) is preferable, and R ¹³¹ contained in the repeating unit represented by the following formula (4) as the organic modified (poly)siloxane structure described below R ¹³¹ is included more preferably. In addition, the above-mentioned silicon atom or the above-mentioned organomodified (poly)siloxane structure may be included in the side chain of polyimide, but it is preferably included in the main chain of polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably at least 1% by mass, more preferably at most 20% by mass.

-Ethylenically unsaturated bond- It is preferable that polyimide has an ethylenically unsaturated bond from the viewpoint of the film strength of the obtained organic film. Polyimide may have an ethylenically unsaturated bond at the end of the main chain, or may have an ethylenically unsaturated bond at the side chain, and preferably has an ethylenically unsaturated bond at the side chain. It is preferable that the said ethylenically unsaturated bond has radical polymerizability. R ¹³² contained in the repeating unit represented by the following formula (4) or R ¹³¹ in the repeating unit represented by the following formula (4) having an ethylenically unsaturated bond is preferred as a group having an ethylenically unsaturated bond On the other hand, R ¹³² contained in the repeating unit represented by the formula (4) described below or R ¹³¹ included in the repeating unit represented by the formula (4) described below is more preferable. Among them, R ¹³¹ whose ethylenically unsaturated bond is contained in the repeating unit represented by the formula (4) described below is preferable, and is contained in the repeating unit represented by the formula (4) described below as a group having an ethylenically unsaturated bond. R ¹³¹ in the repeating unit is included more preferably. Examples of the group having an ethylenically unsaturated bond include vinyl, allyl, vinylphenyl and other groups having a vinyl group that may be substituted directly bonded to an aromatic ring, (meth)acryl An amino group, a (meth)acryloxy group, a group represented by the following formula (IV), and the like.

[chemical formula 10]

In formula (IV), R ²⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group.

In formula (IV), R ²¹ represents an alkylene group with 2 to 12 carbons, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH- , a (poly)alkyleneoxy group with 2 to 30 carbon atoms (the carbon number of the alkylene group is preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 or 3; the number of repetitions is 1 to 12 is Preferably, 1 to 6 are more preferred, and 1 to 3 are particularly preferred) or a combination of two or more of these. In addition, as the above-mentioned alkylene group having 2 to 12 carbon atoms, any of alkylene groups represented by linear, branched, cyclic, or combinations thereof may be used. As the above-mentioned alkylene group having 2 to 12 carbons, an alkylene group having 2 to 8 carbons is preferable, and an alkylene group having 2 to 4 carbons is more preferable.

式（R1）～（R3）中，L表示單鍵或碳數2～12的伸烷基、碳數2～30的（聚）伸烷氧基或將該等鍵結2個以上而成之基團，X表示氧原子或硫原子，*表示與其他結構的鍵結部位，**表示與式（IV）中的R ²¹所鍵結之氧原子的鍵結部位。 式（R1）～（R3）中，L中的碳數2～12的伸烷基或碳數2～30的（聚）伸烷氧基的較佳態樣與上述R ²¹中的碳數2～12的伸烷基或碳數2～30的（聚）伸烷氧基的較佳態樣相同。 式（R1）中，X為氧原子為較佳。 式（R1）～（R3）中，*與式（IV）中的*的含義相同，較佳態樣亦相同。 由式（R1）表示之結構例如可藉由使酚性羥基等具有羥基之聚醯亞胺與具有異氰酸基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-異氰酸基乙酯等）進行反應來獲得。 由式（R2）表示之結構例如可藉由使具有羧基之聚醯亞胺與具有羥基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-羥乙酯等）進行反應來獲得。 由式（R3）表示之結構例如可藉由使酚性羥基等具有羥基之聚醯亞胺與具有環氧丙基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸環氧丙酯等）進行反應來獲得。 Among them, R ²¹ is preferably a group represented by any one of the following formulas (R1) to formula (R3), more preferably a group represented by formula (R1). [chemical formula 11]

In the formulas (R1) to (R3), L represents a single bond or an alkylene group having 2 to 12 carbons, a (poly)alkyleneoxy group having 2 to 30 carbons, or a combination of two or more of these. A group, X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ** represents a bonding site with an oxygen atom bonded to R ²¹ in formula (IV). In the formulas (R1) to (R3), the preferred embodiment of the alkylene group with 2 to 12 carbons or the (poly)alkoxyl group with 2 to 30 carbons in L is the same as the carbon number 2 in ^R21 above. Preferred aspects of the alkylene group of ∼12 or the (poly)alkyleneoxy group having 2 to 30 carbon atoms are the same. In the formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same. The structure represented by the formula (R1) can be obtained by, for example, combining a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, methacrylic acid 2-isocyanate group) Ethyl ester, etc.) to obtain by reaction. The structure represented by formula (R2) can be obtained, for example, by reacting polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.). The structure represented by the formula (R3) can be obtained by, for example, combining polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.) react to obtain.

In formula (IV), * represents a bonding site with other structures, and the bonding site with the main chain of polyimide is preferable.

The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, more preferably 0.0005 to 0.05 mol/g.

-Polymerizable group other than the group having an ethylenically unsaturated bond- The polyimide may contain a polymerizable group other than a group having an ethylenically unsaturated bond. Examples of polymerizable groups other than groups having ethylenically unsaturated bonds include cyclic ether groups such as epoxy groups and oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. wait. For example, R ¹³¹ in which a polymerizable group other than a group having an ethylenically unsaturated bond is contained in a repeating unit represented by formula (4) described later is preferable. The amount of polymerizable groups other than groups having an ethylenically unsaturated bond is preferably 0.0001 to 0.1 mol/g, more preferably 0.001 to 0.05 mol/g, based on the total mass of the polyimide.

-Polarity conversion group- The polyimide may have a polarity conversion group, such as an acid-decomposable group. The acid-decomposable groups in the polyimide are the same as the acid-decomposable groups described for R ¹¹³ and R ¹¹⁴ in the above formula (2), and preferred aspects are also the same. The polarity switching group includes, for example, R ¹³¹ , R ¹³² , the terminal of polyimide, etc. included in the repeating unit represented by the formula (4) described later.

-acid value- When polyimide is used for alkali development, from the viewpoint of improving developability, the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and 70 mgKOH/g or more. good. Moreover, the above-mentioned acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and still more preferably 200 mgKOH/g or less. In addition, when polyimide is used in development using a developer containing an organic solvent as the main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 1 to 35 mgKOH/g, and 2 -30 mgKOH/g is more preferable, and 5-20 mgKOH/g is still more preferable. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Moreover, as an acid group contained in a polyimide, the acid group whose pKa is 0-10 is preferable from a viewpoint of both storage stability and developability, and the acid group of 3-8 is more preferable. pKa considers the dissociation reaction of releasing hydrogen ions from an acid and expresses its equilibrium constant Ka by its negative common logarithm pKa. In this specification, unless otherwise specified, pKa is a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, you can refer to the values described in "Revised 5th edition: Chemistry Handbook - Basic Edition" edited by the Chemical Society of Japan. Also, when the acid group is, for example, a polybasic acid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant. As such an acid group, it is preferable that polyimide contains at least 1 sort(s) selected from the group containing a carboxyl group and a phenolic hydroxyl group, and it is more preferable that it contains a phenolic hydroxyl group.

-Phenolic hydroxyl group- It is preferable that polyimide has a phenolic hydroxyl group from a viewpoint of making the developing speed by alkali developing solution suitable. Polyimide may have a phenolic hydroxyl group at a main chain terminal, or may have a phenolic hydroxyl group at a side chain. The phenolic hydroxyl group, for example, R ¹³² contained in the repeating unit represented by the formula (4) described below or R ¹³¹ contained in the repeating unit represented by the formula (4) described below, is preferable. The amount of the phenolic hydroxyl group is preferably 0.1 to 30 mol/g with respect to the total mass of the polyimide, more preferably 1 to 20 mol/g.

式（4）中，R ¹³¹表示2價有機基團，R ¹³²表示4價有機基團。 具有聚合性基時，聚合性基可以位於R ¹³¹及R ¹³²中的至少1個上，亦可以如下述式（4-1）或式（4-2）所示，位於聚醯亞胺的末端。 式（4-1） [化學式13]

式（4-1）中，R ¹³³為聚合性基，其他基團與式（4）的含義相同。 式（4-2） [化學式14]

R ¹³⁴及R ¹³⁵中的至少1個為聚合性基，不是聚合性基的情況下為有機基團，其他基團與式（4）的含義相同。 The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but preferably includes a repeating unit represented by the following formula (4). [chemical formula 12]

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. When having a polymerizable group, the polymerizable group may be located on at least one of R ¹³¹ and R ¹³² , or may be located at the end of polyimide as shown in the following formula (4-1) or formula (4-2) . Formula (4-1) [Chemical Formula 13]

In formula (4-1), R ¹³³ is a polymerizable group, and other groups have the same meanings as in formula (4). Formula (4-2) [Chemical Formula 14]

At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups have the same meaning as in formula (4).

As a polymeric group, the group containing the said ethylenically unsaturated bond, or the crosslinkable group other than the group containing the said ethylenically unsaturated bond is mentioned. R ¹³¹ represents a divalent organic group. As a divalent organic group, the thing similar to ^R111 in formula (2) can be illustrated, and the preferable range is also the same. Moreover, as ^R131 , the diamine residue which remains after removing the amine group of diamine is mentioned. As diamine, aliphatic, cycloaliphatic, or aromatic diamine etc. are mentioned. As a specific example, the example of ^R111 in the formula (2) of a polyimide precursor is mentioned.

From the viewpoint of more effectively suppressing warpage during firing, R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in the main chain. More preferably, it is a diamine containing a total of two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and it is still more preferable that it is a diamine residue containing no aromatic ring.

Examples of diamines containing a total of two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (the above are trade names, manufactured by Huntsman Corporation), 1-(2-(2-(2-amine ylpropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine etc., but not limited to such.

R ¹³² represents a tetravalent organic group. As a tetravalent organic group, the thing similar to ^R115 in formula (2) can be illustrated, and the preferable range is also the same. For example, four bonds of the tetravalent organic group exemplified as R ¹¹⁵ are bonded to four -C(=O)- moieties in the above formula (4) to form a condensed ring.

Moreover, the tetracarboxylic acid residue etc. which remain after removing an acid anhydride group from tetracarboxylic dianhydride as ^R132 are mentioned. As a specific example, the example of ^R115 in the formula (2) of a polyimide precursor is mentioned. From the viewpoint of the strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable to have an OH group on at least one of R ¹³¹ and R ¹³² . More specifically, examples of R ¹³¹ include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoro Propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, the above (DA-1)～( DA-18) As a preferable example, as ^R132 , the said (DAA-1)-(DAA-5) is mentioned as a more preferable example.

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

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

In addition, in order to improve the storage stability of the resin composition, it is preferable that the end of the main chain of the polyimide is blocked by a blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacyl chloride compound, or active monoester compound. Among these, it is more preferable to use a monoamine, and examples of preferable compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxy Quinoline, 1-hydroxy-7-aminenaphthalene, 1-hydroxy-6-aminenaphthalene, 1-hydroxy-5-aminenaphthalene, 1-hydroxy-4-aminenaphthalene, 2-hydroxy-7-aminenaphthalene, 2- Hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-amine Naphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5 -aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxy Pyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more kinds of these can be used, and a plurality of different end groups can be introduced by reacting a plurality of end-capping agents.

-Imidation ratio (loop closure ratio)- The imidization ratio (also called "loop closure ratio") of polyimide is 70% or more from the viewpoint of the film strength and insulation properties of the obtained organic film. More than 80% is more preferable, and more than 90% is more preferable. The upper limit of the above-mentioned imidization rate is not particularly limited, and may be 100% or less. For example, the above-mentioned imidization rate can be measured by the following method. The infrared absorption spectrum of polyimide was measured, and the peak intensity P1 around 1377 cm ^-1 which is the absorption peak derived from the imide structure was obtained. Next, after heat-treating this polyimide at 350° C. for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P2 around 1377 cm ⁻¹ was obtained. Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be calculated from the following formula. Amide imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

Polyimide may have a repeating unit represented by the above formula (4) that contains all one type of R ¹³¹ or R ¹³² , or may have the above formula (4) that contains two or more different types of R ¹³¹ or R ¹³² Represents the repeating unit. In addition, the polyimide may contain other types of repeating units other than the repeating unit represented by the above formula (4). As another kind of repeating unit, the repeating unit represented by said formula (2), etc. are mentioned, for example.

For example, polyimide can use the method of reacting tetracarboxylic dianhydride and diamine (replacing part with monoamine, that is, end-capping agent) at low temperature, and making tetracarboxylic dianhydride (replacing part It is a method of reacting an acid anhydride or monoacyl chloride compound or an active monoester compound (that is, an end-capping agent) with a diamine, and after obtaining a diester from tetracarboxylic dianhydride and alcohol, make it in diamine (substituting part of it with monoamine That is, the method of reacting in the presence of an end-capping agent) and a condensing agent, after obtaining a diester from tetracarboxylic dianhydride and alcohol, chlorinating the remaining dicarboxylic acid and making it with diamine (substituting part of it with monoamine That is, the method of reaction of the end-capping agent) and other methods to obtain the polyimide precursor, and use the method of complete imidization by the known imidization reaction method or stop the imidization reaction halfway and introduce A part of the imide structure is synthesized by further mixing the fully imidized polymer and its polyimide precursor to introduce a part of the imide structure. In addition, other known polyimide synthesis methods can also be applied.

The weight average molecular weight (Mw) of polyimide becomes like this. Preferably it is 5,000-100,000, More preferably, it is 10,000-50,000, More preferably, it is 15,000-40,000. By making the weight average molecular weight 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical properties (for example, elongation at break), it is particularly preferable that the weight average molecular weight is 15,000 or more. Moreover, the number average molecular weight (Mn) of polyimide becomes like this. Preferably it is 2,000-40,000, More preferably, it is 3,000-30,000, More preferably, it is 4,000-20,000. The molecular weight dispersion of the polyimide is preferably at least 1.5, more preferably at least 1.8, and still more preferably at least 2.0. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited. For example, 7.0 or less is preferable, 6.5 or less is more preferable, and 6.0 or less is still more preferable. Also, when the resin composition contains a plurality of polyimides as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyimide are within the above-mentioned ranges. Furthermore, it is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated using the above-mentioned plurality of polyimides as one resin are within the above-mentioned ranges, respectively.

式（3）中，R ¹²¹表示2價有機基團，R ¹²²表示4價有機基團，R ¹²³及R ¹²⁴分別獨立地表示氫原子或1價有機基團。 [Polybenzoxazole Precursor] The structure of the polybenzoxazole precursor used in the present invention is not particularly limited, but preferably includes a repeating unit represented by the following formula (3). [chemical formula 15]

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

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

（式中，Z為碳數1～6的烴基，n為1～6的整數。） [chemical formula 16]

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

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

式中，A表示選自包括-CH ₂-、-O-、-S-、-SO ₂-、-CO-、-NHCO-、-C（CF ₃） ₂-及-C（CH ₃） ₂-之群組中之2價基團，*分別獨立地表示與其他結構的鍵結部位。 [chemical formula 17]

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

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

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

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

式中，X ₁表示-O-、-S-、-C（CF ₃） ₂-、-CH ₂-、-SO ₂-、-NHCO-，*及#分別表示與其他結構的鍵結部位。R表示氫原子或1價取代基，氫原子或烴基為較佳，氫原子或烷基為更佳。又，R ¹²²為由上述式表示之結構亦較佳。R ¹²²為由上述式表示之結構時，共計4個*及#中，任意2個為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位且另2個為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位為較佳，2個*為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位或2個*為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位為更佳，2個*為與式（3）中的R ¹²²所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R ¹²²所鍵結之氮原子的鍵結部位為進一步較佳。 [chemical formula 18]

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

It is also preferable that the bisaminophenol derivative is a compound represented by the formula (As). [chemical formula 19]

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 An organic group in the group of formula (A-sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R ₃ is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

（式（A-sc）中，*表示與由上述式（A-s）表示之雙胺基苯酚衍生物的胺基苯酚基的芳香環鍵結。） [chemical formula 20]

(In the formula (A-sc), * indicates that it is bonded to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

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

In addition, in the above-mentioned formula (As), when _R2 is an alkyl group and _R3 is an alkyl group, high transparency to i-rays and the effect of high cyclization rate during curing at low temperature can be maintained, which is preferable.

Also, in the above formula (As), R ₁ is further preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and substituted alkylene group related to _R1 include straight-chain or branched-chain alkyl groups having 1 to 8 carbon atoms. -CH 2 -, -CH(CH 3 )-, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ - is more preferred.

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

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

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

式（SL）中，Z具有a結構和b結構，R ^1s為氫原子或碳數1～10的烴基，R ^2s為碳數1～10的烴基，R ^3s、R ^4s、R ^5s、R ^6s中的至少1個為芳香族基，剩餘部分為氫原子或碳數1～30的有機基團且分別可以相同，亦可以不同。a結構及b結構的聚合可以為嵌段聚合或無規聚合。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 21]

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

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

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

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

式（X）中，R ¹³³表示2價有機基團，R ¹³⁴表示4價有機基團。 具有聚合性基或酸分解性基等極性轉換基時，聚合性基或酸分解性基等極性轉換基可以位於R ¹³³及R ¹³⁴中的至少1個上，亦可以如下述式（X-1）或式（X-2）所示位於聚苯并噁唑的末端。 式（X-1） [化學式23]

式（X-1）中，R ¹³⁵及R ¹³⁶中的至少1個為聚合性基或酸分解性基等極性轉換基，不是聚合性基或酸分解性基等極性轉換基的情況下為有機基團，其他基團與式（X）的含義相同。 式（X-2） [化學式24]

式（X-2）中，R ¹³⁷為聚合性基或酸分解性基等極性轉換基，其餘為取代基，其他基團與式（X）的含義相同。 [Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but a compound represented by the following formula (X) is preferred, and is represented by the following formula (X): The compound represented by formula (X) and having a polymerizable group is more preferable. As said polymerizable group, a radical polymerizable group is preferable. Moreover, it may be a compound represented by the following formula (X) and having a polarity converting group such as an acid decomposable group. [chemical formula 22]

In the formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group. When there is a polarity conversion group such as a polymerizable group or an acid decomposable group, the polarity conversion group such as a polymerizable group or an acid decomposable group can be located on at least one of R ¹³³ and R ¹³⁴ , or it can be as shown in the following formula (X-1 ) or formula (X-2) at the end of polybenzoxazole. Formula (X-1) [Chemical Formula 23]

In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polarity conversion group such as a polymerizable group or an acid decomposable group, and when it is not a polarity conversion group such as a polymerizable group or an acid decomposable group, it is organic group, other groups have the same meaning as formula (X). Formula (X-2) [Chemical Formula 24]

In formula (X-2), R ¹³⁷ is a polarity conversion group such as a polymerizable group or an acid decomposable group, and the rest are substituents, and the meanings of other groups are the same as in formula (X).

The polarity conversion group such as a polymerizable group or an acid-decomposable group has the same meaning as that of the polymerizable group described above in the polymerizable group contained in the polyimide precursor.

R ¹³³ represents a divalent organic group. An aliphatic group or an aromatic group is mentioned as a divalent organic group. As a specific example, the example of ^R121 in the formula (3) of a polybenzoxazole precursor is mentioned. Also, preferred examples thereof have the same meaning as R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. Examples of the tetravalent organic group include R ¹²² in the formula (3) of the polybenzoxazole precursor. Also, preferred examples thereof have the same meaning as ^R122 . For example, four bonds of the tetravalent organic group exemplified as R ¹²² are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. In the following structures, * respectively represents a bonding site with a nitrogen atom or an oxygen atom in formula (X). [chemical formula 25]

The oxazole rate of polybenzoxazole is preferably 85% or more, more preferably 90% or more. The upper limit is not particularly limited, and may be 100%. Since the oxazolization rate is above 85%, the shrinkage of the film caused by the ring closure that occurs when it is oxazolized by heating becomes smaller, and warpage can be effectively suppressed. For example, the above-mentioned oxazole yield can be measured by the following method. The infrared absorption spectrum of polybenzoxazole was measured to obtain the peak intensity Q1 around 1650 cm ^-1 which is the absorption peak derived from the amide structure of the precursor. Next, normalization was performed using the absorption intensity of the aromatic ring observed around 1490 cm ⁻¹ . After heat-treating the polybenzoxazole precursor at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity Q2 around 1650 cm ^-1 was obtained by using the absorption intensity of the aromatic ring observed around 1490 cm ^-1 Normalized. Using the obtained standard values of peak intensities Q1 and Q2, the oxazole yield of polybenzoxazole can be calculated from the following formula. Oxazole conversion rate (%) = (standard value of peak intensity Q1/standard value of peak intensity Q2) × 100

The polybenzoxazole may have a repeating unit of the above formula (X) containing all one type of R ¹³¹ or R ¹³² , or may have the above formula (X) containing two or more different types of R ¹³¹ or R ¹³² repeat unit. In addition, polybenzoxazole may contain other types of repeating units other than the repeating unit of the above formula (X).

For example, reacting a bisaminophenol derivative with a dicarboxylic acid containing R ¹³³ or a compound selected from dicarboxylic acid dichloride and dicarboxylic acid derivatives of the above-mentioned dicarboxylic acids to obtain a polybenzoxazole precursor Compounds can be oxazolized by the known oxazolization reaction method to obtain polybenzoxazole. In addition, in the case of dicarboxylic acids, active ester-type dicarboxylic acid derivatives that have previously reacted 1-hydroxy-1,2,3-benzotriazole or the like can also be used in order to increase the reaction yield or the like.

As for the weight average molecular weight (Mw) of polybenzoxazole, 5,000-70,000 are preferable, 8,000-50,000 are more preferable, 10,000-30,000 are still more preferable. By making the weight average molecular weight 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical properties, it is particularly preferable that the weight average molecular weight is 20,000 or more. Moreover, when containing 2 or more types of polybenzoxazole, it is preferable that the weight average molecular weight of at least 1 type of polybenzoxazole exists in the said range. Moreover, the number average molecular weight (Mn) of polybenzoxazole becomes like this. Preferably it is 7,200-14,000, More preferably, it is 8,000-12,000, More preferably, it is 9,200-11,200. The molecular weight dispersion of the polybenzoxazole is preferably at least 1.4, more preferably at least 1.5, and still more preferably at least 1.6. The upper limit of the molecular weight dispersion of polybenzoxazole is not particularly limited, for example, preferably 2.6 or less, more preferably 2.5 or less, still more preferably 2.4 or less, still more preferably 2.3 or less, 2.2 or less For further better. Moreover, when the resin composition contains plural kinds of polybenzoxazoles as specific resins, it is preferable that the weight average molecular weight, number average molecular weight and degree of dispersion of at least one kind of polybenzoxazole are within the above-mentioned ranges. Furthermore, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of polybenzoxazoles mentioned above as one type of resin be within the above ranges, respectively.

