Photosensitive resin composition, cured product, laminate, method for producing cured product, method for manufacturing laminate, method for manufacturing semiconductor device, semiconductor device, and compound

Abstract

To provide a photosensitive resin composition capable of obtaining a cured product excellent in resolution, a cured product obtained by curing the photosensitive resin composition, a laminate including the cured product, a method for producing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product, and to provide a new compound.SOLUTION: There are provided a photosensitive resin composition which contains a resin selected from the group consisting of a polyimide precursor and polyimide, a photopolymerization initiator, and a compound A represented by the following formula (A-1) or formula (A-2), and satisfies at least one of the following condition 1 and condition 2; a cured product obtained by curing the composition and a method for producing the same; a laminate including the cured product and a method for manufacturing the same; a semiconductor device and a method for manufacturing the same; and a compound. Condition 1: The resin has a polymerizable group. Condition 2: The photosensitive resin composition further contains a polymerizable compound.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, a semiconductor device, and a compound.

Background Art

[0002] In modern times, in various fields, utilization of resin materials produced from photosensitive resin compositions containing resins is being carried out. For example, resins such as polyimide are excellent in heat resistance, insulation, etc., and are applied to various uses. Although not particularly limited as the above uses, taking a semiconductor device for mounting as an example, examples include materials for insulating films and encapsulants, or utilization as a protective film. It is also used as a base film or coverlay of a flexible substrate.

[0003] For example, in the above-described uses, resins such as polyimide are used in the form of a photosensitive resin composition containing a resin such as a polyimide precursor. Such a photosensitive resin composition can be applied to a substrate by, for example, coating or the like to form a photosensitive film, and then, if necessary, by performing exposure, development, heating, etc., a cured product can be formed on the substrate. Since the photosensitive resin composition can be applied by a known coating method or the like, it can be said that it is excellent in manufacturing adaptability, for example, the degree of freedom in design such as the shape, size, application position, etc. of the resin composition at the time of application is high. In addition to the high performance of polyimide, from the viewpoint of such excellent manufacturing adaptability, industrial application development of the above-described photosensitive resin composition is increasingly expected.

[0004] Patent Document 2 describes a photosensitive resin composition containing the following components: (A) a polyimide precursor with a specific structure; (B) an imidazole silane compound; and (C) a photoinitiator. The above-mentioned (B) imidazole silane compound has a substituent containing at least one selected from the group consisting of (trihydroxysilylpropyl) aminomethyl group, (methoxydihydroxysilylpropyl) aminomethyl group, (hydroxydimethoxysilylpropyl) aminomethyl group, (trimethoxysilylpropyl) aminomethyl group, trihydroxysilylpropyl group, methoxydihydroxysilylpropyl group, hydroxydimethoxysilylpropyl group, trimethoxysilylpropyl group, (trihydroxysilylpropyl) ureidopropyl group, (methoxydihydroxysilylpropyl) ureidopropyl group, (hydroxydimethoxysilylpropyl) ureidopropyl group, (trimethoxysilylpropyl) ureidopropyl group, and (trimethoxysilylpropyl) ureidoethyl group, bonded to the imidazole ring.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] In recent years, the high-speedization of signals in inter-chip wiring has become increasingly important, and the miniaturization of rewiring connecting between chips has been progressing. Therefore, there is an increasing demand for further high resolution even in the cured product of the photosensitive resin composition used for forming patterns for the purpose of rewiring formation, insulation, etc.

[0007] An object of the present invention is to provide a photosensitive resin composition capable of obtaining a cured product having excellent resolution, a cured product obtained by curing the photosensitive resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product. Another object of the present invention is to provide a novel compound.

Means for Solving the Problems

[0008] Examples of typical embodiments of the present invention are shown below. <1> A resin selected from the group consisting of a polyimide precursor and polyimide, a photoinitiator, and a compound A represented by the following formula (A-1) or formula (A-2), satisfying at least one of the following condition 1 and condition 2 photosensitive resin composition. Condition 1: The resin has a polymerizable group. Condition 2: The photosensitive resin composition further contains a polymerizable compound.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0009] According to the present invention, there are provided a photosensitive resin composition capable of obtaining a cured product excellent in resolution, a cured product obtained by curing the photosensitive resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product. Further, according to the present invention, a novel compound is provided. [Modes for Carrying Out the Invention]

[0010] Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the disclosed embodiments. In this specification, a numerical range represented by the symbol "~" means a range including the numerical values described before and after "~" as a lower limit value and an upper limit value, respectively. In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the intended action of the step can be achieved. In the notation of a group (atomic group) in this specification, a notation without indicating substitution or non-substitution includes both a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In this specification, "exposure" includes, unless otherwise specified, not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Further, examples of the light used for exposure include actinic rays or radiation such as the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate", or either one of them, "(meth)acrylic" means both "acrylic" and "methacrylic", or either one of them, and "(meth)acryloyl" means both "acryloyl" and "methacryloyl", or either one of them. In this specification, Me in a structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of the components obtained by removing the solvent from all the components of the composition. Further, in this specification, the solid content concentration is the mass percentage of the components other than the solvent with respect to the total mass of the composition. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using the gel permeation chromatography (GPC) method, unless otherwise specified, and are defined as polystyrene conversion values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and connecting in series a guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all of the above are manufactured by Tosoh Corporation) as columns. Unless otherwise specified, those molecular weights are measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, when NMP is not suitable as the eluent, for example, in the case of low solubility, THF (tetrahydrofuran) can also be used. Further, unless otherwise specified, detection in GPC measurement is performed using a detector with a UV (ultraviolet) wavelength of 254 nm. In this specification, when describing the positional relationship of each layer constituting the laminate as "upper" or "lower", it is sufficient that there is another layer above or below the reference layer among the plurality of layers being focused on. That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not necessarily have to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "upper", or when there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "upper", and the opposite direction is referred to as "lower". Note that such a setting of the up and down directions is for convenience in this specification, and in an actual embodiment, the "upper" direction in this specification may be different from the vertically upward direction. In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to each component as each component contained in the composition. Also, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise stated, the temperature is 23 °C, the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH. In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0011] (Photosensitive resin composition) The photosensitive resin composition of the present invention (hereinafter, also simply referred to as "resin composition") contains a resin selected from the group consisting of a polyimide precursor and a polyimide, a photoinitiator, and a compound A represented by formula (A-1) or formula (A-2), and satisfies at least one of the following condition 1 and condition 2. Condition 1: The above resin has a polymerizable group. Condition 2: The photosensitive resin composition further contains a polymerizable compound. Also, in this specification, the "resin selected from the group consisting of a polyimide precursor and a polyimide" is also referred to as a "specific resin".

[0012] The resin composition of the present invention is preferably used for forming a photosensitive film to be exposed and developed, and more preferably used for forming a film to be exposed and developed using a developer containing an organic solvent. The resin composition of the present invention can be used, for example, for forming an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used for forming an interlayer insulating film for a rewiring layer. Further, the resin composition of the present invention is preferably a negative photosensitive resin composition. In the present invention, negative development refers to development in which the unexposed portion is removed by development during exposure and development, and positive development refers to development in which the exposed portion is removed by development. As the above exposure method, the above developer, and the above development method, for example, the exposure method described in the exposure step in the description of the method for producing a cured product described later, the developer and the development method described in the development step are used.

[0013] According to the resin composition of the present invention, a cured product excellent in resolution can be obtained. Conventionally, when a photosensitive resin composition containing polyimide or its precursor is exposed and developed for patterning, a sensitizer such as N-phenyldiethanolamine has been used for the purpose of improving exposure sensitivity and the like. Here, the present inventors have found that the resolution is further improved by using Compound A represented by the formula (A-1) or the formula (A-2) in the photosensitive resin composition. The reason for obtaining the above effect is not clear, but it is presumed as follows. Compound A represented by the formula (A-1) or the formula (A-2) is an amino group having a structure represented by the formula (R-1), and contains n amino groups bonded by a single bond without a linking group to an aromatic ring. By having such a structure, the molecular weight of Compound A increases, the volatilization of Compound A is suppressed during the formation of the photosensitive film before exposure, etc., and it is likely to remain in the photosensitive film. Therefore, it is considered that the sensitizing action occurs efficiently. Furthermore, it is considered that the above n amino groups serve as a radical source and react with the polymerizable groups present in the resin or the polymerizable compound in the cured product, contributing to the improvement of the resolution by forming crosslinks by compound A between these compounds. In addition, in the cured product obtained from the composition, since the above compound A remaining in the cured product exhibits an antioxidant effect, it is considered that the cured product is less likely to deteriorate over a long period of time and the reliability is also improved.

[0014] Here, Patent Documents 1 and 2 do not describe a resin composition containing compound A.

[0015] Hereinafter, the details of the resin composition of the present invention will be described.

[0016] <Condition 1, Condition 2> The resin composition of the present invention satisfies at least one of the above Condition 1 and Condition 2, and preferably satisfies at least Condition 2. In addition, satisfying both Condition 1 and Condition 2 is also one of the preferred embodiments of the present invention. Preferred embodiments of the polymerizable group in Condition 1 and preferred embodiments of the polymerizable compound in Condition 2 will be described later.

[0017] <Specific resin> The resin composition of the present invention contains a resin (specific resin) selected from the group consisting of a polyimide precursor and a polyimide.

[0018] From the viewpoint of resolution and the like, the resin composition of the present invention preferably contains a polyimide precursor. Also, from the viewpoint of suppressing shrinkage during curing and the like, it is preferable to contain a polyimide. When the resin composition of the present invention contains a polyimide precursor, it is preferably a polyimide precursor containing a repeating unit represented by the following formula (1-1). In the present specification, polyimide refers to a resin having a repeating unit containing an imide structure in the molecular chain, and preferably a resin having a repeating unit containing an imide ring structure in the molecular chain. When the polyimide is a linear resin, the polyimide is preferably a resin having a repeating unit containing an imide structure in the main chain, and more preferably a resin having a repeating unit containing an imide ring structure in the main chain. In this specification, the "main chain" refers to the relatively longest bond chain in the resin molecule, and the "side chain" refers to the other bond chains. In this specification, the imide structure refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. In this specification, the imide ring structure refers to a ring structure containing all two carbon atoms and the nitrogen atom in the above imide structure as ring members. The imide ring structure is preferably a 5-membered ring. In addition to the imide structure, the polyimide may be a so-called polyamide-imide having an amide structure in the molecular chain. In this specification, the amide bond refers to a structure represented by *-C(=O)N(-#)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. Also, # represents a bonding site with another structure, preferably a bonding site with a hydrogen atom or a carbon atom, and more preferably a bonding site with a hydrogen atom.

[0019] In the present invention, the polyimide precursor refers to a resin that undergoes a chemical structure change upon external stimulation to become a polyimide. A resin that undergoes a chemical structure change upon heat to become a polyimide is preferred, and a resin that undergoes a ring closure reaction upon heat to form a ring structure and thus becomes a polyimide is more preferred. The preferred embodiment of the formed polyimide is as described above.

