Resin composition, insulating film and method for producing interlayer insulating film for redistribution layers

Abstract

The present invention provides a resin composition which enables the achievement of a film having a low dielectric loss tangent, an insulating film which has a low dielectric loss tangent, and a method for producing an interlayer insulating film for redistribution layers, the method using the resin composition by means of a resin composition which contain at least one polymer that is selected from the group consisting of polyimides and polyimide precursors, a liquid crystal compound and a solvent, an insulating film which comprises at least one polymer that is selected from the group consisting of polyimides and polyimide precursors, and a liquid crystal compound, and a method for producing an interlayer insulating film for redistribution layers, the method using the resin composition.

Description

Resin composition, insulating film, and method for manufacturing interlayer insulating film for rewiring layer

[0001] The present invention relates to a resin composition, an insulating film, and a method for producing an interlayer insulating film for a rewiring layer.

[0002] Polyimides have excellent heat resistance and insulating properties and are therefore used as insulating films in electronic devices. Patent Document 1 describes a method for manufacturing a semiconductor device using a resin composition containing a polyimide precursor having a specific structure, a crosslinking agent (specifically, tetraethylene glycol dimethacrylate), and a solvent. Patent Document 2 describes a retardation plate having an alignment film formed by stretching a film containing a polymer having a specific structure and an optically anisotropic layer containing a liquid crystal compound whose alignment is controlled by the alignment film.

[0003] US Patent Application Publication No. 2022 / 0091505 Japanese Patent Application Publication No. 2006-133483

[0004] The fifth-generation mobile communication system (5G), a new communications standard, uses the millimeter-wave (10 GHz to 80 GHz) frequency band, enabling high-speed, high-capacity transmission, low signal latency, and simultaneous connection of multiple devices, which were not possible with conventional communications. In the millimeter-wave band, transmission loss in signal wiring on printed wiring boards is significant, raising concerns about heat generation and transmission delays. To suppress transmission loss, it is necessary to reduce the dielectric loss tangent of packaging materials. Polyimide compositions are widely used as packaging materials due to their excellent film properties. However, polyimides contain polar imide groups, and photosensitive polyimide precursor compositions contain many polar compounds, such as photopolymerization initiators and crosslinkers, resulting in high dielectric constants and dielectric loss tangents, and a need for reduced dielectric properties.

[0005] Therefore, an object of the present invention is to provide a resin composition that can provide a film with a low dielectric loss tangent. Another object of the present invention is to provide an insulating film with a low dielectric loss tangent, and a method for producing an interlayer insulating film for a redistribution layer using the resin composition.

[0006] Examples of typical embodiments of the present invention are given below.

[0007] [1] A resin composition comprising at least one polymer selected from the group consisting of polyimides and polyimide precursors, a liquid crystal compound, and a solvent. [2] The resin composition according to [1], which contains a solvent in which the solubility of at least one polymer selected from the group consisting of the polyimides and polyimide precursors at 23°C is 1 mass % or more. [3] The resin composition according to [1] or [2], wherein the solvent contains at least one selected from the group consisting of N-methyl-2-pyrrolidone, γ-butyrolactone, and dimethyl sulfoxide. [4] The resin composition according to any one of [1] to [3], which further contains a migration inhibitor. [5] The resin composition according to [1], which further contains at least one polymer selected from the group consisting of the polyimides and polyimide precursors, wherein the mass M Ａ the mass M of the liquid crystal compound relative to Ｂ The ratio M Ｂ / M Ａ is 0.01 to 0.60. [6] The resin composition according to any one of [1] to [5], further comprising a compound containing Ti. [7] The resin composition according to any one of [1] to [6], wherein the liquid crystal compound is a discotic liquid crystal compound. [8] The resin composition according to any one of [1] to [7], wherein the liquid crystal compound is a compound represented by the following formula (1):

[0008]

[0009] In formula (1), R １ ~R ６each independently represents an organic group having 3 or more carbon atoms. [9] The resin composition according to any one of [1] to [8], wherein the liquid crystal compound has a molecular weight of 600 to 2500.

[10] The resin composition according to any one of [1] to [9], wherein the liquid crystal compound has a radically polymerizable unsaturated bond.

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

[10] , further comprising a photopolymerization initiator.

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

[11] , wherein the content of a colorant in the total solid content is 1 mass % or less.

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

[12] , which is used for organic solvent development.

[14] An insulating film comprising at least one polymer selected from the group consisting of polyimides and polyimide precursors, and a liquid crystal compound.

[15] The insulating film according to

[14] , wherein the liquid crystal compound is a discotic liquid crystal compound.

[16] The insulating film according to

[14] or

[15] , which is an interlayer insulating film for a redistribution layer.

[17] A method for producing an interlayer insulating film for a redistribution layer, comprising: a photosensitive film forming step of applying the resin composition according to any one of [1] to

[13] onto a substrate to form a photosensitive film, an exposure step of exposing the photosensitive film to light to form an exposed film, and a pattern forming step of developing the exposed film with a developer to form an insulating pattern.

[18] The method for producing an interlayer insulating film for a redistribution layer according to

[17] , wherein the developer is an organic solvent.

[0010] According to the present invention, it is possible to provide a resin composition capable of obtaining a film with a low dielectric loss tangent. Furthermore, according to the present invention, it is possible to provide an insulating film with a low dielectric loss tangent and a method for producing an interlayer insulating film for a redistribution layer using the resin composition.

[0011] 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. In this specification, unless otherwise specified, 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.

