TWI878445B - Curable resin composition, resin film, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Abstract

The present invention provides a curable resin composition, a resin film formed by applying the curable resin composition to a substrate, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for manufacturing the cured film, and a semiconductor device including the cured film or the laminate. The curable resin composition includes at least one resin selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, and a polybenzoxazole precursor, and at least two solvents.

Description

Curable resin composition, resin film, cured film, laminate, method for producing cured film, and semiconductor device

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

Polyimide and polybenzoxazole are suitable for various applications due to their excellent heat resistance and insulation properties. The above applications are not particularly limited, but for example, for semiconductor devices for actual mounting, they can be used as materials for insulating films or seals or protective films. In addition, they are also used as base films or coverlay films for flexible substrates.

For example, in the above-mentioned application, polyimide or polybenzoxazole is used in the form of at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor. Such a curable resin composition is applied to a substrate, for example, by coating, to form a resin film, and then exposure, development, heating, etc. are performed as needed, so that a cured film can be formed on the substrate. The above-mentioned polyimide precursor and the above-mentioned polybenzoxazole precursor are cyclized, for example, by heating, and become polyimide and polybenzoxazole, respectively, in the cured film. Since the curable resin composition can be applied by a known coating method, it can be said that it has excellent adaptability in manufacturing, for example, the curable resin composition has a high degree of design freedom in the shape, size, and application position when applied. In addition to the high performance of polyimide, polybenzoxazole, etc., from the perspective of such excellent adaptability in manufacturing, the application development of the above-mentioned curable resin composition in the industry is increasingly expected.

For example, Patent Document 1 describes a composition comprising: at least one of a resin including a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole, a crosslinking agent, a first solvent selected from alcohols, esters, ketones, ethers, sulfur-containing compounds, carbonates and ureas that dissolves 5% by mass or more of the above resin at 25°C, and a second solvent having a solubility parameter distance of 3.0 to 11.0 from the above first solvent. Patent Document 2 discloses a resin composition comprising (a) a polyimide precursor or a polybenzoxazole precursor, and one or more polar solvents selected from the group consisting of a compound represented by a specific general formula (1), a compound represented by a specific general formula (2), and a compound containing a sulfur atom, wherein the content of N-methyl-2-pyrrolidone (NMP) in the resin composition is 0.1 mass % or less.

[Patent Document 1] International Publication No. 2017/038664 [Patent Document 2] International Publication No. 2014/115233

It is desirable to provide a curable resin composition in which the film thickness uniformity of the obtained resin film is excellent even when the curable resin composition is stored at a low temperature for a long period of time.

The object of the present invention is to provide a curable resin composition, a resin film formed by applying the curable resin composition to a substrate, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate, wherein the resin film obtained by the curable resin composition has excellent film thickness uniformity even when stored for a long period of time at a low temperature.

Representative embodiments of the present invention are shown below. <1> A curable resin composition comprising at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor and at least two solvents. <2> The curable resin composition as described in <1> further comprises a migration inhibitor of a compound having one or more heterocyclic rings selected from the group consisting of imidazole ring, triazole ring, oxadiazole ring, thiazole ring, pyrazole ring, isoxadiazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyrimidine ring, pyrimidine ring, piperidine ring, piperidine ring and tririmidine ring and an amine group. <3> The curable resin composition as described in <1> or <2>, further comprising a migration inhibitor of at least one compound selected from the group consisting of 5-methylbenzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole and 5-amino-1H-tetrazole. <4> The curable resin composition as described in any one of <1> to <3>, wherein the solvent comprises dimethyl sulfoxide and ethyl lactate, the content of ethyl lactate is 40% by mass or more relative to the total mass of the solvent, and the content of γ-butyrolactone is 40% by mass or less relative to the total mass of the solvent. <5> The curable resin composition as described in any one of <1> to <4>, wherein the solvent includes a solvent having a nitrogen-containing heterocyclic structure. <6> The curable resin composition as described in any one of <1> to <5>, wherein the solvent includes a solvent having an ether bond. <7> The curable resin composition as described in any one of <1> to <6>, wherein the content of the second most abundant solvent in the above solvent is 20% by mass or more relative to the total mass of the solvent. <8> The curable resin composition as described in any one of <1> to <7>, further comprising a silane coupling agent. <9> The curable resin composition as described in any one of <1> to <8> is used for storage at least once at -15 to 16°C in a storage container, and the filling rate of the curable resin composition during the above-mentioned refrigeration is 50 to 90% relative to the total storage volume of the above-mentioned storage container. <10> The curable resin composition as described in any one of <1> to <9> is used for forming an interlayer insulating film for a redistribution layer. <11> A resin film, which is formed by applying the curable resin composition as described in any one of <1> to <10> to a substrate. <12> A cured film, which is formed by curing the curable resin composition as described in any one of <1> to <10> or the resin film as described in <11>. <13> A laminate comprising two or more layers of the cured films described in <12>, and comprising a metal layer between any of the cured films. <14> A method for producing a cured film, comprising: a film forming step of applying the curable resin composition described in any one of <1> to <10> to a substrate to form a film. <15> The method for producing a cured film as described in <14>, comprising: an exposure step of exposing the film; and a development step of developing the film. <16> The method for producing a cured film as described in <14> or <15>, comprising: a heating step of heating the film at 50 to 450°C. <17> A semiconductor device comprising the cured film described in <12> or the laminate described in <13>. [Effect of the invention]

According to the present invention, there are provided a curable resin composition, a resin film formed by applying the curable resin composition to a substrate, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate. The resin film obtained by the curable resin composition has excellent film thickness uniformity even when stored for a long period of time at a low temperature.

The main embodiments of the present invention are described below. However, the present invention is not limited to the embodiments indicated. In this specification, the numerical range represented by the symbol "～" indicates a range including the numerical values before and after "～" as the lower limit and the upper limit, respectively. In this specification, the term "step" not only indicates an independent step, but also includes steps that cannot be clearly distinguished from other steps as long as the expected effect of the step can be achieved. Regarding the marking of groups (atomic groups) in this specification, the marking of unsubstituted and unsubstituted includes both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (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, as light used for exposure, there can be cited the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV rays), X-rays, electron beams and other actinic rays or radiation. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic acid" means both or either of "acrylic acid" and "methacrylic acid", and "(meth)acryl" means both or either of "acryl" and "methacryl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of all components of the composition except the solvent. In addition, in this specification, the solid content concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC measurement). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by using, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION) and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as columns. Unless otherwise specified, the molecular weights are measured using THF (tetrahydrofuran) as a washing liquid. In addition, unless otherwise specified, the detection in the GPC measurement is the detection using a UV (ultraviolet) ray detector with a wavelength of 254nm. In this specification, when the positional relationship of each layer constituting a laminate is described as "upper" or "lower", it is sufficient as long as there are other layers on the upper side or lower side of the layer serving as a reference among the plurality of layers concerned. In other words, a third layer or a third element may be further interposed between the layer serving as a reference and the other layers mentioned above, and the layer serving as a reference and the other layers mentioned above do not need to be in contact. Furthermore, unless otherwise specified, the direction in which the layers are gradually stacked with respect to the substrate is referred to as "upper", or, in the case of a photosensitive layer, the direction from the substrate toward the photosensitive layer is referred to as "upper", and the opposite direction is referred to as "lower". In addition, the setting of the up and down directions is for the convenience of explaining this manual. In actual forms, the "up" direction in this manual may also be different from the vertical direction. In this manual, unless otherwise stated, in a composition, each component contained in the composition may include two or more compounds corresponding to the component. In addition, unless otherwise stated, the content of each component in the composition represents the total content of all compounds corresponding to the component. In this manual, unless otherwise stated, the temperature is 23°C, the air pressure is 101,325Pa (1 atmosphere), and the relative humidity is 50%RH. In this manual, the combination of the best form is the best form.

(Curing resin composition) The curable resin composition of the present invention comprises at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor (hereinafter, also referred to as "specific resin") and at least two solvents.

The curable resin composition of the present invention has excellent uniformity of film thickness of the obtained resin film even when stored for a long time at low temperature. According to the research of the inventors, when a curable resin composition containing only one solvent is stored for a long time (for example, more than 6 months) at low temperature (for example, below 5°C, and further below -5°C, etc.) and then applied to a substrate to form a resin film, the obtained resin film has poor uniformity of film thickness. Poor uniformity of film thickness of the resin film means that the difference in film thickness between a thin film thickness portion and a thick film thickness portion in the resin film is large. Therefore, the inventors of the present invention have conducted in-depth research and found that the hardening resin composition containing two or more solvents can obtain a resin film with excellent film thickness uniformity even when stored for a long time at low temperature. The mechanism by which the above effect can be obtained is not yet clear, but it is speculated as follows.

When a curable resin composition containing only one solvent is stored at low temperature for a long time, a component with low solubility in the solvent may precipitate. In this way, it is speculated that when a certain component in the composition precipitates, a certain reaction may occur due to the concentration of other components being locally increased or components such as polymerization inhibitors being precipitated and polymerizing, and part of the components contained in the composition may change. In this way, it is believed that in a composition in which part of the components are changed, even if the precipitate is dissolved again by, for example, heating or stirring after storage, the film thickness uniformity of the resin film is poor. However, it is believed that when the curable resin composition contains two or more solvents, even if the solubility of a component in a certain solvent contained in the composition is low, it may be excellent in solubility in other solvents contained in the composition, thereby suppressing the above-mentioned precipitation. As a result, it is estimated that the above-mentioned change is suppressed, and the film thickness uniformity of the resin film after storage is excellent.

Furthermore, it is speculated that when the curable resin composition contains two or more solvents, compared with the case where only one solvent is contained, especially when stored for a long time at low temperature, the precipitation of components such as polymers in the curable resin composition or the changes caused by crosslinking of crosslinking groups in the polymer and crosslinking groups in the crosslinking agent are suppressed, so that, for example, the resolution of the obtained resin film when it is provided for development is also easily improved. Furthermore, it is estimated that when the curable resin composition contains two or more solvents, the distribution of components in the resin film when the resin film is formed is likely to be nearly uniform, compared with the case where only one solvent is contained, especially when stored for a long period of time at a low temperature, and the chemical resistance of the obtained cured film is also likely to be improved.

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

<Solvent> The curable resin composition of the present invention contains at least two solvents. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, hydrocarbons, sulfones, amides, and alcohols.

As esters, preferred examples include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3- ethyl ethoxypropionate, etc.), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. Among them, from the viewpoint of film thickness uniformity, acyclic ester compounds are preferred as esters. Acyclic ester compounds refer to compounds that do not have a cyclic structure (i.e., a lactone structure) including an ester structure in the molecule.

As ethers, preferred examples include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiourea acetate, ethyl thiourea acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl 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 the like.

As ketones, preferred examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosan, and dihydrolevoglucosan.

As hydrocarbons, preferred examples include toluene, xylene, anisole, limonene, etc. Among them, aromatic hydrocarbons or terpenes are preferred as hydrocarbons.

As the sulfoxides, dimethyl sulfoxide can be preferably mentioned, for example.

As amides, preferred ones include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, etc. As amides, among these, compounds having an amide structure or compounds having an ether bond and an amide bond in the structure are more preferred. Furthermore, commercially available products may be used as amides, and examples of commercially available products include Equamide series manufactured by Idemitsu Kosan Co., Ltd. (for example, Equamide B-100, Equamide M-100) and the like.

As alcohols, 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, methylphenylmethanol, n-pentanol, methylpentanol and diacetone alcohol can be cited. As ureas, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like can be cited as preferred ones.

Among them, from the viewpoint of film thickness uniformity, the curable resin composition of the present invention preferably contains at least two selected from the group consisting of esters, ethers, ketones, hydrocarbons, sulfoxides and amides, more preferably contains at least two selected from the group consisting of amides and sulfoxides, or contains at least one selected from the group consisting of amides and sulfoxides and at least one selected from the group consisting of esters, ethers, ethers and hydrocarbons, further preferably contains at least two selected from the group consisting of amides and sulfoxides, or contains at least one selected from the group consisting of amides and sulfoxides and at least one selected from the group consisting of ketones and esters, and particularly preferably contains sulfoxides and esters.

Furthermore, from the viewpoint of resolution (especially, resolution after the composition is stored at low temperature for a long time), the curable resin composition of the present invention preferably contains at least one selected from amides and at least one selected from ketones, and more preferably contains N-methyl-2-pyrrolidone and cyclopentanone. In the above embodiment, the content of the solvent corresponding to the amide is preferably 10 to 90% by mass relative to the total mass of the solvent, and more preferably 30 to 70% by mass. In the above embodiment, the content of the solvent corresponding to the ketone is preferably 20 to 90% by mass relative to the total mass of the solvent, and more preferably 30 to 70% by mass.

Furthermore, from the viewpoint of the chemical resistance of the obtained cured film (especially, the chemical resistance of the cured film after the composition is stored at low temperature for a long time), the curable resin composition of the present invention preferably contains at least one selected from the solvents having an ether bond described below and at least one selected from the sulfoxides, more preferably contains a compound having an ether bond and an amide bond in the above structure and dimethyl sulfoxide, and further preferably contains 3-butoxy-N,N-dimethylpropionamide and dimethyl sulfoxide. In the above aspect, the content of the solvent corresponding to the amide is preferably 10 to 90 mass % relative to the total mass of the solvent, and more preferably 30 to 70 mass %. In the above aspect, the content of the solvent corresponding to sulfoxides is preferably 10 to 90 mass % relative to the total mass of the solvent, and more preferably 30 to 70 mass %.

Furthermore, from the viewpoint of being able to form a thick resin film, it is preferred that the curable resin composition of the present invention contains at least one selected from solvents having a boiling point of 160°C or more at one atmospheric pressure and at least one selected from solvents having a boiling point of less than 160°C at one atmospheric pressure. As solvents having a boiling point of 160°C or more at one atmospheric pressure, γ-butyrolactone (204°C), dimethyl sulfoxide (189°C), N-methyl-2-pyrrolidone (202°C), 3-butoxy-N,N-dimethylpropionamide (215°C), etc. can be cited. As solvents having a boiling point of less than 160°C at 1 atmosphere, cyclopentanone (131°C), ethyl lactate (154°C), propylene glycol monomethyl ether acetate (146°C), etc. can be cited. The temperature in the above brackets indicates the boiling point of each solvent at 1 atmosphere. In the above embodiment, the content of the solvent having a boiling point of 160°C or more at 1 atmosphere is preferably 10 to 90% by mass, and more preferably 30 to 70% by mass, relative to the total mass of the solvent. In the above embodiment, the content of the solvent having a boiling point of less than 160°C at 1 atmosphere is preferably 10 to 90% by mass, and more preferably 30 to 70% by mass, relative to the total mass of the solvent.

The curable resin composition of the present invention preferably contains at least two selected from aprotic solvents or contains at least one selected from aprotic solvents and at least one selected from protic solvents. It is believed that the curable resin composition of the present invention contains a protic solvent, which improves the uniformity of the film thickness when the curable resin composition contains a compound having a salt structure such as an onium salt described later. As aprotic solvents, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, 3-butoxy-N,N-dimethylpropionamide, cyclopentanone, propylene glycol monomethyl ether acetate, etc. can be cited. As protic solvents, ethyl lactate, etc. can be cited. In the above-mentioned aspect, the content of the aprotic solvent is preferably 10% by mass or more relative to the total mass of the solvent, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more. The upper limit of the above-mentioned content is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less. In the above-mentioned aspect, the content of the protic solvent is preferably 10% by mass or more relative to the total mass of the solvent, more preferably 20% by mass or more, and further preferably 30% by mass or more. The upper limit of the above-mentioned content is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and particularly preferably 60% by mass or less. In addition, it is also a preferred embodiment that the aprotic solvent is contained in an amount of 10 to 90% by mass relative to the total mass of the solvent and the protic solvent is contained in an amount of 10 to 90% by mass. In the above embodiment, it is preferred that the aprotic solvent is contained in an amount of 20 to 80% by mass and the protic solvent is contained in an amount of 20 to 80% by mass, and it is more preferred that the aprotic solvent is contained in an amount of 40 to 80% by mass and the protic solvent is contained in an amount of 20 to 60% by mass.

Furthermore, from the viewpoint of being able to form a thick resin film, the curable resin composition of the present invention preferably contains at least one selected from solvents having a molecular weight of 90 or more and at least one selected from solvents having a molecular weight of less than 90. In the above aspect, the content of the solvent having a molecular weight of 90 or more is preferably 10 to 90% by mass relative to the total mass of the solvent, and 30 to 70% by mass is more preferably. In the above aspect, the content of the solvent having a molecular weight of less than 90 is preferably 10 to 90% by mass relative to the total mass of the solvent, and 30 to 70% by mass is more preferably.

Furthermore, from the perspective of film thickness uniformity, it is preferred that the curable resin composition of the present invention contains at least one selected from solvents having an SP value of 21.4 MPa or more and at least one selected from solvents having an SP value of less than 21.4 MPa. As solvents having an SP value of 21.4 MPa or more, γ-butyrolactone (26.3 MPa), dimethyl sulfoxide (29.7 MPa), N-methyl-2-pyrrolidone (23.1 MPa), 3-butoxy-N,N-dimethylpropionamide (21.5 MPa), etc. can be cited. As solvents having an SP value of less than 21.4 MPa, cyclopentanone (21.3 MPa), ethyl lactate (20.5 MPa), propylene glycol monomethyl ether acetate (23.1 MPa) and the like can be cited. The temperature in the above brackets indicates the SP value of each solvent. In the above embodiment, the content of the solvent having an SP value of 21.4 MPa or more is preferably 10 to 90% by mass relative to the total mass of the solvent, and 30 to 70% by mass is more preferably. In the above embodiment, the content of the solvent having an SP value of less than 21.4 MPa is preferably 10 to 90% by mass relative to the total mass of the solvent, and 30 to 70% by mass is more preferably.

Furthermore, from the perspective of film thickness uniformity, it is also preferable to use a solvent having an SP value higher than the SP value of the solute (for example, a specific resin described later) and a solvent having an SP value lower than the SP value of the solute at the same time.

Furthermore, from the perspective of film thickness uniformity, the difference in SP value between the solvent with the highest SP value and the solvent with the lowest SP value in the curable resin composition of the present invention is preferably 0.2 to 11.5 MPa, and more preferably 1.5 to 10.0 MPa. It is believed that according to such an aspect, the solubility of various solutes contained in the curable resin composition can be improved, so that the film thickness uniformity is easy to be excellent.

In the present invention, the SP value represents the value of the solubility parameter. The SP value in the present invention is a Hansen solubility parameter based on the formula described in Hansen Solubility Parameters: A User's Handbook, Second Edition, C.M. Hansen (2007), Taylor and Francis Group, LLC (HSPiP Manual). Specifically, the "Practical Hansen Solubility Parameters HSPiP Version 3" (software version 4.0.05) is used, and the SP value is calculated using the following formula. (SP value) ² = (δHd) ² + (δHp) ² + (δHh) ² Hd: Dispersion contribution Hp: Polar contribution Hh: Hydrogen bond contribution

Among them, the curable resin composition of the present invention preferably contains at least one solvent selected from the following group A and at least one solvent selected from the following group B, or contains at least one solvent selected from the group including the following group A and group B and at least one solvent selected from the following group C. Group A: dimethyl sulfoxide Group B: N-methyl 2-pyrrolidone, 3-butoxy-N,N-dimethylpropionamide Group C: γ-butyrolactone, cyclopentanone, ethyl lactate, propylene glycol monomethyl ether acetate Moreover, the above-mentioned group C is more preferably the following group C'. Group C': cyclopentanone, ethyl lactate, propylene glycol monomethyl ether acetate

Moreover, among the above, as one of the preferred embodiments of the curable resin composition of the present invention, there can be cited an embodiment in which the solvent contains dimethyl sulfoxide and ethyl lactate, and the content of ethyl lactate is 40% by mass or more relative to the total mass of the above solvent. The content of ethyl lactate is preferably 40 to 80% by mass, and 45 to 60% by mass is further preferred. Moreover, in the above embodiment, the content of γ-butyrolactone is preferably 40% by mass or less relative to the total mass of the solvent, more preferably 30% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 1% by mass or less. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more. In the above aspect, the total content of dimethyl sulfoxide and ethyl lactate relative to the total mass of the solvent is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, further preferably 95% by mass or more, and most preferably 99% by mass or more. The upper limit of the above total content is not particularly limited and can be 100% by mass.

In addition, the curable resin composition of the present invention preferably contains a solvent having a nitrogen atom in its structure as a solvent, and more preferably contains a solvent having a nitrogen-containing heterocyclic structure. As the above-mentioned solvent having a nitrogen atom in its structure, the above-mentioned amides can be cited. As the above-mentioned solvent having a nitrogen-containing heterocyclic structure, the above-mentioned compound having a lactam structure is preferred, and N-methyl-2-pyrrolidone is more preferred. The content of the above-mentioned solvent having a nitrogen atom in its structure is preferably 20 to 80 mass %, more preferably 30 to 70 mass %, and further preferably 40 to 60 mass % relative to the total mass of the solvent.

In addition, the curable resin composition of the present invention preferably contains a solvent having an ether bond as a solvent. As the solvent having an ether bond, compounds having an ether bond and an amide bond in the structure of the above-mentioned ethers or the above-mentioned amides can be cited. The content of the above-mentioned solvent having an ether bond is preferably 20 to 80 mass % relative to the total mass of the solvent, more preferably 30 to 70 mass %, and even more preferably 40 to 60 mass %.

In addition, regarding the solvent contained in the curable resin composition of the present invention, the content of the second most abundant solvent is preferably 20% by mass or more relative to the total mass of the solvent. The above content is preferably 25% by mass or more, more preferably 30% by mass or more, and can be 40% by mass or more. Among them, in the present invention, for example, when containing 40% by mass of N-methylpyrrolidone, 40% by mass of dimethyl sulfoxide, and 20% by mass of cyclopentanone, the content of the second most abundant solvent is 40% by mass.