式（PAI-2）中，R ¹¹⁷表示3價有機基團，R ¹¹¹表示2價有機基團，A ²表示氧原子或-NH-，R ¹¹³表示氫原子或1價有機基團。 [Polyamideimide Precursor] The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2). [chemical formula 26]

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

In the formula (PAI-2), R ¹¹⁷ can be exemplified by a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or these are linked by a single bond or a linking group 2 A group consisting of more than one, straight-chain aliphatic group with 2 to 20 carbons, branched aliphatic group with 3 to 20 carbons, cyclic aliphatic group with 3 to 20 carbons, and aliphatic group with 6 to 20 carbons An aromatic group or a group formed by combining two or more of these through a single bond or a linking group is preferred. An aromatic group with 6 to 20 carbons or a group with 6 to 20 carbons connected through a single bond or a linking group is preferred. A combination of two or more aromatic groups is more preferable. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) ₂ -, alkylene group, halogenated alkylene group, arylylene group, or a combination of two of these The above linking group is preferred, and -O-, -S-, alkylene, halogenated alkylene, arylylene or a linking group in which two or more of these are bonded is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is still more preferable. As the alkylene halide, a alkylene halide having 1 to 20 carbons is preferable, an alkylene halide having 1 to 10 carbons is more preferable, and an alkylene halide having 1 to 4 carbons is more preferable. Moreover, examples of the halogen atom in the above-mentioned halogenated alkylene group include fluorine atom, chlorine atom, bromine atom, iodine atom and the like, among which fluorine atom is preferred. The aforementioned halogenated alkylene group may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, but all hydrogen atoms are preferably replaced by halogen atoms. Examples of preferred alkylene halides include (bistrifluoromethyl)methylene and the like. As said aryl group, phenylene or naphthylene is preferable, phenylene is more preferable, and 1,3-phenylene or 1,4-phenylene is still more preferable.

Also, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As the above-mentioned halogenation, chlorination is preferable. In the present invention, a compound having three carboxyl groups is called a tricarboxylic acid compound. Among the three carboxyl groups of the tricarboxylic acid compound, two carboxyl groups may be anhydrided. Examples of the tricarboxylic acid compound that may be halogenated for the production of the polyamideimide precursor include branched aliphatic, cycloaliphatic, or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used only by 1 type, and may use 2 or more types.

Specifically, as a tricarboxylic acid compound, a straight-chain aliphatic group having 2 to 20 carbons, a branched aliphatic group having 3 to 20 carbons, a cyclic aliphatic group having 3 to 20 carbons, a cyclic aliphatic group having 6 to 20 carbons, A tricarboxylic acid compound having an aromatic group of ~20 or a group formed by combining two or more of them through a single bond or a linking group is preferred, including an aromatic group with a carbon number of 6 to 20 or through a single bond Or a tricarboxylic acid compound in which two or more aromatic groups having 6 to 20 carbon atoms are combined as a linking group is more preferable.

Moreover, specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6 -Naphthalene tricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid via single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ - or compounds formed by linking phenylene groups, etc. These compounds may be compounds in which two carboxyl groups are anhydrided (for example, trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (for example, trimellitic anhydride).

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

The polyamideimide precursor may further comprise other repeating units. As another repeating unit, the repeating unit represented by said formula (2), the repeating unit represented by following formula (PAI-1), etc. are mentioned. [chemical formula 27]

In the formula (PAI-1), R ¹¹⁶ represents a divalent organic group, and R ¹¹¹ represents a divalent organic group. In the formula (PAI-1), R ¹¹⁶ can be exemplified by a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or these are linked by a single bond or a linking group 2 A group consisting of more than one, straight-chain aliphatic group with 2 to 20 carbons, branched aliphatic group with 3 to 20 carbons, cyclic aliphatic group with 3 to 20 carbons, and aliphatic group with 6 to 20 carbons An aromatic group or a group formed by combining two or more of these through a single bond or a linking group is preferred. An aromatic group with 6 to 20 carbons or a group with 6 to 20 carbons connected through a single bond or a linking group is preferred. A combination of two or more aromatic groups is more preferable. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) ₂ -, alkylene group, halogenated alkylene group, arylylene group, or a combination of two of these The above linking group is preferred, and -O-, -S-, alkylene, halogenated alkylene, arylylene or a linking group in which two or more of these are bonded is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is still more preferable. As the alkylene halide, a alkylene halide having 1 to 20 carbons is preferable, an alkylene halide having 1 to 10 carbons is more preferable, and an alkylene halide having 1 to 4 carbons is more preferable. Moreover, examples of the halogen atom in the above-mentioned halogenated alkylene group include fluorine atom, chlorine atom, bromine atom, iodine atom and the like, among which fluorine atom is preferred. The aforementioned halogenated alkylene group may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, but all hydrogen atoms are preferably replaced by halogen atoms. Examples of preferred alkylene halides include (bistrifluoromethyl)methylene and the like. As said aryl group, phenylene or naphthylene is preferable, phenylene is more preferable, and 1,3-phenylene or 1,4-phenylene is still more preferable.

Also, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide compound. The carboxyl group in the dicarboxylic acid dihalide compound may be halogenated, for example, preferably chlorinated. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. Examples of halogenated dicarboxylic acid compounds or dicarboxylic acid dihalide compounds used in the production of polyamideimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic Dicarboxylic acid compound or dicarboxylic acid dihalide compound, etc. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used only by 1 type, and may use 2 or more types.

Specifically, as a dicarboxylic acid compound or a dicarboxylic acid dihalide compound, a straight-chain aliphatic group having 2 to 20 carbons, a branched aliphatic group having 3 to 20 carbons, a ring having 3 to 20 carbons, Aliphatic groups, aromatic groups with 6 to 20 carbon atoms, or dicarboxylic acid compounds or dicarboxylic acid dihalide compounds in which two or more of these are combined through a single bond or a linking group are preferred. A dicarboxylic acid compound or a dihalogenated dicarboxylic acid containing an aromatic group with 6 to 20 carbons or a group formed by combining two or more aromatic groups with 6 to 20 carbons through a single bond or a linking group Compounds are better.

Further, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, Tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2- Methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, hexane Diacid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid , sebacic acid, hexadecanedioic acid, 1,9- azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, Heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, docosanedioic acid, tricosanedioic acid, tetradecanedioic acid Acid, pentadecanedioic acid, hexacanedioic acid, heptacanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacanedioic acid, triundecanedioic acid, Docosanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, diphenyl Ketone-4,4'-dicarboxylic acid, etc. As a specific example of the dicarboxylic acid dihalide compound, the compound of the structure which halogenated two carboxyl groups in the said specific example of a dicarboxylic acid compound is mentioned.

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

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

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

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

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

〔Polyamideimide〕 The polyamide-imide used in the present invention may be alkali-soluble polyamide-imide, or may be a polyamide-imide soluble in a developing solution mainly composed of an organic solvent. In this specification, the term "alkali-soluble polyamide imide" refers to a polyamide imide that dissolves 0.1 g or more in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C, and is considered from the viewpoint of pattern formation. It is preferable to dissolve more than 0.5 g of polyamide imide, and it is further more preferable to dissolve more than 1.0 g of polyamide imide. The upper limit of the above-mentioned dissolved amount is not particularly limited, but is preferably 100 g or less. Also, from the viewpoint of the film strength and insulating properties of the obtained organic film, it is preferable that polyamide imide is a polyamide imide having a plurality of amide bonds and a plurality of amide structures in the main chain. good.

-Fluorine atoms- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyamideimide has a fluorine atom. A fluorine atom, for example, R ¹¹⁷ or R ¹¹¹ contained in the repeating unit represented by the formula (PAI-3) described below is preferable, and a fluorinated alkyl group contained in the repeating unit represented by the formula (PAI-3) described below R ¹¹⁷ or R ¹¹¹ is more preferred. The amount of fluorine atoms relative to the total mass of polyamideimide is preferably at least 5% by mass, and more preferably at most 20% by mass.

-Ethylenically unsaturated bond- From the viewpoint of the film strength of the obtained organic film, polyamideimide may have an ethylenically unsaturated bond. Polyamideimide may have an ethylenically unsaturated bond at the end of the main chain, or may have an ethylenically unsaturated bond at the side chain, but preferably has an ethylenically unsaturated bond at the side chain. It is preferable that the said ethylenically unsaturated bond has radical polymerizability. It is preferable that ^R117 or ^R111 whose ethylenically unsaturated bond is included in the repeating unit represented by the formula (PAI-3) described below is contained in the repeating unit represented by the formula (PAI-3) described below as a group having an ethylenically unsaturated bond. ) in the repeating unit represented by R ¹¹⁷ or R ¹¹¹ is more preferred. The preferable aspect of the group which has an ethylenically unsaturated bond is the same as the preferable aspect of the group which has an ethylenically unsaturated bond in the said polyimide.

The amount of ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.0001 to 0.1 mol/g, more preferably 0.001 to 0.05 mol/g.

-Polymerizable group other than an ethylenically unsaturated bond- The polyamide imide may have a polymerizable group other than an ethylenically unsaturated bond. Examples of the polymerizable group other than the ethylenically unsaturated bond in the polyimide include the same groups as the polymerizable groups other than the ethylenically unsaturated bond in the above-mentioned polyimide. For example, R ¹¹¹ in which a polymerizable group other than an ethylenically unsaturated bond is contained in a repeating unit represented by formula (PAI-3) described later is preferable. The amount of polymerizable groups other than ethylenically unsaturated bonds is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g, based on the total mass of the polyamideimide.

-Polarity conversion group- The polyamideimide may have a polarity conversion group, such as an acid-decomposable group. The acid-decomposable groups in the polyamideimide are the same as the acid-decomposable groups described for R ¹¹³ and R ¹¹⁴ in the above formula (2), and preferred aspects are also the same.

-acid value- When polyamide imide is used for alkali development, from the viewpoint of improving developability, the acid value of polyamide imide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and 70 mgKOH/g The above are further preferred. Moreover, the above-mentioned acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and still more preferably 200 mgKOH/g or less. In addition, when polyamide imide is used in development using a developer containing an organic solvent as the main component (for example, "solvent development" described later), the acid value of the polyamide imide is 2 to 35 mgKOH/g. Preferably, 3-30 mgKOH/g is more preferable, and 5-20 mgKOH/g is still more preferable. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Moreover, as an acidic group contained in a polyamideimide, the thing similar to the acidic group in the said polyimide is mentioned, and a preferable aspect is also the same.

-Phenolic hydroxyl group- It is preferable that polyamide imide has a phenolic hydroxyl group from a viewpoint of making the developing speed appropriate by alkali developing solution. Polyamideimide may have a phenolic hydroxyl group at a main chain terminal, or may have a phenolic hydroxyl group at a side chain. The phenolic hydroxyl group, for example, is preferably R ¹¹⁷ or R ¹¹¹ contained in a repeating unit represented by the formula (PAI-3) described later. The amount of the phenolic hydroxyl group is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g, relative to the total mass of the polyamideimide.

式（PAI-3）中，R ¹¹¹及R ¹¹⁷分別與式（PAI-2）中的R ¹¹¹及R ¹¹⁷的含義相同，較佳態樣亦相同。 具有聚合性基時，聚合性基可以位於R ¹¹¹及R ¹¹⁷中的至少1個上，亦可以位於聚醯胺醯亞胺的末端。 The polyamide imide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, and it is preferable to include a repeating unit represented by the following formula (PAI-3). good. [chemical formula 28]

In formula (PAI-3), R ¹¹¹ and R ¹¹⁷ have the same meanings as R ¹¹¹ and R ¹¹⁷ in formula (PAI-2), respectively, and preferred embodiments are also the same. When having a polymerizable group, the polymerizable group may be located on at least one of R ¹¹¹ and R ¹¹⁷ , or may be located at a terminal of polyamideimide.

Also, in order to improve the storage stability of the resin composition, it is better to block the end of the main chain of polyamide imide with monoamine, acid anhydride, monocarboxylic acid, monoacyl chloride compound, active monoester compound, etc. . A preferred aspect of the end-blocking agent is the same as that of the above-mentioned end-blocking agent in polyimide.

-Imidation rate (ring closure rate)- From the viewpoints of film strength and insulation of the obtained organic film, the imidization rate (also referred to as "loop closure rate") of polyamide imide is preferably 70% or more, and 80% or more is more preferable. Good, more than 90% is better. The upper limit of the above-mentioned imidization rate is not particularly limited, and may be 100% or less. The above-mentioned imidization rate can be measured by the same method as the ring-closure rate of the above-mentioned polyimide.

Polyamidoimide may have a repeating unit represented by the above formula (PAI-3) that contains all one type of R ¹¹¹ or R ¹¹⁷ , or may have the above-mentioned formula (PAI-3) that contains two or more different types of R ¹³¹ or R ¹³² A repeating unit represented by formula (PAI-3). In addition, the polyamideimide may contain other types of repeating units other than the repeating unit represented by the above formula (PAI-3). Examples of other types of repeating units include repeating units represented by the above-mentioned formula (PAI-1) or formula (PAI-2), and the like.

Polyamidoimide can be synthesized by, for example, a method in which a polyamidoimide precursor is obtained by a known method, and it is completely imidized by a known imidization reaction method or stopped midway. A method of imidization reaction and introduction of a part of the imide structure, a method of introducing a part of the imide structure by further mixing the fully imidized polymer with the polyamidoimide precursor.

The weight average molecular weight (Mw) of polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and still more preferably 10,000 to 30,000. By making the weight average molecular weight 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film excellent in mechanical properties, it is particularly preferable that the weight average molecular weight is 20,000 or more. Also, the number average molecular weight (Mn) of the polyamideimide is preferably from 800 to 250,000, more preferably from 2,000 to 50,000, still more preferably from 4,000 to 25,000. The molecular weight dispersion of the polyamideimide precursor is preferably at least 1.5, more preferably at least 1.8, and still more preferably at least 2.0. The upper limit of the dispersion degree of molecular weight of polyamideimide is not specifically limited, For example, 7.0 or less is preferable, 6.5 or less is more preferable, 6.0 or less is still more preferable. Also, when the resin composition contains a plurality of polyamideimides as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyamideimide are within the above-mentioned ranges. Furthermore, it is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated by using the above-mentioned plural kinds of polyamideimides as one resin are within the above-mentioned ranges, respectively.

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

-Encapping agent- When producing polyimide precursors, etc., in order to further improve storage stability, it is better to block carboxylic anhydrides, acid anhydride derivatives, or amine groups remaining at the ends of resins such as polyimide precursors. When blocking the carboxylic acid anhydride and acid anhydride derivatives remaining at the end of the resin, examples of the blocking agent include monoalcohols, phenols, mercaptans, thiophenols, monoamines, etc. Alcohols, phenols, and monoamines are more preferable. Preferred compounds of the monoalcohol include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloro Methanol, furfuryl alcohol and other primary alcohols, isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, tertiary butanol, adamantanol and other tertiary alcohols alcohol. Preferable compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. In addition, preferred compounds of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7- Aminenaphthalene, 1-hydroxy-6-aminenaphthalene, 1-hydroxy-5-aminenaphthalene, 1-hydroxy-4-aminenaphthalene, 2-hydroxy-7-aminenaphthalene, 2-hydroxy-6-aminenaphthalene, 2- Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-amine Naphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6- Aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3 -Aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. Two or more kinds of these can be used, and a plurality of different end groups can be introduced by reacting a plurality of end-capping agents. Also, when blocking the amine group at the terminal of the resin, it can be blocked with a compound having a functional group capable of reacting with the amine group. Preferred end-capping agents for amino groups are carboxylic acid anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic acid anhydride, etc., and carboxylic anhydride and carboxylic acid chloride are more preferred. Preferred compounds of carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-di Carboxylic anhydride, etc. In addition, preferred compounds of carboxylic acid chlorides include acetyl chloride, acryl chloride, propionyl chloride, methacryl chloride, pivalyl chloride, cyclohexaneformyl chloride, 2-ethylhexyl chloride, and Acyl chloride, cinnamyl chloride, 1-adamantaneformyl chloride, heptafluorobutyryl chloride, stearyl chloride, benzoyl chloride, etc.

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

〔content〕 The content of the specific resin in the resin composition of the present invention is preferably at least 20% by mass, more preferably at least 30% by mass, more preferably at least 40% by mass, and even more preferably at least 50% by mass, based on the total solid content of the resin composition. The above are further preferred. In addition, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, and 97% by mass relative to the total solid content of the resin composition. % or less is still more preferable, and 95 mass % or less is still more preferable. The resin composition of this invention may contain only 1 type of specific resin, and may contain 2 or more types. When containing 2 or more types, it is preferable that the total amount is in the said range.

Moreover, it is also preferable that the resin composition of this invention contains at least 2 types of resins. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described later, or may contain two or more specific resins, and preferably contains two or more specific resins. When the resin composition of the present invention contains two or more specific resins, for example, it preferably contains two or more polyimide precursors having different structures derived from dianhydrides (R ¹¹⁵ in the above formula (2)).

<Other resins> The resin composition of the present invention may contain other resins (hereinafter also simply referred to as “other resins”) different from the specific resins in addition to or instead of the specific resins described above. Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, aminoformaldehyde resins, Ester resin, butyral resin, styrene resin, polyether resin, polyester resin, etc. In particular, by using a (meth)acrylic resin having an acid-decomposable group, the resin composition can be used as a composition for pattern formation. Examples of the (meth)acrylic resin having such an acid-decomposable group include resins (B) described in paragraphs 0069 to 0170 of JP-A-2019-174549 and the like. Moreover, by further adding a (meth)acrylic resin, a resin composition excellent in applicability can be obtained, and a pattern (cured product) excellent in solvent resistance can be obtained. For example, by adding a (meth)acrylic resin to the resin composition instead of the polymerizable compound described later or adding a (meth)acrylic resin in addition to the polymerizable compound described later, the coatability and pattern of the resin composition can be improved. (hardened product) solvent resistance, etc., the weight average molecular weight of the (meth)acrylic resin is 20,000 or less and the polymerizable group value is high (for example, the molar amount of the polymerizable group contained in 1 g of the resin is 1×10 ^-3 mol ears/g or more).

When the resin composition of the present invention contains other resins, the content of the other resins is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, and still more preferably at least 1% by mass, based on the total solid content of the resin composition. It is more preferably 2 mass % or more, 5 mass % or more is still more preferable, and 10 mass % or more is still more preferable. In addition, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, and 60% by mass relative to the total solid content of the resin composition. It is still more preferable that it is below mass %, and it is still more preferable that it is below 50 mass %. Moreover, as a preferable aspect of the resin composition of this invention, it can also set it as the aspect with low content of another resin. In the above-mentioned aspect, the content of other resins is preferably not more than 20% by mass, more preferably not more than 15% by mass, still more preferably not more than 10% by mass, and not more than 5% by mass, based on the total solid content of the resin composition. It is still more preferable, and 1 mass % or less is still more preferable. The lower limit of the content is not particularly limited, and it may be 0% by mass or more. The resin composition of this invention may contain only 1 type of other resins, and may contain 2 or more types. When containing 2 or more types, it is preferable that the total amount is in the said range.

＜Specific base generator＞ The resin composition of the 1st aspect of this invention and the resin composition of the 2nd aspect of this invention contain a specific base generator.

The base generator of the first aspect of the present invention has an α,β-unsaturated ketone group at a site to be a generated base and the generated base is cyclized into a tertiary amine in the molecule. Here, the base generated from the base generator has a base (secondary amino group) and an α,β-unsaturated ketone group by having an α,β-unsaturated ketone group at a site to be the generated base. Afterwards, the above-mentioned base reacts with the α,β-unsaturated ketone group in the molecule, and cyclizes into a tertiary amine.

Here, the base generated from the base generator of the first aspect of the present invention only has to be at least partly cyclized into a tertiary amine intramolecularly, and all of the base does not need to be cyclized intramolecularly into a tertiary amine. For example, a case will be described where a secondary amine represented by the formula (S-2) is produced from a compound represented by the following formula (S-1) and is cyclized intramolecularly to a compound represented by the formula (S-3). Tertiary amine. The secondary amine represented by the formula (S-2) may be all of the tertiary amine represented by the formula (S-3), or a part of the secondary amine represented by the formula (S-2) may be the same as that represented by the formula Compounds represented by (S-1), other secondary amines represented by formula (S-2), or other components in the resin composition (for example, resins with polymeric groups, polymerizable compounds described later, etc.) react to form The tertiary amine may exist in the form of a secondary amine instead of a part of the secondary amine represented by the formula (S-2) as a tertiary amine. [chemical formula 29]

式（C-1）中，*表示與其他結構的鍵結部位，#表示與碳原子的鍵結部位。 In the present invention, the α,β-unsaturated ketone group refers to one in which the α-carbon and β-carbon of at least one of the ketone groups are bonded by a C=C double bond. Specifically, the α,β-unsaturated ketone group is preferably a group represented by the following formula (C-1). [chemical formula 30]

In the formula (C-1), * represents a bonding site with other structures, and # represents a bonding site with a carbon atom.

式（C-2）中，#表示與碳原子的鍵結部位，R ^C1～R ^C3分別獨立地表示氫原子或取代基。 式（C-2）中，R ^C1為氫原子或烴基為較佳，氫原子、烷基或芳香族烴基為更佳，氫原子、碳數1～10的烷基或苯基為進一步較佳，氫原子為特佳。 上述烴基、烷基或芳香族烴基中的氫原子可以進一步被鹵素原子等取代。 式（C-2）中，R ^C2及R ^C3均為氫原子為較佳。 式（C-2）中，作為R ^C2及R ^C3中的取代基，可舉出烴基。作為上述烴基，烷基或芳香族烴基為較佳，碳數1～10的烷基或苯基為更佳。 Moreover, it is preferable that the specific compound contains a structure represented by the following formula (C-2) as a structure containing an α,β-unsaturated ketone group. [chemical formula 31]

In formula (C-2), # represents a bonding site with a carbon atom, and R ^C1 to R ^C3 each independently represent a hydrogen atom or a substituent. In formula (C-2), R ^C1 is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and is further preferably a hydrogen atom, an alkyl group with 1 to 10 carbons, or a phenyl group , a hydrogen atom is particularly preferred. Hydrogen atoms in the above hydrocarbon groups, alkyl groups or aromatic hydrocarbon groups may be further substituted with halogen atoms or the like. In formula (C-2), R ^C2 and R ^C3 are preferably hydrogen atoms. In formula (C-2), examples of the substituents in R ^C2 and R ^C3 include hydrocarbon groups. As the above-mentioned hydrocarbon group, an alkyl group or an aromatic hydrocarbon group is preferable, and an alkyl group or phenyl group having 1 to 10 carbon atoms is more preferable.