[0012] <Resin Composition> The resin composition of the present invention contains at least one polymer selected from the group consisting of polyimides and polyimide precursors, a liquid crystal compound, and a solvent. The resin composition of the present invention is preferably used to form a photosensitive film to be exposed to light and developed, and is preferably used to form a film to be exposed to light and developed using a developer containing an organic solvent. The resin composition of the present invention can be used, for example, to form an insulating film for a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer. The resin composition of the present invention may also be used to form a photosensitive film to be subjected to negative development. In the present invention, negative development refers to development in which unexposed areas are removed by development in exposure and development, and positive development refers to development in which exposed areas are removed by development. The exposure method, developer, and development method may, for example, be the exposure method, developer, and development method described in the exposure step and development step in the description of the method for producing a cured product described below.

[0013] The resin composition of the present invention can provide a film with a low dielectric loss tangent. The mechanism by which this effect is achieved is unclear, but is presumed to be as follows. It is believed that in a film formed using a resin composition containing at least one polymer selected from the group consisting of polyimides and polyimide precursors, a liquid crystal compound, and a solvent, the liquid crystal compound is oriented, promoting polymer stacking, which in turn suppresses polymer movement and reduces the dielectric loss tangent.

[0014] Furthermore, the film obtained from the resin composition of the present invention is preferably a film having excellent elongation. It is believed that the film obtained from the resin composition of the present invention has improved elongation due to the formation of a three-dimensional network structure caused by the polymer stacking via the liquid crystal compound.

[0015] The components contained in the resin composition of the present invention will be described in detail below.

[0016] <At least one polymer (specific resin) selected from the group consisting of polyimides and polyimide precursors> The resin composition of the present invention contains at least one polymer (also referred to as specific resin) selected from the group consisting of polyimides and polyimide precursors. The specific resin is preferably a resin containing an imide ring structure in its main chain structure. In the present invention, the term "main chain" refers to the relatively longest bonding chain in the resin molecule, and the term "side chain" refers to any other bonding chain. The polyimide precursor refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a polyimide, preferably a resin that undergoes a change in chemical structure due to heat to become a polyimide, and more preferably a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a polyimide. The specific resin preferably has a polymerizable group, more preferably a radically polymerizable group. When the specific resin has a radically polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator, more preferably a radical polymerization initiator and a radical crosslinking agent. If necessary, a sensitizer can also be added. From such a resin composition, for example, a negative-tone photosensitive film can be formed. The specific resin may also have a polarity conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive-type photosensitive film or negative-type photosensitive film is formed.

[0017] [Polyimide Precursor] The polyimide precursor used in the present invention is not particularly limited in type, but preferably contains a repeating unit represented by the following formula (2).

[0018]

[0019] In formula (2), A １ and A ２ are each independently an oxygen atom or —NR ｚ represents -, and R １１１ represents a divalent organic group, and R １１５ represents a tetravalent organic group, R １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group; R ｚrepresents a hydrogen atom or a monovalent organic group.

[0020] A in formula (2) １ and A ２ are each independently an oxygen atom or —NR ｚ -, and an oxygen atom is preferred. ｚ represents a hydrogen atom or a monovalent organic group, and preferably a hydrogen atom. １１１ represents a divalent organic group. Examples of the divalent organic group include groups containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, and 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 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. R in formula (2) １１１ 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.

[0021] R １１１ is preferably derived from a diamine. Examples of diamines used in the production of the polyimide precursor 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, R １１１is 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.

[0022]

[0023] 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.

[0024] 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.

[0025] Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017 / 038598.

[0026] 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.

[0027] R １１１ is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the resulting organic 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.

[0028] Also, R １１１ 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).

[0029]

[0030] 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 the nitrogen atom in formula (2). 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).

[0031]

[0032] 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 the nitrogen atom in formula (2). 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.

[0033] R in formula (2) １１５ represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In formula (5) or formula (6), * each independently represents a bonding site to another structure.

[0034]

[0035] In formula (5), R １１２ represents 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, -O-, -CO-, -S-, -SO ２-, -NHCO-, and a group selected from a combination thereof are preferred, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO ２ - is more preferably a group selected from -CH ２ -, -C(CF ３ ) ２ -, -C(CH ３ ) ２ -, -O-, -CO-, -S- and -SO ２ It is more preferably a divalent group selected from the group consisting of -.

[0036] R １１５ Specifically, R may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. １１５ The tetracarboxylic acid dianhydride may contain only one kind or two or more kinds of tetracarboxylic acid dianhydride residues as a structure corresponding to the formula (I). The tetracarboxylic acid dianhydride is preferably represented by the following formula (O).

[0037]

[0038] In formula (O), R １１５ represents a tetravalent organic group. １１５ The preferred range of R in formula (2) is １１５ The same applies to the preferred range.

[0039] 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.

[0040] Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598 are also preferred examples.

[0041] In formula (2), R １１１ and R １１５ At least one of R may have an OH group. １１１Examples of the amino acid residue include residues of bisaminophenol derivatives.

[0042] R in formula (2) １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. １１３ and R １１４ Preferably, at least one of R contains a polymerizable group, and more preferably, both of R １１３ and R １１４ 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 polyimide precursor 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.

[0043]

[0044] In formula (III), R ２００ represents 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. ２０１Examples 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.

[0045] In formula (2), R １１３is a hydrogen atom, or R １１４ When is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0046] In formula (2), R １１３ and R １１４ At least one of the groups may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group. Preferred examples include an acetal group, a ketal group, a silyl group, a silyl ether group, and a tertiary alkyl ester group. 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, and a trimethylsilyl ether group. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

[0047] The polyimide precursor preferably contains fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0048] Furthermore, for the purpose of improving adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include embodiments using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.

