Resin composition

Abstract

This resin composition contains a resin having at least one selected from the group consisting of repeating units represented by formula (1A) and repeating units represented by formula (2A). X1, X2, Y1, and Y2 each independently represent an organic group. W1, W2, W3, and W4 each independently represent a linking group. P01, P02, P03, and P04 each independently represent at least one organic group selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, and a fluoroalkylene group. a, b, c, and d each independently represent an integer of 0 or more. At least one of a and b represents an integer of one or more, and at least one of c and d represents an integer of one or more. m, n, p, and q each independently represent an integer of one or more. W1, W2, W3, W4, P01, P02, P03, and P04, when existing in a quantity of more than one, may each be the same or may each be different.

Description

resin composition

[0001] The present invention relates to a resin composition.

[0002] Polyimides and polyamides are used in a variety of fields, such as semiconductor devices and the aerospace industry.

[0003] Patent Document 1 describes a varnish composition containing a polyimide resin having a radical polymerizable group or a cation polymerizable group bonded to the main chain of the polyimide resin and containing a skeleton derived from a bisphenol of a specific structure in the structural units constituting the main chain of the polyimide resin, and an organic solvent. Also, Patent Document 2 describes a photosensitive resin composition containing a polyimide precursor having a specific structure, a photosensitizer, and a solvent.

[0004] Japanese Patent Publication No. 2022-73127 Japanese Patent Publication No. 2022-54416

[0005] One application of polyimides and polyamides is films used in semiconductor devices (e.g., insulating films such as interlayer insulating films for redistribution layers). Recently, with the increasing miniaturization and high integration of semiconductor devices, high resolution is required for resin compositions, which are materials for forming films. Furthermore, with the increasing miniaturization and high integration of semiconductor devices, films are more susceptible to heat. Therefore, from the viewpoint of preventing deformation (warping, distortion, void generation, etc.) when exposed to heat, films are required to have a low coefficient of expansion when exposed to heat. In other words, there is a demand for resin compositions capable of forming films with a low coefficient of thermal expansion (CTE).

[0006] An object of the present invention is to provide a resin composition that is excellent in resolution and capable of forming a film having a small CTE.

[0007] Examples of typical embodiments of the present invention are given below.

[0008] [1] A resin composition containing a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1A) and a repeating unit represented by the following formula (2A):

[0009]

[0010] In formula (1A) and formula (2A), X １ , X ２ , Y １ and Y ２ Each independently represents an organic group. １ , W ２ , W ３ and W ４ each independently represents a linking group. ０１ , P ０２ , P ０３ and P ０４ each independently represents an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, and a fluoroalkylene group. a, b, c, and d each independently represent an integer of 0 or more. However, at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more. m, n, p, and q each independently represent an integer of 1 or more. W １ , W ２ , W ３ , W ４ , P ０１ , P ０２ , P ０３ and P ０４ [2] A resin composition containing a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2):

[0011]

[0012] In formula (1) and formula (2), X １ , X ２ , Y １ and Y ２ Each independently represents an organic group. １ , W ２ , W ３ and W ４ each independently represents a linking group. １ , P２ , P ３ and P ４ each independently represents an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, and a fluoroalkylene group. １ , Q ２ , Q ３ and Q ４ Each independently represents a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxy group, a thiol group, or a hydrogen atom. a, b, c, and d each independently represent an integer of 0 or more. However, at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more. m, n, p, and q each independently represent an integer of 1 or more. W １ , W ２ , W ３ , W ４ , P １ , P ２ , P ３ , P ４ , Q １ , Q ２ , Q ３ and Q ４ When a plurality of P are present, they may be the same or different. ０１ and P ０２ at least one of the groups P in the formula (2A) contains at least one group selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, and a phenylene ether group; ０３ and P ０４ [4] The resin composition according to [1], wherein at least one of P in the formula (1A) contains at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, and a phenylene ether group. ０１ and P ０２ at least one of the P in the formula (2A) has a branched structure; ０３ and P ０４ [5] The resin composition according to [1] or [3], wherein at least one of P in the formula (1A) has a branched structure. ０１ and P ０２at least one of the repeating units has at least one selected from the group consisting of repeating units represented by the following formula (1-PA) and repeating units represented by the following formula (2-PA), ０３ and P ０４ The resin composition according to [1], [3] or [4], wherein at least one of the repeating units has at least one selected from the group consisting of a repeating unit represented by the following formula (1-PA) and a repeating unit represented by the following formula (2-PA):

[0013]

[0014] In formula (1-PA) and formula (2-PA), X １ｐ , X ２ｐ , Y １ｐ and Y ２ｐ Each independently represents an organic group. １ｐ , W ２ｐ , W ３ｐ and W ４ｐ each independently represents a linking group. ０１ｐ , P ０２ｐ , P ０３ｐ and P ０４ｐ each independently represents an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenyl ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, and a fluoroalkylene group. ap, bp, cp, and dp each independently represent an integer of 0 or greater. However, at least one of ap and bp represents an integer of 1 or greater, and at least one of cp and dp represents an integer of 1 or greater. mp, np, pp, and qp each independently represent an integer of 1 or greater. W １ｐ , W ２ｐ , W ３ｐ , W ４ｐ , P ０１ｐ , P ０２ｐ , P ０３ｐ and P ０４ｐ [6] The resin composition according to any one of [1] to [5], wherein the resin has at least one crosslinkable group at at least one terminal thereof. [7] P in the formula (1A) ０１and P ０２ at least one of the groups P in the formula (2A) has a crosslinkable group; ０３ and P ０４ [8] The resin composition according to any one of [1] and [3] to [5], wherein at least one of the crosslinkable groups comprises at least one selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group. [9] The resin composition according to [6] or [7], wherein P in formula (1A) ０１ and P ０２ At least one of the groups has a phenol group, and P in the above formula (2A) ０３ and P ０４ The resin composition according to any one of [1], [3] to [5], and [7], wherein at least one of the groups has a phenol group.

[10] The resin composition according to any one of [1] to [9], further comprising a polymerization initiator.

[11] The resin composition according to any one of [1] to

[10] , further comprising a polymerizable compound.

[12] The resin composition according to any one of [1] to

[11] , further comprising a light absorber.

[13] The resin composition according to

[12] , wherein the light absorber is at least one selected from the group consisting of naphthoquinone diazide compounds, spiropyran compounds, diarylethene compounds, azobenzene compounds, nifedipine compounds, and coumarin compounds.

[14] The resin composition according to any one of [1] to

[12] , wherein the light absorber is at least one selected from the group consisting of naphthoquinone diazide compounds, spiropyran compounds, diarylethene compounds, azobenzene compounds, nifedipine compounds, and coumarin compounds.

[15] The resin composition according to any one of [1] to

[14] , wherein the light absorber is at least one selected from the group consisting of naphthoquinone diazide compounds, spiropyran compounds, diarylethene compounds, azobenzene compounds, nifedipine compounds, and coumarin compounds. ２

[15] The resin composition according to any one of [1] to

[13] , wherein, when the dissolution rate of the film in γ-butyrolactone is measured before and after exposure with 100 mJ / cm 2 , the value obtained by subtracting the dissolution rate after exposure from the dissolution rate before exposure is 0.5 μm / sec or more. ２The resin composition according to any one of [1] to

[14] , wherein, when the dissolution rates of the film in an aqueous tetramethylammonium hydroxide solution are measured before and after exposure, the value obtained by subtracting the dissolution rate after exposure from the dissolution rate before exposure is 0.5 μm / sec or more.

[16] The resin composition according to any one of [1], [3] to [5], [7], and [9], wherein the resin has a repeating unit represented by formula (1A) above and a repeating unit represented by formula (2A) above.

[17] The resin composition according to any one of [1] to

[16] , which is used for forming an insulating film.

[18] The resin composition according to any one of [1] to

[17] , which is used for forming an interlayer insulating film for a redistribution layer.

[0015] According to the present invention, it is possible to provide a resin composition that is capable of forming a film having excellent resolution and a small CTE.

[0016] The following describes the main embodiments of the present invention. However, the present invention is not limited to the explicitly described embodiments. In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits, respectively. In this specification, the term "process" refers not only to an independent process but also to a process that cannot be clearly distinguished from other processes as long as the process achieves its intended effect. In the description of a group (atomic group), a notation that does not specify whether it is substituted or unsubstituted encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams. As used herein, "(meth)acrylate" refers to either or both of "acrylate" and "methacrylate," "(meth)acrylic" refers to either or both of "acrylic" and "methacrylic," and "(meth)acryloyl" refers to either or both of "acryloyl" and "methacryloyl." In the structural formulae herein, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent. Furthermore, as used herein, the term "solid content concentration" refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. As used herein, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values, unless otherwise specified.In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, when THF is not suitable as the eluent, for example, due to low solubility, NMP (N-methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise specified, detection in GPC measurement is assumed to be performed using a UV (ultraviolet) detector at a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting a laminate is described as "above" or "below," it is sufficient that another layer is above or below the reference layer among the multiple layers being considered. In other words, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "above." Alternatively, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as "above," and the opposite direction is referred to as "below." Note that such vertical directions are defined for convenience in this specification, and in actual embodiments, the "above" direction in this specification may differ from the vertically upward direction. In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to each component contained in the composition. Furthermore, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. Unless otherwise specified herein, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, a combination of preferred embodiments is a more preferred embodiment. In this specification, the term "organic group" refers to a group containing at least one carbon atom.

[0017] [Resin Composition] The resin composition of the present invention will be described. The resin composition of the present invention is a resin composition containing a resin (also referred to as "resin (A)" or "specific resin") having at least one type selected from the group consisting of repeating units represented by the following formula (1A) and repeating units represented by the following formula (2A):

[0018]

[0019] In formula (1A) and formula (2A), X １ , X ２ , Y １ and Y ２ Each independently represents an organic group. １ , W ２ , W ３ and W ４ each independently represents a linking group. ０１ , P ０２ , P ０３ and P ０４ each independently represents an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, and a fluoroalkylene group. a, b, c, and d each independently represent an integer of 0 or more. However, at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more. m, n, p, and q each independently represent an integer of 1 or more. W １ , W ２ , W ３ , W ４ , P ０１ , P ０２ , P ０３ and P ０４ When there are a plurality of each, they may be the same or different.

[0020] According to the resin composition of the present invention, a film having excellent resolution and a small CTE can be formed. The mechanism by which the above-mentioned effects are obtained by the present invention has not been clarified, but the inventors have speculated as follows. However, the present invention is not limited by the speculated mechanism below. It is believed that the resin contained in the resin composition of the present invention has at least one selected from the group consisting of repeating units represented by formula (1A) and repeating units represented by formula (2A), and thereby the density of the three-dimensional network structure of the exposed film obtained by exposing a film formed from the resin composition of the present invention is improved, and the resolution is improved. In addition, P in formula (1A) and formula (2A) ０１ , P ０２ , P ０３ and P ０４ It is believed that the presence of a specific group represented by the formula (I) reduces entanglement of resin molecules and improves orientation, thereby improving CTE.

[0021] The components contained in the resin composition of the present invention will be described in detail below.

[0022] <Resin (A)> The resin composition of the present invention contains at least one resin (A). The resin (A) is a resin having at least one selected from the group consisting of the repeating unit represented by the above formula (1A) and the repeating unit represented by the above formula (2A). The resin (A) may be a polyimide or a polyamide. The resin (A) may have a repeating unit represented by the above formula (1A) and a repeating unit represented by the above formula (2A). The resin (A) may further have a repeating unit other than the repeating unit represented by the above formula (1A) and the repeating unit represented by the above formula (2A). The resin (A) may be a precursor of a cyclized resin. The precursor of a cyclized resin refers to a resin whose chemical structure changes upon external stimulation to become a cyclized resin. A resin whose chemical structure changes upon heating to become a cyclized resin is preferred, and a resin whose ring structure is formed by a ring-closing reaction upon heating to become a cyclized resin is more preferred. Examples of precursors of cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors.

[0023] The repeating unit represented by formula (1A) will be described. When resin (A) is a resin having a repeating unit represented by formula (1A), resin (A) is a polyimide, and therefore, in the following description, resin (A) having a repeating unit represented by formula (1A) will also be referred to as "polyimide."

[0024] X in formula (1A) １ represents an organic group, more specifically, an organic group having a valence of 4+a. Since a represents an integer of 0 or more, in the following, when a represents 0 (i.e., X １ represents a tetravalent organic group) will be described as an example (when a represents an integer of 1 or more, X １ a number of -W １ - (P ０１ ) ｍ is replaced by X １ ) X １ The tetravalent organic group represented by is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6): In formulas (5) and (6), * represents the bonding site with -C(=O)- in formula (1A).

[0025]

[0026] In formula (5), R １１２ is a single bond or a divalent linking group, and is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an aromatic group (which may be an aromatic hydrocarbon group or an aromatic heterocyclic group), -O-, -CO-, -S-, -SO ２ -, -NHCO-, and a group selected from combinations thereof are preferred, and examples thereof include a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, -O-, -CO-, -S-, and -SO ２ - is more preferably a group selected from -CH ２ -, -C(CF ３ ) ２ -, -C(CH ３ ) ２ -, a phenylene group, -O-, -CO-, -S- and -SO ２It is more preferably a divalent group selected from the group consisting of -.

[0027] X １ Specific examples of X include tetracarboxylic acid residues remaining after removal of the anhydride groups from tetracarboxylic dianhydride. １ The tetracarboxylic acid dianhydride may contain only one type of tetracarboxylic acid residue or two or more types of tetracarboxylic acid residues as a structure corresponding to the formula (I). The tetracarboxylic acid dianhydride is preferably represented by the following formula (I):

[0028]

[0029] In formula (O), R １１５ represents a tetravalent organic group. １１５ The preferred range of X １ is the same as:

[0030] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2 2,3,3',4'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and alkyl and alkoxy derivatives having 1 to 6 carbon atoms thereof.

[0031] Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598 are also preferred examples.

[0032] From the viewpoint of film strength, X １ is preferably a tetracarboxylic acid residue having 1 to 4 aromatic rings.

[0033] Y in formula (1A) １ represents an organic group, more specifically, represents an organic group having a valence of 2+b. Since b represents an integer of 0 or more, in the following, when b represents 0 (i.e., Y １ represents a divalent organic group) will be described as an example (when b represents an integer of 1 or more, １ b arbitrary hydrogen atoms of ２ - (P ０２ ) ｎ is replaced by Y １ (It becomes like this). Y １ Examples of the divalent organic group represented by are groups containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group. A linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic heterocyclic group preferably contains one or more heteroatoms selected from the group consisting of nitrogen atoms, sulfur atoms, and oxygen atoms as ring members. The number of ring members of the aromatic group is preferably 5 to 20, more preferably 6 to 15. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Y １ Examples of the group include groups represented by -Ar- and -Ar-L-Ar-, and the group represented by -Ar-L-Ar- is preferred, where each Ar is independently an aromatic group, L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ２ - or -NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges for these are as described above.

[0034] Y １ is preferably derived from a diamine. Examples of the diamine include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, Y１ is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Examples of groups containing an aromatic group include the following.

[0035]

[0036] In the formula, A represents a single bond or a divalent linking group, and is selected from the group consisting of a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C(═O)—, —S—, and —SO ２ -, -NHCO-, or a group selected from a combination thereof, and is preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO ２ - is more preferably a group selected from -CH ２ -, -O-, -S-, -SO ２ -, -C(CF ３ ) ２ - or -C(CH ３ ) ２ In the formula, * represents a bonding site to another structure.

[0037] Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 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 parafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether fluorene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,At least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl can be mentioned.

[0038] Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017 / 038598.

[0039] Also preferably used are diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of WO 2017 / 038598.

[0040] Y １ is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the resulting film, wherein each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ２ Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ２ The aliphatic hydrocarbon group here is preferably an alkylene group.

[0041] Also, Y １ is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-line transmittance. In particular, from the viewpoint of i-line transmittance and ease of availability, it is more preferably a divalent organic group represented by formula (61).

[0042]

[0043] In formula (51), R ５０ ~R ５７ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R ５０ ~R ５７ At least one of R is a fluorine atom, a methyl group, or a trifluoromethyl group, and each * independently represents a bonding site with a nitrogen atom. ５０ ~R ５７ Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0044]

[0045] In formula (61), R ５８ and R ５９ are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with a nitrogen atom. Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

[0046] Y １ is preferably a diamine residue having at least two alkylene glycol units in the main chain (a group remaining after removal of the amino groups of the diamine) in order to more effectively suppress the occurrence of warping during firing. It is also preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and more preferably a diamine residue of the above diamine that does not contain an aromatic ring.

[0047] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0048] P in formula (1A) ０１ and P ０２ each independently represents an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, and a fluoroalkylene group (also referred to as a "specific group (X)"). It is believed that the presence of the specific group (X) in the resin (A) reduces entanglement between polymers, improving orientation in the film and thereby lowering the CTE.