In the curable resin composition of the present invention, from the viewpoint of suppressing coating defects during coating and improving storage stability, the water content relative to the total mass of the solvent is preferably 5 mass% or less. The water content is preferably 3 mass% or less, more preferably 1 mass% or less, and even more preferably 0.1 mass% or less. In addition, the water content can be set to 0 mass%.

From the viewpoint of coating properties, the total content of the solvent is preferably an amount in which the total solid content concentration of the curable resin composition of the present invention is 5 to 80 mass %, more preferably an amount in which the total solid content concentration of the curable resin composition of the present invention is 5 to 75 mass %, more preferably an amount in which the total solid content concentration of the curable resin composition of the present invention is 10 to 70 mass %, more preferably an amount in which the total solid content concentration of the curable resin composition of the present invention is 20 to 70 mass %, and even more preferably an amount in which the total solid content concentration of the curable resin composition of the present invention is 40 to 70 mass %. The solvent content can be adjusted according to the desired thickness and coating method. The curable resin composition of the present invention may contain only two solvents or three or more solvents.

<Specific resin> The curable resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor. The curable resin composition of the present invention preferably contains polyimide or polyimide precursor as the specific resin, and more preferably contains polyimide precursor. In addition, the specific resin preferably has a free radical polymerizable group. When the specific resin has a radical polymerizable group, the curable resin composition preferably includes the photoradical polymerization initiator described below as a photosensitizer, more preferably includes the photoradical polymerization initiator described below as a photosensitizer and includes the radical crosslinking agent described below, and further preferably includes the photoradical polymerization initiator described below as a photosensitizer, includes the radical crosslinking agent described below, and includes the sensitizer described below. Such a curable resin composition, for example, forms a negative photosensitive layer. In addition, the specific resin may have a polar conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the curable resin composition preferably includes the photoacid generator described below as a photosensitizer. Such a curable resin composition can form, for example, a chemically amplified positive photosensitive layer or a negative photosensitive layer.

[Polyimide Precursor] The type of the polyimide precursor used in the present invention is not particularly limited, but it is preferably a polyimide precursor comprising a repeating unit represented by the following formula (2). Formula (2) [Chemical Formula 1] In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

^A1 and ^A2 in formula (2) each independently represent an oxygen atom or NH, preferably an oxygen atom. ^R111 in formula (2) represents a divalent organic group. Examples of the divalent organic group include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, preferably groups containing linear or branched aliphatic groups having 2 to 20 carbon atoms, cyclic aliphatic groups having 6 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms or combinations thereof, and more preferably groups containing aromatic groups having 6 to 20 carbon atoms. As a particularly preferred embodiment of the present invention, a group represented by -Ar-L-Ar- can be exemplified. Wherein, Ar is independently an aromatic group, and L is an aliphatic alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, or a combination of two or more thereof. The preferred ranges are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one diamine may be used, or two or more diamines may be used. Specifically, a diamine containing a group including a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof is preferred, and a diamine containing a group including an aromatic group having 6 to 20 carbon atoms is more preferred. Examples of the group containing an aromatic group include the following.

[Chemical formula 2] In the formula, A is preferably a single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO ₂ -, -NHCO-, or a combination thereof; more preferably a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO ₂ -; and even more preferably -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or -C(CH ₃ ) ₂ -. In the formula, * indicates a bonding site with other structures.

As the diamine, specifically, at least one diamine selected from the group consisting of 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’- and 3,3’-diaminodiphenylmethane, 4,4’- and 3,3’-diaminodiphenyl sulfide, 4,4’- and 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-diaminodiphenyl (4-aminophenyl) propane, 2,2-bis(4-aminophenyl) hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl) propane, 2,2-bis(3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl) propane, 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfide, bis(4-amino-3-hydroxyphenyl) sulfide, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] sulfide 、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, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diamino Aminodiphenylmethane, 2,4- and 2,5-diaminoisopropylbenzene, 2,5-dimethyl-p-phenylenediamine, ethylguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1 ,5-Bis(4-aminophenyl)decafluoropentane, 1,7-Bis(4-aminophenyl)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, 4,4'-Bis(4-amino-2-trifluoromethylphenoxy) )biphenyl, 4,4’-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4’-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4’-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3’,5,5’-tetramethyl-4,4’-diaminobiphenyl, 4,4’-diamino-2,2’-bis(trifluoromethyl)biphenyl, 2,2’,5,5’,6,6’-hexafluorotriphenylmethane and 4,4’-diaminotetraphenyl.

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

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

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

Furthermore, from the viewpoint of the i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of the i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred. Formula (51) [Chemical Formula 3] In formula (51), R ⁵⁰ to R ⁵⁷ are independently a hydrogen atom, a fluorine atom or a monovalent organic group, at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoromethyl group, and * independently represents a bonding site with the nitrogen atom in formula (2). Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like. [Chemical Formula 4] In formula (61), R ⁵⁸ and R ⁵⁹ are independently a fluorine atom or a trifluoromethyl group. Examples of diamine compounds that provide 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 compounds may be used alone or in combination of two or more.

In addition, the following diamines can also be preferably used. [Chemical Formula 5]

R ¹¹⁵ in formula (2) 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), * independently represents a bonding site with other structures. [Chemical Formula 6] In formula (5), R ¹¹² is preferably a single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO ₂ - and -NHCO-, and combinations thereof; more preferably a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S- and -SO ₂ -; and even more preferably a divalent group selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO ₂ -.

Specifically, R ¹¹⁵ includes a tetracarboxylic acid residue remaining after removing anhydride groups from tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical Formula 7] In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as that of R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-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 C1-6 alkyl and C1-6 alkoxy derivatives thereof.

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

It is also preferred that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, examples of R ¹¹¹ include a residual group of a diaminophenol derivative.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, preferably a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkylene group, and more preferably a polyalkylene group. In addition, at least one of R ¹¹³ and R ¹¹⁴ preferably contains a polymerizable group, and more preferably both contain a polymerizable group. The polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenic unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxobutyl group, a benzoxazolyl group, a blocked isocyanate group, a hydroxymethyl group, and an amino group. As the radical polymerizable group possessed by the polyimide precursor, a group having an ethylenic unsaturated bond is preferred. Examples of the group having an ethylenic unsaturated bond include a vinyl group, a (meth)allyl group, and a group represented by the following formula (III). The group represented by the following formula (III) is preferred.

[Chemical formula 8]

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and a hydrogen atom or a methyl group is preferred. In formula (III), * represents a bonding site with other structures. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH ₂ -, or a polyalkylene group. Preferred examples of R ²⁰¹ include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, -CH ₂ CH (OH) CH ₂ -, and a polyalkylene group, and ethylene, propylene, trimethylene, -CH ₂ CH (OH) CH ₂ -, and a polyalkylene group are more preferred, and a polyalkylene group is further preferred. In the present invention, a polyalkoxyl group refers to a group directly bonded with two or more alkoxyl groups. The alkylene groups in the multiple alkoxyl groups contained in the polyalkoxyl group may be the same or different. In the case where the polyalkoxyl group contains multiple alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement, an arrangement with blocks, or an arrangement with alternating patterns. The carbon number of the above-mentioned alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, 2 to 10 is more preferred, 2 to 6 is more preferred, 2 to 5 is further preferred, 2 to 4 is further preferred, 2 or 3 is particularly preferred, and 2 is the best. In addition, the above-mentioned alkylene group may have a substituent. As preferred substituents, alkyl groups, aryl groups, halogen atoms, etc. can be cited. In addition, the number of alkoxy groups contained in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is preferably 2 to 20, more preferably 2 to 10, and further preferably 2 to 6. As the polyalkoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethoxy, polypropoxy, polytrimethyleneoxy, polytetramethyleneoxy or a group formed by bonding a plurality of ethoxy groups and a plurality of propoxy groups is preferred, polyethoxy or polypropoxy is more preferred, and polyethoxy is further preferred. In the group formed by bonding a plurality of ethoxy groups and a plurality of propoxy groups, the ethoxy groups and propoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in alternating patterns. The preferred aspects of the number of repetitions of the ethoxy groups and the like in these groups are as described above.

R ¹¹³ and R ¹¹⁴ are independently a hydrogen atom or a monovalent organic group. As the monovalent organic group, there can be mentioned an aromatic group and an aralkyl group having an acidic group bonded to one, two or three carbon atoms, preferably one of the carbon atoms constituting the aromatic group. Specifically, there can be mentioned an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms. More specifically, there can be mentioned a phenyl group having an acidic group and a benzyl group having an acidic group. It is preferred that the acidic group is an OH group. It is also more preferred that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group or a 4-hydroxybenzyl group.

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and more preferably an alkyl group substituted with an aromatic group. The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be any of a linear, branched, and cyclic group. Examples of the linear or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, 2-ethylhexyl, 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy, 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy, 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy, and 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy). The cyclic alkyl group may be a monocyclic or polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, bornadiyl, bicyclohexyl, and pinenyl. Among them, cyclohexyl is the most preferred from the viewpoint of both high sensitivity and stability. In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferred. The aromatic group may be a substituted or unsubstituted benzene ring, a naphthyl ring, a pentylene ring, an indene ring, an azulene ring, a heptalene ring, an indenyl ring, a perylene ring, a condensed pentadiene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a condensed benzene ring, a chrysene ring, a tert-butylbenzene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxadiazole ring, a thiazole ring, a pyridine ... The ring may be a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinoline ring, a quinoline ring, a quinazoline ring, a quinazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrone ring, a chromene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring or a phenanthrene ring. The benzene ring is the most preferred.

In formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor can form a conjugate 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.

At least one of ^R113 and ^R114 may be a polar conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, and the like are preferred. From the viewpoint of exposure sensitivity, an acetal group is more preferred. Specific examples of the acid-decomposable group include a tert-butyloxycarbonyl group, an isopropyloxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butyloxycarbonylmethyl group, a trimethylsilyl ether group, and the like. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

Furthermore, the polyimide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10 mass % or more and preferably 20 mass % or less.

In order to improve the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be mentioned.

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By setting such a structure, the width of the exposure tolerance can be further expanded. Formula (2-A) [Chemical Formula 9] In formula (2-A), ^A1 and ^A2 represent oxygen atoms, ^R111 and ^R112 each independently represent a divalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, at least one of ^R113 and ^R114 is a group containing a polymerizable group, and preferably both are groups containing a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ have the same meanings as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2) respectively, and their preferred ranges are also the same. R ¹¹² has the same meanings as R ¹¹² in formula (5), and its preferred ranges are also the same.

The polyimide precursor may contain one or more types of the repeating unit represented by formula (2). Furthermore, it may contain structural isomers of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit represented by formula (2).

As an embodiment of the polyimide precursor of the present invention, a polyimide precursor in which 50 mol% or more, further 70 mol% or more, and particularly 90 mol% or more of all repeating units are repeating units represented by formula (2) can be exemplified.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and further preferably 22,000 to 25,000. Moreover, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and further preferably 9,200 to 11,200. The molecular weight dispersion of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly specified, for example, 4.5 or less is preferred, 4.0 or less is more preferred, 3.8 or less is further preferred, 3.2 or less is further preferred, 3.1 or less is further preferred, 3.0 or less is further preferred, and 2.95 or less is particularly preferred. On the other hand, from the viewpoint of developing properties, the weight average molecular weight (Mw) is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. In addition, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and further preferably 4,000 to 20,000. From the viewpoint of developing properties, the molecular weight dispersion of the polyimide precursor is preferably 1.8 or more, more preferably 2.0 or more, and further preferably 2.2 or more. There is no particular upper limit for the molecular weight dispersion of the polyimide precursor, but for example, 7.0 or less is preferred, 6.5 or less is more preferred, and 6.0 or less is further preferred. In this specification, the molecular weight dispersion is a value calculated using weight average molecular weight/number average molecular weight.

[Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer having an organic solvent as a main component. In this specification, an alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more of a 2.38 mass % tetramethylammonium aqueous solution at 23°C relative to 100 g. From the viewpoint of pattern formation, it is preferred to dissolve 0.5 g or more of a polyimide, and it is further preferred to dissolve 1.0 g or more of a polyimide. The upper limit of the above-mentioned dissolution amount is not particularly limited, but it is preferably 100 g or less. In addition, from the perspective of the membrane strength and insulation of the obtained organic membrane, polyimide having multiple imide structures in the main chain is preferred. In this specification, "main chain" refers to the longest bond in the molecule of the polymer compound constituting the resin, and "side chain" refers to other bonds.

-Fluorine Atom- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has fluorine atoms. The fluorine atoms are preferably contained in R ¹³² in the repeating unit represented by the formula (4) described below or R ¹³¹ in the repeating unit represented by the formula (4) described below, and are more preferably contained in R 132 in the repeating unit represented by the formula (4) described below or R ¹³¹ in the repeating unit represented by the formula (4) described below as a fluorinated alkyl ^group . The amount of fluorine atoms is preferably 1 to 50 mol/g, more preferably 5 to 30 mol/g, relative to the total mass of the polyimide.

-Silicon Atoms- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has silicon atoms. The silicon atom is preferably contained in R ¹³¹ in the repeating unit represented by the formula (4) described later, and is more preferably contained in R ¹³¹ in the repeating unit represented by the formula (4) described later as an organic modified (poly)siloxane structure described later. In addition, the above-mentioned silicon atom or the above-mentioned organic modified (poly)siloxane structure may also be contained in the side chain of the polyimide, but it is preferably contained in the main chain of the polyimide. The amount of silicon atoms is preferably 0.01 to 5 mol/g, and more preferably 0.05 to 1 mol/g relative to the total mass of the polyimide.

- Ethylenically unsaturated bonds - From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has ethylenically unsaturated bonds. The polyimide may have ethylenically unsaturated bonds at the ends of the main chain or in the side chains, but it is preferable that the ethylenically unsaturated bonds are in the side chains. It is preferable that the above-mentioned ethylenically unsaturated bonds have free radical polymerizability. It is preferred that the ethylenic unsaturated bond is contained in ^R132 in the repeating unit represented by the formula (4) described below or in ^R131 in the repeating unit represented by the formula (4) described below, and it is more preferred that the ethylenic unsaturated bond is contained in ^R132 in the repeating unit represented by the formula (4) described below or in ^R131 in the repeating unit represented by the formula (4) described below as a group having an ethylenic unsaturated bond. Among them, it is preferred that the ethylenic unsaturated bond is contained in ^R131 in the repeating unit represented by the formula (4) described below, and it is more preferred that the ethylenic unsaturated bond is contained in ^R131 in the repeating unit represented by the formula (4) described below as a group having an ethylenic unsaturated bond. Examples of the group having an ethylenic unsaturated bond include a group having a vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, a vinylphenyl group, and an optionally substituted group having a vinyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

[Chemical formula 10]

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

In formula (IV), ^R21 represents an alkylene group having 2 to 12 carbon atoms, -O- _CH2CH (OH) _CH2- , -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 carbon atoms repeated is preferably 1 to 12, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), or a group consisting of two or more of the above groups in combination.

Among them, ^R21 is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1). [Chemical Formula 11] In formula (R1) to formula (R3), L represents a single bond or an alkylene group having 2 to 12 carbon atoms, a (poly)alkoxyene group having 2 to 30 carbon atoms, or a group formed by bonding two or more of them, X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ● represents a bonding site with the oxygen atom bonded to R ²⁰¹ in formula (III). In formula (R1) to formula (R3), preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkoxyene group having 2 to 30 carbon atoms in L are the same as preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkoxyene group having 2 to 30 carbon atoms in R ²¹ described above. In formula (R1), X is preferably an oxygen atom. In formula (R1) to formula (R3), * has the same meaning as * in formula (IV), and the preferred embodiment is also the same. The structure represented by formula (R1) is obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenic unsaturated bond (for example, 2-isocyanateethyl methacrylate). The structure represented by formula (R2) is obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenic unsaturated bond (for example, 2-hydroxyethyl methacrylate). The structure represented by the formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenic unsaturated bond (for example, glycidyl methacrylate).

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

The amount of ethylenic unsaturated bonds relative to the total mass of the polyimide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g.

- Crosslinking groups other than ethylenic unsaturated bonds - Polyimide may have crosslinking groups other than ethylenic unsaturated bonds. Examples of crosslinking groups other than ethylenic unsaturated bonds include cyclic ether groups such as epoxy groups and cyclobutyl groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups. Crosslinking groups other than ethylenic unsaturated bonds are preferably contained in R ¹³¹ in the repeating unit represented by the formula (4) described below. The amount of crosslinking groups other than ethylenic unsaturated bonds is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g, relative to the total mass of the polyimide.

-Polarity Converting Group- The polyimide may have a polarity converting group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred embodiment is also the same.

-Acid value- When polyimide is subjected to alkaline development, from the viewpoint of improving the developing property, 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. In addition, 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. Furthermore, when the polyimide is subjected to development using a developer having an organic solvent as a main component (for example, "solvent development" described below), the acid value of the polyimide is preferably 2 to 35 mgKOH/g, more preferably 3 to 30 mgKOH/g, and even more preferably 5 to 20 mgKOH/g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Furthermore, as the acid group contained in the polyimide, from the viewpoint of both storage stability and development properties, an acid group having a pKa of 0 to 10 is preferred, and an acid group having a pKa of 3 to 8 is more preferred. pKa is the equilibrium constant Ka expressed as its negative common logarithm pKa in consideration of the dissociation reaction of releasing hydrogen ions from the acid. In this specification, unless otherwise specified, pKa is a calculated value based on ACD/ChemSketch (registered trademark). In addition, the values disclosed in the "Revised 5th Edition Chemical Handbook Basic Edition" compiled by the Chemical Society of Japan can be referred to. Alternatively, in the case where the acid group is a polyacid such as phosphoric acid, the above pKa is the first dissociation constant. As such an acid group, the polyimide preferably contains at least one selected from the group including a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

- Phenolic hydroxyl group - From the viewpoint of making the developing speed based on the alkaline developer appropriate, it is preferable that the polyimide has a phenolic hydroxyl group. The polyimide may have a phenolic hydroxyl group at the end of the main chain or in the side chain. The phenolic hydroxyl group is preferably contained in R ¹³² in the repeating unit represented by the formula (4) described later or in R ¹³¹ in the repeating unit represented by the formula (4) described later. The amount of the phenolic hydroxyl group is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g, relative to the total mass of the polyimide.

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably comprises a repeating unit represented by the following formula (4), and more preferably comprises a repeating unit represented by the formula (4) and has a polymerizable group. Formula (4) [Chemical Formula 12] In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. When a polymerizable group is present, the polymerizable group may be located on at least one of R ¹³¹ and R ¹³² , as shown in the following formula (4-1) or formula (4-2), or may be located at the end of the polyimide. Formula (4-1) [Chemical Formula 13] In formula (4-1), R ¹³³ is a polymerizable group, and the other groups have the same meanings as in formula (4). Formula (4-2) [Chemical formula 14] At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other groups have the same meanings as in formula (4).

The polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group of the polyimide precursor. R ¹³¹ represents a divalent organic group. As the divalent organic group, the same as R ¹¹¹ in formula (2) can be exemplified, and the preferred range is also the same. In addition, as R ¹³¹ , a diamine residue remaining after removing the amino group of the diamine can be cited. As the diamine, aliphatic, cycloaliphatic or aromatic diamine can be cited. As a specific example, the example of R ¹¹¹ in formula (2) of the polyimide precursor can be cited.

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

Examples of the diamine containing two or more ethylene glycol chains or propylene glycol chains or both in total in one molecule include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (these are 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, but are not limited to these.

R ¹³² represents a tetravalent organic group. Examples of the tetravalent organic group include the same ones as those for R ¹¹⁵ in formula (2), and the preferred range is also the same. For example, four bonders of the tetravalent organic group exemplified as R ¹¹⁵ bond to four -C(=O)- moieties in the above formula (4) to form a condensed ring.

^R132 may be a tetracarboxylic acid residue remaining after removing anhydride groups from tetracarboxylic dianhydride. As a specific example, ^R115 in the formula (2) of the polyimide precursor may be cited. From the viewpoint of the strength of the organic film, ^R132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferred that at least one of R ¹³¹ and R ¹³² has an OH group. More specifically, as R ¹³¹ , preferred examples 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-mentioned (DA-1) to (DA-18), and as R ¹³² , more preferred examples include the above-mentioned (DAA-1) to (DAA-5).

Furthermore, the polyimide preferably has fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10 mass % or more and preferably 20 mass % or less.

In order to improve the adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be mentioned.

In order to improve the storage stability of the composition, it is preferred to seal the main chain terminal of the polyimide with a capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochloride compound, a monoactive ester compound, etc. Among them, it is more preferred to use a monoamine. As preferred compounds of the monoamine, there can be mentioned aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy- 5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-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 a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

- Imidization rate (ring closure rate) - From the viewpoint of the film strength and insulation of the obtained organic film, the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more. There is no particular upper limit to the above imidization rate, as long as it is 100% or less. The above imidization rate is measured, for example, by the following method. The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm ^-1 , which is the absorption peak from the imide structure, is obtained. Next, the polyimide was heat treated at 350°C for 1 hour, and the infrared absorption spectrum was measured again to obtain the peak intensity P2 near 1377 cm ^-1 . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be calculated according to the following formula. Imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

The polyimide may contain all repeating units of the above formula (4) containing one type of R ¹³¹ or R ¹³² , or may contain repeating units of the above formula (4) containing two or more different types of R ¹³¹ or R ^132. Furthermore, the polyimide may contain repeating units of other types in addition to the repeating units of the above formula (4).

Polyimide can be synthesized by, for example, the following methods: a method of reacting tetracarboxylic dianhydride with a diamine compound (a capping agent in which a part is substituted with a monoamine) at low temperature; a method of reacting tetracarboxylic dianhydride (a capping agent in which a part is substituted with an acid anhydride, a monochloride compound, or a monoactive ester compound) with a diamine compound at low temperature; a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then reacting the diester with a diamine (a capping agent in which a part is substituted with a monoamine) in the presence of a condensation agent; A method of obtaining a polyimide precursor by obtaining a diester from tetracarboxylic dianhydride and an alcohol, then chlorinating the remaining dicarboxylic acid, and reacting the resulting product with a diamine (a capping agent partially substituted with a monoamine), and then completely imidizing the product using a known imidization reaction method; or a method of stopping the imidization reaction midway and introducing a portion of the imide structure; and a method of introducing a portion of the imide structure by mixing a completely imidized polymer with the polyimide precursor. Commercially available products of polyimide include Durimide (registered trademark) 284 (manufactured by FUJIFILM Co., Ltd.) and Matrimide 5218 (manufactured by HUNTSMAN).