[0049] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by formula (2-A). When the polyimide precursor contains a repeating unit represented by formula (2-A), it becomes possible to further widen the width of the exposure latitude. Formula (2-A)

[0050]

[0051] In formula (2-A), A １ and A ２ represents an oxygen atom, R １１１ and R １１２ each independently represents a divalent organic group; R １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group; R １１３ and R １１４ At least one of the groups is a group containing a polymerizable group, and it is preferred that both of the groups are groups containing a polymerizable group.

[0052] A １ , A ２ , R １１１ , R １１３ and R １１４ are each independently A in formula (2). １ , A ２ , R １１１ , R １１３ and R １１４ The same definition and preferred range are also true. １１２ is R in formula (5). １１２ The same applies to the preferred range.

[0053] The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2). The polyimide precursor may also contain other types of repeating units in addition to the repeating unit of formula (2).

[0054] In one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) 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 polyimide precursor except for the terminal repeating units may be repeating units represented by formula (2).

[0055] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) of the polyimide precursor 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 precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor 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. In this specification, the molecular weight dispersity is a value calculated by dividing the weight-average molecular weight by the number-average molecular weight. When the resin composition contains multiple polyimide precursors as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as a single resin are each within the above-mentioned ranges.

[0056] [Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or may be 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 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23°C. 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 organic film, the polyimide is preferably a polyimide having multiple imide structures in its main chain.

[0057] -Fluorine Atom- From the viewpoint of the film strength of the obtained organic film, it is also preferable that the polyimide contains a fluorine atom. The fluorine atom is, for example, R １３２ or R in the repeating unit represented by formula (4) described below １３１ and R in the repeating unit represented by formula (4) described below is preferably included. １３２ or R in the repeating unit represented by formula (4) described below １３１ 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.

[0058] -Silicon Atom- From the viewpoint of the film strength of the obtained organic film, it is also preferable that the polyimide contains a silicon atom. The silicon atom is, for example, R in the repeating unit represented by formula (4) described later. １３１ and R in the repeating unit represented by formula (4) described below is preferably included. １３１ It is more preferable that the silicon atom or the organic modified (poly)siloxane structure described below is contained in the polyimide. 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.

[0059] - Ethylenically unsaturated bond - From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has an ethylenically unsaturated bond. The polyimide may have the ethylenically unsaturated bond at the end of the main chain or in a side chain, but it is preferable that the ethylenically unsaturated bond is in a side chain. The ethylenically unsaturated bond is preferably radically polymerizable. The ethylenically unsaturated bond is formed by the R １３２ or R １３１ and R １３２ or R １３１ Among these, the ethylenically unsaturated bond is more preferably contained as a group having an ethylenically unsaturated bond in R １３１ and R １３１ 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):

[0060]

[0061] 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.

[0062] 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.

[0063] 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).

[0064]

[0065] 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). ２１The 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).

[0066] In formula (IV), * represents a bonding site to another structure, and is preferably a bonding site to the main chain of the polyimide.

[0067] 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.

[0068] -Polymerizable group other than a group having an ethylenically unsaturated bond- The polyimide may have a polymerizable group other than a group having an ethylenically unsaturated bond. Examples of the polymerizable group other than a 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 a group having an ethylenically unsaturated bond include R in the repeating unit represented by formula (4) below. １３１ 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.

[0069] - 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 R １１３ and R １１４ The polarity conversion group is, for example, R in the repeating unit represented by formula (4) described later. １３１ , R １３２ , contained in the terminals of polyimides, etc.

[0070] -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.

[0071] -Phenol Hydroxy Group- From the viewpoint of ensuring an appropriate development rate 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, R in the repeating unit represented by formula (4) described below. １３２ or R １３１ The 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.

[0072] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains a repeating unit represented by the following formula (4).

[0073]

[0074] In formula (4), R １３１ represents a divalent organic group, and R １３２ represents a tetravalent organic group. When the compound has a polymerizable group, the polymerizable group is １３１ and R １３２ or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2):

[0075]

[0076] In formula (4-1), R １３３ is a polymerizable group, and the other groups have the same meanings as in formula (4).

[0077]

[0078] R １３４ and R １３５ At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group has the same meaning as in formula (4).

[0079] Examples of the polymerizable group include the above-mentioned group containing an ethylenically unsaturated bond and a crosslinkable group other than the above-mentioned group having an ethylenically unsaturated bond. １３１ represents a divalent organic group. The divalent organic group is R １１１ The same examples as those listed above are given, and the preferred ranges are also the same. １３１ The diamine residues include those remaining after removal of the amino groups of the diamine. Examples of the diamine include aliphatic, cycloaliphatic, and aromatic diamines. Specific examples include R in the formula (2) of the polyimide precursor. １１１ Examples include:

[0080] R １３１ is preferably a diamine residue having at least two alkylene glycol units in the main chain, in order to more effectively suppress the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue of the above diamine that does not contain an aromatic ring.

[0081] 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.

[0082] R １３２ represents a tetravalent organic group. The tetravalent organic group is R １１５ Examples of the group R are the same as those of the group R, and the preferred ranges are also the same. １１５ The four bonds of the tetravalent organic group exemplified by: are bonded to the four —C(═O)— moieties in formula (4) to form a condensed ring.

[0083] R １３２ Examples of the tetracarboxylic acid residues include those remaining after removal of the anhydride groups from tetracarboxylic dianhydrides. １１５ From the viewpoint of the strength of the organic film, R １３２ is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

[0084] R １３１ and R １３２ It is also preferable that at least one of R １３１ Preferred examples of R 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). １３２ As the above, (DAA-1) to (DAA-5) are more preferred examples.