[0049] The imide group is preferably a group represented by the following formula (PN-1): The amide group is preferably a group represented by the following formula (PN-2): In formula (PN-2), R Ｘ１ represents a hydrogen atom or a substituent. The phenylene ether group is preferably a group represented by the following formula (PN-3). In formula (PN-3), R Ｘ２ represents a substituent. k1 represents an integer of 0 to 4. The benzoxazole group is preferably a group represented by the following formula (PN-4). In formula (PN-4), R Ｘ３ represents a substituent. k2 represents an integer of 0 to 3. The sulfonamide group is preferably a group represented by the following formula (PN-5). In formula (PN-5), R Ｘ４ represents a hydrogen atom or a substituent. The group having three or more ester groups is preferably a group represented by the following formula (PN-6) or formula (PN-6-2). In formula (PN-6), E １ and E２ each independently represents a divalent organic group; k3 represents an integer of 2 or greater. ３ represents a divalent organic group. k31 represents an integer of 3 or more. The siloxane group is preferably a group represented by the following formula (PN-7). In formula (PN-7), R Ｘ５ and R Ｘ６ each independently represents a hydrogen atom or a substituent. The fluoroalkylene group may be linear or branched. There is no particular limitation on the number of carbon atoms in the fluoroalkylene group, but it is preferable that the number of carbon atoms is 1 to 30. The fluoroalkylene group may be a perfluoroalkylene group. The fluoroalkylene group may have a substituent other than a fluorine atom. The phenol group is preferably a group represented by the following formula (PN-8). In formula (PN-8), R Ｘ７ represents a substituent. k4 represents an integer of 0 to 4. The phenoxy group is preferably a group represented by the following formula (PN-9). In formula (PN-9), R Ｘ８ represents a substituent. k5 represents an integer of 0 to 5. In the following formulas (PN-1) to (PN-9), * represents the bonding position to other structures.

[0050]

[0051] P ０１ and P ０２ The organic group represented by is not particularly limited except that it contains the specific group (X). ０１ and P ０２ The organic group represented by may be the specific group (X) or may be a group consisting of the specific group (X) and another group. ０１ and P ０２ The organic group represented by may have a repeating unit (may be a polymer chain). ０１ and P ０２ The specific group (X) contained in the organic group represented by may be one type or two or more types.

[0052] W in formula (1A) １ and W ２ each independently represents a linking group. １ and W ２The linking group represented by is not particularly limited, but preferably represents an organic group, and examples thereof include a carbonyl group, an ester group, an amide group, an alkylene group, an arylene group, a cycloalkylene group, an alkyleneoxy group, an aryleneoxy group, a cycloalkyleneoxy group, and a group formed by combining two or more of these. These organic groups may further have a substituent. １ and W ２ There is no particular limitation on the number of carbon atoms in the linking group represented by, but it may be, for example, 1 to 100 carbon atoms.

[0053] In formula (1A), a and b each independently represent an integer of 0 or greater. However, at least one of a and b represents an integer of 1 or greater. a and b each independently may represent an integer of 0 or greater and 100 or less, preferably an integer of 0 or greater and 10 or less, and more preferably an integer of 0 or greater and 5 or less. m and n in formula (1A) each independently represent an integer of 1 or greater, and may represent an integer of 1 or greater and 100 or less, preferably an integer of 1 or greater and 10 or less, and more preferably an integer of 1 or greater and 5 or less.

[0054] X １ and Y １ It is also preferable that at least one of Y １ Preferred examples of X include 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, and the above (DA-1) to (DA-18). １ As the above, (DAA-1) to (DAA-5) are more preferred examples.

[0055] The polyimide may be an alkali-soluble polyimide or a polyimide soluble in a developer containing an organic solvent as a main component. In this specification, alkali-soluble polyimide refers to a polyimide that dissolves at 23°C in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium at 0.1 g or more. From the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferred, and a polyimide that dissolves at 1.0 g or more is even more preferred. The upper limit of the solubility is not particularly limited, but is preferably 100 g or less. From the viewpoint of the film strength and insulating properties of the resulting film, the polyimide is preferably a polyimide having multiple imide structures in the main chain. In the present invention, the term "main chain" refers to the relatively longest bonding chain in a resin molecule, and the term "side chain" refers to other bonding chains.

[0056] -Fluorine Atom- From the viewpoint of the strength of the resulting film, it is also preferable that the polyimide contains a fluorine atom. １ or Y １ and X １ or Y １ The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and 20% by mass or less.

[0057] -Silicon Atom- From the viewpoint of the strength of the resulting film, it is also preferable that the polyimide contains a silicon atom. １ or Y １ It is more preferable that the silicon atom or the organic modified (poly)siloxane structure is contained in the polyimide as an organic modified (poly)siloxane structure. The silicon atom or the organic modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1 mass % or more, and more preferably 20 mass % or less.

[0058] - Ethylenically unsaturated bond - From the viewpoint of the strength of the resulting film, the polyimide preferably has an ethylenically unsaturated bond. The ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is preferably a bond represented by X １ and Y １ It is preferable that the compound is contained in at least one of X １ and Y １ It is more preferable that the ethylenically unsaturated bond is contained as a group having an ethylenically unsaturated bond in at least one of Y １ More preferably, Y １ Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring, such as a vinyl group, an allyl group, or a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV):

[0059]

[0060] In formula (IV), R ２０ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.

[0061] In formula (IV), R ２１ represents an alkylene group having 2 to 12 carbon atoms, —O—CH ２ CH(OH)CH ２ -, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms; the number of repeating alkyleneoxy groups is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3 carbon atoms), or a group combining two or more of these. The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, or alkylene groups represented by a combination thereof. The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0062] Among these, R ２１ is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1).

[0063]

[0064] In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R ２１ In formulas (R1) to (R3), a preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L is R in formula (IV). ２１ The preferred embodiments are the same as those of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms. In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and the preferred embodiments are also the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate).

[0065] In formula (IV), * represents a bonding site to another structure, and is preferably a bonding site to the main chain of the polyimide.

[0066] The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0067] -Polymerizable group other than group having ethylenically unsaturated bond- The polyimide may have a polymerizable group other than group having an ethylenically unsaturated bond. Examples of the polymerizable group other than group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group. Examples of the polymerizable group other than group having an ethylenically unsaturated bond include, for example, Y １ The amount of polymerizable groups other than groups having an ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0068] - Polarity conversion group - The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide 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 hydroxy group or a carboxy group. However, an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred. The polarity conversion group is, for example, X １ , Y １ , contained in the terminals of polyimides, etc.

[0069] -Acid Value- When the polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more. The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. When the polyimide is subjected to development using a developer containing an organic solvent as a main component (e.g., "solvent development"), the acid value of the polyimide is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g. The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. From the viewpoint of achieving both storage stability and developability, the acid group contained in the polyimide preferably has a pKa of 0 to 10, more preferably 3 to 8. pKa refers to the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm, pKa. In this specification, pKa refers to a value calculated using ACD / ChemSketch (registered trademark) unless otherwise specified. For pKa, reference may be made to the value listed in the "Revised 5th Edition Chemistry Handbook: Basics" compiled by the Chemical Society of Japan. When the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant. As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably a phenolic hydroxy group.

[0070] -Phenol Hydroxy Group- From the viewpoint of ensuring an appropriate development speed with an alkaline developer, the polyimide preferably has a phenolic hydroxy group. The polyimide may have the phenolic hydroxy group at the end of the main chain or on a side chain. The phenolic hydroxy group can be, for example, X １ or Y １The amount of phenolic hydroxy groups relative to the total mass of the polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0071] The polyimide preferably contains fluorine atoms in its structure, and the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0072] To improve adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0073] In order to improve the storage stability of the resin composition, it is also preferable that the main chain terminals of the polyimide are blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. Among these, it is more preferable to use a monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy 2-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 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-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different terminal groups may be introduced by reacting multiple terminal-capping agents.

[0074] -Imidization rate (ring closure rate)- The imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the strength, insulating properties, etc. of the resulting film. The upper limit of the imidization rate is not particularly limited, and it is sufficient if it is 100% or less. The imidization rate is measured, for example, by the following method. The infrared absorption spectrum of the polyimide is measured, and the absorption peak at 1377 cm due to the imide structure is detected. －１Next, the polyimide is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again to determine the peak intensity P1 around 1377cm. －１ The peak intensity P2 around the peak intensity P1 is measured. The imidization rate of the polyimide can be calculated using the obtained peak intensities P1 and P2 according to the following formula: Imidization rate (%) = (peak intensity P1 / peak intensity P2) x 100

[0075] The polyimide may contain only one type of repeating unit represented by formula (1A), or may contain two or more types. The polyimide may contain other types of repeating units in addition to the repeating unit represented by formula (1A). Examples of other types of repeating units include repeating units represented by formula (2A).

[0076] Polyimides can be synthesized by, for example, reacting a tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-capping agent) at low temperature, reacting a tetracarboxylic dianhydride with a diamine (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-capping agent) at low temperature, preparing a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine (partially substituted with a monoamine end-capping agent) in the presence of a condensing agent, preparing a diester from a tetracarboxylic dianhydride with an alcohol and then converting the remaining dicarboxylic acid to an acid chloride and reacting it with a diamine (partially substituted with a monoamine end-capping agent), or by completely imidizing the resulting polyimide precursor using a known imidization reaction method, or by terminating the imidization reaction midway to introduce a partial imide structure, or by blending a fully imidized polymer with the polyimide precursor to introduce a partial imide structure. Other known polyimide synthesis methods can also be used. The polyimide precursor may be, for example, a polyamide having a repeating unit represented by formula (2A).

[0077] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the fold resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., breaking elongation), the weight-average molecular weight is particularly preferably 15,000 or more. The number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersity of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide is not particularly specified, but is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the molecular weight dispersity is a value calculated by weight average molecular weight / number average molecular weight. When the resin composition contains multiple types of polyimides, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyimide are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating multiple types of polyimides as one resin are each within the above ranges.

[0078] The repeating unit represented by formula (2A) will be described. When resin (A) is a resin having a repeating unit represented by formula (2A), resin (A) is a polyamide, and therefore, in the following description, resin (A) having a repeating unit represented by formula (2A) will also be referred to as "polyamide." The polyamide may be a polyimide precursor for producing a polyimide having a repeating unit represented by formula (1A).

[0079] X in formula (2A) ２ represents an organic group, more specifically, a 2+c-valent organic group. Since c represents an integer of 0 or more, in the following, when c represents 0 (i.e., X ２ represents a divalent organic group) will be described as an example (when c represents an integer of 1 or more, X ２ c arbitrary hydrogen atoms of ３ - (P０３ ) ｐ is replaced by X ２ ) X ２ The divalent organic group represented by is preferably a divalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5-1) or formula (6-1): In formula (5-1) and formula (6-1), * represents the bonding site with -C(=O)- in formula (2A).

[0080]

[0081] In formula (5-1), R １１２ is a single bond or a divalent linking group, and is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an aromatic group (which may be an aromatic hydrocarbon group or an aromatic heterocyclic group), -O-, -CO-, -S-, -SO ２ -, -NHCO-, and a group selected from combinations thereof are preferred, and examples thereof include a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, -O-, -CO-, -S-, and -SO ２ - is more preferably a group selected from -CH ２ -, -C(CF ３ ) ２ -, -C(CH ３ ) ２ -, a phenylene group, -O-, -CO-, -S- and -SO ２ It is more preferably a divalent group selected from the group consisting of -.

[0082] X ２ Specific examples of X include tetracarboxylic acid residues remaining after removal of the anhydride groups from tetracarboxylic dianhydride. ２ The tetracarboxylic acid dianhydride may contain only one type of tetracarboxylic acid residue or two or more types of tetracarboxylic acid residues as a structure corresponding to the formula (I). The tetracarboxylic acid dianhydride is preferably represented by the following formula (I):

[0083]

[0084] In formula (O), R １１５ represents a tetravalent organic group. １１５The preferred range of X in the above formula (1A) is １ Specific examples of the tetracarboxylic dianhydride include X １ From the viewpoint of the strength of the film, X ２ is preferably a tetracarboxylic acid residue having 1 to 4 aromatic rings.

[0085] Y in formula (2A) ２ represents an organic group, more specifically, an organic group having a valence of 2+d. Since d represents an integer of 0 or more, in the following, when d represents 0 (i.e., Y ２ represents a divalent organic group) will be described as an example (when d represents an integer of 1 or more, ２ d arbitrary hydrogen atoms of ４ - (P ０４ ) ｑ is replaced by Y ２ (It becomes like this). Y ２ The description, specific examples and preferred range of the divalent organic group represented by Y in the above formula (1A) are １ It is the same as in

[0086] P in formula (2A) ０３ and P ０４ The description, specific examples and preferred ranges of P in the above formula (1A) ０１ and P ０２ The W in formula (2A) is the same as that in ３ and W ４ The description, specific examples and preferred ranges of W in the above formula (1A) １ and W ２ It is the same as in

[0087] In formula (2A), c and d each independently represent an integer of 0 or greater. However, at least one of c and d represents an integer of 1 or greater. c and d each independently may represent an integer of 0 or greater and 100 or less, preferably an integer of 0 or greater and 10 or less, and more preferably an integer of 0 or greater and 5 or less. p and q in formula (2A) each independently represent an integer of 1 or greater, and may represent an integer of 1 or greater and 100 or less, preferably an integer of 1 or greater and 10 or less, and more preferably an integer of 1 or greater and 5 or less.

[0088] X ２ and Y ２ At least one of Y may have an OH group. ２ Examples of the amino acid residue include residues of bisaminophenol derivatives.

[0089] X ２ and Y ２ It is also preferable that at least one of X contains a polymerizable group, and it is also preferable that both of X contain a polymerizable group. ２ and Y ２ It is also preferable that at least one of the groups contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, or the like, and a radically polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radically polymerizable group possessed by the polyamide is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), with a group represented by the following formula (III) being preferred.

[0090]

[0091] In formula (III), R ２００represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and is preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site with another structure. In formula (III), R ２０１ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ -, a cycloalkylene group or a polyalkyleneoxy group. ２０１ Examples of the alkylene group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a dodecamethylene group; a 1,2-butanediyl group, a 1,3-butanediyl group; a —CH ２ CH(OH)CH ２ alkylene groups such as ethylene and propylene; ２ CH(OH)CH ２More preferred are alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups. 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 multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When a polyalkyleneoxy group contains multiple alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an arrangement having an alternating pattern. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent if the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. The alkylene group may also have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group. In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. The preferred embodiments of the number of repeating ethyleneoxy groups and the like in these groups are as described above.

[0092] X ２ and Y２ At least one of the groups may have a polarity conversion group such as an acid-decomposable group. The description, specific examples, and preferred range of the acid-decomposable group are as described above for X １ and Y １ It is the same as in

[0093] The polyamide preferably has fluorine atoms in its structure. The fluorine atom content in the polyamide is preferably 10% by mass or more and 20% by mass or less.

[0094] Furthermore, in order to improve adhesion to the substrate, the polyamide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.

[0095] The polyamide may contain only one type of repeating unit represented by formula (2A), or may contain two or more types of repeating units. The polyamide may contain other types of repeating units in addition to the repeating unit represented by formula (2A).

[0096] In one embodiment of the polyamide, the content of the repeating units represented by formula (2A) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyamide except for the terminal repeating units may be repeating units represented by formula (2A).

[0097] The weight-average molecular weight (Mw) of the polyamide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) of the polyamide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The polyamide molecular weight dispersity is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the polyamide molecular weight dispersity is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When the resin composition contains multiple types of polyamides, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamide be within the above-mentioned ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity, calculated by treating the plurality of polyamides as one resin, are each within the above ranges.

[0098] [Method for Producing Polyamide] Polyamide can be obtained by, for example, reacting a tetracarboxylic dianhydride with a diamine at low temperature, reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid, and then esterifying the polyamic acid using a condensing agent or an alkylating agent, obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting the diester with a diamine in the presence of a condensing agent, or obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine. Among the above-mentioned production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine is more preferred. 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, and trifluoroacetic anhydride. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the polyamide production method, it is preferable to use an organic solvent during the reaction. One or more organic solvents may be used. The organic solvent can be appropriately selected depending on the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing polyamide, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types.The basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0099] -End-capping agent- In order to further improve storage stability during the production method of polyamide, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyamide. When capping the carboxylic acid anhydride or acid anhydride derivative remaining at the resin terminal, examples of the end-capping agent include monoalcohols, phenols, thiols, thiophenols, and monoamines. In terms of reactivity and film stability, it is more preferable to use monoalcohols, phenols, or monoamines. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecynol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.Preferred examples of the monoamine compound include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples of suitable end-capping agents include 2-carboxy-7-aminonaphthalene, 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-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple end-capping agents may be reacted to introduce multiple different end groups. Furthermore, when capping the amino groups at the resin ends, they can be capped with a compound having a functional group capable of reacting with the amino group. Preferred examples of the capping agent for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, etc., and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides. Preferred carboxylic acid anhydride compounds include acetic anhydride, propionic acid anhydride, oxalic acid anhydride, succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, benzoic acid anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride.Preferred examples of carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.

[0100] -Solid Precipitation- The method for producing polyamide may include a step of precipitating a solid. Specifically, after filtering out water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution as needed, the resulting polymer component is added to a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof to precipitate the polymer component as a solid, which is then dried to obtain polyamide. To improve the degree of purification, the polyamide may be redissolved, reprecipitated, dried, or other procedures. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.