The base generator of the first aspect of the present invention preferably has an α,β-unsaturated keto group, a group represented by -NR ¹ C(=O)-, and a group selected from the group consisting of carboxyl and hydroxyl At least one of the above-mentioned α,β-unsaturated ketone groups exists on the side of the nitrogen atom of the group represented by the above-mentioned -NR ¹ C(=O)-, and at least one of the above-mentioned carboxyl groups and hydroxyl groups R 1 exists on the carbon atom side of the above-mentioned -NR ¹ C(=O)-, and the above-mentioned R ¹ is a monovalent organic group. Here, the nitrogen atom side of the group represented by -NR ¹ C(=O)- means the side represented by * of the group represented by *-NR ¹ C(=O)-**. The carbon atom side of the group represented by -NR ¹ C(=O)- means the side represented by ** of the group represented by *-NR ¹ C(=O)-**. Details of such a base generator are the same as those of the base generator of the second aspect of the present invention.

The base generator of the second aspect of the present invention has an α,β-unsaturated ketone group, a group represented by -NR ¹ C(=O)-, and at least one selected from the group consisting of carboxyl and hydroxyl Group, at least one of the above-mentioned α,β-unsaturated ketone groups exists on the side of the nitrogen atom of the group represented by the above-mentioned -NR ¹ C(=O)-, and at least one of the above-mentioned carboxyl and hydroxyl groups exists on On the carbon atom side of the aforementioned -NR ¹ C(=O)-, the aforementioned R ¹ is a monovalent organic group.

Details of the α,β-unsaturated ketone group in the base generator of the second aspect of the present invention are the same as those of the base generator of the first aspect of the present invention described above.

In the group represented by -NR ¹ C(=O)- in the base generator of the second aspect of the present invention, R ¹ may be a structure containing an α,β-unsaturated ketone group, or may not contain The structure of α, β unsaturated keto group. The preferred aspect of this group is the case where R ¹ in the formula (1-1) described later contains an α, β-unsaturated ketone group and the case where R ¹ does not contain an α, β-unsaturated ketone group is preferred The appearance is the same. Also, it is preferable that both of the two bonding sites in the group represented by -NR ¹ C(=O)- are bonded to carbon atoms. In addition, the above-mentioned R ¹ may be bonded to another structure to form a ring structure. When R ¹ forms a ring structure with another structure, it is preferable to form a ring structure by bonding to a structure on the side of the nitrogen atom of -NR ¹ C(=O)-. A preferable aspect of such a structure is the same as when two R ¹ bonded to the same nitrogen atom are bonded to form a ring structure in formula (1-1) described later.

The base generator of the second aspect of the present invention generates a secondary amine by cleavage of a group represented by -NR ¹ C(=O)- and the amine group in the secondary amine and the above α, A compound in which a β-unsaturated keto group reacts to form a tertiary amine is preferred. Here, at least a part of the above-mentioned secondary amines may be tertiary amines, and all of them do not need to be tertiary amines. In addition, at least a part of the above-mentioned secondary amine may react with other components in the resin composition (for example, a resin having a polymerizable group, a polymerizable compound described later, etc.) to become a tertiary amine, or it may be in the form of a secondary amine exist.

Also, in the second aspect of the present invention, the base generated from the base generator is preferably cyclized into a tertiary amine in the molecule. Details of such a base generator are the same as those of the base generator of the first aspect of the present invention.

The specific base generator is preferably a compound that generates a base by at least one of light and heat, more preferably a compound that generates a base by heat. In addition, the specific base generating agent may be, for example, one that generates a base by cleavage of amide by a known catalyst or the like.

It is preferable that the specific base generator generate the above-mentioned tertiary amine by heating at 250°C, more preferably generate the above-mentioned tertiary amine by heating at 220°C, and further preferably generate the above-mentioned tertiary amine by heating at 200°C, It is still more preferable to generate the above-mentioned tertiary amine by heating at 190°C, and it is particularly preferable to generate the above-mentioned tertiary amine by heating at 180°C. The lower limit of the temperature at which the tertiary amine is generated is not particularly limited, but is preferably 100° C. or higher, for example, from the viewpoint of storage stability of the composition. Whether a certain compound A exhibits the property of generating the above-mentioned tertiary amine at a certain temperature X°C is judged by the following method. After heating 1 mole of compound A in a closed container at 1 atmosphere and at the above-mentioned X°C for 3 hours, the amount of decomposition is quantified by HPLC (high performance liquid chromatography) and other methods, and when 0.01 mole or more of the above-mentioned three compounds are produced In the case of a tertiary amine, it was judged that compound A produced the above-mentioned tertiary amine by heating at X°C. For example, by using ¹ H-NMR, it is confirmed whether or not the generated tertiary amine is cyclized into a tertiary amine structure in the same molecule. The generation amount of the above-mentioned tertiary amine is preferably 0.1 mol or more, more preferably 0.5 mol or more. The upper limit of the generation amount of the above-mentioned tertiary amine is not particularly limited, and can be set to, for example, 1000 mol or less.

Also, when the specific base generator generates a base by light, prepare a composition A in which the specific base generator is dissolved in a solvent, and expose the light with a wavelength of 190 to 800 nm at an exposure illuminance of 25 W under 1 atmosphere and 25° C. / ^cm2 for 30 seconds and heated at 100°C for 1 hour, quantify the amount of decomposition by HPLC (high performance liquid chromatography) and other methods, and generate 0.01 mole Tertiary amines with more than 1% are preferred. The production amount of the above-mentioned tertiary amine is preferably 0.1 mol% or more, more preferably 0.5 mol% or more. The upper limit of the generation amount of the above-mentioned tertiary amine is not particularly limited, for example, it can be set to 1000 mol % or less. When the resin composition contains a solvent, the concentration of the nonionic base generator in the above-mentioned composition A can be set to be the same as that in the resin composition, and the type of solvent in the above-mentioned composition can be set to be the same as that of the resin composition. The solvent contained in the product is the same. Also, when the resin composition does not contain a solvent, the concentration of the nonionic base generating agent in the composition A can be set to about 1.0% by mass relative to the total mass of the composition A, and the solvent type can be N-methyl-2- pyrrolidone etc.

The boiling point of the tertiary amine generated from the specific base generator is preferably from 160 to 350°C, more preferably from 180 to 280°C, and still more preferably from 200 to 260°C. The molecular weight of the tertiary amine generated from the specific base generator is preferably 100-500, more preferably 100-200, and more preferably 110-180. From the viewpoint of pattern rectangularity, the molecular weight of the tertiary amine generated from the specific base generator is preferably 110 or more, more preferably 110-120, and still more preferably 120-180. From the viewpoint of elongation at break, the molecular weight of the tertiary amine generated from the specific base generator is preferably 120 or more, more preferably 120 to 150, and more preferably 120 or more and less than 150. From the viewpoint of chemical resistance, the molecular weight of the tertiary amine generated from the specific base generator is preferably 120-160.

It is preferable that the tertiary amine generated from the specific base generator comprises a ring structure having nitrogen atoms constituting the tertiary amine as ring members. The aforementioned cyclic structure may form a condensed ring with other cyclic structures. Examples of other ring structures include ring structures in which the above-mentioned R ¹ forms a ring structure with other structures. Also, the tertiary amine generated from the specific base generator preferably has a 5-membered ring structure having a nitrogen atom constituting the tertiary amine as a ring member or a 6-membered ring structure having a nitrogen atom constituting the tertiary amine as a ring member.

Also, it is preferable that the tertiary amine generated from the specific base generator is a tertiary amine having a ketone group and a cyclic structure. Among the tertiary amines having a keto group and a cyclic structure, carbon atoms containing a ketone group are preferred as ring members of the cyclic structure. Moreover, it is preferable that the above-mentioned ketone group is a ketone group derived from the above-mentioned α,β-unsaturated ketone group. The aforementioned ring structure is preferably a 5-membered ring structure or a 6-membered ring structure. The aforementioned cyclic structure may form a condensed ring with other cyclic structures. Examples of other ring structures include ring structures in which the above-mentioned R ¹ forms a ring structure with other structures. Among tertiary amines having a keto group and a cyclic structure, it is preferable that the cyclic structure further includes nitrogen atoms constituting the tertiary amine as ring members. That is, the tertiary amine having a keto group and a cyclic structure is a 5-membered ring structure having a nitrogen atom constituting a tertiary amine and a carbon atom of a ketone group as ring members or having a nitrogen atom constituting a tertiary amine and a ketone group A tertiary amine with a 6-membered ring structure in which carbon atoms are used as ring members is preferred.

Specific examples of the tertiary amine generated from the specific base generator include tertiary amines generated from A-1 to A-40 in Examples, but are not limited thereto.

式（1-1）中，L ¹表示n+m價連結基，R ¹表示1價有機基團，R ¹存在複數個時分別可以相同或不同。R ¹中的至少1個包含α,β-不飽和酮基，X分別獨立地表示羥基或羧基，m表示1以上的整數，n表示1以上的整數。 It is preferred that the specific base generator contains a compound represented by formula (1-1). The compound represented by the formula (1-1) generates a secondary amine by cleavage of the group represented by -NR ¹ C(=O)- in the formula (1-1) and by the above-mentioned secondary amine A compound in which the amine group in the formula (1-1) reacts with the α,β-unsaturated ketone group included in R ¹ to form a tertiary amine is preferred. [chemical formula 32]

In formula (1-1), L ¹ represents an n+m valent linking group, R ¹ represents a monovalent organic group, and when there are plural R ¹ s, they may be the same or different. At least one of R ¹ contains an α,β-unsaturated ketone group, X each independently represents a hydroxyl group or a carboxyl group, m represents an integer of 1 or more, and n represents an integer of 1 or more.

In formula (1-1), L ¹ is a hydrocarbon group or is composed of more than one hydrocarbon group selected from the group consisting of heterocyclic group, -O-, -C(=O)-, -S-, -S(=O) ₂ The group represented by a combination of at least one structure in the group of - and -NR ^N - is preferably a hydrocarbon group or a group consisting of one or more hydrocarbon groups selected from the group consisting of -O-, -S- and -NR ^N - A group represented by a combination of at least one structure in the group is more preferable. As the aforementioned heterocyclic group, a heteroaromatic ring group is preferred. Moreover, examples of the heteroatom contained in the heterocyclic group include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The above R ^N represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. As the above-mentioned hydrocarbon group, it can be any one of aliphatic hydrocarbon group, aromatic hydrocarbon group or a group represented by a combination thereof. It is preferred to include at least an aromatic hydrocarbon group. The group represented by a combination of an aromatic hydrocarbon group and an aliphatic hydrocarbon group is better. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, and a group obtained by removing a plurality of hydrogen atoms from a benzene ring is more preferable. Moreover, the said aromatic hydrocarbon group may have a substituent, and may form a condensed ring with another ring structure. As the aforementioned aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is preferred, a saturated aliphatic hydrocarbon group having 1 to 20 carbons is more preferred, a saturated aliphatic hydrocarbon group having 1 to 10 carbons is further preferred, and a saturated aliphatic hydrocarbon group having 1 to 4 carbons is more preferred. Aliphatic hydrocarbon groups are particularly preferred.

From the viewpoint of base generation efficiency, L ¹ preferably includes an aromatic ring structure. Examples of the aromatic ring structure in ^L1 include the aforementioned aromatic hydrocarbon group and the aforementioned heteroaromatic ring group, with an aromatic hydrocarbon group being preferred.

Also, when X in formula (1-1) is a hydroxyl group, the number of atoms (chain length) on the shortest path of the connecting chain between X and -C(=O)- in ^L1 is 3 to 6. Preferably, 3 or 4 are more preferred. When X in formula (1-1) is a carboxyl group, the number of atoms (chain length) on the shortest path of the connecting chain between X and -C(=O)- in L ¹ is preferably 2 to 5 , 2 or 3 is better. In any of the above cases, it is preferable that ^L1 contains an aromatic ring structure (preferably a phenylene group that may have a substituent or a condensed ring, more preferably a 1,2-phenylene group that may have a substituent or a condensed ring) , it is more preferable to include an aromatic ring structure on the above-mentioned shortest path. In addition, it is also preferable that L ¹ contains an oxygen atom or a sulfur atom on the above-mentioned shortest path.

From the viewpoint of chemical resistance, ^L1 preferably has a polymerizable group, and more preferably has a radical polymerizable group. Examples of radical polymerizable groups include vinyl, allyl, vinylphenyl, (meth)acryloxy, maleimide, (meth)acrylamide, etc. A (meth)acryloxy group, a (meth)acrylamide group, or a vinylphenyl group is preferable, and a (meth)acryloxy group is more preferable from a reactivity viewpoint. In addition, when ^L1 has a radical polymerizable group, it is preferable that the precursor of the cyclization resin has a radical polymerizable group or that the resin composition contains at least one of the radical crosslinking agents described below. According to such aspects, it is considered that since the base generator is added to the polymer formed by polymerization, for example, the distribution of the base generator in the composition becomes nearly uniform, and the pattern rectangularity is further improved.

Specific examples of ^L1 include, for example, the following structures, but are not limited thereto. In the following specific examples, * represents a bonding site with X in formula (1-1), and # represents a bonding site with -C(=O)- in formula (1-1). [chemical formula 33]

In formula (1-1), at least one of R ¹ contains an α,β-unsaturated ketone group. Preferred aspects of the α,β-unsaturated keto group are as described above.

式（R-1）中，L ^R1表示x+1價連結基，Z ^R1表示α,β-不飽和酮基，x表示1以上的整數，*表示與式（1-1）中的氮原子的鍵結部位。 When R ¹ contains an α,β-unsaturated ketone group, R ¹ is preferably a group represented by the following formula (R-1). [chemical formula 34]

In the formula (R-1), L ^R1 represents the x+1 valent linking group, Z ^R1 represents the α, β-unsaturated ketone group, x represents an integer greater than 1, and * represents the nitrogen atom in the formula (1-1) the bonding site.

In the formula (R-1), L ^R1 represents an x+1 valent linking group, preferably a hydrocarbon group, more preferably a saturated hydrocarbon group. The number of carbon atoms in the above-mentioned hydrocarbon group and saturated hydrocarbon group is preferably 1-10, more preferably 1-4. In the formula (R-1), x is preferably 1 to 4, more preferably 1 or 2, and further preferably 1. In the formula (R-1), Z ^R1 is preferably a group represented by the above formula (C-2). Also, in formula (R-1), the number of atoms on the shortest path of the connecting chain between Z ^R1 and * in L ^R1 is preferably 1 to 4, more preferably 1 or 2. When x is 2 or more, it is preferable that the number of atoms on the shortest path of the link chain between at least one of Z ^R1 and * is within the above range.

Specific examples of the group represented by the formula (R-1) include the following structures, but the present invention is not limited thereto. In the following structure, * represents the bonding site with the nitrogen atom in formula (1-1). [chemical formula 35]

In formula (1-1), when R ¹ does not contain an α, β-unsaturated ketone group, R ¹ is a hydrocarbon group or is composed of more than one hydrocarbon group and is selected from the group consisting of heterocyclic group, -O-, -C (=O )-, -S-, -S(=O ₂ )-, and -NR ^N - are preferably groups represented by a combination of at least one structure. As the hydrocarbon group, an alkyl group with 1 to 10 carbons, an aromatic hydrocarbon group with 6 to 20 carbons, or an aralkyl group with 7 to 20 carbons is preferable, and an alkyl group with 1 to 6 carbons or benzyl group is more preferable. good. The above-mentioned hydrocarbon group, alkyl group or aralkyl group may have a substituent, and examples of the substituent include a halogen atom and the like. When ^R1 does not contain an α,β-unsaturated ketone group, examples of ^R1 include alkyl groups such as methyl, methyl, propyl, isopropyl, and cyclohexyl, and alkylaminocarbonyl groups such as methylaminocarboxyalkyl. Alkyl, alkoxycarbonylalkyl such as methoxycarbonylmethyl, and the like.

In formula (1-1), one of R ¹ contains an α,β-unsaturated ketone group and the other does not contain an α,β-unsaturated ketone group, which is also one of the preferred aspects of the present invention.

式（R-2）中，Cy表示環狀結構，L ^R2表示單鍵或x+1價連結基，Z ^R2表示α,β不飽和酮基，x表示1以上的整數，y表示1以上的整數。 In addition, in formula (1-1), two R ¹ bonded to the same nitrogen atom may bond to form a ring structure. In the above aspect, it is preferable that the group consisting of two R ¹ and a nitrogen atom in the formula (1-1) is a group represented by the following formula (R-2). [chemical formula 36]

In the formula (R-2), Cy represents a ring structure, L ^R2 represents a single bond or x+1 valent linking group, Z ^R2 represents an α, β unsaturated ketone group, x represents an integer of 1 or more, and y represents a value of 1 or more integer.

In the formula (R-2), Cy is preferably an aliphatic ring structure, more preferably a saturated aliphatic ring structure. In addition, Cy may have a known substituent within the range in which the effects of the present invention are obtained. Also, Cy is preferably a 5-membered ring structure or a 6-membered ring structure. Cy may contain a heteroatom other than the nitrogen atom in the formula (R-2) as a ring member, and preferably contains only a nitrogen atom in the formula (R-2) as a ring member. Among them, Cy is preferably a pyrrolidine ring or a piperidine ring.

In the formula (R-2), L ^R2 is preferably a single bond or a hydrocarbon group, more preferably a single bond or a saturated aliphatic hydrocarbon group, and even more preferably a single bond. The carbon number of the above-mentioned hydrocarbon group or saturated aliphatic hydrocarbon group is preferably 1-10, more preferably 1-4. In the formula (R-2), x is preferably 1 to 4, more preferably 1 or 2, and further preferably 1. In the formula (R-2), y is preferably 1 to 4, more preferably 1 or 2, and further preferably 1. In the formula (R-2), Z ^R2 is preferably a group represented by the above formula (C-2).

Also, in formula (R-2), the number of atoms on the shortest path of the connecting chain between Z ^R1 in Cy and ^LR2 and the nitrogen atom recorded in formula (R-2) is preferably 1 to 4, 1 or 2 is better. When the formula (R-2) includes a plurality of Z ^R1 , the number of atoms on the shortest path of the connecting chain between at least one of Z ^R1 and the nitrogen atom is preferably within the above range.

Specific examples of the group represented by the formula (R-2) include the following structures, but the present invention is not limited thereto. In the following structure, * represents the bonding site with the carbonyl group in formula (1-1). [chemical formula 37]

In formula (1-1), X each independently represent a hydroxyl group or a carboxyl group, preferably a hydroxyl group. In formula (1-1), n is preferably an integer of 1 to 4, more preferably 1 or 2, and further preferably 1. In formula (1-1), m is preferably an integer of 1 to 4, more preferably 1 or 2, and further preferably 1.

式（1-2）中，L ²及L ³分別獨立地表示單鍵或2價連結基，Ar表示可以具有取代基的芳香族基，R ¹分別獨立地表示1價有機基團，R ¹中的至少1個包含α,β-不飽和酮基，X分別獨立地為羥基或羧基，x表示1以上的整數，y表示1以上的整數。 Moreover, it is preferable that a specific base generator is a compound represented by following formula (1-2). [chemical formula 38]

In formula (1-2), L ² and L ³ independently represent a single bond or a divalent linking group, Ar represents an aromatic group that may have a substituent, R ¹ represents a monovalent organic group independently, and R ¹ At least one of them contains an α,β-unsaturated ketone group, X is each independently a hydroxyl group or a carboxyl group, x represents an integer of 1 or more, and y represents an integer of 1 or more.

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

In formula (1-2), L ² is a single bond, a hydrocarbon group, or more than one hydrocarbon group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O ₂ )- A group represented by a combination of at least one structure in the group of -NR ^N - is preferable, a single bond or a hydrocarbon group is more preferable, and a single bond or an alkylene group is still more preferable. As the above-mentioned hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms is preferable, and a hydrocarbon group having 1 to 4 carbon atoms is more preferable. As the above-mentioned alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 4 carbon atoms is more preferable.

In formula (1-2), Ar is preferably an aromatic hydrocarbon group that may have at least one of substituents and condensed rings, and multiple hydrogens are removed from the benzene ring structure that may have at least one of substituents and condensed rings A group of atoms is more preferred. As a substituent in Ar, a nitro group, a vinyl group, an ester group, etc. are mentioned. Examples of the aromatic hydrocarbon group having a condensed ring include, but are not limited to, a benzofuran ring, a benzothiophene ring, and an indole ring.

In formula (1-2), L ³ is a single bond or selected from the group including hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O ₂ )- and -NR ^N - At least one group in the group or the group represented by these bonds is preferred, at least one group selected from the group consisting of hydrocarbon group, -O- and -C(=O)- or Groups represented by such bonds are more preferred. ^RN is as described above.

Also, when X in formula (1-2) is a hydroxyl group, the number of atoms on the shortest path of the connecting chain between X and -C(=O)- in -L ² -Ar-L ³ - (the connecting chain Long) is 3-6 is better, 3 or 4 is more preferable. When X in formula (1-2) is a carboxyl group, the number of atoms on the shortest path of the connecting chain between X in -L ² -Ar-L ³ - and -C(=O)- (linking chain length) 2-5 is preferable, and 2 or 3 is more preferable. In addition, it is preferable that L ³ contains an oxygen atom or a sulfur atom on the above-mentioned shortest path.

In formula (1-2), x is preferably an integer of 1 to 4, more preferably 1 or 2, and further preferably 1. In formula (1-2), y is preferably an integer of 1 to 4, more preferably 1 or 2, and further preferably 1.

式（1-3）中，L ³表示單鍵或2價連結基，R ¹分別獨立地表示1價有機基團，R ¹中的至少1個包含α,β-不飽和酮基，R ²分別獨立地表示氫原子或1價有機基團，2個以上的R ²可以鍵結而形成環結構。 式（1-3）中，R ¹及L ³分別與式（1-2）中的R ¹及L ³的含義相同，較佳態樣亦相同。 式（1-3）中，R ²分別獨立地表示氫原子或1價有機基團，氫原子為較佳。 R ²為1價有機基團時，R ²可舉出烴基、羥基、羧基、硝基、醯胺基等。 Moreover, it is preferable that a specific base generator is a compound represented by following formula (1-3). [chemical formula 39]

In formula (1-3), L ³ represents a single bond or a divalent linking group, R ¹ independently represents a monovalent organic group, at least one of R ¹ contains an α,β-unsaturated ketone group, R ² Each independently represents a hydrogen atom or a monovalent organic group, and two or more R ² may be bonded to form a ring structure. In formula (1-3), R ¹ and L ³ have the same meanings as R ¹ and L ³ in formula (1-2), respectively, and preferred embodiments are also the same. In the formula (1-3), R ² each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom. When R ² is a monovalent organic group, examples of R ² include a hydrocarbon group, a hydroxyl group, a carboxyl group, a nitro group, an amido group, and the like.

〔Molecular weight〕 The molecular weight of the specific base generator is preferably from 150 to 1,000, more preferably from 180 to 800, and still more preferably from 200 to 700.

[Molar Absorption Coefficient] From the viewpoint of improving the light transmittance of the resin composition during exposure, the molar absorptivity of the above-mentioned base generator at a wavelength of 365 nm is preferably 100 mol ^-1 ·L·cm ^-1 or less. It is more preferably not more than 95 mol ^-1 ·L·cm ^-1 , and is still more preferably not more than 90 mol ^-1 ·L·cm ^-1 . The molar absorptivity can be calculated as a value obtained by measuring three samples using UV-2600 (manufactured by Shimadzu Corporation) as a measuring device and arithmetically averaging the results. Other details can be performed in accordance with the contents described in JISK0115:2004 (Japanese Industrial Standards).