[0085] 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.

[0086] 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.

[0087] In order to improve the storage stability of the resin composition, it is 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.

[0088] -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 film strength, insulating properties, etc. of the resulting organic 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

[0089] Polyimide is a polymer in which all repeating units are R １３１ and R １３２ The repeating unit may contain the repeating unit represented by the above formula (4) in which the combination of R １３１ and R １３２ The polyimide may contain a repeating unit represented by the formula (4) above, which contains two or more different combinations of repeating units. In addition to the repeating unit represented by the formula (4), the polyimide may contain other types of repeating units. Examples of other types of repeating units include the repeating unit represented by the formula (2) above.

[0090] 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.

[0091] 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, 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 polyimides as specific resins, 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 the multiple types of polyimides as one resin are each within the above ranges.

[0092] [Method for Producing Polyimide Precursors, etc.] Polyimide precursors, etc., 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, obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine with the diamine. Among the above-mentioned production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine with 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 method for producing a polyimide precursor or the like, 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 a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types.The basic compound can be appropriately 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.

[0093] -End-capping agent- In order to further improve storage stability during the production method of a polyimide precursor or the like, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like. 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, monoamines, etc., and 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.

[0094] -Solid Precipitation- The method for producing a polyimide precursor or the like 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 poured into 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 a polyimide precursor or the like. To improve the degree of purification, the polyimide precursor or the like may be repeatedly subjected to operations such as redissolving, reprecipitation, and drying. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.

[0095] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, 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 the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, 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 specific resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0096] It is also preferable that the resin composition of the present invention contains at least two kinds of resins. Specifically, the resin composition of the present invention may contain a total of two or more kinds of the specific resin and other resins described later, or may contain two or more kinds of specific resins, but it is preferable that the resin composition of the present invention contains two or more kinds of specific resins. When the resin composition of the present invention contains two or more kinds of specific resins, for example, a polyimide precursor having a structure derived from a dianhydride (R １１５ ) preferably contains two or more different polyimide precursors.

[0097] <Other Resins> The resin composition of the present invention may contain the specific resin described above and other resins different from the specific resin (hereinafter simply referred to as "other resins"). Examples of other resins include polybenzoxazole, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane resin, butyral resin, styryl resin, polyether resin, polyester resin, etc. Examples of polybenzoxazole precursors include the compounds described in paragraphs

[0073] to

[0095] of WO 2022 / 145355. The above descriptions are incorporated herein. Examples of polybenzoxazoles include the compounds described in paragraphs

[0096] to

[0103] of WO 2022 / 145355. The above descriptions are incorporated herein. Examples of polyamideimide precursors include the compounds described in paragraphs

[0104] to

[0119] of WO 2022 / 145355. The above description is incorporated herein by reference. Examples of polyamideimides include the compounds described in paragraphs 0120 to 0133 of WO 2022 / 145355. The above description is incorporated herein by reference.

[0098] For example, by further adding a (meth)acrylic resin, a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described later, a polymerizable compound 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).

[0099] 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.

[0100] <Liquid Crystal Compound> The resin composition of the present invention contains a liquid crystal compound. A liquid crystal compound refers to a compound having molecular orientation. The liquid crystal compound is preferably a rod-shaped liquid crystal compound or a discotic liquid crystal compound, and more preferably a discotic liquid crystal compound. The liquid crystal compound is preferably a compound represented by the following formula (1):

[0101]

[0102] In formula (1), R １ ~R ６R each independently represents an organic group having 3 or more carbon atoms. １ ~R ６ The number of carbon atoms in the organic group represented by R is preferably 3 or more and 30 or less, and more preferably 5 or more and 20 or less. １ ~R ６ is preferably an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an acyl group, an acyloxy group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an arylcarbonyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an alkylamino group, a cycloalkylamino group, an arylamino group, or a group formed by combining two or more of these.

[0103] The liquid crystal compound may or may not be a polymerizable compound, but is preferably a polymerizable compound. The liquid crystal compound preferably has a radically polymerizable unsaturated bond, more preferably an ethylenically unsaturated bond. A liquid crystal compound having a radically polymerizable unsaturated bond can function as a radical crosslinking agent. The liquid crystal compound is a compound represented by the above formula (1), and R １ ~R ６ Preferably, at least one of R １ ~R ６ It is more preferable that at least two of the above have an ethylenically unsaturated bond. An example of an embodiment in which the liquid crystal compound has an ethylenically unsaturated bond is an embodiment in which the liquid crystal compound has a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include the group represented by the above formula (III), and specific examples include a vinyl group, an allyl group, a (meth)acrylamide group, and a (meth)acryloyloxy group, with a (meth)acryloyloxy group being particularly preferable.

[0104] The molecular weight of the liquid crystal compound is preferably 600 to 2,500, more preferably 1,000 to 2,300, and even more preferably 1,500 to 1,900.

[0105] The content of the liquid crystal compound is preferably more than 1% by mass and not more than 60% by mass, based on the total solid content of the resin composition. The lower limit of the content of the liquid crystal compound is more preferably 5% by mass or more. The upper limit of the content of the liquid crystal compound is more preferably 50% by mass or less, and even more preferably 40% by mass or less.

[0106] The liquid crystal compound may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range. The liquid crystal compound can be synthesized by a known method.