[0101] Next, preferred embodiments of formula (1A) and formula (2A) will be described. ０１ and P ０２ at least one of the groups represented by P in formula (2A) contains at least one group selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, and a phenylene ether group; ０３ and P ０４ It is preferable that at least one of them contains at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group and a phenylene ether group.

[0102] P in formula (1A) ０１ and P ０２ At least one of the groups represented by formula (2A) has a branched structure, ０３ and P ０４Preferably, at least one of the above has a branched structure. A branched structure refers to a structure in which the polymer chain in the resin (A) is branched. For example, when the resin (A) has a form such as a branched polymer, a graft polymer, a network polymer, a star polymer, or a dendrimer, it has a branched structure. A preferred embodiment of the branched structure is one in which the branched structure is composed of a main chain of the resin (A) and a branched chain bonded to the main chain. In this embodiment, it is more preferable that the formula weight of the branched chain constituting the branched structure is 100 or more. Another preferred embodiment of the branched structure is one in which the resin (A) is a network polymer. In this embodiment, it is more preferable that the formula weight of the group between the branch points of the network structure is 100 or more.

[0103] P in formula (1A) ０１ and P ０２ at least one of the repeating units has at least one selected from the group consisting of repeating units represented by the following formula (1-PA) and repeating units represented by the following formula (2-PA), and P in formula (2A) ０３ and P ０４ It is preferable that at least one of the repeating units has at least one selected from the group consisting of a repeating unit represented by the following formula (1-PA) and a repeating unit represented by the following formula (2-PA).

[0104]

[0105] In formula (1-PA) and formula (2-PA), X １ｐ , X ２ｐ , Y １ｐ and Y ２ｐ Each independently represents an organic group. １ｐ , W ２ｐ , W ３ｐ and W ４ｐ each independently represents a linking group. ０１ｐ , P ０２ｐ , P ０３ｐ and P ０４ｐeach independently represents an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenyl ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, and a fluoroalkylene group. ap, bp, cp, and dp each independently represent an integer of 0 or greater. However, at least one of ap and bp represents an integer of 1 or greater, and at least one of cp and dp represents an integer of 1 or greater. mp, np, pp, and qp each independently represent an integer of 1 or greater. W １ｐ , W ２ｐ , W ３ｐ , W ４ｐ , P ０１ｐ , P ０２ｐ , P ０３ｐ and P ０４ｐ When there are a plurality of each, they may be the same or different.

[0106] X in formula (1-PA) and formula (2-PA) １ｐ , X ２ｐ , Y １ｐ and Y ２ｐ The explanation, specific examples and preferred ranges of X in the above formula (1A) and formula (2A) are as follows. １ , X ２ , Y １ and Y ２ The W in formula (1-PA) and formula (2-PA) is the same as that in １ｐ , W ２ｐ , W ３ｐ and W ４ｐ The explanation, specific examples and preferred ranges of W in the above formula (1A) and formula (2A) are １ , W ２ , W ３ and W ４ P in formula (1-PA) and formula (2-PA) is the same as ０１ｐ , P ０２ｐ , P ０３ｐ and P ０４ｐ The description, specific examples and preferred ranges of P in the above formula (1A) and formula (2A) are ０１ , P ０２ , P ０３ and P ０４In formula (1-PA) and formula (2-PA), ap, bp, cp, and dp each independently represent an integer of 0 or more. However, at least one of ap and bp represents an integer of 1 or more, and at least one of cp and dp represents an integer of 1 or more. ap, bp, cp, and dp each independently may represent an integer of 0 or more and 100 or less. In formula (1-PA) and formula (2-PA), mp, np, pp, and qp each independently represent an integer of 1 or more, and may represent an integer of 1 or more and 100 or less.

[0107] P in formula (1A) ０１ and P ０２ has at least one repeating unit selected from the group consisting of a repeating unit represented by formula (1-PA) and a repeating unit represented by formula (2-PA), any hydrogen atom in the structure having at least one repeating unit selected from the group consisting of a repeating unit represented by formula (1-PA) and a repeating unit represented by formula (2-PA) is removed to form W １ and W ２ P in formula (1A) ０１ and P ０２ When at least one of the repeating units represented by formula (1-PA) and the repeating unit represented by formula (2-PA) is selected from the group consisting of repeating units represented by formula (1-PA), P ０１ and P ０２ may have at least one repeating unit selected from the group consisting of repeating units represented by formula (1-PA) and repeating units represented by formula (2-PA), as well as other structures (which may or may not be repeating units). ０３ and P ０４ has at least one repeating unit selected from the group consisting of the repeating unit represented by formula (1-PA) and the repeating unit represented by formula (2-PA), any hydrogen atom in the structure having at least one repeating unit selected from the group consisting of the repeating unit represented by formula (1-PA) and the repeating unit represented by formula (2-PA) is removed to form W ３ and W ４ P in formula (2A)０３ and P ０４ When at least one of the repeating units represented by formula (1-PA) and the repeating unit represented by formula (2-PA) is selected from the group consisting of repeating units represented by formula (1-PA), P ０３ and P ０４ may have at least one repeating unit selected from the group consisting of repeating units represented by formula (1-PA) and repeating units represented by formula (2-PA), as well as other structures (which may or may not be repeating units).

[0108] For example, in formula (1A), a represents 0, b represents 1, n represents 2, and two P ０２ has a repeating unit represented by formula (1-PA) (ap=0, bp=1, np=1), and P in formula (1-PA) ０２ｐ Any one hydrogen atom of W in formula (1A) is removed to form ２ When the repeating unit represented by formula (1A) is bonded to the repeating unit represented by formula (1A-1-PA) below,

[0109]

[0110] The definitions, explanations, specific examples and preferred ranges of each symbol in formula (1A-1-PA) are the same as those in formula (1A) and formula (1-PA) above, respectively.

[0111] It is preferable that at least one crosslinkable group is present at at least one terminal of the resin (A). The crosslinkable group preferably contains at least one selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group. Since the resin (A) has the specific group (X), there is little entanglement between polymers, but the presence of a crosslinkable group at the terminal increases the proportion of crosslinkable groups with little steric hindrance, improving crosslinking efficiency, which is thought to enable the formation of a film with high exposure curability and further improving resolution.

[0112] P in formula (1A) ０１ and P ０２ at least one of the groups has a crosslinkable group, and P in formula (2A) ０３ and P ０４Preferably, at least one of the above has a crosslinkable group. The crosslinkable group preferably contains at least one selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group.

[0113] P in formula (1A) ０１ and P ０２ At least one of the groups has a phenol group, and P in formula (2A) ０３ and P ０４ It is preferable that at least one of them has a phenol group.

[0114] Resin (A) may be a resin having at least one selected from the group consisting of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2): That is, the resin composition of the present invention may be a resin composition containing a resin having at least one selected from the group consisting of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2):

[0115]

[0116] In formula (1) and formula (2), X １ , X ２ , Y １ and Y ２ Each independently represents an organic group. １ , W ２ , W ３ and W ４ each independently represents a linking group. １ , P ２ , P ３ and P ４ each independently represents an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, and a fluoroalkylene group. １ , Q ２ , Q ３ and Q ４Each independently represents a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxy group, a thiol group, or a hydrogen atom. a, b, c, and d each independently represent an integer of 0 or more. However, at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more. m, n, p, and q each independently represent an integer of 1 or more. W １ , W ２ , W ３ , W ４ , P １ , P ２ , P ３ , P ４ , Q １ , Q ２ , Q ３ and Q ４ When there are a plurality of each, they may be the same or different.

[0117] X in formula (1) and formula (2) １ , X ２ , Y １ and Y ２ The explanation, specific examples and preferred ranges of X in the above formula (1A) and formula (2A) are as follows. １ , X ２ , Y １ and Y ２ The W in the formula (1) and the formula (2) is the same as １ , W ２ , W ３ and W ４ The explanation, specific examples and preferred ranges of W in the above formula (1A) and formula (2A) are １ , W ２ , W ３ and W ４In formula (1), a and b each independently represent an integer of 0 or more. However, at least one of a and b represents an integer of 1 or more. a and b each independently may represent an integer of 0 or more and 100 or less, preferably an integer of 0 or more and 10 or less, and more preferably an integer of 0 or more and 5 or less. In formula (1), m and n each independently represent an integer of 1 or more and may represent an integer of 1 or more and 100 or less, preferably an integer of 1 or more and 10 or less, and more preferably an integer of 1 or more and 5 or less. In formula (2), c and d each independently represent an integer of 0 or more. However, at least one of c and d represents an integer of 1 or more. c and d each independently may represent an integer of 0 or more and 100 or less, preferably an integer of 0 or more and 10 or less, and more preferably an integer of 0 or more and 5 or less. In formula (2), p and q each independently represent an integer of 1 or more, and may represent an integer of 1 or more and 100 or less, preferably an integer of 1 or more and 10 or less, and more preferably an integer of 1 or more and 5 or less.

[0118] P in formula (1) and formula (2) １ , P ２ , P ３ and P ４each independently represents an organic group containing at least one type (specific group (X)) selected from the group consisting of an imide group, an amide group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, and a fluoroalkylene group. The imide group is preferably a group represented by the aforementioned formula (PN-1). The amide group is preferably a group represented by the aforementioned formula (PN-2). The phenylene ether group is preferably a group represented by the aforementioned formula (PN-3). The benzoxazole group is preferably a group represented by the aforementioned formula (PN-4). The sulfonamide group is preferably a group represented by the aforementioned formula (PN-5). The group having three or more ester groups is preferably a group represented by the aforementioned formula (PN-6) or formula (PN-6-2). The siloxane group is preferably a group represented by the aforementioned formula (PN-7). The fluoroalkylene group may be linear or branched. The number of carbon atoms in the fluoroalkylene group is not particularly limited, but it is preferably 1 to 30. The fluoroalkylene group may be a perfluoroalkylene group. The fluoroalkylene group may have a substituent other than a fluorine atom.

[0119] P １ , P ２ , P ３ and P ４ The organic group represented by is not particularly limited except that it contains the specific group (X). １ , P ２ , P ３ and P ４ The organic group represented by may be the specific group (X) or may be a group consisting of the specific group (X) and another group. １ , P ２ , P ３ and P ４ The organic group represented by may have a repeating unit (may be a polymer chain). １ , P ２ , P ３ and P ４ The specific group (X) contained in the organic group represented by may be one type or two or more types.

[0120] Q in formula (1)１ and Q ２ each independently represents a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxy group, a thiol group, or a hydrogen atom. １ and Q ２ The monovalent organic group represented by is not particularly limited, and examples thereof include alkyl groups, aryl groups, cycloalkyl groups, alkoxy groups, aryloxy groups, cycloalkyloxy groups, acyl groups, heterocyclic groups, alkenyl groups, alkynyl groups, and groups formed by combining two or more of these groups. These organic groups may further have a substituent. １ and Q ２ There is no particular limitation on the number of carbon atoms of the monovalent organic group represented by Q, but it may be, for example, 1 to 100 carbon atoms. １ and Q ２ The halogen atom represented by is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0121] Q in formula (2) ３ and Q ４ The explanation, specific examples and preferred ranges of Q in the above formula (1) are １ and Q ２ It is the same as in

[0122] Next, preferred embodiments of formula (1) and formula (2) will be described. １ and P ２ at least one of the groups represented by P in formula (2) contains at least one selected from the group consisting of an imide group, an amide group, and a phenylene ether group; ３ and P ４ It is preferable that at least one of them contains at least one selected from the group consisting of an imide group, an amide group and a phenylene ether group.

[0123] P in formula (1) １ and P ２ At least one of P in formula (2) has a branched structure. ３ and P ４It is preferable that at least one of the above has a branched structure. The branched structure is as described above. A preferred embodiment of the branched structure is one in which the branched structure is composed of a main chain of the resin (A) and a branched chain bonded to the main chain. In this embodiment, it is more preferable that the formula weight of the branched chain constituting the branched structure is 100 or more. Another preferred embodiment of the branched structure is one in which the resin (A) is a network polymer. In this embodiment, it is more preferable that the formula weight of the group between the branch points of the network structure is 100 or more.

[0124] P in formula (1) １ and P ２ at least one of the repeating units has at least one selected from the group consisting of repeating units represented by the following formula (1-P) and repeating units represented by the following formula (2-P), ３ and P ４ It is preferable that at least one of the repeating units has at least one selected from the group consisting of repeating units represented by the following formula (1-P) and repeating units represented by the following formula (2-P).

[0125]

[0126] In formula (1-P) and formula (2-P), X １ｐ , X ２ｐ , Y １ｐ and Y ２ｐ Each independently represents an organic group. １ｐ , W ２ｐ , W ３ｐ and W ４ｐ each independently represents a divalent organic group. １ｐ , P ２ｐ , P ３ｐ and P ４ｐ each independently represents an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenyl ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, a fluoroalkyl group, and a fluoroalkylene group. １ｐ , Q ２ｐ , Q ３ｐ and Q ４ｐEach independently represents a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxy group, a thiol group, or a hydrogen atom. ap, bp, cp, and dp each independently represent an integer of 0 or greater. However, at least one of ap and bp represents an integer of 1 or greater, and at least one of cp and dp represents an integer of 1 or greater. mp, np, pp, and qp each independently represent an integer of 1 or greater. W １ｐ , W ２ｐ , W ３ｐ , W ４ｐ , P １ｐ , P ２ｐ , P ３ｐ , P ４ｐ , Q １ｐ , Q ２ｐ , Q ３ｐ and Q ４ｐ When there are a plurality of each, they may be the same or different.

[0127] X in formula (1-P) and formula (2-P) １ｐ , X ２ｐ , Y １ｐ and Y ２ｐ The explanation, specific examples and preferred ranges of X in the above formula (1) and formula (2) are as follows. １ , X ２ , Y １ and Y ２ The W in formula (1-P) and formula (2-P) is the same as １ｐ , W ２ｐ , W ３ｐ and W ４ｐ The explanation, specific examples and preferred ranges of W in the above formula (1) and formula (2) are １ , W ２ , W ３ and W ４ P in formula (1-P) and formula (2-P) is the same as １ｐ , P ２ｐ , P ３ｐ and P ４ｐ The explanation, specific examples and preferred ranges of P in the above formula (1) and formula (2) are １ , P ２ , P ３ and P ４ Q in formula (1-P) and formula (2-P) is the same as １ｐ , Q２ｐ , Q ３ｐ and Q ４ｐ The explanation, specific examples and preferred ranges of Q in the above formula (1) and formula (2) are １ , Q ２ , Q ３ and Q ４ In formula (1-P) and formula (2-P), ap, bp, cp, and dp each independently represent an integer of 0 or greater. However, at least one of ap and bp represents an integer of 1 or greater, and at least one of cp and dp represents an integer of 1 or greater. ap, bp, cp, and dp each independently may represent an integer of 0 or greater and 100 or less. In formula (1-P) and formula (2-P), mp, np, pp, and qp each independently represent an integer of 1 or greater, and may represent an integer of 1 or greater and 100 or less.

[0128] P in formula (1) １ and P ２ has at least one repeating unit selected from the group consisting of the repeating unit represented by formula (1-P) and the repeating unit represented by formula (2-P), any hydrogen atom in the structure having at least one repeating unit selected from the group consisting of the repeating unit represented by formula (1-P) and the repeating unit represented by formula (2-P) is removed to form W １ and W ２ P in formula (1) １ and P ２ When at least one of the repeating units represented by formula (1-P) and the repeating unit represented by formula (2-P) is selected from the group consisting of repeating units represented by formula (1-P), P １ and P ２ may have at least one repeating unit selected from the group consisting of repeating units represented by formula (1-P) and repeating units represented by formula (2-P), as well as other structures (which may or may not be repeating units). ３ and P ４has at least one repeating unit selected from the group consisting of the repeating unit represented by formula (1-P) and the repeating unit represented by formula (2-P), any hydrogen atom in the structure having at least one repeating unit selected from the group consisting of the repeating unit represented by formula (1-P) and the repeating unit represented by formula (2-P) is removed to form W ３ and W ４ P in formula (2) ３ and P ４ When at least one of the repeating units represented by formula (1-P) and the repeating unit represented by formula (2-P) is selected from the group consisting of repeating units represented by formula (1-P), P ３ and P ４ may have at least one repeating unit selected from the group consisting of repeating units represented by formula (1-P) and repeating units represented by formula (2-P), as well as other structures (which may or may not be repeating units).

[0129] The resin (A) preferably has at least one crosslinkable group at at least one terminal thereof, and the crosslinkable group preferably contains at least one group selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group.

[0130] Q in formula (1) １ and Q ２ At least one of the groups has a crosslinkable group, and Q in formula (2) ３ and Q ４ Preferably, at least one of the above has a crosslinkable group. The crosslinkable group preferably contains at least one selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group.

[0131] P in formula (1) １ , P ２ , Q １ and Q ２ satisfies at least one of the following (i) and (ii), and P in formula (2) ３ , P ４ , Q ３ and Q ４It is preferable that P satisfies at least one of the following conditions (iii) and (iv): １ represents a phenylene ether group, and Q １ represents a hydrogen atom. (ii): P ２ represents a phenylene ether group, and Q ２ represents a hydrogen atom. (iii): P ３ represents a phenylene ether group, and Q ３ represents a hydrogen atom. (iv): P ４ represents a phenylene ether group, and Q ４ represents a hydrogen atom.