[0020] 〔Polymerizable group〕 The specific resin preferably has a polymerizable group. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, etc., and a group having an ethylenically unsaturated bond is preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, a (meth)acrylamide group, and the like. Among these, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group or a maleimide group is preferable, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferable. Further, from the viewpoint of reducing the dielectric loss tangent, a vinylphenyl group or a maleimide group is preferable. Moreover, a radical polymerizable group is preferable as the polymerizable group.

[0021] The content of the polymerizable group (polymerizable group value) relative to the total mass of the specific resin is preferably 0.2 to 5.0 mmol / g, more preferably 0.25 to 4.0 mmol / g, and still more preferably 0.3 to 3.0 mmol / g. In the present specification, the polymerizable group value is defined as the molar amount of the polymerizable group contained in 1 mol of the compound / the number average molecular weight of the compound.

[0022] [Repeating unit represented by formula (1-1)] The specific resin preferably contains a repeating unit represented by the following formula (1-1), and more preferably is a polyimide precursor containing a repeating unit represented by the following formula (1-1). [Chemical formula] In formula (1-1), X is a tetravalent organic group, Y is a divalent organic group, and R 1 and R 2 are each independently a hydrogen atom or a group represented by the following formula (III). [Chemical formula] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group or a polyalkyleneoxy group, and * represents the bonding site with an oxygen atom.

[0023] -X- In formula (1-1), the number of carbon atoms of X is preferably 4 or more, more preferably 4 to 50, and even more preferably 6 to 40. In formula (1-1), X is preferably a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride described in paragraphs 0055 to 0057 of JP-A-2023-003421.

[0024] Among these, X in formula (1-1) is preferably any one of the following formulas (a) to (i), and more preferably a group represented by the following formula (a) or the following formula (b). Particularly, from the viewpoint of improving chemical resistance by reducing the solvent permeability so that the resin obtained in the cured product is likely to be stacked, a group represented by formula (b) is preferable.

Chemical formula

[0025] Particularly, the specific resin is a repeating unit represented by the above formula (1-1), and preferably includes a repeating unit A in which X in formula (1-1) is represented by the above formula (a), and a repeating unit represented by the above formula (1-1) in which X in formula (1-1) is represented by the above formula (b).

[0026] The molar amount of the repeating unit A relative to the total molar amount of the repeating unit A and the repeating unit B is preferably 30 to 90 mol%, more preferably 40 to 85 mol%, and even more preferably 50 to 80 mol%.

[0027] In addition, the proportion of the total molar amount of the repeating unit A and the repeating unit B in all repeating units of the specific resin is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, particularly preferably 80 mol% or more, and even more preferably 90 mol% or more. The upper limit of the above proportion is not particularly limited and may be 100 mol%.

[0028] In addition, X preferably does not contain an imide bond in its structure. In addition, X preferably does not contain a urethane bond, a urea bond, and an amide bond in its structure. In the present invention, the urethane bond is a bond represented by *-O-C(=O)-NR N -*, where R N represents a hydrogen atom or a monovalent organic group, and * each represents a bonding site with a carbon atom. R N is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and still more preferably a hydrogen atom. In the present invention, the urea bond is a bond represented by *-NR N -C(=O)-NR N -*, where R N each independently represents a hydrogen atom or a monovalent organic group, and * each represents a bonding site with a carbon atom. The preferred embodiments of R N are as described above. Furthermore, X preferably does not contain an ester bond in its structure. In the present invention, the ester bond is a bond represented by *-O-C(=O)-*. Among these, X preferably does not contain an imide bond, a urethane bond, a urea bond, and an amide bond, and more preferably does not contain an imide bond, a urethane bond, a urea bond, an amide bond, and an ester bond.

[0029] -Y- In formula (1-1), the carbon number of Y is preferably 4 or more, more preferably 4 to 50, and still more preferably 6 to 40. Y is preferably based on the description in paragraphs 0042 to 0053 of JP-A-2023-003421.

[0030] Among these, Y in formula (1-1) is preferably any of the following formulas (Ya) to (Yr). The hydrogen atoms of the benzene ring in these structures may be substituted with substituents such as an alkyl group having 1 to 4 carbon atoms and a trifluoromethyl group.

Chemical formula

[0031] Further, Y preferably does not contain an imide bond in its structure. Further, Y preferably does not contain a urethane bond, a urea bond, and an amide bond in its structure. Furthermore, Y preferably does not contain an ester bond in its structure. Among these, Y preferably does not contain an imide bond, a urethane bond, a urea bond, and an amide bond, and more preferably does not contain an imide bond, a urethane bond, a urea bond, an amide bond, and an ester bond.

[0032] -R 1 , R 2 - In formula (1-1), at least one of R 1 and R 2 is preferably a group represented by formula (III), and more preferably both are groups represented by formula (III).

[0033] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group, or a hydroxymethyl group, and a hydrogen atom or a methyl group is preferred. In formula (III), * represents the bonding site with another structure. In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkyleneoxy group. Suitable R 201 Examples of the group include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group, etc., 1,2-butanediyl group, 1,3-butanediyl group, -CH2CH(OH)CH2-, polyalkyleneoxy group. Alkylene groups such as ethylene group and propylene group, -CH2CH(OH)CH2-, cyclohexyl group, and polyalkyleneoxy group are more preferable, and alkylene groups such as ethylene group and propylene group, or polyalkyleneoxy group are even more preferable. 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 contained in the polyalkyleneoxy group may be the same or different from each other. When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as an alternating pattern. The number of carbon atoms of the above alkylene group (when the alkylene group has a substituent, including the number of carbon atoms of the substituent) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, still more preferably 2 to 5, still even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. Further, the above alkylene group may have a substituent. Preferred substituents include an alkyl group, an aryl group, a halogen atom, etc. In addition, the number of alkyleneoxy groups (the repeating number of the polyalkyleneoxy group) contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. As the polyalkyleneoxy group, from the viewpoints of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group formed by bonding a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is even more preferable. In the group formed by bonding a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups, the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged, may form blocks and be arranged, or may be arranged in a pattern such as alternating. The preferable embodiments of the repeating numbers of ethyleneoxy groups and the like in these groups are as described above.

[0034] In formula (1-1), R 1 is a hydrogen atom, or when R 2 is a hydrogen atom, the specific resin may form a counter salt with a tertiary amine compound having an ethylenic unsaturated bond. Examples of such a tertiary amine compound having an ethylenic unsaturated bond include N,N-dimethylaminopropyl methacrylate.

[0035] Further, the specific resin may further contain a repeating unit represented by any one of the following formulas (3), (4), and (5). For example, when a part of the repeating unit represented by formula (1-1) is cyclized to form an imide structure, it becomes a repeating unit represented by any one of the following formulas (3), (4), and (5).

Chemical formula

[0036] In formulas (3), (4), and (5), the preferable embodiments of X, Y, R 1 and R 2 are respectively the X, Y, R in formula (1-1)1 and R 2 is the same as the preferred embodiment thereof.

[0037] As one embodiment when the specific resin in the present invention is a polyimide precursor, an embodiment in which the content of the repeating unit represented by the formula (1-1) is 50 mol% or more of all the repeating units can be mentioned. The above content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above content is not particularly limited, and all the repeating units in the polyimide precursor excluding the terminals may be the repeating unit represented by the formula (1-1).

[0038] Further, as another embodiment when the specific resin in the present invention is a polyimide precursor, an embodiment in which the total content of the repeating unit represented by the formula (1-1), the repeating unit represented by the formula (3), the repeating unit represented by the formula (4), and the repeating unit represented by the formula (5) is 50 mol% or more of all the repeating units can be mentioned. The above total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all the repeating units in the polyimide precursor excluding the terminals may be the repeating unit represented by the formula (1-1), the repeating unit represented by the formula (3), the repeating unit represented by the formula (4), or the repeating unit represented by the formula (5).

[0039] When the specific resin is a polyimide precursor, the imidization rate (also referred to as the "ring closure rate") of the polyimide precursor is preferably less than 70%, more preferably less than 50%, and still more preferably less than 30% from the viewpoints of the film strength, insulation, etc. of the obtained organic film. The lower limit of the above imidization rate is preferably 0% or more, more preferably 5% or more, and still more preferably 10% or more. The above imidization rate is measured by the method described later.

[0040] [Repeating unit represented by formula (2)] The specific resin preferably contains a repeating unit represented by the following formula (2), and more preferably is a polyimide containing a repeating unit represented by the following formula (2). [Chemical formula] In formula (2), X 1 represents an organic group having 4 or more carbon atoms, and Y 1 represents an organic group having 4 or more carbon atoms, and R 1 each independently represents a structure represented by formula (R-1), n and m each independently represent an integer of 0 to 4, and n + m is 1 or more. [Chemical formula] In formula (R-1), L 1 represents an a1 + 1-valent linking group, A 1 represents a polymerizable group, a1 represents an integer of 1 or more, and * represents the bonding site with X 1 or Y 1 in formula (2).

[0041] -X 1 - In formula (2), the number of carbon atoms of X 1 is 4 or more, preferably 4 to 50, and more preferably 4 to 40. The preferred embodiment of X 1 is the same as the preferred embodiment of X in formula (1-1) above, except that it may have a bonding site with R 1 . When it has a bonding site with R 1 , the hydrogen atom in X above can be replaced by R 1 .

[0042] -Y 1 - In formula (2), the number of carbon atoms of Y 1 is 4 or more, preferably 4 to 50, and more preferably 4 to 40. The preferred embodiment of Y 1 is the same as the preferred embodiment of Y in formula (1-1) above, except that it may have a bonding site with R 1 .1 When it has a binding site with the above-mentioned Y, the hydrogen atom in Y can be replaced by R 1 in the following manner.

[0043] -R 1 - R in formula (2) 1 is a group represented by formula (R-1). In formula (R-1), L 1 is preferably a group represented by the following formula (L-2).

Chemical formula

[0044] In formula (L-2), Z 2 is preferably -O- or -C(=O)O-. Also, when Z 2 is -NR N -, R N is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or a phenyl group, and even more preferably a hydrogen atom. In formula (L-2), when a1 is 1, L x is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group. In formula (L-2), when a1 is 2 or more, L xis preferably a group represented by a hydrocarbon group, a heterocyclic group, or a combination thereof, more preferably a saturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, and even more preferably a saturated aliphatic hydrocarbon group having 3 to 15 carbon atoms. In formula (L-2), a1 has the same meaning as a1 in formula (R-1).

[0045] In formula (R-1), A 1 represents a polymerizable group. Preferred embodiments of the polymerizable group are as in the preferred embodiments of the polymerizable groups possessed by the above-mentioned specific resins. Here, A 1 is preferably a (meth)acryloxy group, a maleimide group, or a vinylphenyl group, more preferably a maleimide group or a vinylphenyl group from the viewpoint of reducing the dielectric tangent of the cured product. Also, from the viewpoint of reactivity and the like, a (meth)acryloxy group is more preferable.

[0046] Among these, A in formula (R-1) 1 is a vinylphenyl group, and L 1 is preferably a group represented by formula (L-2-1).