[0107] In order to achieve both a low dielectric loss tangent and mechanical properties, the mass of at least one polymer selected from the group consisting of polyimides and polyimide precursors (total mass of polyimides and polyimide precursors) M Ａ Mass of liquid crystal compounds (total mass of liquid crystal compounds) M Ｂ M is the ratio of Ｂ / M Ａ is preferably 0.01 to 0.60, more preferably 0.05 to 0.30, and even more preferably 0.10 to 0.20.

[0108] <Polymerizable Compound> The resin composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include a radical crosslinking agent and other crosslinking agents. The polymerizable compound may be the liquid crystal compound described above or a compound other than the liquid crystal compound described above.

[0109] [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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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. Oligomer types of these agents can also be used.

[0116] 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).

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] The crosslinking agent U preferably has a structure represented by the following formula (U-1):

[0123]

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129]

[0130] [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.

[0131] [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.

[0132] 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.

[0133] Specific examples of the crosslinking agent U are shown below, but the crosslinking agent U is not limited to these.

[0134]

[0135]

[0136]

[0137] 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, 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 diacrylate 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 a urethane bond 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 polyethylene glycol chain formula weight of approximately 200. 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.

[0138] 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.

[0139] 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.

[0140] [Other Crosslinking Agents] Other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022 / 145355, the disclosures of which are incorporated herein by reference.

[0141] <Solvent> The resin composition of the present invention 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.

[0142] 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, γ-valerolactone, alkyl alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters ...alkyloxypropionate, ethyl 3-alkyloxypropionate, 2-alkyloxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 3- Preferred examples thereof include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, 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.

[0143] 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.

[0144] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0145] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0146] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0147] 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.

[0148] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0149] 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.

[0150] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0151] 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. Furthermore, 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 content may be determined in consideration of the solubility of the components, such as the specific resin, contained in the resin composition.Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide, relative to the total mass of the solvent.

[0152] In order to ensure uniformity in the thickness of the coating film, the resin composition of the present invention preferably contains a solvent in which at least one polymer selected from the group consisting of polyimides and polyimide precursors has a solubility of 1% by mass or more at 23°C, more preferably a solvent in which the solubility is 5% by mass or more and 60% by mass or less, and even more preferably a solvent in which the solubility is 10% by mass or more and 50% by mass or less. The solvent preferably contains at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, and dimethyl sulfoxide (DMSO).

[0153] 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.

[0154] <Polymerization initiator> The resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable that the resin composition contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, the resin composition may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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).

[0160] 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).

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165]

[0166] 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.

[0167]

[0168] 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.

[0169] 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 ＯＸ１ Examples 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.

[0170] 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).

[0171]

[0172] 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 Ｘ１４ each independently represents a hydrogen atom or a substituent. Ｘ１０ ~R Ｘ１４ At least one of the groups is an electron-withdrawing group.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] 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.

[0179] 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.

[0180] 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.

[0181] <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 actions such as electron transfer, energy transfer, and heat generation. This causes the thermal radical polymerization initiator or the photoradical polymerization initiator to undergo a chemical change and decompose, generating a radical, an acid, or a 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.

[0182] 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.

[0183] <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.

[0184] 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.

[0185] 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.

[0186] <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 such as a polyimide precursor, the resin composition preferably contains a base generator. By containing a thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted 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, and acyloxyimino compounds. Specific examples of non-ionic base generators include the compounds described in paragraphs 0249 to 0277 of WO 2022 / 145355. The above descriptions are incorporated herein by reference. Examples of base generators include, but are not limited to, the following compounds:

[0187]

[0188] 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.

[0189] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0190] Specific examples of ammonium salts include, but are not limited to, the following compounds:

[0191]

[0192] Specific examples of iminium salts include, but are not limited to, the following compounds:

[0193]

[0194] 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.

[0195] <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.

[0196] [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.

[0197]

[0198] 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.

[0199] [Aluminum-Based Adhesion Aid] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0200] 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.

[0201] 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.

[0202] <Migration Inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively inhibited.

[0203] The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (e.g., a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring, a 6H-pyran ring, a triazine ring, etc.), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0204] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0205] Other migration inhibitors, for example, other migration inhibitors, the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compounds described in paragraph 0052 of JP-A-2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, the compounds described in paragraph 0166 of WO 2015 / 199219, and the like can be used, the contents of which are incorporated herein by reference.

[0206] Specific examples of the migration inhibitor include the following compounds.

[0207]

[0208] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the resin composition.

[0209] The migration inhibitor may be one kind or two or more kinds. When two or more kinds of migration inhibitors are used, the total amount thereof is preferably within the above range.

[0210] <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.

[0211] 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.

[0212] 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.

[0213] 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.

[0214] <Organometallic Complex> The resin composition of the present invention may contain an organometallic complex from the viewpoint of chemical resistance. The organometallic complex is not particularly limited as long as it is an organic complex compound containing a metal atom. However, it is preferably a complex compound containing a metal atom and an organic group, more preferably a compound in which an organic group is coordinated to a metal atom, and even more preferably a metallocene compound. The metallocene compound refers to an organometallic complex having two optionally substituted cyclopentadienyl anion derivatives as η5-ligands. The organic group is not particularly limited, but is preferably a hydrocarbon group or a group consisting of a combination of a hydrocarbon group and a heteroatom. Preferred heteroatoms are oxygen, sulfur, and nitrogen atoms. At least one of the organic groups is preferably a cyclic group, and more preferably at least two are cyclic groups. The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, more preferably a 5-membered cyclic group. The cyclic group may be a hydrocarbon ring or a heterocyclic ring, but is preferably a hydrocarbon ring. A cyclopentadienyl group is preferred as the 5-membered cyclic group. The organometallic complex preferably contains 2 to 4 cyclic groups in one molecule.