[0132] [Content] The content of resin (A) in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of resin (A) in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of resin (A), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0133] The resin composition of the present invention preferably contains at least two resins. Specifically, the resin composition of the present invention may contain two or more resins in total, including the resin (A) and other resins described later, or may contain two or more resins (A). However, it is preferable to contain two or more resins (A). When the resin composition of the present invention contains two or more resins (A), for example, a polyamide having a structure derived from a dianhydride (X in formula (2A) ２ ) preferably contains two or more different polyamides.

[0134] <Other Resins> The resin composition of the present invention may contain resin (A) and another resin (hereinafter simply referred to as "other resin") different from resin (A). Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, and polybenzoxazole. For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described below, a resin having a high polymerizable group value and a weight average molecular weight of 20,000 or less (for example, a polymerizable group content of 1×10 per 1 g of resin) can be used. －３ By adding a (meth)acrylic resin (having a molecular weight of 1000 to 1000 mol / g or more) to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0135] When the resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. The content of the other resin in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. A preferred embodiment of the resin composition of the present invention may also be an embodiment in which the content of the other resin is low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, as long as it is 0% by mass or more. The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0136] <Polymerizable Compound> The resin composition of the present invention preferably contains a polymerizable compound (crosslinking agent). Examples of the polymerizable compound include a radical crosslinking agent and other crosslinking agents.

[0137] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group. Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

[0138] 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. The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds. From the viewpoint of the film strength of the obtained pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.

[0139] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0140] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, amino group, or sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogeno group or a tosyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0141] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0142] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0143] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), and dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue. Oligomers of these agents can also be used.

[0144] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates having four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, a trifunctional acrylate having three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers such as Examples of such an ester include UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and 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, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corporation).

[0145] Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418. Compounds having an amino structure or a sulfide structure in the molecule, such as those described in JP-A Nos. 63-277653, 63-260909, and JP-A No. 01-105238, can also be used as radical crosslinking agents.

[0146] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group. Particularly preferred is a radical crosslinking agent obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers M-510 and M-520 manufactured by Toagosei Co., Ltd.

[0147] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, more preferably 1 to 100 mgKOH / g. When the acid value of the radical crosslinking agent is within the above range, the agent has excellent handleability in production and developability. Furthermore, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0148] As the radical crosslinking agent, a radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond (hereinafter also referred to as "crosslinking agent U") is also preferred. In the present invention, the urea bond is a radical crosslinking agent having at least one selected from the group consisting of *-NR Ｎ —C(═O)—NR Ｎ- is a bond represented by *, and R Ｎ Each of the *'s independently represents a hydrogen atom or a monovalent organic group, and each * represents a bonding site with a carbon atom. In the present invention, the urethane bond is *—O—C(═O)—NR Ｎ - is a bond represented by *, and R Ｎ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. The inclusion of crosslinker U in a resin composition may improve chemical resistance, resolution, and the like. While the mechanism by which this effect is achieved is unclear, it is thought that, for example, a portion of crosslinker U thermally decomposes during curing by heating, generating amines, etc., which then promote the cyclization of precursors of cyclized resins such as polyimide precursors. Crosslinker U may have only one urea bond or urethane bond, one or more urea bonds and one or more urethane bonds, no urethane bonds and two or more urea bonds, or no urea bonds and two or more urethane bonds. The total number of urea bonds and urethane bonds in crosslinker U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When crosslinker U does not have a urethane bond, the number of urea bonds in crosslinker U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When the crosslinking agent U does not have a urea bond, the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0149] The radical polymerizable group in the crosslinking agent U is not particularly limited, but examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. A (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred. When the crosslinking agent U has two or more radical polymerizable groups, the structures of the respective radical polymerizable groups may be the same or different. The number of radical polymerizable groups in the crosslinking agent U may be only one or may be two or more, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. The radical polymerizable group value (mass of the compound per mole of radical polymerizable group) in the crosslinking agent U is preferably 150 to 400 g / mol. From the viewpoint of chemical resistance of the cured product, the lower limit of the radical polymerizable group value is more preferably 200 g / mol or more, even more preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, still more preferably 240 g / mol or more, and particularly preferably 250 g / mol or more. From the viewpoint of developability, the upper limit of the radical polymerizable group value is more preferably 350 g / mol or less, even more preferably 330 g / mol or less, and particularly preferably 300 g / mol or less. In particular, the polymerizable group value of crosslinking agent U is preferably 210 to 400 g / mol, and more preferably 220 to 400 g / mol.

[0150] The crosslinking agent U preferably has a structure represented by the following formula (U-1):

[0151]

[0152] In formula (U-1), R Ｕ１ represents a hydrogen atom or a monovalent organic group, and A represents —O— or —NR Ｎ - and R Ｎ is a hydrogen atom or a monovalent organic group, Z Ｕ１ is an m-valent organic group, and Z Ｕ２is an (n+1)-valent organic group, X is a radical polymerizable group, n is an integer of 1 or more, and m is an integer of 1 or more.

[0153] R Ｕ１ R is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom. Ｎ is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom. Ｕ１ represents a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded is preferred, and a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ - and -NR Ｎ - is more preferred. The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination of these. R Ｎ represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group. Ｕ２ represents a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded is preferred, and a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ - and -NR Ｎ A group bonded to at least one group selected from the group consisting of - is more preferred. Ｕ１Examples of the groups include those listed in 1. and preferred embodiments are also the same. X is not particularly limited, but examples include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group, with a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group being preferred, and a (meth)acryloxy group being more preferred. n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably 1 or 2, and particularly preferably 1. m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

[0154] It is also preferable that the crosslinking agent U has at least one of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group. From the viewpoint of the chemical resistance of the resulting cured film, the hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group, but an alcoholic hydroxy group is preferred. From the viewpoint of the chemical resistance of the resulting cured film, the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, even more preferably an alkyleneoxy group having 2 to 4 carbon atoms, even more preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. The alkyleneoxy group may be contained in the crosslinking agent U as a polyalkyleneoxy group. In this case, the number of repeating alkyleneoxy groups is preferably 2 to 10, more preferably 2 to 6. The amide group is a -C(=O)-NR Ｎ - refers to a bond represented by R Ｎ When the crosslinking agent U has an amide group, the crosslinking agent U may be, for example, R—C(═O)—NR Ｎ - a group represented by *, or *-C(=O)-NR ＮIt can be contained as a group represented by -R. R represents a hydrogen atom or a monovalent substituent, and is preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group. Crosslinking agent U may have two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (however, when a polyalkyleneoxy group is formed, a polyalkyleneoxy group), an amide group, and a cyano group in the molecule, but an embodiment in which only one structure is present in the molecule is also preferred. The hydroxy group, alkyleneoxy group, amide group, and cyano group may be present at any position in crosslinking agent U, but from the viewpoint of chemical resistance, it is also preferred that at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group is linked to at least one radically polymerizable group contained in crosslinking agent U via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-1"). In particular, when crosslinking agent U contains only one radically polymerizable group, it is preferred that the radically polymerizable group contained in crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group are linked via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2"). When crosslinking agent U contains an alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2, the structure bonded to the side of the alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. As the hydrocarbon group, a hydrocarbon group having 20 or fewer carbon atoms is preferred, a hydrocarbon group having 18 or fewer carbon atoms is more preferred, and a hydrocarbon group having 16 or fewer carbon atoms is even more preferred. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination thereof. Preferred embodiments of the radical polymerizable group are the same as those of the radical polymerizable group in the crosslinking agent U.When crosslinking agent U contains an amide group and has the linking group L2-1 or L2-2, the structure bonded to the side of the amide group opposite the linking group L2-1 or L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. The hydrocarbon group is preferably a hydrocarbon group having 20 or fewer carbon atoms, more preferably a hydrocarbon group having 18 or fewer carbon atoms, and even more preferably a hydrocarbon group having 16 or fewer carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination thereof. Preferred aspects of the radically polymerizable group are the same as those of the radically polymerizable group in crosslinking agent U described above. In the above aspect, the carbon atom side of the amide group may be bonded to the linking group L2-1 or L2-2, or the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or L2-2. Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferable that crosslinking agent U have a hydroxy group.

[0155] From the viewpoint of compatibility with the specific resin, etc., the crosslinking agent U preferably contains an aromatic group. The aromatic group is preferably directly bonded to a urea bond or urethane bond contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring structure. The aromatic heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocycle in such an aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings may be condensed with other rings, for example, indole or benzimidazole. The heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The aromatic group is preferably contained in a linking group that links two or more radical polymerizable groups and contains a urea bond or a urethane bond, or a linking group that links at least one selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, amide group, and cyano group to at least one radical polymerizable group contained in the crosslinking agent U.

[0156] The number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group in crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10. When crosslinking agent U contains a total of two or more urea bonds or urethane bonds, when it contains two or more radical polymerizable groups, or when it contains two or more urea bonds or urethane bonds and two or more radical polymerizable groups, the minimum number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group may be within the above range. In this specification, the "number of atoms (linking chain length) between the urea bond or urethane bond and the polymerizable group" refers to the atomic chain on the path connecting the two atoms or atomic groups to be linked that connects these objects via the shortest distance (minimum number of atoms). For example, in the structure represented by the following formula, the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.

[0157]

[0158] [Axis of symmetry] It is also preferable that the crosslinking agent U is a compound having a structure that does not have an axis of symmetry. The fact that the crosslinking agent U does not have an axis of symmetry means that the crosslinking agent U is a bilaterally asymmetric compound that does not have an axis that would produce a molecule identical to the original molecule by rotating the entire compound. Furthermore, when the structural formula of the crosslinking agent U is written on paper, the fact that the crosslinking agent U does not have an axis of symmetry means that the structural formula of the crosslinking agent U cannot be written in a form that has an axis of symmetry. It is believed that the fact that the crosslinking agent U does not have an axis of symmetry suppresses aggregation of the crosslinking agent U molecules in the composition film.

[0159] [Molecular Weight] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 200 to 900.

[0160] The method for producing the crosslinking agent U is not particularly limited, but it can be obtained, for example, by reacting a radical polymerizable compound and a compound having an isocyanate group with a compound having at least one of a hydroxy group and an amino group.

[0161] Specific examples of the crosslinking agent U are shown below, but the crosslinking agent U is not limited to these.

[0162]

[0163]

[0164]

[0165] From the viewpoints of pattern resolution and film stretchability, the resin composition preferably uses a bifunctional methacrylate or acrylate. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 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, ethylene oxide (EO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, isocyanuric acid-modified dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of approximately 200 for the polyethylene glycol chain. From the viewpoint of suppressing warpage of the pattern (cured product), a monofunctional radical crosslinking agent can preferably be used as the radical crosslinking agent in the resin composition of the present invention.Preferred examples of monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. Preferred monofunctional radical crosslinking agents include compounds having a boiling point of 100°C or higher under normal pressure in order to suppress volatilization before exposure. Other examples of bifunctional or higher radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0166] When a radical crosslinking agent is contained, the content of the radical crosslinking agent is preferably more than 0% by mass and not more than 60% by mass, based on the total solid content of the resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0167] The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount thereof is preferably within the above range.

[0168] [Other Crosslinking Agents] The resin composition of the present invention preferably contains another crosslinking agent different from the radical crosslinking agent described above. The other crosslinking agent refers to a crosslinking agent other than the radical crosslinking agent described above. The other crosslinking agent is preferably a compound having, in its molecule, a plurality of groups that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products upon exposure to light by a photoacid generator or a photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products under the action of an acid or a base. The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step. The other crosslinking agent is preferably a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group, and more preferably a compound having a structure in which at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group is directly bonded to a nitrogen atom. Furthermore, the other crosslinking agent preferably has a total of two or more acyloxymethyl groups, methylol groups, ethylol groups, and alkoxymethyl groups. Among these, compounds having two or more acyloxymethyl groups, compounds having two or more methylol groups, compounds having two or more ethylol groups, or compounds having two or more alkoxymethyl groups are more preferred. Examples of other crosslinking agents include compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and an alcohol, and the hydrogen atom of the amino group is substituted with an acyloxymethyl group, methylol group, ethylol group, or alkoxymethyl group. The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compound produced by the above method may be used. Oligomers formed by self-condensation of methylol groups of these compounds may also be used.As the amino group-containing compound, a crosslinking agent using melamine is called a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea, or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluril-based crosslinking agents and melamine-based crosslinking agents, which will be described later.

[0169] Examples of compounds containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the urea structure described below, or on a triazine. The alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the above compound is preferably 1,500 or less, more preferably 180 to 1,200.

[0170]

[0171] R １００ represents an alkyl group or an acyl group. １０１ and R １０２ each independently represents a monovalent organic group, and may be bonded to each other to form a ring.

[0172] Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula:

[0173]

[0174] In the formula, X represents a single bond or a divalent organic group, and each R １０４ each independently represents an alkyl group or an acyl group, R １０３represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes under the action of an acid to generate an alkali-soluble group (for example, a group that is eliminated under the action of an acid, -C(R ４ ) ２ COOR ５ A group represented by R ４ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ５ represents a group that is eliminated by the action of an acid. １０５ each independently represents an alkyl group or an alkenyl group, a, b, and c each independently represent 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. A group that decomposes under the action of an acid to produce an alkali-soluble group, a group that is eliminated under the action of an acid, -C(R ４ ) ２ COOR ５ R in the group represented by ５ For example, -C(R ３６ ) (R ３７ ) (R ３８ ), -C(R ３６ ) (R ３７ ) (OR ３９ ), -C(R ０１ ) (R ０２ ) (OR ３９ In the formula, R ３６ ~R ３９ R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ３６ and R ３７may be bonded to each other to form a ring. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may be either linear or branched. The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, more preferably a cycloalkyl group having 3 to 8 carbon atoms. The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group. The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 16 carbon atoms. The aralkyl group refers to an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the alkyl and aryl groups described above. The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms. These groups may further have a known substituent.

[0175] R ０１ and R ０２ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0176] The group that decomposes under the action of an acid to generate an alkali-soluble group or the group that is eliminated under the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc., more preferably a tertiary alkyl ester group or an acetal group.

[0177] Furthermore, as the compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group, a compound having at least one group selected from the group consisting of a urea bond and a urethane bond is also preferred. The preferred embodiments of the above compound are the same as the preferred embodiments of the above crosslinking agent U, except that the polymerizable group is not a radical polymerizable group but at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group.

[0178] Specific examples of compounds having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an ethylol group include the following structures: Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group in the following compound is replaced with an acyloxymethyl group: Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds:

[0179]

[0180]

[0181]

[0182] The compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be a commercially available compound or may be synthesized by a known method. 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 triazine ring is preferred.

[0183] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0184] Specific examples of the urea-based crosslinking agent include glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril; urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; Ethylene urea-based crosslinking agents such as monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea, or dibutoxymethylated ethylene urea; propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea; Examples thereof include 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

[0185] Specific examples of benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0186] In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidenetris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], and 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol.

[0187] As other crosslinking agents, commercially available products may be used, and suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Chemicals Co., Ltd.), 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, and 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 (all manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac (registered trademark, the same applies hereinafter) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), and the like.

[0188] The resin composition of the present invention also preferably contains, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0189] - Epoxy Compound (Compound Having Epoxy Group) - The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at 200°C or less, and since dehydration reactions resulting from crosslinking do not occur, film shrinkage is unlikely to occur. Therefore, the inclusion of an epoxy compound is effective in low-temperature curing of the resin composition and suppressing warpage.

[0190] The epoxy compound preferably contains a polyethylene oxide group, which further reduces the modulus of elasticity and suppresses warpage. The polyethylene oxide group refers to a group having two or more repeating ethylene oxide units, and preferably has 2 to 15 repeating units.

[0191] Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane. Specifically, Epicron (registered trademark, the same applies hereinafter) 850-S, Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron HP-4770, Epicron EXA-830LVP, Epicron EXA-8183, Epicron EXA-8169, Epicron N-660, Epicron N-665-EXP-S, Epicron N-740 (all trade names, manufactured by DIC Corporation), Rikaresin (registered trademark, the same applies below) BEO-20E, Rikaresin BEO-60E, Rikaresin HBE-100, Rikaresin DME-100, Rikaresin L-200 (all trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (all trade names, manufactured by ADEKA Corporation), Ceroxa Epolead (registered trademark, the same applies hereinafter) 2021P, Celloxide 2081, Celloxide 2000, EHPE3150, Epolead (registered trademark, the same applies hereinafter) GT401, Epolead PB4700, Epolead PB3600 (all trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-30 00-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 (all trade names, manufactured by Nippon Kayaku Co., Ltd.), and the like.The following compounds are also preferably used:

[0192]

[0193] In the formula, n is an integer of 1 to 5, and m is an integer of 1 to 20.

[0194] Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7 in order to achieve both improved heat resistance and improved elongation.

[0195] -Oxetane Compound (Compound Having an Oxetanyl Group)- Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, such as 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. Specific examples include the Aron Oxetane series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd., which may be used alone or in combination of two or more.

