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

Abstract

The present invention provides a curable resin composition, a resin film obtained by applying the curable resin composition to a substrate, a cured film obtained by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, and a semiconductor device comprising the cured film or the laminate. The curable resin composition contains at least one resin selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, and polybenzoxazole precursors, and at least two solvents.

Description

[0001] This application is a divisional application of the application number 202180012209.8 filed by the applicant and the invention name is "Curable resin composition, resin film, cured film, laminate, method for manufacturing cured film and semiconductor device". The filing date of the parent case of this application is February 2, 2021, and the earliest priority date is February 3, 2020. Technical Field

[0002] The present invention relates to a curable resin composition, a resin film, a cured film, a laminate, a method for producing a cured film, and a semiconductor device. Background Art

[0003] Polyimide or polybenzoxazole is suitable for various applications due to its excellent heat resistance and insulation properties. The above-mentioned applications are not particularly limited, and if an example is given of a semiconductor device for actual installation, the use as an insulating film or a sealing material or a protective film can be cited. In addition, it is also used as a base film or a cover film of a flexible substrate.

[0004] 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, a polyimide precursor, polybenzoxazole, and a polybenzoxazole precursor.

[0005] Such a curable resin composition is applied to a substrate by, for example, coating to form a resin film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured film on the substrate.

[0006] The polyimide precursor and the polybenzoxazole precursor are cyclized, for example, by heating, and become polyimide and polybenzoxazole, respectively, in a cured film.

[0007] Since the curable resin composition can be applied by a known coating method, it can be said that the adaptability in manufacturing is excellent, for example, the curable resin composition has a high degree of freedom in designing 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 industry is increasingly expected.

[0008] For example, Patent Document 1 describes a composition comprising: at least one of a polyimide precursor, a polyimide, a polybenzoxazole precursor and a polybenzoxazole resin, a crosslinking agent, a first solvent selected from alcohols, esters, ketones, ethers, sulfur-containing compounds, carbonates and ureas that dissolves more than 5% by mass of the above-mentioned resin at 25°C, and a second solvent having a solubility parameter distance of 3.0 to 11.0 from the above-mentioned first solvent.

[0009] Patent document 2 describes a resin composition comprising (a) a polyimide precursor or a polybenzoxazole precursor, and one or more polar solvents selected from 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 above resin composition is less than 0.1% by mass.

[0010] Previous technical literature

[0011] Patent Literature

[0012] Patent Document 1: International Publication No. 2017 / 038664

[0013] Patent Document 2: International Publication No. 2014 / 115233 Summary of the invention

[0014] Technical issues to be solved by the invention

[0015] It is desired to provide a curable resin composition that can produce a resin film having excellent uniformity in film thickness even after the curable resin composition is stored at low temperatures for a long period of time.

[0016] An object of the present invention is to provide a curable resin composition, wherein the resin film obtained by applying the curable resin composition to a substrate has excellent film thickness uniformity even when the curable resin composition is stored for a long period of time at a low temperature, a cured film obtained by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, and a semiconductor device comprising the cured film or the laminate.

[0017] Means for solving technical problems

[0018] Examples of representative embodiments of the present invention are shown below.

[0019] <1> A curable resin composition comprising:

[0020] At least one resin selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, and a polybenzoxazole precursor; and

[0021] At least two solvents.

[0022] <2> according to <1> The curable resin composition further comprises a migration inhibitor,

[0023] The migration inhibitor is a compound having one or more heterocyclic rings selected from imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring and triazine ring and an amino group.

[0024] <3> according to <1> or <2> The curable resin composition further comprises a migration inhibitor,

[0025] The migration inhibitor is at least one compound selected from 5-methylbenzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole and 5-amino-1H-tetrazole.

[0026] <4> according to <1> to <3> The curable resin composition according to any one of the preceding claims, wherein

[0027] The solvent contains dimethyl sulfoxide and ethyl lactate, the content of ethyl lactate is 40% by mass or more based on the total mass of the solvent, and the content of γ-butyrolactone is 40% by mass or less based on the total mass of the solvent.

[0028] <5> according to <1> to <4> The curable resin composition according to any one of the preceding claims, wherein

[0029] The above-mentioned solvent includes a solvent having a nitrogen-containing heterocyclic structure.

[0030] <6> according to <1> to <5> The curable resin composition according to any one of the preceding claims, wherein

[0031] The above-mentioned solvents include solvents having an ether bond.

[0032] <7> according to <1> to <6> The curable resin composition according to any one of the preceding claims, wherein

[0033] Among the above solvents, the content of the solvent having the second highest content is 20% by mass or more relative to the total mass of the solvents.

[0034] <8> according to <1> to <7> The curable resin composition described above further comprises a silane coupling agent.

[0035] <9> according to <1> to <8> The curable resin composition according to any one of the preceding claims, wherein

[0036] The curable resin composition is used for at least one cold storage at -15 to 16° C. in a storage container, and the filling rate of the curable resin composition during the cold storage is 50 to 90% relative to the total storage volume of the storage container.

[0037] <10> according to <1> to <9> The curable resin composition described in any one of the above is used for forming an interlayer insulating film for a redistribution layer.

[0038] <11> A resin film, which is <1> to <10> The curable resin composition described in any one of the above is applied to a substrate.

[0039] <12> A cured film, which is <1> to <10> The curable resin composition described in any one of the above <11> The resin film is solidified.

[0040] <13> A laminate comprising two or more layers <12> The cured film comprises a metal layer between any of the cured films.

[0041] <14> A method for manufacturing a cured film, comprising:

[0042] The film forming step <1> to <10> The curable resin composition described above is applied to a substrate to form a film.

[0043] <15> according to <14> The method for manufacturing the cured film comprises:

[0044] an exposure step of exposing the film to light and a development step of developing the film.

[0045] <16> according to <14> or <15> The method for manufacturing the cured film comprises:

[0046] The film is heated at 50 to 450°C.

[0047] <17> A semiconductor device comprising <12> The cured film or <13> The laminated body.

[0048] Effects of the Invention

[0049] According to the present invention, there are provided a curable resin composition, a resin film obtained by applying the curable resin composition to a substrate, a cured film obtained 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 curable resin composition has excellent film thickness uniformity even when stored for a long period of time at a low temperature. DETAILED DESCRIPTION

[0050] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described above.

[0051] In the present specification, a numerical range expressed using a symbol such as “to” means a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit, respectively.

[0052] In the present specification, the term "step" refers not only to an independent step but also to a step that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.

[0053] Regarding the marking of groups (atomic groups) in this specification, the marking not indicating substitution and unsubstituted includes both groups (atomic groups) without substitution and groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0054] In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams and other actinic rays or radiation.

[0055] 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)acryloyl” means both or either of “acryloyl” and “methacryloyl”.

[0056] In the present 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.

[0057] In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent. In addition, in this specification, the solid content concentration is the mass percentage of the other components excluding the solvent relative to the total mass of the composition.

[0058] In this specification, unless otherwise stated, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene conversion values ​​according to gel permeation chromatography (GPC determination). In this specification, weight average molecular weight (Mw) and number average molecular weight (Mn) can be obtained, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION), and using guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION) as a column. Unless otherwise stated, these molecular weights are measured using THF (tetrahydrofuran) as eluent. And, unless otherwise stated, the detection in GPC determination uses a wavelength 254nm detector of UV line (ultraviolet rays).

[0059] In this specification, when the positional relationship of each layer constituting the stack is recorded as "up" or "down", it is sufficient as long as there are other layers on the upper side or lower side of the layer that serves as the reference among the multiple layers of interest. That is, a third layer or a third element may be further inserted between the layer that serves as the reference and the above-mentioned other layers, and the layer that serves as the reference and the above-mentioned other layers do not need to be in contact. In addition, unless otherwise specified, the direction in which the layers are gradually stacked with respect to the substrate is referred to as "up", or, in the case of a photosensitive layer, the direction from the substrate toward the photosensitive layer is referred to as "up", and the opposite direction is referred to as "down". In addition, such setting of the up and down directions is for the convenience of explaining this specification, and in actual practice, the "up" direction in this specification may also be different from the vertically upward direction.

[0060] In this specification, unless otherwise stated, in a composition, as each component contained in the composition, two or more compounds corresponding to the component may be contained. And, unless otherwise stated, the content of each component in the composition represents the total content of all compounds corresponding to the component.

[0061] In this specification, unless otherwise specified, the temperature is 23° C., the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0062] In the present specification, a combination of preferred embodiments is a more preferred embodiment.

[0063] (Curable resin composition)

[0064] The curable resin composition of the present invention comprises at least one resin selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, and a polybenzoxazole precursor (hereinafter, also referred to as “specific resin”) and at least two solvents.

[0065] The curable resin composition of the present invention has excellent uniformity in film thickness of the obtained resin film even when stored at low temperature for a long period of time.

[0066] Through the research conducted by the present inventors, it is found that when a curable resin composition containing only one solvent is stored at a low temperature (for example, below 5°C, and further below -5°C, etc.) for a long period of time (for example, more than 6 months) and then applied to a substrate to form a resin film, the film thickness uniformity of the obtained resin film is poor.

[0067] Poor uniformity of the film thickness of the resin film means that, in the resin film, there is a large difference in film thickness between a thin portion and a thick portion.

[0068] Therefore, the present inventors have conducted intensive studies and have found that a curable resin composition containing two or more solvents can produce a resin film having excellent uniformity in film thickness even when the composition is stored for a long period of time.

[0069] The mechanism by which the above-mentioned effects can be obtained is not yet clear, but is presumed to be as follows.

[0070] 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 estimated that when a certain component in the composition precipitates, the concentration of other components locally increases and a certain reaction proceeds, or components such as polymerization inhibitors precipitate and polymerize, and some of the components contained in the composition may change.

[0071] In this way, in a composition in which a part of the components is changed, even if the precipitate is dissolved again by, for example, heating or stirring after storage, it is considered that the film thickness uniformity of the resin film is poor.

[0072] However, when the curable resin composition contains two or more solvents, even if a component has low solubility in one solvent contained in the composition, it may have excellent solubility in other solvents contained in the composition, thereby suppressing the above-mentioned precipitation.

[0073] 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.

[0074] Furthermore, it is speculated that when the curable resin composition contains two or more solvents, compared with the case where it contains only one solvent, 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, crosslinking groups in the crosslinking agent, etc. are suppressed, so that, for example, the resolution of the obtained resin film when it is subjected to development is also easily improved.

[0075] Furthermore, it is speculated 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 become nearly uniform, compared with the case where it contains only one solvent, especially when stored for a long time at low temperature, so that the chemical resistance of the obtained cured film is also likely to be improved.

[0076] Hereinafter, the components contained in the curable resin composition of the present invention will be described in detail.

[0077] <Solvent>

[0078] 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. As the organic solvent, compounds such as esters, ethers, ketones, hydrocarbons, sulfoxides, amides, and alcohols can be cited.

[0079] Preferred examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl 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-ethoxypropionate, etc.) ethyl 2-methoxypropionate, 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 acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

[0080] Among these, from the viewpoint of film thickness uniformity, the esters are preferably non-cyclic ester compounds. The non-cyclic ester compound refers to a compound that does not have a cyclic structure (ie, a lactone structure) including an ester structure in the molecule.

[0081] As the ethers, for example, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol 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 can be mentioned.

[0082] Preferred examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosan, and dihydrolevoglucosan.

[0083] Preferred examples of hydrocarbons include toluene, xylene, anisole, and limonene.

[0084] Among these, as hydrocarbons, aromatic hydrocarbons or terpenes are preferred.

[0085] As the sulfoxides, for example, dimethyl sulfoxide is preferably used.

[0086] As amides, preferably there are mentioned N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide and the like.

[0087] Among these, as the amides, a compound having a lactam structure or a compound having an ether bond and an amide bond in the structure is more preferable.

[0088] Furthermore, commercially available products may be used as the amides, and examples of the commercially available products include Equamide series manufactured by Idemitsu Kosan Co., Ltd. (for example, Equamide B-100 and Equamide M-100).

[0089] Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methyl phenylcarbinol, n-pentanol, methylpentanol and diacetone alcohol.

[0090] Preferred ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0091] Among these, from the viewpoint of film thickness uniformity, the curable resin composition of the present invention preferably contains at least two selected from esters, ethers, ketones, hydrocarbons, sulfoxides and amides, more preferably contains at least two selected from amides and sulfoxides, or contains at least one selected from amides and sulfoxides and at least one selected from esters, ethers, ethers and hydrocarbons, further preferably contains at least two selected from amides and sulfoxides, or contains at least one selected from amides and sulfoxides and at least one selected from ketones and esters, and particularly preferably contains sulfoxides and esters.

[0092] Furthermore, from the viewpoint of resolution (especially, the 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.

[0093] In the above embodiment, the content of the solvent corresponding to the amides is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, based on the total mass of the solvent.

[0094] In the above embodiment, the content of the solvent corresponding to ketones is preferably 20 to 90% by mass, more preferably 30 to 70% by mass, based on the total mass of the solvent.

[0095] 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 later 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.

[0096] In the above embodiment, the content of the solvent corresponding to the amides is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, based on the total mass of the solvent.

[0097] In the above embodiment, the content of the solvent corresponding to the sulfoxides is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, based on the total mass of the solvent.

[0098] 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 boiling point of 160° C. or higher at 1 atmosphere and at least one selected from solvents having a boiling point of less than 160° C. at 1 atmosphere.

[0099] Examples of the solvent having a boiling point of 160° C. or higher at 1 atmosphere include γ-butyrolactone (204° C.), dimethyl sulfoxide (189° C.), N-methyl-2-pyrrolidone (202° C.), and 3-butoxy-N,N-dimethylpropionamide (215° C.).

[0100] Examples of the solvent having a boiling point of less than 160° C. at 1 atmosphere include cyclopentanone (131° C.), ethyl lactate (154° C.), and propylene glycol monomethyl ether acetate (146° C.).

[0101] The temperature in the above brackets indicates the boiling point of each solvent at 1 atmosphere.

[0102] In the above embodiment, the content of the solvent having a boiling point of 160° C. or higher at 1 atmosphere is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, based on the total mass of the solvent.

[0103] 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, more preferably 30 to 70% by mass, based on the total mass of the solvent.

[0104] 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.

[0105] It is considered that the inclusion of a protic solvent in the curable resin composition of the present invention improves the uniformity of film thickness when the curable resin composition contains a compound having a salt structure such as an onium salt described later.

[0106] Examples of the aprotic solvent include γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, 3-butoxy-N,N-dimethylpropionamide, cyclopentanone, and propylene glycol monomethyl ether acetate.

[0107] Examples of the protic solvent include ethyl lactate and the like.

[0108] In the above embodiment, the content of the aprotic solvent is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more relative to the total mass of the solvent. The upper limit of the above content is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.

[0109] In the above embodiment, the content of the protic solvent is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more relative to the total mass of the solvent. The upper limit of the above 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.

[0110] Furthermore, 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.

[0111] 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.

[0112] In the above embodiment, the content of the solvent having a molecular weight of 90 or more is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, based on the total mass of the solvent.

[0113] In the above embodiment, the content of the solvent having a molecular weight of less than 90 is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, based on the total mass of the solvent.

[0114] Furthermore, from the viewpoint of film thickness uniformity, the curable resin composition of the present invention preferably 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.

[0115] Examples of the solvent having an SP value of 21.4 MPa or more include γ-butyrolactone (26.3 MPa), dimethyl sulfoxide (29.7 MPa), N-methyl-2-pyrrolidone (23.1 MPa), and 3-butoxy-N,N-dimethylpropionamide (21.5 MPa).

[0116] Examples of the solvent having an SP value of less than 21.4 MPa include cyclopentanone (21.3 MPa), ethyl lactate (20.5 MPa), and propylene glycol monomethyl ether acetate (23.1 MPa).

[0117] The temperature in the above brackets represents the SP value of each solvent.

[0118] 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, more preferably 30 to 70% by mass, based on the total mass of the solvent.

[0119] 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, more preferably 30 to 70% by mass, based on the total mass of the solvent.

[0120] Furthermore, from the viewpoint of film thickness uniformity, it is also preferable to use a solvent having an SP value higher than the SP value of the dissolved substance (for example, a specific resin described below) and a solvent having an SP value lower than the SP value of the dissolved substance.

[0121] Furthermore, from the viewpoint of film thickness uniformity, the difference in SP value between the solvent having the highest SP value and the solvent having the lowest SP value among the solvents contained in the curable resin composition of the present invention is preferably 0.2 to 11.5 MPa, more preferably 1.5 to 10.0 MPa.

[0122] According to such an embodiment, it is considered that the solubility of a plurality of dissolved substances contained in the curable resin composition can be improved, and thus the film thickness uniformity is likely to be excellent.

[0123] 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, CM Hansen (2007), Taylor and Francis Group, LLC (HSPiP Manual). Specifically, the SP value was calculated using the following formula using "Practical Hansen Solubility Parameters HSPiP Version 3" (software version 4.0.05).

[0124] (SP value) 2 =(δHd) 2 +(δHp) 2 +(δHh) 2

[0125] Hd: Dispersed contribution

[0126] Hp: Polar contribution

[0127] Hh: Hydrogen bond contribution

[0128] Among these, 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 following Group A and Group B and at least one solvent selected from the following Group C.

[0129] Group A: Dimethyl sulfoxide

[0130] Group B: N-methyl 2-pyrrolidone, 3-butoxy-N,N-dimethylpropionamide

[0131] Group C: gamma-butyrolactone, cyclopentanone, ethyl lactate, propylene glycol monomethyl ether acetate

[0132] Furthermore, the above group C is more preferably the following group C'.

[0133] Group C': Cyclopentanone, Ethyl lactate, Propylene glycol monomethyl ether acetate

[0134] Among these, one preferred embodiment of the curable resin composition of the present invention is an embodiment in which the solvent contains dimethyl sulfoxide and ethyl lactate, and the content of ethyl lactate is 40% by mass or more based on the total mass of the solvent.