〔resolve resolution〕 The specific base generator can be obtained, for example, by heating and stirring in an organic solvent in the presence of triethylamine the hydrochloride salt of the amine corresponding to the final desired structure contained in the specific base generator and corresponding to the final desired structure. Esters are synthesized. In addition, it can also be synthesized by other known synthesis methods, and the synthesis method is not particularly limited.

Although it does not specifically limit as a specific example of a specific base generator, A-1 - A-40 used in the Example are mentioned.

It is preferable that content of the specific base generating agent with respect to the total solid content of a resin composition of this invention is 0.5-20 mass %. The lower limit is more preferably at least 1% by mass. The upper limit is more preferably at most 15% by mass, and is still more preferably at most 10% by mass. The specific base generator may be used alone or in combination of two or more. When using 2 or more types simultaneously, it is preferable that the total amount is in the said range. Also, when the resin composition of the present invention includes a specific base generator and a base generator (a base generator different from the specific base generator) described later, the specific base generator and the base generator (a base generator different from the specific base generator) agent) in a total content of 1 to 25% by mass is preferred. The lower limit is more preferably at least 2% by mass. The upper limit is more preferably 20% by mass or less, and more preferably 15% by mass or less. In order to improve the pattern squareness while maintaining the amount of tertiary amines generated, it is considered effective to increase the total amount of the base generator compared to the case of using only a specific base generator. Moreover, the content of the specific base generator in the resin composition of the present invention is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, relative to 100 parts by mass of the specific resin.

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

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

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

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

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

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

式（P）中，M為金屬原子，R分別獨立地為取代基。 上述R分別獨立地選自芳香族基、烷基、鹵素原子及烷基磺醯氧基為較佳。 As an organometallic complex, the compound represented by following formula (P) is mentioned preferably. [chemical formula 40]

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

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

Specific examples of organometallic complexes are not particularly limited, and tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, and diisopropoxybis(ethylacetate)titanium can be exemplified. , Diisopropoxybis(acetylacetonate)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl) ) phenyl) titanium, pentamethylcyclopentadienetrimethoxytitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium and the following compound. [chemical formula 41]

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

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

＜Polymerizable compound＞ It is preferable that the resin composition of this invention contains a polymeric compound. Examples of the polymerizable compound include radical crosslinking agents and other crosslinking agents.

〔Free radical crosslinking agent〕 It is preferable that the resin composition of the present invention contains a radical crosslinking agent. The free radical crosslinking agent is a compound having a free radical polymerizable group. As the radical polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of groups containing the aforementioned ethylenically unsaturated bonds include vinyl, allyl, vinylphenyl, (meth)acryl, maleimide, (meth)acryl A group having an ethylenically unsaturated bond such as an amino group. Among them, (meth)acryl, (meth)acrylamide, and vinylphenyl are preferable as the group containing the above-mentioned ethylenically unsaturated bond. From the viewpoint of reactivity, (meth)acryl base) acryl group is more preferred.

The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. As a compound having two or more of the above-mentioned ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferred, a compound having 2 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 2 to 10 ethylenically unsaturated bonds is more preferred. A compound having 6 ethylenically unsaturated bonds is further preferred. Also, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention includes a compound having two ethylenically unsaturated bonds and a compound having three or more of the above-mentioned ethylenically unsaturated bonds. better.

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

Specific examples of radically polymerizable compounds include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters, acyl acids, etc. The amines are preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, it is also preferable to use unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfhydryl groups, and monofunctional or polyfunctional isocyanates or epoxy compounds. , Dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. Also, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and further have halogen groups Or the substitution reactants of unsaturated carboxylic acid esters or amides with detachable substituents such as toluenesulfonyloxy and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Moreover, as another example, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, and allyl ether can also be used. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the content is incorporated in this specification.

Moreover, it is also preferable that a radical crosslinking agent is a compound which has a boiling point of 100 degreeC or more under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol tri (Meth)acrylate, Neopentylthritol tetra(meth)acrylate, Dineopentylthritol penta(meth)acrylate, Dineopentylthritol hexa(meth)acrylate, Hexylene glycol di( Meth) acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trimethylolethane, etc. in polyfunctional alcohols Compounds that undergo (meth)acrylation after adding ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Application Publication No. 51-037193 Urethane (meth)acrylates described in the gazettes, polyester acrylates described in the gazettes of JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490 polyfunctional acrylates or methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid; and mixtures thereof. Also, compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also preferred. Moreover, the polyfunctional (meth)acrylate obtained by making polyfunctional carboxylic acid and the compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, react, etc. are also mentioned.

In addition, as preferred radical crosslinking agents other than those mentioned above, those having an oxene ring and having an oxene ring described in JP-A-2010-160418, JP-A-2010-129825, and JP-A-4364216 can also be used. Compounds having two or more ethylenically unsaturated bond groups, cardo resins.

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

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

Also, the compounds described in Japanese Patent Application Laid-Open No. 10-062986 as formula (1) and formula (2) together with their specific examples can also be used as radical crosslinking agents. A compound obtained by (meth)acrylic esterification of ethylene oxide or propylene oxide.

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

As a radical crosslinking agent, diperythritol hexaacrylate, diperythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), diperythritol tetra Acrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), dipenteoerythritol penta(meth)acrylate (A commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), Dineopentaerythritol hexa(meth)acrylate (a commercially available product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.) and the structure in which the (meth)acryl groups are bonded via ethylene glycol residues or propylene glycol residues is preferable, and dipentivalyl hexaacrylate Esters are especially preferred. These oligomer types can also be used.

Commercially available radical crosslinking agents include, for example, tetrafunctional acrylate SR-494 having four ethyleneoxy chains and bifunctional methacrylate having four ethyleneoxy chains manufactured by Sartomer Company, Inc. SR-209, 231, 239 manufactured by Sartomer Company, Inc, hexafunctional acrylate DPCA-60 having 6 pentyloxy chains manufactured by Nippon Kayaku Co., Ltd., trifunctional acrylate having 3 isobutoxy chains Acrylate TPA-330, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600 , T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), etc.

As the radical crosslinking agent, carbamic acid described in JP-A-48-041708, JP-A-51-037193, JP-02-032293, JP-02-016765 Ester acrylates, Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 have an oxirane-based skeleton The urethane compounds are also preferred. Furthermore, as a radical crosslinking agent, it is also possible to use those having an amino group structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-01-105238. , Compounds with thioether structure.

The free radical crosslinking agent may be a free radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. The free radical crosslinking agent with acid groups is preferably an ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid, which reacts the unreacted hydroxyl group of aliphatic polyhydroxy compound with non-aromatic carboxylic acid anhydride to make it have acid group Free radical crosslinking agents are more preferred. Particularly preferred are the following compounds: Among free radical crosslinking agents that react unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic acid anhydrides to have acid groups, the aliphatic polyhydroxy compounds are neopentylitol or dichloromethane Pentaerythritol. As a commercial item, polyacid-modified acrylic oligomer M-510, M-520 etc. by TOAGOSEI CO., LTD. are mentioned, for example.

The preferred acid value of the free radical crosslinking agent with acid groups is 0.1-300 mgKOH/g, particularly preferably 1-100 mgKOH/g. If the acid value of a radical crosslinking agent exists in the said range, it will be excellent in workability|operativity in manufacture, and also will be excellent in developability. Also, the polymerizability is good. The said acid value is measured according to description of JISK0070:1992.

From the viewpoint of pattern resolution and film stretchability, it is preferable to use bifunctional methacrylate or acrylate for the resin composition. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 Diacrylate, PEG200 Dimethacrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate , Neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate , dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct of bisphenol A diacrylate, bisphenol A EO adduct dimethacrylate, PO adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloxypropyl methyl acrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylate with urethane bond, 2 functional acrylate with urethane bond Functional methacrylate. These can mix and use 2 or more types as needed. In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a polyethylene glycol chain formula weight of about 200. The resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as the radical crosslinking agent from the viewpoint of suppressing warpage accompanying elastic modulus control of the pattern (cured product). As monofunctional radical crosslinking agents, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth) Butoxyethyl acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (Meth)acrylic acid derivatives such as (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc., N- N-vinyl compounds such as vinylpyrrolidone and N-vinylcaprolactam, and allylglycidyl ether. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable. Moreover, allyl compounds, such as diallyl phthalate and triallyl trimellitate, are mentioned as a difunctional or more radical crosslinking agent.

When a radical crosslinking agent is contained, its content is preferably more than 0% by mass and not more than 60% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably at least 5% by mass. The upper limit is more preferably at most 50% by mass, and more preferably at most 30% by mass.

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

〔Other crosslinking agents〕 It is also preferable that the resin composition of the present invention contains other crosslinking agents different from the above radical crosslinking agents. In the present invention, other cross-linking agents refer to cross-linking agents other than the above-mentioned radical cross-linking agents, which have a plurality of cross-linking agents in the molecule that are promoted by the photosensitization of the above-mentioned photoacid generator or photobase generator (in the composition). The compound that forms a covalent bond between other compounds or their reaction products) is preferably a compound that has a plurality of reaction groups in the molecule that are promoted by the action of an acid or base (with other compounds in the composition or A compound that is a reactive group that forms a covalent bond between its reaction products is more preferable. It is preferable that the above-mentioned acid or base is an acid or base generated from a photoacid generator or a photobase generator in the exposure step. As other crosslinking agents, compounds having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl and alkoxymethyl groups are preferred, and compounds having groups selected from the group consisting of acyloxymethyl A compound having a structure in which at least one group of the group of hydroxymethyl, alkoxymethyl, and alkoxymethyl is directly bonded to a nitrogen atom is more preferable. Examples of other crosslinking agents include compounds having a structure in which formaldehyde is reacted with an amino group-containing compound such as melamine, acetylene urea, urea, alkylene urea, or benzoguanamine, or formaldehyde is used in combination with an alcohol. A structure in which the hydrogen atom of the above-mentioned amine group is replaced by an acyloxymethyl group, a hydroxymethyl group or an alkoxymethyl group. The production method of these compounds is not particularly limited, as long as it is a compound having the same structure as the compound produced by the above-mentioned method. Moreover, it may be an oligomer obtained by self-condensing the methylol groups of these compounds. As the above-mentioned amine group-containing compound, the cross-linking agent using melamine is called melamine-based cross-linking agent, the cross-linking agent using acetylene carbamide, urea or alkylene urea is called urea-based cross-linking agent, and the cross-linking agent using alkylene urea A urea crosslinking agent is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. Among them, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of urea-based cross-linking agents and melamine-based cross-linking agents, including acetylene carbamide-based cross-linking agents and At least one compound of the group of melamine-based crosslinking agents is more preferable.

As a compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention, those having an alkoxymethyl group or an acyloxymethyl group directly on an aromatic group, the following urea structure Compounds substituted on a nitrogen atom or on a trichodium atom are examples of structures. Regarding the alkoxymethyl group or acyloxymethyl group possessed by the above-mentioned compounds, the number of carbon atoms is preferably 2 to 5, more preferably 2 or 3 carbon atoms, and still more preferably 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6. The molecular weight of the above compound is preferably 1500 or less, more preferably 180-1200.

[chemical formula 42]

R ₁₀₀ represents an alkyl or acyl group. R ₁₀₁ and R ₁₀₂ each independently represent a monovalent organic group, which may be bonded to each other to form a ring.

Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds of the following general formula.

[chemical formula 43]

In the formula, X represents a single bond or a divalent organic group, each R ₁₀₄ independently represents an alkyl or acyl group, and R ₁₀₃ represents a hydrogen atom, an alkyl, an alkenyl, an aryl, an aralkyl, or A group that decomposes and generates an alkali-soluble group (for example, a group detached by the action of an acid, a group represented by -C(R ⁴ ) ₂ COOR ⁵ (R ⁴ independently represents a hydrogen atom or a carbon number 1 ~4 alkyl groups, R ⁵ represents the group that is removed by the action of acid.)). R ₁₀₅ each independently represent an alkyl or alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. Regarding R ⁵ in the group decomposed by the action of acid to form an alkali-soluble group, the group detached by the action of acid, and the group represented by -C(R ⁴ ) ₂ COOR ⁵ , for example, -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), etc. In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. The above-mentioned alkyl group may be either linear or branched. As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable. The above-mentioned cycloalkyl group may have a monocyclic structure or may have a polycyclic structure such as a condensed ring. The above-mentioned aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group. As the above-mentioned aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an alkyl group having 7 to 16 carbon atoms is more preferable. The aforementioned aralkyl group refers to an aryl group substituted with an alkyl group, and preferred aspects of the alkyl group and aryl group are the same as those of the aforementioned alkyl group and aryl group. The aforementioned alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms. In addition, these groups may further have known substituents within the range in which the effects of the present invention are obtained.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

Such groups are preferably tertiary alkyl ester groups, acetal ester groups, cumyl ester groups, enol ester groups, and the like. Further preferred are tertiary alkyl ester groups and acetal ester groups.

Specific examples of the compound having an alkoxymethyl group include the following structures. Examples of the compound having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compounds is changed to an acyloxymethyl group. Examples of compounds having an alkoxymethyl group or an acyloxymethyl group in the molecule include the following compounds, but are not limited thereto.

[chemical formula 44]

[chemical formula 45]

As a compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercial product may be used, or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a trioxane ring is preferable.

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

Specific examples of urea-based crosslinking agents include, for example, monomethylolated acetylene carbamide, dimethylolated acetylene carbamide, trimethylolated acetylene carbamide, tetramethylolated acetylene carbamide, monomethoxy Dimethoxymethylated acetylene carbamide, dimethoxymethylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetramethoxymethylated acetylene carbamide, monoethoxymethylated acetylene carbamide, diethoxy Methylated acetylene carbamide, triethoxymethylated acetylene carbamide, tetraethoxymethylated acetylene carbamide, monopropoxymethylated acetylene carbamide, dipropoxymethylated acetylene carbamide, triproxymethylated acetylene carbamide Methylated acetylene carbamide, tetrapropoxymethylated acetylene carbamide, monobutoxymethylated acetylene carbamide, dibutoxymethylated acetylene carbamide, tributoxymethylated acetylene carbamide or tetrabutoxy Acetylene carbamide cross-linking agents such as methylated acetylene carbamide; Bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea and other urea-based crosslinking agents, Monomethylolated ethylene urea or dimethylolated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxy Methylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea, etc. joint agent, Monomethylolated propylene urea, dimethylolated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxy Propylene urea, such as methylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea, etc. joint agent, 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole pyridone etc.

Specific examples of benzoguanamine-based crosslinking agents include monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, tetramethylolated benzoguanamine, and tetramethylolated benzoguanamine. Methylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine Benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine Guanamine, Monopropoxymethylated Benzoguanamine, Dipropoxymethylated Benzoguanamine, Tripropoxymethylated Benzoguanamine, Tetrapropoxymethylated Benzoguanamine , Monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc.

In addition, as a compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl groups, it is also preferable to use A compound in which at least one group is directly bonded to an aromatic ring (preferably a benzene ring). Specific examples of such compounds include benzenedimethanol, bis(methylol)cresol, bis(methylol)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(methylol) base) benzophenone, hydroxymethylbenzene, hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis( Methoxymethyl) cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxy Methoxymethylbenzene, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylene triphenyl [2,6-Bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1 ,3‐benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

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

Moreover, it is also preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxan compounds as other crosslinking agents.

-Epoxy compounds (compounds with epoxy groups)- As an epoxy compound, the compound which has 2 or more epoxy groups in one molecule is preferable. The epoxy group undergoes cross-linking reaction below 200°C and does not cause dehydration reaction due to cross-linking, so it is not easy to cause film shrinkage. Therefore, low-temperature hardening and warpage of the resin composition of this invention can be suppressed effectively by containing an epoxy compound.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the modulus of elasticity is further reduced, and warpage can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2-15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, Ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; Polyalkylene glycol-type epoxy resins such as propylene glycol diglycidyl ether; polymethyl (glycidoxypropyl) siloxane and other polysiloxanes containing epoxy groups, but not limited to this wait. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP- 4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are product names, manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) Trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700 , EPOLEAD (registered trademark) PB3600 (the above are trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000- L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER- 1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. Moreover, the following compounds can also be preferably used.

[chemical formula 46]

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

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

-Oxetane compounds (compounds having an oxetane group)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyl oxetane, 1,4-bis{[( 3-Ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxy Acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these may be used individually, or may mix 2 or more types.

-Benzoxazone compounds (compounds having a benzoxazolyl group)- The benzoxazone compound is preferable because it does not produce outgassing during hardening due to the crosslinking reaction caused by the ring-opening addition reaction, thereby reducing heat shrinkage and suppressing warpage.

Preferable examples of benzoxanthane compounds include P-d type benzoxanthine, F-a type benzoxanthine (the above are trade names, manufactured by Shikoku Chemicals Corporation), and benzoxanthine compound of polyhydroxystyrene resin. Products, phenol novolak type dihydrobenzoxa 𠯤 compound. These can be used individually or in mixture of 2 or more types.

The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and 1.0 to 10% by mass relative to the total solid content of the resin composition of the present invention. Quality % is especially good. Other crosslinking agents may contain only 1 type, and may contain 2 or more types. When two or more other thermal crosslinking agents are contained, it is preferable that the total is within the above-mentioned range.

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

It is preferable that the photoradical polymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 L·mol ^-1 ·cm ^-1 in the wavelength range of about 240-800 nm (preferably 330-500 nm). The molar absorptivity of a compound can be measured by a known method. For example, it is preferable to measure at a concentration of 0.01 g/L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As a photoradical polymerization initiator, a well-known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (such as compounds having a trioxadiazole skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbis Oxime compounds such as imidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxyl compounds such as hydroxyacetophenone Ketone compounds, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. For details of these, the descriptions in paragraphs 0165 to 0182 of JP-A-2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and these contents are incorporated in this specification. In addition, examples include paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in JP-A-6301489, and peroxides described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019. Material-based photopolymerization initiator, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, and the photopolymerization initiator described in Japanese Patent Laid-Open No. 2019-043864 The photopolymerization initiator, the photopolymerization initiator described in Japanese Patent Application Laid-Open No. 2019-044030, the peroxide-based initiator described in Japanese Patent Application Laid-Open No. 2019-167313, these contents are incorporated into this specification .

As the ketone compound, for example, compounds described in paragraph 0087 of JP-A-2015-087611 can be exemplified, and the content thereof is incorporated in the present specification. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

In one embodiment of the present invention, as photoradical polymerization initiators, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used. in this manual.

As the α-hydroxyketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959 can be used , IRGACURE 127 (trade name: both manufactured by BASF Corporation).

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

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

Examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. In addition, Omnirad 819, Omnirad TPO (the above are manufactured by IGM Resins B.V.), IRGACURE-819, and IRGACURE-TPO (trade names: all are manufactured by BASF Corporation) can be used.

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

More preferably, an oxime compound is mentioned as a photoradical polymerization initiator. By using an oxime compound, exposure latitude can be improved more effectively. Since the exposure latitude (exposure margin) of an oxime compound is wide and it also functions as a photocuring accelerator, it is especially preferable.

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

As preferred oxime compounds, for example, compounds of the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetyloxyiminobutan-2-one, 3 -Propionyloxyiminobutan-2-one, 2-Acetyloxyiminopentan-3-one, 2-Acetyloxyimino-1-phenylpropan-1-one , 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-tosyloxy)iminobutan-2-one and 2-ethoxycarbonyloxy imino-1-phenylpropan-1-one, etc. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based radical photopolymerization initiator) as the radical photopolymerization initiator. The oxime-based photoradical polymerization initiator has a linking group>C=N-O-C(=O)- in the molecule.

[chemical formula 47]

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, JP 2012-014052 The photoradical polymerization initiator 2 described in the Publication No. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. . In addition, DFI-091 (manufactured by Daito Chemix Corporation) and SpeedCure PDO (manufactured by Sartomer Arkema) can be used. Moreover, the oxime compound of the following structures can also be used. [chemical formula 48]

An oxime compound having an oxene ring can also be used as a photoradical polymerization initiator. Specific examples of the oxime compound having an oxene ring include compounds described in JP-A-2014-137466 and compounds described in JP-A-06636081, the contents of which are incorporated herein.

As a photoradical polymerization initiator, the oxime compound which has at least one benzene ring which has a carbazole ring as a skeleton of a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505, and the content is incorporated in this specification.

Oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, JP-A-2013 - Compound (C-3) and the like described in Paragraph 0101 of Publication No. 164471 are incorporated in this specification.

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

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

An oxime compound in which a substituent having a hydroxyl group is bonded to the carbazole skeleton can also be used as the photoradical polymerization initiator. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019/088055, and the contents are incorporated in this specification.

As the photopolymerization initiator, an oxime compound (hereinafter also referred to as an oxime compound OX) having an aromatic ring group Ar ^OX1 having an electron-withdrawing group introduced into an aromatic ring can also be used. Examples of the electron-withdrawing group included in the aromatic ring group Ar ^OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, An arylsulfonyl group, a cyano group, an acyl group, and a nitro group are preferable, an acyl group is more preferable, and a benzoyl group is still more preferable from the viewpoint of being easy to form a film excellent in light resistance. The benzoyl group may have a substituent. As a substituent, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic epoxy group, an alkenyl group, an alkylthiol group, an arylhydrogen group Thio group, acyl group or amino group are preferred, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic epoxy group, alkyl sulfide group, aryl sulfide group or amine group are more preferred, alkyl group An oxy group, an alkylsulfhydryl group or an amine group is further preferred.

式中，R ^X1表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基氫硫基、芳基氫硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯基、醯氧基、胺基、膦醯基、胺甲醯基或胺磺醯基， R ^X2表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基氫硫基、芳基氫硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯氧基或胺基， R ^X3～R ^X14分別獨立地表示氫原子或取代基。 其中，R ^X10～R ^X14中的至少1個為拉電子基團。 The oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), more preferably the compound represented by the formula (OX2). [chemical formula 49]

In the formula, R ^X1 represents an alkyl group, an alkenyl group, an alkoxyl group, an aryl group, an aryloxy group group, a heterocyclic group, a heterocyclic epoxy group group, an alkyl mercapto group, an aryl mercapto group, an alkyl sulfinyl group , arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphonyl, carbamoyl or sulfamoyl, R ^X2 represents alkyl, Alkenyl, alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylsulfenyl, arylsulfenyl, alkylsulfinyl, arylsulfinyl, alkyl A sulfonyl group, an arylsulfonyl group, an acyloxy group or an amino group, and R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent. Among them, at least one of R ^X10 to R ^X14 is an electron withdrawing group.