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. In addition, when containing two or more polyimides, it is preferred that the weight average molecular weight of at least one polyimide is within the above range. On the other hand, from the viewpoint of chemical resistance, the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000.

[Polybenzoxazole precursor] The structure of the polybenzoxazole precursor used in the present invention is not particularly limited, but preferably includes a repeating unit represented by the following formula (3). Formula (3) [Chemical Formula 15] In formula (3), ^R121 represents a divalent organic group, ^R122 represents a tetravalent organic group, and ^R123 and ^R124 each independently represent a hydrogen atom or a monovalent organic group.

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

As the dicarboxylic acid residue, dicarboxylic acids containing aliphatic groups and dicarboxylic acid residues containing aromatic groups are preferred, and dicarboxylic acid residues containing aromatic groups are more preferred. As the dicarboxylic acid containing aliphatic groups, dicarboxylic acids containing straight-chain or branched-chain (preferably straight-chain) aliphatic groups are preferred, and dicarboxylic acids containing straight-chain or branched-chain (preferably straight-chain) aliphatic groups and 2 -COOH groups are more preferred. The carbon number of the straight-chain or branched-chain (preferably straight-chain) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, further preferably 4 to 15, and particularly preferably 5 to 10. The straight-chain aliphatic group is preferably an alkylene group. As dicarboxylic acids containing a linear aliphatic group, there can be mentioned malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethyl Pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid Monoacanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, docosanedioic acid, diglycolic acid acid) and the dicarboxylic acid represented by the following formula, etc.

[Chemical formula 16] (In the formula, Z is a carbonyl group having 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids containing only a group having an aromatic group and two -COOH groups are more preferred.

[Chemical formula 17] In the formula, A represents a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ -, and * represents a bonding site with other structures independently.

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

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

Among the diaminophenol derivatives, the following diaminophenol derivatives having an aromatic group are preferred.

[Chemical formula 18] In the formula, _X1 represents -O-, -S-, -C( _CF3 ) _2- , _-CH2- , _-SO2- , -NHCO-, * and # represent the bonding site with other structures respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a alkyl group, more preferably a hydrogen atom or an alkyl group. Moreover, ^R122 is also preferably a structure represented by the above formula. When R ¹²² is a structure represented by the above formula, any two of the four * and # in total are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, and the other two are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is more preferred that two * are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded, and two # are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, or two * are bonding sites to the nitrogen atom to which R 122 in formula (3) is bonded, and two # are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is more preferred that two * are bonding sites to the oxygen atom to which R 122 in formula (3) is bonded, and two # are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is further preferred that the two #s are bonding sites to the oxygen atom to which ^{R 122} is bonded and the two #s are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded.

[Chemical formula 19]

In formula (As), _R1 is a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, _-SO2- , -CO-, -NHCO-, a single bond, or an organic group selected from the group of the following formula (A-sc). _R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different. _R3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different.

[Chemical formula 20] (In formula (A-sc), * represents a bond to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

In the above formula (As), it is considered that having a substituent at the adjacent position of the phenolic hydroxyl group, that is, at _R3 , makes the carbonyl carbon of the amide bond and the hydroxyl group closer, which is particularly preferred from the viewpoint of further improving the effect of achieving a high cyclization rate during curing at a low temperature.

In the above formula (As), when R ₂ and R ₃ are both alkyl groups, it is preferred because high transparency to I-rays and high cyclization rate can be maintained when curing at low temperature.

In the above formula (As), _R1 is more preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group for _R1 include linear or branched alkyl groups having 1 to 8 carbon atoms. Among them, -CH2-, -CH(CH3)-, and -C( _CH3 ) _2- are more preferred from the viewpoint of obtaining a polybenzoxazole precursor having an excellent balance of _high transparency to I-rays and high cyclization rate when _hardened at low temperature while having sufficient solubility in solvents.

For a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Laid-Open No. 2013-256506, the contents of which are incorporated herein.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of JP-A-2013-256506, and the contents thereof are incorporated into the present specification. Of course, the present invention is not limited to these.

In addition to the repeating units of the above formula (3), the polybenzoxazole precursor may also contain other types of repeating units. From the viewpoint of being able to suppress the warp caused by ring closure, it is preferred to contain a diamine residue represented by the following formula (SL) as other types of repeating units.

[Chemical formula 21] In formula (SL), Z has structure a and structure b, R ^1s is a hydrogen atom or a alkyl group having 1 to 10 carbon atoms, R ^2s is a alkyl group having 1 to 10 carbon atoms, at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. Regarding the molar % of the Z portion, structure a is 5 to 95 molar %, structure b is 95 to 5 molar %, and a+b is 100 molar %.

In formula (SL), as preferred Z, R ^5s and R ^6s in structure b are phenyl groups. In addition, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By setting the molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be more effectively reduced, and the effect of suppressing warp and the effect of improving solvent solubility can be taken into account.

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

For example, when the polybenzoxazole precursor is used in the composition described below, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further preferably 22,000 to 28,000. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and further preferably 9,200 to 11,200. The molecular weight dispersion of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the molecular weight dispersion of the polybenzoxazole precursor is not particularly specified, but is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and further preferably 2.2 or less.

[Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but a compound represented by the following formula (X) is preferred, and a compound represented by the following formula (X) and having a polymerizable group is more preferred. As the above-mentioned polymerizable group, a free radical polymerizable group is preferred. In addition, it may be a compound represented by the following formula (X) and having a polar conversion group such as an acid decomposable group. [Chemical Formula 22] In formula (X), ^R133 represents a divalent organic group, and ^R134 represents a tetravalent organic group. When a polar conversion group such as a polymerizable group or an acid-decomposable group is present, the polymerizable group or the polar conversion group such as an acid-decomposable group may be located on at least one of ^R133 and ^R134 , as shown in the following formula (X-1) or formula (X-2), or may be located at the end of the polybenzoxazole. Formula (X-1) [Chemical Formula 23] In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polymerizable group or an acid-decomposable group or other polar conversion group, and if it is not a polymerizable group or an acid-decomposable group or other polar conversion group, it is an organic group, and the other groups have the same meanings as in formula (X). Formula (X-2) [Chemical Formula 24] In formula (X-2), R ¹³⁷ is a polar conversion group such as a polymerizable group or an acid-decomposable group, and the others are substituents. The other groups have the same meanings as in formula (X).

The polarity-converting group such as the polymerizable group or the acid-decomposable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group of the polyimide precursor.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include an aliphatic group and an aromatic group. As a specific example, R ¹²¹ in the formula (3) of the polybenzoxazole precursor can be cited. Preferred examples are the same as R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. As a tetravalent organic group, R ¹²² in the formula (3) of the polybenzoxazole precursor can be cited as an example. Moreover, its preferred example is the same as R ^122. For example, the four bonders of the tetravalent organic group exemplified as R ¹²² are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. [Chemical Formula 25]

The polybenzoxazole has an oxadiazole rate of preferably 85% or more, and more preferably 90% or more. The upper limit is not particularly limited, and may be 100%. When the oxadiazole rate is 85% or more, the film shrinkage caused by ring closure generated during oxadiazole by heating is reduced, thereby being able to more effectively suppress the generation of warp.

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

The polybenzoxazole can be obtained by, for example, reacting a diaminophenol derivative with a dicarboxylic acid containing R ¹³³ or a compound selected from dicarboxylic acid dichloride and dicarboxylic acid derivatives thereof to obtain a polybenzoxazole precursor, and then oxazolidinizing the obtained product by a known oxazolidinization reaction method. In the case of dicarboxylic acids, active ester-type dicarboxylic acid derivatives obtained by preliminarily reacting 1-hydroxy-1,2,3-benzotriazole or the like can be used in order to increase the reaction yield.

The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. In addition, when containing two or more polybenzoxazoles, it is preferred that the weight average molecular weight of at least one polybenzoxazole is within the above range.

[Method for producing polyimide precursors, etc.] Polyimide precursors, etc. are obtained by reacting dicarboxylic acid or dicarboxylic acid derivatives with diamines. Preferably, dicarboxylic acid or dicarboxylic acid derivatives are halogenated with a halogenating agent and then reacted with diamines. In the method for producing polyimide precursors, etc., it is preferred to use an organic solvent during the reaction. The organic solvent may be one or more. As the organic solvent, it can be appropriately specified according to the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone. Polyimide can be produced by cyclizing a polyimide precursor by thermal imidization, chemical imidization (for example, by promoting a cyclization reaction by the action of a catalyst), or the like, or directly synthesizing the polyimide.

Furthermore, it is also preferable to use a non-halogen catalyst for synthesis instead of the above-mentioned halogenating agent. As the above-mentioned non-halogen catalyst, a known amidation catalyst that does not contain a halogen atom can be used without particular limitation, for example, boroxine compounds, N-hydroxy compounds, tertiary amines, phosphates, amine salts, urea compounds, and carbodiimide compounds can be mentioned. As the above-mentioned carbodiimide compound, N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, etc. can be mentioned.

-Capping agent- In the production method of polyimide precursors, in order to further improve storage stability, it is preferred to seal the ends of polyimide precursors with a capping agent such as anhydride, monocarboxylic acid, monochloride compound, monoactive ester compound, etc. As the capping agent, it is more preferred to use monohydric alcohol, phenol, thiol, thiophenol, monoamine. As preferred compounds of monohydric alcohols, there can be mentioned primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, secondary alcohols such as isopropyl alcohol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, tertiary alcohols such as tertiary butyl alcohol and adamantane alcohol, etc. As preferred phenol compounds, phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, etc. can be cited. As preferred monoamine compounds, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2 -Carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-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 can be used, and multiple different terminal groups can be introduced by reacting multiple end-capping agents. Furthermore, when sealing the amine group at the end of the resin, a compound having a functional group that can react with the amine group can be used for sealing. Preferred sealants for amine groups are carboxylic anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic anhydride, etc., and carboxylic acid anhydride and carboxylic acid chloride are more preferred. Preferred compounds of carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, etc. Moreover, as a preferable compound of the carboxylic acid chloride, acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, trimethylacetyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamyl chloride, 1-adamantanenecarbonyl chloride, heptafluorobutyl chloride, stearyl chloride, benzoyl chloride and the like can be cited.

-Solid precipitation- When manufacturing a polyimide precursor, a solid precipitation step may be included. Specifically, the polyimide precursor in the reaction solution is precipitated in water and dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor is soluble, thereby allowing the solid to precipitate. Then, the polyimide precursor is dried to obtain a powdered polyimide precursor.

[Content] The content of the specific resin in the composition of the present invention is preferably 20% by mass or more, 30% by mass or more, 40% by mass or more, and 50% by mass or more relative to the total solid content of the composition. In addition, the content of the resin in the composition of the present invention is preferably 99.5% by mass or less, 99% by mass or less is more preferred, 98% by mass or less is more preferred, 97% by mass or less is more preferred, and 95% by mass or less is more preferred relative to the total solid content of the composition. The composition of the present invention may contain only one specific resin or two or more. When containing two or more, it is preferred that the total amount be within the above range.

<Other resins> The composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also referred to as "other resins" for short). As other resins, polyamide imide, polyamide imide precursor, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, acrylic resin, etc. can be cited. For example, by further adding an acrylic resin, a composition with excellent coating properties can be obtained, and an organic film with excellent solvent resistance can be obtained. For example, by adding a high polymerizable acrylic resin having a weight average molecular weight of 20,000 or less to the composition instead of or in addition to the polymerizable compound described below, the coating properties of the composition and the solvent resistance of the organic film can be improved.

When the composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass or more relative to the total solid content of the composition. In addition, the content of the other resins in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass or less, more preferably 60% by mass or less, and more preferably 50% by mass or less relative to the total solid content of the composition. In addition, as a preferred embodiment of the composition of the present invention, the content of other resins can also be set to a low content. In the above embodiment, the content of other resins relative to the total solid content of the composition is preferably 20% by mass or less, 15% by mass or less is more preferred, 10% by mass or less is further preferred, 5% by mass or less is further preferred, and 1% by mass or less is further preferred. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more. The composition of the present invention may contain only one other resin, or may contain two or more. When containing two or more, it is preferred that the total amount be within the above range.

<Photosensitive agent> The composition of the present invention preferably contains a photosensitizer. As the photosensitizer, a photopolymerization initiator is preferred.

[Photopolymerization initiator] The composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer. The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet region to the visible region is preferred. In addition, it can also be an activator that generates active radicals by some kind of reaction with a photoexcited sensitizer. In addition, as the above-mentioned photoradical polymerization initiator, the oxime compound described later is preferred.

The photo-free radical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L/mol ^-1 /cm ^-1 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferably measured using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photoradical polymerization initiator, any known compound can be used. For example, alkyl halides derivatives (e.g., compounds having a trioxane skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketone oxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic complexes, etc. can be cited. For the details thereof, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, the contents of which are incorporated into this specification.

Examples of the ketone compound include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

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

As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available products such as IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF Corporation) can be used.

As the aminoacetophenone-based initiator, the compound described in Japanese Patent Application Laid-Open No. 2009-191179, which has an absorption maximum wavelength matching a light source of wavelength such as 365 nm or 405 nm, can also be used.

Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, etc. Commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

Examples of the metallocene compound include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF).

As a photo-radical polymerization initiator, an oxime compound can be preferably cited. By using an oxime compound, the exposure tolerance can be more effectively improved. Oxime compounds are particularly preferred because they have a wide exposure tolerance (exposure margin) and also function as a photohardening accelerator.

Specific examples of the oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, and compounds described in Japanese Patent Application Laid-Open No. 2006-342166.

Preferred oxime compounds include, for example, compounds having the following structures or 3-benzyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetyloxyiminopentane-3-one, 2-acetyloxyimino-1-phenylpropane-1-one, 2-benzyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. Oxime-based photopolymerization initiators have a linking group of >C=N-O-C(=O)- in the molecule.

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, DFI-091 (manufactured by Daito Chemix Corporation) can be used.

An oxime compound having the following structure can also be used. [Chemical Formula 26]

In addition, oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Unexamined Patent Publication No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Unexamined Patent Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Unexamined Patent Publication No. 2013-164471.

As the most preferable oxime compound, there can be mentioned an oxime compound having a specific substituent as disclosed in Japanese Patent Application Laid-Open No. 2007-269779 or an oxime compound having a thioaryl group as disclosed in Japanese Patent Application Laid-Open No. 2009-191061.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyl trioxane compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzyl-iron complexes and their salts, halogenated methyl oxadiazole compounds, and 3-aryl substituted coumarin compounds.

Further preferred photoradical polymerization initiators are trihalogenomethyl trioxane compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. At least one compound selected from the group consisting of trihalogenomethyl trioxane compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds is further preferred. It is further preferred to use metallocene compounds or oxime compounds, and it is still further preferred to use oxime compounds.

In addition, the photoradical polymerization initiator may include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michelle's ketone) and the like, aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propanone-1, quinones with aromatic ring condensation such as alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin and benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like. In addition, the compound represented by the following formula (I) may be used.

[Chemical formula 27]

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

[Chemical formula 28]

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

Furthermore, the photoradical polymerization initiator may also include the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

When a photopolymerization initiator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, further preferably 0.5 to 15 mass %, and further preferably 1.0 to 10 mass % relative to the total solid content of the composition of the present invention. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

[Photoacid generator] In addition, it is also preferred that the composition of the present invention contains a photoacid generator as a photosensitizer. By containing a photoacid generator, for example, acid is generated in the exposed part of the composition layer, and the solubility of the exposed part in the developer (for example, alkaline aqueous solution) is increased, and a positive pattern in which the exposed part is removed by the developer can be obtained. In addition, it is also possible to set it as follows: by containing a photoacid generator and a polymerizable compound other than a free radical polymerizable compound described later, for example, the acid generated in the exposed part is used to promote the crosslinking reaction of the polymerizable compound, so that the exposed part is less likely to be removed by the developer than the non-exposed part. According to such an aspect, a negative pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid by exposure, and examples thereof include quinonediazide compounds, onium salt compounds such as diazo salts, phosphonium salts, coronium salts, and iodonium salts, sulfonate compounds such as acylimidesulfonates, oximesulfonates, diazodisulfonates, disulfonates, and o-nitrobenzylsulfonates.

Examples of the quinone diazide compound include a quinone diazide sulfonic acid bonded to a polyhydroxy compound via an ester bond, a quinone diazide sulfonic acid bonded to a polyamine compound via a sulfonamide bond, a quinone diazide sulfonic acid bonded to a polyhydroxy polyamine compound via an ester bond and a sulfonamide bond, etc. In the present invention, for example, preferably, 50 mol% or more of the functional groups of the polyhydroxy compound or polyamine compound are substituted with quinone diazide groups.

In the present invention, the quinone diazide can preferably use either 5-naphthoquinone diazide sulfonyl or 4-naphthoquinone diazide sulfonyl. The 4-naphthoquinone diazide sulfonyl compound has absorption in the i-ray region of a mercury lamp and is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazide sulfonyl compound extends to the g-ray region of a mercury lamp and is suitable for g-ray exposure. In the present invention, it is preferred to select the 4-naphthoquinone diazide sulfonyl compound or the 5-naphthoquinone diazide sulfonyl compound according to the exposure wavelength. Furthermore, it may contain a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule, or it may contain a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound.

The naphthoquinone diazide compound can be synthesized by an esterification reaction of a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized by a known method. By using the naphthoquinone diazide compound, the resolution, sensitivity, and residual film rate are further improved. As the naphthoquinone diazide compound, for example, 1,2-naphthoquinone-2-diazido-5-sulfonic acid or 1,2-naphthoquinone-2-diazido-4-sulfonic acid, salts or ester compounds of the compounds, etc. can be cited.

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

[Chemical formula 29]

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

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

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

[Chemical formula 30]

In formula (OS-103) to formula (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, a plurality of R ^s2 may exist and each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, a plurality of R ^s6 may exist and each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer of 0 to 6. In formula (OS-103) to formula (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms) or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by R ^s1 may have a substituent T.

In formula (OS-103) to formula (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), and a hydrogen atom or an alkyl group is more preferred. In a compound, when there are two or more R ^s2 , one or two are preferably an alkyl group, an aryl group or a halogen atom, one is more preferably an alkyl group, an aryl group or a halogen atom, and one is particularly preferably an alkyl group and the rest are hydrogen atoms. The alkyl group or aryl group represented by R ^s2 may have a substituent T. In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, and O is preferred. In the above formulae (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

In formula (OS-103) to formula (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2. In formula (OS-103) to formula (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and the alkoxy group (preferably having 1 to 30 carbon atoms) represented by ^Rs6 may have a substituent. In formula (OS-103) to formula (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Furthermore, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the compound represented by the above formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is particularly preferably a compound represented by the following formula (OS-108) or formula (OS-109). [Chemical Formula 31]

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

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

In formula (OS-106) to formula (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom. R ^t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In addition, in the above-mentioned oxime sulfonate compound, the stereostructure (E, Z) of the oxime may be any one of them or a mixture. As specific examples of the oxime sulfonate compounds represented by the above-mentioned formula (OS-103) to formula (OS-105), the compounds described in paragraphs 0088 to 0095 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Application Publication No. 2015-194674 can be exemplified, and the contents are incorporated into this specification.

As another preferred embodiment of the oxime sulfonate compound containing at least one oxime sulfonate group, compounds represented by the following formula (OS-101) and formula (OS-102) can be cited.

[Chemical formula 32]

In formula (OS-101) or (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfonyl group, a sulfonyl group, a cyano group, an aryl group, or a heteroaryl group. It is more preferred that R ^u9 is a cyano group or an aryl group, and it is further preferred that R ^u9 is a cyano group, a phenyl group, or a naphthyl group. In formula (OS-101) or (OS-102), R ^u2a represents an alkyl group or an aryl group. In formula (OS-101) or (OS-102), Xu represents -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, -CR ^u6 H-, or CR ^u6 R ^u7 -, and R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

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

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102). In addition, in the above oxime sulfonate compound, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring may be any one of them, or a mixture. As specific examples of the compound represented by the formula (OS-101), the compounds described in paragraphs 0102 to 0106 of Japanese Patent Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Publication No. 2015-194674 can be exemplified, and the contents are incorporated into this specification. Among the above compounds, the following b-9, b-16, b-31, and b-33 are preferred. [Chemical Formula 33]

As the onium salt compound or sulfonate salt compound, there can be cited compounds described in paragraphs 0064 to 0122 of Japanese Patent Application Publication No. 2008-013646. In addition, commercially available products can also be used as photoacid generators. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-699 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), Omnicat 250 and Omnicat 270 (all manufactured by IGM Resins B.V.), Irgacure 250, Irgacure 270, and Irgacure 290 (all manufactured by BASF), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

As a more preferred example, the compound represented by the following structural formula can also be cited. [Chemical Formula 34]

As photoacid generators, organic halogenated compounds can also be used. As organic halogenated compounds, specifically, there can be cited Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-004605, Japanese Patent Application Publication No. 48-036281, Japanese Patent Application Publication No. 55-032070, Japanese Patent Application Publication No. 60-239736, Japanese Patent Application Publication No. 61-169835, Japanese Patent Application Publication No. 61-169837, Japanese Patent Application Publication No. 62-058241, Japanese Patent Application Publication No. 62-212401, Japanese Patent Application Publication No. 63-070243, Japanese Patent Application Publication No. 63-298339, M.P. Hutt, "Jurnal of Heterocyclic The compounds described in "Chemistry" 1 (No. 3), (1970), etc., in particular, include trihalomethyl-substituted oxadiazole compounds: S-triazole compounds. More preferably, s-triazole derivatives formed by at least one mono-, di- or trihalomethyl-substituted methyl group bonded to the s-triazole ring can be listed. Specifically, for example, 2,4,6-tris(monochloromethyl)-s-triazole, 2,4,6-tris(dichloromethyl)-s-triazole, 2,4,6-tris(trichloromethyl)-s-triazole, 2-methyl-4,6-bis(trichloromethyl)-s-triazole, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazole can be listed. -trisinium, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-trisinium, 2-phenyl-4,6-bis(trichloromethyl)-s-trisinium, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-trisinium, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-trisinium, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-trisinium, 2-〔1-(p-methoxyphenyl)- phenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-trisinyl, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-trisinyl, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-trisinyl, 2-(p-isopropoxyphenyl)-4,6-bis(trichloromethyl)-s-trisinyl, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-trisinyl, 2-(4-naphthyloxyphenyl)-4,6-bis(trichloromethyl)-s-trisinyl, s-triazine, 2-naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-methoxy-4,6-bis(tribromomethyl)-s-triazine, etc.