[0196] - Benzoxazine Compound (Compound Having a Benzoxazolyl Group) - Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and further, they reduce thermal shrinkage and suppress the occurrence of warping.

[0197] Preferred examples of the benzoxazine compound include Pd-type benzoxazine, Fa-type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

[0198] The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total amount thereof is preferably within the above range.

[0199] [Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator (also referred to as "initiator"). The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to contain a photopolymerization initiator. The photopolymerization initiator may be a photoradical polymerization initiator or a photoacid generator.

[0200] (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 that is photosensitive to light in the ultraviolet to visible range is preferred. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0201] The photoradical polymerization initiator has a capacity of at least about 50 L·mol within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１ The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure the molar absorption coefficient using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0202] Any known compound can be used as the photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, and iron arene complexes. For details of these compounds, please refer to paragraphs

[0165] to

[0182] of JP 2016-027357 A and paragraphs

[0138] to

[0151] of WO 2015 / 199219 A, the contents of which are incorporated herein by reference. Further, paragraphs 0065 to 0111 of JP 2014-130173 A, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3,2019 described peroxide-based photopolymerization initiators, photopolymerization initiators described in WO 2018 / 221177, photopolymerization initiators described in WO 2018 / 110179, photopolymerization initiators described in JP 2019-043864 A, photopolymerization initiators described in JP 2019-044030 A, peroxide-based initiators described in JP 2019-167313 A can be mentioned, the contents of which are incorporated herein by reference.

[0203] Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0204] In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, or an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 or an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

[0205] Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).

[0206] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), and IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF).

[0207] As the aminoacetophenone initiator, acylphosphine oxide initiator, and metallocene compound, for example, compounds described in paragraphs 0161 to 0163 of WO 2021 / 112189 can also be suitably used. The contents of this specification are incorporated herein by reference.

[0208] As the photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. An oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0209] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), compounds described in J. C. S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232) described compounds, compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017 / 164127, compounds described in WO 2013 / 167515 and the like, the contents of which are incorporated herein.

[0210] Preferred oxime compounds include, for example, compounds having the following structure: 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

[0211]

[0212] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito ChemiX Co., Ltd.), and SpeedCure PDO (SARTOMER Also, an oxime compound having the following structure can be used.

[0213]

[0214] Examples of photoradical polymerization initiators include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, and oxime compounds having a fluorine atom, as described in paragraphs 0169 to 0171 of WO 2021 / 112189. Also usable are oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxy group is bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of WO 2021 / 020359. The contents of these compounds are incorporated herein by reference.

[0215] As the photopolymerization initiator, an aromatic ring group Ar in which an electron-withdrawing group is introduced into the aromatic ring can be used. ＯＸ１ It is also possible to use an oxime compound having the aromatic ring group Ar ＯＸ１Examples of the electron-withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. Acyl and nitro groups are preferred, and an acyl group is more preferred because it is easier to form a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group. An alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group is more preferred, and an alkoxy group, an alkylsulfanyl group, or an amino group is even more preferred.

[0216] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2).

[0217]

[0218] In the formula, R Ｘ１ represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group; R Ｘ２ represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group; R Ｘ３ ~R Ｘ１４each independently represents a hydrogen atom or a substituent. Ｘ１０ ~R Ｘ１４ At least one of the groups is an electron-withdrawing group.

[0219] In the above formula, R Ｘ１２ is an electron-withdrawing group, and R Ｘ１０ , R Ｘ１１ , R Ｘ１３ , R Ｘ１４ is preferably a hydrogen atom.

[0220] Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.

[0221] Particularly preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP-A-2007-269779 and oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, the contents of which are incorporated herein by reference.

[0222] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

[0223] The photoradical polymerization initiator is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound, more preferably at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, or a benzophenone compound, and even more preferably a metallocene compound or an oxime compound.

[0224] As the photoradical polymerization initiator, the compounds described in paragraphs 0175 to 0179 of WO 2021 / 020359 and the compounds described in paragraphs 0048 to 0055 of WO 2015 / 125469 can also be used, the contents of which are incorporated herein by reference.

[0225] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thereby obtaining good sensitivity. Furthermore, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, and improving the stability of the resin composition over time. Specific examples of the bifunctional or trifunctional or higher functional photoradical polymerization initiator include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO 2015 / 004565, WO 2016-532675, paragraphs 0407 to 0412, and WO 2017 / 033680, paragraphs 0039 to 0055; compounds (E) and (G) described in JP-T-2013-522445; oxime ester photoinitiators described in paragraph 0007 of JP-T-2017-523465, photoinitiators described in paragraphs 0020 to 0033 of JP-A-2017-167399, photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, and oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0226] When the resin composition contains a photopolymerization initiator, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. Note that the photopolymerization initiator may also function as a thermal polymerization initiator, and therefore crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, hot plate, or the like.

[0227] (Photoacid Generator) The polymerization initiator may be a photoacid generator. The photoacid generator refers to a compound that generates at least one of a Bronsted acid and a Lewis acid when irradiated with light having a wavelength of 200 nm to 900 nm. The irradiated light is preferably light having a wavelength of 300 nm to 450 nm, more preferably light having a wavelength of 330 nm to 420 nm. The photoacid generator is preferably a photoacid generator that can generate an acid upon exposure to light, either alone or in combination with a sensitizer. Preferred examples of the acid that can be generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acids, phosphoric acid monoesters, phosphoric acid diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogenated peroxides, and sulfonamides.

[0228] Examples of photoacid generators include quinone diazide compounds, oxime sulfonate compounds, organic halide compounds, organic borate compounds, disulfone compounds, onium salt compounds, etc. From the viewpoints of sensitivity and storage stability, organic halide compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the viewpoints of the mechanical properties of the film to be formed, etc., oxime esters are preferred.

[0229] Examples of quinone diazide compounds include those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent hydroxy compound, those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent amino compound via sulfonamide, and those in which the sulfonic acid of quinone diazide is ester-bonded and / or sulfonamide-bonded to a polyhydroxy polyamino compound. Not all functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxy polyamino compounds need to be substituted with quinone diazide, but it is preferred that on average 40 mol% or more of the total functional groups are substituted with quinone diazide. By incorporating such quinone diazide compounds, it is possible to obtain a resin composition that is photosensitive to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which are common ultraviolet rays.

[0230] Specific examples of hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, and BisOCP. -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PC HP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriM L-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP -PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (product names, Asahi Yu Examples of suitable phenolic resins include, but are not limited to, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and novolak resins.

[0231] Specific examples of the amino compound include, but are not limited to, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0232] Specific examples of polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

[0233] Among these, it is preferable that the quinone diazide compound contains an ester of a phenol compound and a 4-naphthoquinone diazide sulfonyl group, which can provide higher sensitivity to i-line exposure and higher resolution.

[0234] The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the resin. By setting the content of the quinone diazide compound within this range, a contrast between exposed and unexposed areas can be obtained, thereby achieving higher sensitivity, which is preferable. Furthermore, a sensitizer or the like may be added as necessary.

[0235] The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter simply referred to as an "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably a compound represented by the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105).

[0236]

[0237] In formula (OS-1), X ３ represents an alkyl group, an alkoxy group, or a halogen atom. ３ When there are a plurality of X, they may be the same or different. ３ The alkyl group and alkoxy group in may have a substituent. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom is preferably a chlorine atom or a fluorine atom. m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or 3, a plurality of X３ may be the same or different. ３４ represents an alkyl group or an aryl group, and is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

[0238] In formula (OS-1), m3 is 3, and X ３ is a methyl group, and X ３ is substituted at the ortho position, and R ３４ Particularly preferred are compounds in which is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group, or a p-tolyl group.

[0239] Specific examples of the oxime sulfonate compound represented by Formula (OS-1) include the following compounds described in paragraphs

[0064] to

[0068] of JP2011-209692A and paragraphs

[0158] to

[0167] of JP2015-194674A, the contents of which are incorporated herein by reference.

[0240]

[0241] In formulas (OS-103) to (OS-105), R ｓ１ represents an alkyl group, an aryl group, or a heteroaryl group, and R may be present in plural. ｓ２ R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and R may be present in plural. ｓ６ each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer of 0 to 6. R ｓ１The alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms) or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by the formula (I) may have a substituent.

[0242] R ｓ２ is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), more preferably a hydrogen atom or an alkyl group. ｓ２ Among R, it is preferred that one or two of them are an alkyl group, an aryl group, or a halogen atom, it is more preferred that one of them is an alkyl group, an aryl group, or a halogen atom, and it is particularly preferred that one of them is an alkyl group and the remaining one is a hydrogen atom. ｓ２ The alkyl group or aryl group represented by the following formula may have a substituent. Xs represents O or S, and is preferably O. In the above formulae (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered or 6-membered ring.

[0243] ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2. R ｓ６ The alkyl group (preferably having 1 to 30 carbon atoms) and alkyloxy group (preferably having 1 to 30 carbon atoms) represented by the following formula may have a substituent. ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0244] The compound represented by formula (OS-103) is preferably a compound represented by the following formula (OS-106), formula (OS-110), or formula (OS-111); the compound represented by formula (OS-104) is preferably a compound represented by the following formula (OS-107); and the compound represented by formula (OS-105) is particularly preferably a compound represented by the following formula (OS-108) or formula (OS-109).

[0245]

[0246] In formulas (OS-106) to (OS-111), Rｔ１ represents an alkyl group, an aryl group, or a heteroaryl group; R ｔ７ represents a hydrogen atom or a bromine atom, R ｔ８ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group; R ｔ９ represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group; R ｔ２ represents a hydrogen atom or a methyl group.

[0247] R ｔ７ represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom. ｔ８ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group, and is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0248] R ｔ９ represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, and is preferably a hydrogen atom. ｔ２ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. In the above oxime sulfonate compounds, the stereochemistry (E, Z) of the oxime may be either one or a mixture. Specific examples of the oxime sulfonate compounds represented by Formulae (OS-103) to (OS-105) include the compounds described in JP-A-2011-209692, paragraphs

[0088] to

[0095] and JP-A-2015-194674, paragraphs

[0168] to

[0194] , the contents of which are incorporated herein by reference.

[0249] Other preferred embodiments of the compound containing at least one oxime sulfonate group include compounds represented by the following formula (OS-101) and formula (OS-102).

[0250]

[0251] In formula (OS-101) and formula (OS-102), R ｕ９ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. ｕ９ is preferably a cyano group or an aryl group, more preferably a cyano group, a phenyl group or a naphthyl group. ｕ２ａ represents an alkyl group or an aryl group. Xu represents —O—, —S—, —NH—, —NR ｕ５ -, -CH ２ -, -CR ｕ６ H- or CR ｕ６ R ｕ７ represents -, and R ｕ５ ~R ｕ７ each independently represents an alkyl group or an aryl group.

[0252] R ｕ１ ~R ｕ４ R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amido group, a sulfo group, a cyano group, or an aryl group. ｕ１ ~R ｕ４ Two of the groups may be bonded to each other to form a ring. In this case, the rings may be condensed together with the benzene ring to form a condensed ring. ｕ１ ~R ｕ４ is preferably a hydrogen atom, a halogen atom or an alkyl group. ｕ１ ~R ｕ４ At least two of these may be bonded to each other to form an aryl group. ｕ１ ~R ｕ４ are preferably all hydrogen atoms. Each of the above-mentioned substituents may further have a substituent.

[0253] The compound containing at least one oxime sulfonate group is more preferably a compound represented by formula (OS-102). Furthermore, in the oxime sulfonate compound, the stereostructures (E, Z, etc.) of the oxime and benzothiazole rings may each be either one or a mixture. Specific examples of the compound represented by formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of JP-A No. 2011-209692 and paragraphs 0195 to 0207 of JP-A No. 2015-194674, the contents of which are incorporated herein by reference. Among the above compounds, the following compounds b-9, b-16, b-31, and b-33 are preferred.

[0254]

[0255] Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and MBZ-101 (manufactured by Midori Chemical Industries, Ltd.).

[0256] Further, compounds represented by the following structural formulas are also preferred examples.

[0257]

[0258] Examples of organic halogenated compounds include compounds described in paragraphs 0042 to 0043 of JP 2015-087409 A, the contents of which are incorporated herein by reference.

[0259] The content of the photoacid generator is preferably 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, even more preferably 0.5 to 10% by mass, even more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass, based on the total solid content of the resin composition. The photoacid generator may be used alone or in combination with multiple types. In the case of a combination of multiple types, it is preferable that the total amount thereof is within the above range. It is also preferable to use a sensitizer in combination with the photoacid generator to impart photosensitivity to a desired light source.

[0260] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and undergoes electron transfer, energy transfer, heat generation, and other actions. This causes the thermal radical polymerization initiator or the photoradical polymerization initiator to undergo a chemical change and decompose, generating a radical, acid, or base. Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds.Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, and Non, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Examples of sensitizing dyes include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details of sensitizing dyes, please refer to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein by reference.

[0261] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and still more preferably 0.5 to 10 mass %, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0262] [Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of chain transfer agents include those having -S-S-, -SO ２ Compounds having -S-, -N-O-, SH, PH, SiH, and GeH, and dithiobenzoates, trithiocarbonates, dithiocarbamates, xanthate compounds, and the like having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization can be used. These compounds can donate hydrogen to a low-activity radical to generate a radical, or can be oxidized and then deprotonated to generate a radical. In particular, thiol compounds can be preferably used.

[0263] In addition, the chain transfer agent may be a compound described in paragraphs 0152 to 0153 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0264] When the resin composition contains 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, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, the total content thereof is preferably within the above range.

[0265] <Base Generator> The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example, by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in excellent performance as an interlayer insulating film for a rewiring layer included in a semiconductor package. 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 is not particularly limited, and known base generators can be used. Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxyimino compounds, etc. Specific examples of non-ionic base generators include compounds represented by formula (B1), formula (B2), or formula (B3).

[0266]

[0267] In formula (B1) and formula (B2), Rb １ , Rb ２ and Rb ３ each independently represents an organic group not having a tertiary amine structure, a halogen atom, or a hydrogen atom, provided that Rb １ and Rb ２ cannot be hydrogen atoms at the same time. １ , Rb ２ and Rb ３None of the above has a carboxy group. In this specification, the term "tertiary amine structure" refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to carbon atoms of a hydrocarbon group. Therefore, if the carbon atom bonded to the trivalent nitrogen atom is a carbon atom constituting a carbonyl group, i.e., if it forms an amide group together with the nitrogen atom, it is not a tertiary amine structure.

[0268] In formula (B1) and formula (B2), Rb １ , Rb ２ and Rb ３ Preferably, at least one of these contains a cyclic structure, and more preferably, at least two contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a fused ring, and a monocyclic ring or a fused ring in which two monocyclic rings are fused is preferred. The monocyclic ring is preferably a 5-membered or 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably a cyclohexane ring.

[0269] More specifically, Rb １ and Rb ２ is preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). These groups may have a substituent. Rb １ and Rb ２ may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. １ and Rb ２is preferably a linear, branched, or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, more preferably a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, and even more preferably a cyclohexyl group which may have a substituent.

[0270] Rb ３ Examples of the alkyl group include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and even more preferably having 2 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), an arylalkenyl group (preferably having 8 to 24 carbon atoms, more preferably having 8 to 20 carbon atoms, and even more preferably having 8 to 16 carbon atoms), an alkoxyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), and an arylalkyloxy group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). Among these, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferred. ３ may further have a substituent.

[0271] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or (B1-2):

[0272]

[0273] In the formula, Rb １１ and Rb １２ , and Rb ３１ and Rb ３２ respectively represent Rb in formula (B1). １ and Rb ２ is the same as Rb１３ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), which may have a substituent. １３ is preferably an arylalkyl group.

[0274] Rb ３３ and Rb ３４ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and still more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 8 carbon atoms, and still more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and still more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and still more preferably having 7 to 11 carbon atoms), and a hydrogen atom is preferred.

[0275] Rb ３５ represents an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), with an aryl group being preferred.

[0276] The compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a).

[0277]

[0278] Rb １１ and Rb １２ represents Rb in formula (B1-1). １１ and Rb １２ Rb １５ and Rb１６ is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and even more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and even more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 11 carbon atoms), and preferably a hydrogen atom or a methyl group. １７ represents an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and among these, an aryl group is preferred.

[0279]

[0280] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the path of a linking chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the linking chain is 3 or more. Ｎ１ and R Ｎ２ each independently represents a monovalent organic group.

[0281] In this specification, the term "linking chain" refers to the chain of atoms on the path connecting two atoms or groups of atoms to be linked, which links these atoms or groups of atoms in the shortest possible manner (with the smallest number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group and has an ethylene group as the saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length" or "length of the linking chain") is 4.

[0282]

[0283] The number of carbon atoms in L in formula (B3) (including carbon atoms other than those in the connecting chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly progressing the intramolecular cyclization reaction, the upper limit of the connecting chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the connecting chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds for the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of WO 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of WO 2018 / 038002.

[0284] The base generator also preferably contains a compound represented by the following formula (N1).