In the above formula, R ^X12 is an electron-withdrawing group, and R ^X10 , R ^X11 , R ^X13 , and R ^X14 are preferably hydrogen atoms.

Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, and the contents thereof are incorporated in the present specification.

Preferred oxime compounds include oxime compounds having specific substituents disclosed in JP-A-2007-269779, oxime compounds having a thioaryl group disclosed in JP-A-2009-191061, etc. , which is included in this manual.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is selected from the group consisting of trihalomethyl trisulfone compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl Compounds in the group of -benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds are preferred.

More preferable photo-radical polymerization initiators are trihalomethyl trisulfone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salts Compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyl tristannium compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds It is still more preferable to use at least one kind of compound in the group, and it is still more preferable to use a metallocene compound or an oxime compound.

In addition, as the photoradical polymerization initiator, N, such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), can also be used. ,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-𠰌linylphenyl)-butanone-1, Aromatic ketones such as 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌linyl-acetone-1, quinones such as alkylanthraquinones 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, etc. Moreover, the compound represented by following formula (I) can also be used.

[chemical formula 50]

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

[chemical formula 51]

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

In addition, as the photoradical polymerization initiator, compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used, and the content is incorporated in this specification.

As the radical photopolymerization initiator, a difunctional or trifunctional or more photoradical polymerization initiator can be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity decreases, the solubility in a solvent or the like increases, and precipitation becomes difficult over time, thereby improving the temporal stability of the resin composition. Specific examples of difunctional or trifunctional or more photoradical polymerization initiators include JP 2010-527339, JP 2011-524436, International Publication No. 2015/004565, JP Paragraphs 0407 to 0412 of Table No. 2016-532675, dimers of oxime compounds described in paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E) described in Japanese Patent Publication No. 2013-522445, and Compound (G), Cmpd 1-7 described in International Publication No. 2016/034963, oxime ester photoinitiator described in paragraph 0007 of JP 2017-523465 A, JP 2017-167399 A Photoinitiators described in paragraphs 0020 to 0033, photopolymerization initiators (A) described in paragraphs 0017 to 0026 of Japanese Patent Application Laid-Open No. 2017-151342, oxime ester photoinitiators described in Japanese Patent No. 6469669 Initiators, etc., are included in this manual.

When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15% by mass, based on the total solid content of the resin composition of the present invention. , and still more preferably 1.0 to 10% by mass. A photoinitiator may contain only 1 type, and may contain 2 or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since a photopolymerization initiator may also function as a thermal polymerization initiator, heating by an oven, a hot plate, etc. may further promote the crosslinking by a photopolymerization initiator.

〔Sensitizer〕 The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and enters an electronically excited state. The sensitizer in an electronically excited state contacts with thermal radical polymerization initiators, photoradical polymerization initiators, etc. to produce electron transfer, energy transfer, and heat generation. Thereby, a thermal radical polymerization initiator and a photoradical polymerization initiator cause a chemical change and decompose to generate a radical, an acid, or a base. As sensitizers that can be used, benzophenone series, Michelerone series, coumarin series, pyrazole azo series, anilino azo series, triphenylmethane series, anthraquinone series, anthracene series, Anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenanthrene series, pyrrolopyrazole azomethine series , 𠮿kou galaxy, phthalocyanine, benzopyran, indigo and other compounds. Examples of sensitizers include Michelerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene) ring Pentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidene indanone, p-dimethyl Aminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylidene)benzothiazole, 2-(p- Dimethylaminophenylvinylene)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene) Acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylamine Diethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethyl Aminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluene Ethanolamine, N-Phenylethanolamine, 4-Phenylbenzophenone, Isoamyl Dimethylaminobenzoate, Isoamyl Diethylaminobenzoate, 2-Mercaptobenzimidazole, 1-Phenyl- 5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene) Aminostyrene)naphthalene(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzylaniline, N-methylacetanilide, 3',4'-Dimethylacetaniline, etc. In addition, other sensitizing dyes can also be used. For details of the sensitizing dye, reference can be made to the description in paragraphs 0161 to 0163 of JP-A-2016-027357, and the content is incorporated in this specification.

When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, relative to the total solid content of the resin composition. good. A sensitizer may be used individually by 1 type, and may use 2 or more types together.

[Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in Polymer Dictionary 3rd Edition (edited by The Society of Polymer Science, Japan, 2005) pp. 683-684. As the chain transfer agent, for example, compounds having -SS-, -SO ₂ -S-, -NO-, SH, PH, SiH, and GeH in the molecule, used in RAFT (Reversible Addition Fragmentation chain Transfer: reversible Addition fragmentation chain transfer) Polymerized dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds with thiocarbonylthio group. These can generate free radicals by donating hydrogen to low-activity free radicals, or can generate free radicals by deprotonation after being oxidized. In particular, thiol compounds can be preferably used.

In addition, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used, and the content is incorporated in this specification.

When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. , 0.5 to 5 parts by mass is still more preferable. The chain transfer agent may be only 1 type, or may be 2 or more types. When there are two or more types of chain transfer agents, the total is preferably within the above range.

<Base Generator> The resin composition of the present invention may contain a base generator. Here, the base generator refers to a compound capable of generating a base by physical action or chemical action. A thermal base generator and a photobase generator are mentioned as a base generator suitable for the resin composition of this invention. Among them, the base generators belonging to the above-mentioned specific base generators do not belong to the base generators mentioned here. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. When the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be accelerated by heating, and the mechanical properties and chemical resistance of the cured product will be improved. For example, it can be used as an interlayer insulating film for rewiring layers included in semiconductor packages. performance becomes better. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator of the present invention is not particularly limited, and known base generators can be used. As known base generators, for example, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamate compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylamines, etc., can be used. carbamate compound, nitrobenzyl carbamate compound, sulfonamide compound, imidazole derivative compound, amidoimide compound, pyridine derivative compound, α-aminoacetophenone derivative compound, tetra Grade ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amidoimide compounds, phthalimide derivative compounds, acyloxyimine compounds, and the like. Specific examples of the nonionic base generator include compounds represented by formula (B1), formula (B2) or formula (B3). [chemical formula 52]

In formula (B1) and formula (B2), Rb ¹ , Rb ² and Rb ³ are each independently an organic group not having a tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. Moreover, none of Rb ¹ , Rb ² and Rb ³ has a carboxyl group. In addition, in this specification, a tertiary amine structure means the structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-type carbon atom. Therefore, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with a nitrogen atom, it is not limited thereto.

In the formulas (B1) and (B2), at least one of Rb ¹ , Rb ² and Rb ³ preferably has a cyclic structure, and at least two of them have a cyclic structure. The ring structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring formed by condensing two monocyclic rings is preferable. The single ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, more preferably a cyclohexane ring.

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

Examples of Rb ³ include alkyl (preferably 1-24 carbons, more preferably 2-18, still more preferably 3-12), aryl (preferably 6-22 carbons, 6-18 is more preferred, 6-10 is further preferred), alkenyl (carbon number 2-24 is preferred, 2-12 is more preferred, 2-6 is further preferred), aralkyl group (carbon number 7-23 is preferred, 7-19 is more preferred, 7-12 is further preferred), aralkenyl (8-24 carbons is preferred, 8-20 is more preferred, 8-16 is further preferred), alkane Oxygen (preferably 1-24 carbons, more preferably 2-18, further preferably 3-12), aryloxy (preferably 6-22 carbons, more preferably 6-18, 6-18 12 is further preferred) or aralkoxy group (with 7 to 23 carbons is preferred, 7 to 19 is more preferred, 7 to 12 is further preferred). Among them, cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and still more preferably having 3 to 12 carbon atoms), aralkenyl groups and aralkoxy groups are preferred. Rb ³ may further have a substituent within the range of exerting the effect of the present invention.

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 53]

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ³² have the same meanings as Rb ¹ and Rb ² in the formula (B1), respectively. Rb ¹³ is alkyl (preferably 1-24 carbons, more preferably 2-18, further preferably 3-12), alkenyl (preferably 2-24 carbons, more preferably 2-18, 3-12 is more preferred), aryl group (6-22 carbon number is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl group (7-23 carbon number is preferred, 7-19 are more preferable, and 7-12 are still more preferable), and may have a substituent within the range which exhibits the effect of this invention. Among them, Rb ¹³ is preferably an aralkyl group.

Rb ³³ and Rb ³⁴ are independently a hydrogen atom, an alkyl group (preferably 1-12 carbons, more preferably 1-8, more preferably 1-3), alkenyl (2-12 carbons are relatively preferably, 2 to 8 are more preferred, 2 to 3 are further preferred), aryl (6 to 22 carbons are preferred, 6 to 18 are preferred, 6 to 10 are further preferred), aralkyl ( Carbon number 7-23 is preferable, 7-19 is more preferable, 7-11 is still more preferable), hydrogen atom is more preferable.

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

It is also preferable that the compound represented by formula (B1-1) is a compound represented by formula (B1-1a). [chemical formula 54]

Rb ¹¹ and Rb ¹² have the same meanings as Rb ¹¹ and Rb ¹² in formula (B1-1). Rb ¹⁵ and Rb ¹⁶ are hydrogen atom, alkyl (preferably 1-12 carbons, more preferably 1-6, further preferably 1-3), alkenyl (preferably 2-12 carbons, 2 ～6 is more preferred, 2～3 is further preferred), aryl group (carbon number 6～22 is preferred, 6～18 is more preferred, 6～10 is further preferred), aralkyl group (carbon number 7 ～23 is preferred, 7～19 is more preferred, 7～11 is further preferred), hydrogen atom or methyl group are preferred. Rb ¹⁷ is alkyl (preferably 1-24 carbons, more preferably 1-12, further preferably 3-8), alkenyl (preferably 2-12 carbons, more preferably 2-10, 3-8 is more preferred), aryl group (6-22 carbon number is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl group (7-23 carbon number is preferred, 7-19 is more preferred, and 7-12 is further preferred), among which aryl is preferred.

[chemical formula 55]

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

In this specification, the "connecting chain" refers to the chain of atoms on the path between two atoms or atomic groups connecting the connecting objects, which connects the connecting objects at the shortest (minimum number of atoms) distance. For example, in a compound represented by the following formula, L consists of styrene, has a vinyl group as a saturated hydrocarbon group, the linking chain consists of 4 carbon atoms, and the number of atoms on the path of the linking chain (that is, the number of atoms constituting the linking chain The number of atoms, hereinafter, also referred to as "linkage chain length" or "linkage chain length".) is 4. [chemical formula 56]

It is preferable that the number of carbons (carbon atoms other than the carbon atoms in the linking chain) in L in the formula (B3) is 3-24. The upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. The upper limit of the linkage chain length of L is preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and particularly preferably 5 or less, from the viewpoint of rapidly advancing the intramolecular cyclization reaction. In particular, the linkage chain length of L is preferably 4 or 5, and 4 is the most optimal. Specific examples of preferred compounds as base generators include, for example, compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/066416, and compounds described in paragraphs 0143 to 0177 of International Publication No. 2018/038002. compound.

Moreover, it is also preferable that a base generator contains the compound represented by following formula (N1). [chemical formula 57]

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, R ^C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. As an upper limit, 12 or less is preferable, 8 or less is more preferable, and 5 or less is still more preferable. The linkage chain length refers to the number of atoms present in the arrangement of atoms that forms the shortest path between two carbonyl groups in the formula.

In the formula (N1), R ^N1 and R ^N2 are independently monovalent organic groups (preferably 1-24 carbons, more preferably 2-18, more preferably 3-12), hydrocarbon groups (carbon number 1 to 24 is preferable, 1 to 12 is more preferable, and 1 to 10 is still more preferable), and specifically, an aliphatic hydrocarbon group can be mentioned (preferably 1 to 24 carbons, 1 to 12 are More preferably, 1 to 10 are more preferably) or aromatic hydrocarbon groups (6 to 22 carbons are more preferable, 6 to 18 are more preferable, 6 to 10 are still more preferable), and aliphatic hydrocarbon groups are more preferable. When an aliphatic hydrocarbon group is used as R ^N1 and R ^N2 , the resulting base has a high basicity, which is preferable. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the substituent in the aliphatic hydrocarbon chain or in the aromatic ring. In particular, an aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain can be exemplified.

Examples of the aliphatic hydrocarbon groups constituting R ^N1 and R ^N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain alkyl groups and cyclic alkyl groups, groups having Alkyl group of oxygen atom. The number of carbon atoms in the linear or branched chain alkyl group is preferably 1-24, more preferably 2-18, and still more preferably 3-12. Examples of linear or branched chain alkyl include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Base, isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, isohexyl, etc. The carbon number of the cyclic alkyl group is preferably 3-12, more preferably 3-6. As a cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned, for example. The carbon number of the group related to the combination of a chain alkyl group and a cyclic alkyl group is preferably 4-24, more preferably 4-18, and still more preferably 4-12. As for the combination of a chain alkyl group and a cyclic alkyl group, for example, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, methylcyclohexylmethyl group, ethylcyclohexylethyl group, etc. are mentioned. The carbon number of the alkyl group having an oxygen atom in the chain is preferably 2-12, more preferably 2-6, and still more preferably 2-4. The alkyl group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched. Among them, R ^N1 and R ^N2 are preferably alkyl groups having 5 to 12 carbons from the viewpoint of increasing the boiling point of a base decomposed to be described later. Among them, a group having a cyclic alkyl group and an alkyl group having 1 to 8 carbon atoms are preferable in formulations where adhesion to a metal (such as copper) is emphasized.

R ^N1 and R ^N2 may be connected to each other to form a ring structure. When forming a ring structure, an oxygen atom etc. may be contained in a chain. Also, the ring structure formed by R ^N1 and R ^N2 may be a single ring or a condensed ring, and a single ring is preferred. As the formed ring structure, a 5-membered ring or a 6-membered ring containing a nitrogen atom in formula (N1) is preferable, for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, and a pyrrolidine ring , an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperidine ring, and a piperidine ring, etc., preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperridine ring, and a piperidine ring.

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

As the protecting group, a protecting group decomposed by the action of an acid or a base is preferable, and a protecting group decomposed by an acid is preferable.

Specific examples of the protecting group include chain or cyclic alkyl groups or chain or cyclic alkyl groups having an oxygen atom in the chain. Examples of chain or cyclic alkyl groups include methyl, ethyl, isopropyl, tertiary butyl, cyclohexyl and the like. Specific examples of chain alkyl groups having an oxygen atom in the chain include alkoxyalkyl groups, and more specific examples include methoxymethyl (MOM) and ethoxyethyl (EE). wait. Examples of the cyclic alkyl group having an oxygen atom in the chain include epoxy group, glycidyl group, oxetanyl group, tetrahydrofuryl group, tetrahydropyranyl (THP) group and the like.

Although it does not specifically limit as a divalent linking group which comprises L, Hydrocarbon group is preferable, and aliphatic hydrocarbon group is more preferable. The hydrocarbon group may have a substituent, and may have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linking group that may have an oxygen atom in the chain is preferable, a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a related group that may have an oxygen atom in the chain A combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group is more preferable, and a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is still more preferable. These groups preferably do not have an oxygen atom. The number of carbon atoms in the divalent hydrocarbon linking group is preferably 1-24, more preferably 2-12, and still more preferably 2-6. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1-12, more preferably 2-6, and still more preferably 2-4. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably from 6 to 22, more preferably from 6 to 18, and still more preferably from 6 to 10. The carbon number of the group (for example, arylalkyl group) related to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group is preferably 7-22, more preferably 7-18, and even more preferably 7-10. good.

As the linking group L, specifically, a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and a group having oxygen in the chain. Atomic alkylene groups, linear or branched chain alkenylene groups, cyclic alkenylene groups, arylylene groups, and arylylenealkylene groups are preferred. The number of carbon atoms in the linear or branched chain alkylene group is preferably 1-12, more preferably 2-6, and still more preferably 2-4. The number of carbon atoms in the cyclic alkylene group is preferably 3-12, more preferably 3-6. The carbon number of the group related to the combination of a chain alkylene group and a cyclic alkylene group is preferably 4-24, more preferably 4-12, and still more preferably 4-6. The alkylene group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched. The carbon number of the alkylene group having an oxygen atom in the chain is preferably 1-12, more preferably 1-6, and still more preferably 1-3.

The number of carbon atoms in the linear or branched chain alkenylene group is preferably 2-12, more preferably 2-6, and still more preferably 2-3. The number of C=C bonds in the linear or branched chain alkenylene group is preferably 1-10, more preferably 1-6, and still more preferably 1-3. The carbon number of the cyclic alkenylene group is preferably 3-12, more preferably 3-6. The number of C=C bonds in the cyclic alkenylene group is preferably 1-6, more preferably 1-4, and still more preferably 1-2. The number of carbon atoms in the arylylene group is preferably 6-22, more preferably 6-18, and still more preferably 6-10. The number of carbon atoms in the arylalkylene group is preferably 7-23, more preferably 7-19, and still more preferably 7-11. Among them, chain alkylene, cyclic alkylene, alkylene with oxygen atoms in the chain, chain alkenylene, aryl, arylalkylene are preferred, 1,2-vinyl, Propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis-vinylene), phenylene (1, 2-phenylene), phenylene methylene (especially 1,2-phenylene methylene), vinyloxyvinyl (especially 1,2-vinyloxy-1,2-vinyl) are better.

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

[chemical formula 58]

The molecular weight of the nonionic base generator is preferably at most 800, more preferably at most 600, and still more preferably at most 500. The lower limit is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.

Specific examples of preferable compounds of the ionic base generator include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.

Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto. [chemical formula 59]

Specific examples of imide salts include the following compounds, but the present invention is not limited thereto. [chemical formula 60]

When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably at least 0.3 parts by mass, and more preferably at least 0.5 parts by mass. The upper limit is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, may be 5 parts by mass or less, and may be 4 parts by mass or less. The base generator can be used 1 type or 2 or more types. When using 2 or more types, it is preferable that a total amount exists in the said range. Moreover, the resin composition of this invention can also be made into the form which does not contain base generating agents other than a specific base generating agent substantially. Specifically, the content of the base generators other than the specific base generator is preferably at most 1% by mass, more preferably at most 0.5% by mass, and still more preferably at most 0.1% by mass, based on the total mass of the resin composition. The lower limit is not particularly limited, and may be 0% by mass.

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

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate , butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (e.g., methyl alkoxyacetate, alkanes Ethyl oxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., 2-alkoxy Methyl oxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkane Ethyl oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate , ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate , dimethyl malonate, diethyl malonate, etc. are preferred.

Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol Alcohol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celuxo acetate, ethyl celuxo acetate, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether , ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, etc. are preferred.

Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydro Levoglucosone and the like are preferred.

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

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

Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetyl Amine, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-formyl methionine, N-acetyl methionine, etc. are preferred.

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

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy 2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol Monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methyl benzyl alcohol, n-pentanol, methyl pentanol and diacetone alcohol wait.

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

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

The content of the solvent is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass from the viewpoint of coatability, and the total solid content concentration is 5 to 75% by mass. The quantity is more preferable, and the quantity which makes total solid content concentration 10-70 mass % is still more preferable, and the total solid content concentration is 20-70 mass %, and it is still more preferable. The solvent content can be adjusted according to the required thickness of the coating film and the coating method.

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

＜Metal Adhesion Improver＞ It is preferable that the resin composition of the present invention contains a metal adhesion improving agent for improving adhesion with metal materials used for electrodes, wiring, and the like. Examples of metal adhesion improvers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesive additives, titanium-based adhesive additives, compounds with a sulfonamide structure and compounds with a thiourea structure, phosphoric acid-derived Compounds, β-ketoester compounds, amino compounds, etc.

〔Silane coupling agent〕 Examples of the silane coupling agent include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, compounds described in paragraphs 0063 to 0073 of Japanese Patent Application Laid-Open No. 2011/080992, and Compounds described in Paragraph 0071, Compounds described in Paragraphs 0060 to 0061 of JP-A-2014-191252, Compounds described in Paragraphs 0045-0052 of JP-A-2014-041264, Paragraph 0055 of International Publication No. 2014/097594 The compounds described in , and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Laid-Open No. 2018-173573 are incorporated into this specification. Moreover, as described in paragraphs 0050 to 0058 of JP 2011-128358 A, it is also preferable to use two or more different silane coupling agents. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulae, Me represents a methyl group, and Et represents an ethyl group.

[chemical formula 61]

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropylene Oxypropylmethyldimethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropylmethyldiethoxysilane, 3-Glycidoxypropyl Propyltriethoxysilane, p-Styryltrimethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 -(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-amine propyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureapropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3 - Mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

〔Aluminum-based adhesive agent〕 Examples of the aluminum-based adhesive agent include tris(ethyl acetate)aluminum, tris(acetylacetonate)aluminum, ethyl acetate diisopropyl aluminum, and the like.

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

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

＜Migration Inhibitor＞ It is preferable that the resin composition of this invention further contains a migration inhibitor. By including a migration inhibitor, the transfer of metal ions originating in the metal layer (metal wiring) into the film can be effectively suppressed.

The migration inhibitor is not particularly limited, and examples include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, Azole ring, pyridine ring, pyridine ring, pyrimidine ring, pyrimidine ring, piperidine ring, piperyl ring, phylloline ring, 2H-pyranyl ring and 6H-pyranyl ring, tri-pyranyl ring) compounds, with sulfur Urea and mercapto compounds, hindered phenolic compounds, salicylic acid derivatives, hydrazide derivatives. In particular, 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole can be preferably used Triazole-based compounds such as azoles, tetrazole-based compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole.

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

As other migration inhibitors, the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073-0076 of JP-A-2009-283711, and the compounds described in JP-A-2011-059656 can be used. The compounds described in Paragraph 0052 of Japanese Patent Publication No. 2012-194520, the compounds described in Paragraphs 0114, 0116 and 0118 of Japanese Patent Laid-Open No. 2012-194520, the compounds described in Paragraph 0166 of International Publication No. 2015/199219, etc. incorporated into this manual.

Specific examples of migration inhibitors include the following compounds.

[chemical formula 62]

When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 2.0% by mass relative to the total solid content of the resin composition of the present invention. 1.0 mass % is more preferable.

The migration inhibitor may be only 1 type, or may be 2 or more types. When there are two or more kinds of migration inhibitors, it is preferable that the total thereof is within the above-mentioned range.

＜Polymerization inhibitor＞ It is preferable that the resin composition of this invention contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone-based compounds, amino-based compounds, N-oxyl radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, metal compounds, etc. .

As specific compounds of polymerization inhibitors, p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tertiary butyl-p-cresol, gallicol, p-tertiary Butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'- Methylbis(4-methyl-6-tertiary butylphenol), N-nitrosophenylhydroxylamine first cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N -Nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tertiary butyl -4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-( N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthalene)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane , 1,3,5-tris(4-tertiary butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H ,5H)-triketone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 2,2,6,6-tetramethylpiperidine 1-oxyl radical, Thiosulfone, Phytoxanthine, 1,1-Diphenyl-2-Picrylhydrazino, Copper(II) Dibutyl Dithiocarbonate, Nitrobenzene, N-Nitroso-N-Phenylhydroxylamine Aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. Also, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used, and the content is incorporated in this specification.