As the photoacid generator, an organic borate compound can also be used. As the organic borate compound, specific examples thereof include Japanese Patent Publication No. 62-143044, Japanese Patent Publication No. 62-150242, Japanese Patent Publication No. 9-188685, Japanese Patent Publication No. 9-188686, Japanese Patent Publication No. 9-188710, Japanese Patent Publication No. 2000-131837, Japanese Patent Publication No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, and Kunz, Martin "Rad Tech '98. Proceeding April 19-22, 1998, Chicago" etc., the organic borate salts described in Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, Japanese Patent Laid-Open No. 6-175561, the organic boron-zirconium complexes or organic boron-oxygen-zirconium complexes described in Japanese Patent Laid-Open No. 6-175554, Japanese Patent Laid-Open No. 6-175553 The organic boron transition metal complex described in JP-A-9-188710, the organic boron phosphonium complex described in JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, and the like.

As the photoacid generator, a disulfide compound can also be used. Examples of the disulfide compound include compounds described in Japanese Patent Application Laid-Open No. 61-166544, Japanese Patent Application No. 2001-132318, and diazodisulfide compounds.

Examples of the onium salt compounds include S.I.Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T.S.Bal et al. al, Polymer, 21,423 (1980), the diazonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Laid-Open No. 4-365049, etc., the phosphonium salts described in the specifications of U.S. Patent No. 4,069,055 and U.S. Patent No. 4,069,056, the specifications of European Patent No. 104,143, U.S. Patent No. 339,049, U.S. Patent No. 410,201, the iodine salts described in Japanese Patent Laid-Open No. 2-150848 and Japanese Patent Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 390, Copper salts described in the specifications of U.S. Patent No. 214, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, U.S. Patent No. 4,933,377, U.S. Patent No. 161,811, U.S. Patent No. 410,201, U.S. Patent No. 339,049, U.S. Patent No. 4,760,013, U.S. Patent No. 4,734,444, U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, German Patent No. 3,604,581, J.V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), selenium salts described in J.V.Crivello et al, J.Polymer Sci., Polymer Chem.Ed., 17, 1047 (1979), arsenic salts described in C.S.Wen et al, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, Oct (1988), pyridinium salts and the like.

Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III). [Chemical Formula 35] In formula (RI-I), Ar ₁₁ represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. In view of stability, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, and sulfinic acid ions are preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. _Z21- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a ^thiosulfonic acid ion, or a sulfate ion. In terms of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, or carboxylic acid ions are preferred. In formula (RI-III), _R31 , _R32 , and _R33 each independently represent an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 20 or less carbon atoms and which may have 1 to 6 substituents. In terms of reactivity and stability, an aryl group is preferred. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₃₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. In view of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, and carboxylic acid ions are preferred.

As a specific example, the following can be cited. [Chemical formula 36] [Chemical formula 37] [Chemical formula 38] [Chemical formula 39]

When a photoacid generator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and even more preferably 2 to 15 mass % relative to the total solid content of the composition of the present invention. The photoacid generator may contain only one type or two or more types. When two or more types of photoacid generators are contained, their total content is preferably within the above range.

<Thermal polymerization initiator> The composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals by heat energy to initiate or promote the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also be carried out in the heating step described later, thereby further improving the solvent resistance.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 5 to 15 mass % relative to the total solid content of the composition of the present invention. The thermal polymerization initiator may contain only one kind or two or more kinds. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.

<Thermal acid generator> The composition of the present invention may contain a thermal acid generator. The thermal acid generator has the following effect: by generating an acid by heating, the cross-linking reaction of at least one compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxobutane compound and a benzophenone compound is promoted.

The thermal decomposition start temperature of the thermal acid generator is preferably 50°C to 270°C, and more preferably 50°C to 250°C. In addition, if a thermal acid generator is selected that does not generate acid when the composition is applied to the substrate and dried (pre-baking: about 70 to 140°C), but generates acid when patterned in the subsequent exposure and development and then finally heated (hardening: about 100 to 400°C), it is preferred because it can suppress the decrease in sensitivity during development. Regarding the thermal decomposition start temperature, the peak temperature of the lowest temperature heat peak is obtained when the thermal acid generator is heated to 500°C at 5°C/min in a pressure-resistant capsule. As an instrument used to measure the thermal decomposition starting temperature, Q2000 (manufactured by TA Instruments) and the like can be cited.

The acid generated from the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, or a halogenated alkylsulfonic acid such as trifluoromethanesulfonic acid. Examples of such thermal acid generators include those described in paragraph 0055 of Japanese Patent Application Publication No. 2013-072935.

Among them, from the viewpoint of less residue in the organic film and less deterioration of the physical properties of the organic film, those that produce alkylsulfonic acids having 1 to 4 carbon atoms or halogenated alkylsulfonic acids having 1 to 4 carbon atoms are more preferred, including (4-hydroxyphenyl)dimethylcopperium methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylcopperium methanesulfonate, benzyl(4-hydroxyphenyl)methylcopperium methanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylcopperium methanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)copperium methanesulfonate, (4-hydroxyphenyl)dimethylcopperium trifluoromethanesulfonate, Preferred as the thermal acid generator are (4-((methoxycarbonyl)oxy)phenyl)dimethylcopperium trifluoromethanesulfonate, benzyl(4-hydroxyphenyl)methylcopperium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylcopperium trifluoromethanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)copperium trifluoromethanesulfonate, 3-(5-(((propylsulfonyl)oxy)imino)thiophen-2(5H)-ylidene)-2-(o-tolyl)propionitrile, and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

Furthermore, the compound described in paragraph 0059 of JP-A-2013-167742 is also preferred as a thermal acid generator.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the specific resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, thereby further improving the mechanical properties and solvent resistance of the organic film. In addition, from the perspective of the electrical insulation of the organic film, 20 parts by mass or less is preferably, 15 parts by mass or less is more preferably, and 10 parts by mass or less is even more preferably.

<Onium salt> The curable resin composition of the present invention may further contain an onium salt. In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain an onium salt. The type of onium salt is not particularly specified, and ammonium salts, ammonium salts, stibnium salts, iodine salts, or phosphonium salts can be preferably cited. Among them, ammonium salts or ammonium salts are preferred from the viewpoint of high thermal stability, and stibnium salts, iodonium salts or phosphonium salts are preferred from the viewpoint of compatibility with polymers.

Furthermore, the onium salt is a salt of a cation and anion having an onium structure, and the cation and anion may be bonded by covalent bonding or not. That is, the onium salt may be an intramolecular salt having a cation part and anion part in the same molecular structure, or an intermolecular salt formed by ionic bonding between cation molecules and anion molecules of different molecules, but intermolecular salts are preferred. Furthermore, in the curable resin composition of the present invention, the cation part or cation molecule and the anion part or anion molecule may be bonded by ionic bonding or may be dissociated. As the cation in the onium salt, ammonium cation, pyridinium cation, coronium cation, iodine cation or phosphonium cation is preferred, and at least one cation selected from the group consisting of tetraalkylammonium cation, coronium cation and iodine cation is more preferred.

The onium salt used in the present invention may be a thermal alkali generator described below. The thermal alkali generator refers to a compound that generates an alkali by heating, for example, a compound that generates an alkali when heated to 40°C or above.

[Ammonium salt] In the present invention, ammonium salt refers to a salt of ammonium cations and anions.

-Ammonium cation- As the ammonium cation, a quaternary ammonium cation is preferred. Furthermore, as the ammonium cation, a cation represented by the following formula (101) is preferred. [Chemical formula 40] In formula (101), R ¹ to R ⁴ each independently represents a hydrogen atom or a hydrocarbon group, and at least two of R ¹ to R ⁴ may be bonded to form a ring.

In formula (101), R ¹ to R ⁴ are each independently preferably a alkyl group, more preferably an alkyl group or an aryl group, and further preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. R ¹ to R ⁴ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. When at least two of R ¹ to R ⁴ are bonded to form a ring, the ring may contain a heteroatom. Examples of the heteroatom include a nitrogen atom.

The ammonium cation is preferably represented by any one of the following formulas (Y1-1) and (Y1-2). [Chemical Formula 41]

In formula (Y1-1) and (Y1-2), ^R101 represents an n-valent organic group, ^R1 has the same meaning as ^R1 in formula (101), ^Ar101 and ^Ar102 each independently represent an aromatic group, and n represents an integer greater than 1. In formula (Y1-1), ^R101 is preferably a group formed by removing n hydrogen atoms from an aliphatic hydrocarbon, an aromatic hydrocarbon, or a structure formed by such a bond, and more preferably a group formed by removing n hydrogen atoms from a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene, or naphthalene. In formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. In formula (Y1-2), Ar ¹⁰¹ and Ar ¹⁰² are each independently preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

-Anions- As the anion in the ammonium salt, one selected from carboxylic acid anions, phenol anions, phosphoric acid anions and sulfuric acid anions is preferred, and carboxylic acid anions are more preferred for the sake of both stability and thermal decomposition of the salt. That is, the ammonium salt is preferably a salt of ammonium cation and carboxylic acid anions. The carboxylic acid anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and an anion of a divalent carboxylic acid is more preferred. According to this aspect, the stability, curability and developing properties of the curable resin composition can be further improved. In particular, by using anions of divalent carboxylic acids, the stability, curability, and developing properties of the curable resin composition can be further improved.

The carboxylic acid anion is preferably represented by the following formula (X1). [Chemical Formula 42] In formula (X1), EWG represents an electron-withdrawing group.

In the present embodiment, the electron-withdrawing group indicates that the Hammett substituent constant σm shows a positive value. Here, σm is described in detail in Yufu Mitsuno's General Commentary, Journal of the Organic Synthetic Chemistry Association, Vol. 23, No. 8 (1965), p. 631-642. In addition, the electron-withdrawing group in the present embodiment is not limited to the substituents described in the above literature. Examples of substituents having a positive value for σm include CF ₃ group (σm=0.43), CF ₃ C (=O) group (σm=0.63), HC≡C group (σm=0.21), CH ₂ =CH group (σm=0.06), Ac group (σm=0.38), MeOC (=O) group (σm=0.37), MeC (=O) CH=CH group (σm=0.21), PhC (=O) group (σm=0.34), H ₂ NC (=O) CH ₂ group (σm=0.06), etc. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (the same shall apply hereinafter).

Preferably, EWG is a group represented by the following formula (EWG-1) to (EWG-6). [Chemical Formula 43] In formulae (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group.

In the present invention, the carboxylic acid anion is preferably represented by the following formula (XA). [Chemical Formula 44] In formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an aromatic group, -NR ^X -, and a combination thereof, and ^RX represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

Specific examples of the carboxylic acid anion include a maleic acid anion, a phthalic acid anion, an N-phenyliminodiacetic acid anion, and an oxalic acid anion.

From the viewpoint of facilitating the cyclization of the pre-driver containing the heterocyclic polymer at low temperature and improving the storage stability of the curable resin composition, the onium salt in the present invention contains ammonium cations as cations, and the onium salt contains anions having a pKa (pKaH) of 2.5 or less of the conjugated acid as anions, and more preferably contains anions having a pKa of 1.8 or less. The lower limit of the above pKa is not particularly limited, but from the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of the pre-driver containing the heterocyclic polymer is improved, -3 or more is preferred, and -2 or more is more preferred. As the above pKa, the values described in Determination of Organic Structures by Physical Methods (Author: Brown, H.C., McDaniel, D.H., Hafliger, O., Nachod, F.C.; Editor: Braude, E.A., Nachod, F.C.; Academic Press, New York, 1955) or Data for Biochemical Research (Author: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959) can be referred to. For compounds not described in these documents, values calculated from the structural formula using ACD/pKa (manufactured by ACD/Labs) software were used.

As specific examples of ammonium salts, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 45]

[Ammonium salt] In the present invention, ammonium salt means a salt of an ammonium cation and an anion. Examples of anions include the same anions as those in the above-mentioned ammonium salts, and the preferred embodiments are also the same.

-Ammonium cation- As the ammonium cation, pyridinium cation is preferred. Also, as the ammonium cation, the cation represented by the following formula (102) is also preferred. [Chemical formula 46]

In formula (102), ^R5 and ^R6 each independently represent a hydrogen atom or a alkyl group, ^R7 represents a alkyl group, and at least two of ^R5 to ^R7 may be bonded to form a ring. In formula (102), ^R5 and ^R6 have the same meanings as ^R1 to ^R4 in formula (101), and preferred embodiments are also the same. In formula (102), it is preferred that ^R7 is bonded to at least one of ^R5 and ^R6 to form a ring. The ring may contain a heteroatom. As the heteroatom, a nitrogen atom may be mentioned. In addition, as the ring, a pyridine ring is preferred.

The ammonium cation is preferably represented by any one of the following formulas (Y1-3) to (Y1-5). [Chemical Formula 47] In formula (Y1-3) to (Y1-5), ^R101 represents an n-valent organic group, ^R5 has the same meaning as ^R5 in formula (102), ^R7 has the same meaning as ^R7 in formula (102), and n and m represent integers greater than 1. In formula (Y1-3), ^R101 is preferably a group formed by removing n hydrogen atoms from an aliphatic hydrocarbon, an aromatic hydrocarbon, or a structure formed by such a bond, and more preferably a group formed by removing n hydrogen atoms from a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene, or naphthalene. In formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. In formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and even more preferably 1.

As specific examples of ammonium salts, the following compounds can be cited, but the present invention is not limited to them. [Chemical Formula 48]

[Zirconium salt] In the present invention, the zinc salt refers to a salt of zinc cation and anion. As the anion, the same anion as that in the above-mentioned ammonium salt can be exemplified, and the preferred embodiment is also the same.

- Copper cation - As the copper cation, a tertiary copper cation is preferred, and a triaryl copper cation is more preferred. In addition, as the copper cation, a cation represented by the following formula (103) is preferred. [Chemical Formula 49]

In formula (103), R ⁸ to R ¹⁰ each independently represents a alkyl group. R ⁸ to R ¹⁰ each independently represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R ⁸ to R ¹⁰ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among these, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R ⁸ to R ¹⁰ may be the same group or different groups, but from the viewpoint of synthetic suitability, the same group is preferred.

As specific examples of the cobalt salt, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 50]

[Iodine salt] In the present invention, an iodine salt refers to a salt of an iodine cation and an anion. Examples of anions include the same anions as those in the above-mentioned ammonium salts, and the preferred embodiments are also the same.

-Ion cation- As the iodine cation, a diaryl iodine cation is preferred. Also, as the iodine cation, a cation represented by the following formula (104) is preferred. [Chemical Formula 51]

In formula (104), R ¹¹ and R ¹² each independently represent a alkyl group. R ¹¹ and R ¹² each independently represent an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R ¹¹ and R ¹² may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among these, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R ¹¹ and R ¹² may be the same group or different groups, but from the viewpoint of synthetic suitability, the same group is preferred.

As specific examples of iodine salts, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 52]

[Phosphonium salt] In the present invention, phosphonium salt means a salt of a phosphonium cation and an anion. Examples of anions include the same anions as those in the above-mentioned ammonium salts, and the preferred embodiments are also the same.

-Phosphonium cation- As the phosphonium cation, a quaternary phosphonium cation is preferred, and examples thereof include tetraalkylphosphonium cations and triarylmonoalkylphosphonium cations. Furthermore, as the phosphonium cation, a cation represented by the following formula (105) is preferred. [Chemical Formula 53]

In formula (105), R ¹³ to R ¹⁶ each independently represent a hydrogen atom or a alkyl group. R ¹³ to R ¹⁶ each independently represent an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R ¹³ to R ¹⁶ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among these, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R ¹³ to R ¹⁶ may be the same group or different groups, but from the viewpoint of synthetic suitability, the same group is preferred.

As specific examples of phosphonium salts, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 54]

When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50 mass % relative to the total solid content of the curable resin composition of the present invention. The lower limit is preferably 0.5 mass % or more, 0.85 mass % or more is further preferred, and 1 mass % or more is further preferred. The upper limit is preferably 30 mass % or less, 20 mass % or less is further preferred, 10 mass % or less is further preferred, and it can also be 5 mass % or less, and it can also be 4 mass % or less. One or more onium salts can be used. When two or more are used, the total amount is preferably within the above range.

<Thermal alkali generator> The curable resin composition of the present invention may further contain a thermal alkali generator. In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain a thermal alkali generator. Other thermal alkali generators may be compounds corresponding to the above-mentioned onium salts, or thermal alkali generators other than the above-mentioned onium salts. As thermal alkali generators other than the above-mentioned onium salts, non-ionic thermal alkali generators can be cited. As non-ionic thermal alkali generators, compounds represented by formula (B1) or formula (B2) can be cited. [Chemical Formula 55]

In formula (B1) and formula (B2), ^Rb1 , ^Rb2 and ^Rb3 are independently an organic group, a halogen atom or a hydrogen atom that does not have a tertiary amine structure. However, ^Rb1 and ^Rb2 will not be hydrogen atoms at the same time. Moreover, ^Rb1 , ^Rb2 and ^Rb3 will not all have carboxyl groups. In addition, in this specification, a tertiary amine structure refers to a structure in which the three bonds of a trivalent nitrogen atom are covalently bonded to a carbon atom of a hydrocarbon system. Therefore, when the carbon atom to which the bond is a carbon atom constituting a carbonyl group, that is, when an amide group is formed together with a nitrogen atom, it is not limited to this.

In formula (B1) and formula (B2), at least one of ^Rb1 , ^Rb2 and ^Rb3 preferably has a cyclic structure, and at least two of them more preferably have a cyclic structure. The cyclic structure may be a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring formed by condensing two monocyclic rings is preferred. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and a 6-membered ring is preferred. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and a cyclohexane ring is more preferred.

More specifically, ^Rb1 and ^Rb2 are preferably hydrogen atoms, alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), or arylalkyl groups (preferably having 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms). These groups may have substituents within the range in which the effects of the present invention are exerted. ^Rb1 and ^Rb2 may be bonded to each other to form a ring. As the ring formed, a 4-7-membered nitrogen-containing heterocyclic ring is preferred. ^Rb1 and ^Rb2 are preferably linear, branched or cyclic alkyl groups which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), more preferably cycloalkyl groups which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), and further preferably cyclohexyl groups which may have a substituent.

Examples of Rb ³ include alkyl (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryl (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), alkenyl (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms), arylalkyl (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), Arylalkenyl (preferably having 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, and more preferably 8 to 16 carbon atoms), alkoxy (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryloxy (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or arylalkoxy (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms). Among them, cycloalkyl (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), arylalkenyl, and arylalkoxy are preferred. ^Rb3 may further have a substituent within the range in which the effect of the present invention is exerted.

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical Formula 56]

In the formula, ^Rb11 and ^Rb12 as well as ^Rb31 and ^Rb32 are the same as ^Rb1 and ^Rb2 in formula (B1), respectively. ^Rb13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), and may have a substituent within the range in which the effect of the present invention is exerted. Among them, ^Rb13 is preferably an arylalkyl group.

^Rb33 and ^Rb34 are independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms), preferably a hydrogen atom.

Rb ³⁵ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 12 carbon atoms), and an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms), and aryl group is preferred.

The compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a). [Chemical Formula 57]

^Rb11 and ^Rb12 have the same meanings as ^Rb11 and ^Rb12 in formula (B1-1). ^Rb15 and ^Rb16 are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), arylalkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms), preferably hydrogen atoms or methyl groups. Rb ¹⁷ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms), wherein the aryl group is preferred.

The molecular weight of the non-ionic thermal alkali generator is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. As the lower limit, it is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

As specific examples of the compound serving as a thermal alkali generator among the above-mentioned onium salts or specific examples of the thermal alkali generator other than the above-mentioned onium salts, the following compounds can be cited.

[Chemical formula 58]

[Chemical formula 59]

[Chemical formula 60]

The content of other alkali generators is preferably 0.1 to 50% by mass relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. The alkali generator can be used alone or in combination. When two or more types are used, the total amount is preferably within the above range.

<Crosslinking agent> The hardening resin composition of the present invention preferably contains a crosslinking agent. As the crosslinking agent, free radical crosslinking agents or other crosslinking agents can be cited.

<Free radical crosslinking agent> The curable resin composition of the present invention preferably further contains a free radical crosslinking agent. The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenic unsaturated bond is preferred. As the above-mentioned group containing an ethylenic unsaturated bond, there can be cited groups having an ethylenic unsaturated bond such as vinyl, allyl, vinylphenyl, (meth)acryloyl, etc. Among them, as the above-mentioned group containing an ethylenic unsaturated bond, a (meth)acryloyl group is preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

The radical crosslinking agent may be a compound having one or more ethylenic unsaturated bonds, and a compound having two or more ethylenic unsaturated bonds is more preferred. The compound having two ethylenic unsaturated bonds is preferably a compound having two of the above-mentioned groups containing ethylenic unsaturated bonds. In addition, from the viewpoint of the film strength of the obtained pattern (cured film), the curable resin composition of the present invention preferably contains a compound having three or more ethylenic unsaturated bonds as a radical crosslinking agent. As the above-mentioned compound having three or more ethylenic unsaturated bonds, a compound having 3 to 15 ethylenic unsaturated bonds is more preferred, a compound having 3 to 10 ethylenic unsaturated bonds is more preferred, and a compound having 3 to 6 ethylenic unsaturated bonds is further preferred. Furthermore, the compound having more than 3 ethylenic unsaturated bonds is preferably a compound having more than 3 groups containing ethylenic unsaturated bonds, a compound having 3 to 15 is more preferably, a compound having 3 to 10 is further preferably, and a compound having 3 to 6 is particularly preferably. On the other hand, from the viewpoint of developing properties, the radical crosslinking agent is particularly preferably a compound having 2 ethylenic unsaturated bonds. Furthermore, from the viewpoint of film strength of the obtained pattern (cured film), it is also preferred that the curable resin composition of the present invention contains a compound having 2 ethylenic unsaturated bonds and the compound having 3 or more ethylenic unsaturated bonds.