[0135] The content of ethyl lactate is preferably 40 to 80% by mass, more preferably 45 to 60% by mass.

[0136] Furthermore, in the above embodiment, the content of γ-butyrolactone is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, particularly preferably 10% by mass or less, further preferably 5% by mass or less, and most preferably 1% by mass or less relative to the total mass of the solvent. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more.

[0137] Furthermore, in the above embodiment, the total content of dimethyl sulfoxide and ethyl lactate 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 relative to the total mass of the solvent. The upper limit of the above total content is not particularly limited and may be 100% by mass.

[0138] Furthermore, 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.

[0139] Examples of the solvent having a nitrogen atom in the structure include the above-mentioned amides.

[0140] As the solvent having a nitrogen-containing heterocyclic structure, the compound having a lactam structure is preferred, and N-methyl-2-pyrrolidone is more preferred.

[0141] The content of the solvent having a nitrogen atom in its structure is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and even more preferably 40 to 60% by mass, based on the total mass of the solvent.

[0142] Furthermore, the curable resin composition of the present invention also preferably contains a solvent having an ether bond as a solvent.

[0143] Examples of the solvent having an ether bond include compounds having an ether bond and an amide bond in the structure among the above-mentioned ethers or the above-mentioned amides.

[0144] The content of the solvent having an ether bond is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and even more preferably 40 to 60% by mass, based on the total mass of the solvent.

[0145] In addition, regarding the solvents 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 solvents. 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.

[0146] In the present invention, for example, when 40% by mass of N-methylpyrrolidone, 40% by mass of dimethyl sulfoxide, and 20% by mass of cyclopentanone are contained, the content of the second most abundant solvent is 40% by mass.

[0147] In the curable resin composition of the present invention, from the viewpoints of suppressing coating defects during coating, improving storage stability, etc., the content of water is preferably 5% by mass or less relative to the total mass of the solvent. The content of the above water is preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.1% by mass or less.

[0148] Furthermore, the water content may be 0% by mass.

[0149] From the viewpoint of coating properties, the total content of the solvent is preferably set to an amount in which the total solid content concentration of the curable resin composition of the present invention becomes 5 to 80% by mass, more preferably set to an amount in which the total solid content concentration of the curable resin composition of the present invention becomes 5 to 75% by mass, further preferably set to an amount in which the total solid content concentration of the curable resin composition of the present invention becomes 10 to 70% by mass, further preferably set to an amount in which the total solid content concentration of the curable resin composition of the present invention becomes 20 to 70% by mass, and further preferably set to an amount in which the total solid content concentration of the curable resin composition of the present invention becomes 40 to 70% by mass. The solvent content can be adjusted according to the desired thickness and coating method.

[0150] The curable resin composition of the present invention may contain only two solvents, or may contain three or more solvents.

[0151] <Specific resin>

[0152] The curable resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, and a polybenzoxazole precursor.

[0153] The curable resin composition of the present invention preferably contains a polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.

[0154] Furthermore, the specific resin preferably has a radical polymerizable group.

[0155] When the specific resin has a radical polymerizable group, the curable resin composition preferably contains the photo radical polymerization initiator described below as a photosensitizer, more preferably contains the photo radical polymerization initiator described below as a photosensitizer and contains a radical crosslinking agent described below, and further preferably contains the photo radical polymerization initiator described below as a photosensitizer, contains a radical crosslinking agent described below, and contains a sensitizer described below. Such a curable resin composition, for example, forms a negative photosensitive layer.

[0156] Furthermore, the specific resin may have a polarity conversion group such as an acid-decomposable group.

[0157] When the specific resin has an acid-decomposable group, the curable resin composition preferably contains a photoacid generator as 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.

[0158] 〔Polyimide precursor〕

[0159] The polyimide precursor used in the present invention is not particularly limited in its type and the like, but preferably contains a repeating unit represented by the following formula (2).

[0160] Formula (2)

[0161] [Chemical formula 1]

[0162]

[0163] In formula (2), A 1 and A 2 Each independently represents an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group.

[0164] A in formula (2) 1 and A 2 Each independently represents an oxygen atom or NH, preferably an oxygen atom.

[0165] R in formula (2) 111Represents a divalent organic group. As a divalent organic group, a group comprising a straight-chain or branched aliphatic group, a cyclic aliphatic group and an aromatic group can be exemplified, preferably a straight-chain 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 of these, and more preferably a group comprising an aromatic group 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. Among them, Ar is independently an aromatic group, and L is a group comprising an aliphatic hydrocarbon group having 1 to 10 carbon atoms that can be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2- or -NHCO- or a combination of two or more of the above. These preferred ranges are as described above.

[0166] R 111 It is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cycloaliphatic or aromatic diamines. The diamine may be used alone or in combination of two or more.

[0167] 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.

[0168] [Chemical formula 2]

[0169]

[0170] In the formula, A is preferably a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, -NHCO- or a combination of these, more preferably a single bond, a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S- or -SO2-, further preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2- or -C(CH3)2-.

[0171] In the formula, * indicates the bonding position with other structures.

[0172] The diamines include, specifically, at least one 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 sulfone, 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-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4 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, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane alkane, 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'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-Diaminoisopropylbenzene, 2,5-dimethyl-p-phenylenediamine, ethoxyguanidine, 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)biphenyl sulfone, 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'-hexafluorotriazine and 4,4'-diaminobiphenylene.

[0173] Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0174] 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.

[0175] From the viewpoint of the flexibility of the obtained organic film, R 111 Preferably, it is represented by -Ar-L-Ar-. Ar is independently an aromatic group, and L is a group including an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2- or -NHCO-, or a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- or -SO2-. The aliphatic hydrocarbon group here is preferably an alkylene group.

[0176] Furthermore, from the perspective of i-ray transmittance, R 111 Preferred are divalent organic groups represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, divalent organic groups represented by formula (61) are more preferred.

[0177] Formula (51)

[0178] [Chemical formula 3]

[0179]

[0180] In formula (51), R 50 ~R 57 are independently a hydrogen atom, a fluorine atom or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding position to a nitrogen atom in formula (2).

[0181] As R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0182] [Chemical formula 4]

[0183]

[0184] In formula (61), R 58 and R 59 are each independently a fluorine atom or a trifluoromethyl group.

[0185] Examples of the diamine compound that provides the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

[0186] In addition, the following diamines can also be preferably used.

[0187] [Chemical formula 5]

[0188]

[0189] R in formula (2) 115 The tetravalent organic group is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or (6).

[0190] In formula (5) or (6), * independently represents a bonding position to another structure.

[0191] [Chemical formula 6]

[0192]

[0193] In formula (5), R 112 It is preferably a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2- and -NHCO-, and a combination of these. It is more preferably a single bond, a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- and -SO2-. It is further preferably a divalent group selected from -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0194] Specifically, R 115 Examples thereof include a tetracarboxylic acid residue remaining after an anhydride group is removed from tetracarboxylic dianhydride. The tetracarboxylic dianhydride may be used alone or in combination of two or more.

[0195] Tetracarboxylic dianhydride is preferably represented by the following formula (0).

[0196] [Chemical formula 7]

[0197]

[0198] In formula (O), R 115 represents a tetravalent organic group. 115 The preferred range of R in formula (2) 115 The meanings are the same, and the preferred ranges are also the same.

[0199] 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'-diphenyl sulfone 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, and 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 alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms thereof.

[0200] Furthermore, as preferred examples, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can also be mentioned.

[0201] R is also preferred 111 and R 115 More specifically, as R 111 , for example, residues of bisaminophenol derivatives can be mentioned.

[0202] R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, preferably a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkyleneoxy group, more preferably a polyalkyleneoxy group. 113 and R 114At least one of the two includes a polymerizable group, and more preferably both include a polymerizable group. As a polymerizable group, a group that can undergo a crosslinking reaction by the action of heat, free radicals, etc. is preferably a free radical polymerizable group. As a specific example of a polymerizable group, a group with an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group, and an amino group can be cited. As a free radical polymerizable group possessed by a polyimide precursor, a group with an ethylenically unsaturated bond is preferably a group.

[0203] Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a group represented by the following formula (III). Among them, a group represented by the following formula (III) is preferred.

[0204] [Chemical formula 8]

[0205]

[0206] In formula (III), R 200 It represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and is preferably a hydrogen atom or a methyl group.

[0207] In formula (III), * indicates a bonding position with other structures.

[0208] In formula (III), R 201 It represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, or a polyalkyleneoxy group.

[0209] Preferred R 201 Examples include alkylene groups such as vinyl, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, -CH2CH(OH)CH2-, and polyalkyleneoxy groups. More preferred groups include vinyl, propylene, trimethylene, -CH2CH(OH)CH2-, and polyalkyleneoxy groups. Still more preferred groups include polyalkyleneoxy groups.

[0210] In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups included in the polyalkyleneoxy group may be the same or different.

[0211] When the polyalkyleneoxy group includes a plurality of alkyleneoxy groups of different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, an arrangement having an alternating pattern, or the like.

[0212] The number of carbon atoms of the alkylene group (including the carbon atoms of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, further preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.

[0213] Furthermore, the above-mentioned alkylene group may have a substituent, and preferred substituents include an alkyl group, an aryl group, a halogen atom, and the like.

[0214] Furthermore, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.

[0215] As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, preferably, a group consisting of a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups is used, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and further preferably a polyethyleneoxy group. In the group consisting of a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in alternating patterns. The preferred form of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

[0216] R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, 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 aryl group can be cited. Specifically, an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms can be cited. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be cited. The acidic group is preferably an OH group.

[0217] R 113 or R 114 More preferred are a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, and a 4-hydroxybenzyl group.

[0218] From the viewpoint of solubility in organic solvents, R 113 or R 114 The monovalent organic group is preferably a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.

[0219] The number of carbon atoms of the alkyl group is preferably 1 to 30. The alkyl group may be any of a straight chain, a branched chain, or a cyclic chain. Examples of the straight chain or branched chain alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group, a 2-ethylhexyl group, a 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy group, a 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy group, and a 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. As monocyclic cyclic alkyl, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl can be mentioned. As polycyclic cyclic alkyl, for example, adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphoryl, dicyclohexyl and pinacolyl can be mentioned. Among them, from the viewpoint of taking into account high sensitivity, cyclohexyl is most preferred. And, as the alkyl substituted with an aromatic group, a linear alkyl substituted with an aromatic group described later is preferred.

[0220] Specific examples of the aromatic group include a substituted or unsubstituted benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, a benzodiindene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a tetracene ring, Preferably, the ring is a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thiophene ring, a benzopyran ring, a xanthene ring, a phenoxathiol ring, a phenothiazine ring or a phenazine ring. The most preferred ring is a benzene ring.

[0221] In formula (2), R 113 In the case of a hydrogen atom or in R 114 When it is a hydrogen atom, the polyimide precursor can form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N,N-dimethylaminopropyl methacrylate.

[0222] R 113 and R 114At least one of the groups may be a polar conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes under the action of 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, etc. are preferred, and an acetal group is more preferred from the viewpoint of exposure sensitivity.

[0223] Specific examples of the acid-decomposable group include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, trimethylsilyl ether, etc. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0224] Furthermore, the polyimide precursor preferably has fluorine atoms in the structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and preferably 20% by mass or less.

[0225] Furthermore, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0226] 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 latitude can be further expanded.

[0227] Formula (2-A)

[0228] [Chemical formula 9]

[0229]

[0230] In formula (2-A), A 1 and A 2 represents oxygen atom, R 111 and R 112 Each independently represents a divalent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, R 113 and R 114 At least one of them is a group containing a polymerizable group, and preferably both of them are groups containing a polymerizable group.

[0231] A 1 , A 2 , R 111 , R 113 and R114 and A in formula (2) independently. 1 , A 2 , R 111 , R 113 and R 114 The meanings are the same, and the preferred ranges are also the same.

[0232] R 112 With R in formula (5) 112 The meanings are the same, and the preferred ranges are also the same.

[0233] The polyimide precursor may contain one or more repeating units represented by formula (2). Furthermore, it may contain structural isomers of the repeating units represented by formula (2). Furthermore, it is self-evident that the polyimide precursor may contain other types of repeating units in addition to the repeating units of the above formula (2).

[0234] As one embodiment of the polyimide precursor in the present invention, there can be exemplified 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).

[0235] 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. 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.

[0236] 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, preferably 4.5 or less, more preferably 4.0 or less, further preferably 3.8 or less, further preferably 3.2 or less, further preferably 3.1 or less, further preferably 3.0 or less, and particularly preferably 2.95 or less.

[0237] On the other hand, from the viewpoint of developability, 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. 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.

[0238] From the viewpoint of developability, 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. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly specified, but is preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0239] In this specification, the molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.

[0240] 〔Polyimide〕

[0241] The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer mainly composed of an organic solvent.

[0242] In this specification, the alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more in 100 g of a 2.38 mass % tetramethylammonium aqueous solution at 23° C., and preferably dissolves 0.5 g or more of the polyimide from the viewpoint of pattern formation, and more preferably dissolves 1.0 g or more of the polyimide. The upper limit of the above-mentioned dissolution amount is not particularly limited, but is preferably 100 g or less.

[0243] Furthermore, from the viewpoint of film strength and insulation properties of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.

[0244] In the present specification, the “main chain” refers to the longest bond chain in the molecule of the polymer compound constituting the resin, and the “side chain” refers to other bond chains.

[0245] -Fluorine atom-

[0246] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has fluorine atoms.

[0247] The fluorine atom is preferably contained in R in the repeating unit represented by the formula (4) described below. 132 or R in the repeating unit represented by the formula (4) described below 131 Among them, R contained in the repeating unit represented by the formula (4) described later as a fluorinated alkyl group is more preferably 132 or R in the repeating unit represented by the formula (4) described below 131 middle.

[0248] The amount of fluorine atoms is preferably 1 to 50 mol / g, more preferably 5 to 30 mol / g, based on the total mass of the polyimide.

[0249] -Silicon Atoms-

[0250] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has a silicon atom.

[0251] For example, the silicon atom is preferably contained in R in the repeating unit represented by the formula (4) described below. 131 Among them, R in the repeating unit represented by the formula (4) described below as an organo-modified (poly)siloxane structure described below is more preferably 131 middle.

[0252] Furthermore, the silicon atom or the organo-modified (poly)siloxane structure may be included in the side chain of the polyimide, but is preferably included in the main chain of the polyimide.

[0253] The amount of silicon atoms is preferably 0.01 to 5 mol / g, more preferably 0.05 to 1 mol / g, based on the total mass of the polyimide.

[0254] -Ethylenically unsaturated bond-

[0255] From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond.

[0256] The polyimide may have an ethylenically unsaturated bond at a main chain terminal or in a side chain, but preferably has an ethylenically unsaturated bond in a side chain.

[0257] The ethylenically unsaturated bond preferably has radical polymerizability.

[0258] The ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (4) described below. 132 or R in the repeating unit represented by the formula (4) described below 131 Among them, R contained in the repeating unit represented by the formula (4) described later as a group having an ethylenically unsaturated bond is more preferably 132 or R in the repeating unit represented by the formula (4) described below 131 middle.

[0259] Among these, the ethylenically unsaturated bond is preferably contained in R 131 Among them, R contained in the repeating unit represented by the formula (4) described later as a group having an ethylenically unsaturated bond is more preferably 131 middle.

[0260] Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, and a vinylphenyl group which may be substituted, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

[0261] [Chemical formula 10]

[0262]

[0263] In formula (IV), R 20 It represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and is preferably a hydrogen atom or a methyl group.

[0264] In formula (IV), R 21 It 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, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group consisting of a combination of two or more of these.

[0265] Among these, R 21 The group is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1).

[0266] [Chemical formula 11]

[0267]

[0268] In formula (R1) to formula (R3), L represents a single bond or an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these groups, X represents an oxygen atom or a sulfur atom, * represents a bonding position with other structures, and ● represents the bonding position with R in formula (III). 201 The bonding position of the bonded oxygen atom.

[0269] In formula (R1) to formula (R3), the preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the same as the above R 21 The preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms are the same.

[0270] In formula (R1), X is preferably an oxygen atom.

[0271] In formula (R1) to formula (R3), * has the same meaning as * in formula (IV), and preferred aspects are also the same.

[0272] The structure represented by formula (R1) can be obtained by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanateethyl methacrylate).

[0273] The structure represented by Formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate).

[0274] The structure represented by the formula (R3) can be obtained by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate).

[0275] In formula (IV), * represents a bonding position to other structures, and is preferably a bonding position to the main chain of the polyimide.

[0276] The amount of the ethylenically unsaturated bonds is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g, based on the total mass of the polyimide.

[0277] - Crosslinking groups other than ethylenically unsaturated bonds-

[0278] The polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.

[0279] Examples of the crosslinkable group other than the ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.

[0280] The crosslinkable group other than the ethylenically unsaturated bond is preferably contained in, for example, R 131 middle.

[0281] The amount of the crosslinkable groups other than the ethylenically unsaturated bonds is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g, based on the total mass of the polyimide.

[0282] -Polarity conversion group-

[0283] The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide and R in the above formula (2) 113 and R 114 The acid-decomposable groups described above are the same and the preferred embodiments are also the same.

[0284] -Acid value-

[0285] When the polyimide is subjected to alkali development, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more from the viewpoint of improving developability.

[0286] Furthermore, 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.

[0287] When the polyimide is subjected to development using a developer containing 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.

[0288] The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0289] Furthermore, as the acid group contained in the polyimide, 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, from the viewpoint of achieving both storage stability and developability.

[0290] pKa is a dissociation reaction in which hydrogen ions are released from an acid and its equilibrium constant Ka is expressed by its negative common logarithm pKa. In this specification, unless otherwise specified, pKa is a calculated value based on ACD / ChemSketch (registered trademark). In addition, the values ​​disclosed in "Revised 5th Edition of Chemical Handbook Basic Edition" compiled by the Chemical Society of Japan can be referred to.

[0291] Alternatively, when the acid group is a polyacid such as phosphoric acid, the pKa is the first dissociation constant.