[0285]

[0286] In formula (N1), R Ｎ１ and R Ｎ２ each independently represents a monovalent organic group, R Ｃ１ represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0287] L is a divalent linking group, and is preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms present in the atomic sequence that forms the shortest path between the two carbonyl groups in the formula.

[0288] In formula (N1), R Ｎ１ and R Ｎ２R each independently represents a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), and is preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms). Specific examples include an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), and an aliphatic hydrocarbon group is preferred. Ｎ１ and R Ｎ２ When an aliphatic hydrocarbon group is used as the base, the basicity of the generated base is high, and this is preferable. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain, in the aromatic ring, or in the substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

[0289] R Ｎ１ and R Ｎ２Examples of the aliphatic hydrocarbon group constituting the alkyl group include linear or branched chain alkyl groups, cyclic alkyl groups, groups containing a combination of a linear alkyl group and a cyclic alkyl group, and alkyl groups having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, and isohexyl groups. The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. The group containing a combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms. Examples of the group containing a combination of a chain alkyl group and a cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group. The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched. In particular, from the viewpoint of increasing the boiling point of the decomposition product base described below, R Ｎ１ and R Ｎ２ is preferably an alkyl group having 5 to 12 carbon atoms. However, in a formulation where importance is placed on adhesion when laminating with a metal (e.g., copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

[0290] R Ｎ１ and R Ｎ２ may be linked to each other to form a cyclic structure. The cyclic structure may have an oxygen atom or the like in the chain. Ｎ１ and R Ｎ２The cyclic structure formed by may be a monocyclic ring or a fused ring, but is preferably a monocyclic ring. The cyclic structure formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc., and preferred examples include a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.

[0291] R Ｃ１ represents a hydrogen atom or a protecting group, preferably a hydrogen atom. The protecting group is preferably a protecting group that decomposes under the action of an acid or a base, and preferably a protecting group that decomposes with an acid. Specific examples of the protecting group include linear or cyclic alkyl groups and linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a cyclohexyl group. Examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and preferred are a methyloxymethyl (MOM) group and an ethyloxyethyl (EE) group. Examples of cyclic alkyl groups having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl (THP) group.

[0292] In formula (N1), the divalent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent and may have atoms other than carbon atoms in the hydrocarbon chain. The divalent linking group is more preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a group containing a combination of a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, and even more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. These groups may not have an oxygen atom. The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group containing a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10 carbon atoms.

[0293] Specific examples of the linking group L include linear or branched chain alkylene groups, cyclic alkylene groups, groups containing a combination of linear alkylene groups and cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, linear or branched chain alkenylene groups, cyclic alkenylene groups, arylene groups, and arylene alkylene groups. The linear or branched chain alkylene groups preferably have 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The cyclic alkylene groups preferably have 3 to 12 carbon atoms, more preferably 3 to 6. The groups containing a combination of linear alkylene groups and cyclic alkylene groups preferably have 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. The alkylene groups having an oxygen atom in the chain may be linear or cyclic, linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0294] The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The linear or branched chain alkenylene group preferably has 1 to 10 C═C bonds, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenylene group preferably has 1 to 6 C═C bonds, more preferably 1 to 4, and even more preferably 1 to 2. The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among these, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferred, and a 1,2-ethylene group, a propanediyl group (particularly a 1,3-propanediyl group), a cyclohexanediyl group (particularly a 1,2-cyclohexanediyl group), a vinylene group (particularly a cis-vinylene group), a phenylene group (1,2-phenylene group), a phenylenemethylene group (particularly a 1,2-phenylenemethylene group), and an ethyleneoxyethylene group (particularly a 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.

[0295] Examples of the base generator include, but are not limited to, the following compounds:

[0296]

[0297] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0298] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0299] Specific examples of ammonium salts include, but are not limited to, the following compounds:

[0300]

[0301] Specific examples of iminium salts include, but are not limited to, the following compounds:

[0302]

[0303] When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass per 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generators can be used. When two or more types are used, the total amount is preferably within the above range.

[0304] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0305] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionates, Preferred examples of the alkyl cypropionate include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

[0306] Suitable 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 dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve 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, and dipropylene glycol dimethyl ether.

[0307] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0308] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0309] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0310] Preferred examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0311] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0312] 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, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

[0313] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0314] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more solvents, is preferred. Particularly preferred are a combination of dimethyl sulfoxide and γ-butyrolactone, a combination of dimethyl sulfoxide and γ-valerolactone, a combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, a combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or a combination of N-methyl-2-pyrrolidone and ethyl lactate. An embodiment in which toluene is further added to these combined solvents in an amount of approximately 1 to 10% by mass, based on the total mass of the solvent, is also a preferred embodiment of the present invention. In particular, from the viewpoint of the storage stability of the resin composition, an embodiment in which γ-valerolactone is included as a solvent is also a preferred embodiment of the present invention. In such an embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass. The above content may be determined taking into consideration the solubility of components such as the specific resin contained in the resin composition, etc. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90 mass% of γ-valerolactone and 10 to 40 mass% of dimethyl sulfoxide, more preferably 70 to 90 mass% of γ-valerolactone and 10 to 30 mass% of dimethyl sulfoxide, and even more preferably 75 to 85 mass% of γ-valerolactone and 15 to 25 mass% of dimethyl sulfoxide, relative to the total mass of the solvent.

[0315] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solids concentration of the resin composition of the present invention is 5 to 80 mass%, more preferably an amount such that the total solids concentration is 5 to 75 mass%, even more preferably an amount such that the total solids concentration is 10 to 70 mass%, and even more preferably an amount such that the total solids concentration is 20 to 70 mass%. The solvent content may be adjusted depending on the desired thickness of the coating film and the coating method. When two or more solvents are contained, the total amount of the solvents is preferably within the above range.

[0316] <Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, and an amino compound.

[0317] [Silane Coupling Agent] Examples of silane coupling agents include the compounds described in paragraph 0316 of WO 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of JP 2011-128358 A. It is also preferable to use the following compound as the silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group.

[0318]

[0319] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0320] [Aluminum-Based Adhesion Aid] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0321] Other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935, the contents of which are incorporated herein by reference.

[0322] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By ensuring that the content is equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer is improved, and by ensuring that the content is equal to or less than the above upper limit, the heat resistance and mechanical properties of the pattern are improved. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0323] <Polymerization Inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0324] Specific examples of the polymerization inhibitor include the compounds described in paragraph 0310 of WO 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and phenoxazine, the contents of which are incorporated herein by reference.

[0325] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass%, more preferably 0.02 to 15 mass%, and even more preferably 0.05 to 10 mass%, based on the total solid content of the resin composition.

[0326] The polymerization inhibitor may be one kind or two or more kinds. When two or more kinds of polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0327] <Acid Scavenger> The resin composition of the present invention preferably contains an acid scavenger to reduce performance changes over time from exposure to heating. Here, the acid scavenger refers to a compound capable of capturing generated acid by its presence in the system, and is preferably a compound with low acidity and high pKa. The acid scavenger is preferably a compound having an amino group, and is preferably a primary amine, a secondary amine, a tertiary amine, an ammonium salt, or a tertiary amide. Primary amines, secondary amines, tertiary amines, or ammonium salts are preferred, with secondary amines, tertiary amines, or ammonium salts being more preferred. Preferred examples of the acid scavenger include compounds having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure, or a pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, and aniline derivatives having a hydroxyl group and / or an ether bond. When the acid scavenger has an onium structure, it is preferably a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, or the like, and an anion of an acid less acidic than the acid generated by the acid generator.

[0328] Examples of acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers having a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N,N-bis(hydroxyethyl)aniline.

[0329] Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane ... diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, ethylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, and the like.

[0330] The acid scavenger may be used alone or in combination of two or more. The composition according to the present invention may or may not contain an acid scavenger, but when it contains an acid scavenger, the content of the acid scavenger is preferably 0.001 to 10 mass %, more preferably 0.01 to 5 mass %, based on the total solid content of the composition.

[0331] The ratio of the acid generator to the acid scavenger used is preferably acid generator / acid scavenger (molar ratio) = 2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing a decrease in resolution due to thickening of the relief pattern over time after exposure until heat treatment, it is preferably 300 or less. The acid generator / acid scavenger (molar ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.

[0332] <Other Additives> The resin composition of the present invention may contain various additives, as needed, within the scope of obtaining the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymer compounds, light absorbers, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.). By appropriately incorporating these components, properties such as film physical properties can be adjusted. For details of these components, please refer to, for example, the descriptions in paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812 ), and the descriptions in paragraphs 0101 to 0104 and 0107 to 0109 of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are blended, the total content thereof is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0333] [Surfactant] Various surfactants can be used as the surfactant, such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0334] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (particularly fluidity) of the coating liquid composition when prepared can be further improved, and the uniformity of the coating thickness and the liquid saving can be further improved. That is, when a film is formed using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and the coatability of the surface to be coated. Therefore, it is possible to more suitably form a uniform film with little thickness unevenness.

[0335] Examples of fluorine-based surfactants include the compounds described in paragraph 0328 of WO 2021 / 112189, the contents of which are incorporated herein by reference. As the fluorine-based surfactant, fluorine-containing polymer compounds containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used, and examples thereof include the following compounds.

[0336]

[0337] The weight-average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP 2010-164965 A, the contents of which are incorporated herein by reference. Commercially available products include Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0338] The fluorine content in the fluorine-containing surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-containing surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and also has good solubility in the composition.

[0339] Examples of silicone surfactants, hydrocarbon surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329 to 0334 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0340] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition.

[0341] [Higher Fatty Acid Derivative] In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention, and the higher fatty acid derivative may be unevenly distributed on the surface of the resin composition of the present invention during drying after application.

[0342] In addition, the higher fatty acid derivative may be a compound described in paragraph 0155 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0343] When the resin composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% based on the total solid content of the resin composition. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more types of higher fatty acid derivatives are used, the total content thereof is preferably within the above range.

[0344] [Thermal Polymerization Initiator] Examples of thermal polymerization initiators include thermal radical polymerization initiators. Thermal radical polymerization initiators are compounds that generate radicals by thermal energy and initiate or promote the polymerization reaction of a polymerizable compound. Addition of a thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance. In addition, photopolymerization initiators may also have the function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

[0345] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein by reference.

[0346] When a thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, it is preferable that the total amount is in the above range.

[0347] [Inorganic Particles] Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0348] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle size of the inorganic particles is the primary particle size and also the volume average particle size. The volume average particle size can be measured, for example, by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can also be measured by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction / scattering method.

[0349] [Ultraviolet absorber] Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, etc. Specific examples of the ultraviolet absorber include the compounds described in paragraphs 0341 to 0342 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0350] The ultraviolet absorbers may be used singly or in combination of two or more. When the resin composition contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less, based on the total solid mass of the resin composition.

[0351] [Organotitanium Compound] When the resin composition contains an organotitanium compound, a resin layer having excellent chemical resistance can be formed even when cured at low temperatures.

[0352] 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 below in I) to VII): I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability to the resin composition and a good curing pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate). II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc. III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Monoalkoxytitanium compounds: for example, titanium tris(dioctylphosphate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, etc. V) Titanium oxide compounds: for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

[0353] Among these, from the viewpoint of better chemical resistance, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0354] When an organotitanium compound is contained, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 part by mass or more, the heat resistance and chemical resistance of the obtained cured pattern are improved, and when it is 10 parts by mass or less, the storage stability of the composition is superior.

[0355] [Antioxidant] By including an antioxidant as an additive, the elongation properties of the cured film and adhesion to metal materials can be improved. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. Specific examples of antioxidants include the compounds described in paragraphs 0348 to 0357 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0356] The content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By adding an amount of 0.1 part by mass or more, it is easy to obtain the effect of improving elongation properties and adhesion to metal materials even in high-temperature, high-humidity environments, and by adding an amount of 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, through interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof be within the above range.

[0357] [Anti-aggregating Agent] Examples of the anti-aggregating agent include sodium polyacrylate.

[0358] The anti-aggregating agent may be used singly or in combination of two or more. When the resin composition contains an anti-aggregating agent, the content of the anti-aggregating agent is preferably 0.01 mass % or more and 10 mass % or less, and more preferably 0.02 mass % or more and 5 mass % or less, relative to the total mass of the solid content of the resin composition.

[0359] [Phenol-based compounds] Examples of phenol-based 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, Methylenetrith-FR-CR, and BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0360] The phenolic compound may be used alone or in combination of two or more. When the resin composition contains a phenolic compound, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid mass of the resin composition.

[0361] [Other Polymer Compounds] Examples of other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. The other polymer compounds may be modified compounds into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups have been introduced.

[0362] The other polymer compounds may be used singly or in combination of two or more. When the resin composition contains the other polymer compounds, the content of the other polymer compounds is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid mass of the resin composition.

[0363] [Light absorber] The resin composition of the present invention may further contain a light absorber (a compound whose absorbance at the exposure wavelength is reduced by exposure). Examples of the light absorber include the compounds described in paragraphs 0159 to 0183 of WO 2022 / 202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of these compounds are incorporated herein by reference.

[0364] In addition, a preferred embodiment of the present invention is to include a photochromic compound as a light absorber. A photochromic compound is a compound whose absorption spectrum changes as a result of a change in the molecular geometric structure upon absorption of light. Specific examples of photochromic compounds are shown below, but the present invention is not limited to these.

[0365]

[0366] The light absorber is preferably at least one selected from the group consisting of naphthoquinone diazide compounds, spiropyran compounds, diarylethene compounds, azobenzene compounds, nifedipine compounds, and coumarin compounds.

[0367] When the resin composition of the present invention contains a light absorber, the content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%.

[0368] <Characteristics of Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, and 2,500 mm ２ / s~8,000mm ２ Within the above range, it is easy to obtain a highly uniform coating film. ２ If the thickness is more than 12,000 mm / s, it is easy to apply the coating to a thickness required for an insulating film for rewiring, for example. ２ If the viscosity is 1 / s or less, a coating film having excellent coating surface condition can be obtained.

[0369] 100 mJ / cm for a film formed from the resin composition of the present invention ２ When the dissolution rate of the film in γ-butyrolactone is measured before and after exposure, the value obtained by subtracting the dissolution rate after exposure from the dissolution rate before exposure is preferably 0.5 μm / sec or more, more preferably 0.6 μm / sec or more, and even more preferably 0.8 μm / sec or more. A value of 0.5 μm / sec or more is preferred because it results in a large dissolution contrast and improved resolution.

[0370] 100 mJ / cm for a film formed from the resin composition of the present invention ２When the dissolution rate of the film in an aqueous tetramethylammonium hydroxide solution is measured before and after exposure, the value obtained by subtracting the dissolution rate after exposure from the dissolution rate before exposure is preferably 0.5 μm / sec or more. A value of 0.5 μm / sec or more is preferred because it results in a large dissolution contrast and improved resolution. The concentration of tetramethylammonium hydroxide in the aqueous tetramethylammonium hydroxide solution may be, for example, 2.38% by mass.

[0371] <Restrictions on substances contained in the 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 even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0372] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, the total amount of these metals is preferably within the above range.

[0373] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as raw materials for constituting the resin composition of the present invention, filtering the raw materials for constituting the resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.

[0374] Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosion. In particular, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above-mentioned range. Preferred methods for adjusting the content of halogen atoms include ion exchange treatment.

[0375] A conventionally known container can be used as a container for storing the resin composition of the present invention. For the purpose of preventing impurities from being mixed into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six resin layers, or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

[0376] <Cured Product of Resin Composition> A cured product of the resin composition can be obtained by curing the resin composition of the present invention. The cured product of the present invention is a cured product obtained by curing the resin composition. The resin composition is preferably cured by heating, with a heating temperature of 120°C to 400°C being more preferred, 140°C to 380°C being even more preferred, and 170°C to 350°C being particularly preferred. The form of the cured product of the resin composition is not particularly limited, and can be selected depending on the application, such as a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. By patterning the resin composition, the shape of the cured product can be selected depending on the application, such as forming a protective film on a wall surface, forming via holes for electrical conductivity, adjusting impedance, capacitance, or internal stress, or imparting heat dissipation functionality. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage of change in volume of the resin composition before and after curing, and can be calculated by the following formula: Shrinkage rate [%] = 100 - (volume after curing / volume before curing) x 100

[0377] <Characteristics of cured product of resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent 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 even more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or more, more preferably 210°C or more, and even more preferably 230°C or more.

[0378] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be carried out by a conventionally known method. Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0379] Filtration using a filter is preferably performed to remove foreign matter such as dust and fine particles from the resin composition of the present invention. The filter pore size is, for example, preferably 5 μm or less, more preferably 1 μm or less, even more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferable. The filter may be pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. An example of a connection mode is a mode in which an HDPE filter with a pore size of 1 μm is connected in series as the first stage and an HDPE filter with a pore size of 0.2 μm is connected in series as the second stage. Various materials may also be filtered multiple times. When filtration is performed multiple times, circulating filtration may be used. Filtration may also be performed under pressure. When filtering under pressure, the pressure to be applied is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtering using a filter, a process of removing impurities using an adsorbent may be performed. Filter filtration and a process of removing impurities using an adsorbent may be combined. Known adsorbents can be used as the adsorbent. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtering using a filter, the resin composition filled in a bottle may be subjected to a degassing process by placing it under reduced pressure.