Chemical formula

[0047] Also, A in formula (R-1) 1 is a maleimide group, and L 1 is a group represented by formula (L-2), and L XIt is preferably an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms. The aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but an aromatic hydrocarbon group is preferred. As the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 10 carbon atoms is preferred, and an aromatic hydrocarbon group having 6 carbon atoms is more preferred. Examples of the heteroatom in the aromatic heterocyclic group include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms in the aromatic heterocyclic group is preferably 1 or 2. Further, as the aromatic heterocyclic group, a 5-membered ring or a 6-membered ring containing the above heteroatom is preferred. Furthermore, another aromatic heterocyclic group or another aromatic hydrocarbon ring group may be condensed to the aromatic heterocyclic group. The aliphatic saturated hydrocarbon group having 4 or more carbon atoms may have any structure represented by a linear, branched, cyclic, or a combination thereof. The aliphatic saturated hydrocarbon group having 4 or more carbon atoms preferably has 4 to 20 carbon atoms, and more preferably 5 to 10 carbon atoms.

[0048] In formula (R-1), a1 is preferably an integer of 1 to 4, and more preferably an integer of 1 to 2. Also, the aspect where a1 is 1 is also one of the preferred aspects of the present invention.

[0049] Also, the number of ester bonds contained in formula (R-1) is preferably 1 or 0.

[0050] -n and m- In formula (2), m is preferably an integer of 0 to 2, and more preferably 0 or 1. Also, the aspect where m is 0 is also one of the preferred aspects of the present invention. In formula (2), n is preferably 1 or 2, and more preferably 2.

[0051] When the specific resin is polyimide, the content of the repeating unit represented by the formula (2) with respect to the total mass of the specific resin is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass. When the specific resin contains the repeating unit represented by the formula (2), it may contain two or more repeating units represented by the formula (2) having different structures. In that case, the total amount is preferably within the above range.

[0052] When the specific resin is polyimide, the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, from the viewpoints of the film strength and insulation of the obtained organic film. The upper limit of the above imidization rate is not particularly limited and may be 100% or less. When the specific resin is polyimide, the content of the imide structure in the specific resin is preferably 3 mmol / g or less, and more preferably 2.5 mmol / g or less. The lower limit of the above content is not particularly limited, but for example, it can be 0.5 mmol / g or more. The above imidization rate is measured, for example, by the following method. Measure the infrared absorption spectrum of the specific resin, and obtain the peak intensity P1 near 1377 cm -1 which is the absorption peak derived from the imide structure. Next, after heat-treating the specific resin at 350 °C for 1 hour, measure the infrared absorption spectrum again, and obtain the peak intensity P2 near 1377 cm -1 Using the obtained peak intensities P1 and P2, the imidization rate of the specific resin can be obtained based on the following formula. Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0053] The weight average molecular weight (Mw) of the specific resin is preferably 100,000 or less, more preferably 50,000 or less, and still more preferably 40,000 or less. Also, the above Mw is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, and particularly preferably 15,000 or more. The number average molecular weight (Mn) of the specific resin is preferably 40,000 or less, more preferably 30,000 or less, and still more preferably 20,000 or less. Also, the above Mn is preferably 2,000 or more, more preferably 3,000 or more, and still more preferably 4,000 or more. The dispersity of the molecular weight of the specific resin is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. The upper limit value of the dispersity is not particularly defined, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and still more preferably 6.0 or less. In this specification, the dispersity of the molecular weight is a value calculated by weight average molecular weight / number average molecular weight. When the resin composition contains a plurality of resins as the specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one resin are within the above ranges. Also, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated for the plurality of resins as one resin are respectively within the above ranges.

[0054] 〔Method for producing specific resin〕 The specific resin can be synthesized, for example, according to the method described in paragraphs 0134 to 0136 of International Publication No. 2022 / 145355 or with reference to this method. The above description is incorporated into this specification. Also, it may be synthesized with reference to other known methods.

[0055] 〔Content〕 The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one kind of the specific resin, or may contain two or more kinds. When two or more kinds are contained, it is preferable that the total amount is within the above range.

[0056] <Other resin> The resin composition of the present invention may contain the above-described specific resin and another resin different from the specific resin (hereinafter also simply referred to as "other resin"). Examples of the other resin include phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane resin, butyral resin, styryl resin, polyether resin, polyester resin, and the like. For example, by further adding a (meth)acrylic resin, a resin composition excellent in coatability can be obtained, and a pattern (cured product) excellent in solvent resistance can be obtained. For example, instead of the polymerizable compound described later, or in addition to the polymerizable compound described later, a (meth)acrylic resin having a high polymerizable group value and a weight average molecular weight of 20,000 or less (for example, the content molar amount of the polymerizable group in 1 g of the resin is 1×10 -3 mol / g or more) is added to the resin composition, whereby the coatability of the resin composition, the solvent resistance of the pattern (cured product), and the like can be improved.

[0057] <Compound A> The resin composition of the present invention contains a compound A represented by the following formula (A-1) or formula (A-2), and preferably contains the compound represented by the following formula (A-1). [Chemical formula] In formula (A-1), R 11 and R 12 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R 11 and R 12 contains a group represented by formula (R-1), Ar 1 represents an aromatic ring structure which may have a substituent or a condensed ring, n1 represents an integer of 2 or more, when n1 is 2, X represents a single bond or a divalent linking group, and when n1 is 3 or more, X represents an n1-valent linking group. In formula (A-2), R 21 and R 22 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R 21 and R 22 contains a group represented by formula (R-1), Ar 2 represents an aromatic ring structure which may have a substituent or a condensed ring, and n2 represents an integer of 2 or more. [Chemical formula] In formula (R-1), R R1 and R R2 each independently represent a hydrogen atom or a monovalent organic group, m R R1 may be the same or different from each other, m R R2 may be the same or different from each other, m represents an integer of 2 or more, and * represents a bonding site with another structure.

[0058] [R 11 and R 12 In formula (A-1), it is preferable that both R 11 and R 12 are groups represented by formula (R-1). R 11 and R 12 When one of them is a hydrogen atom or a monovalent organic group different from the group represented by formula (R-1), R 11 and R 12One of them is preferably a monovalent organic group different from the group represented by the formula (R-1). Examples of the monovalent organic group different from the group represented by the formula (R-1) include an alkyl group, an aryl group, etc., an alkyl group is preferable, and a methyl group is more preferable.

[0059] - the group represented by the formula (R-1)- In the group represented by the formula (R-1), R R1 and R R2 each independently represent a hydrogen atom or a monovalent organic group, preferably represent a hydrogen atom or an alkyl group, and more preferably represent a hydrogen atom or a methyl group. Also, it is one of the preferable embodiments that both R R1 and R R2 are hydrogen atoms. In the formula (R-1), m represents an integer of 2 or more, preferably an integer of 2 to 4, more preferably 2 or 3, and still more preferably 2. Specific examples of the group represented by the formula (R-1) are given below, but the present invention is not limited thereto. In the following specific examples, * has the same meaning as * in the formula (R-1).

Chemical formula

[0060] 〔Ar 1 〕 In the formula (A-1), Ar 1 represents an aromatic ring structure which may have a substituent or a condensed ring. In the formula (A-1), the aromatic ring structure of Ar 1 may be either an aromatic hydrocarbon ring structure or an aromatic heterocyclic ring structure, but an aromatic hydrocarbon ring structure is preferable, and a benzene ring structure is more preferable. Examples of the above-mentioned substituent include an alkyl group, an aryl group, a halogen atom, etc., an alkyl group is preferable, and a methyl group is more preferable. Examples of the above-mentioned condensed ring include cycloalkane, aromatic ring, etc., and a cyclopropane ring is preferable.

[0061] 〔n1〕 In formula (A-1), n1 represents an integer of 2 to 4, preferably 2 or 3, and more preferably 2.

[0062] [X] In formula (A-1), when n1 is 2, X represents a single bond or a divalent linking group. The divalent linking group is preferably a group represented by an alkylene group, a haloalkylene group, an arylene group, or a combination thereof. The hydrogen atoms in these groups may be substituted by known substituents such as a hydroxy group and a halogen atom. As the alkylene group, an alkylene group having 1 to 4 carbon atoms is preferable, and a methylene group, an ethylene group, or an isopropylene group is more preferable. As the arylene group, it may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group, and more preferably a phenylene group.

[0063] In formula (A-1), when n1 is 3 or more, X represents an n1-valent linking group. The n1-valent linking group is preferably a group represented by an aliphatic hydrocarbon group, an aromatic group, or a combination thereof. The hydrogen atoms in these groups may be substituted by known substituents such as a hydroxy group. As the aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable. As the aromatic group, an aromatic hydrocarbon group is preferable, and an aromatic hydrocarbon group having 6 carbon atoms is more preferable.

[0064] Specific examples of the structure formed by X and Ar are given below, but the present invention is not limited thereto. In the following specific examples, * represents the bonding site with the nitrogen atom in formula (A-1). 1 Specific examples of the structure formed by X and Ar are given below, but the present invention is not limited thereto. In the following specific examples, * represents the bonding site with the nitrogen atom in formula (A-1). [Chemical formula]

[0065] [R 21 and R 22 ​In formula (A-2), R 21 and R 22 preferred embodiments are the same as the preferred embodiments of R 11 and R 12 in formula (A-1).

[0066] [Ar 2 In formula (A-2), Ar 2 represents an aromatic ring structure which may have a substituent or a fused ring. Examples of the above aromatic ring structure include a benzene ring structure, a carbazole ring structure, a fluorene ring structure and the like. Examples of the above substituent include an alkyl group, an aryl group, a halogen atom and the like, an alkyl group is preferred, and a methyl group is more preferred. Examples of the above fused ring include cycloalkane, aromatic ring and the like, and a cyclopropane ring is preferred. Specific examples of Ar 2 are given below, but the present invention is not limited thereto. In the following specific examples, * represents the bonding site with the nitrogen atom in formula (A-2). [Chemical formula]

[0067] Among these, the above compound A is a compound represented by the above formula (A-1), and R 11 and R 12 in the above formula (A-1) are both groups represented by formula (R-1), and an embodiment in which m in formula (R-1) is 2 is preferred. Preferred embodiments of other symbols in the above embodiment are as described in the description of the above formula (A-1).

[0068] Also, compound A is preferably a compound represented by the following formula (AA-1), formula (AA-2), or formula (AA-3). [Chemical formula]

[0069] [Molecular weight] ​The molecular weight of Compound A is preferably 1,000 or less, more preferably 800 or less, and even more preferably 500 or less. The lower limit of the above molecular weight is not particularly limited. For example, it is preferably 150 or more, and more preferably 200 or more.

[0070] 〔Synthesis Method〕 Compound A can be synthesized, for example, by the method described in the examples below. However, the synthesis method is not particularly limited as long as the structure corresponding to the specific compound can be obtained. In addition, if there is a commercially available compound, it can also be used.

[0071] 〔Specific Examples〕 Specific examples of Compound A include (A-1)-1 to (A-1)-31, (A-2)-1 to (A-2)-3, etc. described in the examples below, but the present invention is not limited thereto.