[0292] As such an acid group, the polyimide preferably contains at least one selected from a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0293] -Phenolic hydroxyl group-

[0294] From the viewpoint of making the development speed with an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxyl group.

[0295] The polyimide may have a phenolic hydroxyl group at a main chain terminal or may have a phenolic hydroxyl group in a side chain.

[0296] The phenolic hydroxyl group is preferably contained in R in the repeating unit represented by the formula (4) described below. 132 or R in the repeating unit represented by the formula (4) described below 131 middle.

[0297] The amount of the phenolic hydroxyl group is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g, based on the total mass of the polyimide.

[0298] 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 contains a repeating unit represented by the following formula (4), and more preferably contains a repeating unit represented by the formula (4) and has a polymerizable group.

[0299] Formula (4)

[0300] [Chemical formula 12]

[0301]

[0302] In formula (4), R 131 represents a divalent organic group, R 132 It represents a tetravalent organic group.

[0303] In the case of having a polymerizable group, the polymerizable group may be located at R 131 and R 132 At least one of them may be located at the terminal of the polyimide as shown in the following formula (4-1) or formula (4-2).

[0304] Formula (4-1)

[0305] [Chemical formula 13]

[0306]

[0307] In formula (4-1), R 133 is a polymerizable group, and the other groups have the same meanings as in formula (4).

[0308] Formula (4-2)

[0309] [Chemical formula 14]

[0310]

[0311] R 134 and R 135 At least one of them is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups have the same meanings as in formula (4).

[0312] The polymerizable group has the same meaning as the polymerizable group described in the polymerizable group possessed by the above-mentioned polyimide precursor and the like.

[0313] R 131 The divalent organic group includes the following: 111 The same groups have the same preferred range.

[0314] And, as R 131, and the 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, R in the formula (2) of the polyimide precursor can be cited. 111 Example.

[0315] From the perspective of more effectively suppressing the warping during calcination, R 131 Preferably, the diamine residue has at least two alkylene glycol units in the main chain. More preferably, the diamine residue contains two or more ethylene glycol chains or propylene glycol chains or both in total in one molecule. Still more preferably, the diamine residue contains no aromatic ring.

[0316] 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), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, and 1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, but are not limited to these.

[0317] R 132 represents a tetravalent organic group. Examples of the tetravalent organic group include 115 The same groups have the same preferred range.

[0318] For example, as R 115 The four bonders of the exemplified tetravalent organic group are bonded to the four -C(=O)- moieties in the above formula (4) to form a condensed ring.

[0319] And, R 132 Examples thereof include tetracarboxylic acid residues remaining after the anhydride groups are removed from tetracarboxylic dianhydride. Specific examples thereof include R in the formula (2) of the polyimide precursor. 115 From the perspective of the strength of the organic film, R 132 An aromatic diamine residue having 1 to 4 aromatic rings is preferred.

[0320] R is also preferred 131 and R 132 More specifically, at least one of R 131As preferred examples, 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, the above (DA-1) to (DA-18) can be cited as R 132 As more preferred examples, the above-mentioned (DAA-1) to (DAA-5) can be mentioned.

[0321] Furthermore, the polyimide also preferably has fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more and preferably 20% by mass or less.

[0322] Furthermore, the polyimide may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0323] In addition, in order to improve the storage stability of the composition, it is preferred to seal the main chain end of the polyimide with a capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochloride compound, or a monoactive ester compound. Among these, a monoamine is more preferably used, and preferred compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy- -5-aminonaphthalene, 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.

[0324] -Imidization rate (ring closure rate)-

[0325] From the viewpoint of film strength and insulation properties of the obtained organic film, the imidization ratio (also referred to as "ring closure ratio") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0326] The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

[0327] The imidization ratio is measured, for example, by the following method.

[0328] The infrared absorption spectrum of polyimide was measured and the absorption peak at 1377 cm-1 derived from the imide structure was found. -1 Next, the polyimide was heat treated at 350°C for 1 hour, and then the infrared absorption spectrum was measured again to obtain the peak intensity P1 at 1377 cm -1 The imidization ratio of the polyimide can be determined from the following formula using the obtained peak intensities P1 and P2.

[0329] Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0330] Polyimides may all contain one R 131 or R 132 The repeating unit of the above formula (4) may also contain two or more different types of R 131 or R 132 The polyimide may contain other types of repeating units in addition to the repeating units of the above formula (4).

[0331] 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 condensing agent; a method of obtaining a polyimide precursor by a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, then chlorinating the remaining dicarboxylic acid, and reacting the diester with a diamine (a capping agent in which a part is substituted with a monoamine), and completely imidizing the diester using a known imidization reaction method; or a method of stopping the imidization reaction midway and introducing a part of the imide structure; and a method of introducing a part of the imide structure by mixing a completely imidized polymer and the polyimide precursor.

[0332] Examples of commercially available products of polyimide include Durimide (registered trademark) 284 (manufactured by FUJIFILM Co., Ltd.) and Mattimide 5218 (manufactured by HUNTSMAN).

[0333] The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and further 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, the weight average molecular weight is particularly preferably 20,000 or more. In addition, in the case of containing two or more polyimides, it is preferred that the weight average molecular weight of at least one polyimide is within the above range.

[0334] 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.

[0335] 〔Polybenzoxazole precursor〕

[0336] The structure and the like of the polybenzoxazole precursor used in the present invention are not particularly limited, but it is preferred that the polybenzoxazole precursor contains a repeating unit represented by the following formula (3).

[0337] Formula (3)

[0338] [Chemical formula 15]

[0339]

[0340] In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, R 123 and R 124 Each independently represents a hydrogen atom or a monovalent organic group.

[0341] In formula (3), R 123 and R 124 Respectively with R in formula (2) 113 The meanings of and the preferred ranges are the same. That is, at least one of them is preferably a polymerizable group.

[0342] 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. 121 A dicarboxylic acid residue is preferred. Only one type of the dicarboxylic acid residue may be used, or two or more types may be used.

[0343] As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferred, and a dicarboxylic acid residue containing an aromatic group is more preferred.

[0344] As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably a linear) aliphatic group is preferred, and a dicarboxylic acid containing a linear or branched (preferably a linear) aliphatic group and two -COOH groups is more preferred. The number of carbon atoms in the linear or branched (preferably a linear) 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 linear aliphatic group is preferably an alkylene group.

[0345] Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetrafluorohexane. Methyl 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, behenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid acid) and dicarboxylic acids represented by the following formula, etc.

[0346] [Chemical formula 16]

[0347]

[0348] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

[0349] 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.

[0350] [Chemical formula 17]

[0351]

[0352] In the formula, A represents a divalent group selected from -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2- and -C(CH3)2-, and * independently represents the bonding position to other structures.

[0353] Specific examples of the dicarboxylic acid containing an aromatic group include 4,4′-carbonyldibenzoic acid, 4,4′-dicarboxydiphenyl ether, and terephthalic acid.

[0354] In formula (3), R 122 represents a tetravalent organic group. As a tetravalent organic group, R 115 The meanings are the same, and the preferred ranges are also the same.

[0355] R 122 Also preferred are groups derived from bisaminophenol derivatives. Examples of groups derived from bisaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, 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-( 4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

[0356] Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferred.

[0357] [Chemical formula 18]

[0358]

[0359] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, -NHCO-, and * and # represent the bonding positions with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. 122 The structure represented by the above formula is also preferred. 122 In the case of the structure represented by the above formula, among the total of 4 * and #, it is preferred that any two of them are the same as R in formula (3). 122 The bonding position of the nitrogen atom to which it is bonded and the other two are the same as R in formula (3)122 The bonding position of the oxygen atom to which the two * are bonded is preferably the same as that of R in formula (3). 122 The bonding position of the oxygen atom to which the two # are bonded is the same as R in formula (3). 122 The bonding position of the nitrogen atom to which it is bonded, or the two * are the same as R in formula (3) 122 The bonding position of the nitrogen atom to which the two # are bonded is the same as R in formula (3). 122 The bonding position of the oxygen atom to which the two * are bonded is preferably the same as that of R in formula (3). 122 The bonding position of the oxygen atom to which the two # are bonded is the same as R in formula (3). 122 The bonding position of the bonded nitrogen atom.

[0360] [Chemical formula 19]

[0361]

[0362] 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, which may be the same or different. R3 is any one of a hydrogen atom, a straight-chain or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, which may be the same or different.

[0363] [Chemical formula 20]

[0364]

[0365] (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).)

[0366] In the above formula (As), having a substituent at the ortho position of the phenolic hydroxyl group, i.e., R3, is considered to bring the carbonyl carbon of the amide bond and the hydroxyl group closer together, which is particularly preferred from the viewpoint of further improving the effect of achieving a high cyclization rate during curing at low temperatures.

[0367] In the above formula (As), when R2 is an alkyl group and R3 is an alkyl group, it is preferable because high transparency to i-rays and a high cyclization rate can be maintained during curing at a low temperature.

[0368] Furthermore, 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 of R1 include a linear or branched alkyl group having 1 to 8 carbon atoms, wherein -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferred from the viewpoint of obtaining a well-balanced polybenzoxazole precursor having sufficient solubility in a solvent while maintaining high transparency to i-rays and a high cyclization rate when cured at low temperatures.

[0369] As a method for producing the bisaminophenol derivative represented by the above formula (As), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A-2013-256506, the contents of which are incorporated herein.

[0370] Specific examples of the structure of the bisaminophenol derivative represented by the formula (As) include structures described in paragraphs 0070 to 0080 of JP-A-2013-256506, and these contents are incorporated into the present specification. Of course, the structure is not limited to these.

[0371] In addition to the repeating unit of the above formula (3), the polybenzoxazole precursor may also contain other types of repeating units.

[0372] From the viewpoint of being able to suppress the occurrence of warping associated with ring closure, it is preferred that a diamine residue represented by the following formula (SL) is contained as another type of repeating unit.

[0373] [Chemical formula 21]

[0374]

[0375] In formula (SL), Z has structure a and structure b, and R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 2s is a hydrocarbon group having 1 to 10 carbon atoms, R 3s , R 4s , R 5s , R 6s At least one of them is an aromatic group, and the rest are 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 mole % of the Z part, structure a is 5 to 95 mole %, structure b is 95 to 5 mole %, and a+b is 100 mole %.

[0376] In formula (SL), preferred Z includes R in structure b. 5s and R 6sZ is a phenyl group. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be more effectively reduced, and both the effect of suppressing warpage and the effect of improving solvent solubility can be achieved.

[0377] When the diamine residue represented by the formula (SL) is included as another type of repeating unit, it is also preferred to further 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 in the formula (2): 115 Example.

[0378] For example, when a 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. 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.

[0379] 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, for example, 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.

[0380] 〔Polybenzoxazole〕

[0381] As polybenzoxazole, as long as it is a polymer compound having a benzoxazole ring, it is not particularly limited, but is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) and having a polymerizable group. As the above-mentioned polymerizable group, a free radical polymerizable group is preferred. In addition, it can also be a compound represented by the following formula (X) and having a polar conversion group such as an acid decomposable group.

[0382] [Chemical formula 22]

[0383]

[0384] In formula (X), R 133 represents a divalent organic group, R 134 It represents a tetravalent organic group.

[0385] In the case of having a polarity conversion group such as a polymerizable group or an acid-decomposable group, the polymerizable group or the acid-decomposable group may be located at R 133 and R 134 At least one of them may be located at the terminal of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2).

[0386] Formula (X-1)

[0387] [Chemical formula 23]

[0388]

[0389] In formula (X-1), R 135 and R 136 At least one of them is a polarity converting group such as a polymerizable group or an acid-decomposable group, and when it is not a polarity converting group such as a polymerizable group or an acid-decomposable group, it is an organic group, and the other groups have the same meanings as in formula (X).

[0390] Formula (X-2)

[0391] [Chemical formula 24]

[0392]

[0393] In formula (X-2), R 137 is a polarity 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).

[0394] 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 polymerizable group possessed by the above-mentioned polyimide precursor and the like.

[0395] 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 in the formula (3) of the polybenzoxazole precursor may be 121 And, its preferred example is the same as R 121 same.

[0396] R 134 represents a tetravalent organic group. Examples of the tetravalent organic group include R in the formula (3) of the polybenzoxazole precursor: 122 And, its preferred example is the same as R 122 same.

[0397] For example, as R 122 The four bonders of the exemplified tetravalent organic group are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. 134In the case of the following organic groups, the following structures are formed.

[0398] [Chemical formula 25]

[0399]

[0400] The oxazolidinylation rate of the polybenzoxazole is preferably 85% or more, more preferably 90% or more. The upper limit is not particularly limited, and may be 100%. When the oxazolidinylation rate is 85% or more, the film shrinkage caused by the ring closure generated during the oxazolidinylation by heating is reduced, thereby being able to more effectively suppress the occurrence of warping.

[0401] The polybenzoxazoles may all contain one R 131 or R 132 The repeating unit of the above formula (X) may also contain two or more different types of R 131 or R 132 In addition to the repeating unit of the above formula (X), the polybenzoxazole may also contain other types of repeating units.

[0402] Regarding polybenzoxazole, for example, by reacting a bisaminophenol derivative with a poly(vinyl alcohol) containing R 133 The polybenzoxazole precursor is obtained by reacting a dicarboxylic acid or a compound selected from dicarboxylic acid dichloride and dicarboxylic acid derivatives of the above dicarboxylic acids, and then oxazolidinylating the oxazolidinylating agent by a known oxazolidinylating reaction method.

[0403] In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to improve the reaction yield.

[0404] The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and further 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, the weight average molecular weight is particularly preferably 20,000 or more. In addition, in the case of containing two or more polybenzoxazoles, it is preferred that the weight average molecular weight of at least one polybenzoxazole is within the above range.

[0405] [Method for producing polyimide precursor, etc.]

[0406] The polyimide precursor is obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with diamine, and is preferably obtained by halogenating dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting with diamine.

[0407] In the method for producing a polyimide precursor, etc., it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one kind or two or more kinds.

[0408] The organic solvent can be appropriately specified depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

[0409] The polyimide can be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (for example, by promoting a cyclization reaction by causing a catalyst to act), or the polyimide can be directly synthesized.

[0410] Furthermore, it is also preferred to synthesize using a non-halogen catalyst 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.

[0411] -Capping agent-

[0412] In the method for producing a polyimide precursor, in order to further improve storage stability, it is preferred to seal the ends of the polyimide precursor with an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monochloride compound, or a monoactive ester compound. As the end-capping agent, monohydric alcohols, phenols, thiols, thiophenols, or monoamines are more preferably used.

[0413] Preferred monohydric alcohols include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, and 1-methoxy-2-propanol, and tertiary alcohols such as tert-butyl alcohol and adamantane alcohol. Preferred phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, and naphthalene-2-ol.

[0414] Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 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.

[0415] Furthermore, when sealing the amino group at the end of the resin, it is possible to seal with a compound having a functional group that can react with the amino group. Preferred sealants for amino groups are preferably carboxylic anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic anhydride, etc., more preferably carboxylic anhydride, carboxylic acid chloride. As preferred compounds of carboxylic anhydride, acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, etc. can be cited. Furthermore, as preferred compounds of carboxylic acid chlorides, acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, etc. can be cited.

[0416] -Solid Precipitation-

[0417] When producing a polyimide precursor, etc., a step of precipitating a solid may be included. Specifically, the polyimide precursor, etc. in the reaction solution is precipitated in water and dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor, etc. is soluble, thereby precipitating a solid.

[0418] Then, the polyimide precursor etc. are dried to obtain a powdery polyimide precursor etc.

[0419] 〔content〕

[0420] The content of the specific resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 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, more preferably 99% by mass or less, further preferably 98% by mass or less, further preferably 97% by mass or less, and further preferably 95% by mass or less, relative to the total solid content of the composition.

[0421] The composition of the present invention may contain only one specific resin or two or more specific resins. When containing two or more specific resins, the total amount is preferably within the above range.

[0422] <Other resins>

[0423] The composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also simply referred to as "other resins").

[0424] Examples of other resins include polyamideimide, polyamideimide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, and acrylic resins.

[0425] For example, by further adding an acrylic resin, a composition having excellent coating properties can be obtained, and an organic film having excellent solvent resistance can be obtained.

[0426] 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.

[0427] When the composition of the present invention contains other resins, the content of other resins is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, further preferably 1 mass % or more, further preferably 2 mass % or more, further preferably 5 mass % or more, and further preferably 10 mass % or more, relative to the total solid content of the composition.

[0428] Furthermore, the content of other resins in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and further preferably 50% by mass or less, relative to the total solid content of the composition.

[0429] Furthermore, 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 is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less relative to the total solid content of the composition. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more.

[0430] The composition of the present invention may contain only one type of other resin or may contain two or more types. When containing two or more types, it is preferred that the total amount is within the above range.

[0431] <Photosensitizer>

[0432] The compositions of the present invention preferably comprise a photosensitizer.

[0433] As the photosensitizer, a photopolymerization initiator is preferred.

[0434] 〔Photopolymerization initiator〕

[0435] The composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer.

[0436] 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 having photosensitivity to light in the ultraviolet region to the visible region is preferred. In addition, it can also be an activator that generates active free radicals by reacting with a photoexcited sensitizer.

[0437] Furthermore, as the photoradical polymerization initiator, an oxime compound described later is preferred.

[0438] The photo-radical polymerization initiator preferably contains at least one photopolymerization initiator having a wavelength of at least about 50 L / mol in the range of about 300 to 800 nm (preferably 330 to 500 nm). -1 / cm -1 The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferably measured by an ultraviolet visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.

[0439] As a photo-radical polymerization initiator, known compounds can be used arbitrarily. For example, halogenated hydrocarbon derivatives (for example, compounds with triazine skeletons, compounds with oxadiazole skeletons, compounds with trihalomethyl groups, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azides, metallocene compounds, organic boron compounds, iron aromatic complexes, etc. can be cited. For details of these, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, and the content is incorporated into this specification.