[0215] The metal contained in the organometallic complex is not particularly limited, but is preferably a metal corresponding to a Group 4 element, more preferably at least one metal selected from the group consisting of titanium, zirconium, and hafnium, even more preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium. The resin composition of the present invention preferably contains a compound containing titanium (Ti).

[0216] The organometallic complex may contain two or more metal atoms or only one metal atom, but preferably contains only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one type of metal atom, or may contain two or more types of metal atoms.

[0217] The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound or a hafnocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, still more preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.

[0218] An embodiment in which the organometallic complex has photoradical polymerization initiation ability is also preferred. In the present invention, having photoradical polymerization initiation ability means being able to generate free radicals that can initiate radical polymerization upon irradiation with light. For example, the presence or absence of photoradical polymerization initiation ability can be confirmed by irradiating a composition containing a radical crosslinking agent and an organometallic complex with light in a wavelength range in which the organometallic complex absorbs light but in which the radical crosslinking agent does not absorb light, and by confirming whether or not the radical crosslinking agent has disappeared. To confirm whether or not the radical crosslinking agent has disappeared, an appropriate method can be selected depending on the type of radical crosslinking agent, but it can be confirmed by, for example, IR measurement (infrared spectroscopy measurement) or HPLC measurement (high performance liquid chromatography). When the organometallic complex has photoradical polymerization initiation ability, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, even more preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound. When the organometallic complex does not have photoradical polymerization initiation ability, the organometallic complex is preferably at least one compound selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds, and hafnocene compounds, more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds, and hafnocene compounds, even more preferably at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds, and particularly preferably a titanocene compound.

[0219] The molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.

[0220] The organometallic complex is preferably a compound represented by the following formula (P):

[0221]

[0222] In formula (P), M is a metal atom, and each R is independently a substituent. Each R is preferably independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

[0223] The metal atom represented by M in formula (P) is preferably an iron atom, a titanium atom, a zirconium atom, or a hafnium atom, more preferably a titanium atom, a zirconium atom, or a hafnium atom, still more preferably a titanium atom or a zirconium atom, and particularly preferably a titanium atom. Examples of the aromatic group represented by R in formula (P) include aromatic groups having 6 to 20 carbon atoms, preferably aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as a phenyl group, a 1-naphthyl group, or a 2-naphthyl group. Examples of the alkyl group represented by R in formula (P) include alkyl groups having 1 to 20 carbon atoms, more preferably alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group. Examples of the halogen atom represented by R include F, Cl, Br, and I. The alkyl group constituting the alkylsulfonyloxy group in R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group. R may further have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, and a diarylamino group.

[0224] Specific examples of organometallic complexes include, but are not limited to, tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonato)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and the following compounds:

[0225]

[0226] Further, examples include compounds described in paragraphs 0078 to 0088 of WO 2018 / 025738, the contents of which are incorporated herein by reference.

[0227] The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solid content of the resin composition. The lower limit is more preferably 1.0% by mass or more, even more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less. One or more types of organometallic complexes can be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0228] <Colorant> The resin composition of the present invention preferably contains a colorant in an amount of 1% by mass or less based on the total solid content. The colorant refers to a colored organic pigment or organic dye. Examples of colorants include those used for color filters. The resin composition of the present invention preferably does not contain a colorant (i.e., the content of the colorant in the total solid content is 0% by mass).

[0229] <Other Additives> The resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, UV absorbers, organic titanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), as needed, within the scope of obtaining the effects of the present invention. By appropriately incorporating these components, properties such as film physical properties can be adjusted. For details of these components, please refer to, for example, paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101 to 0104, 0107 to 0109, etc. of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are incorporated, the total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention. These other additives include the compounds described in paragraphs 0316 to 0358 of WO 2022 / 145355, the disclosures of which are incorporated herein by reference.

[0230] The resin composition of the present invention is preferably used for organic solvent development (i.e., for organic solvent development). Organic solvent development is development using an organic solvent as a developer, and will be described in detail later.

[0231] <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.

[0232] <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.

[0233] 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.

[0234] 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.

[0235] 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.

[0236] 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.

[0237] <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

[0238] <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.

[0239] <Insulating Film> The insulating film of the present invention contains at least one polymer selected from the group consisting of polyimides and polyimide precursors, and a liquid crystal compound. The insulating film of the present invention can be formed by curing the resin composition of the present invention described above. That is, the insulating film of the present invention is a preferred embodiment of a cured product of the resin composition described above. The at least one polymer selected from the group consisting of polyimides and polyimide precursors and the liquid crystal compound are as described above. The insulating film of the present invention can contain other components in addition to the at least one polymer selected from the group consisting of polyimides and polyimide precursors, and the liquid crystal compound. Examples of other components include the components that can be contained in the resin composition of the present invention described above. The liquid crystal compound contained in the insulating film of the present invention is preferably a discotic liquid crystal compound. The insulating film of the present invention is preferably an interlayer insulating film for a redistribution layer.

[0240] <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.

[0241] 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.

[0242] (Method for producing a cured product) The method for producing a cured product of the present invention preferably includes a film-forming step of applying a resin composition to a substrate to form a film. The method for producing an insulating film of the present invention is similar to the method for producing a cured product. The method for producing a cured product more preferably includes the film-forming step, an exposure step of selectively exposing the film formed in the film-forming step, and a development step of developing the film exposed in the exposure step 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 of heating the pattern obtained in the development step and a post-development exposure step of exposing the pattern obtained in the development step. 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.

[0243] <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.

[0244] [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.

[0245] 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.

[0246] 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.