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

Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, sulfhydryl groups, etc., and monofunctional or polyfunctional isocyanates or epoxides, or dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. Furthermore, addition reaction products of unsaturated carboxylates or amides having electron-withdrawing substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylates or amides having dissociative substituents such as halogeno groups or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols can also be preferably used. Furthermore, as another example, a compound group in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, and the like can also be used. As a specific example, reference can be made to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated into this specification.

In addition, the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as polyethylene glycol di(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trihydroxymethylpropane tri(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, glycerol or trihydroxymethylethane, and then performing (meth)acrylation. Esterified compounds, such as urethane (meth) acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193, polyester acrylates described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 52-030490, epoxy acrylates as reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. In addition, there can be mentioned polyfunctional (meth)acrylates obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate with a polyfunctional carboxylic acid.

Furthermore, as a preferred radical crosslinking agent other than the above, a compound having a fluorene ring and having two or more groups containing ethylenic unsaturated bonds, or a cardo resin described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent Application No. 4364216, etc. can also be used.

As other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, or vinylphosphonic acid compounds described in Japanese Patent Publication No. 02-025493 can be cited. In addition, compounds containing perfluoroalkyl groups described in Japanese Patent Publication No. 61-022048 can also be used. In addition, those introduced as photopolymerizable monomers and oligomers in the Journal of the Japan Adhesion Society, vol. 20, No. 7, pp. 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of WO-2015/199219 can also be preferably used, and the contents thereof are incorporated into the present specification.

In addition, compounds described in Japanese Patent Application Laid-Open No. 10-062986 as formula (1) and formula (2) together with specific examples thereof, in which ethylene oxide or propylene oxide is added to a polyfunctional alcohol and then (meth)acrylic acid is esterified, can also be used as a radical crosslinking agent.

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

As the free radical crosslinking agent, dipentatriol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentatriol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.) and the structure in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue is preferred. The oligomer type of the same can also be used.

As commercially available free radical crosslinking agents, for example, SR-494 manufactured by Sartomer Company, Inc., which is a tetrafunctional acrylate having four ethoxy chains, SR-209, 231, 239 manufactured by Sartomer Company, Inc., which are bifunctional methacrylates having four ethoxy chains, DPCA-60 manufactured by Nippon Kayaku Co., Ltd., which is a hexafunctional acrylate having six pentyloxy chains, TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains, urethane oligomers 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, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As the free radical crosslinking agent, urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, or urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. In addition, as the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 01-105238 can also be used.

The free radical crosslinking agent may also be a free radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. The free radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a free radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound is more preferably. It is particularly preferred that, in the free radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is a compound of neopentyl triol or dipentyl triol. As commercially available products, for example, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., LTD. include M-510 and M-520.

The preferred acid value of the free radical crosslinking agent having an acid group is 0.1 to 40 mgKOH/g, and the particularly preferred acid value is 5 to 30 mgKOH/g. As long as the acid value of the free radical crosslinking agent is within the above range, the operability in manufacturing is excellent, and the developing property is excellent. In addition, the polymerizability is good. On the other hand, from the perspective of the developing speed during alkaline development, the preferred acid value of the free radical crosslinking agent having an acid group is 0.1 to 300 mgKOH/g, and the particularly preferred acid value is 1 to 100 mgKOH/g. The above acid value is measured in accordance with the description of JIS K 0070:1992.

From the viewpoint of pattern resolution and film stretchability, the curable resin composition of the present invention preferably uses a bifunctional methacrylate or acrylate. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate (polyethylene glycol diacrylate with a polyethylene glycol chain weight of about 200), PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol Diacrylate, 1,6-hexanediol dimethacrylate, dihydroxymethyl tricyclodecane diacrylate, dihydroxymethyl tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO modified diacrylate of isocyanuric acid, modified dimethacrylate of isocyanuric acid, bifunctional acrylate with other urethane bonds, bifunctional methacrylate with urethane bonds. Two or more of these can be used in combination as needed. In addition, as a radical crosslinking agent having two or more functions, diallyl phthalate, triallyl trimellitate, etc. can be cited. From the viewpoint of suppressing the warp caused by the elastic modulus control of the pattern (cured film), a monofunctional radical crosslinking agent can be preferably used as a radical crosslinking agent. As the monofunctional free radical crosslinking agent, (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-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate can be preferably used. As a monofunctional free radical crosslinking agent, a compound having a boiling point of 100° C. or higher at normal pressure is also preferred in order to suppress volatility before exposure.

When a free radical crosslinking agent is contained, its content is preferably more than 0 mass % and less than 60 mass % relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.

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

<Other crosslinking agents> The curable resin composition of the present invention preferably contains other crosslinking agents different from the above-mentioned free radical crosslinking agents. In the present invention, other crosslinking agents refer to crosslinking agents other than the above-mentioned free radical crosslinking agents, preferably compounds having multiple groups in the molecule that promote the reaction of forming covalent bonds with other compounds in the composition or their reaction products by the photosensitization of the above-mentioned photosensitizer, and preferably compounds having multiple groups in the molecule that promote the reaction of forming covalent bonds with other compounds in the composition or their reaction products by the action of acids or bases. The above-mentioned acid or base is preferably an acid or base generated from the photosensitizer in the exposure step. As other crosslinking agents, compounds having at least one group selected from the group including hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group including hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred. As other crosslinking agents, for example, compounds having a structure in which formaldehyde or formaldehyde and alcohol react with compounds containing amino groups such as melamine, glycoluril, urea, alkyl urea, benzoguanamine, etc., and the hydrogen atom of the above amino group is replaced by a hydroxymethyl or alkoxymethyl group can be cited. The method for preparing these compounds is not particularly limited, as long as they are compounds having the same structure as the compounds prepared by the above method. In addition, they can also be oligomers formed by self-condensation of the hydroxymethyl groups of these compounds. A crosslinking agent using melamine as the above-mentioned amino group-containing compound is called a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. Among them, the curable resin composition of the present invention preferably contains at least one compound selected from the group including urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group including glycoluril-based crosslinking agents and melamine-based crosslinking agents described later.

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

Specific examples of urea-based crosslinking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monoprop ... Glycoluril-based crosslinking agents such as methylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril or tetrabutoxymethylated glycoluril; Urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, dipropoxymethyl urea, dibutoxymethyl urea; Monohydroxymethylated ethylurea or dihydroxymethyl Ethyl urea crosslinking agents such as ethyl urea, monomethoxymethyl ethyl urea, dimethoxymethyl ethyl urea, monoethoxymethyl ethyl urea, diethoxymethyl ethyl urea, monopropoxymethyl ethyl urea, dipropoxymethyl ethyl urea, monobutoxymethyl ethyl urea or dibutoxymethyl ethyl urea; Monohydroxymethyl ethyl urea, dihydroxymethyl ethyl urea, monomethoxymethyl ethyl urea, dimethoxymethyl ethyl urea, monoethoxymethyl ethyl urea, diethoxymethyl ethyl urea, monopropoxymethyl ethyl urea, dipropoxymethyl ethyl urea, monobutoxymethyl ethyl urea or dibutoxymethyl ethyl urea; Propylene urea crosslinking agents such as methylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea; 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

Specific examples of the benzoguanamine-based crosslinking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

In addition, as the compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl, a compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used. Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl) benzophenone, methoxymethylphenyl methoxymethyl benzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

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

In addition, the curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, cyclohexane compounds and benzophenone compounds as another crosslinking agent.

[Epoxy compounds (compounds having epoxy groups)] As epoxy compounds, compounds having two or more epoxy groups in one molecule are preferred. Epoxy groups undergo crosslinking reactions below 200°C and do not produce dehydration reactions from crosslinking, so film shrinkage is less likely to occur. Therefore, containing epoxy compounds is effective for inhibiting low-temperature curing and warping of curable resin compositions.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and can suppress warping. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trihydroxymethylpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl ether and other polyalkylene glycol type epoxy resins; epoxy epoxy silicones such as polymethyl (glycidyloxypropyl) siloxane, etc., but are not limited to these. Specifically, we can cite EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICL ON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740, Rika Resin (registered trademark) BEO-20E (the above are trade names, manufactured by DIC Corporation), Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD (registered trademark) GT400, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 CELVENUS (registered trademark) B0134, B0177 (the above are product names, Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc.

[Oxycyclobutane compounds (compounds having an oxycyclobutyl group)] As oxycyclobutane compounds, compounds having two or more oxycyclobutane rings in one molecule, 3-ethyl-3-hydroxymethyloxycyclobutane, 1,4-bis{[(3-ethyl-3-oxycyclobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxycyclobutane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxycyclobutyl)methyl]ester, etc. can be cited. As specific examples, ARON OXETANE series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

[Benzothiocyanate compounds (compounds having a benzothiocyanate group)] Benzothiocyanate compounds are preferred because they do not produce degassing during curing due to the cross-linking reaction from the ring-opening addition reaction, and further reduce thermal shrinkage to suppress the occurrence of warping.

Preferred examples of benzophenone compounds include B-a type benzophenone, B-m type benzophenone, P-d type benzophenone, F-a type benzophenone (these are trade names, manufactured by SHIKOKU CHEMICALS CORPORATION), benzophenone adducts of polyhydroxystyrene resins, and phenol novolac type dihydrobenzophenone compounds. These may be used alone or in combination of two or more.

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

<Compounds with sulfonamide structure, compounds with thiourea structure> From the perspective of improving the adhesion of the obtained pattern (cured film) to the substrate, it is preferred that the curable resin composition of the present invention further comprises at least one compound selected from the group consisting of compounds with sulfonamide structure and compounds with thiourea structure.

[Compounds having a sulfonamide structure] The sulfonamide structure is a structure represented by the following formula (S-1). [Chemical Formula 61] In formula (S-1), R represents a hydrogen atom or an organic group, and R may form a ring structure by bonding with other structures, and * independently represents the bonding site with other structures. It is preferred that the above R is the same group as ^R2 in the following formula (S-2). The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but a compound having one sulfonamide structure is preferred.

The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2). [Chemical Formula 62] In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, and two or more of R ¹ , R ² and R ³ may be bonded to each other to form a ring structure. It is preferred that R ¹ , R ² and R ³ each independently represent a monovalent organic group. Examples of R ¹ , R ² and R ³ include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl. Examples of the cycloalkyl group include cycloalkyl groups having 5 to 10 carbon atoms, and cycloalkyl groups having 6 to 10 carbon atoms are more preferred. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are more preferred. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and pentyloxy. Examples of the alkoxysilyl group include alkoxysilyl groups having 1 to 10 carbon atoms, and alkoxysilyl groups having 1 to 4 carbon atoms are more preferred. Examples of the alkoxysilyl group include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Examples of the aryl group include 6 to 20 carbon atoms, and 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl. Examples of the heterocyclic group include groups obtained by removing one hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxadiazole ring, a thiazole ring, a pyrazole ring, an isoxadiazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a piperidine ring, a piperidine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran ring, and a trihydropyran ring.

Among them, the compound in which R ¹ is an aryl group and R ² and R ³ are independently a hydrogen atom or an alkyl group is preferred.

Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1-sulfonamide, naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethylsulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethanesulfonamide.

[Compounds having a thiourea structure] The thiourea structure is represented by the following formula (T-1). [Chemical formula 63] In formula (T-1), ^R4 and ^R5 each independently represent a hydrogen atom or a monovalent organic group, ^R4 and ^R5 may be bonded to form a ring structure, ^R4 may be bonded to another structure to which * is bonded to form a ring structure, ^R5 may be bonded to another structure to which * is bonded to form a ring structure, and * each independently represents a bonding site to another structure.

^R4 and ^R5 are preferably independently a hydrogen atom. Examples of ^R4 and ^R5 include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group formed by combining two or more of them. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. As the above-mentioned alkyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group, etc. are cited. As the above-mentioned cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are more preferred. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and pentyloxy. Examples of the alkoxysilyl group include alkoxysilyl groups having 1 to 10 carbon atoms, and alkoxysilyl groups having 1 to 4 carbon atoms are more preferred. Examples of the alkoxysilyl group include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Examples of the aryl group include aryl groups having 6 to 20 carbon atoms, and aryl groups having 6 to 12 carbon atoms are more preferred. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl. Examples of the heterocyclic group include groups obtained by removing one hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, a thiazole ring, a pyrazole ring, an iso-pyrazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a piperidine ring, a piperidine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran ring, and a trihydropyran ring. The compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferred.

The compound having a thiourea structure is preferably a compound represented by the following formula (T-2). [Chemical Formula 64] In formula (T-2), R ⁴ to R ⁷ each independently represent a hydrogen atom or a monovalent organic group, and at least two of R ⁴ to R ⁷ may be bonded to each other to form a ring structure.

In formula (T-2), ^R4 and ^R5 have the same meanings as ^R4 and ^R5 in formula (T-1), and preferred embodiments are also the same. In formula (T-2), ^R6 and ^R7 are each independently a monovalent organic group, which is preferred. In formula (T-2), the preferred ^monovalent organic group of R6 and ^R7 is the same as the preferred monovalent organic group of ^R4 and ^R5 in formula (T-1).

Examples of compounds having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1-adamantylthiourea, N-benzoylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea, N,N-diphenylthiourea, ethylenethiourea (2-imidazolinethione), carbimazole, and 1,3-dimethyl-2-thiohydantoin.

[Content] The total content of the compound having a sulfonamide structure and the compound having a thiourea structure is preferably 0.05 to 10 mass %, more preferably 0.1 to 5 mass %, and further preferably 0.2 to 3 mass % relative to the total mass of the curable resin composition of the present invention. The curable resin composition of the present invention may contain only one compound selected from the group including compounds having a sulfonamide structure and compounds having a thiourea structure, or may contain two or more. When only one compound is contained, the content of the compound is within the above range, and when two or more compounds are contained, the total amount thereof is preferably within the above range.

<Migration inhibitor> The curable resin composition of the present invention preferably further comprises a migration inhibitor. By comprising the migration inhibitor, it is possible to effectively inhibit metal ions from the metal layer (metal wiring) from migrating into the curable resin composition layer.

The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, triazole ring, oxadiazole ring, thiazole ring, pyrazole ring, isoxadiazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, trioxadiazole ring), compounds having thiourea and thiohydrin, hindered phenol-based compounds, salicylic acid derivative-based compounds, and hydrazide derivative-based compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 5-methylbenzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, 5-amino-1H-tetrazole, purine compounds such as purine, adenine, and guanine can be preferably used. Among them, the curable resin composition of the present invention further includes at least one compound selected from the group including 5-methylbenzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole and 5-amino-1H-tetrazole as a migration inhibitor, which is also one of the preferred embodiments of the present invention. From the viewpoint of improving the adhesion to metal wiring, the curable resin composition of the present invention preferably contains a compound having an amino group as a migration inhibitor, more preferably contains a compound having a heterocyclic ring and an amino group, further preferably contains a compound having one or more heterocyclic rings selected from the group consisting of an imidazole ring, a triazole ring, a pyrazole ring, a thiazole ring, a pyrazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a piperidine ring, a piperidine ring and a triazole ring and an amino group, particularly preferably contains an azole compound having an amino group, and most preferably contains a triazole compound having an amino group or a tetrazole compound having an amino group.

Alternatively, an ion scavenger that captures anions such as halogen ions may be used.

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015/199219, etc. can be used.

As specific examples of the migration inhibitor, the following compounds can be cited.

[Chemical formula 65]

When the curable resin composition 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 % relative to the total solid content of the curable resin composition.

The migration inhibitor may be only one kind or two or more kinds. When there are two or more kinds of migration inhibitors, it is preferred that the total amount thereof is within the above range.

<Polymerization inhibitor> The curable resin composition of the present invention preferably contains a polymerization inhibitor.

As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, p-tert-butyl-o-catechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine first barium salt, 2,2'-methylenebis(4- Methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiocyanate, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso- 1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4 ... H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidinium 1-oxyl radical, phenanthridine, 1,1-diphenyl-2-picrylhydrazine, dibutyldithiocarbamate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, 2,2,6,6-tetramethylpiperidinium 1-oxyl radical, phenanthridine, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

Furthermore, the following compounds (Me is methyl group) can be used.

[Chemical formula 66]

When the curable resin composition of the present invention contains a polymerization inhibitor, for example, the content of the polymerization inhibitor is 0.01 to 20.0 mass % relative to the total solid content of the curable resin composition of the present invention, preferably 0.01 to 5 mass %, more preferably 0.02 to 3 mass %, and even more preferably 0.05 to 2.5 mass %. Furthermore, when the storage stability of the curable resin composition solution is required, the content is preferably 0.02 to 15.0 mass %, and in this case, it is more preferably 0.05 to 10.0 mass %.

The polymerization inhibitor may be one or more than one. When there are two or more polymerization inhibitors, the total amount thereof is preferably within the above range.

<Metal Adhesion Improver> The curable resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes or wiring. Examples of metal adhesion improvers include silane coupling agents, aluminum-based adhesion promoters, titanium-based adhesion promoters, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds. Among them, the curable resin composition of the present invention preferably comprises a silane coupling agent, an aluminum-based bonding aid, a titanium-based bonding aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, an amino compound, etc.

Examples of silane coupling agents include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, and compounds described in paragraph 0055 of International Publication No. 2014/097594. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358, it is also preferable to use two or more different silane coupling agents. Furthermore, it is also preferable to use the following compounds as silane coupling agents. In the following formula, Et represents an ethyl group.

[Chemical formula 67]

As other silane coupling agents, for example, vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidyloxypropyl methyl dimethoxysilane, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl methyl diethoxysilane, 3-glycidyloxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxy Propyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyl trimethoxysilane, tris-(trimethoxysilylpropyl) isocyanurate, 3-ureidopropyl trialkoxysilane, 3-butylenepropyl methyldimethoxysilane, 3-butylenepropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used alone or in combination of two or more.

Furthermore, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used.

[Aluminum-based bonding aid] As aluminum-based bonding aids, for example, tris(ethyl acetylacetate)aluminum, tris(acetylacetone)aluminum, ethyl acetylacetate aluminum diisopropyl, etc. can be cited.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the specific resin. By setting it to above the above lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it to below the above upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver can be only one kind or two or more kinds. When using two or more kinds, it is better that the total is within the above range.

<Metallic Adhesion Improver> The curable resin composition of the present invention preferably contains a metallic adhesion improver for improving adhesion to metal materials used in electrodes or wiring. As the metallic adhesion improver, compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935 can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the polymer precursor containing the heterocyclic ring. By setting it to be above the above lower limit, the adhesion between the cured film and the metal layer after the curing step becomes good, and by setting it to be below the above upper limit, the heat resistance and mechanical properties of the cured film after the curing step become good. The metal adhesion improver may be only one kind or may be two or more kinds. When two or more kinds are used, it is preferred that the total is within the above range.

<Other additives> The curable resin composition of the present invention can be formulated with various additives as needed within the scope of obtaining the effects of the present invention, such as sensitizers, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-agglomeration agents, etc. When such additives are formulated, the total amount thereof is preferably set to be less than 3% by weight of the solid content of the curable resin composition.

[Sensitizer] The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with a thermal curing accelerator, a thermal free radical polymerization initiator, a photo-free radical polymerization initiator, etc., and produces electron transfer, energy transfer, heat, etc. Thereby, the thermal curing accelerator, the thermal free radical polymerization initiator, and the photo-free radical polymerization initiator cause chemical changes and decompose, thereby generating free radicals, acids or bases. For example, compounds such as ethanolamine, benzophenone, michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxocyanine, pyrazolotriazole azo, pyridone azo, cyanine, phenathiophene, pyrrolopyrazole azo methine, phthalocyanine, benzopyran, and indigo can be used. Examples of the sensitizer include michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidenedihydroindanone, p-Dimethylaminobenzylidenedihydroindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethyl Aminocumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-pyrrolidone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Amyl ester, 2-benzimidazole, 1-phenyl-5-benzyltetrazolyl, 2-benzthiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. As the sensitizer, a sensitizing dye can also be used. For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated into this specification.

When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass % relative to the total solid content of the curable resin composition of the present invention. The sensitizer may be used alone or in combination of two or more.

[Chain transfer agent] The curable 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 Polymer Society, 2005), pages 683-684. As chain transfer agents, for example, a compound group having -SS-, -SO ₂ -S-, -NO-, SH, PH, SiH, and GeH in the molecule, dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds having a thiocarbonylthio group for RAFT (Reversible Addition Fragmentation chain Transfer) polymerization, etc. can be used. These can generate free radicals by donating hydrogen to low-activity free radicals, or generate free radicals by deprotonation after oxidation. In particular, thiol compounds can be preferably used.

Furthermore, the chain transfer agent may also include compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219.

When the curable resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the curable resin composition of the present invention. The chain transfer agent may be only one kind or two or more kinds. When there are two or more kinds of chain transfer agents, the total amount thereof is preferably within the above range.