[0440] 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.

[0441] In one embodiment of the present invention, as the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can be preferably used. 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.

[0442] 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 Corporation) can be used.

[0443] 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.

[0444] As the aminoacetophenone-based initiator, compounds described in Japanese Patent Application Laid-Open No. 2009-191179, which have an absorption maximum wavelength that matches a light source having a wavelength of 365 nm or 405 nm, can also be used.

[0445] Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. Commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF Corporation) can also be used.

[0446] Examples of the metallocene compound include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF).

[0447] As the photoradical polymerization initiator, an oxime compound can be more preferably used. By using an oxime compound, the exposure latitude can be more effectively improved. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.

[0448] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, and compounds described in JP-A-2006-342166.

[0449] Preferred oxime compounds include, for example, compounds of the following structures or 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-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 a photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of >C=NOC(=O)- in the molecule.

[0450] Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE03, IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in JP-A-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.

[0451] Oxime compounds of the following structures can also be used.

[0452] [Chemical formula 26]

[0453]

[0454] In addition, oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of JP-A-2014-500852, and compound (C-3) described in paragraph 0101 of JP-A-2013-164471.

[0455] As the most preferred oxime compound, there can be mentioned an oxime compound having a specific substituent as disclosed in JP-A-2007-269779 or an oxime compound having a thioaryl group as disclosed in JP-A-2009-191061.

[0456] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably selected from trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-ben-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0457] Further preferred photoradical polymerization initiators are trihalomethyl triazine 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. Further preferred are at least one compound selected from trihalomethyl triazine compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds. Further preferred are metallocene compounds or oxime compounds, and further preferred are oxime compounds.

[0458] In addition, the photoradical polymerization initiator may also be benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone) and other N,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1 and other aromatic ketones, quinones condensed with aromatic rings such as alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin, benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, compounds represented by the following formula (I) may also be used.

[0459] [Chemical formula 27]

[0460]

[0461] 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 the following: R I01 is a group represented by formula (II) or is I00 The same group, R I02 ~R I04 Each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0462] [Chemical formula 28]

[0463]

[0464] In the formula, R I05 ~R I07 R of the above formula (I) I02 ~R I04 same.

[0465] Furthermore, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used.

[0466] When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and further preferably 1.0 to 10% by mass relative to the total solid content of the composition of the present invention. The photopolymerization initiator may contain only one or more than one. When containing two or more photopolymerization initiators, the total amount is preferably within the above range.

[0467] 〔Photoacid generator〕

[0468] Furthermore, the composition of the present invention also preferably contains a photoacid generator as a photosensitizer.

[0469] By containing a photoacid generator, for example, an acid is generated in an exposed portion of the composition layer, so that the solubility of the exposed portion in a developer (eg, an alkaline aqueous solution) increases, and a positive pattern in which the exposed portion is removed by the developer can be obtained.

[0470] Furthermore, the composition may contain a photoacid generator and a polymerizable compound other than a radical polymerizable compound described later, and the crosslinking reaction of the polymerizable compound may be promoted by utilizing the acid generated in the exposed portion, so that the exposed portion is less likely to be removed by a developer than the non-exposed portion. According to such a mode, a negative pattern may be obtained.

[0471] The photoacid generator is not particularly limited as long as it generates acid by exposure, and examples thereof include onium salt compounds such as quinonediazide, diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts; sulfonate compounds such as imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzylsulfonate.

[0472] Examples of the quinonediazide include a compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound via an ester bond, a compound in which a sulfonic acid of quinonediazide is bonded to a polyamino compound via a sulfonamide bond, and a compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxypolyamino compound via at least one of an ester bond and a sulfonamide bond. In the present invention, for example, it is preferred that 50 mol% or more of the total functional groups of these polyhydroxy compounds or polyamino compounds are substituted with quinonediazide groups.

[0473] In the present invention, the quinone diazide can preferably use any one of 5-naphthoquinone diazide sulfonyl and 4-naphthoquinone diazide sulfonyl. The 4-naphthoquinone diazide sulfonyl ester compound has absorption in the i-ray region of the mercury lamp and is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazide sulfonyl ester compound extends to the g-ray region of the mercury lamp and is suitable for g-ray exposure. In the present invention, it is preferred to select a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound according to the exposure wavelength. In addition, a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, and a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may also be contained.

[0474] The naphthoquinone diazide 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 these naphthoquinone diazides, the resolution, sensitivity, and residual film rate can be further improved.

[0475] Examples of the naphthoquinone diazide include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds thereof.

[0476] The photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as an "oxime sulfonate compound").

[0477] The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably 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).

[0478] [Chemical formula 29]

[0479]

[0480] In formula (OS-1), X 3 represents an alkyl group, an alkoxy group or a halogen atom. 3 In the case of , they may be the same or different. 3 The alkyl group and the alkoxy group in the above-mentioned X may have a substituent. 3 The alkyl group in is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. 3 The alkoxy group in the above-mentioned X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. 3 The halogen atom in the formula (I) is preferably a chlorine atom or a fluorine atom.

[0481] In formula (OS-1), m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or 3, a plurality of X 3 Can be the same or different.

[0482] In formula (OS-1), R 34 W represents an alkyl group or an aryl group, and is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an 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.

[0483] In formula (OS-1), m3 is preferably 3, X 3 Methyl, X 3 The substitution position is ortho, R 34 A compound which is a straight-chain alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorbornylmethyl or p-tolyl group.

[0484] 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.

[0485] [Chemical formula 30]

[0486]

[0487] In formula (OS-103) to formula (OS-105), R s1 represents an alkyl group, an aryl group or a heteroaryl group, and sometimes there are multiple R s2 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and a plurality of R may exist. s6 Each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer of 0-6.

[0488] In formula (OS-103) to formula (OS-105), R s1 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 may have a substituent T.

[0489] In formula (OS-103) to formula (OS-105), R s2 Preferably, it is 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 more preferably a hydrogen atom or an alkyl group. s2 Among them, preferably 1 or 2 are alkyl groups, aryl groups or halogen atoms, more preferably 1 is alkyl groups, aryl groups or halogen atoms, and particularly preferably 1 is alkyl groups and the rest are hydrogen atoms. s2 The alkyl group or aryl group represented may have a substituent T.

[0490] In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, and is preferably 0. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

[0491] In formula (OS-103) to formula (OS-105), ns represents 1 or 2. When Xs is 0, ns is preferably 1, and when Xs is S, ns is preferably 2.

[0492] In formula (OS-103) to formula (OS-105), R s6 The alkyl group (preferably having 1 to 30 carbon atoms) and alkoxy group (preferably having 1 to 30 carbon atoms) represented by the above-mentioned group may have a substituent.

[0493] 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.

[0494] 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).

[0495] [Chemical formula 31]

[0496]

[0497] 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, and Rt9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R t2 represents a hydrogen atom or a methyl group.

[0498] In formula (OS-106) to formula (OS-111), R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

[0499] In formula (OS-106) to formula (OS-111), R t8 It represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, and is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0500] In formula (OS-106) to formula (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.

[0501] R t2 It represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

[0502] Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z) of the oxime may be any one or a mixture.

[0503] Specific examples of the oxime sulfonate compounds represented by the formula (OS-103) to (OS-105) include compounds described in paragraphs 0088 to 0095 of JP-A-2011-209692 and paragraphs 0168 to 0194 of JP-A-2015-194674, and these contents are incorporated into the present specification.

[0504] As another preferred embodiment of the oxime sulfonate compound containing at least one oxime sulfonate group, compounds represented by the following formula (0S-101) and formula (0S-102) can be mentioned.

[0505] [Chemical formula 32]

[0506]

[0507] In formula (OS-101) or formula (OS-102), R u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group or a heteroaryl group. u9 In the embodiment where R is cyano or aryl, it is further preferred that u9 The phenyl group is cyano, phenyl or naphthyl.

[0508] In formula (OS-101) or formula (OS-102), R u2a represents an alkyl group or an aryl group.

[0509] In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, or -NR u5 -、-CH2-、-CR u6 H- or CR u6 R u7 -, R u5 ~R u7 Each independently represents an alkyl group or an aryl group.

[0510] In formula (OS-101) or formula (OS-102), R u1 ~R u4 R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfone group, a cyano group or an aryl group. u1 ~R u4 In this case, the ring can be condensed to form a condensed ring with the benzene ring. u1 ~R u4 , preferably a hydrogen atom, a halogen atom or an alkyl group, and also preferably R u1 ~R u4 At least two of them are bonded to each other to form an aromatic group. Among them, R u1 ~R u4 All of the above substituents may further have a substituent.

[0511] The compound represented by the above formula (OS-101) is more preferably a compound represented by formula (OS-102).

[0512] Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring may be any one or a mixture thereof.

[0513] Specific examples of the compound represented by formula (0S-101) include compounds described in paragraphs 0102 to 0106 of JP-A-2011-209692 and paragraphs 0195 to 0207 of JP-A-2015-194674, and the contents thereof are incorporated into the present specification.

[0514] Among the above compounds, the following b-9, b-16, b-31 and b-33 are preferred.

[0515] [Chemical formula 33]

[0516]

[0517] Examples of the onium salt compound or the sulfonate compound include compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.

[0518] In addition, commercial products can also be used as photoacid generators. Examples of commercial 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 BV), Irgacure 250, Irgacure 270, and Irgacure 290 (all manufactured by BASF), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

[0519] Furthermore, as preferred examples, there can be mentioned compounds represented by the following structural formulas.

[0520] [Chemical formula 34]

[0521]

[0522] As the photoacid generator, an organic halide can also be used. Specifically, Wakabayashi et al. "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-36281, Japanese Patent Publication No. 55-32070, Japanese Patent Publication No. 60-239736, Japanese Patent Publication No. 61-169835, Japanese Patent Publication No. 61-169837, Japanese Patent Publication No. 62-58241, Japanese Patent Publication No. 62-212401, Japanese Patent Publication No. 63-70243, Japanese Patent Publication No. 63-298339, MP Hutt "Jurnal of Heterocyclic The compounds described in "Chemistry" 1 (No. 3), (1970) and the like, in particular, include trihalomethyl-substituted oxazole compounds: S-triazine compounds.

[0523] More preferably, there can be mentioned s-triazine derivatives in which at least one mono-, di- or tri-halogen-substituted methyl group is bonded to the s-triazine ring, and specifically, for example, there can be mentioned 2,4,6-tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)- s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-isopropoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-naphthyloxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 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 and the like.

[0524] 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 sulfonium complexes or organic boron oxysulfonium complexes described in Japanese Patent Laid-Open No. 6-175554, Japanese Patent Laid-Open No. 6-175553 The organoboron iodine complex described in JP-A-9-188710, the organoboron phosphine 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.

[0525] As the photoacid generator, a disulfone compound can also be used. Examples of the disulfone compound include compounds described in Japanese Patent Application Laid-Open No. 61-166544, Japanese Patent Application No. 2001-132318, and diazodisulfone compounds.

[0526] Examples of the onium salt compound include diazonium salts described in S. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), and T. S. Balet al, Polymer, 21, 423 (1980), ammonium salts described in U.S. Pat. No. 4,069,055, Japanese Patent Application Laid-Open No. 4-365049, etc., phosphonium salts described in U.S. Pat. No. 4,069,055, and U.S. Pat. No. 4,069,056, European Patent No. 104,143, U.S. Pat. No. 339,049, and U.S. Pat. No. 410,201, Japanese Patent Application Laid-Open No. 2-150848, and Japanese Patent Application Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 390 , 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, JV Crivello et al, Macromolecules, 10(6), 1307 (1977), selenium salts described in JV Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), arsenic salts and onium salts such as pyridinium salts described in CS Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and the like.

[0527] Examples of the onium salt include onium salts represented by the following general formulae (RI-I) to (RI-III).

[0528] [Chemical formula 35]

[0529]

[0530] In formula (RI-I), Ar 11Z represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and 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. 11 - represents a monovalent anion, which is a halide ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion. From the perspective of stability, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, or a sulfinate ion is preferred. 21 ,Ar 22 Each independently represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and 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. 21 - represents a monovalent anion, which is a halide ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion. In view of stability and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, or a carboxylate ion is preferred. In formula (RI-III), R 31 , R 32 , R 33Each independently represents 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. Preferably, an aryl group is preferred in terms of reactivity and stability. 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 - The monovalent anion is a halide ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion. From the perspective of stability and reactivity, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion is preferred.

[0531] As specific examples, the following can be cited.

[0532] [Chemical formula 36]

[0533]

[0534] [Chemical formula 37]

[0535]

[0536] [Chemical formula 38]

[0537]

[0538] [Chemical formula 39]

[0539]

[0540] When a photoacid generator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 2 to 15% by 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 photoacid generators are contained, the total amount thereof is preferably within the above range.

[0541] <Thermal Polymerization Initiator>

[0542] 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 thermal energy to initiate or promote the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, a polymerization reaction of the resin and the polymerizable compound can also be carried out in the heating step described later, so that the solvent resistance can be further improved.

[0543] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

[0544] When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 5 to 15% by mass relative to the total solid content of the composition of the present invention. The thermal polymerization initiator may contain only one or more than one. When containing two or more thermal polymerization initiators, the total amount is preferably within the above range.

[0545] <Thermal Acid Generator>

[0546] The compositions of the present invention may contain a thermal acid generator.

[0547] The thermal acid generator has an effect of promoting a crosslinking reaction of at least one compound selected from the group consisting of compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound by generating an acid upon heating.

[0548] The thermal decomposition starting temperature of the thermal acid generator is preferably 50° C. to 270° C., more preferably 50° C. to 250° C. Furthermore, it is preferred that a substance which does not generate acid when the composition is applied to a substrate and then dried (pre-baking: about 70 to 140° C.) but generates acid when finally heated (curing: about 100 to 400° C.) after patterning in subsequent exposure and development is selected as the thermal acid generator, because a decrease in sensitivity during development can be suppressed, which is preferred.

[0549] The thermal decomposition starting temperature was determined as the peak temperature of the lowest exothermic peak when the thermal acid generator was heated to 500° C. at 5° C. / min in a pressure-resistant capsule.

[0550] As an instrument used when measuring the thermal decomposition starting temperature, Q2000 (produced by TA Instruments) and the like can be mentioned.

[0551] The acid generated from the thermal acid generator is preferably a strong acid, for example, arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or halogenated alkylsulfonic acids such as trifluoromethanesulfonic acid, etc. Examples of such thermal acid generators include those described in paragraph 0055 of JP-A-2013-072935.

[0552] Among them, from the viewpoint of less residue in the organic film and less deterioration of the physical properties of the organic film, a thermal acid generator that generates an alkylsulfonic acid having 1 to 4 carbon atoms or a halogenated alkylsulfonic acid having 1 to 4 carbon atoms is more preferred. As the thermal acid generator, (4-hydroxyphenyl)dimethylsulfonium methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium methanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium methanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium methanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium methanesulfonate, trifluoromethanesulfonate are preferred. trifluoromethanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium trifluoromethanesulfonate, 3-(5-((propylsulfonyl)oxy)imino)thiophen-2(5H)-ylidene)-2-(o-tolyl)propionitrile, and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

[0553] Furthermore, the compounds described in paragraph 0059 of JP-A-2013-167742 are also preferred as the thermal acid generator.

[0554] The content of the thermal acid generator is preferably 0.01 parts by mass or more, 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 cross-linking reaction is promoted, so the mechanical properties and solvent resistance of the organic film can be further improved. In addition, from the viewpoint of the electrical insulation of the organic film, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less.

[0555] <Onium salt>

[0556] The curable resin composition of the present invention may further contain an onium salt.

[0557] 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 preferred to contain an onium salt.

[0558] The type of the onium salt is not particularly limited, but preferably, an ammonium salt, an iminium salt, a sulfonium salt, an iodonium salt or a phosphonium salt is used.

[0559] Among these, ammonium salts or iminium salts are preferred from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts or phosphonium salts are preferred from the viewpoint of compatibility with the polymer.

[0560] Furthermore, the onium salt is a salt of a cation having an onium structure and an anion, and the cation and the anion may or may not be bonded via a covalent bond.

[0561] That is, the onium salt may be an intramolecular salt having a cationic part and an anionic part in the same molecular structure, or an intermolecular salt formed by ionic bonding of cationic molecules and anionic molecules of different molecules, but is preferably an intermolecular salt. Furthermore, in the curable resin composition of the present invention, the cationic part or cationic molecule and the anionic part or anionic molecule may be bonded by ionic bonding or may be dissociated.

[0562] The cation in the onium salt is preferably an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation, and more preferably at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation.

[0563] The onium salt used in the present invention may be a thermal base generator described below.

[0564] The thermal base generator is a compound that generates a base when heated, and examples thereof include compounds that generate a base when heated to 40° C. or higher.

[0565] 〔Ammonium salt〕

[0566] In the present invention, the ammonium salt means a salt of an ammonium cation and an anion.

[0567] -Ammonium cation-

[0568] As the ammonium cation, a quaternary ammonium cation is preferred.

[0569] Furthermore, as the ammonium cation, a cation represented by the following formula (101) is preferred.

[0570] [Chemical formula 40]

[0571]

[0572] In formula (101), R 1 ~R 4 Each independently represents a hydrogen atom or a hydrocarbon group, R 1 ~R 4 At least two of them may be bonded to form a ring.

[0573] In formula (101), R 1 ~R 4Each of R is independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and still more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. 1 ~R 4 It 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.

[0574] In R 1 ~R 4 When at least two of the above are bonded to form a ring, the above ring may contain a hetero atom. Examples of the above hetero atom include a nitrogen atom.

[0575] The ammonium cation is preferably represented by any one of the following formulas (Y1-1) and (Y1-2).

[0576] [Chemical formula 41]

[0577]

[0578] In formula (Y1-1) and (Y1-2), R 101 represents an n-valent organic group, R 1 With R in formula (101) 1 The meaning is the same as Ar 101 and Ar 102 Each independently represents an aryl group, and n represents an integer of 1 or greater.