[0072] 〔Content〕 The content of Compound A in the resin composition of the present invention is preferably 0.1 to 10.0% by mass, more preferably 0.2 to 5.0% by mass, and even more preferably 0.3 to 3.0% by mass based on the total solid content of the resin composition. In the resin composition of the present invention, when the content of the specific resin is 100 parts by mass, the content of Compound A is preferably 0.1 to 10.0 parts by mass, more preferably 0.2 to 5.0 parts by mass, and even more preferably 0.3 to 3.0 parts by mass. The resin composition of the present invention may contain only one kind of Compound A or may contain two or more kinds. When two or more kinds of Compound A are contained, the total amount is preferably within the above range.

[0073] <Compound B> The resin composition of the present invention preferably further contains Compound B represented by the following formula (B-1).

Chemical Formula

[0074] In formula (B-1), the preferred embodiment of Ar B is the same as the preferred embodiment of Ar 2 in the above formula (A-2). In formula (B-1), the preferred embodiments of R B1 and R B2 and formula (R-1) are the same as the preferred embodiments of R 21 and R 22 and formula (R-1) in the above formula (A-2).

[0075] [Molecular weight] The molecular weight of compound B is preferably 1,000 or less, more preferably 800 or less, still more preferably 500 or less, and particularly preferably 300 or less. The lower limit of the above molecular weight is not particularly limited, but for example, it is preferably 100 or more, and more preferably 150 or more.

[0076] [Specific examples] Specific examples of compound B include (B-1)-1 to (B-1)-10 described in the examples below, etc., but the present invention is not limited thereto.

[0077] [Content] The content of compound B in the resin composition of the present invention is preferably 0.1 to 10.0% by mass, more preferably 0.2 to 5.0% by mass, and still more preferably 0.3 to 3.0% by mass based on the total solid content of the resin composition. In the resin composition of the present invention, when the content of the specific resin is 100 parts by mass, the content of Compound A is preferably 0.1 to 10.0 parts by mass, more preferably 0.2 to 5.0 parts by mass, and still more preferably 0.3 to 3.0 parts by mass. When the total content of Compound A and Compound B is based on 100 parts by mass of the total content of the above photoinitiator, it is preferably 30 to 200 parts by mass, more preferably 40 to 150 parts by mass, and still more preferably 50 to 100 parts by mass. The resin composition of the present invention may contain only one kind of Compound B or may contain two or more kinds. When two or more kinds of Compound B are contained, the total amount is preferably within the above range.

[0078] <Compound X> The resin composition of the present invention preferably contains Compound X represented by the following formula (X-1), formula (X-2), or formula (X-3).

Chemical formula

[0079] By including Compound X, the storage stability of the composition is improved. Although the reason is not clear, it is considered that because Compound X has a high polarity, the solvent solubility of the components in the composition is improved and precipitation over time is suppressed.

[0080] The content of Compound X with respect to the total solid content of the resin composition is preferably 0.00001 to 1% by mass, more preferably 0.00005 to 0.5% by mass, and still more preferably 0.0001 to 0.1% by mass. In addition, when the content of Compound A contained in the resin composition is 100 parts by mass, the content of Compound X is preferably 0.001 to 20 parts by mass, more preferably 0.005 to 10 parts by mass, and still more preferably 0.01 to 5 parts by mass. The resin composition may contain two or more kinds of Compound X. When two or more kinds of Compound X are contained, the total amount thereof is preferably within the above range.

[0081] Compound Y The resin composition may further contain a compound Y represented by the following formula (Y-1). The compound Y may be contained in the resin composition as a derivative of the compound A.

Chemical formula

[0082] In formula (Y-1), the preferred embodiments of R 11 , R 12 and Ar 1 are the same as the preferred embodiments of R 11 , R 12 and Ar 1 in the above formula (A-1). In formula (Y-1), the preferred embodiments of R 13 and R 14 are the same as the preferred embodiments of R 13 and R 14 in the above formula (A-1). Also, the preferred embodiments of the group represented by the above formula (R-1) in R 11 , R 12 , R 13 and R 14 are also as described above. In formula (Y-1), X is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond thereof. The hydrogen atoms in these hydrocarbon groups may be substituted with known substituents such as a hydroxy group and a halogen atom. In formula (Y-1), when m1 + m2 is 2, X is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and *=CH-* is more preferable. In formula (Y-1), when m1 + m2 is 3, X is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and *=C(-*)-* is more preferable. In formula (Y-1), m1 is preferably 1 or 2, and more preferably 1. In formula (Y-1), m2 is preferably 1 or 2, and more preferably 1.

[0083] Specific examples of compound Y are shown below, but the present invention is not limited thereto. For example, the compound represented by the following formula (Y-1) can be obtained as a structure in which the compound represented by the above formula (AA-1) is in a cationic form. In addition, a compound having a structure in which the structure corresponding to compound A is in a cationic form can be used as compound Y.

Chemical formula

[0084] By including compound Y, the storage stability of the composition is improved. The reason is not clear, but it is considered that the stability is improved because compound Y forms a salt with an acidic component in the resin or composition.

[0085] The content of compound Y relative to the total solid content of the resin composition is preferably 0.00001 to 1% by mass, more preferably 0.00005 to 0.5% by mass, and even more preferably 0.0001 to 0.1% by mass. In addition, the total content of Compound A and Compound Y contained in the resin composition is preferably 0.1 to 10.0% by mass, more preferably 0.15 to 5.0% by mass, and even more preferably 0.2 to 3.0% by mass based on the total solid content of the resin composition. The resin composition may contain two or more kinds of Compound Y. When two or more kinds of Compound Y are contained, it is preferable that the total amount thereof is within the above range.

[0086] <Polymerizable compound> The resin composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include a polymerizable compound having a radical polymerizable group (radical crosslinking agent) or other crosslinking agents.

[0087] 〔Radical crosslinking agent〕 The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. As the radical polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, a (meth)acrylamide group, and the like. Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferable, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferable. In particular, the resin composition of the present invention preferably contains a compound containing a (meth)acryloyl group as the polymerizable compound.

[0088] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 ethylenically unsaturated bonds is even more preferable. From the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0089] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0090] Examples of the radical crosslinking agent include the compounds described in paragraphs 0125 to 0144 of International Publication No. 2023 / 190064.

[0091] Among these, it is preferable that the resin composition of the present invention contains a compound represented by the following formula (M-1) as the polymerizable compound.

Chemical formula

[0092] When containing a radical crosslinking agent, the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less based on the total solid content of the resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0093] The radical crosslinking agent may be used alone or in combination of two or more. When using two or more in combination, it is preferable that the total amount is within the above range.

[0094] 〔Other crosslinking agents〕 It is also preferable that the resin composition of the present invention contains other crosslinking agents different from the above-described radical crosslinking agent. The other crosslinking agent refers to a crosslinking agent other than the radical crosslinking agent described above, and is preferably a compound having a plurality of groups in the molecule that promote a reaction to form a covalent bond between the other compound in the composition or its reaction product by the photosensitivity of a photoacid generator or a photobase generator. A compound having a plurality of groups in the molecule that promote a reaction to form a covalent bond between the other compound in the composition or its reaction product by the action of an acid or a base is preferred. Examples of the other crosslinking agent include the compounds described in paragraphs 0179 to 0207 of WO 2022 / 145355. The above description is incorporated herein.

[0095] The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass based on the total solid content of the resin composition. The other crosslinking agent may contain only one kind or two or more kinds. When two or more kinds of the other crosslinking agents are contained, the total thereof is preferably within the above range.

[0096] 〔Polymerization initiator〕 The resin composition of the present invention contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photoinitiator, but it is particularly preferred to contain a photoinitiator. The photoinitiator is preferably a photo radical polymerization initiator. There is no particular limitation on the photo radical polymerization initiator, and it can be appropriately selected from known photo radical polymerization initiators. For example, a photo radical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferred. It may also be an activator that acts on a photoexcited sensitizer to generate active radicals.

[0097] The photo radical polymerization initiator has at least about 50 L·mol within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm) -1 ·cm -1It is preferable to contain at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.

[0098] As the photo radical polymerization initiator, known compounds can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc. can be mentioned. Regarding the details of these, the descriptions in paragraphs 0165 to 0182 of JP-A No. 2016-027357 and paragraphs 0138 to 0151 of WO 2015 / 199219 can be referred to, and this content is incorporated herein. In addition, the compounds described in paragraphs 0065 to 0111 of JP-A No. 2014-130173, Japanese Patent No. 6301489, the peroxide-based photoinitiators described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, the photoinitiators described in WO 2018 / 221177, the photoinitiators described in WO 2018 / 110179, the photoinitiators described in JP-A No. 2019-043864, the photoinitiators described in JP-A No. 2019-044030, and the peroxide-based initiators described in JP-A No. 2019-167313 can be mentioned, and the contents of these are incorporated herein.

[0099] Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the content of which is incorporated herein. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0100] In one embodiment of the present invention, as the photo radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Patent No. 4225898 can be used, the content of which is incorporated herein.

[0101] Examples of the α-hydroxyketone-based initiator include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (manufactured by BASF).

[0102] Examples of the α-aminoketone-based initiator include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (manufactured by BASF).

[0103] Examples of the aminoacetophenone-based initiator, acylphosphine oxide-based initiator, and metallocene compound also preferably include the compounds described in paragraphs 0161 to 0163 of WO 2021 / 112189. The content of which is incorporated herein.

[0104] As the photo radical polymerization initiator, an oxime compound is more preferably used. By using the oxime compound, it becomes possible to more effectively improve the exposure latitude. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0105] Specific examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, the compounds described in JP-A-2006-342166, the compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), the compounds described in J.C.S. Perkin II (1979, pp. 156-162), the compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), the compounds described in JP-A-2000-066385, the compounds described in JP-T-2004-534797, the compounds described in JP-A-2017-019766, the compounds described in Patent No. 6065596, the compounds described in International Publication No. 2015 / 152153, the compounds described in International Publication No. 2017 / 051680, the compounds described in JP-A-2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, the compounds described in International Publication No. 2013 / 167515, etc., and this content is incorporated herein.

[0106] Preferred oxime compounds include, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, etc. In the resin composition, it is particularly preferable to use an oxime compound as a photoinitiator. The oxime compound as a photoinitiator has a linking group of >C=N-O-C(=O)- in the molecule.

[0107]

Chemical formula

[0108] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by Adeka Corporation, photoinitiator 2 described in JP-A-2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Arcles NCI-730, NCI-831 and Adeka Arcles NCI-930 (manufactured by Adeka Corporation), DFI-091 (manufactured by Daito Chemical Co., Ltd.), SpeedCure PDO (manufactured by SARTOMER ARKEMA). In addition, oxime compounds having the following structures can also be used.

Chemical formula

[0109] As the photoinitiator, for example, an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of International Publication No. 2021 / 112189, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, and an oxime compound having a fluorine atom can also be used. In addition, an oxime compound having a nitro group described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359, an oxime compound having a benzofuran skeleton, and an oxime compound having a substituent having a hydroxy group bonded to a carbazole skeleton can also be used. These contents are incorporated herein.

[0110] Among these, the photoinitiator preferably contains a compound represented by the following formula (P-1). [Chemical formula]

[0111] In addition, as the photoinitiator, the compounds described in paragraphs 0113 to 0117 of Japanese Patent Application Laid-Open No. 2023-058585 can also be used. This description is incorporated herein.