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

The polymerization inhibitor may be only 1 type, or may be 2 or more types. When there are two or more kinds of polymerization inhibitors, it is preferable that the total is within the above-mentioned range.

＜Other additives＞ The resin composition of the present invention can contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, as needed, within the range of obtaining the effects of the present invention , antioxidants, photoacid generators, anti-coagulation agents, phenolic compounds, other polymer compounds, plasticizers and other additives (such as defoamers, flame retardants, etc.), etc. Properties such as film physical properties can be adjusted by appropriately containing these components. For these components, for example, reference can be made to the descriptions in paragraphs 0183 and later of Japanese Patent Application Laid-Open No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013/0034812 specification), and the descriptions in Japanese Patent Laid-Open No. 2008-250074. 0101-0104, 0107-0109, etc., these contents are incorporated into this specification. When compounding these additives, the total compounding amount thereof is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

〔Surfactant〕 As the surfactant, various surfactants such as fluorine-based surfactants, polysiloxane-based surfactants, and hydrocarbon-based surfactants can be used. The surfactant can be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (especially fluidity) when it is made into a coating liquid can be further improved, and the uniformity of coating thickness and liquid-saving property can be further improved. That is, when a film is formed by applying a coating solution containing a surfactant-containing composition, the interfacial tension between the surface to be coated and the coating solution decreases, thereby improving wettability to the surface to be coated, and Improves coatability on the surface to be coated. Therefore, it is possible to more preferably form a film having a uniform thickness with less thickness unevenness.

Examples of fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479 , MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (the above are manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, Novec FC4432 (the above are manufactured by 3M Japan Limited), Surflon S-382 , Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon SC-393, Surflon KH-40 (the above are ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and compounds described in paragraphs 0117-0132 of JP-A-2011-132503 can also be used, and these contents are incorporated in this specification. . A block polymer can also be used as a fluorine-type surfactant, and as a specific example, the compound described in Unexamined-Japanese-Patent No. 2011-89090 is mentioned, The content is incorporated in this specification. Fluorine-based surfactants can also preferably use fluorine-containing polymer compounds (including repeating units derived from (meth)acrylate compounds with fluorine atoms and derived from 2 or more (preferably 5 or more) As the repeating unit of (meth)acrylate compound of alkyleneoxy group (preferably ethyleneoxy group, propyleneoxy group), the following compounds can also be exemplified as the fluorine-based surfactant used in the present invention. [chemical formula 63]

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

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

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

Examples of hydrocarbon-based surfactants include PIONIN A-76, NEWKALGEN FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, PIONIN P-4050-T, etc. (the above are manufactured by TAKEMOTO OIL & FAT CO.,LTD), etc.

Glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerin propoxylate, glycerol ethoxylate, etc.) can be exemplified as nonionic surfactants. compounds, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilauryl ether esters, macrogol distearate, sorbitan fatty acid esters, etc. Commercially available products include PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF Corporation), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF Corporation), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT CO ., LTD), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry CO., Ltd.), etc.

Specific examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer POLYFLOW No. 75, No.77, No.90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), etc.

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

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

〔Higher fatty acid derivatives〕 In order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide can be added to the resin composition of the present invention so that it is biased in the drying process after coating. surface of the resin composition.

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

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

〔Thermal polymerization initiator〕 The resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates free radicals by thermal energy, and initiates or accelerates the polymerization reaction of polymerizable compounds. Since the polymerization reaction of resin and a polymeric compound can also be advanced by adding a thermal radical polymerization initiator, solvent resistance can be improved further. In addition, the above-mentioned photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

As a thermal radical polymerization initiator, the compound described in paragraph 0074-0118 of Unexamined-Japanese-Patent No. 2008-063554 is mentioned specifically, The content is incorporated in this specification.

When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15% by mass, relative to the total solid content of the resin composition of the present invention. . A thermal-polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.

〔Inorganic particles〕 The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.

The average particle diameter of the inorganic particles is preferably from 0.01 to 2.0 μm, more preferably from 0.02 to 1.5 μm, still more preferably from 0.03 to 1.0 μm, and particularly preferably from 0.04 to 0.5 μm. The said average particle diameter of an inorganic particle is a primary particle diameter, and is a volume average particle diameter. The volume average particle diameter can be measured by the dynamic light scattering method based on Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO., LTD.). When it is difficult to perform the above measurement, it can also be measured by the centrifugal sedimentation light transmission method, the X-ray transmission method, and the laser diffraction/scattering method.

〔UV absorber〕 The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and trisulfone-based ultraviolet absorbers can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-tertiary butylphenyl salicylate, etc., as benzophenone-based ultraviolet absorbers. Examples of agents include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxydiphenyl Methanone etc. Also, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl)-5-chlorobenzotriazole, 2 -(2'-Hydroxy-3'-tertiary butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-Hydroxy-3'-tertiary pentyl-5' -isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2- (2'-Hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-Hydroxy-3',5'-di-tertiary butyl Phenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetra Methyl) phenyl] benzotriazole, etc.

Examples of substituted acrylonitrile-based UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, etc. . Furthermore, as an example of a trioxane-based ultraviolet absorber, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6- Bis(2,4-Dimethylphenyl)-1,3,5-trimethanone, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxybenzene base]-4,6-bis(2,4-dimethylphenyl)-1,3,5-trimethylphenyl, 2-(2,4-dihydroxyphenyl)-4,6-bis(2, 4-Dimethylphenyl)-1,3,5-trimethanone and other mono(hydroxyphenyl)trimethanium compounds; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-( 2,4-Dimethylphenyl)-1,3,5-trimethanone, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methyl phenyl)-1,3,5-trimethanone, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl )-1,3,5-tris(hydroxyphenyl)tris(hydroxyphenyl)tris(2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxy) phenyl)-1,3,5-trimethanone, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-trimethanium, 2,4,6- Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-trisanthene and other tris(hydroxyphenyl)trisanthene compounds, etc.

In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more. The composition of the present invention may or may not contain an ultraviolet absorber, but when included, the content of the ultraviolet absorber is 0.001% by mass to 1% by mass relative to the total solid content of the composition of the present invention Below is preferable, and 0.01 mass % or more and 0.1 mass % or less are more preferable.

〔Organotitanium compound〕 The resin composition of this embodiment may contain an organic titanium compound. When the resin composition contains the organotitanium compound, it is possible to form a resin layer having excellent chemical resistance even when cured at a low temperature.

Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organic titanium compounds are shown in the following I) to VII). I) Chelate titanium compound: Among them, a chelate titanium compound having two or more alkoxy groups is more preferable in terms of excellent storage stability of the resin composition and good hardening pattern. Specific examples are bis(triethanolamine)diisopropoxytitanium, bis(n-butoxy)bis(2,4-glutarate)titanium, diisopropoxybis(2,4-glutarate) ) titanium, diisopropoxy bis (tetramethylpimelate) titanium, diisopropoxy bis (ethyl acetylacetate) titanium, etc. II) Tetraalkoxytitanium compounds: such as tetra(n-butoxy)titanium, tetraethoxytitanium, tetrakis(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium Titanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonyloxy)titanium, tetra(n-propoxy)titanium, tetrastearyloxytitanium, Tetra[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc. III) Titanocene compounds: e.g. pentamethylcyclopentadienetrimethoxytitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium , bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Monoalkoxytitanium compound: For example, tris(dioctyl phosphate) isopropoxytitanium, tris(dodecylbenzenesulfonate)isopropoxytitanium, and the like. V) Titanium oxide compound: For example, bis(glutarate)titanium oxide, bis(tetramethylpimelate)titanium oxide, titanium phthalocyanine oxide, and the like. VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetonate and the like. VII) Titanate coupling agent: for example, isopropyl docosylbenzenesulfonyl titanate and the like.

Among them, the organotitanium compound is selected from the group consisting of the above-mentioned I) chelated titanium compound, II) tetraalkoxytitanium compound and III) titanocene compound from the viewpoint of exhibiting better chemical resistance. At least one compound is preferred. In particular, diisopropoxybis(ethyl acetate)titanium, tetrakis(n-butoxy)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-bis Fluoro-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

When an organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the specific resin. When the compounding amount is 0.05 parts by mass or more, the obtained cured pattern more effectively exhibits good heat resistance and chemical resistance, while on the other hand, when the amount is 10 parts by mass or less, the storage stability of the composition is more excellent.

〔Antioxidants〕 The compositions of the present invention may contain antioxidants. By containing an antioxidant as an additive, the tensile properties of the film after hardening and the adhesiveness with a metal material can be improved. As an antioxidant, a phenolic compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. A hindered phenol compound is mentioned as a preferable phenol compound. A compound having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) is preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Also, as an antioxidant, a compound having a phenol group and a phosphite group in the same molecule is also preferable. Moreover, phosphorus antioxidant can also be used preferably as an antioxidant. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2] Dioxaphosphine-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tertiary butyldibenzo[d,f] [1,3,2]dioxaphosphine-2-yl)oxy]ethyl]amine, bis(2,4-di-tertiary-butyl-6-methylphenylphosphite ) ethyl ester etc. Examples of commercially available antioxidants include ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60, and ADEKA STAB AO-60. STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (the above are manufactured by ADEKA CORPORATION), etc. In addition, as an antioxidant, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, and the content is incorporated in this specification. Moreover, the composition of this invention may contain a latent antioxidant as needed. As a potential antioxidant, there can be mentioned a compound in which the part acting as an antioxidant is protected by a protecting group. In this compound, the protecting group is heated at 100-250° C. ~200°C is heated to detach, thereby functioning as an antioxidant. Examples of potential antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Laid-Open No. 2017-008219, the contents of which are incorporated in this specification. As a commercial item of a latent antioxidant, ADEKA ARKLS GPA-5001 (made by ADEKA CORPORATION) etc. are mentioned. As examples of preferred antioxidants, 2,2-thiobis(4-methyl-6-tertiary butylphenol), 2,6-two-tertiary butylphenol and formula (3) indicated compound.

[chemical formula 64]

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

The compound represented by formula (3) suppresses the oxidation degradation of the aliphatic group and phenolic hydroxyl group which the resin has. In addition, metal oxidation can be suppressed by the antirust effect on metal materials.

In order to act simultaneously on the resin and the metal material, k is more preferably an integer of 2-4. Examples of R ⁷ include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, A vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, a combination thereof, and the like may further have a substituent. Among them, it is preferable to have an alkyl ether or -NH- from the viewpoint of solubility in a developer and metal adhesion, and from the viewpoint of interaction with a resin and metal adhesion by formation of a metal complex , -NH- is more preferred.

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

[chemical formula 65]

[chemical formula 66]

[chemical formula 67]

[chemical formula 68]

The amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. By setting the addition amount to 0.1 parts by mass or more, even in a high-temperature and high-humidity environment, it is easy to obtain the effects of tensile properties and improved adhesion to metal materials, and by setting it to 10 parts by mass or less, for example, using The interaction with the photosensitizer improves the sensitivity of the resin composition. Antioxidant may use only 1 type, and may use 2 or more types. When using 2 or more types, it is preferable that these total amounts are in the said range.

〔Anti-coagulation agent〕 The resin composition of this embodiment may contain an anti-agglomeration agent as needed. Sodium polyacrylate etc. are mentioned as an anti-agglomeration agent.

In the present invention, one type of anti-aggregation agent may be used alone, or two or more types may be used in combination. The composition of the present invention may or may not contain an anti-aggregating agent, but when included, the content of the anti-aggregating agent is 0.01% by mass or more and 10% by mass relative to the total solid content of the composition of the present invention. Below is preferable, and 0.02 mass % or more and 5 mass % or less are more preferable.

〔Phenolic compounds〕 The resin composition of this embodiment may contain a phenolic compound as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP- CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR -PTBP, BIR-BIPC-F (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), etc.

In the present invention, the phenolic compound may be used alone or in combination of two or more. The composition of the present invention may or may not contain a phenolic compound, but when included, the content of the phenolic compound is 0.01% by mass or more and 30% by mass relative to the total solid content of the composition of the present invention. Below is preferable, and 0.02 mass % or more and 20 mass % or less are more preferable.

〔Other polymer compounds〕 Examples of other polymer compounds include siloxane resins, (meth)acrylic acid polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. wait. Other high molecular compounds may be modified bodies introduced with cross-linking groups such as methylol, alkoxymethyl, and epoxy groups.

In the present invention, other polymer compounds may be used alone or in combination of two or more. The composition of the present invention may or may not contain other high molecular compounds, but when included, the content of other high molecular compounds relative to the total solid content of the composition of the present invention is 0.01% by mass or more and 30 mass % or less is preferable, and 0.02 mass % or more and 20 mass % or less are more preferable.

<Characteristics of the resin composition> The viscosity of the resin composition of the present invention can be adjusted according to the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000mm ² /s to 12,000mm ² /s is preferable, 2,000mm ² /s to 10,000mm ² /s is more preferable, and 2,500mm ² /s to 8,000mm ² /s is more preferable for further improvement. As long as it is within the above range, it is easy to obtain a coating film with high uniformity. For example, if it is 1,000 mm ² /s or more, it will be easy to coat with a film thickness required as an insulating film for rewiring, and if it is 12,000 mm ² /s or less, a coating film with excellent coating surface shape can be obtained.

<Restrictions on Substances Contained in Resin Composition> The 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 still more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of a resin composition will improve. As a method for maintaining the water content, humidity adjustment under storage conditions, porosity reduction of the storage container during storage, and the like can be mentioned.

From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million (parts per million)), more preferably less than 1 mass ppm, and less than 0.5 mass ppm for further improvement. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel and the like, but metals contained as complexes of organic compounds and metals are excluded. When a plurality of metals are included, the total of these metals is preferably within the above range.

In addition, as a method of reducing metal impurities accidentally included in the resin composition of the present invention, the following method can be mentioned: selecting a raw material with a small metal content as the raw material constituting the resin composition of the present invention, and improving the composition of the resin composition of the present invention. The raw material of the product is filtered through a filter, and the inside of the device is lined with polytetrafluoroethylene, etc., and the distillation is carried out under the condition of suppressing pollution as much as possible.

With regard to the resin composition of the present invention, considering the use as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosion. Mass ppm is further preferred. Among them, those present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is preferably within the above-mentioned ranges. As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.

As a container for the resin composition of the present invention, a conventionally known container can be used. Also, as a storage container, for the purpose of preventing impurities from being mixed into the raw material or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is composed of 6 kinds of 6-layer resins, or a bottle with 7-layer structure formed by 6 kinds of resins. . As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

＜Cured product of resin composition＞ By curing the resin composition of the present invention, a hardened product of the resin composition can be obtained, The cured product of the first aspect of the present invention is a cured product obtained by curing the resin composition of the present invention. The hardening of the resin composition is preferably performed by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, more preferably in the range of 140°C to 380°C, and in the range of 170°C to 350°C The inside is especially good.

The cured product of the second aspect of the present invention includes a resin and a tertiary amine having a ketone group and a cyclic structure. The above-mentioned resin is the resin contained in the above-mentioned resin composition modified by heating (for example, the precursor of the cyclized resin is cyclized, and the polymerizable group contained in the resin is polymerized with other resins or polymerizable compounds. successful) is preferred. According to such an aspect, the cured product has excellent pattern squareness. As described above, it is considered that the diffusibility of the tertiary amine is excellent, so the cured product according to the second aspect of the present invention is considered to be excellent in squareness. In addition, it is considered that the reaction by alkali in the resin layer such as cyclization of the resin proceeds easily and uniformly, and as a result, the cured product is also excellent in elongation at break. Furthermore, it is considered that the reduction of polymerizable groups such as C=C groups contained in resins and polymerizable compounds due to the reaction with the above-mentioned base can be suppressed, so the crosslinking density in the cured film becomes high and the chemical resistance is also excellent. In addition, it is considered that the second aspect of the present invention is also excellent in the adhesion between the cured product and the metal because the base of the tertiary amine is higher than that of the secondary amine and the migration of metal ions from the metal to the cured product is easily suppressed. . The preferable aspect of the tertiary amine which has the said ketone group and a cyclic structure is the same as the preferable aspect of the tertiary amine which has a ketone group and a cyclic structure contained in the said resin composition. In the present invention, the cured product of the first aspect and the cured product of the second aspect are simply collectively referred to as "hardened product". Also, the cured product of the first aspect of the present invention may contain a tertiary amine having a ketone group and a cyclic structure.

From the viewpoint of adhesion to metal, the content of the tertiary amine having a ketone group and a cyclic structure relative to the total mass of the cured product of the present invention is preferably 0.010 to 0.100% by mass, and 0.015 to 0.050% by mass. More preferably, 0.020-0.030 mass % is still more preferable.

The form of the cured product of the present invention is not particularly limited, and film, rod, spherical, granular and the like can be selected according to the application. In the present invention, it is preferable that the cured product is in the form of a film. In addition, by patterning the resin composition, the shape of the cured product can also be selected according to purposes such as forming a protective film on the wall surface, forming a via hole for conduction, adjusting impedance, capacitance, or internal stress, and imparting a heat dissipation function. The film thickness of the cured product (film composed of the cured product) is preferably not less than 0.5 μm and not more than 150 μm. The shrinkage rate of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less. Here, the shrinkage rate refers to the percentage of volume change before and after curing of the resin composition, and can be calculated according to the following formula. Shrinkage [%]=100-(volume after hardening ÷ volume before hardening)×100

<Characteristics of hardened resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or higher, more preferably 80% or higher, and still more preferably 90% or higher. If it is 70% or more, it may become a cured product excellent in mechanical properties. The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and still more preferably 230°C or higher.

＜Preparation of resin composition＞ The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and it can be performed by a conventionally known method. For mixing, mixing by a stirring blade, mixing by a ball mill, mixing by rotating the tank itself, etc. can be used. The temperature during mixing is preferably from 10 to 30°C, more preferably from 15 to 25°C.

Moreover, for the purpose of removing foreign substances such as dust and fine particles in the resin composition of the present invention, it is preferable to perform filtration using a filter. Regarding the filter pore size, for example, an aspect of 5 μm or less is mentioned, preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, HDPE (high density polyethylene) is more preferable. Filters can be used pre-cleaned with organic solvents. In the filtration step of the filter, a plurality of types of filters may be used in series or parallel connection. When using multiple types of filters, filters with different pore diameters or materials can be used in combination. As an aspect of connection, for example, an aspect in which an HDPE filter with a pore diameter of 1 μm is used as the first stage, an HDPE filter with a pore diameter of 0.2 μm is used as the second stage, and both are connected in series. Also, various materials can be filtered multiple times. When filtering multiple times, it can be cyclic filtering. In addition, pressure filtration may be performed. In the case of pressure filtration, for example, the applied pressure is 0.01 MPa to 1.0 MPa, preferably 0.03 MPa to 0.9 MPa, more preferably 0.05 MPa to 0.7 MPa, and 0.05 MPa It is more preferably above and below 0.5 MPa. In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, known adsorbents can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtering with a filter, a step of degassing the resin composition filled in the bottle under reduced pressure may be further performed.

(Manufacturing method of hardened product) The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film. In addition, the method for producing a cured product of the present invention includes the above-mentioned film forming step, an exposure step of selectively exposing the film formed in the film forming step, and developing the film exposed in the exposing step using a developer to form a pattern. The development step is better. The method for producing a cured product of the present invention includes the above-mentioned film forming step, the above-mentioned exposure step, the above-mentioned developing step, a heating step of heating the pattern obtained in the developing step, and a post-development step of exposing the pattern obtained in the developing step. At least one of the exposure steps is particularly preferred. Moreover, it is also preferable that the production method of the present invention includes the above-mentioned film forming step and the step of heating the above-mentioned film. The details of each step will be described below.

＜Film formation process＞ The resin composition of the present invention can be used in a film forming step for forming a film on a base material. The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film.

〔Substrate〕 The type of substrate can be appropriately determined according to the application, and examples include substrates for semiconductor production such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, deposited films, and magnetic films. , reflective film, metal substrates such as Ni, Cu, Cr, Fe (for example, the substrate and metal layer formed of metal can be any of the substrates formed by plating, deposition, etc.), paper, SOG (Spin On Glass: spin-on glass), TFT (Thin Film Transistor) array substrate, mold substrate, electrode plate of plasma display panel (PDP), etc., are not particularly limited. In the present invention, especially, a base material for semiconductor production is preferable, and a silicon base material, a Cu base material, and a mold base material are more preferred. In addition, layers such as an adhesive layer and an oxide layer formed of hexamethyldisilazane (HMDS) or the like may be provided on the surface of these substrates. Moreover, the shape of a base material is not specifically limited, It may be a circular shape, or may be a rectangular shape. As a dimension of a base material, if it is a circular shape, it is 100-450 mm in diameter, for example, Preferably it is 200-450 mm. If it is a rectangular shape, the length of a short side is 100-1000 mm, for example, Preferably it is 200-700 mm. Also, as the base material, for example, a plate-shaped base material (substrate) can be used, and it is preferable to use a panel-shaped base material (substrate).

Also, when a resin composition is applied to the surface of a resin layer (for example, a layer made of a cured product) or a metal layer to form a film, the resin layer and the metal layer serve as base materials.

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

As the applicable method, specifically, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slot coating method, etc. Coating method and inkjet method, etc. From the viewpoint of film thickness uniformity, spin coating method, slit coating method, spray coating method, or inkjet method are more preferable. From the viewpoint of film thickness uniformity and productivity, spin coating method and slit coating method Slot coating is preferred. A film having a desired thickness can be obtained by adjusting the solid content concentration of the resin composition and coating conditions according to the method. In addition, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, and inkjet methods are preferred. For rectangular substrates, slit coating is preferred. Cloth method or spraying method, inkjet method, etc. are preferred. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. In addition, a method of transferring a coating film formed on a dummy support in advance by the above-mentioned application method to a base material can also be applied. Regarding the transfer method, in the present invention, the production method described in paragraphs 0023, 0036-0051 of JP-A-2006-023696 or paragraphs 0096-0108 of JP-A-2006-047592 can also be preferably used. . Moreover, you may perform the process of removing an excess film at the edge part of a base material. Examples of such steps include edge bead rinse (EBR), backside rinse, and the like. In addition, a pre-wetting step may also be adopted: before applying the resin composition to the substrate, after applying various solvents to the substrate to improve the wettability of the substrate, and then applying the resin composition.

＜Drying procedure＞ The above-mentioned film may be used in a step (drying step) of drying the formed film (layer) to remove the solvent after the film forming step (layer forming step). That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step. Moreover, it is preferable to perform the said drying process after a film formation process and before an exposure process. The drying temperature of the film in the drying step is preferably from 50°C to 150°C, more preferably from 70°C to 130°C, and still more preferably from 90°C to 110°C. Moreover, drying can be performed by reducing pressure. As a drying time, 30 seconds - 20 minutes can be illustrated, Preferably it is 1 minute - 10 minutes, More preferably, it is 2 minutes - 7 minutes.