[0579] In formula (Y1-1), R 101 It is preferably a group formed by removing n hydrogen atoms from an aliphatic hydrocarbon, an aromatic hydrocarbon, or a structure formed by bonding these hydrocarbons, 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.

[0580] In formula (Y1-1), n ​​is preferably 1 to 4, more preferably 1 or 2, and further preferably 1.

[0581] In formula (Y1-2), Ar 101 and Ar 102 Each independently is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

[0582] -Anions-

[0583] The anion in the ammonium salt is preferably one selected from carboxylic acid anions, phenolic anions, phosphate anions and sulfate anions, and carboxylic acid anions are more preferred for the sake of both salt stability and thermal decomposition. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.

[0584] The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this embodiment, the stability, curability and developability of the curable resin composition can be further improved. In particular, by using an anion of a divalent carboxylic acid, the stability, curability and developability of the curable resin composition can be further improved.

[0585] The carboxylate anion is preferably represented by the following formula (X1).

[0586] [Chemical formula 42]

[0587]

[0588] In formula (X1), EWG represents an electron withdrawing group.

[0589] In this embodiment, the electron withdrawing group represents a group having a positive Hammett substituent constant σm. Here, σm is described in detail in General Comments of Yufu Miyamoto, Journal of the Society of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) p. 631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituents described in the above literature.

[0590] Examples of substituents having a positive value of σm include CF3 group (σm=0.43), CF3C (=O) group (σm=0.63), HC≡C group (σm=0.21), CH2=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), H2NC (=O)CH2 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 applies hereinafter).

[0591] EWG is preferably a group represented by the following formulae (EWG-1) to (EWG-6).

[0592] [Chemical formula 43]

[0593]

[0594] In formulas (EWG-1) to (EWG-6), R x1 ~R x3 Each independently represents 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.

[0595] In the present invention, the carboxylate anion is preferably represented by the following formula (XA).

[0596] [Chemical formula 44]

[0597]

[0598] In formula (XA), L 10 represents a single bond or is selected from alkylene, alkenylene, aromatic group, -NR X - and the divalent linking group in the combination thereof, R X represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

[0599] 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.

[0600] From the viewpoint of facilitating the cyclization of the precursor containing the heterocyclic polymer at low temperature and facilitating the improvement of the storage stability of the curable resin composition, the onium salt in the present invention preferably contains an ammonium cation as a cation, and the onium salt contains an anion having a pKa (pKaH) of a conjugate acid of 2.5 or less as an anion, more preferably containing an anion having a pKa of 1.8 or less.

[0601] The lower limit of the pKa is not particularly limited, but is preferably -3 or more, more preferably -2 or more, from the viewpoint that the generated base is less likely to be neutralized and the cyclization efficiency of the heterocyclic polymer-containing precursor is improved.

[0602] As the above-mentioned pKa, the values ​​described in Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliget, O., Nachod, FC; Edited by: Braude, EA, Nachod, FC; Academic Press, New York, 1955) or Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 1959) can be referred to. For compounds not described in these documents, the values ​​calculated from the structural formula using ACD / pKa software (manufactured by ACD / Labs) are used.

[0603] Specific examples of the ammonium salt include the following compounds, but the present invention is not limited to these.

[0604] [Chemical formula 45]

[0605]

[0606] 〔Iminium salt〕

[0607] In the present invention, the iminium salt means a salt of an iminium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and the preferred embodiments are also the same.

[0608] -Iminium cation-

[0609] As the iminium cation, a pyridinium cation is preferred.

[0610] Furthermore, as the iminium cation, a cation represented by the following formula (102) is also preferred.

[0611] [Chemical formula 46]

[0612]

[0613] In formula (102), R 5 and R 6 Each independently represents a hydrogen atom or a hydrocarbon group, R 7 Represents a hydrocarbon group, R 5 ~R 7 At least two of them may be bonded to form a ring.

[0614] In formula (102), R 5 and R 6 With R in the above formula (101) 1 ~R 4 The meanings are the same and the preferred aspects are also the same.

[0615] In formula (102), R 7 Preferred with R 5 and R 6 At least one of the above is bonded to form a ring. The above ring may contain a heteroatom. As the above heteroatom, a nitrogen atom can be mentioned. And, as the above ring, a pyridine ring is preferred.

[0616] The iminium cation is preferably represented by any one of the following formulas (Y1-3) to (Y1-5).

[0617] [Chemical formula 47]

[0618]

[0619] In formulas (Y1-3) to (Y1-5), R 101 represents an n-valent organic group, R 5 With R in formula (102) 5 has the same meaning, R 7 With R in formula (102) 7 , and n and m represent an integer greater than 1.

[0620] In formula (Y1-3), R101 It is preferably a group formed by removing n hydrogen atoms from an aliphatic hydrocarbon, an aromatic hydrocarbon, or a structure formed by bonding these hydrocarbons, 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.

[0621] In formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and further preferably 1.

[0622] In the formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and even more preferably 1.

[0623] Specific examples of the iminium salt include the following compounds, but the present invention is not limited to these.

[0624] [Chemical formula 48]

[0625]

[0626] In the present invention, the sulfonium salt means a salt of a sulfonium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and preferred embodiments are also the same.

[0627] -Sulfonium cation-

[0628] As the sulfonium cation, a tertiary sulfonium cation is preferred, and a triarylsulfonium cation is more preferred.

[0629] Furthermore, as the sulfonium cation, a cation represented by the following formula (103) is preferred.

[0630] [Chemical formula 49]

[0631]

[0632] In formula (103), R 8 ~R 10 Each independently represents a hydrocarbon group.

[0633] R 8 ~R 10 Each independently is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and further preferably a phenyl group.

[0634] R 8 ~R 10It 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, an acyloxy group, etc. Among these, as a substituent, it is preferred to have an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and even more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0635] R 8 ~R 10 The groups may be the same or different, but are preferably the same from the viewpoint of synthetic suitability.

[0636] Specific examples of the sulfonium salt include the following compounds, but the present invention is not limited to these.

[0637] [Chemical formula 50]

[0638]

[0639] In the present invention, the iodine salt refers to a salt of an iodine cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and the preferred embodiments are also the same.

[0640] -Iodide cation-

[0641] As the iodonium cation, a diaryliodonium cation is preferred.

[0642] Furthermore, as the iodine cation, a cation represented by the following formula (104) is preferred.

[0643] [Chemical formula 51]

[0644]

[0645] In formula (104), R 11 and R 12 Each independently represents a hydrocarbon group.

[0646] R 11 and R 12 Each independently is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and further preferably a phenyl group.

[0647] R 11 and R 12It 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, an acyloxy group, etc. Among these, as a substituent, it is preferred to have an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and even more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0648] R 11 and R 12 The groups may be the same or different, but are preferably the same from the viewpoint of synthetic suitability.

[0649] Specific examples of the iodine salt include the following compounds, but the present invention is not limited to these.

[0650] [Chemical formula 52]

[0651]

[0652] In the present invention, the phosphonium salt means a salt of a phosphonium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and the preferred embodiments are also the same.

[0653] -Phosphonium cation-

[0654] As the phosphonium cation, a quaternary phosphonium cation is preferred, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation.

[0655] Furthermore, as the phosphoric acid cation, a cation represented by the following formula (105) is preferred.

[0656] [Chemical formula 53]

[0657]

[0658] In formula (105), R 13 ~R 16 Each independently represents a hydrogen atom or a hydrocarbon group.

[0659] R 13 ~R 16 Each independently is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and further preferably a phenyl group.

[0660] R 13 ~R 16It 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, an acyloxy group, etc. Among these, as a substituent, it is preferred to have an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and even more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0661] R 13 ~R 16 The groups may be the same or different, but are preferably the same from the viewpoint of synthetic suitability.

[0662] Specific examples of the phosphoric acid salt include the following compounds, but the present invention is not limited to these.

[0663] [Chemical formula 54]

[0664]

[0665] When the curable resin composition of the present invention includes an onium salt, the content of the onium salt 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, further preferably 0.85% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, and may be 5% by mass or less, or 4% by mass or less.

[0666] The onium salt can be used alone or in combination of two or more. When two or more are used, the total amount is preferably within the above range.

[0667] <Thermal alkali generator>

[0668] The curable resin composition of the present invention may further contain a thermal base generator.

[0669] 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 preferred to contain a thermal base generator.

[0670] The other thermal base generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermal base generator other than the above-mentioned onium salt.

[0671] Examples of the thermal base generator other than the above-mentioned onium salts include nonionic thermal base generators.

[0672] Examples of the nonionic thermal base generator include compounds represented by formula (B1) or formula (B2).

[0673] [Chemical formula 55]

[0674]

[0675] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 are independently an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom. 1 and Rb 2 will not become a hydrogen atom at the same time. 1 , Rb 2 and Rb 3 In addition, in this specification, the tertiary amine structure refers to a structure in which the three bonds of the trivalent nitrogen atom are covalently bonded to the carbon atoms of the hydrocarbon system. Therefore, when the bonded carbon atom is a carbon atom constituting a carbonyl group, that is, when an amide group is formed together with the nitrogen atom, it is not limited to this.

[0676] In formula (B1) and formula (B2), regarding Rb 1 , Rb 2 and Rb 3 , preferably at least one of these contains a cyclic structure, more preferably at least two contain a cyclic structure. As the cyclic structure, it can be any one of a monocyclic ring and a condensed ring, preferably a monocyclic ring or a condensed ring formed by condensation of two monocyclic rings. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, more preferably a cyclohexane ring.

[0677] More specifically, Rb 1 and Rb 2 Preferably, it is a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12). These groups may have a substituent within the range in which the effects of the present invention are exerted. Rb 1 and Rb 2 They may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. 1 and Rb 2 Particularly preferred are linear, branched or cyclic alkyl groups which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12 carbon atoms), more preferred are cycloalkyl groups which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18, and further preferably 3 to 12 carbon atoms), and further preferred are cyclohexyl groups which may have a substituent.

[0678] As Rb3 , examples include alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 12, and further preferably 2 to 6), arylalkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), arylalkenyl groups (preferably having 8 to 24 carbon atoms, more preferably 8 to 20, and further preferably 8 to 16), alkoxy groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), aryloxy groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), and arylalkoxy groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12). Among them, cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), arylalkenyl groups, and arylalkoxy groups are preferred. 3 The compound may further have a substituent within a range where the effects of the present invention are exhibited.

[0679] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

[0680] [Chemical formula 56]

[0681]

[0682] In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 Respectively with Rb in formula (B1) 1 and Rb 2 same.

[0683] R 13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), and may have a substituent within the range in which the effects of the present invention are exerted. 13 Arylalkyl is preferred.

[0684] R 33 and Rb 34Each of them independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), and is preferably a hydrogen atom.

[0685] R 35 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), and an aryl group is preferred.

[0686] The compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a).

[0687] [Chemical formula 57]

[0688]

[0689] R 11 and Rb 12 With Rb in formula (B1-1) 11 and Rb 12 have the same meaning.

[0690] R 15 and Rb 16 It is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), and preferably a hydrogen atom or a methyl group.

[0691] R 17 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), and an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), among which an aryl group is preferred.

[0692] The molecular weight of the nonionic thermal base generator is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

[0693] Specific examples of the compound serving as the thermal base generator among the above-mentioned onium salts or specific examples of the thermal base generator other than the above-mentioned onium salts include the following compounds.

[0694] [Chemical formula 58]

[0695]

[0696] [Chemical formula 59]

[0697]

[0698] [Chemical formula 60]

[0699]

[0700] The content of other thermal alkali generating agents 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. One or more thermal alkali generating agents can be used. When two or more are used, the total amount is preferably within the above range.

[0701] <Crosslinking agent>

[0702] The curable resin composition of the present invention preferably contains a cross-linking agent.

[0703] Examples of the crosslinking agent include radical crosslinking agents and other crosslinking agents.

[0704] <Free Radical Crosslinking Agent>

[0705] The curable resin composition of the present invention preferably further contains a radical crosslinking agent.

[0706] The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenically unsaturated bond is preferred. As the above-mentioned group containing an ethylenically unsaturated bond, groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth)acryloyl group can be cited.

[0707] Among these, as the group containing an ethylenically unsaturated bond, a (meth)acryloyl group is preferred, and a (meth)acryloyloxy group is more preferred from the viewpoint of reactivity.

[0708] The radical crosslinking agent may be a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more ethylenically unsaturated bonds.

[0709] The compound having two ethylenically unsaturated bonds is preferably a compound having two of the above-mentioned groups containing an ethylenically unsaturated bond.

[0710] Furthermore, 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 3 or more ethylenically unsaturated bonds as a free radical crosslinking agent. As the compound having 3 or more ethylenically unsaturated bonds, a compound having 3 to 15 ethylenically unsaturated bonds is preferred, a compound having 3 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 3 to 6 ethylenically unsaturated bonds is further preferred.

[0711] Furthermore, the compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing ethylenically unsaturated bonds, more preferably a compound having 3 to 15 groups, further preferably a compound having 3 to 10 groups, and particularly preferably a compound having 3 to 6 groups.

[0712] On the other hand, from the viewpoint of developability, the radical crosslinking agent is particularly preferably a compound having two ethylenically unsaturated bonds.

[0713] Furthermore, from the viewpoint of film strength of the obtained pattern (cured film), the curable resin composition of the present invention preferably contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.

[0714] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0715] 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, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxies, or dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. Moreover, it is also preferred to have an unsaturated carboxylic acid ester or amides with electrophilic substituents such as isocyanate or epoxy groups and monofunctional or polyfunctional alcohols, amines, thiols addition reaction products, and unsaturated carboxylic acid esters or amides with dissociative substituents such as halogeno groups or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, thiols substitution reaction products. Moreover, as another example, it is also possible to use a compound group replaced by vinylbenzene derivatives such as unsaturated phosphonic acid, styrene, vinyl ether, allyl ether, etc. instead of the above-mentioned unsaturated carboxylic acid. As a specific example, it is possible to refer to the records of paragraphs 0113 to 0122 of Japanese Patent Publication No. 2016-027357, and these contents are incorporated into this specification.

[0716] Furthermore, the radical crosslinking agent is preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples thereof include compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as polyethylene glycol di(meth)acrylate, trimethylolethane 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, trimethylolpropane tri(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, glycerol or trimethylolethane, and then (meth)acrylating the resulting mixture. 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 polyfunctional acrylates or methacrylates and mixtures thereof. In addition, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. In addition, polyfunctional (meth) acrylates obtained by reacting compounds having a cyclic ether group and an ethylenically unsaturated bond such as (meth) acrylate glycidyl with a polyfunctional carboxylic acid can also be cited.

[0717] Furthermore, as preferred radical crosslinking agents other than the above, compounds having a fluorene ring and having two or more groups containing ethylenically unsaturated bonds, or cardo resins described in JP-A-2010-160418, JP-A-2010-129825, and JP-4364216 may be used.

[0718] In addition, 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 also be cited. In addition, compounds containing perfluoroalkyl groups described in Japanese Patent Publication No. 61-022048 can also be used. In addition, compounds introduced as photopolymerizable monomers and oligomers in the Journal of the Japanese Adhesion Association, vol. 20, No. 7, pages 300 to 308 (1984) can also be used.

[0719] In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and compounds described in paragraphs 0087 to 0131 of WO-2015 / 199219 can also be preferably used, and the contents thereof are incorporated into the present specification.

[0720] Furthermore, 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)acrylated, can also be used as radical crosslinking agents.

[0721] 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 the present specification.

[0722] As the radical crosslinking agent, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which (meth)acryloyl groups of these are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

[0723] Commercially available products of the radical crosslinking agent include, for example, SR-494 manufactured by Sartomer Company, Inc., which is a tetrafunctional acrylate having four vinyloxy chains; SR-209, 231, and 239 manufactured by Sartomer Company, Inc., which are bifunctional methacrylates having four vinyloxy chains; DPCA-60 manufactured by Nippon Kayaku Co., Ltd., which is a hexafunctional acrylate having six oxypentylene chains; TPA-330 manufactured by Nippon Kayaku Co., Ltd., 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.); 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.

[0724] As the radical crosslinking agent, polyurethane 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 carbamate 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, 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 Publication No. 63-277653, Japanese Patent Publication No. 63-260909, and Japanese Patent Publication No. 01-105238 can also be used.

[0725] 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 more preferably 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. It is particularly preferred that, among the free radical crosslinking agents 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 pentaerythritol or dipentaerythritol. As commercially available products, for example, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., LTD. include M-510 and M-520.

[0726] The preferred acid value of the free radical crosslinking agent having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 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 further the developability is excellent. In addition, the polymerizability is good. On the other hand, from the perspective of the developing speed during alkali development, the preferred acid value of the free radical crosslinking agent having an acid group is 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. The above acid value is measured according to the description of JIS K0070:1992.

[0727] From the viewpoint of pattern resolution and film stretchability, it is preferred that a bifunctional methacrylate or acrylate be used in the curable resin composition of the present invention.

[0728] 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, dimethylol tricyclodecane diacrylate, dimethylol 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-acryloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, bifunctional acrylates having other urethane bonds, and bifunctional methacrylates having urethane bonds. Two or more of these can be used in combination as needed.

[0729] In addition, examples of bifunctional or higher-functional radical crosslinking agents include diallyl phthalate and triallyl trimellitate.

[0730] From the viewpoint of suppressing the warping caused by the elastic modulus control of the accompanying pattern (cured film), as a free radical crosslinking agent, a monofunctional free radical crosslinking agent can be preferably used. As a monofunctional free radical crosslinking agent, 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, (meth) acrylic acid glycidyl ester, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and other (meth) acrylic acid derivatives, N-vinyl pyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, allyl glycidyl ether, diallyl phthalate, trimellitic acid triallyl ester and other allyl compounds can be preferably used. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100° C. or higher under normal pressure is also preferred in order to suppress volatilization before exposure.

[0731] When a free radical crosslinking agent is contained, its content is preferably more than 0% by mass and less than 60% by mass relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.