[0380] (Method for producing a cured product) The method for producing a cured product of the present invention preferably includes a film-forming step in which a resin composition is applied to a substrate to form a film. The method for producing a cured product more preferably includes the film-forming step, an exposure step in which the film formed in the film-forming step is selectively exposed to light, and a development step in which the film exposed in the exposure step is developed using a developer to form a pattern. The method for producing a cured product particularly preferably includes the film-forming step, the exposure step, the development step, and at least one of a heating step in which the pattern obtained in the development step is heated and a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product also preferably includes the film-forming step and a step of heating the film. Details of each step are described below.

[0381] <Film Forming Step> The resin composition of the present invention can be used in a film forming step of applying the resin composition to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film.

[0382] [Substrate] The type of substrate can be appropriately determined depending on the application and is not particularly limited. Examples of substrates include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal and substrates on which a metal layer is formed by, for example, plating or vapor deposition), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, and plasma display panel (PDP) electrode plates. Substrates are particularly preferably semiconductor production substrates, with silicon substrates, Cu substrates, and mold substrates being more preferred. These substrates may have a surface layer such as an adhesion layer or an oxide layer formed by hexamethyldisilazane (HMDS) or the like. The shape of the substrate is not particularly limited and may be circular or rectangular. The size of the substrate is preferably, for example, a diameter of 100 to 450 mm, more preferably 200 to 450 mm, if it is circular. If it is rectangular, the length of the short side is preferably, for example, 100 to 1000 mm, more preferably 200 to 700 mm. As the substrate, for example, a plate-shaped, preferably a panel-shaped substrate (substrate) is used.

[0383] When a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the substrate.

[0384] Coating is preferred as a means for applying the resin composition to a substrate. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating is preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the resin composition and coating conditions depending on the application method, a film of the desired thickness can be obtained. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, inkjet coating, etc. are preferred, and for rectangular substrates, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Alternatively, a method can be used in which a coating film formed by applying the coating composition to a temporary support in advance using the above-described application method is transferred onto the substrate. Regarding the transfer method, the preparation methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used. A step of removing excess film from the edge of the substrate may also be performed. Examples of such a step include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may also be employed in which the substrate is coated with various solvents before applying the resin composition to the substrate, improving the wettability of the substrate and then applying the resin composition.

[0385] <Drying Step> After the film-forming step (layer-forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) to remove the solvent. 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. The drying step is preferably carried out after the film-forming step and before the exposure step. The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be carried out under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0386] <Exposure Step> The film may be subjected to an exposure step in which the film is selectively exposed to light. The method for producing a cured product may include an exposure step in which the film formed in the film formation step is selectively exposed to light. Selective exposure means that a portion of the film is exposed to light. Furthermore, selective exposure forms exposed regions (exposed portions) and unexposed regions (unexposed portions) in the film. The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention, but for example, it is 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. ２ is preferred, and 200 to 8,000 mJ / cm ２ is more preferred.

[0387] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0388] The exposure wavelengths, in relation to the light source, are: (1) semiconductor laser (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.); (2) metal halide lamp; (3) high-pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-line); (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ２Examples of such light include excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser second harmonic 532 nm and third harmonic 355 nm. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited as long as it is a method that exposes at least a portion of the film made of the resin composition of the present invention, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0389] <Post-Exposure Bake Step> The film may be subjected to a heating step (post-exposure bake step) after exposure. That is, the method for producing a cured product of the present invention may include a post-exposure bake step in which the film exposed in the exposure step is heated. The post-exposure bake step can be carried out after the exposure step and before the development step. The heating temperature in the post-exposure bake step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure bake step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The temperature rise rate in the post-exposure bake step from the temperature at the start of heating to the maximum heating temperature is preferably 1 to 12°C / min, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The temperature rise rate may also be changed as appropriate during heating. The heating means in the post-exposure bake step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. may be used. It is also preferable to carry out the heating in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0390] <Development step> The above-mentioned film after exposure may be subjected to a development step in which it is developed using a developer to form a pattern. That is, the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed using a developer to form a pattern. By carrying out development, one of the exposed and unexposed parts of the film is removed to form a pattern. Here, development in which the unexposed parts of the film are removed in the development step is called negative development, and development in which the exposed parts of the film are removed in the development step is called positive development.

[0391] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0392] When the developer is an alkaline aqueous solution, examples of the basic compound that can be contained in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferred is TMAH. The content of the basic compound in the developer is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, and even more preferably from 0.3 to 3% by mass, based on the total mass of the developer.

[0393] When the developer contains an organic solvent, the organic solvent may be a compound described in paragraph

[0387] of WO 2021 / 112189, the contents of which are incorporated herein by reference. Suitable examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol, and suitable examples of amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0394] When the developer contains an organic solvent, the organic solvent may be used alone or in combination. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0395] 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, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Alternatively, the content may be 100% by mass.

[0396] When the developer contains an organic solvent, the developer may further contain at least one of a basic compound and a base generator. When at least one of the basic compound and the base generator in the developer permeates into the pattern, the performance of the pattern, such as breaking elongation, may be improved.

[0397] As the basic compound, from the viewpoint of reliability when it remains in the film after curing (adhesion to the substrate when the cured product is further heated), an organic base is preferred. As the basic compound, a basic compound having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred. However, to promote the imidization reaction, primary amines, secondary amines, tertiary amines, or ammonium salts are preferred, secondary amines, tertiary amines, or ammonium salts are more preferred, secondary amines or tertiary amines are even more preferred, and tertiary amines are particularly preferred. As the basic compound, from the viewpoint of the mechanical properties (elongation at break) of the cured product, it is preferred that it is difficult for the amount remaining to decrease before heating due to vaporization, etc., is preferred. Therefore, the boiling point of the basic compound is preferably 30°C to 350°C at normal pressure (101,325 Pa), more preferably 80°C to 270°C, and even more preferably 100°C to 230°C. The boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer. For example, when the boiling point of the organic solvent is 100° C., the boiling point of the basic compound used is preferably 80° C. or higher, and more preferably 100° C. or higher. The developer may contain only one type of basic compound, or may contain two or more types.

[0398] Specific examples of the basic compound include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diamino Examples of the alkyl ester include pentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, and N,N,N,N-tetramethyl-1,3-propanediamine.

[0399] The preferred embodiments of the base generator are the same as those of the base generator contained in the composition described above. In particular, the base generator is preferably a thermal base generator.

[0400] When the developer contains at least one of a basic compound and a base generator, the content of the basic compound or base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the developer. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more. When the basic compound or base generator is solid in the environment in which the developer is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, based on the total solid content of the developer. The developer may contain only one type of basic compound or base generator, or two or more types. When two or more types of at least one of the basic compound and base generator are used, the total content thereof is preferably within the above-mentioned range.

[0401] The developer may further contain other components, such as known surfactants and known defoaming agents.

[0402] [Method of Supplying Developer] The method of supplying the developer is not particularly limited as long as it can form the desired pattern, and includes a method of immersing a substrate on which a film has been formed in the developer, puddle development in which the developer is supplied to the film formed on the substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer using a straight nozzle or a method of continuously supplying the developer using a spray nozzle is preferred, and from the viewpoint of the permeability of the developer to the image areas, a method of supplying using a spray nozzle is more preferred. In addition, a process may be adopted in which the developer is continuously supplied using a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again using a straight nozzle, and the substrate is spun to remove the developer from the substrate, or this process may be repeated multiple times. Methods of supplying the developer in the development process include a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept substantially stationary on the substrate, a process in which the developer is vibrated on the substrate using ultrasound or the like, and a combination thereof.

[0403] The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0404] In the developing step, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse liquid. Alternatively, a method may be employed in which a rinse liquid is supplied before the developer in contact with the pattern is completely dried.

[0405] [Rinse Liquid] When the developer is an alkaline aqueous solution, for example, water can be used as the rinse liquid. 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 liquid.

[0406] When the rinse solution contains an organic solvent, examples of the organic solvent include the same organic solvents as those exemplified when the developer contains an organic solvent. The organic solvent contained in the rinse solution is preferably different from the organic solvent contained in the developer, and more preferably an organic solvent that has a lower solubility for the pattern than the organic solvent contained in the developer.

[0407] When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), or propylene glycol monomethyl ether (PGME), more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.

[0408] When the rinse solution contains an organic solvent, the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more of the total mass of the rinse solution, and may also account for 100% by mass of the total mass of the rinse solution.

[0409] The rinse solution may contain at least one of a basic compound and a base generator. Although not particularly limited, when the developer contains an organic solvent, an embodiment in which the rinse solution contains the organic solvent and at least one of a basic compound and a base generator is also one of the preferred embodiments of the present invention. Examples of the basic compound and base generator contained in the rinse solution include the compounds exemplified as the basic compound and base generator that may be contained when the developer contains an organic solvent, and the same applies to preferred embodiments. The basic compound and base generator contained in the rinse solution may be selected taking into consideration the solubility in the solvent in the rinse solution, etc.

[0410] When the rinse solution contains at least one of a basic compound and a base generator, the content of the basic compound or base generator is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the rinse solution. The lower limit of the content is not particularly limited, but is preferably 0.1% by mass or more, for example. When the basic compound or base generator is solid in the environment in which the rinse solution is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, based on the total solid content of the rinse solution. When the rinse solution contains at least one of a basic compound and a base generator, the rinse solution may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types. When at least one of the basic compound and the base generator is two or more types, the total content thereof is preferably within the above-mentioned range.

[0411] The rinse liquid may further contain other components, such as known surfactants and known defoaming agents.

[0412] [Method of Supplying Rinse Liquid] The method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples thereof include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like. From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, methods of supplying the rinse liquid using a shower nozzle, straight nozzle, spray nozzle, etc. are available, and a method of continuously supplying using a spray nozzle is preferred, and from the viewpoint of the permeability of the rinse liquid into the image areas, a method of supplying using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples include a straight nozzle, shower nozzle, spray nozzle, etc. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinse liquid to the exposed film using a straight nozzle, and more preferably a step of supplying the rinse liquid using a spray nozzle. The method of supplying the rinse liquid in the rinsing step may include a step of continuously supplying the rinse liquid to the substrate, a step of keeping the rinse liquid substantially stationary on the substrate, a step of vibrating the rinse liquid on the substrate by ultrasonic waves or the like, and a combination of these steps.

[0413] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0414] The developing step may include a step of contacting the pattern with a treatment liquid after treatment with a developer or after washing the pattern with a rinse liquid. Alternatively, a method may be employed in which the treatment liquid is supplied before the developer or rinse liquid in contact with the pattern is completely dried.

[0415] The treatment liquid may include a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator. Preferred aspects of the organic solvent, the basic compound, and the base generator are the same as the preferred aspects of the organic solvent, the basic compound, and the base generator used in the rinse liquid described above. The treatment liquid can be supplied to the pattern using the same method as the rinse liquid described above, and preferred aspects are also the same.

[0416] The content of the basic compound or base generator in the treatment liquid is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the treatment liquid. There is no particular limitation on the lower limit of the content, but it is preferably, for example, 0.1% by mass or more. Furthermore, when the basic compound or base generator is solid in the environment in which the treatment liquid is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, relative to the total solid content of the treatment liquid. When the treatment liquid contains at least one of a basic compound and a base generator, the treatment liquid may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types. When there are two or more types of at least one of the basic compound and the base generator, it is preferable that the total amount thereof is within the above-mentioned range.

[0417] <Heating Step> The pattern obtained by the development step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention may include a heating step in which the pattern obtained by the development step is heated. Furthermore, the method for producing a cured product of the present invention may include a heating step in which a pattern obtained by another method without performing a development step, or a film obtained by a film formation step, is heated. In the heating step, a resin such as a polyimide precursor is cyclized to form a resin such as a polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in a crosslinking agent other than the specific resin also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0418] The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of a base or the like generated from the base generator due to heating.

[0419] The heating step is preferably carried out at a temperature increase rate of 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. By setting the temperature increase rate to 1°C / min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature increase rate to 12°C / min or less, it is possible to alleviate residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the temperature at the start of heating to the maximum heating temperature at a temperature increase rate of 1 to 8°C / sec, more preferably 2 to 7°C / sec, and even more preferably 3 to 6°C / sec.

[0420] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature is the temperature of the film (layer) after this drying, and it is preferable to raise the temperature from, for example, a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0421] The heating time (heating time at the maximum heating temperature) is preferably from 5 to 360 minutes, more preferably from 10 to 300 minutes, and even more preferably from 15 to 240 minutes.

[0422] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, even more preferably 100° C. or higher, and particularly preferably 120° C. or higher. The upper limit of the heating temperature is preferably 350° C. or lower, more preferably 250° C. or lower, and even more preferably 240° C. or lower.

[0423] Heating may be performed in stages. For example, the temperature may be increased from 25°C to 120°C at a rate of 3°C / min, held at 120°C for 60 minutes, increased from 120°C to 180°C at a rate of 2°C / min, and held at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Pat. No. 9,159,547. Such a pretreatment step can improve the film's properties. The pretreatment step is preferably performed for a short period of time, such as 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, a first pretreatment step may be performed at a temperature in the range of 100 to 150°C, followed by a second pretreatment step at a temperature in the range of 150 to 200°C. Furthermore, cooling may be performed after heating. In this case, the cooling rate is preferably 1 to 5°C / min.

[0424] The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by carrying out the heating step under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less. The heating means used in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0425] <Post-development exposure step> The pattern obtained in the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern obtained in the development step is exposed to light, instead of or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed to light. 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 only one of the heating step and the post-development exposure step. The post-development exposure step can promote, for example, a reaction in which cyclization of a polyimide precursor or the like progresses due to exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group progresses due to exposure of a photoacid generator. In the post-development exposure step, it is sufficient that at least a portion of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed. The exposure dose in the post-development exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity. ２ is preferred, and 100 to 15,000 mJ / cm ２ The post-development exposure step can be carried out using, for example, the light source used in the exposure step described above, and it is preferable to use broadband light.

[0426] <Metal Layer Forming Step> The pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step) may be subjected to a metal layer forming step of forming a metal layer on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step).

[0427] The metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

[0428] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP 2007-157879 A, ​​JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used. Examples of suitable methods include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and combinations of these. More specifically, examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating. Preferred plating methods include electroplating using a copper sulfate or copper cyanide plating solution.

[0429] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0430] <Applications> Fields to which the method for producing a cured product of the present invention or the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), and the etching of insulating films for packaging applications such as those described above. For these applications, reference can be made to, for example, Science & Technology Co., Ltd.'s "High Performance Polyimide and Application Technology" (April 2008), edited by Masaaki Kakimoto, CMC Technical Library "Fundamentals and Development of Polyimide Materials" (November 2011), and Japan Polyimide and Aromatic Polymer Research Association's "Latest Polyimide Fundamentals and Applications" (NTS, August 2010).

[0431] The method for producing the cured product of the present invention, or the cured product of the present invention, can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, for producing protective lacquers and dielectric layers in electronics, especially microelectronics, etc.

[0432] (Laminate and method for manufacturing laminate) The laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention. The laminate is a laminate including two or more layers each made of the cured product, and may be a laminate including three or more layers. At least one of the two or more layers each made of the cured product contained in the laminate is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.

[0433] 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 method for producing a cured product of the present invention multiple times.

[0434] The laminate of the present invention preferably includes two or more layers made of a cured product and a metal layer between any of the layers made of the cured product. The metal layer is preferably formed by the metal layer-forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer-forming step of forming a metal layer on a layer made of a cured product between multiple cured product production processes. A preferred embodiment of the metal layer-forming step is as described above. Examples of the laminate include a laminate having at least a layer structure in which three layers are stacked in this order: a layer made of a first cured product, a metal layer, and a layer made of a second cured product. It is preferred that both the layer made of the first cured product and the layer made of the second cured product are layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring, such as a rewiring layer.

[0435] <Lamination Step> The method for producing a laminate of the present invention preferably includes a lamination step. The lamination step is a series of steps including performing at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, and (d) a heating step and a post-development exposure step again on the surface of the pattern (resin layer) or the metal layer in this order. However, at least one of (a) the film formation step and (d) the heating step and the post-development exposure step may be repeated. Furthermore, after at least one of (d) the heating step and the post-development exposure step, (e) a metal layer formation step may be included. It goes without saying that the lamination step may further include the above-mentioned drying step or the like as appropriate.

[0436] When a further lamination step is performed after the lamination step, a surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step. An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.

[0437] The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times. For example, a structure having 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure having 2 to 9 resin layers is even more preferred. Each of the layers may be the same or different in composition, shape, film thickness, etc.

[0438] In the present invention, a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.Specific examples include an embodiment in which the steps of (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order, or an embodiment in which the steps of (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order.By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

[0439] (Surface Activation Treatment Step) The method for producing a laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the resin composition layer are surface-activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be surface-activated before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or may be performed on at least a portion of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region of the metal layer on which the resin composition layer is to be formed. In this way, by performing the surface activation treatment on the surface of the metal layer, adhesion with the resin composition layer (film) provided on the surface can be improved. The surface activation treatment is also preferably performed on part or all of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, adhesion with the metal layer or resin layer provided on the surface that has been surface-activated can be improved. In particular, when negative development is performed, when the resin composition layer is cured, it is less susceptible to damage due to surface treatment and adhesion is likely to be improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. The contents of this specification are incorporated herein by reference.