[0247] <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) in order 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.

[0248] <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.

[0249] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0250] 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.

[0251] <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.

[0252] <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.

[0253] [Developer] The developer used in the development step may be an alkaline aqueous solution or a developer containing an organic solvent.

[0254] 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.

[0255] 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.

[0256] 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.

[0257] 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.

[0258] 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.

[0259] 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.

[0260] 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.

[0261] 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.

[0262] 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.

[0263] The developer may further contain other components, such as known surfactants and known defoaming agents.

[0264] [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.

[0265] 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.

[0266] 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.

[0267] [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.

[0268] 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.

[0269] 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.

[0270] 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.

[0271] 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.

[0272] 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.

[0273] The rinse liquid may further contain other components, such as known surfactants and known defoaming agents.

[0274] [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.

[0275] 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.

[0276] 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.

[0277] 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.

[0278] 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.

[0279] <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.

[0280] 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.

[0281] 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.

[0282] 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.

[0283] 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.

[0284] 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.

[0285] 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.

[0286] 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.

[0287] <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.

[0288] <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).

[0289] 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.

[0290] 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.

[0291] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0292] <Method for manufacturing an interlayer insulating film for a redistribution layer> The method for manufacturing an interlayer insulating film for a redistribution layer of the present invention includes a photosensitive film forming step of applying the above-mentioned resin composition of the present invention to a substrate to form a photosensitive film, an exposure step of exposing the photosensitive film to light to form an exposed film, and a pattern forming step of developing the exposed film with a developer to form an insulating pattern. The developer is preferably an organic solvent.

[0293] <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).

[0294] 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.

[0295] (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.

[0296] 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.

[0297] 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.

[0298] <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.

[0299] 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.

[0300] 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.

[0301] 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.

[0302] (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.

[0303] (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.

[0304] 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.

[0305] Examples and Comparative Examples In each example and comparative example, the components listed in Table 1 below were mixed to obtain a resin composition. Specifically, the content of each component listed in Table 1 was the amount (parts by mass) listed in the "Amount" column of each column in the table. The obtained resin composition was pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.5 μm. In the table, "-" indicates that the resin composition did not contain the corresponding component. Note that for the resin compositions of all examples and comparative examples, the content of colorant in the total solids was 0 mass% (i.e., none of the resin compositions of all examples and comparative examples contained a colorant).

[0306]

[0307] Details of each component listed in the table are as follows:

[0308] [Resins] Polyimide precursors PIP-1 to PIP-3 and polyimides PI-1 to PI-3 were used. Their structural formulas are shown below. The weight average molecular weight (Mw) and polydispersity (PD) of each of PIP-1 to PIP-3 are also shown below.

[0309]

[0310]

[0311] [Liquid Crystal Compounds] DLC-1 to DLC-4 are discotic liquid crystal compounds having a radically polymerizable unsaturated bond, SLC-1 to SLC-3 are rod-shaped liquid crystal compounds having a radically polymerizable unsaturated bond, DLN-1 is a discotic liquid crystal compound having no radically polymerizable unsaturated bond, and SLN-1 is a rod-shaped liquid crystal compound having no radically polymerizable unsaturated bond. The structural formulas of each are shown below.

[0312]

[0313]

[0314]

[0315]

[0316] [Polymerizable Compounds (Non-Liquid Crystal Compounds)] L-1 and L-2 represented by the following structural formulas were used.

[0317]

[0318] [Photopolymerization initiator] S-1 and S-2 represented by the following structural formulas were used.

[0319]

[0320] [Metal Adhesion Improver] A-1 represented by the following structural formula was used.

[0321]

[0322] [Migration Inhibitor (Copper Corrosion Inhibitor)] A-2 represented by the following structural formula was used.

[0323]

[0324] [Polymerization inhibitor] A-3 represented by the following structural formula was used.

[0325]

[0326] [Thermal Base Generator] A-4 and A-5 represented by the following structural formulas were used.

[0327]

[0328] [Ti-containing compound] A-6 represented by the following structural formula was used.

[0329]

[0330] [Solvents] DMSO: dimethyl sulfoxide GBL: γ-butyrolactone NMP: N-methyl-2-pyrrolidone In the table, the notation "G / D" indicates that a mixture of GBL and DMSO was used in a mixing ratio (mass ratio) of GBL:DMSO = 4:1.

[0331] <Preparation of Cured Film> In each of the Examples and Comparative Examples, the resin composition was applied to a silicon wafer by spin coating to form a coating film. The silicon wafer having the coating film was dried on a hot plate at 100°C for 5 minutes to obtain a uniform film with a thickness of 15 µm on the silicon wafer. The entire surface of the obtained film was exposed to 500 mJ / cm using a stepper (Nikon NSR 2005 i9C). ２ The exposed film was heated at a rate of 10°C / min in a nitrogen atmosphere until it reached 230°C, at which point it was heated at 230°C for 3 hours. In this manner, cured films for the respective Examples and Comparative Examples were prepared.