[0732] The radical crosslinking agent may be used alone or in combination of two or more. When two or more radical crosslinking agents are used simultaneously, the total amount thereof is preferably within the above range.

[0733] <Other crosslinking agents>

[0734] The curable resin composition of the present invention preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.

[0735] 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 through the photosensitization of the above-mentioned photosensitizer, 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 through the action of acids or bases.

[0736] The acid or base is preferably an acid or base generated from a photosensitizer in an exposure step.

[0737] As other crosslinking agents, compounds having at least one group selected from methylol groups and alkoxymethyl groups are preferred, and compounds having a structure in which at least one group selected from methylol groups and alkoxymethyl groups is directly bonded to a nitrogen atom are more preferred.

[0738] As other crosslinking agents, for example, compounds having a structure in which the hydrogen atoms of the amino groups are substituted with methylol or alkoxymethyl groups by reacting formaldehyde or formaldehyde and alcohol with amino-containing compounds such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine. The production method of these compounds is not particularly limited, as long as they are compounds having the same structure as the compounds produced by the above methods. In addition, oligomers formed by self-condensation of methylol groups of these compounds may also be used.

[0739] A cross-linking agent using melamine as the amino group-containing compound is referred to as a melamine-based cross-linking agent, a cross-linking agent using glycoluril, urea or alkylene urea is referred to as a urea-based cross-linking agent, a cross-linking agent using alkylene urea is referred to as an alkylene urea-based cross-linking agent, and a cross-linking agent using benzoguanamine is referred to as a benzoguanamine-based cross-linking agent.

[0740] Among these, the curable resin composition of the present invention preferably contains at least one compound selected from urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from glycoluril-based crosslinking agents and melamine-based crosslinking agents described below.

[0741] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, and the like.

[0742] 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, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril;

[0743] Urea crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, and bisbutoxymethyl urea;

[0744] Ethylene urea crosslinking agents such as monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea;

[0745] Acryl urea crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea;

[0746] 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

[0747] 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.

[0748] In addition, as the compound having at least one group selected from hydroxymethyl and alkoxymethyl groups, a compound in which at least one group selected from hydroxymethyl and alkoxymethyl groups is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used.

[0749] 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) methyl) benzophenone, methoxymethylphenyl methoxymethyl benzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4"-ethylenetris[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, and the like.

[0750] As other crosslinking agents, commercially available products may be used. Preferred commercially available 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, and 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, NIKARACMX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

[0751] Furthermore, the curable resin composition of the present invention also preferably contains at least one compound selected from epoxy compounds, oxetane compounds, and benzoxazine compounds as another crosslinking agent.

[0752] [Epoxy compounds (compounds having epoxy groups)]

[0753] As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a crosslinking reaction below 200°C and does not produce a dehydration reaction resulting from the crosslinking, so film shrinkage is not likely to occur. Therefore, containing an epoxy compound is effective for low-temperature curing of the curable resin composition and suppression of warpage.

[0754] The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and can suppress warping. The polyethylene oxide group represents a group having 2 or more repeating units of ethylene oxide, and preferably has 2 to 15 repeating units.

[0755] Examples of epoxy compounds include bisphenol A epoxy resins; bisphenol F epoxy resins; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; silicones containing epoxy groups such as polymethyl (glycidyloxypropyl) siloxane, etc., but are not limited to these. Specific examples include 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, EPICLON (registered trademark) HP ... 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 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, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (these 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 (these are trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc. .

[0756] [Oxetane compounds (compounds having an oxetane group)]

[0757] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, ARON OXETANE series (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.

[0758] [Benzoxazine compounds (compounds having a benzoxazolyl group)]

[0759] Benzoxazine compounds are preferred because they do not generate outgassing during curing due to a crosslinking reaction caused by a ring-opening addition reaction and further reduce thermal shrinkage to suppress the generation of warpage.

[0760] Preferred examples of the benzoxazine compound include Ba-type benzoxazine, Bm-type benzoxazine, Pd-type benzoxazine, Fa-type benzoxazine (these are trade names, manufactured by SHIKOKU CHEMICALS CORPORATION), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

[0761] The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass relative to the total solid content of the curable resin composition of the present invention. Other crosslinking agents may contain only one or more. In the case of containing two or more other crosslinking agents, it is preferred that the total is within the above range.

[0762] <Compounds Having a Sulfonamide Structure, Compounds Having a Thiourea Structure>

[0763] From the viewpoint of improving the adhesion of the obtained pattern (cured film) to the substrate, the curable resin composition of the present invention preferably further contains at least one compound selected from compounds having a sulfonamide structure and compounds having a thiourea structure.

[0764] [Compounds having a sulfonamide structure]

[0765] The sulfonamide structure is a structure represented by the following formula (S-1).

[0766] [Chemical formula 61]

[0767]

[0768] In formula (S-1), R represents a hydrogen atom or an organic group, and R may be bonded to other structures to form a ring structure, and * independently represents the bonding position to other structures.

[0769] The above R is preferably the same as R in the following formula (S-2): 2 Same group.

[0770] The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but is preferably a compound having one sulfonamide structure.

[0771] The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).

[0772] [Chemical formula 62]

[0773]

[0774] In formula (S-2), R 1 , R 2 and R 3 Each independently represents a hydrogen atom or a monovalent organic group, R 1 , R 2 and R 3 Two or more of them may be bonded to each other to form a ring structure.

[0775] R 1 , R 2 and R 3 Each independently is preferably a monovalent organic group.

[0776] As R 1 , R 2 and R 3 Examples of the group include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group formed by combining two or more of these groups.

[0777] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl.

[0778] The cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0779] The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group.

[0780] The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, and more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.

[0781] The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 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.

[0782] Examples of the heterocyclic group include a group 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 oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran ring, and a triazine ring.

[0783] Among them, R is preferred 1 is an aromatic group and R 2 and R 3 A compound wherein each of them is independently a hydrogen atom or an alkyl group.

[0784] 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-aminoethylsulfonamide.

[0785] 〔Compounds with thiourea structure〕

[0786] The thiourea structure is a structure represented by the following formula (T-1).

[0787] [Chemical formula 63]

[0788]

[0789] In formula (T-1), R 4 and R 5 Each independently represents a hydrogen atom or a monovalent organic group, R 4 and R 5 Can bond to form a ring structure, R 4 It can bond with other structures bonded by * to form a ring structure, R 5 It may bond with other structures bonded with * to form a ring structure, and * each independently represents a bonding position with other structures.

[0790] R 4 and R 5 Each independently is preferably a hydrogen atom.

[0791] As R 4 and R 5Examples of the group include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group formed by combining two or more of these groups.

[0792] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl.

[0793] The cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0794] The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group.

[0795] The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, and more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.

[0796] The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 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.

[0797] Examples of the heterocyclic group include a group 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 oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran ring, and a triazine ring.

[0798] The compound having a thiourea structure may be a compound having two or more thiourea structures, but is preferably a compound having one thiourea structure.

[0799] The compound having a thiourea structure is preferably a compound represented by the following formula (T-2).

[0800] [Chemical formula 64]

[0801]

[0802] In formula (T-2), R4 ~R 7 Each independently represents a hydrogen atom or a monovalent organic group, R 4 ~R 7 At least two of them may be bonded to each other to form a ring structure.

[0803] In formula (T-2), R 4 and R 5 With R in formula (T-1) 4 and R 5 The meanings are the same and the preferred aspects are also the same.

[0804] In formula (T-2), R 6 and R 7 Each independently is preferably a monovalent organic group.

[0805] In formula (T-2), R 6 and R 7 The preferred embodiment of the monovalent organic group in formula (T-1) is the same as R 4 and R 5 The preferred embodiment of the monovalent organic group in is the same as that in the above examples.

[0806] Examples of the compound 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.

[0807] 〔content〕

[0808] The total content of the compound having a sulfonamide structure and the compound having a thiourea structure is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.2 to 3% by mass based on the total mass of the curable resin composition of the present invention.

[0809] The curable resin composition of the present invention may contain only one compound selected from the group consisting of 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 preferably within the above range, and when two or more compounds are contained, the total amount thereof is preferably within the above range.

[0810] <Migration Inhibitor>

[0811] The curable resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, it is possible to effectively suppress the migration of metal ions from the metal layer (metal wiring) into the curable resin composition layer.

[0812] 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, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds having thiourea and sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 5-methylbenzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole, and purine compounds such as purine, adenine, and guanine can be preferably used.

[0813] Among these, an embodiment in which the curable resin composition of the present invention further contains at least one compound selected from 5-methylbenzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole and 5-amino-1H-tetrazole as a migration inhibitor is also one of the preferred embodiments of the present invention.

[0814] From the viewpoint of improving the adhesion to the 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 imidazole rings, triazole rings, oxazole rings, thiazole rings, pyrazole rings, isoxazole rings, isothiazole rings, tetrazole rings, pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, piperidine rings, piperazine rings and triazine rings 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.

[0815] Alternatively, an ion capture agent that captures anions such as halogen ions may also be used.

[0816] As other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Laid-Open No. 2011-059656, the compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015 / 199219, etc. can be used.

[0817] Specific examples of the migration inhibitor include the following compounds.

[0818] [Chemical formula 65]

[0819]

[0820] When the curable resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass based on the total solid content of the curable resin composition.

[0821] The migration inhibitor may be one kind or two or more kinds. When there are two or more kinds of migration inhibitors, the total amount thereof is preferably within the above range.

[0822] <Polymerization Inhibitor>

[0823] The curable resin composition of the present invention preferably contains a polymerization inhibitor.

[0824] As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine cerium salt, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, 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-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidinium 1-oxyl free radical, phenothiazine, 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 free radical, phenoxazine, etc. Furthermore, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO 2015 / 125469 can also be used.

[0825] Furthermore, the following compounds (Me is methyl group) can be used.

[0826] [Chemical formula 66]

[0827]

[0828] When the curable resin composition of the present invention has a polymerization inhibitor, for example, the content of the polymerization inhibitor is 0.01 to 20.0% by mass relative to the total solid content of the curable resin composition of the present invention, preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and further preferably 0.05 to 2.5% by mass. In addition, when the storage stability of the curable resin composition solution is required, the content is preferably 0.02 to 15.0% by mass, in which case, it is more preferably 0.05 to 10.0% by mass.

[0829] The polymerization inhibitor may be one kind or two or more kinds. When there are two or more kinds of polymerization inhibitors, the total amount thereof is preferably within the above range.

[0830] <Metal Adhesion Improver>

[0831] The curable resin composition of the present invention preferably contains a metal adhesion improver for improving the adhesion to the metal material used in the electrode or wiring, etc. As the metal adhesion improver, silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds with sulfonamide structures, compounds with thiourea structures, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, etc. can be cited.

[0832] Among these, the curable resin composition of the present invention preferably contains a silane coupling agent, an aluminum-based adhesion promoter, a titanium-based adhesion promoter, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, an amino compound, and the like.

[0833] 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 Laid-Open 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 Laid-Open No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-041264, and compounds described in paragraph 0055 of International Publication No. 2014 / 097594. In addition, as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358, it is also preferred to use two or more different silane coupling agents. Furthermore, the following compounds are also preferably used as the silane coupling agent. In the following formula, Et represents an ethyl group.

[0834] [Chemical formula 67]

[0835]

[0836] Examples of other silane coupling agents include vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, 3-glycidoxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3- Acryloxypropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, 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-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used alone or in combination of two or more.

[0837] 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.

[0838] 〔Aluminum-based adhesive additive〕

[0839] Examples of the aluminum-based adhesion promoter include tris(ethylacetoacetate)aluminum, tris(acetylacetonate)aluminum, and ethylacetoacetate aluminum diisopropoxide.

[0840] The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and further preferably in the range of 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 may be only one or more than two. When using two or more, it is preferred that the total is within the above range.

[0841] <Metal Adhesion Improver>

[0842] 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, etc. As the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of Japanese Unexamined Patent Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Unexamined Patent Publication No. 2013-072935 can also be used.

[0843] The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and further preferably in the range of 0.5 to 5 parts by mass, relative to 100 parts by mass of the polymer precursor containing the heterocycle. By setting it to above the above lower limit, the adhesion between the cured film after the curing process and the metal layer becomes good, and by setting it to below the above upper limit, the heat resistance and mechanical properties of the cured film after the curing process become good. The metal adhesion improver may be only one or more than two. When using two or more, it is preferred that the total is within the above range.

[0844] <Other additives>

[0845] The curable resin composition of the present invention can be formulated with various additives as needed within the range in which the effects of the present invention can be obtained, 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 these additives are formulated, the total amount thereof is preferably set to 3% by mass or less of the solid content of the curable resin composition.

[0846] 〔Sensitizer〕

[0847] 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 an electronically excited state contacts with a thermal curing accelerator, a thermal free radical polymerization initiator, a photo-free radical polymerization initiator, etc. to generate electron transfer, energy transfer, heat generation, etc. As a result, 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.

[0848] For example, compounds such as ethanolamine, benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azo methine, xanthene, phthalocyanine, benzopyran, and indigo can be used.

[0849] 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-dimethylaminophenylallylidene dihydroindanone, p- dimethylaminobenzylidene dihydroindanone, 2-(p-dimethylaminophenyl biphenylene)-benzothiazole, 2-(p-dimethylaminophenyl vinylene)benzothiazole, 2-(p-dimethylaminophenyl vinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylamino 3-methoxycarbonyl-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-morpholinobenzophenone, isopentyl dimethylaminobenzoate, isopentyl diethylaminobenzoate amyl ester, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminophenylvinyl)benzoxazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc.

[0850] As the sensitizer, a sensitizing dye may also be used.

[0851] For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and the contents are incorporated into this specification.

[0852] When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and further preferably 0.5 to 10% by 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.

[0853] 〔Chain transfer agent〕

[0854] 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) on pages 683-684. As chain transfer agents, for example, a compound group having -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH in the molecule, a dithiobenzoate, a trithiocarbonate, a dithiocarbamate, a xanthate compound having a thiocarbonylthio group for RAFT (Reversible Addition Fragmentation chain Transfer: reversible addition fragmentation chain transfer) polymerization, etc. can be used. These can supply hydrogen to low-activity free radicals to generate free radicals, or generate free radicals by deprotonation after oxidation. In particular, thiol compounds can be preferably used.

[0855] Furthermore, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219 can also be used.

[0856] When the curable resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and further 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 or more than two. When there are two or more chain transfer agents, it is preferred that the total is within the above range.

[0857] 〔Surfactant〕

[0858] From the viewpoint of further improving the coating property, various types of surfactants can be added to the curable resin composition of the present invention. As surfactants, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, silicone surfactants can be used. And, the following surfactants are also preferred. In the following formula, the brackets representing the repeating units of the main chain represent the content (mol %) of each repeating unit, and the brackets representing the repeating units of the side chains represent the number of repetitions of each repeating unit.

[0859] [Chemical formula 68]

[0860]

[0861] Furthermore, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International Publication No. 2015 / 199219 can also be used.

[0862] Regarding fluorine-based surfactants, fluorine-containing polymers having ethylenically unsaturated groups in the side chains can also be used as fluorine-based surfactants. As specific examples, 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. In addition, as commercially available products, for example, MEGAFACE RS-101, RS-102, RS-718K, etc. manufactured by DIC CORPORATION can be cited.

[0863] The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. From the perspective of uniformity of the thickness of the coating film or liquid saving, a fluorine-based surfactant having a fluorine content within this range is effective and has good solubility in the composition.

[0864] Examples of the silicone 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.), BYK307, BYK323, and BYK330 (all manufactured by BYK Chemie GmbH).

[0865] Examples of the hydrocarbon-based surfactant 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.).

[0866] Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, nonylphenol polyoxyethylene ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, and the like. Examples of 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.

[0867] Specific examples of cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0868] 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.).

[0869] When the curable resin composition of the present invention has 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 or more than two. When there are two or more surfactants, it is preferred that the total is within the above range.

[0870] 〔Higher fatty acid derivatives〕

[0871] In order to prevent polymerization inhibition caused by oxygen, the curable resin composition of the present invention may contain a higher fatty acid derivative such as behenic acid or behenic acid amide so as to be unevenly distributed on the surface of the curable resin composition during drying after coating.

[0872] Furthermore, as the higher fatty acid derivatives, compounds described in paragraph 0155 of International Publication No. 2015 / 199219 can also be used.

[0873] When the curable resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the curable resin composition of the present invention. The higher fatty acid derivative may be only one or more than two. When there are two or more higher fatty acid derivatives, it is preferred that the total is within the above range.

[0874] 〔Inorganic particles〕

[0875] 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, and the like.

[0876] 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.

[0877] When the average particle diameter of the inorganic particles is large, the mechanical properties of the cured film may be deteriorated. Also, when the average particle diameter of the inorganic particles exceeds 2.0 μm, the resolution may be reduced due to scattering of exposure light.

[0878] 〔Ultraviolet light absorber〕

[0879] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, or other ultraviolet absorber may be used.

[0880] Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like. 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. In addition, 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-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0881] Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triazine-based ultraviolet absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; Bis(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine; and the like.

[0882] In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.

[0883] The composition of the present invention may contain a UV absorber or may not contain a UV absorber. However, when a UV absorber is contained, the content of the UV absorber is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less, relative to the total solid content mass of the composition of the present invention.

[0884] 〔Organotitanium compounds〕

[0885] The resin composition of the present 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 the resin composition is cured at a low temperature.

[0886] Examples of the organic titanium compound that can be used include compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.

[0887] Specific examples of the organic titanium compound are shown in the following I) to VII):

[0888] I) Titanium chelate compound: Among them, from the viewpoint that the storage stability of the negative photosensitive resin composition is good and a good cured pattern can be obtained, a titanium chelate compound having two or more alkoxy groups is more preferred. Specific examples include bis(triethanolamine)diisopropoxytitanium, bis(2,4-pentanedioate)di(n-butoxy)titanium, bis(2,4-pentanedioate)diisopropoxytitanium, bis(tetramethylpimelate)diisopropoxytitanium, bis(ethylacetoacetate)diisopropoxytitanium, etc.