<Exposure step> The above-mentioned film can be used in the exposure step of selectively exposing the film. That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed in the film formation step. Selective exposure refers to exposing a portion of the film. Moreover, by selective exposure, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film. The amount of exposure is not particularly limited as long as it can harden the resin composition of the present invention. For example, in terms of exposure energy at a wavelength of 365 nm, it is preferably 50 to 10,000 mJ/cm ² , more preferably 200 to 8,000 mJ/cm ² good.

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

Regarding the exposure wavelength, in terms of the relationship with the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamp, (3) High-pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide wavelength (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF quasi- Molecular laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ₂ excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) ) YAG laser second harmonic 532nm, third harmonic 355nm, etc. Regarding the resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferable, and among them, exposure by i-rays is preferable. Accordingly, particularly high exposure sensitivity can be obtained. In addition, the method of exposure is not particularly limited, as long as at least a part of the film composed of the resin composition of the present invention is exposed, exposure using a photomask, exposure by laser direct imaging, etc. .

＜Heating step after exposure＞ The above film may be used in a heating step after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposing step. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably from 50°C to 140°C, more preferably from 60°C to 120°C. The heating time in the post-exposure heating step is preferably from 30 seconds to 300 minutes, more preferably from 1 minute to 10 minutes. Regarding the rate of temperature increase in the post-exposure heating step, from the temperature at the start of heating to the maximum heating temperature, it is preferably 1 to 12°C/minute, more preferably 2 to 10°C/minute, and further preferably 3 to 10°C/minute. better. In addition, the rate of temperature increase can be appropriately changed during the heating process. The heating method in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters, and the like can be used. Moreover, when heating, it is also preferable to carry out under the environment of low oxygen concentration by passing inert gas, such as nitrogen, helium, and argon.

＜Development step＞ The said film after exposure can be used in the image development process which develops with a developing solution and forms a pattern. That is, the method for producing a cured product of the present invention may include a developing step of developing a film exposed in the exposing step using a developer to form a pattern. By developing, one of the exposed part and the non-exposed part of a film is removed, and a pattern is formed. Here, the image development that removes the non-exposed portion of the film by the image development step is called negative image development, and the image image that removes the exposed portion of the film by the image image development step is called positive image image development.

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

When the developing solution is an alkaline aqueous solution, the basic compounds that can be included in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably TMAH (hydroxide Tetramethylammonium), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyl di Ethylamine, Dimethylethanolamine, Triethanolamine, Tetraethylammonium Hydroxide, Tetrapropylamine Hydroxide, Tetrabutylamine Hydroxide, Tetrapentylamine Hydroxide, Tetrahexylamine Hydroxide, Tetraoctylamine Hydroxide Amine, Ethyltrimethylammonium Hydroxide, Butyltrimethylammonium Hydroxide, Methyltripentylammonium Hydroxide, Dibutyldipentylammonium Hydroxide, Dimethylbis(2-Hydroxyethylammonium Hydroxide) base) ammonium, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, piperidine, more preferably TMAH. For example, when TMAH is used, the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.3 to 3% by mass, based on the total amount of the developer.

When the developing solution contains an organic solvent, regarding the organic solvent, examples of the esters preferably include ethyl acetate, n-butyl acetate, amyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, Isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate ( Examples: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid methyl ester, ethyl ethoxy acetate, etc.)), alkyl 3-alkoxypropionate (e.g. methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionate Alkyl esters (e.g. methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g. methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy-2- Methyl methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl acetate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate etc., and as the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cyrusuacetate, ethyl cyrus Threoacetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N -Methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene, and cyclic terpenes such as As the argon, preferably dimethyl argon, and as alcohols, preferably methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol , propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and as amides, preferably N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide wait.

Moreover, when a developing solution contains an organic solvent, organic solvent can be used 1 type or in mixture of 2 or more types. In the present invention, especially, at least one developer selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone and cyclohexanone is included More preferably, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethylsulfide is more preferred, and a developer containing cyclopentanone is most preferred.

When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% by mass or more. Excellent. Moreover, the said content may be 100 mass %.

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

[How to supply the developer] The method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and there are the following methods: a method of immersing the substrate on which the film is formed in the developer, and supplying the developer with a nozzle to the film formed on the substrate. The method of spin immersion development or continuous supply of developer. The type of nozzle is not particularly limited, and examples thereof include straight-line nozzles, shower nozzles, and spray nozzles. From the perspective of the permeability of the developer, the removability of the non-image area, and the efficiency of production, the method of supplying the developer with a straight-line nozzle or the method of continuously supplying the developer with a spray nozzle is preferable. From the perspective of the developer to the image In view of the permeability of the part, the method of supplying with a spray nozzle is more preferable. In addition, the following steps may be adopted: after continuously supplying the developing solution through the DC nozzle, rotating the base material to remove the developing solution from the base material, and after spinning drying and continuously supplying the developing solution through the DC nozzle again, rotating the base material to remove the developing solution from the base material , and this step can also be repeated multiple times. Also, as a method for supplying the developing solution in the developing step, a step of continuously supplying the developing solution on the substrate, a step of maintaining the developing solution on the substrate in a substantially static state, or using ultrasonic wave or the like to apply the developing solution on the substrate can be adopted. The steps of vibrating and the steps of combining them, etc.

As developing time, 10 seconds - 10 minutes are preferable, and 20 seconds - 5 minutes are more preferable. The temperature of the developing solution at the time of image development is not specifically limited, Preferably it can carry out at 10-45 degreeC, More preferably, it can carry out at 18-30 degreeC.

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

〔rinsing fluid〕 When the developing solution is an alkaline aqueous solution, water, for example, can be used as a rinse solution. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse solution.

When the rinse solution contains an organic solvent, examples of esters include ethyl acetate, n-butyl acetate, pentyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, Isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate ( Examples: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid methyl ester, ethyl ethoxy acetate, etc.)), alkyl 3-alkoxypropionate (e.g. methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionate Alkyl esters (e.g. methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g. methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy-2- Methyl methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl acetate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate etc., and as the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cyrusuacetate, ethyl cyrus Threoacetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N -Methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene, and cyclic terpenes such as As the argon, preferably dimethyl argon, and as alcohols, preferably methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol , propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and as amides, preferably N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide wait.

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

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

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

[How to supply the rinse solution] The method of supplying the rinsing liquid is not particularly limited as long as the desired pattern can be formed, and there are the following methods: a method of immersing the base material in the rinsing liquid, a method of supplying the rinsing liquid on the base material by spin-coating, spraying, etc. A method of supplying a rinse liquid on a substrate by a shower head, and a method of continuously supplying a rinse liquid on a substrate by means of a straight-line nozzle or the like. From the viewpoint of the permeability of the rinse liquid, the removability of the non-image area, and the efficiency of production, the method of supplying the rinse liquid with a shower nozzle, a straight-line nozzle, a spray nozzle, etc., and the method of continuously supplying it with a spray nozzle are preferable. , from the viewpoint of the permeability of the rinse liquid to the image portion, the method of supplying it with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples thereof include straight-line nozzles, shower nozzles, and spray nozzles. That is, the rinsing step is preferably a step of supplying or continuously supplying a rinsing liquid to the above-mentioned exposed film using a straight-line nozzle, and more preferably a step of supplying a rinsing liquid through a spray nozzle. Also, as a method of supplying the rinse liquid in the rinse step, a step of continuously supplying the rinse liquid on the base material, a step of maintaining the rinse liquid on the base material in a substantially static state, and making the rinse liquid flow on the base material by ultrasonic wave or the like can be adopted. The steps of vibrating and the steps of combining them, etc.

The rinsing time is preferably from 10 seconds to 10 minutes, more preferably from 20 seconds to 5 minutes. The temperature of the rinsing solution during rinsing is not particularly limited, but it is preferably 10 to 45°C, more preferably 18 to 30°C.

＜Heating step＞ The pattern obtained by the developing step (the pattern after washing when the washing step is performed) can be used in the heating step of heating the pattern obtained by the above-mentioned developing. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the developing step. In addition, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing the developing step or a film obtained by the film forming step. In the heating step, resins such as polyimide precursors are cyclized into resins such as polyimide. In addition, crosslinking of unreacted crosslinkable groups in a specific resin or a crosslinking agent other than the specific resin is also performed. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, still more preferably 150 to 250°C, still more preferably 160 to 250°C, and more preferably 160 to 250°C. 230°C is particularly preferred.

The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern using the action of the base or the like generated from the base generator by heating.

It is preferable to carry out the heating in the heating step at a temperature increase rate of 1 to 12° C./min from the temperature at the start of heating to the highest heating temperature. The temperature increase rate is more preferably 2 to 10° C./minute, more preferably 3 to 10° C./minute. By setting the temperature increase rate at 1° C./min or more, excessive volatilization of acid or solvent can be prevented while ensuring productivity, and by setting the temperature increase rate at 12° C./min or less, residual stress of the cured product can be relaxed. In addition, in the case of an oven capable of rapid heating, it is better to carry out the temperature increase rate from the temperature at the beginning of heating to the highest heating temperature at a rate of 1 to 8°C/sec, more preferably 2 to 7°C/sec, and 3 to 7°C/sec. 6° C./second is more preferable.

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

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

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

Heating can be done in stages. As an example, the following steps can be performed: ramping from 25°C to 120°C at 3°C/min and holding at 120°C for 60 minutes, ramping from 120°C to 180°C at 2°C/min and holding at 180°C for 120 minutes. Moreover, as described in US Patent No. 9159547, it is also preferable to perform treatment while irradiating ultraviolet rays. The properties of the membrane can be improved by such pretreatment steps. The pretreatment step can be carried out within a short period of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more stages. For example, the first stage pretreatment step may be performed at 100°C to 150°C, and the second stage pretreatment step may be performed at 150°C to 200°C. Furthermore, cooling may be performed after heating, and the cooling rate at this time is preferably 1 to 5° C./min.

Regarding the heating step, it is preferable to carry out under reduced pressure by flowing an inert gas such as nitrogen, helium, or argon in an environment with a low oxygen concentration from the viewpoint of preventing decomposition of a specific resin. The oxygen concentration is preferably not more than 50 ppm (volume ratio), more preferably not more than 20 ppm (volume ratio). It does not specifically limit as a heating method in a heating process, For example, a hot plate, an infrared oven, an electric oven, a hot-air oven, an infrared oven, etc. are mentioned.

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

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

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

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. The method of recording. For example, photolithography, PVD (Physical Deposition), CVD (Chemical Vapor Deposition), lift off, electrolytic plating, electroless plating, etching, printing, methods combining these, and the like can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating are mentioned. As a preferable aspect of electroplating, electrolytic plating using a copper sulfate electroplating solution and a copper cyanide electroplating solution is mentioned.

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

＜Use＞ Examples of fields to which the method for producing a cured product of the present invention or the cured product of the present invention can be applied include insulating films of electronic devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. Other examples include sealing films, substrate materials (base film, cover film, and interlayer insulating film for flexible printed circuit boards), or cases where patterns are formed on insulating films for actual mounting applications such as those described above by etching. Regarding such uses, for example, Science & Technology Co., Ltd. "Highly functionalized and applied technology of polyimide" April 2008, Masakimoto Kakimoto/Supervisor, CMC Technical Library "Polyimide materials "Basic and Development of Polyimide" published in November 2011, edited by the Japan Polyimide and Aromatic Polymer Research Society/edited "Basic and Application of the Latest Polyimide" NTS, August 2010, etc.

In addition, the method for producing a cured product of the present invention or the cured product of the present invention can also be used in the production of offset printing plates or screen plates, the use of molded parts in etching, and protective varnishes and dielectrics in electronics, especially microelectronics. Fabrication of electrical layers, etc.

(Laminated body and method for manufacturing the laminated body) The layered system of the present invention refers to a structure having a plurality of layers composed of the cured product of the present invention. The layered system of the present invention may be a layered body comprising two or more layers of hardened materials, or may be a layered body formed by layering three or more layers. Among the two or more layers composed of the above-mentioned cured product contained in the above-mentioned laminated body, at least one layer is a layer composed of the cured product of the present invention. It is also preferable that all the layers composed of the cured product included in the above laminate are layers composed of the cured product of the present invention.

That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the steps of the method for producing a laminate of the present invention a plurality of times.

The laminate of the present invention includes two or more layers made of cured products, and it is preferable that any layer made of the above-mentioned cured products contains a metal layer between each other. It is preferable that the above-mentioned metal layer is formed by the above-mentioned metal layer forming step. That is, it is preferable that the method for producing a laminate of the present invention further includes a metal layer forming step of forming a metal layer on a layer made of the cured product between performing the manufacturing method of the cured product a plurality of times. A preferred aspect of the metal layer forming step is as described above. As the above-mentioned laminate, for example, a laminate having a layer structure including at least three layers in which a layer composed of a first cured product, a metal layer, and a layer composed of a second cured product are sequentially laminated is preferred. . It is preferable that both the layer composed of the first cured product and the layer composed of the second cured product are layers composed of the cured product of the present invention. The resin composition of the present invention for forming the layer composed of the above-mentioned first cured product and the resin composition of the present invention for forming the layer composed of the above-mentioned second cured product may have the same composition or may be form different compositions. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a rewiring layer.

＜Stacking procedure＞ It is preferable that the manufacturing method of the laminated body of this invention includes a lamination step. The lamination step includes (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step and A series of steps of at least one of post-development exposure steps. However, at least one of the (a) film forming step, (d) heating step, and post-development exposure step may be repeated. Moreover, (e) metal layer formation process may be included after at least 1 of (d) heating process and post-development exposure process. Obviously, the above-mentioned drying step and the like may be further appropriately included in the lamination step.

When the layering step is further performed after the layering step, a surface activation treatment step may be further performed after the above-mentioned exposure step, after the above-mentioned heating step, or after the above-mentioned metal layer forming step. As the surface activation treatment, plasma treatment is exemplified. Details of the surface activation treatment will be described later.

It is better to carry out the above lamination step 2 to 20 times, more preferably 2 to 9 times. For example, a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer or the like is preferably a structure in which the resin layer is 2 or more and 20 or less, and it is more than 2 and 9 layers. The structure below the layer is further preferable. The composition, shape, film thickness, etc. of each of the above-mentioned layers may be the same or different.

In the present invention, after providing the metal layer, it is preferable to further form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer. Specifically, at least one of (a) film formation step, (b) exposure step, (c) development step, (d) heating step, and post-development exposure step, (e) metal layer formation step or an aspect in which the order of (a) film forming step, (d) at least one of heating step and post-development exposure step, and (e) metal layer forming step is repeated. By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer forming step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately laminated.

(Surface Activation Treatment Step) The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a part of the metal layer and the resin composition layer to a surface activation treatment. The surface activation treatment step is usually performed after the metal layer formation step, but it may also be performed after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) to surface activate the resin composition layer. The processing step is followed by a metal layer forming step. The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the exposed resin composition layer, or may be performed on at least a part of both the metal layer and the exposed resin composition layer. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is more preferred to perform the surface activation treatment on a part or all of the region of the metal layer on which the resin composition layer is formed. Thus, by surface-activating the surface of a metal layer, the adhesiveness with the resin composition layer (film) provided on the surface can be improved. In addition, it is also preferable to perform the surface activation treatment on a part or all of the exposed resin composition layer (resin layer). Thus, by performing surface activation treatment on the surface of the resin composition layer, the adhesiveness with the metal layer and resin layer provided in the surface activation-treated surface can be improved. In particular, when the resin composition layer is hardened, such as when performing negative tone development, it is less likely to be damaged by surface treatment, and it is easier to improve the adhesiveness. As the surface activation treatment, specifically, it can be selected from plasma treatment, corona discharge treatment, CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ etching treatment, surface treatment by ultraviolet (UV) ozone method, dipping in hydrochloric acid aqueous solution to remove oxide film, dipping Treatment in an organic surface treatment agent of at least one compound of amine group and thiol group, mechanical roughening treatment using a brush, plasma treatment is preferable, especially oxygen plasma treatment using oxygen as a raw material gas is better. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J/m ² , more preferably 1,000 to 100,000 J/m ² , and most preferably 10,000 to 50,000 J/m ² .

(Semiconductor device and manufacturing method thereof) Furthermore, the present invention also discloses a semiconductor device including the cured product of the present invention or the laminate of the present invention. Furthermore, the present invention also discloses a method of manufacturing a semiconductor device including the method of manufacturing a cured product of the present invention or the method of manufacturing a laminate of the present invention. As a specific example of a semiconductor device in which the resin composition of the present invention is used to form an interlayer insulating film for a rewiring layer, reference can be made to the description in paragraphs 0213 to 0218 of JP-A-2016-027357 and the description in FIG. 1 . The content is incorporated into this manual. [Example]

Hereinafter, the present invention will be described in more detail with reference to examples. Materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed unless departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

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

[Synthesis Example 2: Synthesis of the Precursor of Cyclized Resin (Resin 2)] Mix 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme (diethylene glycol dimethyl Ether) was stirred at 60°C for 4 hours to synthesize the diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10°C, and 17.0 g of thionyl chloride was added over 60 minutes while maintaining the temperature at -10±5°C. After diluting with 50mL of N-methylpyrrolidone, a solution of 12.6g of 4,4'-diaminodiphenyl ether dissolved in 100mL of N-methylpyrrolidone was heated at -10±5°C It was added dropwise to the reaction mixture over 60 minutes, and the mixture was stirred at room temperature for 2 hours. Thereafter, 10.0 g of ethanol was added, followed by stirring at room temperature for 1 hour. Next, 6000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was collected by filtration and dissolved in 500 g of tetrahydrofuran. 6000 g of water (poor solvent) was added to the obtained solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (polyimide precursor solid) after stirring was filtered again, and it dried at 45 degreeC under reduced pressure for 3 days. After dissolving 46.6 g of the dried powder in 419.6 g of tetrahydrofuran, 2.3 g of triethylamine was added, followed by stirring at room temperature for 35 minutes. Then, 3000 g of ethanol was added, and the deposit was collected by filtration. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by Ambertech Limited) were added thereto, and stirred for 4 hours. Thereafter, the ion exchange resin was filtered off, and the obtained polymer solution was added to a mixed solution of 4500 g of heptane and 500 g of ethyl acetate to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45° C. for 24 hours to obtain 45.1 g of resin 2 . The structure of the resin 2 is presumed to be represented by the following formula (P-2). As a result of measuring the molecular weight of the resin 2 by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000. In addition, resin 1 having a Mw of 5,000, resin 2 having a Mw of 10,000, and resin 2 having a Mw of 30,000 were also synthesized by appropriately adjusting the equivalent of 4,4'-diaminodiphenyl ether.

[Synthesis examples 3-8: Synthesis of precursors of cyclized resins (resin 3-resin 8)] Resin 3- Resin8. The Mw of resin 3 is 20,000, the Mw of resin 4 is 20,000, the Mw of resin 5 is 20,000, the Mw of resin 6 is 20,000, the Mw of resin 7 is 20,000, and the Mw of resin 8 is 20,000.

[化學式70]

[chemical formula 69]

[chemical formula 70]

[Synthesis Example 9: Synthesis of Resin 9] 30.78 parts by mass of cyclohexanone were heated to 80° C. under a nitrogen stream. While stirring the liquid, 10.21 parts by mass of 2-oxotetrahydrofuran-3-yl methacrylate, 11.78 parts by mass of 1-isopropylcyclopentyl methacrylate, and 57.17 parts by mass of cyclohexanone were added dropwise thereto over 6 hours. Parts by mass and a mixed solution of 0.44 parts by mass of dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by FUJIFILM Wako Pure Chemical Corporation]. After completion of the dropwise addition, stirring was further carried out at 80° C. for 2 hours. After naturally cooling the reaction solution, reprecipitation was carried out with a large amount of methanol/water (9:1 mass ratio), the obtained solid was filtered, and vacuum-dried to obtain 18.69 parts by mass of resin 9 which is an acid-decomposable resin. The structure of resin 9 is presumed to be a structure represented by the following formula (P-9). As a result of measuring the molecular weight of the resin 9 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000.

[Synthesis Example 10: Synthesis of Resin 10] 40.24 parts by mass of cyclohexanone was heated to 80° C. under a nitrogen stream. While stirring the liquid, 11.56 parts by mass of 2-oxohexahydro-2H-3,5-methanecyclopentane[b]furan-6-ylmethacrylate, 1-(1 -17.18 parts by mass of -methoxy-2,2-dimethylpropoxy)-4-vinylbenzene, 74.73 parts by mass of cyclohexanone, and dimethyl 2,2'-azobisisobutyrate [V- 601, manufactured by FUJIFILM Wako Pure Chemical Corporation] a mixed solution of 0.42 parts by mass. After completion of the dropwise addition, stirring was further carried out at 80° C. for 2 hours. After naturally cooling the reaction solution, reprecipitate with a large amount of methanol/water (mass ratio 9:1), filter and vacuum-dry the obtained solid to obtain 26.15 parts by mass of resin 10, which is an acid-decomposable resin. The structure of the resin 10 is presumed to be a structure represented by the following formula (P-10). As a result of measuring the molecular weight of the resin 10 by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 20,000. In the following formulae, the subscripts in parentheses indicate the content ratio (molar ratio) of each repeating unit. [chemical formula 71]

＜Example and Comparative Example＞ In each example, the components described in the following table were mixed, respectively, to obtain each resin composition. Moreover, in the comparative example, the components described in the following table|surface were mixed respectively, and the composition for comparison was obtained by this. Specifically, the content (compounding amount) of each component other than the solvent described in the table was the amount (parts by mass) described in the column of “parts by mass” in each column of the table. Let the content of the solvent (blend amount) be the value (mass %) at which the solid content concentration of the composition becomes the "solid content concentration" in the table, and let the ratio (mass ratio) of the content of each solvent to the total mass of the solvent be The ratio recorded in the "Ratio" column in the table. The obtained resin composition and the composition for comparison were subjected to pressure filtration using a polytetrafluoroethylene filter having a pore width of 0.8 μm. In addition, in the table, description of "-" shows that a composition does not contain a corresponding component.