[0332] <Evaluation> [Dielectric loss tangent] The silicon wafer having the cured film prepared above was immersed in a 3 mass % hydrofluoric acid aqueous solution to peel the cured film from the silicon wafer. The film thickness of the peeled cured film was 10 to 15 μm. The dielectric loss tangent of the peeled cured film at 28 GHz was measured using a resonator. Evaluation was based on the following criteria. Evaluation 3: Dielectric loss tangent less than 0.010 Evaluation 2: Dielectric loss tangent 0.010 or more but less than 0.020 Evaluation 1: Dielectric loss tangent 0.020 or more

[0333] [Elongation] The silicon wafer having the cured film prepared above was immersed in a 3% by mass aqueous solution of hydrofluoric acid to peel the cured film from the silicon wafer. The film thickness of the peeled cured film was 10 to 15 μm. The peeled cured film was cut into a dumbbell shape (Type V) in accordance with ASTM D638-00, and pulled at a speed of 5 mm / min with a chuck distance of 20 mm, and the elongation (%) until breakage was recorded as the breaking elongation. Evaluation was based on the following criteria: Evaluation 3: Elongation of 60% or more Evaluation 2: Elongation of 10% or more but less than 60% Evaluation 1: Elongation of less than 10%

[0334] The dielectric loss tangent and elongation of each example and comparative example are shown in the table below. Ａ Mass M of the liquid crystal compound Ｂ The ratio M Ｂ / M Ａ The solubility of the resin in the solvent at 23°C is also shown in the table below.

[0335]

[0336] The above results show that the cured film made of the resin composition according to the present invention has a low dielectric loss tangent and a high elongation.

[0337] Example 101 The resin composition used in Example 1 was applied by spin coating to the surface of the thin copper layer of a resin substrate having a thin copper layer formed on its surface. The resulting film was dried at 100°C for 4 minutes to form a 20 μm-thick film, which was then exposed using a stepper (Nikon Corporation, NSR1505 i6). The exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After exposure, the film was heated at 100°C for 4 minutes. After the heating, the film was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern. The temperature was then increased at a rate of 10°C / min in a nitrogen atmosphere, reaching 230°C, and maintained at 230°C for 3 hours to form an interlayer insulating film for a redistribution layer. This interlayer insulating film for a redistribution layer had excellent insulating properties. Furthermore, semiconductor devices were manufactured using these interlayer insulating films for a redistribution layer, and it was confirmed that they operated without any problems.

[0338] According to the present invention, it is possible to provide a resin composition capable of obtaining a film with a low dielectric loss tangent. Furthermore, according to the present invention, it is possible to provide an insulating film with a low dielectric loss tangent and a method for producing an interlayer insulating film for a redistribution layer using the resin composition.

[0339] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2022-158657) filed on September 30, 2022, the contents of which are incorporated herein by reference.

Claims

1. A resin composition comprising at least one polymer selected from the group consisting of polyimides and polyimide precursors, a liquid crystal compound, and a solvent.

2. The resin composition according to claim 1, further comprising a solvent in which the solubility of at least one polymer selected from the group consisting of polyimides and polyimide precursors at 23°C is 1% by mass or more.

3. The resin composition according to claim 1, wherein the solvent comprises at least one selected from the group consisting of N-methyl-2-pyrrolidone, γ-butyrolactone, and dimethylsulfoxide.

4. The resin composition according to claim 1 , further comprising a migration inhibitor.

5. The mass M of at least one polymer selected from the group consisting of polyimides and polyimide precursors. Ａ The mass M of the liquid crystal compound Ｂ Ratio of M Ｂ / M Ａ The resin composition according to claim 1, wherein the molecular weight is 0.01 to 0.

60.

6. The resin composition according to claim 1 , further comprising a compound containing Ti.

7. The resin composition according to claim 1 , wherein the liquid crystal compound is a discotic liquid crystal compound.

8. The resin composition according to claim 1 , wherein the liquid crystal compound is a compound represented by the following formula (1): 【Chemistry 1】 In formula (1), R １ ~R ６ each independently represents an organic group having 3 or more carbon atoms.

9. The resin composition according to claim 1, wherein the liquid crystal compound has a molecular weight of 600 to 2,500.

10. The resin composition according to claim 1 , wherein the liquid crystal compound has a radically polymerizable unsaturated bond.

11. The resin composition according to claim 1 , further comprising a photopolymerization initiator.

12. The resin composition according to claim 1 , wherein the content of the colorant in the total solid content is 1% by mass or less.

13. The resin composition according to claim 1 , which is used for organic solvent development.

14. The resin composition described in claim 1, wherein at least one polymer selected from the group consisting of polyimides and polyimide precursors has a radically polymerizable group, and the liquid crystal compound is a discotic liquid crystal compound.

15. The resin composition described in claim 1, wherein at least one polymer selected from the group consisting of polyimides and polyimide precursors has a radical polymerizable group, and the liquid crystal compound is a compound represented by the following formula (1): 【Chemistry 2】 In formula (1), R 1 to R 6 each independently represent an organic group having 3 or more carbon atoms.

16. The resin composition described in claim 1, wherein at least one polymer selected from the group consisting of polyimides and polyimide precursors has a radically polymerizable group, and the liquid crystal compound has a radically polymerizable unsaturated bond.

17. The resin composition according to claim 14, wherein a ratio M B / M A of a mass M B of said liquid crystal compound to a mass M A of said at least one polymer selected from the group consisting of said polyimide and polyimide precursor is 0.01 to 0.

60.

18. An insulating film comprising at least one polymer selected from the group consisting of polyimide and polyimide precursors, and a liquid crystal compound.

19. The insulating film according to claim 18 , wherein the liquid crystal compound is a discotic liquid crystal compound.

20. The insulating film according to claim 18 or 19, which is an interlayer insulating film for a redistribution layer.

21. A photosensitive film forming step of applying the resin composition according to any one of claims 1 to 16 onto a substrate to form a photosensitive film; an exposure step of exposing the photosensitive film to light to form an exposed film; and developing the exposed film with a developer to form an insulating pattern.

22. 22. The method for producing an interlayer insulating film for a redistribution layer according to claim 21, wherein the developer is an organic solvent.

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