[0112] When the resin composition contains a photoinitiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass based on the total solid content of the resin composition. The photoinitiator may contain only one kind or two or more kinds. When two or more kinds of photoinitiators are contained, the total amount is preferably within the above range. Note that since the photoinitiator may also function as a thermal initiator, crosslinking by the photoinitiator may further proceed by heating with an oven, a hot plate, or the like.

[0113] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and enters an electronically excited state. The sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photo radical polymerization initiator, etc., causing actions such as electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiator and the photo radical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases. As the sensitizer that can be used, compounds such as benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based, etc. can be used. Examples of the sensitizer include the compounds described in paragraph 0202 of International Publication No. 2023 / 190064.

[0114] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.5 to 10% by mass based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more.

[0115] [Chain transfer agent] The resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, on pages 683-684 of the Third Edition of the Polymer Dictionary (edited by the Polymer Society, 2005). As the chain transfer agent, for example, a group of compounds having -S-S-, -SO2-S-, -N-O-, SH, PH, SiH, and GeH in the molecule, dithiobenzoate having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation chain Transfer) polymerization, trithiocarbonate, dithiocarbamate, xanthate compounds, etc. are used. These can donate hydrogen to a low-activity radical to generate a radical, or can generate a radical by deprotonating after being oxidized. In particular, a thiol compound can be preferably used.

[0116] Also, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219 can be used, and this content is incorporated herein.

[0117] When the resin composition has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the total solid content of the resin composition. The chain transfer agent may be only one kind or two or more kinds. When there are two or more kinds of chain transfer agents, it is preferable that their total is within the above range.

[0118] Also, it is one of the preferred embodiments of the present invention that the resin composition of the present invention contains two or more kinds of polymerization initiators as the polymerization initiator. Specifically, the resin composition of the present invention may contain a photopolymerization initiator and a thermal polymerization initiator described later.

[0119] By containing a photopolymerization initiator and a thermal polymerization initiator described later, pattern formation by exposure becomes possible, and radical polymerization also easily proceeds during curing by the heating step described later, and in some cases, performance such as chemical resistance is improved. When including a photoinitiator and the thermal initiator described later, as the content ratio, the content of the thermal initiator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, based on the total content of the photoinitiator and the thermal initiator.

[0120] In some cases, performance such as resolution is improved by including a photo radical polymerization initiator and a photoacid generator. When including a photoinitiator and a photoacid generator, as the content ratio, the content of the photoacid generator is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, based on the total content of the photoinitiator and the photoacid generator.

[0121] 〔Thermal initiator〕 Examples of the thermal initiator include thermal radical polymerization initiators. A thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and starts or promotes the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed, so that the solvent resistance can be further improved.

[0122] Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the content of which is incorporated herein.

[0123] When including a thermal initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15% by mass, based on the total solid content of the resin composition. The thermal initiator may contain only one kind or two or more kinds. When two or more kinds of thermal initiators are contained, the total amount is preferably within the above range.

[0124] <Base generator> The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by physical or chemical action. Preferred base generators include thermal base generators and photo base generators. In particular, when the resin composition contains a precursor of a cyclic resin, the resin composition preferably contains a base generator. By containing a thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved. For example, the performance as an interlayer insulating film for a redistribution layer contained in a semiconductor package becomes good. The base generator may be an ionic base generator or a non-ionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like. Specific examples of the non-ionic base generator include the compounds described in paragraphs 0249 to 0275 of International Publication No. 2022 / 145355. The above description is incorporated herein.

[0125] Examples of the base generator include, but are not limited to, the following compounds.

[0126]

Chemical formula

Chemical formula

[0127] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and still more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.

[0128] Specific preferred compounds of the ionic base generator include, for example, the compounds described in paragraph numbers 0148 to 0163 of International Publication No. 2018 / 038002.

[0129] Specific examples of the ammonium salt include, but are not limited to, the following compounds.

Chemical formula

[0130] Specific examples of the iminium salt include, but are not limited to, the following compounds.

Chemical formula

[0131] Further, as the base generator, an amine in which the amino group is protected by a t-butoxycarbonyl group is preferable from the viewpoints of storage stability and generating a base by deprotection during curing.

[0132] Examples of amine compounds protected by a t-butoxycarbonyl group include, but are not limited to, ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidine methanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidine methanol, 3-piperidine methanol, 2-piperidine methanol, 4-piperidine ethanol, 2-piperidine ethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino groups of amino acids and their derivatives are protected by a t-butoxycarbonyl group.

[0133] When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, yet more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One kind or two or more kinds of base generators can be used. When two or more kinds are used, the total amount is preferably within the above range.

[0134] <Solvent> The resin composition of the present invention contains a solvent. As the solvent, known solvents can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0135] As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkyl alkoxyacetate, ethyl alkyl alkoxyacetate, butyl alkyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 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. are preferably exemplified.

[0136] As ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, etc. are mentioned as suitable ones.

[0137] As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone, etc. are mentioned as suitable ones.

[0138] As cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, and cyclic terpenes such as limonene are mentioned as suitable ones.

[0139] As sulfoxides, for example, dimethyl sulfoxide is mentioned as a suitable one.

[0140] Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine, etc.

[0141] Examples of ureas include N,N,N’,N’-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, etc.

[0142] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol, etc.

[0143] From the viewpoint of improving the properties of the coating surface, etc., it is also preferable that the solvent is in a form of mixing two or more kinds.

[0144] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucosenone, dihydrolevoglucosenone, or a mixed solvent composed of two or more thereof is preferred. A combined use of dimethyl sulfoxide and γ-butyrolactone, a combined use of dimethyl sulfoxide and γ-valerolactone, a combined use of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, a combined use of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or a combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred. An embodiment in which about 1 to 10% by mass of toluene is further added to these combined solvents based on the total mass of the solvents is also one of the preferred embodiments of the present invention. In particular, from the viewpoint of storage stability of the resin composition and the like, an embodiment containing γ-valerolactone as a solvent is also one of the preferred embodiments of the present invention. In such an embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more. Further, the upper limit of the above content is not particularly limited and may be 100% by mass. The above content may be determined in consideration of the solubility of components such as a specific resin contained in the resin composition. When dimethyl sulfoxide and γ-valerolactone are used in combination, it is preferable to contain 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide based on the total mass of the solvent, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide.

[0145] Further, the resin composition of the present invention preferably contains one or more solvents selected from the group consisting of γ-butyrolactone and N-methyl-2-pyrrolidone and ethyl lactate as a solvent. By containing ethyl lactate, the film-forming property is excellent. This is presumably because ethyl lactate has low hydrophilicity, and by containing this, precipitation of the resin due to moisture in the residual solvent during drying of the composition is suppressed. In the above aspect, the total content of one or more solvents selected from the group consisting of γ-butyrolactone and N-methyl-2-pyrrolidone and ethyl lactate is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more based on the total mass of the solvent. The upper limit of the above content is not particularly limited as long as it is 100% by mass or less. Further, in the above aspect, the content of one or more solvents selected from the group consisting of γ-butyrolactone and N-methyl-2-pyrrolidone with respect to the total content of one or more solvents selected from the group consisting of γ-butyrolactone and N-methyl-2-pyrrolidone and ethyl lactate is preferably 80 to 99.9% by mass, more preferably 90 to 99.5% by mass, and even more preferably 90 to 99.0% by mass. Further, in the above aspect, the resin composition of the present invention preferably further contains dimethyl sulfoxide as a solvent. By containing dimethyl sulfoxide, the storage stability of the composition is improved. This is presumably because dimethyl sulfoxide has high polarity, and aggregation of the resin in the composition is suppressed. When dimethyl sulfoxide is included, the content of dimethyl sulfoxide relative to the total mass of the solvent is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and still more preferably 20 to 30% by mass.

[0146] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably an amount such that it is 5 to 75% by mass, still more preferably an amount such that it is 10 to 70% by mass, and even more preferably an amount such that it is 20 to 70% by mass. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method. When two or more solvents are contained, it is preferable that their total is within the above range.

[0147] <Metal adhesion improver> The resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving the adhesion to metal materials used for electrodes, wiring, etc. Examples of the metal adhesion improver include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0148] 〔Silane coupling agent〕 Examples of the silane coupling agent and the aluminum-based adhesion aid include the compounds described in paragraph 0202 of International Publication No. 2023 / 190064.

[0149] As other metal adhesion improvers, the compounds described in paragraphs 0046 to 0049 of JP-A No. 2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A No. 2013-072935 can also be used, and the contents of these are incorporated herein.

[0150] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the specific resin. By setting it to be not less than the above lower limit value, the adhesion between the pattern and the metal layer becomes good, and by setting it to be not more than the above upper limit value, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be only one kind or two or more kinds. When two or more kinds are used, it is preferable that the total is within the above range.

[0151] <Migration inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By containing a migration inhibitor, for example, when a film is formed by applying the resin composition to a metal layer (or metal wiring), it is possible to effectively suppress the migration of metal ions derived from the metal layer (or metal wiring) into the film.

[0152] The migration inhibitor is not particularly limited, but includes compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole 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 and 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, 5-amino-1H-tetrazole can be preferably used.

[0153] As the migration inhibitor, an ion trap agent that captures anions such as halogen ions can also be used.

[0154] As other migration inhibitors, rust inhibitors described in paragraph 0094 of JP-A-2013-015701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, compounds described in paragraph 0052 of JP-A-2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, compounds described in paragraph 0166 of WO2015 / 199219, etc. can be used, and this content is incorporated herein.

[0155] Specific examples of the migration inhibitor include the following compounds.

[0156]

Chemical formula

[0157] When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass based on the total solid content of the resin composition.

[0158] The migration inhibitor may be only one kind or two or more kinds. When there are two or more kinds of migration inhibitors, it is preferable that the total thereof is within the above range.

[0159] <Purine derivative> Further, from the viewpoint of improving reliability, it is also preferable that the resin composition of the present invention contains a purine derivative. A purine derivative is a compound having a purine ring as a basic skeleton, and a compound derived from the skeleton is referred to as a purine derivative. By using a purine derivative, an effect of suppressing discoloration of copper or a copper alloy and an effect of improving reliability can be obtained. Although the reason for obtaining the above effects is not clear, it is presumed that a purine derivative containing a nitrogen atom in the molecule and a specific resin containing a heteroatom such as an oxygen atom or a nitrogen atom moderately interact with each other by hydrogen bonding or the like, thereby suppressing an excessive interaction between the resin and copper. Specific examples of the purine derivative include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine and the like, and derivatives thereof. Among these, 8-azaadenine is particularly preferable.

[0160] In addition, examples of the purine derivative include the compounds described in paragraphs 0115 to 0119 of JP-A-2012-194520.

[0161] The content of the purine derivative is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and even more preferably 0.05 to 2 parts by mass based on 100 parts by mass of the specific resin. The purine derivative may be only one kind or two or more kinds. When there are two or more purine derivatives, it is preferable that the total is within the above range.

[0162] <Light absorber> The resin composition of the present invention preferably also contains a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure. Examples of the light absorber include the compounds described in paragraphs 0159 to 0183 of WO 2022 / 202647, the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A, and the like. These contents are incorporated herein.