[Table 1] Example comparative example Example Example Example Example Example Example Example Example Example Example Example Example Example 1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 composition resin type Resin 1 Resin 1 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator type I-2 I-2 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 base generator type A-1 AR-1 A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 A-13 parts by mass 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - polymerization inhibitor type B-2 B-2 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-2 C-2 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type E-1 E-1 - - - - - - - - - - - - - parts by mass 2.4 2.4 - - - - - - - - - - - - - type E-2 E-2 - - - - - - - - - - - - - parts by mass 0.9 0.9 - - - - - - - - - - - - - solvent type NMP NMP GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 45 45 40 40 40 40 40 40 40 40 40 40 40 40 40 type EL EL DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 exposure conditions m m m m m m m m m m m m m m m Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Developing conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 evaluate Evaluation of Pattern Rectangularity B D. B A A B A A B A B A A B A Elongation at break evaluation B D. C B B B B A A B A B B A A Drug Resistance Evaluation C D. C B B B B B C B C B B A A Adhesion evaluation with copper substrate A C A A A A A A A A A B A A B Amount of tertiary amine in cured product (mass%) 0.024 0.001 0.024 0.0277 0.0277 0.0267 0.0317 0.0375 0.0259 0.0405 0.0473 0.0277 0.0277 0.024 0.0277

[Table 2] Example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 15 16 17 18 19 20 twenty one twenty two twenty three twenty four 25 26 27 28 29 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 base generator type A-14 A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 parts by mass 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 exposure conditions m m m m m m m m m m m m m m m Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Developing conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 evaluate Evaluation of Pattern Rectangularity A A A A A A A A A A A A B A A Elongation at break evaluation B B B B B B B B B A A A A A B Drug Resistance Evaluation B B B B B B B B B C C C C C B Adhesion evaluation with copper substrate A A A B B A A B A A A A A A A Amount of tertiary amine in cured product (mass%) 0.0277 0.0277 0.0277 0.0277 0.0317 0.0405 0.0405 0.0277 0.0277 0.044 0.049 0.0392 0.0296 0.0269 0.0306

[table 3] Example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 base generator type A-29 A-30 A-31 A-32 A-33 A-34 A-35 A-36 A-37 A-38 A-39 A-40 A-1 A-1 A-1 parts by mass 2 2 2 2 2 2 2 2 2 2 2 2 3 1 1 type - - - - - - - - - - - - - - A-3 parts by mass - - - - - - - - - - - - - - 1 polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 exposure conditions m m m m m m m m m m m m m m m Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Developing conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 evaluate Evaluation of Pattern Rectangularity B B A C A A A A A B B B C B A Elongation at break evaluation A C B A A B A B A A C C A C B Drug Resistance Evaluation B A B C B B C B B C A A C C B Adhesion evaluation with copper substrate A A A A A A A A B A A A A A A Amount of tertiary amine in cured product (mass%) 0.0436 0.024 0.0339 0.0285 0.0379 0.0326 0.0448 0.0409 0.0487 0.0266 0.024 0.024 0.036 0.010 0.023

[Table 4] Example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 3 Resin 4 Resin 5 Resin 6 Resin 7 Resin 8 Resin 9 mw 20000 20000 20000 30000 10000 5000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 25 45 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 - M-1 - M-1 - parts by mass 6 6 6 6 6 6 6 6 6 6 - 6 - 6 - Polymerization initiator or photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-3 I-1 I-4 I-1 I-3 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 2 1.1 2 1.1 2 base generator type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 parts by mass 1 1 1 2 2 2 2 2 2 2 2 2 2 2 2 type AX-1 AX-2 AX-3 - - - - - - - - - - - - parts by mass 1 1 1 - - - - - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - E-3 - E-3 - E-3 parts by mass - - - - - - - - - - 1 - 1 - 1 type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 exposure conditions m m m m m m m m m m m m m m m Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone TMAH aqueous solution Cyclopentanone TMAH aqueous solution Cyclopentanone TMAH aqueous solution Developing conditions burden burden burden burden burden burden burden burden burden burden just burden just burden just Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 evaluate Evaluation of Pattern Rectangularity B B B A B C B B B B B B B B B Elongation at break evaluation B B B B B B B B B B C B C B C Drug Resistance Evaluation C C C B C C C C C C C C C C C Adhesion evaluation with copper substrate A A A A A A A A A A A A A A A Amount of tertiary amine in cured product (mass%) 0.010 0.011 0.011 0.023 0.023 0.025 0.023 0.021 0.023 0.024 0.025 0.021 0.023 0.022 0.023

[table 5] Example Example Example Example Example Example Example Example Example Example Example Example Example Example 60 61 62 63 64 65 66 67 68 69 70 71 72 73 composition resin type Resin 10 Resin 1/Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 mw 20000 20000/20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 17/17 35 35 35 35 35 35 35 35 35 35 35 35 monomer type - M-1 DPHA M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass - 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator type I-4 I-1 I-1 I-1 I-1 I-2 I-5 I-1/I-2 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 2 1.1 1.1 0.5 3 1.1 2 0.6/0.6 1.1 1.1 1.1 1.1 1.1 1.1 base generator type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 parts by mass 2 2 2 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-2 Bl/B-2 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.05 0.5 0.1 0.05/0.05 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 0.5 3 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type E-3 - - - - - - - - - - - - - parts by mass 1 - - - - - - - - - - - - - type - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DM SO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 405 365 365 365 365 365 365 365 exposure conditions m m m m m m D. m m m m m m m Developer TMAH aqueous solution Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Developing conditions just burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 evaluate Evaluation of Pattern Rectangularity B B B C B B B B B C B B B B Elongation at break evaluation C B C B C B B B B B B B B B Drug Resistance Evaluation C C A C C C A C B C C C C C Adhesion evaluation with copper substrate A A A A A A A A A A A A A A Amount of tertiary amine in cured product (mass%) 0.022 0.023 0.024 0.021 0.023 0.023 0.022 0.021 0.023 0.021 0.022 0.021 0.025 0.022

[Table 6] Example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 base generator type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-3 A-13 A-1 A-13 A-1 A-1 parts by mass 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 - - B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 - - 0.1 0.1 Silane coupling agent type C-2 C-3 C-1/C-2 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 - - C-1 C-1 parts by mass 1 1 0.5/0.5 1 1 1 1 1 1 1 1 - - 1 1 migration inhibitor type D-1 D-1 D-1 D-2 D-3 D-1 D-1 D-1 - - - - - D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 - - - - - 0.2 0.2 additive type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL NMP GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 30 10 20 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO EL DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 20 40 35 10 10 10 10 10 10 10 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 30 10 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 exposure conditions m m m m m m m m m m m m m m m Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Developing conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (°C) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 evaluate Evaluation of Pattern Rectangularity B B B B B B B B B A A B A C A Elongation at break evaluation B B B C C B B B B A A B A B A Drug Resistance Evaluation C C C C C C C C C B A C A B B Adhesion evaluation with copper substrate A A A A A A A A A A A A A A A Amount of tertiary amine in cured product (mass%) 0.021 0.021 0.025 0.024 0.024 0.024 0.025 0.024 0.021 0.025 0.024 0.021 0.022 0.022 0.022

[Table 7] Example Example Example Example 89 90 91 92 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 mw 20000 20000 20000 20000 parts by mass 35 35 35 35 monomer type M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 Polymerization initiator or photoacid generator type I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 base generator type A-1 A-1 A-1 A-1 parts by mass 2 2 2 2 type - - - - parts by mass - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 additive type - - - - parts by mass - - - - type - - - - parts by mass - - - - solvent type GBL GBL GBL GBL ratio 40 40 40 40 type DMSO DMSO DMSO DMSO ratio 10 10 10 10 Solid content concentration 42 42 42 42 Process Film thickness (μm) 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 exposure conditions m m m m Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Developing conditions burden burden burden burden Hardening temperature (°C) 200 180 160 IR Hardening time (min) 120 120 120 180 evaluate Evaluation of Pattern Rectangularity B B C B Elongation at break evaluation B C C B Drug Resistance Evaluation C C C C Adhesion evaluation with copper substrate A A A A Amount of tertiary amine in cured product (mass%) 0.028 0.027 0.015 0.024

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

[resin] ・Resin 1 to Resin 10: Resin 1 to Resin 10 obtained in the above synthesis example

[Monomer (polymerizable compound)] ・M-1: A compound with the following structure, and the subscripts in parentheses indicate the number of repetitions.・DPHA: Dineopentylthritol hexaacrylate [chemical formula 72]

[Polymerization initiator or photoacid generator] ・I-1 to I-5: Compounds with the following structures [Chemical formula 73]

[化學式75]

[化學式76]

[Base Generator] - A-1 to A-40: Compounds of the following structures. All of A-1 to A-40 are compounds belonging to the aforementioned specific base generators.・AX-1 to AX-3: Compounds of the following structures. AX-1 to AX-3 are compounds that do not belong to the aforementioned specific base generators.・AR-1: The compound AR-1 of the following structure is a compound which does not belong to the above-mentioned specific base generator. Also, the molar absorptivity of AR-1 at a wavelength of 365nm is 110mol ^-1 ·L·cm ^-1 , and the molar absorptivity of A-1～A-40 and AX-1～AX-3 at a wavelength of 365nm Both are below 100mol ^-1 ·L·cm ^-1 . [chemical formula 74]

[chemical formula 75]

[chemical formula 76]

The structures of the bases produced from A-1 to A-40, the molecular weights of the derived bases, and the boiling points of the produced bases are described in the following tables, respectively.

[Table 8]

[Table 9]

[Polymerization inhibitors] ・B-1 to B-2: Compounds with the following structures [Chemical formula 77]

[Silane Coupling Agent (Metal Adhesion Improver)] ・C-1 to C-2: Compounds of the following structures In the following formulae, Et represents an ethyl group. [chemical formula 78]

[Migration inhibitors] ・D-1 to D-3: Compounds with the following structures [Chemical formula 79]

[Additives] ・E-1 to E-3: Compounds of the following structure [Chemical Formula 80]

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

<Evaluation> [Evaluation of Pattern Rectangularity] In each of the examples and comparative examples, each resin composition or comparative composition was applied (coated) in a layer on a silicon wafer by the spin coating method. This forms a resin composition film. In each example and comparative example, the silicon wafer to which the obtained resin composition film was applied was dried on a hot plate at 100°C for 3 minutes, and the "film thickness (μm)" in the table was formed on the silicon wafer. A resin film with a thickness recorded in one column and a uniform thickness. In the example described as "M" in the exposure condition, the resin film on the silicon wafer was exposed at an exposure energy of 500mJ/ ^cm2 using the exposure wavelength described in the column "Exposure wavelength (nm)" in the table . Exposure was performed through a mask (a binary mask with a pattern of 1:1 line and space and a line width of 10 μm). In the example described as "D" in the column of exposure conditions, exposure was performed using a direct exposure device (ADTEC DE-6UH III). Regarding exposure, laser direct imaging exposure was performed at a wavelength of 405 nm so that the exposed portion became a line portion in a 1:1 line-and-space pattern with a width of 10 μm. The exposure amount was set to 500 mJ/cm ² . After the above exposure, in the case of positive development (the example described as "positive" in the "Development Conditions" column), use the developer described in the "Developer" column in the table to develop for 60 seconds, and use pure water Rinsing was performed for 20 seconds, thereby obtaining a line-and-space pattern of the exposed resin film. The description of "TMAH aqueous solution" in the table means a 2.5% by mass tetramethylammonium hydroxide aqueous solution. In the case of negative development (the example described as "Negative" in the "Development Conditions" column), use the developer described in the "Developer" column in the table to develop for 60 seconds, and use propylene glycol monomethyl ether acetic acid Ester (PGMEA) was rinsed for 20 seconds, whereby a line and space pattern of the resin film was obtained. In the example where the numerical value is recorded in the column of "curing temperature (°C)", the temperature of the above-mentioned exposed resin composition layer was raised at a rate of 10°C/min under a nitrogen atmosphere using a hot plate to reach the temperature of " After the temperature recorded in the "curing temperature (°C)" column, the above temperature is maintained within the "hardening time (min)" in the table. In the example described as "IR" in the "curing temperature (°C)" column, an infrared lamp heating device (RTP-6 manufactured by ADVANCE RIKO, Inc.) was used in a nitrogen atmosphere at a heating rate of 10°C/min. The temperature of the line and space patterns obtained in each example was raised, and after reaching 230° C., the above temperature was maintained within the “curing time (min)” in the table. For the obtained silicon wafer formed with the line and space pattern, the silicon wafer is cut perpendicular to the line and space pattern, so that the cross section of the pattern is exposed. The pattern cross-section of the line and space pattern was observed at a magnification of 200 times with an optical microscope, and the cross-sectional shape of the pattern was evaluated. Specifically, in each of the Examples and Comparative Examples, the taper angle formed by the surface of the silicon wafer (substrate surface) and the side surface of the cured film was measured, and evaluated according to the following evaluation criteria. The evaluation results are described in the column of "pattern squareness evaluation" in the table. It can be said that the taper angle exceeds 90° and the cross-sectional shape of the pattern is not an hourglass shape, and the closer the taper angle is to 90°, the better the pattern shape is. -Evaluation Criteria- A: The taper angle is not less than 85° and not more than 90°. B: The taper angle is 80° or more and less than 85°. C: The taper angle is 75° or more and less than 80°. D: The taper angle is less than 75°, the cross-sectional shape of the pattern is an inverted cone shape with a taper angle larger than 90°, or the cross-sectional shape of the pattern is an hourglass shape.

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

[Evaluation of Chemical Resistance] The resin composition or comparative composition prepared in each Example or Comparative Example was coated on a silicon wafer by a spin coating method. The above-mentioned silicon wafer was dried on a hot plate at 100°C for 5 minutes, and a resin composition layer with a uniform thickness described in the column "Film thickness (μm)" in the table was formed on the silicon wafer. In the example described as "negative" in the development conditions and "M" in the exposure conditions, the resin composition layer on the silicon wafer was exposed with a stepper. The entire surface of the photosensitive film was exposed without using a photomask using the light of the wavelength described in the "exposure wavelength (nm)" in the table. The exposure amount was set to 500 mJ/cm ² . In the example described as "negative" in the development conditions and "D" in the exposure conditions, exposure was performed using a direct exposure device (ADTEC DE-6UH III). The entire surface of the photosensitive film was exposed using the light of the wavelength described in the "exposure wavelength (nm)" in the table. The exposure amount was set to 500 mJ/cm ² . In the example described as "positive" in the development conditions, no exposure was performed. In the examples where numerical values are described in the column of "curing temperature (°C)", the temperature of the resin film obtained in each example or comparative example was raised at a rate of 10°C/min under a nitrogen atmosphere using a hot plate to reach After the temperature described in "curing temperature (°C)" in the table, the temperature was maintained for the time described in "curing time (min)", thereby forming a cured film. In the example described as "IR" in the "curing temperature (°C)" column, an infrared lamp heating device (RTP-6 manufactured by ADVANCE RIKO, Inc.) was used in a nitrogen atmosphere at a heating rate of 10°C/min. After the temperature of the resin film obtained in each Example was raised to 230° C., the temperature was maintained for the time described in “curing time (min)”, thereby forming a cured film. The obtained cured film was immersed in the following chemicals under the following conditions, and the dissolution rate was calculated. Drug: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution After immersion for 15 minutes, the film thickness of the cured film before and after immersion was compared to calculate the dissolution rate (nm/min). The value of the obtained dissolution rate was evaluated according to the following evaluation criteria, and described in the column of "chemical resistance evaluation". It can be said that the slower the dissolution rate, the better the chemical resistance. -Evaluation Criteria- A: The dissolution rate did not reach 250 nm/min. B: The dissolution rate is 250 nm/minute or more and less than 500 nm/minute. C: The dissolution rate is 500 nm/min or more and less than 750 nm/min. D: The dissolution rate is 750 nm/minute or more.

[Evaluation of Adhesiveness to Copper Substrate] The resin composition prepared in Examples and Comparative Examples or the composition for comparison was applied in layers on a copper substrate by spin coating to form a resin composition layer or The composition layer was used for comparison. The copper substrate on which the obtained resin composition layer or comparative composition layer was formed was dried on a heating plate at 100°C for 5 minutes, and the column "Film thickness (μm)" in the table was made on the copper substrate. A resin composition layer or a composition layer for comparison with a uniform thickness described in . In the example described as "Negative" in the "Development Conditions" column in the table, a photomask having a non-masked portion in a square shape of 100 μm square was used, and "Positive" was described in the "Development Conditions" column in the table. In the example above, a mask with a square-shaped mask portion of 100 μm square is used, and the exposure energy is 500 mJ/cm ² by the light of the exposure wavelength (nm) described in the column of “Exposure wavelength nm” in the table. Exposure was performed on the resin composition layer or the comparative composition layer on the copper substrate. In the example described as "M" in the column of exposure conditions, exposure was performed using a stepper as a light source. In the example described as "D" in the "Exposure" column, a direct exposure device (ADTEC DE-6UH III) was used as the light source, and the laser direct imaging method exposure was performed in the range of 100 μm square without using a mask. . Then, development was performed for 60 seconds with the developer described in the table, and the resin layer of the square shape of 100 micrometers square was obtained. The description of "TMAH aqueous solution" in the table refers to a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. In the examples where numerical values are recorded in the column of "hardening temperature", the temperature of the above-mentioned exposed resin composition layer was raised at a rate of 10°C/min under a nitrogen atmosphere by using a heating plate until it reached the "hardening temperature ( °C)” after the temperature recorded in the column, the above temperature is maintained within the time of “curing time (min)” in the table. In the example described as "IR" in the "curing temperature (°C)" column, an infrared lamp heating device (RTP-6 manufactured by ADVANCE RIKO, Inc.) was used in a nitrogen atmosphere at a heating rate of 10°C/min. The temperature of the resin film obtained in each example was raised to 230° C., and the above-mentioned temperature was maintained for the period of “curing time (min)” in the table. In an environment of 25°C and 65% relative humidity (RH), the shear force was measured on a 100 μm square resin layer on a copper substrate using an adhesion tester (manufactured by XYZTEC, CondorSigma), and the following Evaluation criteria were evaluated. The evaluation results are described in the column of "adhesion evaluation with copper substrate" in a table|surface. It can be said that the larger the shearing force, the better the metal adhesion (copper adhesion) of the cured film. -Evaluation Criteria- A: The shear force exceeded 30gf. B: The shear force exceeds 25 gf and is 30 gf or less. C: The shear force exceeds 20 gf and is 25 gf or less. D: The shearing force is 20 gf or less. Also, 1gf is 0.00980665N.

[Measurement of the amount of tertiary amine in the cured product] In each of the examples and comparative examples, about 10 mg of the cured film prepared for evaluation of the elongation at break was placed in a screw vial, and DMSO:H ₂ was added thereto. O:TMAH (25% in MeOH)=1mL of 8700μL:1000μL:300μL mixture, heated and dissolved at 75°C for 30 minutes, cooled naturally, and measured by LC/MS Filtered with a 0.45μm filter By. The measurement results are described in the column "Amount of tertiary amine in cured product (mass %)" in the table.

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

<Example 101> The resin composition used in Example 1 was applied in a layer form to the surface of the thin copper layer of the resin substrate on which the thin copper layer was formed by spin coating, and dried at 100°C for 5 minutes to form a film. After the photosensitive film with a thickness of 20 μm, exposure was performed with a stepper (manufactured by Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a pattern of 1:1 line-space and a line width of 10 μm). After the above-mentioned exposure, it was developed with cyclohexanone for 2 minutes, and rinsed with PGMEA for 30 seconds, whereby a layer pattern was obtained. Next, in a nitrogen atmosphere, the temperature was raised at a rate of 10° C./minute to reach 230° C., and then maintained at 230° C. for 180 minutes to form an interlayer insulating film for a rewiring layer. The interlayer insulating film for a rewiring layer is excellent in insulating properties. Furthermore, as a result of manufacturing semiconductor devices using these interlayer insulating films for rewiring layers, normal operation was confirmed.

none.

Claims (25)

A resin composition comprising: resin; and The base generator has an α,β-unsaturated ketone group at the site of the generated base and the generated base is cyclized into a tertiary amine in the molecule. A resin composition comprising: a resin; and a base generator having an α,β-unsaturated ketone group, a group represented by -NR ¹ C(=O)-, and a group selected from the group consisting of carboxyl and hydroxyl At least one of the groups, at least one of the aforementioned α,β-unsaturated ketone groups exists on the side of the nitrogen atom of the group represented by the aforementioned -NR ¹ C(=O)-, and the aforementioned group is selected from the group consisting of carboxyl and hydroxyl At least one of at least one group in the group is present on the carbon atom side of the aforementioned -NR ¹ C(=O)-, and the aforementioned R ¹ is a monovalent organic group. The resin composition as described in claim 1 or claim 2, wherein The aforementioned base generator is a compound that generates a base by at least one of light and heat. The resin composition as described in claim 1 or claim 2, wherein The boiling point of the tertiary amine generated from the aforementioned base generator is 180 to 280°C. The resin composition according to claim 1 or claim 2, wherein the base generator comprises a compound represented by the following formula (1-1), [Chemical Formula 1]

In formula (1-1), L ¹ represents an n+m valent linking group, R ¹ independently represents a monovalent organic group, at least one of R ¹ contains an α, β-unsaturated ketone group, and X are independently ground represents a hydroxyl group or a carboxyl group, m represents an integer of 1 or more, and n represents an integer of 1 or more. The resin composition according to claim 5, wherein L ¹ in the aforementioned formula (1-1) contains an aromatic ring structure. The resin composition according to claim 5, wherein L ¹ in the aforementioned formula (1-1) contains a polymerizable group. The resin composition as described in claim 1 or claim 2, wherein The molecular weight of the tertiary amine generated from the aforementioned base generator is 100-200. The resin composition as described in claim 1 or claim 2, wherein The tertiary amine generated from the aforementioned base generator includes a 5-membered ring structure having nitrogen atoms constituting the tertiary amine as ring members or a 6-membered ring structure having nitrogen atoms constituting the tertiary amine as ring members. The resin composition according to claim 1 or claim 2, wherein the molar absorption coefficient of the base generator at a wavelength of 365 nm is 100 mol ^-1 ·L·cm ^-1 or less. The resin composition according to claim 1 or claim 2, which satisfies at least one of the following conditions 1 and 2, Condition 1: The resin has a free radical polymerizable group, Condition 2: It further contains a polymerizable compound having a radically polymerizable group. The resin composition according to claim 1 or claim 2, which includes a photoradical polymerization initiator. The resin composition according to claim 1 or claim 2, which contains a polymerizable compound. The resin composition as described in claim 1 or claim 2, wherein The foregoing resins are precursors of cyclized resins. The resin composition according to claim 1 or claim 2, which contains a cyclized resin or a precursor thereof as the resin and is used for forming an interlayer insulating film for a rewiring layer. A cured product obtained by curing the resin composition described in Claim 1 or Claim 2. A sclerosing product comprising: resin; and Tertiary amine, with ketone group and ring structure. A laminate comprising two or more layers made of the cured product described in claim 16, wherein at least one of the layers made of the cured product includes a metal layer. A method for producing a cured product, comprising a film forming step of applying the resin composition described in Claim 1 or Claim 2 on a substrate to form a film. The manufacturing method of the hardened object as described in Claim 19, which comprises: an exposing step of selectively exposing the aforementioned film; and In the development step, the film is developed using a developer to form a pattern. The method for producing a cured product according to claim 19, which includes a heating step of heating the film at 50 to 450°C. A method for manufacturing a laminate, including the method for manufacturing a cured product described in Claim 19. A method of manufacturing a semiconductor device, including the method of manufacturing a laminate described in Claim 22. A semiconductor device comprising the cured product described in Claim 16. A semiconductor device comprising the laminate described in Claim 18.