[Surfactant] From the viewpoint of further improving the coating properties, various types of surfactants can be added to the curable resin composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, non-ionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants, etc. can be used. In addition, the following surfactants are also preferred. In the following formula, the parentheses representing the repeating units of the main chain represent the content (molar %) of each repeating unit, and the parentheses representing the repeating units of the side chain represent the number of repetitions of each repeating unit. [Chemical Formula 68] Furthermore, the surfactant can also use the compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219. Regarding the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as a fluorine-based surfactant. As a specific example, the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Publication No. 2010-164965 can be cited, and the contents are incorporated into this specification. Moreover, as commercially available products, for example, MEGAFACE RS-101, RS-102, RS-718K, etc. manufactured by DIC CORPORATION can be cited.

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

Examples of the silicone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP341, KF6001, and KF6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK Chemie GmbH).

Examples of hydrocarbon-based surfactants include PIONIN A-76, New Kalgen FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, and PIONIN P-4050-T (all manufactured by Takemoto Oil & Fat Co., Ltd.).

Examples of the nonionic surfactant include glycerin, trihydroxymethylpropane, trihydroxymethylethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Commercially available products include Pluronic L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, and D-6315 (manufactured by TAKEMOTO OIL & FAT CO., LTD.), OLFIN E1010, and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Co., Ltd.), and the like.

Specific examples of the cationic surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No.75, No.77, No.90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

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

When the curable resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass % relative to the total solid content of the curable resin composition of the present invention, and more preferably 0.005 to 1.0 mass %. The surfactant may be only one kind or two or more kinds. When there are two or more kinds of surfactants, the total amount thereof is preferably within the above range.

[Higher fatty acid derivatives] In order to prevent polymerization hindrance caused by oxygen, the curable resin composition of the present invention may add a higher fatty acid derivative such as behenic acid or behenic acid amide so that it is unevenly distributed on the surface of the curable resin composition during the drying process after coating.

Furthermore, as the higher fatty acid derivatives, the compounds described in paragraph 0155 of International Publication No. 2015/199219 can also be used.

When the curable resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the curable resin composition of the present invention. The higher fatty acid derivative may be only one type or two or more types. When there are two or more types of higher fatty acid derivatives, the total amount thereof is preferably within the above range.

[Inorganic particles] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. If the average particle size of the inorganic particles is less than 0.01 μm, the mechanical properties of the cured film may deteriorate. If the average particle size of the inorganic particles exceeds 2.0 μm, the resolution may decrease due to scattering of exposure light.

[Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, tris(III)-based ultraviolet absorbers can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole. 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

Examples of substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Examples of tris(iodine-based ultraviolet absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris(iodine-based ultraviolet absorbers), 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 -bis(2,4-dimethylphenyl)-1,3,5-trisinium, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-trisinium and other mono(hydroxyphenyl)trisinium compounds; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-trisinium, Bis(hydroxyphenyl)triol compounds such as 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triol, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triol; 2,4-bis(2-hydroxy-4- tris(hydroxyphenyl)tris(iota) compounds such as 2,4-dibutoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-tris(iota), 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris(iota), and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris(iota).

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

[Organic titanium compound] The resin composition of this embodiment may contain an organic titanium compound. When the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when hardening is performed at a low temperature.

As the organic titanium compound that can be used, there can be cited those having an organic group bonded to the titanium atom via a covalent bond or an ionic bond. Specific examples of the organic titanium compound are shown in the following I) to VII): I) Titanium chelate compound: Among them, since the storage stability of the negative photosensitive resin composition is good and a good curing pattern can be obtained, a titanium chelate compound having two or more alkoxy groups is more preferred. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium bis(2,4-pentanedioate)di(n-butoxy), titanium bis(2,4-pentanedioate)diisopropoxide, titanium bis(tetramethyl pimelate)diisopropoxide, titanium bis(ethyl acetoacetate)diisopropoxide, etc. II) Tetraalkoxy titanium compounds: for example, tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonyloxy)titanium, tetra(n-propoxy)titanium, tetrastearyloxytitanium, tetra[bis{2,2-(allyloxymethyl)butoxy}]titanium, etc. III) Titanium cyclopentadienyl trimethoxide, for example, titanium pentamethylcyclopentadienyl trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Titanium monoalkoxy compounds: for example, titanium tris(dioctyl phosphate) isopropoxy, titanium tris(dodecylbenzene sulfonate) isopropoxy, etc. V) Titanium oxide compounds: for example, titanium bis(glutarate) oxide, titanium bis(tetramethylpimelate) oxide, titanium phthalocyanine oxide, etc. VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate, etc. VII) Titanium ester coupling agent: for example, isopropyl tri(dodecyl)benzenesulfonyl titanium ester, etc.

Among them, as an organic titanium compound, from the viewpoint of exerting better drug resistance, at least one compound selected from the group including I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) dioctenyl titanium compounds is preferred. In particular, bis(ethylacetyl acetate)diisopropoxytitanium, tetra(n-butoxy)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

When the organic titanium compound is added, the amount thereof is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the precursor of the cyclized resin. When the amount is 0.05 parts by mass or more, the obtained hardened pattern exhibits good heat resistance and chemical resistance, while when the amount is 10 parts by mass or less, the storage stability of the composition is excellent.

[Antioxidant] The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the elongation characteristics of the film after curing or the adhesion to the metal material can be improved. As the antioxidant, phenol compounds, phosphite compounds, thioether compounds, etc. can be cited. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. As a preferred phenol compound, a hindered phenol compound can be cited. Compounds having a substituent at a position adjacent to a phenolic hydroxyl group (adjacent position) are preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, the antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. Furthermore, the antioxidant may preferably be a phosphorus-based antioxidant. Examples of the phosphorus-based antioxidant include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and bis(2,4-di-tert-butyl-6-methylphenol)ethyl phosphite. As commercially available antioxidants, for example, ADKSTAB AO-20, ADKSTAB AO-30, ADKSTAB AO-40, ADKSTAB AO-50, ADKSTAB AO-50F, ADKSTAB AO-60, ADKSTAB AO-60G, ADKSTAB AO-80, ADKSTAB AO-330 (all manufactured by ADEKA CORPORATION) etc. can be cited. In addition, the antioxidant can also use the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967. In addition, the composition of the present invention can contain a potential antioxidant as needed. As potential antioxidants, there can be mentioned compounds in which the site that functions as an antioxidant is protected by a protecting group, and the protecting group is released by heating at 100 to 250°C or heating at 80 to 200°C in the presence of an acid/base catalyst, thereby functioning as an antioxidant. As potential antioxidants, there can be mentioned compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Publication No. 2017-008219. As commercially available products of potential antioxidants, there can be mentioned ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION) and the like. Preferred examples of antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and compounds represented by the general formula (3).

[Chemical formula 69]

In the general formula (3), ^R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, ^R6 represents an alkylene group having 2 or more carbon atoms, ^R7 represents an alkylene group having 2 or more carbon atoms, or a monovalent to tetravalent organic group containing at least one of an O atom and a N atom. k represents an integer of 1 to 4.

The compound represented by the general formula (3) inhibits the oxidative degradation of the aliphatic group or the phenolic hydroxyl group of the resin. In addition, it can inhibit the oxidation of the metal by its rust-proofing effect on the metal material.

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

Examples of the compound represented by the following general formula (3) include the following, but are not limited to the following structure.

[Chemical formula 70]

[Chemical formula 71]

[Chemical formula 72]

[Chemical formula 73]

The amount of antioxidant added is preferably 0.1 to 10 parts by weight relative to the resin, and more preferably 0.5 to 5 parts by weight. When the amount added is less than 0.1 parts by weight, it is difficult to obtain the effect of improving the elongation characteristics after the reliability test or the adhesion to the metal material, and when it is more than 10 parts by weight, the sensitivity of the resin composition may decrease due to the interaction with the photosensitizer. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, the total amount thereof is preferably within the above range.

<Restrictions on other contained substances> From the perspective of coating surface properties, the water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass. Methods for maintaining the water content include adjusting the humidity under storage conditions, reducing the porosity of the storage container, etc.

From the perspective of insulation, the metal content of the hardening 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 the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When multiple metals are included, the total of the metals is preferably within the above range.

In addition, as a method for reducing the metal impurities accidentally contained in the hardening resin composition of the present invention, the following methods can be cited: selecting a raw material with a low metal content as a raw material constituting the hardening resin composition of the present invention; filtering the raw material constituting the hardening resin composition of the present invention with a filter; lining with polytetrafluoroethylene or the like in an apparatus and distilling under conditions that suppress contamination as much as possible, etc.

In the curable resin composition of the present invention, if the use as a semiconductor material is considered, the content of halogen atoms is preferably less than 500 mass ppm, less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosion. Among them, the content of halogen ions is preferably less than 5 mass ppm, less than 1 mass ppm, and less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be cited. It is preferred that the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions are respectively within the above range. As a method for adjusting the content of halogen atoms, ion exchange treatment can be preferably cited.

As a container for storing the curable resin composition of the present invention, a conventionally known container can be used. In addition, as a container, in order to suppress the mixing of impurities into the raw materials or the curable resin composition, it is also preferable to use a multi-layer bottle having an inner wall composed of six types of six layers of resin or a bottle having a seven-layer structure formed of six types of resin. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

<Application of the curable resin composition> The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a redistribution layer. In addition, it can also be used for forming an insulating film of a semiconductor element or forming a stress buffer film, etc.

The hardening resin composition of the present invention is used for storage at least once in a storage container at -15 to 16°C, and the filling rate of the hardening resin composition during the above-mentioned cold storage is preferably 50 to 90% relative to the total storage volume of the above-mentioned storage container. It is estimated that even after such storage, the hardening resin composition of the present invention can obtain a resin film with excellent film thickness uniformity. As the above-mentioned storage container, the above-mentioned storage container can be cited. The above-mentioned cold storage temperature is preferably 1 to 12°C, and 3 to 10°C is more preferably. The above-mentioned cold storage time (when it is provided for multiple cold storages, the total time of multiple cold storages) is preferably 1 hour to 100 days, and 12 hours to 30 days is more preferably. The above storage is preferably carried out under light-shielding conditions. The above filling rate is calculated as the total volume of the curable resin composition relative to the total storage volume of the above storage container, and 50 to 99% is preferred, and 70 to 90% is more preferred.

<Preparation of hardening resin composition> The hardening resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be performed using a conventionally known method.

Furthermore, it is preferred to perform filtering using a filter for the purpose of removing foreign matter such as dust or particles in the curable resin composition. Regarding the pore size of the filter, for example, 5 μm or less can be cited, 1 μm or less is preferred, 0.5 μm or less is more preferred, and 0.1 μm or less is further preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be used after being pre-cleaned with an organic solvent. In the filter filtering step, a plurality of filters can be connected in series or in parallel. When using a plurality of filters, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be cycle filtering. In addition, filtering can be performed by pressurization. When filtering is performed by pressurization, the pressure of pressurization can be, for example, 0.01MPa or more and 1.0MPa or less, 0.03MPa or more and 0.9MPa or less is preferred, 0.05MPa or more and 0.7MPa or less is more preferred, and 0.05MPa or more and 0.3MPa or less is further preferred. In addition to filtering using a filter, impurity removal using an adsorbent can also be performed. Filtering using a filter and impurity removal using an adsorbent can also be combined. As the adsorbent, a known adsorbent can be used, for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

(Resin film, cured film, laminate, semiconductor element, and method for manufacturing the same) Next, the resin film, cured film, laminate, semiconductor element, and method for manufacturing the same are described.

The resin film of the present invention is formed by applying the curable resin composition of the present invention to a substrate. There are no particular limitations on the application method and the type of substrate, but the application method and substrate in the film formation step described later can be preferably cited. As for the film thickness of the resin film, the film thickness of the cured film described later can be set to a film thickness within the range described later. For example, the film thickness of the resin film can be determined by considering the shrinkage caused by curing.

The cured film of the present invention is formed by curing the curable resin composition of the present invention or the resin film of the present invention. The film thickness of the cured film of the present invention can be set to 0.5 μm or more, or 1 μm or more, and the upper limit can be set to 100 μm or less, or 30 μm or less.

The cured film of the present invention can be stacked in 2 or more layers, and further stacked in 3 to 7 layers to form a laminate. The laminate of the present invention is preferably a laminate including 2 or more cured films and a metal layer between any of the above-mentioned cured films. For example, a laminate having a layered structure including at least three layers stacked in sequence, namely, a first cured film, a metal layer, and a second cured film, can be cited as a preferred example. The above-mentioned first cured film and the above-mentioned second cured film are both the cured films of the present invention. As a preferred example, for example, any one of the above-mentioned first cured film and the above-mentioned second cured film can be cited as a film formed by curing the curable resin composition of the present invention. The curable resin composition of the present invention used for forming the first cured film and the curable resin composition of the present invention used for forming the second cured film may have the same composition or different compositions. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a redistribution layer.

Examples of fields to which the cured film of the present invention can be applied include insulating films for semiconductor elements, interlayer insulating films for redistribution layers, stress buffer films, etc. In addition, examples include patterning of sealing films, substrate materials (base films or cover films of flexible printed boards, interlayer insulating films), or insulating films for actual mounting purposes such as those described above by etching. For the use of these, for example, you can refer to SCIENCE AND TECHNOLOGY CO., LTD. "Advanced Functionality and Application Technology of Polyimide" April 2008, supervised by Masaaki Kakimoto, CMC Technical Library "Basics and Development of Polyimide Materials" November 2011, Japan Polyimide/Aromatic Polymer Research Association "Latest Polyimide Fundamentals and Applications" NTS Inc., August 2010, etc.

Furthermore, the cured film of the present invention can also be used in the manufacture of printing plates such as offset printing plates or screen printing plates, in the etching of molded components, in the manufacture of protective varnishes and dielectric layers in electronics, especially microelectronics, and the like.

The method for producing a cured film of the present invention (hereinafter, also referred to as "the method for producing the present invention") preferably includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film (resin film). The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step of exposing the film, and a development step of developing the film. Furthermore, the method for producing a cured film of the present invention preferably includes the film forming step and, if necessary, the development step and a heating step of heating the film at 50 to 450°C. Specifically, it is also preferred to include the following steps (a) to (d). (a) a film forming step of applying a curable resin composition to a substrate to form a film (curable resin composition layer) (b) an exposure step of exposing the film after the film forming step (c) a developing step of developing the exposed film (d) a heating step of heating the developed film at 50 to 450°C By heating in the heating step, the resin layer cured by exposure can be further cured. In the heating step, for example, the hot alkali generator decomposes to obtain sufficient curability.

The method for manufacturing a laminated body of a preferred embodiment of the present invention includes the method for manufacturing a cured film of the present invention. After forming a cured film according to the above-mentioned method for manufacturing a cured film, the method for manufacturing a laminated body of the present embodiment further performs step (a) again or steps (a) to (c) or steps (a) to (d). In particular, it is preferred to perform the above-mentioned steps in sequence a plurality of times, for example 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured film in this way, a laminated body can be formed. In the present invention, it is preferred to provide a metal layer on a portion provided with a cured film or between the cured films or on a portion provided with a cured film and between the cured films. In addition, when manufacturing a laminate, it is not necessary to repeat all steps (a) to (d). As described above, a laminate of a cured film can be obtained by performing at least (a), preferably (a) to (c) or (a) to (d) a plurality of times.

<Film-forming step (layer-forming step)> The manufacturing method of the preferred embodiment of the present invention includes a film-forming step (layer-forming step) of applying a curable resin composition to a substrate to form a film (layer). According to the film-forming step, the resin film of the present invention can be obtained.

The type of substrate can be appropriately specified according to the purpose, and can be semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, evaporated film, magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrate, electrode plate of plasma display panel (PDP), etc., without special restrictions. In addition, a layer such as a close contact layer or an oxide layer can be provided on the surface of such substrates. In the present invention, a semiconductor substrate is particularly preferred, and a silicon substrate, a Cu substrate, and a molded resin substrate are more preferred. In addition, a bonding layer or an oxide layer formed of hexamethyldisilazane (HMDS) or the like may be provided on the surface of the substrate. In addition, as the substrate, for example, a plate-shaped substrate (substrate) may be used. The shape of the substrate is not particularly limited, and may be circular or rectangular, but a rectangular shape is preferred. As for the size of the substrate, as long as it is circular, for example, the diameter is 100 to 450 mm, preferably 200 to 450 mm. As long as it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.

Furthermore, when a curable resin composition layer is formed on the surface of the resin layer or on the surface of the metal layer, the resin layer or the metal layer becomes a base material.

As a method of applying the curable resin composition to the base material, coating is preferred.

Specifically, as the applicable method, there can be exemplified dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of the thickness of the curable resin composition layer, spin coating, slit coating, spray coating, and inkjet coating are more preferred. By appropriately adjusting the solid component concentration or coating conditions according to the method, a resin layer of a desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For a circular substrate such as a wafer, spin coating, spray coating, inkjet coating, etc. are preferred, and for a rectangular substrate, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of spin coating, for example, a rotation speed of 300 to 3,500 rpm can be used for 10 to 180 seconds, and a rotation speed of 500 to 2,000 rpm can be used for about 10 seconds to 1 minute. In addition, a method of transferring a coating film previously applied by the above-mentioned applying method and formed on a temporary support to a substrate can also be applied. Furthermore, in order to obtain uniform film thickness, multiple rotation speeds can be combined for coating. Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Publication No. 2006-047592 can also be preferably used in the present invention. Furthermore, a step of removing excess film can be performed at the end of the substrate. Examples of such a step include edge beading residue rinsing (EBR), air knife, back rinse, etc. Furthermore, a pre-wetting step may be adopted: before applying the resin composition to the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

<Drying step> The manufacturing method of the present invention may include a drying step for removing the solvent after the film forming step (layer forming step) after forming the above-mentioned film (hardening resin composition layer). The preferred drying temperature is 50 to 150°C, 70 to 130°C is more preferred, and 90 to 110°C is further preferred. As drying time, 30 seconds to 20 minutes can be exemplified, 1 minute to 10 minutes is preferred, and 3 minutes to 7 minutes is more preferred. When the amount of solvent in the hardening resin composition solution is large, vacuum drying and heat drying can also be combined. Heat drying uses a heating plate, a hot air oven, etc., and there is no particular limitation.

<Exposure step> The manufacturing method of the present invention may include an exposure step of exposing the above-mentioned film (hardening resin composition layer). There is no particular regulation on the exposure amount as long as the hardening resin composition can be hardened. For example, it is preferably 100 to 10,000 mJ/ ^cm2 , and more preferably 200 to 8,000 mJ/ ^cm2 , in terms of exposure energy at a wavelength of 365 nm.

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

If we explain the exposure wavelength in relation to the light source, we can cite (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), wide (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), _F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet light; EUV (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic of the YAG laser is 532nm and the third harmonic is 355nm. For the curable resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is particularly preferred. In this way, high exposure sensitivity can be particularly obtained. In addition, from the perspective of operation and productivity, a wide (three wavelengths of g, h, and i-rays) light source of a high-pressure mercury lamp or a semiconductor laser 405nm is also preferred. In addition, the exposure method is not particularly limited as long as it is a method of exposing at least a portion of the film including the resin composition of the present invention, but exposure using a mask, exposure based on a laser direct imaging method, etc. can be cited.

<Developing step> The manufacturing method of the present invention may include a developing step of developing (developing the above-mentioned film) the exposed film (hardening resin composition layer). For example, in the case of a negative hardening resin composition, the unexposed portion (non-exposed portion) is removed by developing. There is no particular limitation on the developing method as long as the desired pattern can be formed. For example, spraying the developer from a nozzle, spraying, immersing the substrate in the developer, etc. can be cited. Spraying from a nozzle can be preferably used. The developing step may include a step of continuously supplying the developer to the substrate, a step of keeping the developer on the substrate in a substantially stationary state, a step of vibrating the developer using ultrasound or the like, and a step of combining these.

Development is performed using a developer. For example, in the case of a negative curing resin composition, any developer can be used without particular limitation as long as it can remove the unexposed portion (non-exposed portion). As the developer, a developer containing an organic solvent or an alkaline aqueous solution can be used.

In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained by inputting a structural formula into ChemBioDraw as a calculated value.

In the case where the developer contains an organic solvent, the organic solvent may be preferably esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate), Ester, ethyl ethoxylate, etc.)), 3-alkoxy alkyl propionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxy alkyl propionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.) ethyl 2-ethoxy-2-methylpropionate), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate, ethyl thiocyanate, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate, ethyl thiocyanate, diethylene glycol dimethyl ether, Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. can be preferably cited, and, as hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. can be preferably cited, as sulfoxides, dimethyl sulfoxide can be preferably cited, and mixtures of these organic solvents can also be preferably cited.

When the developer contains an organic solvent, in the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. In addition, the developer may contain a surfactant.

When the developer contains an organic solvent, preferably 50% by mass or more of the developer is the organic solvent, more preferably 70% by mass or more of the developer is the organic solvent, and even more preferably 90% by mass or more of the developer is the organic solvent. In addition, the developer may contain 100% by mass of the organic solvent.

When the developer is an alkaline aqueous solution, examples of the alkaline compound that the alkaline aqueous solution can contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate, etc. TMAH is preferred. For example, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, and even more preferably 0.3 to 3 mass % in the total mass of the developer.

[Developer supply method] There are no particular restrictions on the developer supply method as long as the desired pattern can be formed. There are methods of immersing the substrate with a film formed in the developer, using a nozzle to supply the developer to the film formed on the substrate by immersion development, or continuously supplying the developer. There are no particular restrictions on the type of nozzle, and examples include vertical nozzles, shower nozzles, and mist nozzles. From the perspective of developer permeability, non-image removal, and manufacturing efficiency, a method of supplying developer with a vertical nozzle or a method of continuously supplying developer with a spray nozzle is preferred. From the perspective of developer permeability to the image area, the method of supplying developer with a spray nozzle is more preferred. In addition, after continuously supplying developer with a vertical nozzle, rotating the substrate to remove the developer from the substrate, and performing rotation drying, the developer is continuously supplied with a vertical nozzle again, and the substrate is rotated to remove the developer from the substrate, and this step can be repeated multiple times. In addition, as a method for supplying the developer in the developing step, there can be adopted a step of continuously supplying the developer to the substrate, a step of maintaining the developer in a substantially static state on the substrate, a step of vibrating the developer on the substrate using ultrasound or the like, and a step of combining these steps.