[0163] <Polymerization inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N - oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, metal compounds, and the like.

[0164] Specific examples of the polymerization inhibitor include the compounds described in paragraph 0310 of WO 2021 / 112189, p - hydroquinone, o - hydroquinone, 4 - hydroxy - 2,2,6,6 - tetramethylpiperidine 1 - oxyl free radical, phenoxazine, 1,4,4 - trimethyl - 2,3 - diazabicyclo[3.2.2]non - 2 - ene - N,N - dioxide, and the like. This content is incorporated herein.

[0165] When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and still more preferably 0.05 to 10% by mass based on the total solid content of the resin composition.

[0166] The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more kinds of polymerization inhibitors, the total thereof is preferably within the above range.

[0167] <Other additives> The resin composition of the present invention may contain various additives, for example, surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (such as defoamers, flame retardants, etc.) as long as the effects of the present invention can be obtained. By appropriately containing these components, properties such as film physical properties can be adjusted. These components can refer to, for example, the descriptions in paragraphs 0183 and subsequent paragraphs of JP-A-2012-003225 (paragraph numbers 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, 0107 to 0109, etc. of JP-A-2008-250074, and these contents are incorporated herein. When blending these additives, the total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0168] 〔Surfactant〕 As the surfactant, various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0169] By containing a surfactant in the resin composition of the present invention, the liquid characteristics (especially fluidity) when preparing the coating liquid composition can be further improved, and the uniformity of the coating thickness and the liquid-saving property can be further improved. That is, when forming a film using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, the wettability to the surface to be coated is improved, and the coatability to the surface to be coated is improved. Therefore, a uniform film with small thickness unevenness can be formed more preferably.

[0170] Examples of the fluorine-based surfactant include the compounds described in paragraph 0328 of WO 2021 / 112189, and this content is incorporated herein. As the fluorosurfactant, a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably an ethyleneoxy group or a propyleneoxy group) can also be preferably used. For example, the following compounds can be mentioned.

Chemical formula

[0171] The weight average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorosurfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, and this content is incorporated herein. Commercially available products include, for example, Megafac RS-101, RS-102, RS-718K, etc. manufactured by DIC Corporation.

[0172] The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorosurfactant having a fluorine content within this range is effective in terms of the uniformity of the coating film thickness and the liquid-saving property, and also has good solubility in the composition.

[0173] As the silicone surfactant, hydrocarbon surfactant, nonionic surfactant, cationic surfactant, and anionic surfactant, the compounds described in paragraphs 0329 to 0334 of WO 2021 / 112189 can be mentioned respectively, and this content is incorporated herein.

[0174] Only one type of surfactant may be used, or two or more types may be combined. The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

[0175] [Inorganic particles] Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.

[0176] The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, still more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle diameter of the inorganic particles is the primary particle diameter and also the volume average particle diameter. The volume average particle diameter can be measured, for example, by the dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). When the above measurement is difficult, it can also be measured by the centrifugal sedimentation light transmission method, the X-ray transmission method, or the laser diffraction / scattering method.

[0177] [Organic titanium compound] When the resin composition contains an organic titanium compound, a resin layer excellent in chemical resistance can be formed even when cured at a low temperature.

[0178] Examples of the usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organic titanium compound are shown in the following I) to VII): I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability of the resin composition and a good curing pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethyl acetoacetate), and the like. II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearylroxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and the like. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like. IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and the like. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate, and the like. VII) Titanate coupling agent: For example, isopropyltridodecylbenzenesulfonyl titanate, etc.

[0179] Among them, as the organic titanium compound, from the viewpoint of better chemical resistance, it is preferably at least one compound selected from the group consisting of the above I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0180] Also, it is preferable to contain a compound represented by the following formula (T-1) as the organic titanium compound or in place of the organic titanium compound.

Chemical formula

Chemical formula

[0181] In formula (T-1), from the viewpoint of the storage stability of the composition, M is preferably titanium. In formula (T-1), the aspect where l1 and l2 are 0 is also one of the preferred aspects of the present invention. In formula (T-1), m is preferably 2 or 4, and more preferably 2. In formula (T-1), n is preferably 1 or 2, and more preferably 1. Here, in formula (T-1), it is also preferable that l1 and l2 are 0 and m is 0, 2 or 4.

[0182] In formula (T-1), from the viewpoint of the stability of the specific metal complex, R 11 is preferably a substituted or unsubstituted cyclopentadienyl ligand. Also, the cyclopentadienyl group, alkoxy group and phenoxy group in R 11 may be substituted, but the unsubstituted aspect is also one of the preferred aspects of the present invention.

[0183] In formula (T-1), R 12 is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms. R 12 The hydrocarbon group in may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aromatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group. R 12 The substituent in is preferably a monovalent substituent, and examples thereof include a halogen atom. Also, R 12When it is an aromatic hydrocarbon group, it may have an alkyl group as a substituent. Among these, in the formula (T-1), R 12 is preferably an unsubstituted phenylene group. Further, the phenylene group in R 12 is preferably a 1,2-phenylene group.

[0184] In the formula (T-1), m is 2 or more, and when two or more R 2 are included, the structures of the two or more R 2 may be the same or different from each other. In the formula (T-1), n is 2 or more, and when two or more R 3 are included, the structures of the two or more R 3 may be the same or different from each other.

[0185] In the formula (T-2), X 1 ~X 3 each independently represents -C(-*)= or -N=, and preferably at least one represents -C(-*)=, and more preferably at least two represent -C(-*)=.

[0186] Specific examples of the compound represented by the formula (T-1) include, but are not limited to, the compounds corresponding to I-1 to I-2 in the examples.

[0187] When an organotitanium compound is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern become better, and when it is 10 parts by mass or less, the storage stability of the composition is more excellent.

[0188] When an organotitanium compound is included, its content is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern become better. When the content is 10 parts by mass or less, the storage stability of the composition is more excellent. Examples of other additives include the compounds described in paragraphs 0249 to 0282 and 0316 to 0358 of International Publication No. 2022 / 145355. The above description is incorporated herein.

[0189] <Properties of the resin composition> The viscosity of the resin composition of the present invention can be adjusted according to the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm 2 / s to 12,000 mm 2 / s is preferable, 2,000 mm 2 / s to 10,000 mm 2 / s is more preferable, 2,500 mm 2 / s to 8,000 mm 2 / s is even more preferable. Within the above range, it becomes easy to obtain a coating film with high uniformity. If it is 1,000 mm 2 / s or more, for example, it is easy to coat with a film thickness required for an insulating film for rewiring. If it is 12,000 mm 2 / s or less, a coating film excellent in coating surface condition can be obtained.

[0190] <Restrictions on the substances contained in the resin composition> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Examples of methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0191] From the perspective of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., excluding metals contained as complexes of organic compounds and metals. When multiple metals are contained, it is preferable that the total of these metals is within the above range.

[0192] In addition, as a method for reducing metal impurities unintentionally contained in the resin composition of the present invention, examples include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, performing filter filtration on the raw materials constituting the resin composition of the present invention, and distilling under conditions where the inside of the apparatus is lined with polytetrafluoroethylene or the like to suppress contamination as much as possible.

[0193] Considering the use as a semiconductor material, from the perspective of wiring corrosiveness, the content of halogen atoms in the resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm. Among them, those present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of the chlorine atom and the bromine atom, or the total of the chlorine ion and the bromine ion, is within the above range respectively. As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.

[0194] As the storage container for the resin composition of the present invention, conventionally known storage containers can be used. As the storage container, for the purpose of suppressing the mixing of impurities into the raw materials and the resin composition of the present invention, it is also preferable to use a multilayer bottle whose inner wall is composed of 6 types of resins in 6 layers, or a bottle in which 6 types of resins are in a 7-layer structure. Examples of such containers include the containers described in JP-A-2015-123351.

[0195] <Cured product of the resin composition> By curing the resin composition of the present invention, a cured product of the resin composition can be obtained. The cured product of the present invention is a cured product obtained by curing the resin composition. The curing of the resin composition is preferably by heating, more preferably at a heating temperature of 120°C to 400°C, still more preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited and can be selected according to the use, such as film form, rod form, spherical form, pellet form, etc. In the present invention, the cured product is preferably in film form. By pattern processing of the resin composition, the shape of the cured product can also be selected according to the use, such as forming a protective film on the wall surface, forming via holes for conduction, adjusting impedance, capacitance or internal stress, and imparting heat dissipation function. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less. Here, the shrinkage rate refers to the percentage of the volume change before and after curing of the resin composition and can be calculated from the following formula. Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

[0196] <Properties of the cured product of the resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. If it is 70% or more, a cured product with excellent mechanical properties may be obtained. The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or more, more preferably 210°C or more, and still more preferably 230°C or more.

[0197] <Preparation of the resin composition> The resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by a conventionally known method. Examples of the mixing method include mixing by a stirring blade, mixing by a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0198] For the purpose of removing foreign matters such as dust and fine particles in the resin composition of the present invention, it is preferable to perform filtration using a filter. The pore size of the filter is preferably, for example, 5 μm or less, more preferably 1 μm or less, still more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. When the material of the filter is polyethylene, it is more preferably HDPE (high-density polyethylene). The filter may be one that has been washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel and used. When using a plurality of types of filters, filters having different pore sizes or materials may be combined and used. Examples of the connection mode include a mode in which an HDPE filter with a pore size of 1 μm is connected in series as the first stage and an HDPE filter with a pore size of 0.2 μm is connected in series as the second stage. Also, various materials may be filtered multiple times. When filtering multiple times, it may be a circulating filtration. Also, filtration may be performed under pressure. When performing filtration under pressure, the pressure for pressurization is preferably, for example, 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, still more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using a filter, an impurity removal treatment using an adsorbent may be performed. A combination of filter filtration and an impurity removal treatment using an adsorbent may also be used. As the adsorbent, a known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtration using a filter, the resin composition filled in the bottle may be placed under reduced pressure and degassed.

[0199] (Method for producing a cured product) The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film. The method for producing a cured product more preferably includes the above film forming step, an exposure step of selectively exposing the film formed by the film forming step, and a development step of developing the film exposed by the exposure step using a developer to form a pattern. The method for producing a cured product particularly preferably includes at least one of the above film forming step, the above exposure step, the above development step, a heating step of heating the pattern obtained by the development step, and a post-exposure step of exposing the pattern obtained by the development step. Also, the method for producing a cured product preferably includes the above film forming step and a step of heating the above film. Hereinafter, the details of each step will be described.

[0200] <Film forming step> The resin composition of the present invention can be used in a film forming step of applying it onto a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film.

[0201] 〔Substrate〕 The type of the substrate can be appropriately determined according to the use, and is not particularly limited. Examples of the substrate include semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, and metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals and substrates on which metal layers are formed by, for example, plating or vapor deposition). Papers, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, electrode plates of plasma display panels (PDP), and the like can be mentioned. Particularly, semiconductor manufacturing substrates are preferable as the substrate, and silicon substrates, Cu substrates, and mold substrates are more preferable. Layers such as an adhesion layer or an oxide layer by hexamethyldisilazane (HMDS) or the like may be provided on the surfaces of these substrates. The shape of the substrate is not particularly limited, and it may be circular or rectangular. If the substrate is circular, for example, the diameter is preferably 100 to 450 mm, and more preferably 200 to 450 mm. If the substrate is rectangular, for example, the length of the short side is preferably 100 to 1000 mm, and more preferably 200 to 700 mm. As the substrate, for example, a plate-like, preferably panel-like substrate (substrate) is used.