[0440] (Semiconductor device and manufacturing method thereof) The present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention. The present invention also discloses a manufacturing method for a semiconductor device comprising the manufacturing method for the cured product or the manufacturing method for the laminate of the present invention. Specific examples of semiconductor devices using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer can be found in paragraphs 0213 to 0218 and FIG. 1 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0441] (Resin) The present invention also relates to the resin (A) described above. The resin (A) has been described above.

[0442] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit 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.

[0443] <Synthesis Example of Resin (A)> (Synthesis of A-1) 20.0 g (38.4 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) and 5.41 g (25.0 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl were dissolved in 125 ml of NMP and stirred at 200°C for 3 hours under a nitrogen atmosphere to obtain polyimide (pA-1). GPC analysis at this stage revealed that Mn was 2,800. Next, 1.58 g (4.5 mmol) of 1,3,5-tris(4-aminophenyl)benzene and 1.48 g (13.6 mmol) of 4-aminophenol were added to the solution containing the polyimide (pA-1), and the mixture was stirred at 200°C for 3 hours under a nitrogen atmosphere to obtain polyimide (qA-1). GPC measurement at this point revealed that the Mn was 8,000, and that each polymer had an average branching structure of 1.0 (branching structure with triphenylbenzene as the branching point). The solution containing the obtained polyimide (qA-1) was brought to room temperature, and 0.42 g of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 14.6 g of 4-chloromethylstyrene, 15.9 g of potassium carbonate, and 1.91 g of potassium iodide were added, followed by stirring at 90°C for 14 hours. 375 ml of THF was added to the obtained polyimide solution, and the salt was removed by filtration. The obtained filtrate was added dropwise to 1500 ml of methanol to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day, yielding polyimide (A-1) as a powder. The Mn and Mw of the obtained A-1 were measured, revealing Mn = 8,000 and Mw = 22,000.

[0444] (Synthesis of A-2) 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride, 16.3 g (125 mmol) of 2-hydroxyethyl methacrylate, 0.39 g (1.93 mmol) of 1,12-dodecanediol, and 0.55 g of TEMPO were dissolved in 60 ml of diglyme, and 39.2 g (284 mmol) of pyridine was added and stirred at 60°C for 4 hours. The mixture was then cooled to 0°C, and 15.34 g (129 mmol) of thionyl chloride was added dropwise over 15 minutes. The mixture was stirred for 1 hour, yielding a white precipitate of pyridinium hydrochloride. Next, a solution of 10.3 g (51.6 mmol) of 4,4'-diaminodiphenyl ether in 75 ml of NMP was added dropwise over 30 minutes. The mixture was stirred at room temperature for 1 hour, and 8 ml of ethanol was added, followed by further stirring for 1 hour. The resulting solution was added dropwise to 1500 ml of water to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain polyamide (A-2) as a powder. The Mn and Mw of the resulting A-2 were measured, and found to be Mn = 12,000 and Mw = 28,000. A-2 is also a polyimide precursor.

[0445] (Synthesis of A-3) 18.0 g (58.0 mmol) of 4,4'-oxydiphthalic dianhydride, 17.0 g (46.4 mmol) of 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol), and 2.53 g (23.2 mmol) of 4-aminophenol were dissolved in 100 ml of NMP and stirred at 200°C for 3 hours under a nitrogen atmosphere to obtain polyimide (pA-3). The solution containing the obtained polyimide (pA-3) was brought to room temperature, and 20.2 g of 4-((t-butoxycarbonyl)oxy)benzyl 4-methylbenzenesulfonate, 24.0 g of potassium carbonate, and 2.89 g of potassium iodide were added, followed by stirring at 90°C for 14 hours. 300 ml of THF was added to the obtained polyimide solution, and the salt was removed by filtration. The obtained filtrate was added dropwise to 1500 ml of methanol to precipitate a polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain polyimide (A-3) as a powder. The Mn and Mw of the obtained A-3 were measured to find that Mn was 6,400 and Mw was 13,000.

[0446] (Synthesis of A-4) Polyimide (A-4) was obtained under the same conditions as in the synthesis of A-3, except that N,N'-[[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis(6-hydroxy-3,1-phenylene)]bis[1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxamide] was used instead of 4,4'-oxydiphthalic dianhydride and 4-hydroxymethylphenol was used instead of 4-((t-butoxycarbonyl)oxy)benzyl 4-methylbenzenesulfonate. The Mn and Mw of the obtained A-4 were measured, and were found to be Mn = 7,800 and Mw = 19,000.

[0447] (Synthesis of A-5) 10.0 g (32.2 mmol) of 4,4'-oxydiphthalic dianhydride and 2.27 g (70.9 mmol) of methanol were dissolved in 50 ml of diglyme, and 18.7 g (135 mmol) of pyridine was added and stirred at 60°C for 4 hours. The mixture was then cooled to 0°C, and 8.44 g (70.9 mmol) of thionyl chloride was added dropwise over 15 minutes. The mixture was stirred for 1 hour, yielding a white precipitate of pyridinium hydrochloride. Next, a solution of 6.27 g (29.0 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl in 50 ml of NMP was added dropwise over 30 minutes. The mixture was stirred at room temperature for 1 hour, and then 8 ml of ethanol was added and stirred for an additional hour. The resulting solution was added dropwise to 1,000 ml of water to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain polyamide (pA-5) as a powder. Next, 113 g (290 mmol) of dodecafluorosuberic acid, 60.8 g (232 mmol) of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, and 4.99 g (58.0 mmol) of methacrylic acid were dissolved in 300 ml of THF, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride was added and stirred at room temperature for 6 hours. Polyamide (pA-5) was then added and stirred for another 6 hours. The resulting solution was added dropwise to 3,000 ml of water to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain polyamide (A-5) as a powder. The Mn and Mw of the resulting A-5 were measured, revealing Mn = 13,500 and Mw = 32,000.

[0448] (Synthesis of A-6) 12.0 g (38.7 mmol) of 4,4'-oxydiphthalic dianhydride, 5.02 g (23.2 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl, 0.73 g (5.80 mmol) of 2,4,6-triaminopyrimidine, and 2.11 g (19.3 mmol) of 4-aminophenol were dissolved in 125 ml of NMP and stirred at 200°C for 3 hours under a nitrogen atmosphere to obtain polyimide (pA-6). Next, 0.35 g of TEMPO and 7.60 g of triethylamine were added to the solution containing the polyimide (pA-6). The mixture was cooled to 0°C, and then 6.87 g (65.8 mmol) of methacrylic chloride was added dropwise over 15 minutes. The mixture was stirred for 1 hour, yielding a white precipitate of triethylamine hydrochloride. The resulting solution was added dropwise to 1500 ml of water to precipitate a polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain polyimide (qA-6) as a powder. 0.35 g (5.80 mmol) of 2-aminoethanol, 0.57 g (5.80 mmol) of maleic anhydride, and 0.01 g of TEMPO were dissolved in NMP and stirred at room temperature for 2 hours, followed by stirring at 120°C for 1 hour. The mixture was then returned to room temperature, and 8.01 g (58.0 mmol) of 4-hydroxybenzoic acid and 26.7 g (139 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride were added and stirred for 10 hours. The resulting solution was added dropwise to 2000 ml of water, filtered, and the precipitate was collected and dried under reduced pressure at 40°C for 1 day to obtain polyester (rA-6). Polyester (rA-6), 10.0 g of pyridine, and 0.35 g of TEMPO were dissolved in 100 g of NMP and cooled to 0°C. Then, 0.69 g (5.82 mmol) of thionyl chloride was added dropwise over 15 minutes and the mixture was stirred for 1 hour, yielding a white precipitate of pyridinium hydrochloride. A solution of polyimide (qA-6) in 200 g of NMP was added dropwise over 30 minutes and the mixture was stirred for 3 hours. The resulting solution was added dropwise to 1,500 ml of water to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain polyimide (A-6) as a powder. The Mn and Mw of the resulting A-6 were measured, revealing Mn = 4,500 and Mw = 9,500.

[0449] (Synthesis of A-7) 15.0 g (68.8 mmol) of pyromellitic anhydride and 4.41 g (138 mmol) of methanol were dissolved in 60 ml of diglyme, and 41.8 g (303 mmol) of pyridine was added and stirred at 60°C for 4 hours. The mixture was then cooled to 0°C, and 16.4 g (138 mmol) of thionyl chloride was added dropwise over 15 minutes. The mixture was stirred for 1 hour, yielding a white precipitate of pyridinium hydrochloride. Next, a solution of 14.9 g (138 mmol) of 1,4-phenylenediamine in 60 ml of NMP was added dropwise over 30 minutes, followed by stirring at room temperature for 1 hour. The resulting solution was added dropwise to 1500 ml of water to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain a powder, polyamide (pA-7). GPC analysis at this point revealed an Mn of 450. Next, the resulting polyamide (pA-7) was dissolved in 60 g of cyclohexanone, and a solution of 11.6 g (22.9 mmol) of 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazinane-2,4,6-trione in 30 ml of cyclohexanone was added dropwise at room temperature over 30 minutes. The mixture was stirred for an additional hour, and the precipitated solid was collected by filtration to obtain polyamide (qA-7) having a branched structure. GPC analysis at this point revealed that the Mn was 1,900, and that each polymer contained an average of 1.0 branched structures (branched structures with structures derived from 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazinane-2,4,6-trione as branch points). Next, 469 g (1.51 mol) of 4,4'-oxydiphthalic dianhydride, 149 g (688 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl, 8.6 l (68.8 mmol) of 2,4,6-triaminopyrimidine, and 165 g (1.51 mol) of 4-aminophenol were dissolved in 3000 ml of NMP and stirred at 200°C for 4 hours under a nitrogen atmosphere. The mixture was then cooled to 0°C, and 0.80 g of TEMPO and 140 g of triethylamine were added. 144 g (1.38 mmol) of methacrylic chloride was added dropwise over 30 minutes, followed by stirring for 1 hour, yielding a white precipitate of triethylamine hydrochloride. The resulting solution was added dropwise to 5000 ml of water to precipitate a polymer.The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain polyimide (rA-7) as a powder. GPC analysis at this point revealed an Mn of 700. Next, 15.0 g (68.8 mmol) of pyromellitic anhydride and 2.20 g (68.8 mmol) of methanol were dissolved in 60 ml of diglyme, and 38.0 g (275 mmol) of pyridine was added and stirred at 60°C for 4 hours. The mixture was then cooled to 0°C, and 16.4 g (137 mmol) of thionyl chloride was added dropwise over 15 minutes. The mixture was stirred for 1 hour, yielding a white precipitate of pyridinium hydrochloride. A solution of polyamide (qA-7) dissolved in 150 g of NMP was added dropwise over 1 hour to the resulting white precipitate of pyridinium hydrochloride, and the mixture was stirred for 1 hour while maintaining the temperature at 0°C. Subsequently, the obtained solution was added dropwise over 1 hour to a solution of polyimide (rA-7) dissolved in 2000 ml of NMP, and the mixture was stirred for 2 hours at room temperature. The obtained solution was added dropwise to 8000 ml of water to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain a powder, which was polyimide (A-7). The Mn and Mw of the obtained A-7 were measured to find that Mn = 24,000 and Mw = 68,000, and that each polymer had an average of 1.0 branched structures (branched structures with a structure derived from 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazinane-2,4,6-trione as a branch point).

[0450] (Synthesis of B-1) 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride, 19.0 g (64.5 mmol) of 4,4'-biphthalic anhydride, and 19.6 g (129 mmol) of hydroxylethyl methacrylate were dissolved in 100 ml of γ-butyrolactone, and 39.2 g (142 mmol) of pyridine was added and st...

Claims

1. A resin composition containing a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1A) and a repeating unit represented by the following formula (2A): In formula (1A) and formula (2A), X １ , X ２ , Y １ and Y ２ Each independently represents an organic group. １ , W ２ , W ３ and W ４ Each independently represents a linking group. ０１ , P ０２ , P ０３ and P ０４ Each independently represents an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, and a fluoroalkylene group. Each of a, b, c, and d independently represents an integer of 0 or more. However, at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more. Each of m, n, p, and q independently represents an integer of 1 or more. W １ , W ２ , W ３ , W ４ , P ０１ , P ０２ , P ０３ and P ０４ When multiple of each are present, they may be the same or different.

2. A resin composition containing a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2): In formula (1) and formula (2), X １ , X ２ , Y １ and Y ２ Each independently represents an organic group. １ , W ２ , W ３ and W ４ Each independently represents a linking group. １ , P ２ , P ３ and P ４ each independently represents an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenylene ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, and a fluoroalkylene group. １ , Q ２ , Q ３ and Q. ４ Each independently represents a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxyl group, a thiol group, or a hydrogen atom. Each of a, b, c, and d independently represents an integer of 0 or more. However, at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more. Each of m, n, p, and q independently represents an integer of 1 or more. W １ , W ２ , W ３ , W ４ , P １ , P ２ , P ３ , P ４ , Q １ , Q ２ , Q ３ and Q. ４ When multiple of each are present, they may be the same or different.

3. P in the formula (1A) ０１ and P ０２ at least one of P in the formula (2A) contains at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group and a phenylene ether group; ０３ and P ０４ The resin composition according to claim 1, wherein at least one of the above groups contains at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, and a phenylene ether group.

4. P in the formula (1A) ０１ and P ０２ At least one of P in the formula (2A) has a branched structure. ０３ and P ０４ The resin composition according to claim 1 , wherein at least one of the above has a branched structure.

5. P in the formula (1A) ０１ and P ０２ At least one of the repeating units represented by the following formula (1-PA) and the repeating unit represented by the following formula (2-PA) is selected from the group consisting of repeating units represented by the following formula (2A), ０３ and P ０４ The resin composition according to claim 1, wherein at least one of the repeating units is selected from the group consisting of a repeating unit represented by the following formula (1-PA) and a repeating unit represented by the following formula (2-PA): In formula (1-PA) and formula (2-PA), X １ｐ , X ２ｐ , Y １ｐ and Y ２ｐ Each independently represents an organic group. １ｐ , W ２ｐ , W ３ｐ and W ４ｐ Each independently represents a linking group. ０１ｐ , P ０２ｐ , P ０３ｐ and P ０４ｐ Each independently represents an organic group containing at least one selected from the group consisting of an imide group, an amide group, a phenol group, a phenoxy group, a phenyl ether group, a benzoxazole group, a sulfonamide group, a group having three or more ester groups, a siloxane group, and a fluoroalkylene group. Each of ap, bp, cp, and dp independently represents an integer of 0 or more. However, at least one of ap and bp represents an integer of 1 or more, and at least one of cp and dp represents an integer of 1 or more. Each of mp, np, pp, and qp independently represents an integer of 1 or more. W １ｐ , W ２ｐ , W ３ｐ , W ４ｐ , P ０１ｐ , P ０２ｐ , P ０３ｐ and P ０４ｐ When multiple of each are present, they may be the same or different.

6. The resin composition according to claim 1, wherein the resin has at least one crosslinkable group at at least one terminal.

7. P in the formula (1A) ０１ and P ０２ At least one of P in the formula (2A) has a crosslinkable group. ０３ and P ０４ The resin composition according to claim 1 , wherein at least one of the above has a crosslinkable group.

8. The resin composition according to claim 6, wherein the crosslinkable group comprises at least one selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group.

9. P in the above formula (1A) ０１ and P ０２ At least one of the groups has a phenol group, and P in the formula (2A) ０３ and P ０４ The resin composition according to claim 1 , wherein at least one of the following has a phenol group.

10. The resin composition according to claim 1, further comprising a polymerization initiator.

11. The resin composition according to claim 1, further comprising a polymerizable compound.

12. The resin composition according to claim 1, further comprising a light absorbing agent.

13. The resin composition according to claim 12, wherein the light absorber is at least one selected from the group consisting of naphthoquinone diazide compounds, spiropyran compounds, diarylethene compounds, azobenzene compounds, nifedipine compounds and coumarin compounds.

14. 100 mJ / cm2 for a film formed from the resin composition ２ 2. The resin composition according to claim 1, wherein, when the dissolution rate of the film in γ-butyrolactone is measured before and after exposure to light, the value obtained by subtracting the dissolution rate after exposure from the dissolution rate before exposure is 0.5 μm / sec or more.

15. 100 mJ / cm2 for a film formed from the resin composition ２ 2. The resin composition according to claim 1, wherein, when a dissolution rate of the film in an aqueous tetramethylammonium hydroxide solution is measured before and after exposure to light, a value obtained by subtracting the dissolution rate after exposure from the dissolution rate before exposure is 0.5 μm / sec or more.

16. The resin composition according to claim 1, wherein the resin has a repeating unit represented by the formula (1A) and a repeating unit represented by the formula (2A).

17. The resin composition according to any one of claims 1 to 16, which is used for forming an insulating film.

18. The resin composition according to any one of claims 1 to 16, which is used for forming an interlayer insulating film for a rewiring layer.

Images