The developing time is preferably 10 seconds to 5 minutes. The temperature of the developing solution during the developing process is not particularly specified, but the developing process can generally be performed at 20 to 40°C.

After the treatment with the developer, rinsing may be further performed. The rinsing is preferably performed in a solvent different from the developer. For example, propylene glycol monomethyl ether acetate may be cited. The rinsing time is preferably 5 seconds to 5 minutes. Furthermore, between development and rinsing, a step of applying both the developer and the rinsing solution may be included. The time for the above step is preferably 1 second to 5 minutes. Furthermore, for example, rinsing can be performed using a solvent contained in the hardening resin composition.

The rinse solution may also contain other components. As other components, for example, a well-known surfactant or a well-known defoaming agent can be cited.

[Method for supplying rinsing liquid] There are no particular restrictions on the method for supplying rinsing liquid as long as the desired pattern can be formed. There are methods of immersing the substrate in the rinsing liquid, supplying the rinsing liquid on the substrate by coating the substrate, supplying the rinsing liquid to the substrate using a sprayer, and continuously supplying the rinsing liquid to the substrate using a mechanism such as a vertical nozzle. From the perspective of the permeability of the rinse liquid, the removability of the non-image area, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a vertical nozzle, a spray nozzle, etc. The method of continuous supply using a spray nozzle is preferred. From the perspective of the permeability of the rinse liquid to the image area, the method of supplying using a spray nozzle is more preferred. There is no particular limitation on the type of nozzle, and vertical nozzles, shower nozzles, spray nozzles, etc. can be cited. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the film after exposure using a vertical nozzle, and it is more preferably a step of supplying the rinsing liquid using a spray nozzle. In addition, as a method of supplying the developer in the rinsing step, it is possible to adopt a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid on the substrate in a substantially stationary state, a step of vibrating the rinsing liquid on the substrate using ultrasound, etc., and a step of combining these steps. When the developer contains an organic solvent, PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropyl alcohol), etc. can be cited as the rinse liquid, and PGMEA is preferred. In addition, water is preferred as the rinse liquid for development based on a developer containing an alkaline aqueous solution. The rinse time is preferably 5 seconds to 1 minute.

<Heating step> The manufacturing method of the present invention preferably includes a step of heating the developed film at 50 to 450°C (heating step). It is preferred to include a heating step after the film forming step (layer forming step), the drying step, and the developing step. In the heating step, for example, a cyclization reaction of the specific resin precursor is carried out by generating an alkali by decomposing the above-mentioned hot alkali generator. In addition, the curable resin composition of the present invention may contain a free radical polymerizable compound other than the specific resin precursor, but it is also possible to perform curing of free radical polymerizable compounds other than the unreacted specific resin precursor in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50°C or higher, more preferably 80°C or higher, further preferably 140°C or higher, further preferably 150°C or higher, further preferably 160°C or higher, and further preferably 170°C or higher. As the upper limit, 500°C or lower is preferably, 450°C or lower is more preferably, 350°C or lower is further preferably, 250°C or lower is further preferably, and 220°C or lower is further preferably.

Regarding heating, it is preferred that the heating rate be 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the heating rate to 1°C/min or more, productivity can be ensured while preventing excessive volatility of amines, and by setting the heating rate to 12°C/min or less, the residual stress of the cured film can be reduced. Furthermore, in the case of an oven capable of rapid heating, it is preferred that the heating rate be 1 to 8°C/sec from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C/sec, and even more preferably 3 to 6°C/sec.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when a curable resin composition is applied to a substrate and then dried, it is the temperature of the dried film (layer), and it is preferably to gradually increase the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the curable resin composition.

The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.

In particular, when forming a multi-layer laminate, from the viewpoint of the adhesion between the layers of the cured film, the heating temperature is preferably 180°C to 320°C, and more preferably 180°C to 260°C. The reason for this is not clear, but it is believed that the reason is that the acetylene groups of the specific resin between the layers undergo cross-linking reactions at this temperature.

Heating can be performed in stages. For example, the following pretreatment steps can be performed: heating from 25°C to 180°C at 3°C/min, maintaining at 180°C for 60 minutes, heating from 180°C to 200°C at 2°C/min, and maintaining at 200°C for 120 minutes. The heating temperature for the pretreatment step is preferably 100-200°C, more preferably 110-190°C, and even more preferably 120-185°C. In the pretreatment step, as described in the specification of U.S. Patent No. 9159547, it is also preferred to perform the treatment while irradiating with ultraviolet rays. By such a pretreatment step, the properties of the membrane can be further improved. The pretreatment step can be performed in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pretreatment can also be performed in two or more stages, for example, pretreatment step 1 can be performed in the range of 100 to 150°C, and then pretreatment step 2 can be performed in the range of 150 to 200°C.

Furthermore, cooling may be performed after heating, and the cooling rate at this time is preferably 1 to 5°C/minute.

From the viewpoint of preventing the decomposition of a specific resin, it is preferable to perform the heating step in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon and performing the heating step under vacuum. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less. The heating mechanism is not particularly limited, and examples thereof include a heating plate, an infrared furnace, an electric oven, a hot air oven, and the like.

<Metal layer forming step> The manufacturing method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (hardening resin composition layer).

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

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, and Japanese Patent Publication No. 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and methods combining these methods can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be cited.

The thickness of the metal layer is preferably 0.1 to 50 μm at the thickest wall portion, more preferably 1 to 10 μm.

<Lamination step> The manufacturing method of the present invention preferably also includes a layering step.

The lamination step includes a series of steps including (a) film formation step (layer formation step), (b) exposure step, (c) development step, and (d) heating step, which are sequentially performed again on the surface of the hardened film (resin layer) or metal layer. However, it is also possible to perform only (a) film formation step repeatedly. In addition, it is also possible to perform (d) heating step at the end or in the middle of the lamination. That is, it is possible to perform (a) to (c) repeatedly for a specified number of times, and then perform (d) heating, so that the layer of hardening resin composition that is laminated is cured collectively. Furthermore, after the (c) developing step, the (e) metal layer forming step may be included. In this case, the heating in (d) may be performed each time, or the heating in (d) may be performed all at once after the layering is performed a specified number of times. It is self-evident that the above-mentioned drying step or heating step may be appropriately included in the layering step.

When a further layering step is performed after the layering step, a surface activation treatment step may be performed after the heating step, after the exposure step, or after the metal layer forming step. As the surface activation treatment, plasma treatment may be exemplified.

The above-mentioned lamination step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times. In addition, each layer in the lamination step may be of the same composition, shape, film thickness, etc., or may be different layers.

For example, a structure of resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, in which the number of resin layers is 2 or more and 20 or less is preferred, a structure of resin layer of 3 or more and 7 or less is more preferred, and a structure of 3 or more and 5 or less is further preferred.

In the present invention, after the metal layer is provided, it is preferred to further form a hardened film (resin layer) of the hardening resin composition so as to cover the metal layer. Specifically, there can be cited an embodiment in which (a) film forming step, (b) exposure step, (c) development step, (e) metal layer forming step, and (d) heating step are repeated in this order, or an embodiment in which (a) film forming step, (b) exposure step, (c) development step, and (e) metal layer forming step are repeated in this order and (d) heating step is provided at the end or in the middle. By alternately performing the step of laminating the hardening resin composition layer (resin layer) and the step of forming the metal layer, the hardening resin composition layer (resin layer) and the metal layer can be alternately laminated.

(Surface activation treatment step) The method for manufacturing a laminate of the present invention preferably includes a surface activation treatment step of performing surface activation treatment on at least a portion of the above-mentioned metal layer and the resin composition layer. The surface activation treatment step is usually performed after the metal layer forming step, but the metal layer forming step may also be performed after the above-mentioned developing step and then performing the surface activation treatment step on the resin composition layer. The surface activation treatment may be performed only on at least a portion of the metal layer, may be performed only on at least a portion of the exposed resin composition layer, or may be performed on at least a portion of both the metal layer and the exposed resin composition layer. It is preferred to perform surface activation treatment on at least a portion of the metal layer, and it is preferred to perform surface activation treatment on a portion or all of the region of the metal layer where the resin composition layer is formed on the surface. In this way, by performing surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) disposed on the surface can be improved. In addition, it is preferred to perform surface activation treatment on a portion or all of the resin composition layer (resin layer) after exposure. In this way, by performing surface activation treatment on the surface of the resin composition layer, the adhesion with the metal layer or resin layer disposed on the surface subjected to surface activation treatment can be improved. In particular, when the resin composition layer is hardened, such as during negative tone development, it is less likely to be damaged by surface treatment, and thus the adhesion is easily improved. Specifically, the surface activation treatment includes plasma treatment selected from various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment based on _CF4 / _O2 , _NF3 / _O2 , _SF6 , _NF3 , _NF3 / _O2 , surface treatment based on ultraviolet (UV) ozone method, treatment of removing oxide film by immersion in hydrochloric acid aqueous solution and then immersion in an organic surface treatment agent containing a compound having at least one of an amino group and a thiol group, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/ ^m2 , more preferably 1000-100,000 J/ ^m2 , and most preferably 10,000-50,000 J/ ^m2 .

The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the curable resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Publication No. 2016-027357, which are incorporated into this specification. [Example]

The following examples are given to further illustrate the present invention. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the purpose 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.

<Examples and Comparative Examples> In each example, the components listed in Tables 1 to 7 below were mixed to obtain each curable resin composition. In addition, in each comparative example, the components listed in Table 2 below were mixed to obtain each comparative composition. Specifically, the contents of the components other than the solvents listed in Tables 1 to 7 were set to the amounts (parts by mass) listed in the columns of Tables 1 to 7. In addition, in each composition, the total content of the solvent was set to the value (mass %) of the solid content concentration of the composition being the value listed in Tables 1 to 7, and the content ratio of each solvent was set to the mass ratio based on the values listed in the columns of Tables 1 to 7. The obtained curable resin composition and the comparative composition were filtered under pressure through a polytetrafluoroethylene filter having a pore width of 0.8 μm. In Tables 1 to 7, the entry "-" indicates that the composition does not contain the corresponding component.

[Table 1] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Resin A-1 36.8 36.8 36.8 36.8 36.8 36.8 36.8 36.8 36.8 36.8 36.8 36.8 A-101 - - - - - - - - - - - - A-201 - - - - - - - - - - - - Crosslinking agent B-1 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 B-2 - - - - - - - - - - - - B-3 - - - - - - - - - - - - Photopolymerization initiator C-1 1.288 1.288 1.288 1.288 1.288 1.288 1.288 1.288 1.288 1.288 1.288 1.288 C-2 - - - - - - - - - - - - C-3 - - - - - - - - - - - - Sealing agent D-1 0.736 0.736 0.736 0.736 0.736 0.736 0.736 0.736 0.736 0.736 0.736 0.736 Polymerization inhibitor E-1 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 Migration inhibitors F-1 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 Thermoalkali generator G-1 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 Solid content concentration (%) 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 Solvent NMP 50 50 50 50 - - - - - - - - DMSO 50 - - - 50 50 50 - 50 60 65 55 EL - - 50 - - 50 - - - 40 35 - GBL - - - - - - - - 50 - - 45 Cyptn - 50 - - 50 - - 50 - - - - EA - - - - - - 50 50 - - - - PGMEA - - - 50 - - - - - - - - Film thickness uniformity (just after preparation) 7 7 9 8 6 9 7 7 7 8 7 7 Resolution (immediately after preparation) 6 8 6 5 7 8 6 6 6 8 6 6 Drug resistance (immediately after preparation) 6 7 8 8 7 8 9 8 7 8 7 7 Film thickness uniformity (6 months after preparation) 5 5 5 5 4 8 3 3 3 8 5 3 Resolution (6 months after preparation) 4 7 4 4 5 6 5 5 3 6 4 4 Drug resistance (6 months after preparation) 5 6 7 7 6 6 8 7 6 6 6 5 Comprehensive evaluation (6 months after preparation) 4.7 5.8 5.0 5.0 4.7 7.0 4.5 4.3 3.5 7.0 4.8 3.7

[Table 2] Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20 Embodiment 21 Embodiment 22 Comparison Example 1 Resin A-1 36.8 36.8 36.8 36.8 36.8 - 36.8 36.8 36.8 36.8 36.8 A-101 - - - - 36.8 - - - - - 36.8 A-201 - - - - - 36.8 - - - - - Crosslinking agent B-1 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 - - 5.5237 5.5237 5.5237 B-2 - - - - - - 5.5237 - - - - B-3 - - - - - - - 5.5237 - - - Photopolymerization initiator C-1 1.288 1.288 1.288 1.288 1.288 1.288 1.288 1.288 - - 1.288 C-2 - - - - - - - - 1.288 - - C-3 - - - - - - - - - 1.288 - Sealing agent D-1 0.736 0.736 0.736 0.736 0.736 0.736 0.736 0.736 0.736 0.736 0.736 Polymerization inhibitor E-1 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 Migration inhibitors F-1 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 Thermoalkali generator G-1 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 Solid content concentration (%) 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 Solvent NMP - - - - - - - - - - - DMSO 60 95 45 40 50 50 50 50 50 50 - EL - - 45 40 - - 50 50 50 50 100 GBL 40 5 10 20 50 50 - - - - - Cyptn - - - - - - - - - - - EA - - - - - - - - - - - PGMEA - - - - - - - - - - - Film thickness uniformity (just after preparation) 6 8 8 8 7 7 9 9 9 9 7 Resolution (immediately after preparation) 7 7 6 7 6 6 8 8 8 8 8 Drug resistance (immediately after preparation) 7 7 8 8 7 7 8 8 8 8 7 Film thickness uniformity (6 months after preparation) 4 5 7 6 3 3 8 8 8 8 1 Resolution (6 months after preparation) 3 4 4 5 3 3 6 6 6 6 1 Drug resistance (6 months after preparation) 4 5 6 6 6 6 6 6 6 6 1 Comprehensive evaluation (6 months after preparation) 3.7 4.7 5.8 5.7 3.5 3.5 7.0 7.0 7.0 7.0 1.0

[Table 3] Embodiment 23 Embodiment 24 Embodiment 25 Embodiment 26 Embodiment 27 Embodiment 28 Embodiment 29 Embodiment 30 Embodiment 31 Resin A-1 36.8 36.8 36.8 36.8 36.8 36.8 36.8 36.8 36.8 A-101 - - - - - - - - - A-201 - - - - - - - - - Crosslinking agent B-1 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 B-2 - - - - - - - - - B-3 - - - - - - - - - Photopolymerization initiator C-1 1.288 1.288 1.288 1.288 1.288 - 1.288 1.288 1.288 C-2 - - - - - 1.288 - - - C-3 - - - - - - - - - Sealing agent D-1 0.736 0.736 0.736 0.736 0.736 0.736 0.736 0.736 - D-2 - - - - - - - - 0.736 D-3 - - - - - - - - - Polymerization inhibitor E-1 0.0736 0.0736 0.0736 0.0736 0.0736 - - - 0.0736 E-2 - - - - - 0.0736 0.0736 - - E-3 - - - - - - - 0.0736 - Migration inhibitors F-1 0.1265 - - - - - - - - F-2 - 0.1265 - - - 0.1265 0.1265 0.1265 0.1265 F-3 - - 0.1265 - - - - - - F-4 - - - 0.1265 - - - - - F-5 - - - - 0.1265 - - - - Thermoalkali generator G-1 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 G-2 - - - - - - - - - G-3 - - - - - - - - - Solid content concentration (%) 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 Solvent DMSO 20 20 20 20 20 20 20 20 20 EL - - - - - - - - - GBL 80 80 80 80 80 80 80 80 80 Film thickness uniformity (just after preparation) 7 7 7 7 7 7 7 7 7 Resolution (immediately after preparation) 6 6 6 6 6 7 7 6 6 Drug resistance (immediately after preparation) 6 6 6 6 6 6 6 6 6 Film thickness uniformity (6 months after preparation) 6 6 6 6 6 6 6 6 6 Resolution (6 months after preparation) 5 5 5 5 5 5 6 5 5 Drug resistance (6 months after preparation) 5 5 5 5 5 4 5 4 5 Comprehensive evaluation (6 months after preparation) 5.5 5.5 5.5 5.5 5.5 5.3 5.8 5.3 5.5

[Table 4] Embodiment 32 Embodiment 33 Embodiment 34 Embodiment 35 Embodiment 36 Embodiment 37 Embodiment 38 Embodiment 39 Embodiment 40 Resin A-1 36.8 36.8 36.8 36.8 36.8 36.8 36.8 - - A-101 - - - - - - - 36.8 - A-201 - - - - - - - - 36.8 Crosslinking agent B-1 5.5237 5.5237 5.5237 - - 5.5237 5.5237 5.5237 5.5237 B-2 - - - 5.5237 - - - - - B-3 - - - - 5.5237 - - - - Photopolymerization initiator C-1 1.288 - - 1.288 1.288 1.288 1.288 1.288 1.288 C-2 - 1.288 - - - - - - - C-3 - - 1.288 - - - - - - Sealing agent D-1 - 0.736 0.736 0.736 0.736 0.736 0.736 0.736 0.736 D-2 - - - - - - - - - D-3 0.736 - - - - - - - - Polymerization inhibitor E-1 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 E-2 - - - - - - - - - E-3 - - - - - - - - - Migration inhibitors F-1 - - - - - - - - - F-2 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 F-3 - - - - - - - - - F-4 - - - - - - - - - F-5 - - - - - - - - - Thermoalkali generator G-1 1.0304 1.0304 1.0304 1.0304 1.0304 - - 1.0304 1.0304 G-2 - - - - - 1.0304 - - - G-3 - - - - - - 1.0304 - - Solid content concentration (%) 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 Solvent DMSO 20 20 20 20 20 20 20 20 20 EL - - - - - - - - - GBL 80 80 80 80 80 80 80 80 80 Film thickness uniformity (just after preparation) 7 7 7 7 7 7 7 7 6 Resolution (immediately after preparation) 6 6 6 5 6 6 6 6 6 Drug resistance (immediately after preparation) 6 6 6 7 6 6 6 6 5 Film thickness uniformity (6 months after preparation) 6 6 6 6 6 6 6 6 5 Resolution (6 months after preparation) 5 4 4 4 5 5 5 5 5 Drug resistance (6 months after preparation) 5 4 4 6 5 4 4 5 4 Comprehensive evaluation (6 months after preparation) 5.5 5.0 5.0 5.3 5.5 5.3 5.3 5.5 4.8

[Table 5] Embodiment 41 Embodiment 42 Embodiment 43 Embodiment 44 Embodiment 45 Embodiment 46 Embodiment 47 Embodiment 48 Embodiment 49 Resin A-1 36.8 36.8 36.8 36.8 36.8 36.8 36.8 36.8 36.8 A-101 - - - - - - - - - A-201 - - - - - - - - - Crosslinking agent B-1 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 5.5237 B-2 - - - - - - - - - B-3 - - - - - - - - - Photopolymerization initiator C-1 1.288 1.288 1.288 1.288 - 1.288 1.288 1.288 1.288 C-2 - - - - 1.288 - - - - C-3 - - - - - - - - - Sealing agent D-1 0.736 0.736 0.736 0.736 0.736 0.736 0.736 - - D-2 - - - - - - - 0.736 - D-3 - - - - - - - - 0.736 Polymerization inhibitor E-1 0.0736 0.0736 0.0736 0.0736 - - - 0.0736 0.0736 E-2 - - - - 0.0736 0.0736 - - - E-3 - - - - - - 0.0736 - - Migration inhibitors F-1 - - - - - - - - - F-2 0.1265 - - - 0.1265 0.1265 0.1265 0.1265 0.1265 F-3 - 0.1265 - - - - - - - F-4 - - 0.1265 - - - - - - F-5 - - - 0.1265 - - - - - Thermoalkali generator G-1 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 1.0304 G-2 - - - - - - - - - G-3 - - - - - - - - - Solid content concentration (%) 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 Solvent DMSO 50 50 50 50 50 50 50 50 50 EL 50 50 50 50 50 50 50 50 50 GBL - - - - - - - - - Film thickness uniformity (just after preparation) 9 9 9 9 9 9 9 9 9 Resolution (immediately after preparation) 8 8 8 8 9 9 7 8 8 Drug resistance (immediately after preparation) 8 8 8 7 7 8 8 8 8 Film thickness uniformity (6 months after preparation) 8 8 8 8 8 8 8 8 8 Resolution (6 months after preparation) 6 6 6 6 6 7 6 6 6 Drug resistance (6 months after preparation) 6 6 6 6 5 6 5 6 6 Comprehensive evaluation (6 months after preparation) 7.0 7.0 7.0 7.0 6.8 7.3 6.8 7.0 7.0

[Table 6] Embodiment 50 Embodiment 51 Embodiment 52 Embodiment 53 Embodiment 54 Embodiment 55 Embodiment 56 Embodiment 57 Embodiment 58 Resin A-1 36.8 36.8 36.8 36.8 36.8 36.8 - - 36.8 A-101 - - - - - - 36.8 - - A-201 - - - - - - - 36.8 - Crosslinking agent B-1 5.5237 5.5237 - - 5.5237 5.5237 5.5237 5.5237 5.5237 B-2 - - 5.5237 - - - - - - B-3 - - - 5.5237 - - - - - Photopolymerization initiator C-1 - - 1.288 1.288 1.288 1.288 1.288 1.288 - C-2 1.288 - - - - - - - 1.288 C-3 - 1.288 - - - - - - - Sealing agent D-1 0.736 0.736 0.736 0.736 0.736 0.736 0.736 0.736 0.736 D-2 - - - - - - - - - D-3 - - - - - - - - - Polymerization inhibitor E-1 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0736 0.0733 E-2 - - - - - - - - 0.0300 E-3 - - - - - - - - - Migration inhibitors F-1 - - - - - - - - - F-2 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 0.1265 F-3 - - - - - - - - - F-4 - - - - - - - - - F-5 - - - - - - - - - Thermoalkali generator G-1 1.0304 1.0304 1.0304 1.0304 - - 1.0304 1.0304 1.0304 G-2 - - - - 1.0304 - - - - G-3 - - - - - 1.0304 - - - Solid content concentration (%) 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.5782 45.6079 Solvent DMSO 50 50 50 50 50 50 50 50 20 EL 50 50 50 50 50 50 50 50 - GBL - - - - - - - - 80 Film thickness uniformity (just after preparation) 9 9 9 9 9 9 9 8 7 Resolution (immediately after preparation) 8 8 6 8 8 8 8 8 8 Drug resistance (immediately after preparation) 7 7 9 8 7 7 8 6 6 Film thickness uniformity (6 months after preparation) 8 8 8 8 8 8 8 6 6 Resolution (6 months after preparation) 5 5 5 6 6 6 6 6 6 Drug resistance (6 months after preparation) 5 5 7 6 5 5 6 5 4 Comprehensive evaluation (6 months after preparation) 6.5 6.5 6.8 7.0 6.8 6.8 7.0 5.8 5.7

[Table 7] Embodiment 59 Embodiment 60 Embodiment 61 Embodiment 62 Embodiment 63 Embodiment 64 Resin A-1 36.8 36.8 36.8 36.8 36.8 36.8 A-101 - - - - - - A-201 - - - - - - Crosslinking agent B-1 5.5237 5.5237 5.5237 - - - B-2 - - - 5.5237 5.5237 5.5237 B-3 - - - - - - Photopolymerization initiator C-1 1.288 1.288 - - - 1.288 C-2 - - 1.288 1.288 1.288 - C-3 - - - - - - Sealing agent D-1 0.736 0.736 0.736 0.736 0.736 0.736 D-2 - - - - - - D-3 - - - - - - Polymerization inhibitor E-1 0.0733 - - 0.0736 - - E-2 0.0300 0.0500 0.0500 - 0.0500 0.0500 E-3 - - - - - - Migration inhibitors F-1 - - - 0.1265 0.1265 0.1265 F-2 0.1265 0.1265 0.1265 - - - F-3 - - - - - - F-4 - - - - - - F-5 - - - - - - Thermoalkali generator G-1 1.0304 1.0304 0.2506 1.0304 1.0304 1.0304 G-2 - - - - - - G-3 - - - - - - Solid content concentration (%) 45.6079 45.5546 44.7748 45.5782 45.5782 45.5782 Solvent DMSO 20 20 20 20 20 20 EL - - - - - - GBL 80 80 80 80 80 80 Film thickness uniformity (just after preparation) 7 7 6 7 7 7 Resolution (immediately after preparation) 8 7 7 5 5 5 Drug resistance (immediately after preparation) 6 6 5 5 5 5 Film thickness uniformity (6 months after preparation) 6 6 6 6 6 6 Resolution (6 months after preparation) 6 5 5 4 4 4 Drug resistance (6 months after preparation) 4 4 4 5 5 5 Comprehensive evaluation (6 months after preparation) 5.7 5.3 5.3 5.2 5.2 5.2

The details of each component listed in Tables 1 to 7 are as follows.