[0202] When forming a film by applying a resin composition on the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the substrate.

[0203] As a means for applying the resin composition onto the substrate, coating is preferable. As the applicable means, specifically, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, inkjet method, etc. can be mentioned. From the viewpoint of the uniformity of the film thickness, spin coating method, slit coating method, spray coating method, or inkjet method is preferable, and spin coating method and slit coating method are more preferable from the viewpoints of the uniformity of the film thickness and productivity. By adjusting the solid content concentration and coating conditions of the resin composition according to the applicable means, a film with a desired thickness can be obtained. Also, the coating method can be appropriately selected according to the shape of the substrate. For a circular substrate such as a wafer, spin coating method, spray coating method, inkjet method, etc. are preferable, and for a rectangular substrate, slit coating method, spray coating method, inkjet method, etc. are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. In addition, a method of transferring a coating film formed by applying by the above-described applying method onto a temporary support in advance onto a substrate can also be applied. Regarding the transfer method, the production methods described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096 to 0108 of JP-A-2006-047592 can be preferably used. Also, a step of removing an excess film at the end of the substrate may be performed. Examples of such steps include edge bead rinse (EBR), back rinse, etc. Before applying the resin composition to the substrate, a pre-wet step of applying various solvents to the substrate to improve the wettability of the substrate and then applying the resin composition may be employed.

[0204] <Drying step> The above film may be subjected to a step (drying step) of drying the formed film (layer) in order to remove the solvent after the film formation step (layer formation step). That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film formation step. The above drying process is preferably carried out after the film formation process and before the exposure process. The drying temperature of the film in the drying process is preferably 50 to 150 °C, more preferably 70 °C to 130 °C, and even more preferably 90 °C to 110 °C. Also, drying may be carried out under reduced pressure. Examples of the drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0205] <Exposure process> The above film may be subjected to an exposure process of selectively exposing the film. The method for producing a cured product may include an exposure process of selectively exposing the film formed by the film formation process. Selectively exposing means exposing a part of the film. Also, by selectively exposing, an exposed area (exposed part) and an unexposed area (non-exposed part) are formed in the film. The exposure amount is not particularly limited as long as the resin composition of the present invention can be cured. For example, in terms of exposure energy conversion at a wavelength of 365 nm, it is preferably 50 to 10,000 mJ / cm 2 and more preferably 200 to 8,000 mJ / cm 2 is more preferable.

[0206] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0207] The exposure wavelength, in relation to the light source, includes: (1) semiconductor lasers (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i lines), (4) excimer lasers, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beams, (7) second harmonic of YAG laser 532 nm, third harmonic 355 nm, etc. For the resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferred, and exposure by the i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited, and any method may be used as long as at least a part of the film made of the resin composition of the present invention is exposed. Examples include exposure using a photomask, exposure by the laser direct imaging method, etc.

[0208] <Post-exposure baking process> The above film may be subjected to a process of heating after exposure (post-exposure baking process). That is, the method for producing the cured product of the present invention may include a post-exposure baking process of heating the film exposed in the exposure process. The post-exposure baking process can be performed after the exposure process and before the development process. The heating temperature in the post-exposure baking process is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure baking process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The heating rate in the post-exposure baking process is preferably 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. Also, the heating rate may be appropriately changed during heating. The heating means in the post-exposure baking process is not particularly limited, and known hot plates, ovens, infrared heaters, etc. can be used. Also, when heating, it is also preferable to perform the process in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0209] <Development process> The film after exposure may be subjected to a development process in which a pattern is formed by developing the film using a developer. That is, the method for producing the cured product of the present invention may include a development process in which a film exposed in the exposure process is developed using a developer to form a pattern. By performing development, one of the exposed portion and the non-exposed portion of the film is removed, and a pattern is formed. Here, development in which the non-exposed portion of the film is removed by the development process is called negative development, and development in which the exposed portion of the film is removed by the development process is called positive development.

[0210] 〔Developer〕 Examples of the developer used in the development process include an aqueous alkaline solution or a developer containing an organic solvent.

[0211] When the developer is an alkaline aqueous solution, examples of the basic compound that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Examples thereof include TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. TMAH is more preferred. The content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.3 to 3% by mass in the total mass of the developer.

[0212] When the developer contains an organic solvent, as the organic solvent, the compounds described in paragraph 0387 of WO 2021 / 112189 can be used. This content is incorporated herein. Further, as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are also preferably exemplified.

[0213] When the developer contains an organic solvent, the organic solvent can be used singly or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0214] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Further, the above content may be 100% by mass.

[0215] The developer may further contain other components. Examples of the other components include known surfactants and known antifoaming agents.

[0216] 〔Method for supplying developer〕 The method for supplying the developer is not particularly limited as long as a desired pattern can be formed. There are a method of immersing a substrate on which a film is formed in the developer, paddle development in which the developer is supplied to the film formed on the substrate using a nozzle, or a method of continuously supplying the developer. The type of the nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removability of the non-image portion, and the manufacturing efficiency, a method of supplying the developer with a straight nozzle or a method of continuously supplying the developer with a spray nozzle is preferred. From the viewpoint of the permeability of the developer to the image portion, a method of supplying the developer with a spray nozzle is more preferred. Further, after continuously supplying the developer with a straight nozzle, the substrate may be spun to remove the developer from the substrate, and after spin drying, the developer may be continuously supplied again with a straight nozzle, and then the substrate may be spun to remove the developer from the substrate. This process may be repeated a plurality of times. As a method for supplying a developing solution in the developing process, there are a process in which the developing solution is continuously supplied to the substrate, a process in which the developing solution is kept substantially stationary on the substrate, a process in which the developing solution on the substrate is vibrated by ultrasonic waves or the like, and a process combining them.

[0217] As the developing time, 10 seconds to 10 minutes is preferable, and 20 seconds to 5 minutes is more preferable. Although the temperature of the developing solution during development is not particularly defined, 10 to 45 °C is preferable, and 18 °C to 30 °C is more preferable.

[0218] In the developing process, after the treatment with the developing solution, further, the pattern may be washed (rinsed) with a rinse solution. Also, a method such as supplying the rinse solution before the developing solution in contact with the pattern is completely dried may be adopted.

[0219] 〔Rinse solution〕 When the developing solution is an alkaline aqueous solution, for example, water can be used as the rinse solution. When the developing solution is a developing solution containing an organic solvent, for example, a solvent different from the solvent contained in the developing solution (for example, water, an organic solvent different from the organic solvent contained in the developing solution) can be used as the rinse solution.

[0220] Examples of the organic solvent when the rinse solution contains an organic solvent include the same organic solvents as those exemplified when the above-mentioned developing solution contains an organic solvent. The organic solvent contained in the rinse solution is preferably an organic solvent different from the organic solvent contained in the developing solution, and more preferably an organic solvent having a lower solubility of the pattern than the organic solvent contained in the developing solution.

[0221] When the rinse solution contains an organic solvent, the organic solvent can be used alone or in a mixture of two or more. The organic solvents are preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, PGME, and even more preferably cyclohexanone, PGMEA.

[0222] When the rinsing liquid contains an organic solvent, based on the total mass of the rinsing liquid, it is preferable that the organic solvent accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. Also, based on the total mass of the rinsing liquid, the organic solvent may be 100% by mass.

[0223] The rinsing liquid may further contain other components. Examples of other components include known surfactants and known antifoaming agents, etc.

[0224] 〔Method for supplying the rinsing liquid〕 The method for supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed. There are methods such as immersing the substrate in the rinsing liquid, supplying the rinsing liquid to the substrate by liquid pooling, supplying the rinsing liquid to the substrate by showering, and continuously supplying the rinsing liquid to the substrate by means such as a straight nozzle on the substrate. From the viewpoints of the permeability of the rinsing liquid, the removability of the non-image part, and the efficiency in manufacturing, there are methods of supplying the rinsing liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc. The method of continuously supplying with a spray nozzle is preferable, and from the viewpoint of the permeability of the rinsing liquid to the image part, the method of supplying with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, a spray nozzle, etc. That is, the rinsing step is preferably a step of supplying the rinsing liquid to the film after the above exposure with a straight nozzle or continuously supplying it, and more preferably a step of supplying the rinsing liquid with a spray nozzle. As the method for supplying the rinsing liquid in the rinsing step, a step in which the rinsing liquid is continuously supplied to the substrate, a step in which the rinsing liquid is kept in a substantially stationary state on the substrate, a step in which the rinsing liquid on the substrate is vibrated with ultrasonic waves or the like, and a step combining them can be adopted.

[0225] The rinsing time is preferably from 10 seconds to 10 minutes, more preferably from 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly defined, but is preferably from 10 to 45°C, more preferably from 18°C to 30°C.

[0226] <Heating step> The pattern obtained by the development step (when a rinsing step is performed, the pattern after rinsing) may be subjected to a heating step of heating the pattern obtained by the above development. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the development step. Further, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing a development step, or a film obtained by a film formation step. In the heating step, a resin such as a polyimide precursor is cyclized to become a resin such as polyimide. In addition, crosslinking of unreacted crosslinkable groups in a specific resin or a crosslinking agent other than the specific resin also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably from 50 to 450°C, more preferably from 150 to 350°C, still more preferably from 150 to 250°C, even more preferably from 160 to 250°C, and particularly preferably from 160 to 230°C.

[0227] The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern by the action of a base or the like generated from the base generator by heating.

[0228] The heating in the heating step is preferably performed at a heating rate of 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature. The above heating rate is more preferably 2 to 10°C / min, still more preferably 3 to 10°C / min. By setting the heating rate to 1°C / min or more, excessive volatilization of an acid or a solvent can be prevented while ensuring productivity, and by setting the heating rate to 12°C / min or less, the residual stress of the cured product can be relaxed. In addition, in the case of a rapidly heatable oven, it is preferably carried out at a temperature increase rate of 1 to 8 °C / second, more preferably 2 to 7 °C / second, and still more preferably 3 to 6 °C / second from the temperature at the start of heating to the maximum heating temperature.

[0229] The temperature at the start of heating is preferably 20 °C to 150 °C, more preferably 20 °C to 130 °C, and still more preferably 25 °C to 120 °C. The temperature at the start of heating refers to the temperature at the time of starting the step of heating to the maximum heating temperature. For example, when the resin composition of the present invention is applied onto a substrate and then dried, it is the temperature of the film (layer) after this drying. For example, it is preferable to increase the temperature from a temperature 30 to 200 °C lower than the boiling point of the solvent contained in the resin composition.

[0230] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and still more preferably 15 to 240 minutes.