[0889] II) Tetraalkoxytitanium 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, tetrastearoyloxytitanium, tetrakis[bis{2,2-(allyloxymethyl)butoxy}]titanium, etc.

[0890] III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium 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.

[0891] IV) Monoalkoxy titanium compound: for example, tris(dioctyl phosphate)isopropoxytitanium, tris(dodecylbenzene sulfonate)isopropoxytitanium, and the like.

[0892] V) Titanium oxide compound: for example, bis(glutarate)titanium oxide, bis(tetramethylpimelate)titanium oxide, titanium phthalocyanine oxide, and the like.

[0893] VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate.

[0894] VII) Titanate coupling agent: for example, isopropyl tri(dodecyl)benzenesulfonyl titanate.

[0895] Among them, as the organic titanium compound, from the viewpoint of exerting better chemical resistance, it is preferably at least one compound selected from the above-mentioned I) titanium chelate compound, II) tetraalkoxy titanium compound and III) titanocene compound. In particular, bis(ethyl acetoacetate)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.

[0896] When an 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, good heat resistance and chemical resistance are exhibited in the obtained cured pattern, while when the amount is 10 parts by mass or less, the storage stability of the composition is excellent.

[0897] 〔Antioxidant〕

[0898] The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the elongation characteristics of the cured film or the adhesion to the metal material can be improved. As the antioxidant, phenol compounds, phosphite compounds, thioether compounds, etc. can be mentioned. 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 mentioned. Preferably, a compound has a substituent at a position adjacent to the phenolic hydroxyl group (ortho position). As the 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 phenolic group and a phosphite group in the same molecule. In addition, the antioxidant can also preferably use a phosphorus 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 A0-20, ADKSTAB A0-30, ADKSTAB A0-40, ADKSTAB A0-50, ADKSTAB A0-50F, ADKSTAB A0-60, ADKSTAB A0-60G, ADKSTAB A0-80, ADKSTAB A0-330 (all manufactured by ADEKA CORPORATION) and the like can be cited. In addition, the antioxidant can also use the compounds described in paragraphs 0023 to 0048 of Japanese Patent Gazette No. 6268967. In addition, the composition of the present invention may contain a potential antioxidant as required. As potential antioxidants, compounds in which the site that acts as an antioxidant is protected by a protecting group, and compounds that act as an antioxidant by heating at 100 to 250° C. or heating at 80 to 200° C. in the presence of an acid / base catalyst to remove the protecting group can be cited. As potential antioxidants, compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Publication No. 2017-008219 can be cited. Commercially available products of potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION) and the like. Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and compounds represented by the general formula (3).

[0899] [Chemical formula 69]

[0900]

[0901] In the general formula (3), R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, R 6 represents an alkylene group having 2 or more carbon atoms. 7 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 an N atom. k represents an integer of 1 to 4.

[0902] The compound represented by the general formula (3) can inhibit the oxidative degradation of the aliphatic group or the phenolic hydroxyl group of the resin and can inhibit the oxidation of the metal by its rust-proofing effect on the metal material.

[0903] Since it can act on both the resin and the metal material, k is more preferably an integer of 2 to 4. 7 Examples include alkyl, cycloalkyl, alkoxy, alkyl ether, alkyl silyl, alkoxy silyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and combinations thereof, and may have a substituent. Among them, alkyl ether and -NH- are preferred from the viewpoint of solubility in a developer or metal adhesion, and -NH- is more preferred from the viewpoint of interaction with a resin and metal adhesion by metal complexation.

[0904] Examples of the compound represented by the following general formula (3) include the following, but are not limited to the following structures.

[0905] [Chemical formula 70]

[0906]

[0907] [Chemical formula 71]

[0908]

[0909] [Chemical formula 72]

[0910]

[0911] [Chemical formula 73]

[0912]

[0913] The amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. When the amount added is less than 0.1 parts by mass, it is difficult to obtain the effect of improving the elongation characteristics after reliability or the adhesion to the metal material, and when it is more than 10 parts by mass, it is possible to cause the sensitivity of the resin composition to decrease by 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 of these is preferably within the above range.

[0914] <Regulation on other substances>

[0915] From the viewpoint of the 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 further preferably less than 0.6% by mass. As a method for maintaining the water content, the adjustment of the humidity under the storage conditions, the reduction of the porosity of the storage container, etc. can be cited.

[0916] From the viewpoint of insulation, the metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When multiple metals are included, the total amount of these metals is preferably within the above range.

[0917] In addition, as a method for reducing metal impurities accidentally contained in the curable resin composition of the present invention, the following methods can be cited: selecting raw materials with a low metal content as raw materials constituting the curable resin composition of the present invention; filtering the raw materials constituting the curable resin composition of the present invention; lining the inside of the device with polytetrafluoroethylene or the like to perform distillation under conditions that suppress contamination as much as possible, etc.

[0918] 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, more preferably less than 300 mass ppm, and further preferably less than 200 mass ppm from the viewpoint of wiring corrosion. Among them, the substance existing in the state of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be cited. Preferably, the total of chlorine atoms and bromine atoms or chlorine ions and bromide ions is respectively within the above range.

[0919] As a method for adjusting the content of halogen atoms, preferably, an ion exchange treatment or the like is used.

[0920] As the storage container of the curable resin composition of the present invention, a conventionally known storage container can be used. In addition, as the storage container, for the purpose of suppressing the mixing of impurities into the raw materials or the curable resin composition, it is also preferred to use a multilayer bottle in which the inner wall of the container is composed of 6 kinds of 6 layers of resin or a bottle having a 7-layer structure formed by 6 kinds of resins. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

[0921] <Application of curable resin composition>

[0922] The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a redistribution layer.

[0923] Furthermore, in addition to these, the present invention can also be used for forming an insulating film or a stress buffer film of a semiconductor device.

[0924] The curable resin composition of the present invention is stored in a storage container at least once at -15 to 16°C. The filling rate of the curable resin composition during the refrigeration is preferably 50 to 90% relative to the total storage volume of the storage container.

[0925] It is estimated that the curable resin composition of the present invention can obtain a resin film having excellent uniformity in film thickness even after such storage.

[0926] As the storage container, the above-mentioned storage container can be mentioned.

[0927] The above-mentioned refrigeration temperature is preferably 1 to 12°C, more preferably 3 to 10°C.

[0928] The above-mentioned refrigerated storage time (when refrigerated storage is performed multiple times, the total time of the multiple refrigerated storages) is preferably 1 hour to 100 days, and more preferably 12 hours to 30 days.

[0929] The above storage is preferably performed under light-shielding conditions.

[0930] The filling rate is calculated as the total volume of the curable resin composition relative to the total storage volume of the storage container, and is preferably 50 to 99%, more preferably 70 to 90%.

[0931] <Preparation of Curable Resin Composition>

[0932] The curable resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be performed by a conventionally known method.

[0933] In addition, for the purpose of removing foreign matter such as dust or particles in the curable resin composition, it is preferred to filter using a filter. Regarding the filter pore size, for example, a method of 5 μm or less can be cited, preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can use a filter that has been pre-cleaned with an organic solvent. In the filter filtering process, a variety of filters can be connected in series or in parallel. In the case of using a variety of filters, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. In the case of filtering multiple times, it can be a circulation filter. In addition, it can be filtered by pressurization. In the case of pressurization and filtering, the pressure of pressurization can be, for example, a method of 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and further preferably 0.05 MPa or more and 0.3 MPa or less.

[0934] In addition to filtering using a filter, impurity removal using an adsorbent may also be performed. Filter filtering and impurity removal using an adsorbent may also be combined. As the adsorbent, a known adsorbent may be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be cited.

[0935] (Resin film, cured film, laminate, semiconductor device, and method for producing the same)

[0936] Next, a resin film, a cured film, a laminated body, a semiconductor device, and methods for producing these will be described.

[0937] The resin film of the present invention is obtained by applying the curable resin composition of the present invention to a substrate.

[0938] The application method and the type of substrate are not particularly limited, but preferred examples include the application method and substrate in the film formation step described later.

[0939] The thickness of the resin film may be set to a thickness within the range described below, such as the thickness of the cured film described below. For example, the thickness of the resin film may be determined in consideration of shrinkage due to curing.

[0940] 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, for example, 0.5 μm or more, or 1 μm or more. Also, as an upper limit, it can be 100 μm or less, or 30 μm or less.

[0941] The cured film of the present invention can be stacked in two or more layers, and further stacked in 3 to 7 layers to form a laminate. The laminate of the present invention preferably includes a cured film of two or more layers and includes a metal layer between any of the above-mentioned cured films. For example, as a preferred laminate, there can be cited a laminate having a layer structure including at least three layers of a first cured film, a metal layer, and a second cured film stacked in sequence. The first cured film and the second cured film are both the cured films of the present invention. As a preferred embodiment, for example, there can be cited a embodiment in which any one of the first cured film and the second cured film is a film formed by curing the curable resin composition of the present invention. The curable resin composition of the present invention used for the formation of the first cured film and the curable resin composition of the present invention used for the formation of the second cured film may be a composition of the same composition or a composition of different composition. The metal layer in the laminate of the present invention can be preferably used as a metal wiring such as a redistribution layer.

[0942] As the fields to which the cured film of the present invention can be applied, there can be cited insulating films of semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc. In addition, there can be cited the formation of patterns on sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), or insulating films for actual mounting purposes as described above by etching. For the use of these, for example, reference can be made to SCIENCE AND TECHNOLOGY CO., LTD. "High Functionalization and Application Technology of Polyimide" April 2008, supervised by Masaaki Kakimoto, CMC Technical Library "Basics and Development of Polyimide Materials" November 2011, "Latest Polyimide Basics and Applications" compiled by the Japanese Polyimide / Aromatic Polymer Research Association, NTS Inc., August 2010, etc.

[0943] Furthermore, the cured film of the present invention can also be used in the production of printing plates such as offset printing plates and screen printing plates, in the etching of molded components, and in the production of protective varnishes and dielectric layers in electronics, especially microelectronics.

[0944] The method for producing a cured film of the present invention (hereinafter, also simply referred to as “the production method of 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).

[0945] The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step of exposing the film to light, and a development step of developing the film.

[0946] Furthermore, the method for producing a cured film of the present invention more preferably includes the film forming step and, if necessary, the developing step and a heating step of heating the film at 50 to 450°C.

[0947] Specifically, it is also preferable to include the following steps (a) to (d).

[0948] (a) Film formation step of applying the curable resin composition to a substrate to form a film (curable resin composition layer)

[0949] (b) After the film forming step, an exposure step of exposing the film to light

[0950] (c) A developing step of developing the exposed film

[0951] (d) a heating step of heating the developed film at 50 to 450° C.

[0952] By heating in the heating step, the resin layer cured by exposure can be further cured. In the heating step, for example, the thermal base generator is decomposed to obtain sufficient curability.

[0953] The method for manufacturing a laminated body according to a preferred embodiment of the present invention includes a method for manufacturing a cured film according to the present invention. After forming a cured film according to the method for manufacturing a laminated body of the present embodiment, the process (a) or the processes (a) to (c) or the processes (a) to (d) are further performed again. In particular, it is preferred to perform the above-mentioned processes in sequence multiple times, for example 2 to 5 times (i.e., 3 to 6 times in total). By stacking the cured films in this way, a laminated body can be formed. In the present invention, it is particularly preferred to provide a metal layer on a portion where a cured film is provided or between the cured films or on a portion where a cured film is provided and between the cured films. In addition, when manufacturing a laminated body, it is not necessary to repeatedly perform all the processes (a) to (d). As described above, a laminated body of a cured film can be obtained by performing at least multiple times of (a), preferably (a) to (c) or (a) to (d).

[0954] <Film Formation Step (Layer Formation Step)>

[0955] The production method according to a 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).

[0956] According to the film forming step, the resin film of the present invention can be obtained.

[0957] The type of substrate can be appropriately specified according to the purpose, and can be a semiconductor manufacturing substrate such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor-deposited film, magnetic film, reflective film, Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrate, plasma display panel (PDP) electrode plate, etc., without any particular restrictions. In addition, a bonding layer or an oxide layer and the like can be provided on the surface of these substrates. In the present invention, semiconductor manufacturing substrates are particularly preferred, and silicon substrates, Cu substrates, and molded resin substrates are more preferred.

[0958] Furthermore, an adhesive layer or an oxide layer formed of hexamethyldisilazane (HMDS) or the like may be provided on the surface of these substrates.

[0959] Furthermore, as the base material, for example, a plate-shaped base material (substrate) can be used.

[0960] The shape of the substrate is not particularly limited, and may be circular or rectangular, but is preferably rectangular.

[0961] The size of the substrate is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm, if it is circular, and, for example, 100 to 1000 mm in length of the short side, preferably 200 to 700 mm, if it is rectangular.

[0962] Furthermore, when the curable resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a substrate.

[0963] As a method of applying the curable resin composition to a substrate, coating is preferred.

[0964] Specifically, as the applicable method, dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating and inkjet can be exemplified. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, spin coating, slit coating, spray coating, and inkjet are more preferred. By appropriately adjusting the solid content concentration or coating conditions according to the method, a resin layer of the desired thickness can be obtained. In addition, the coating method can also be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred. If it is a rectangular substrate, slit coating, spray coating, inkjet, etc. are preferred. In the case of the spin coating method, for example, it can be cited that it is applicable to 10 to 180 seconds at a rotation speed of 300 to 3,500 rpm, and it can be applicable to 10 seconds to about 1 minute at a rotation speed of 500 to 2,000 rpm.

[0965] Furthermore, a method of transferring a coating film formed on a temporary support body by the above-mentioned applying method in advance to a substrate can also be applied. Furthermore, in order to obtain uniform film thickness, a plurality of rotation speeds can be combined for coating.

[0966] Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used in the present invention.

[0967] Furthermore, a process of removing excess film may be performed at the end of the substrate. Examples of such a process include edge bead residue rinsing (EBR), air knife, back rinse, and the like.

[0968] Furthermore, a pre-wetting step may be adopted in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

[0969] <Drying process>

[0970] 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 (curable resin composition layer). The drying temperature is preferably 50 to 150°C, more preferably 70°C to 130°C, and further preferably 90°C to 110°C. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes. When the amount of solvent in the curable 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 are no special restrictions.

[0971] <Exposure Process>

[0972] The manufacturing method of the present invention may include an exposure step of exposing the film (curable resin composition layer) to light. There is no particular restriction on the exposure amount as long as the curable resin composition can be cured. For example, it is preferably irradiated with 100 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. 2 , more preferably irradiation 200 to 8,000 mJ / cm 2 .

[0973] The exposure wavelength can be appropriately set within the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[0974] When the exposure wavelength is explained in relation to the light source, examples include (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), broadband (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beams, (7) second harmonics of YAG lasers at 532 nm and third harmonics at 355 nm, etc. For the curable resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferred, and exposure by i-rays is particularly preferred. In this way, particularly high exposure sensitivity can be obtained. Furthermore, from the viewpoint of handling and productivity, a high-pressure mercury lamp with a broad wavelength (three wavelengths of g, h, and i rays) or a semiconductor laser of 405 nm is also preferred.

[0975] The exposure method is not particularly limited as long as it is a method of exposing at least a part of the film including the resin composition of the present invention, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0976] <Development Process>

[0977] The manufacturing method of the present invention may include a developing step of developing the exposed film (curable resin composition layer) (developing the above-mentioned film). For example, in the case of a negative curable resin composition, the unexposed portion (non-exposed portion) is removed by developing. Regarding the developing method, there is no particular restriction as long as the desired pattern can be formed, and for example, the developer can be ejected from a nozzle, sprayed, immersed in the developer of the substrate, etc., and it can be preferably ejected from a nozzle. In the developing step, a process of continuously supplying the developer to the substrate, a process of keeping the developer in a substantially static state on the substrate, a process of vibrating the developer with ultrasound, etc., and a process of combining these, etc. can be adopted.

[0978] Development is performed using a developer. For example, in the case of a negative curable resin composition, any developer can be used without particular limitation as long as it can remove the unexposed portion (non-exposed portion).

[0979] As the developer, a developer containing an organic solvent or an alkaline aqueous solution can be used.

[0980] 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 as a calculated value by inputting a structural formula into ChemBioDraw.

[0981] When the developer is a developer containing 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 alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate), 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, methyl 2- ethyl ethoxypropionate), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, , diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol 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., and, as hydrocarbons, for example, toluene, xylene, anisole, limonene, etc., as sulfoxides, dimethyl sulfoxide, and mixtures of these organic solvents can also be preferably mentioned.

[0982] When the developer contains an organic solvent, in the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred.

[0983] Furthermore, the developer may contain a surfactant.

[0984] When the developer contains an organic solvent, the developer preferably contains 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and further preferably 90% by mass or more of the organic solvent. Furthermore, the developer may contain 100% by mass of the organic solvent.

[0985] When the developer is an alkaline aqueous solution, examples of alkaline compounds that can be contained in the alkaline aqueous solution include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate, etc., preferably TMAH. For example, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.3 to 3% by mass in the total mass of the developer.

[0986] [Developer supply method]

[0987] There are no particular restrictions on the method of supplying the developer as long as the desired pattern can be formed, and there are methods of immersing the substrate formed with the film in the developer, a method of supplying the developer to the film formed on the substrate using a nozzle by immersion development, or a method of continuously supplying the developer. There are no particular restrictions on the type of nozzle, and examples include a straight nozzle, a shower nozzle, a spray nozzle, and the like.

[0988] From the viewpoints of the permeability of the developer, the removability of the non-image area, and the manufacturing efficiency, it is preferred to supply the developer using a straight nozzle or to continuously supply the developer using a spray nozzle. From the viewpoint of the permeability of the developer to the image area, it is more preferred to supply the developer using a spray nozzle.

[0989] Furthermore, a process can be adopted in which the developer is continuously supplied through a straight nozzle, the developer is removed from the substrate by rotating the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the developer is removed from the substrate by rotating the substrate, and this process can be repeated multiple times.