[Resin (specific resin)] ・A-1: Resin having a structure represented by the following formula (A-1) ・A-101: Resin synthesized by the following Synthesis Example 1 ・A-201: Resin synthesized by the following Synthesis Example 2 [Chemical formula 74]

[Synthesis Example 1: Synthesis of polyimide precursor A-101] In a dry reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, 9.49 g (32.25 mmol) of 4,4'-biphenyltetracarboxylic dianhydride and 10.0 g (32.25 mmol) of oxydiphthalic dianhydride were suspended in 140 mL of diethylene glycol dimethyl ether while removing water. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water and 10.7 g (135 mmol) of pyridine were added successively and stirred at 60°C for 18 hours. Next, the mixture was cooled to -20°C, and 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was heated to room temperature (23°C) and stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise over 1 hour to the obtained transparent solution. Then, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Then, the polyimide proto-resin was precipitated in 4 liters of water, and the water-polyimide proto-resin mixture was stirred at 500 rpm for 15 minutes. The polyimide proto-resin was obtained by filtration, and was stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide proto-resin was dried at 45° C. for 3 days under reduced pressure to obtain polyimide proto-resin A-101.

[Synthesis Example 2: Synthesis of polybenzoxazole precursor A-201] Into a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 73.25 g (0.200 mol) of hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane (Bis-AP-AF, manufactured by Central Glass Co., Ltd.), 31.64 g (0.400 mol) of pyridine, and 293 g of NMP were added. The mixture was stirred at room temperature (23°C) and then cooled to -15°C using a dry ice/methanol bath. While maintaining the reaction temperature at -5°C to -15°C, 30.11 g (0.144 mol) of a 30% by mass NMP solution of 1,4-cyclohexanedicarboxylic acid dichloride and a mixed solution of 3.83 g (0.016 mol) of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 96.25 g of NMP were added dropwise to the solution. After the addition, the obtained mixture was stirred at room temperature for 16 hours. Then, the reaction solution was cooled to below -5°C in an ice/methanol bath, and a mixed solution of 9.59 g (0.090 mol) of butyryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 34.5 g of NMP was added dropwise while maintaining the reaction temperature at below -0°C. After the addition was completed, the mixture was stirred for 16 hours. The reaction solution was diluted with 550 g of NMP and added to a 4 L mixture of deionized water/methanol (80/20 by volume) that was stirred vigorously. The precipitated white powder was recovered by filtration and then washed with deionized water. The polymer was dried at 50°C for two days under vacuum to obtain Resin A-1a. 25.00 g of Resin A-1a, 125 g of NMP and 125 g of methyl ethyl ketone were added to a 500 mL eggplant-shaped flask and concentrated under reduced pressure at 60°C until the content became 160 g. 0.43 g (1.85 mmol) of camphorsulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.12 g (0.065 mol) of 2,3-dihydrofuran (manufactured by FUJIFILM Wako Pure Chemical Corporation) were added to the contents, and stirred at room temperature (23°C) for 1.5 hours. 0.37 g of triethylamine and 150 g of NMP were added to the obtained solution for dilution. The obtained solution was poured into a 2 L mixture of deionized water/methanol (80/20 by volume) that was vigorously stirred, and the precipitated white powder was recovered by filtration and then washed with deionized water. The polymer was dried at 50°C for two days under vacuum to obtain polybenzo[beta]zo[iota]zole (PBO) precursor A-201.

(Crosslinking agent) ・B-1: Compound with the following structure ・B-2: Dipentatriol hexaacrylate ・B-3: LIGHT ESTER BP-6EM (manufactured by Kyoeisha Chemical Co., Ltd.) [Chemical formula 75]

[Polymerization initiator (photopolymerization initiator)] ・C-1: Compound having the following structure ・C-2: Irgacure OXE-01 (manufactured by BASF) ・C-3: ADEKA NCI-930 (manufactured by ADEKA CORPORATION) [Chemical formula 76]

[Adhesive (Silane Coupling Agent)] ・D-1: Compound with the following structure ・D-2: N-[3-(Triethoxysilyl)propyl]butenylamine ・D-3: 3-Methacryloyloxypropyltrimethoxysilane [Chemical Formula 77]

[Polymerization inhibitor] ・E-1: Compound with the following structure ・E-2: 4-methoxyphenol ・E-3: 2-nitroso-1-naphthol [chemical formula 78]

[Migration inhibitor] ・F-1: Compound with the following structure ・F-2: 5-amino-1H-tetrazole ・F-3: 3-amino-1,2,4-triazole ・F-4: 3,5-diamino-1,2,4-triazole ・F-5: Adenine [chemical formula 79]

[Thermoalkali generator] ・G-1: Compound with the following structure ・G-2: Compound with the following structure ・G-3: Compound with the following structure [Chemical formula 80]

[Solvent] ・NMP: N-methyl-2-pyrrolidone ・DMSO: dimethyl sulfoxide ・EL: ethyl lactate ・GBL: gamma-butyrolactone ・Cyptn: cyclopentanone ・EA: 3-butoxy-N,N-dimethylpropionamide ・PGMEA: propylene glycol monomethyl ether acetate

<Evaluation> [Evaluation of film thickness uniformity of the composition just prepared] In each embodiment or comparative example, each hardening resin composition or comparative composition just prepared was applied (coated) in layers on a circular silicon wafer with a diameter of 8 inches by spin coating. The coated silicon wafer was dried on a heating plate at 100°C for 4 minutes, thereby forming a resin film with a thickness of 19μm on the silicon wafer. The film thickness was set as the arithmetic mean of the film thickness at 10 locations within the surface. In the resin film on the diameter of the silicon wafer, the film thickness of the resin film is measured at a total of 10 points at equal intervals including both ends of the resin film, and the difference between the maximum and minimum values of the measured values of the 10 points is set as the maximum film thickness difference (μm) in the plane. The film thickness uniformity of the composition just after preparation was evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Film Thickness Uniformity (Just After Preparation)" column of Tables 1 to 7. It can be said that the smaller the above-mentioned maximum film thickness difference (μm) in the plane, the better the film thickness uniformity of the resin film.

-Evaluation criteria- 10: The maximum film thickness difference (μm) within the above plane is 0.5μm or less. 9: The maximum film thickness difference (μm) within the above plane exceeds 0.5μm and is 0.6μm or less. 8: The maximum film thickness difference (μm) within the above plane exceeds 0.6μm and is 0.7μm or less. 7: The maximum film thickness difference (μm) within the above plane exceeds 0.7μm and is 0.8μm or less. 6: The maximum film thickness difference (μm) within the above plane exceeds 0.8μm and is 0.9μm or less. 5: The maximum film thickness difference (μm) within the above plane exceeds 0.9μm and is 1.0μm or less. 4: The maximum film thickness difference (μm) within the above plane exceeds 1.0μm and is 1.1μm or less. 3: The maximum film thickness difference (μm) in the above plane exceeds 1.1μm and is less than 1.2μm. 2: The maximum film thickness difference (μm) in the above plane exceeds 1.2μm and is less than 1.3μm. 1: The maximum film thickness difference (μm) in the above plane exceeds 1.3μm.

[Evaluation of film thickness uniformity of compositions prepared 6 months after preparation] In each embodiment or comparative example, each hardening resin composition or comparative composition just prepared was placed in a storage container and sealed, and stored at 7°C, light-shielded conditions and 23°C, light-shielded conditions were repeated every 24 hours for 6 months. The filling rate of the hardening resin composition was set to 90% relative to the total storage volume of the storage container. After the above storage, in each embodiment or comparative example, each curable resin composition or comparative composition was returned to room temperature (23°C), and then applied (coated) in layers on a circular silicon wafer with a diameter of 8 inches by spin coating, and dried on a hot plate at 100°C for 4 minutes to form a resin film. The coating conditions and the amount of the composition used in the spin coating method were set to be the same as the coating conditions and the amount of the composition in the spin coating method in the film thickness uniformity just after preparation. After that, the maximum film thickness difference (μm) within the surface was calculated in the same manner as the evaluation of the film thickness uniformity of the composition just after preparation, and the film thickness uniformity of the composition 6 months after preparation was evaluated by the same evaluation criteria as the evaluation of the film thickness uniformity of the composition just after preparation. The evaluation results are recorded in the "Film Thickness Uniformity (6 Months After Preparation)" column of Tables 1 to 7. It can be said that the smaller the maximum film thickness difference (μm) within the surface, the better the film thickness uniformity of the resin film.

[Resolution Evaluation of Compositions Just Prepared] In each embodiment or comparative example, a resin film was formed on a circular silicon wafer having a diameter of 8 inches by the same method as the above-mentioned evaluation of film thickness uniformity of compositions just prepared. Thereafter, the resin film was exposed through a mask including a fuse box with a scale of 5 μm to 25 μm and 1 μm. The above-mentioned exposure was performed using a stepper (Nikon NSR2005 i9C) and i-ray, and the exposure amount at a wavelength of 365 nm was 200 to 400 mJ/ ^cm2 , and when changing the exposure amount, the exposure amount that minimized the minimum line width described later was adopted. After the above exposure, the resin film was developed using cyclopentanone at 30°C as a developer and rinsed with PGMEA (propylene glycol monomethyl ether acetate). The pattern after the above rinse was observed by an optical microscope, and the arithmetic mean of the minimum line width exposed at the bottom of the fuse box of the silicon wafer in the line width of 5μm to 25μm with a scale of 1μm was set as the "minimum line width", and evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Resolution (just after preparation)" column of Tables 1 to 7. It can be said that the smaller the above minimum line width, the better the resolution (lithography). -Evaluation Criteria- 10: The above minimum line width is 7μm or less. 9: The above minimum line width exceeds 7μm and is less than 8μm. 8: The above minimum line width exceeds 8μm and is less than 9μm. 7: The above minimum line width exceeds 9μm and is less than 11μm. 6: The above minimum line width exceeds 11μm and is less than 13μm. 5: The above minimum line width exceeds 13μm and is less than 16μm. 4: The above minimum line width exceeds 16μm and is less than 19μm. 3: The above minimum line width exceeds 19μm and is less than 22μm. 2: The above minimum line width exceeds 22μm and is less than 24μm. 1: The above minimum line width exceeds 24μm.

[Evaluation of resolution based on the composition 6 months after preparation] In each embodiment or comparative example, each hardening resin composition or comparative composition just after preparation was stored for 6 months by the same method as described in the above “Evaluation of film thickness uniformity based on the composition 6 months after preparation”. After the above storage, each hardening resin composition or comparative composition in each embodiment or comparative example was returned to room temperature (23°C) and evaluated by the same evaluation method and evaluation criteria as described in the above “Evaluation of resolution based on the composition just after preparation”. The evaluation results are recorded in the “Resolution (6 months after preparation)” column of Tables 1 to 7.

[Evaluation of chemical resistance of the composition just prepared] In each embodiment or comparative example, a resin film was formed on a circular silicon wafer with a diameter of 8 inches by the same method as the evaluation of film thickness uniformity of the composition just prepared. The resin film on the silicon wafer was fully exposed at an exposure energy of 200mJ/ ^cm2 using a stepper (Nikon NSR 2005 i9C). In a nitrogen atmosphere, the resin film after the above-mentioned full-surface exposure was heated at a heating rate of 10°C/min and heated at 200°C for 120 minutes to obtain a cured film. The obtained cured film was immersed in the following chemical solution under the following evaluation conditions and evaluated. Chemical solution: set the temperature to 75℃ The following chemical solution composition was used: Dimethyl sulfoxide (DMSO) 70 mass% Tetramethylammonium hydroxide (TMAH) 2.5 mass% 3-methoxy-3-methyl-1-butanol 10 mass% Water The rest Evaluation conditions: The above cured film was immersed in the above chemical solution for 15 minutes, and after washing with water, the film thickness before and after immersion was compared, and the residual film rate (%) was calculated by the following formula. Residual film rate (%) = Film thickness of cured film after immersion (μm) / Film thickness of cured film before immersion (μm) × 100 Evaluation was performed according to the following evaluation criteria, and the evaluation results are recorded in the "Chemical resistance (immediately after preparation)" column of Tables 1 to 7. It can be said that the larger the above-mentioned residual film rate (%), the better the chemical resistance. -Evaluation criteria- 10: The above-mentioned residual film rate (%) is 90.0% or more. 9: The above-mentioned residual film rate (%) is 89.0% or more and less than 90.0%. 8: The above-mentioned residual film rate (%) is 88.0% or more and less than 89.0%. 7: The above-mentioned residual film rate (%) is 87.0% or more and less than 88.0%. 6: The above-mentioned residual film rate (%) is 86.0% or more and less than 87.0%. 5: The above-mentioned residual film rate (%) is 85.0% or more and less than 86.0%. 4: The above-mentioned residual film rate (%) is 84.0% or more and less than 85.0%. 3: The above-mentioned residual film rate (%) is 83.0% or more and less than 84.0%. 2: The above residual film rate (%) is 82.0% or more and less than 83.0%. 1: The above residual film rate (%) is less than 82.0%.

[Evaluation of chemical resistance based on the composition 6 months after preparation] In each embodiment or comparative example, each hardening resin composition or comparative composition just after preparation was stored for 6 months by the same method as described in the above “Evaluation of film thickness uniformity based on the composition 6 months after preparation”. After the above storage, each hardening resin composition or comparative composition in each embodiment or comparative example was returned to room temperature (23°C) and evaluated by the same method and evaluation criteria as described in the above “Evaluation of chemical resistance based on the composition just after preparation”. The evaluation results are recorded in the “Chemical resistance (6 months after preparation)” column of Tables 1 to 7.

[Comprehensive evaluation] In each embodiment or comparative example, the evaluation point was calculated by the following formula, and the comprehensive evaluation was performed according to the following evaluation criteria. The evaluation points are recorded in the "Comprehensive evaluation (6 months after preparation)" column of Tables 1 to 7. It can be said that the larger the evaluation point, the more suitable the solvent is for practical use. The above weighting is derived by considering the results of past insights on the items that affect the physical properties of the film when the permanent film is finally made in the same system. Evaluation point = (evaluation result based on the film thickness uniformity of the composition 6 months after preparation × 3 + evaluation result based on the resolution of the composition 6 months after preparation × 2 + evaluation result based on the chemical resistance of the composition 6 months after preparation) / 6

According to the above results, it can be seen that the film thickness uniformity of the resin film obtained according to the curable resin composition of the present invention is excellent even after 6 months of storage. The comparative composition of Comparative Example 1 contains only one solvent. It can be seen that the film thickness uniformity of the resin film obtained by the comparative composition of Comparative Example 1 after 6 months of storage is poor.

<Example 101> The curable resin composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by spin coating, and dried at 100°C for 4 minutes to form a 20μm thick curable resin composition layer, and then exposed using a stepper (Nikon Co., Ltd., NSR1505 i6). The exposure was performed at a wavelength of 365nm through a mask (a binary mask with a pattern of 1:1 line and space and a line width of 10μm). After exposure, it was heated at 100°C for 4 minutes. After the above heating, the layer pattern was obtained by developing with cyclohexanone for 2 minutes and rinsing with PGMEA for 30 seconds. Then, the temperature was raised to 200°C at a rate of 10°C/min in a nitrogen atmosphere, and then maintained at 200°C for 120 minutes to form an interlayer insulating film for the redistribution layer. The interlayer insulating film for the redistribution layer has excellent insulation properties. In addition, semiconductor components were manufactured using the interlayer insulating film for the redistribution layer, and normal operation was confirmed.

without.

without.

Claims (19)

A hardening resin composition comprises a material selected from the group consisting of polyimide, polyimide precursor, polybenzoic acid,

Azoles and polybenzo

At least one resin in the group of azole promotors and at least two solvents, wherein the solvent includes a compound having an ether bond and an amide bond in the structure. The hardening resin composition as described in claim 1, wherein the aforementioned solvent comprises dimethyl sulfoxide and ethyl lactate, the content of ethyl lactate is greater than 40% by mass relative to the total mass of the aforementioned solvent, and the content of γ-butyrolactone is less than 40% by mass relative to the total mass of the aforementioned solvent. A hardening resin composition comprises a material selected from the group consisting of polyimide, polyimide precursor, polybenzoic acid,

Azoles and polybenzo

At least one resin in the group of azole promotors and at least two solvents, wherein the solvent comprises any combination of N-methyl-2-pyrrolidone and cyclopentanone, N-methyl-2-pyrrolidone and ethyl lactate, or N-methyl-2-pyrrolidone and propylene glycol monomethyl ether acetate. The hardening resin composition as described in claim 3, wherein the aforementioned solvent comprises dimethyl sulfoxide and ethyl lactate, the content of ethyl lactate is greater than 40% by mass relative to the total mass of the aforementioned solvent, and the content of γ-butyrolactone is less than 40% by mass relative to the total mass of the aforementioned solvent. The hardening resin composition as described in claim 3, wherein the aforementioned solvent includes a solvent having an ether bond. The hardening resin composition as described in any one of claim 1 to claim 5 further comprises a ring selected from the group consisting of an imidazole ring, a triazole ring,

Azole, thiazole, pyrazole, iso

Azole ring, isothiazole ring, tetrazole ring, pyridine ring, tantalum

Ring, pyrimidine ring, pyridine

Ring, piperidine ring, piperidine

Ring and three

Migration inhibitors for compounds containing one or more heterocyclic rings and an amine group. The hardening resin composition as described in any one of claim 1 to claim 5 further comprises a migration inhibitor of at least one compound selected from the group consisting of 5-methylbenzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole and 5-amino-1H-tetrazole. A hardening resin composition as described in any one of claim 1 to claim 5, wherein the aforementioned solvent includes a solvent having a nitrogen-containing heterocyclic structure. A curable resin composition as described in any one of claim 1 to claim 5, wherein the content of the second most abundant solvent in the aforementioned solvent is 20% by mass or more relative to the total mass of the solvent. The curable resin composition as described in any one of claim 1 to claim 5 further comprises a silane coupling agent. The hardening resin composition as described in any one of claim 1 to claim 5 is used for at least one cold storage at -15~16℃ in a storage container, and the filling rate of the hardening resin composition during the cold storage is 50~90% relative to the total storage volume of the storage container. The curable resin composition as described in any one of claim 1 to claim 5 is used for forming an interlayer insulating film for a redistribution layer. A resin film, which is formed by applying the curable resin composition described in any one of claim 1 to claim 12 to a substrate. A cured film, which is formed by curing the curable resin composition described in any one of claim 1 to claim 12 or the resin film described in claim 13. A laminate comprising two or more layers of the hardened films described in claim 14, and comprising a metal layer between any of the aforementioned hardened films. A method for manufacturing a hardened film, comprising: a film forming step, wherein the hardening resin composition described in any one of claim 1 to claim 12 is applied to a substrate to form a film. The method for manufacturing a hardened film as described in claim 16 comprises: an exposure step of exposing the aforementioned film; and a development step of developing the aforementioned film. The method for manufacturing a hardened film as described in claim 16 includes: a heating step, which is to heat the aforementioned film at 50~450℃. A semiconductor component, comprising the hardened film described in claim 14.