[0990] In addition, as a method for supplying the developer in the development process, a process of continuously supplying the developer to the substrate, a process of maintaining the developer in a substantially static state on the substrate, a process of vibrating the developer on the substrate using ultrasonic waves, etc., and a process combining these processes can be adopted.

[0991] The development time is preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but the development can be performed usually at 20 to 40°C.

[0992] 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 can be cited. The rinsing time is preferably 5 seconds to 5 minutes. Furthermore, between development and rinsing, a process of applying both the developer and the rinsing solution may be included. The time of the above process is preferably 1 second to 5 minutes. Furthermore, for example, rinsing can be performed using a solvent contained in the curable resin composition.

[0993] The rinse may also contain other ingredients.

[0994] As other components, a well-known surfactant, a well-known defoaming agent, etc. are mentioned, for example.

[0995] [Method of supplying flushing fluid]

[0996] There are no particular restrictions on the method of supplying the 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 based on spinning immersion, supplying the rinsing liquid to the substrate with a shower, and continuously supplying the rinsing liquid to the substrate using a mechanism such as a straight nozzle.

[0997] From the perspective of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency of manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., preferably a method of continuously supplying using a spray nozzle, and from the perspective of the permeability of the rinse liquid to the image area, a method of supplying using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc.

[0998] That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the exposed film using a straight nozzle, and more preferably a step of supplying the rinsing liquid using a spray nozzle.

[0999] In addition, as a method for supplying the developer in the rinsing step, a process of continuously supplying the rinsing liquid to the substrate, a process of maintaining the rinsing liquid in a substantially static state on the substrate, a process of vibrating the rinsing liquid on the substrate using ultrasonic waves, etc., and a combination of these processes can be adopted.

[1000] When the developer contains an organic solvent, the rinse liquid includes PGMEA (propylene glycol monoethyl ether acetate) and IPA (isopropyl alcohol), and PGMEA is preferred. Water is preferred as a rinse liquid for development with a developer containing an alkaline aqueous solution.

[1001] The rinsing time is preferably 5 seconds to 1 minute.

[1002] <Heating process>

[1003] The production method of the present invention preferably includes a step of heating the developed film at 50 to 450° C. (heating step).

[1004] It is preferred to include a heating process after the film forming process (layer forming process), the drying process and the developing process. In the heating process, for example, the cyclization reaction of the precursor of the specific resin is carried out by generating a base by decomposing the above-mentioned thermal base generating agent. In addition, the curable resin composition of the present invention may contain a radical polymerizable compound other than the precursor of the specific resin, but it is also possible to carry out curing of the radical polymerizable compound other than the precursor of the unreacted specific resin in this process. As the heating temperature (maximum heating temperature) of the layer in the heating process, it is preferably 50°C or more, more preferably 80°C or more, more preferably 140°C or more, more preferably 150°C or more, more preferably 160°C or more, and even more preferably 170°C or more. As an upper limit, it is preferably 500°C or less, more preferably 450°C or less, more preferably 350°C or less, more preferably 250°C or less, and even more preferably 220°C or less.

[1005] Regarding heating, it is preferably carried out at a heating rate of 1 to 12°C / minute from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C / minute, and further preferably 3 to 10°C / minute. By setting the heating rate to be 1°C / minute or more, productivity can be ensured while preventing excessive volatilization of amines. By setting the heating rate to be 12°C / minute or less, the residual stress of the cured film can be reduced. Moreover, in the case of an oven capable of rapid heating, it is preferably carried out at a heating rate of 1 to 8°C / second from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C / second, and further preferably 3 to 6°C / second.

[1006] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and further preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating to the maximum heating temperature. For example, when the curable resin composition is applied to a substrate and then dried, it is preferred to gradually increase the temperature from the temperature of the dried film (layer), for example, a temperature 30 to 200°C lower than the boiling point of the solvent contained in the curable resin composition.

[1007] The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.

[1008] In particular, when a multilayer laminate is formed, 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 this is because the acetylene groups of the specific resin between the layers undergo a cross-linking reaction by setting the temperature to this level.

[1009] Heating can be performed in stages. As an example, the following pretreatment process 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 of the pretreatment process is preferably 100-200°C, more preferably 110-190°C, and further preferably 120-185°C. In this pretreatment process, it is also preferred to treat while irradiating ultraviolet rays as described in the specification of U.S. Patent No. 9159547. By such a pretreatment process, the properties of the film can be further improved. The pretreatment process can be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment can also be set as a process of more than two stages, for example, pretreatment process 1 can be performed in the range of 100-150°C, and then pretreatment process 2 can be performed in the range of 150-200°C.

[1010] Furthermore, the heating may be followed by cooling, and the cooling rate at this time is preferably 1 to 5° C. / min.

[1011] From the viewpoint of preventing decomposition of the specific resin, the heating step is preferably performed 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, more preferably 20 ppm (volume ratio) or less.

[1012] The heating means is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, and a hot air oven.

[1013] <Metal Layer Formation Step>

[1014] The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (curable resin composition layer).

[1015] The metal layer is not particularly limited, and any conventional metal can be used. 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.

[1016] The formation method of the metal layer is not particularly limited, and existing methods can be used. For example, the method described in Japanese Patent Publication No. 2007-157879, Japanese Patent Table No. 2001-521288, Japanese Patent Publication No. 2004-214501, and Japanese Patent Publication No. 2004-101850 can be used. For example, photolithography, peeling (lift off), electrolytic plating, electroless plating, etching, printing and the method of combining these etc. 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.

[1017] The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm, at the thickest portion.

[1018] <Lamination process>

[1019] The production method of the present invention preferably further includes a lamination step.

[1020] The lamination process is a series of processes including performing (a) film formation process (layer formation process), (b) exposure process, (c) development process, and (d) heating process in sequence again on the surface of the cured film (resin layer) or the metal layer. However, it is also possible to repeat only the (a) film formation process. In addition, it can be set as follows: the (d) heating process is performed collectively at the end or in the middle of the lamination. That is, it can be set as follows: the processes (a) to (c) are repeated a specified number of times, and then (d) heating is performed, so that the stacked curable resin composition layer is cured collectively. In addition, the (e) metal layer formation process can be included after the (c) development process, and in this case, the heating of (d) can also be performed each time, or the heating of (d) can be performed collectively after the specified number of laminations. In the lamination process, it is self-evident that the above-mentioned drying process or heating process, etc., can also be appropriately included.

[1021] When the lamination step is further performed after the lamination step, a surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer forming step. As the surface activation treatment, plasma treatment can be exemplified.

[1022] The lamination step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times.

[1023] Furthermore, each layer in the lamination step may be the same in composition, shape, film thickness, etc., or may be different in composition, shape, film thickness, etc.

[1024] For example, a structure such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, preferably the resin layer has more than 2 layers and less than 20 layers, more preferably the resin layer has more than 3 layers and less than 7 layers, and further preferably more than 3 layers and less than 5 layers.

[1025] In the present invention, it is particularly preferred that after the metal layer is provided, a cured film (resin layer) of the curable resin composition is further formed in a manner covering the metal layer. Specifically, a method of repeatedly performing the steps in the order of (a) film forming step, (b) exposure step, (c) developing step, (e) metal layer forming step, and (d) heating step can be cited, or a method of repeatedly performing the steps in the order of (a) film forming step, (b) exposure step, (c) developing step, and (e) metal layer forming step and providing (d) heating step at the end or in the middle can be cited. By alternately performing the stacking step of stacking the curable resin composition layer (resin layer) and the metal layer forming step, the curable resin composition layer (resin layer) and the metal layer can be alternately stacked.

[1026] (Surface activation treatment process)

[1027] The method for producing 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 metal layer and the resin composition layer.

[1028] The surface activation treatment step is usually performed after the metal layer forming step. However, the metal layer forming step may be performed after the above-mentioned development step by subjecting the resin composition layer to the surface activation treatment step.

[1029] The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or at least a portion of the metal layer and the resin composition layer after exposure may be performed separately. Preferably, at least a portion of the metal layer is subjected to surface activation treatment, preferably a portion or all of the region of the metal layer having a resin composition layer formed on the surface is subjected to surface activation treatment. Thus, 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.

[1030] Furthermore, it is preferred that a part or all of the resin composition layer (resin layer) after exposure is also subjected to surface activation treatment. In this way, by subjecting the surface of the resin composition layer to surface activation treatment, 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 cured during negative development, it is not easily damaged by the surface treatment, thereby easily improving the adhesion.

[1031] As the surface activation treatment, specifically, 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, immersion in hydrochloric acid aqueous solution to remove oxide film and then immersion in an organic surface treatment agent containing at least one compound of amino group and thiol group, mechanical roughening treatment using a brush, plasma treatment is preferred, and oxygen plasma treatment using oxygen in the raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J / m 2 , more preferably 1000 to 100,000 J / m 2 , most preferably 10,000 to 50,000 J / m 2 .

[1032] 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 using the curable resin composition of the present invention for forming an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 of Japanese Patent Application Publication No. 2016-027357 and the description of FIG. 1, which are incorporated into this specification.

[1033] Example

[1034] The present invention is further specifically described by giving examples below. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing 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 indicated, "parts" and "%" are weight references.

[1035] <Examples and Comparative Examples>

[1036] In each example, the components described in the following Tables 1 to 7 were mixed to obtain each curable resin composition. In addition, in each comparative example, the components described in the following Table 2 were mixed to obtain each comparative composition.

[1037] Specifically, the contents of the components other than the solvents described in Tables 1 to 7 are the amounts (parts by mass) described in the columns of Tables 1 to 7. Furthermore, in each composition, the total content of the solvents is set so that the solid content concentration (mass %) of the composition becomes the value described in Tables 1 to 7, and the content ratio of each solvent is set to become a mass ratio based on the numerical value described in the columns of Tables 1 to 7.

[1038] The obtained curable resin composition and comparative composition were filtered under pressure through a polytetrafluoroethylene filter having a pore width of 0.8 μm.

[1039] In Tables 1 to 7, "-" indicates that the composition does not contain the corresponding component.

[1040] [Table 1]

[1041]

[1042] [Table 2]

[1043]

[1044] [Table 3]

[1045]

[1046] [Table 4]

[1047]

[1048] [Table 5]

[1049]

[1050] [Table 6]

[1051]

[1052] [Table 7]

[1053]

[1054] The details of each component described in Tables 1 to 7 are as follows.

[1055] 〔Resin (Specified resin)〕

[1056] ·A-1: Resin having a structure represented by the following formula (A-1):

[1057] A-101: Resin synthesized by the following Synthesis Example 1

[1058] A-201: Resin synthesized by the following Synthesis Example 2

[1059] [Chemical formula 74]

[1060]

[1061] [Synthesis Example 1: Synthesis of polyimide precursor A-101]

[1062] 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. Then, after the mixture was cooled to -20°C, 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 9.7g (123 mmol) of pyridine and 25mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Then, a solution obtained by dissolving 11.8g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100mL of NMP was added to the obtained transparent solution by dropwise addition for 1 hour. Then, 5.6g (17.5 mmol) of methanol and 0.05g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45° C. for 3 days under reduced pressure to obtain a polyimide precursor A-101.

[1063] [Synthesis Example 2: Synthesis of polybenzoxazole precursor A-201]

[1064] 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 to a three-necked flask equipped with a thermometer, a stirrer and a nitrogen inlet tube. The mixture was stirred at room temperature (23°C) and then cooled to -15°C using a dry ice / methanol bath. While the reaction temperature was maintained at -5°C to -15°C, a mixed solution of 30.11 g (0.144 mol) of a 30% by mass NMP solution of 1,4-cyclohexanedicarboxylic acid dichloride, 3.83 g (0.016 mol) of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 96.25 g of NMP was added dropwise to the solution. After the dropwise addition was completed, the obtained mixture was stirred at room temperature for 16 hours.

[1065] Next, 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 below -0°C. After the addition was completed, the mixture was stirred for a further 16 hours.

[1066] The reaction solution was diluted with 550 g of NMP and added to a vigorously stirred 4 L mixture of deionized water / methanol (80 / 20 volume ratio), the precipitated white powder was recovered by filtration, and then washed with deionized water. The polymer was dried at 50° C. under vacuum for two days to obtain resin A-1a.

[1067] 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 flask, and the mixture was 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 the mixture was 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.

[1068] The obtained solution was put into a 2L mixture of deionized water / methanol (80 / 20 volume ratio) which was stirred vigorously, 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 polybenzoxazole (PBO) precursor A-201.

[1069] (Crosslinking agent)

[1070] ·B-1: Compound having the following structure

[1071] ·B-2: Dipentaerythritol hexaacrylate

[1072] ·B-3: LIGHT ESTER BP-6EM (manufactured by Kyoeisha Chemical Co., Ltd.)

[1073] [Chemical formula 75]

[1074]

[1075] [Polymerization initiator (photopolymerization initiator)]

[1076] ·C-1: Compound with the following structure

[1077] C-2: Irgacure OXE-01 (manufactured by BASF)

[1078] ·C-3: ADEKA NCI-930 (manufactured by ADEKA CORPORATION)

[1079] [Chemical formula 76]

[1080]

[1081] ·D-1: Compound with the following structure

[1082] ·D-2: N-[3-(Triethoxysilyl)propyl]maleamic acid

[1083] ·D-3: 3-Methacryloxypropyltrimethoxysilane

[1084] [Chemical formula 77]

[1085]

[1086] ·E-1: Compound with the following structure

[1087] ·E-2: 4-Methoxyphenol

[1088] ·E-3: 2-Nitroso-1-naphthol

[1089] [Chemical formula 78]

[1090]

[1091] ·F-1: Compound having the following structure

[1092] ·F-2: 5-amino-1H-tetrazole

[1093] ·F-3: 3-amino-1,2,4-triazole

[1094] ·F-4: 3,5-diamino-1,2,4-triazole

[1095] F-5: Adenine

[1096] [Chemical formula 79]

[1097]

[1098] ·G-1: Compound having the following structure

[1099] ·G-2: Compound having the following structure

[1100] ·G-3: Compound with the following structure

[1101] [Chemical formula 80]

[1102]

[1103] ·NMP: N-methyl-2-pyrrolidone

[1104] DMSO: dimethyl sulfoxide

[1105] EL: Ethyl lactate

[1106] GBL: gamma-butyrolactone

[1107] ·Cyptn:Cyclopentanone

[1108] EA: 3-Butoxy-N,N-dimethylpropionamide

[1109] ·PGMEA: Propylene glycol monomethyl ether acetate

[1110] <Evaluation>

[1111] [Evaluation of film thickness uniformity based on the composition immediately after preparation]

[1112] In each of the Examples or Comparative Examples, each curable resin composition or comparative composition immediately after preparation was applied (coated) in a layer form on a circular silicon wafer having a diameter of 8 inches by spin coating.

[1113] The coated silicon wafer was dried on a hot plate at 100° C. for 4 minutes to form a resin film with a thickness of 19 μm on the silicon wafer. The film thickness was set as the arithmetic mean of the film thicknesses at 10 locations within the plane.

[1114] In the above-mentioned resin film on the diameter of the silicon wafer, the film thickness of the above-mentioned resin film is measured at a total of 10 points at equal intervals including both ends of the above-mentioned resin film, and the difference between the maximum and minimum values ​​of the measured values ​​at the above-mentioned 10 points is set as the maximum film thickness difference (μm) in the plane.

[1115] The film thickness uniformity of the composition immediately after preparation was evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Film Thickness Uniformity (immediately 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.

[1116] -Evaluation Criteria-

[1117] 10: The above-mentioned maximum in-plane film thickness difference (μm) is 0.5 μm or less.

[1118] 9: The above-mentioned maximum in-plane film thickness difference (μm) exceeds 0.5 μm and is 0.6 μm or less.

[1119] 8: The above-mentioned maximum in-plane film thickness difference (μm) exceeds 0.6 μm and is 0.7 μm or less.

[1120] 7: The above-mentioned maximum in-plane film thickness difference (μm) exceeds 0.7 μm and is 0.8 μm...

Claims

1. A curable resin composition comprising: At least one resin selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, and a polybenzoxazole precursor; and At least two solvents.

2. The curable resin composition according to claim 1, further comprising a migration inhibitor, The migration inhibitor is a compound having one or more heterocyclic rings selected from imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring and triazine ring and an amino group.

3. The curable resin composition according to claim 1 or 2, further comprising a migration inhibitor, The migration inhibitor is at least one compound selected from 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 according to claim 1 or 2, wherein The solvent contains dimethyl sulfoxide and ethyl lactate, wherein 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 according to claim 1 or 2, wherein The solvent includes a solvent having a nitrogen-containing heterocyclic structure.

6. The curable resin composition according to claim 1 or 2, wherein The solvent includes a solvent having an ether bond.

7. The curable resin composition according to claim 1 or 2, wherein Among the above solvents, the content of the second most abundant solvent is 20% by mass or more relative to the total mass of the solvents. 8 . The curable resin composition according to claim 1 , further comprising a silane coupling agent.

9. The curable resin composition according to claim 1 or 2, which is used for storage in a storage container at least once at -15°C to 16°C, wherein the filling rate of the curable resin composition during the refrigeration is 50% to 90% relative to the total storage volume of the storage container. 10 . The curable resin composition according to claim 1 , which is used for forming an interlayer insulating film for a redistribution layer. 11 . A resin film, comprising: applying the curable resin composition according to claim 1 to a substrate. 12 . A cured film obtained by curing the curable resin composition according to claim 1 . 13 . A laminate comprising two or more layers of the cured film according to claim 12 , and comprising a metal layer between any of the cured films.

14. A method for producing a cured film, comprising: The film forming step is to apply the curable resin composition according to any one of claims 1 to 10 to a substrate to form a film.

15. The method for producing a cured film according to claim 14, comprising: an exposure step of exposing the film to light and a development step of developing the film.

16. The method for producing a cured film according to claim 14, comprising: The film is heated at 50°C to 450°C. 17 . A semiconductor device comprising the cured film according to claim 12 .

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