[0231] Particularly when forming a multi-layer laminate, from the viewpoint of the adhesion between layers, the heating temperature is preferably 30 °C or higher, more preferably 80 °C or higher, still more preferably 100 °C or higher, and particularly preferably 120 °C or higher. The upper limit of the above heating temperature is preferably 350 °C or lower, more preferably 250 °C or lower, and still more preferably 240 °C or lower.

[0232] The heating may be carried out stepwise. As an example, a process such as increasing the temperature from 25 °C to 120 °C at 3 °C / min, holding at 120 °C for 60 minutes, increasing the temperature from 120 °C to 180 °C at 2 °C / min, and holding at 180 °C for 120 minutes may be carried out. Also, as described in U.S. Patent No. 9,159,547, it is also preferable to carry out the treatment while irradiating ultraviolet rays. It is possible to improve the characteristics of the film by such a pretreatment process. The pretreatment process is preferably carried out in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may also be in two or more steps. For example, the first pretreatment step may be carried out in the range of 100 to 150 °C, and then the second pretreatment step may be carried out in the range of 150 to 200 °C. Furthermore, it may be cooled after heating. In this case, the cooling rate is preferably 1 to 5 °C / min.

[0233] From the viewpoint of preventing decomposition of the specific resin, the heating step is preferably carried out in an atmosphere with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less. The heating means in the heating step is not particularly limited, and examples include a hot plate, an infrared furnace, an electric oven, a hot air oven, an infrared oven, and the like.

[0234] <Post-development exposure step> The pattern obtained by the development step (when a rinse step is performed, the pattern after rinsing) may be subjected to a post-development exposure step of exposing the pattern after the development step instead of or in addition to the above heating step. That is, the method for producing the cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for producing the cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. In the post-development exposure step, for example, reactions such as the cyclization of a polyimide precursor or the like promoted by the photosensitivity of a photo-base generator, or reactions such as the elimination of an acid-decomposable group promoted by the photosensitivity of a photo-acid generator can be promoted. In the post-development exposure step, at least a part of the pattern obtained in the development step may be exposed, but it is preferable that the entire pattern is exposed. The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm 2 in terms of exposure energy conversion at the wavelength at which the photosensitive compound has sensitivity, and more preferably 100 to 15,000 mJ / cm 2 The post-development exposure step can be carried out, for example, using the light source in the above-described exposure step, and it is preferable to use broadband light.

[0235] ​<Metal layer formation process> The pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process) may be subjected to a metal layer formation process for forming a metal layer on the pattern. That is, the method for producing the cured product of the present invention preferably includes a metal layer formation process for forming a metal layer on the pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process).

[0236] As the metal layer, existing metal species can be used without particular limitation, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferable, and copper is even more preferable.

[0237] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP-A-2007-157879, JP-T-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electroplating can be mentioned. A preferable embodiment of plating includes electroplating using a copper sulfate or copper cyanide plating solution.

[0238] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0239] <Use> Examples of the method for producing the cured product of the present invention or fields where the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition, there are examples such as forming a pattern by etching a sealing film, a substrate material (base film, coverlay, and interlayer insulating film of a flexible printed circuit board), or an insulating film for mounting applications as described above. For these applications, reference can be made to, for example, "High-Functionality and Application Technology of Polyimide" published by Science & Technology Co., Ltd. in April 2008, supervised by Masaki Kakinoto, "Fundamentals and Development of Polyimide Materials" published by CMC Technical Library in November 2011, and "Latest Polyimide - Fundamentals and Applications" edited by the Japan Polyimide & Aromatic Polymer Research Society and published by NTS in August 2010, etc.

[0240] The method for producing the cured product of the present invention, or the cured product of the present invention, can also be used for the production of plate surfaces such as offset plate surfaces or screen plate surfaces, the use of molded parts in etching, electronics, particularly the production of protective lacquers and dielectric layers in microelectronics.

[0241] (Laminate, and method for producing laminate) The laminate of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention. The laminate is a laminate including two or more layers made of the cured product, and may be a laminate in which three or more layers are laminated. Among the two or more layers made of the cured product included in the above laminate, at least one layer is a layer made of the cured product of the present invention. From the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product accompanying the above shrinkage, etc., it is also preferable that all the layers made of the cured product included in the above laminate are layers made of the cured product of the present invention.

[0242] That is, the method for producing the laminate of the present invention preferably includes the method for producing the cured product of the present invention, and more preferably includes repeating the method for producing the cured product of the present invention a plurality of times.

[0243] The laminate of the present invention preferably includes two or more layers made of a cured product, and includes a metal layer between any of the layers made of the cured product. The metal layer is preferably formed by the metal layer forming step. That is, the method for manufacturing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer made of a cured product during the method for manufacturing a cured product that is performed multiple times. The preferred embodiment of the metal layer forming step is as described above. As the laminate, for example, a laminate preferably including at least a layer structure in which three layers of a layer made of a first cured product, a metal layer, and a layer made of a second cured product are laminated in this order can be mentioned. Both the layer made of the first cured product and the layer made of the second cured product are preferably layers made of the cured product of the present invention. The resin composition of the present invention used for forming the layer made of the first cured product and the resin composition of the present invention used for forming the layer made of the second cured product may be compositions having the same composition or may be compositions having different compositions. The metal layer in the laminate of the present invention is preferably used as a metal wiring such as a rewiring layer.

[0244] <Lamination step> The method for manufacturing a laminate of the present invention preferably includes a lamination step. The lamination step is a series of steps including performing at least one of (a) a film forming step (layer forming step), (b) an exposure step, (c) a development step, (d) a heating step, and a post-development exposure step, in this order, again on the surface of a pattern (resin layer) or a metal layer. However, an embodiment in which at least one of (a) the film forming step, (d) the heating step, and the post-development exposure step is repeated may also be possible. Further, an (e) metal layer forming step may be included after at least one of (d) the heating step and the post-development exposure step. Needless to say, the drying step and the like may be appropriately included in the lamination step.

[0245] When performing an additional lamination process after the lamination process, a surface activation treatment process may be further performed after the exposure process, after the heating process, or after the metal layer formation process. Examples of the surface activation treatment include plasma treatment. Details of the surface activation treatment will be described later.

[0246] The above lamination process is preferably performed 2 to 20 times, more preferably 2 to 9 times. For example, a configuration in which there are 2 or more and 20 or less resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and a configuration in which there are 2 or more and 9 or less resin layers is more preferable. Each of the above layers may have the same or different compositions, shapes, film thicknesses, etc.

[0247] In particular, in the present invention, an embodiment in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer is preferable. Specifically, a mode of repeating in the order of (a) film formation step, (b) exposure step, (c) development step, (d) heating step and at least one of post-development exposure steps, (e) metal layer formation step, or a mode of repeating in the order of (a) film formation step, (d) heating step and at least one of post-development exposure steps, (e) metal layer formation step can be mentioned. By alternately performing the lamination process of laminating the resin composition layer (resin layer) of the present invention and the metal layer formation process, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately laminated.

[0248] (Surface activation treatment process) The method for manufacturing the laminate of the present invention preferably includes a surface activation treatment step of surface-activating at least a part of the metal layer and the resin composition layer. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), a surface activation treatment step may be performed on the resin composition layer, and then the metal layer formation step may be performed. The surface activation treatment may be performed on only at least a part of the metal layer, or only at least a part of the resin composition layer after exposure, or on both the metal layer and the resin composition layer after exposure, respectively, at least in part. It is preferable to perform the surface activation treatment on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region of the metal layer where the resin composition layer is formed on the surface. Thus, by performing the surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) provided on the surface can be improved. It is also preferable to perform the surface activation treatment on part or all of the resin composition layer (resin layer) after exposure. Thus, by performing the surface activation treatment on the surface of the resin composition layer, the adhesion to the metal layer or resin layer provided on the surface after the surface activation treatment can be improved. Particularly when negative development is performed, etc., when the resin composition layer is cured, it is less likely to be damaged by the surface treatment and the adhesion is likely to be improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This content is incorporated herein.

[0249] (Semiconductor device and method for manufacturing the same) The present invention also discloses a semiconductor device including a cured product of the present invention or a laminate. Further, the present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured product of the present invention or a method for manufacturing a laminate. As a specific example of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer, the descriptions in paragraphs 0213 to 0218 and the description of FIG. 1 of JP-A-2016-027357 can be referred to, and these contents are incorporated herein.

[0250] (Compound) The compound of the present invention is a compound represented by the following formula (A-1) or formula (A-2).

Chemical formula

Chemical formula

Examples

[0251] The present invention will be described in more detail with reference to the following examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

[0252] <Synthesis of Polymer> 〔Synthesis Example P-1: Synthesis of Resin (P-1)〕 155.11 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were added. While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After the exothermic reaction ended, it was allowed to cool to room temperature and further allowed to stand for 16 hours. Next, under ice cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone was added dropwise to the reaction mixture over 40 minutes while stirring. Subsequently, a suspension prepared by suspending 96.0 g of 4,4'-diaminodiphenyl ether in 350 ml of γ-butyrolactone was added dropwise over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour. Then, 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was obtained by filtration to obtain a reaction solution. The obtained reaction solution was added to 3 L of ethyl alcohol to form a precipitate composed of a crude polymer. The formed crude polymer was collected by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then dried under vacuum to obtain a powdery resin P-1. It was 1 confirmed by 1H-NMR that resin P-1 has a structure containing a repeating unit represented by the following formula (P-1). The weight average molecular weight and imidization rate of resin P-1 are shown in the table described later.

[0253] 〔Method for measuring weight average molecular weight〕 In the above and following synthesis examples, unless otherwise specified, the weight average molecular weight and number average molecular weight were measured by the following method. Using a high-speed GPC device HLC-8420GPC (manufactured by Tosoh Corporation), as a guard column, TSK gurdcolumn Super AW-H (4.6 mm × 35 mm), and as columns, two TSKgel Super AWM-H (4.6 mm × 150 mm) were connected in series for GPC measurement. As the eluent, a 0.01 mol / L lithium bromide NMP (N-methyl-2-pyrrolidone) solution was used.

[0254] 〔Measurement method of imidization rate〕 The resin described below was dissolved in γ-butyrolactone, diluted to 2,000 mPa·s, and applied onto a silicon wafer by the spin coating method to form a resin layer. The silicon wafer with the obtained resin layer was dried on a hot plate at 110 °C for 5 minutes to obtain a resin layer with a uniform thickness of about 15 μm after film formation on the silicon wafer. Also, for Resins A-3 and A-6, resins with imidization rates of 16.0% and 14.0% were also synthesized by changing the reaction time. The above resin layer was measured by the ATR method using Nicolet iS20 (manufactured by Thermo Fisher), and the measurement range was 4000~700 cm -1 ., and the measurement was performed 50 times. Near 1380 cm -1 (1350~1450 cm -1 ., when there are multiple peaks, the one with the maximum peak intensity), and the peak height at around 1500 cm -1 (1460~1550 cm -1 ., when there are multiple peaks, the one with the maximum peak intensity), the value obtained by dividing the peak height was defined as the imidization index A of the resin. For the film heated at a heating rate of 10 °C / min in a nitrogen atmosphere and heated at 350 °C for 1 hour, the imidization index B was calculated in the same manner, and the value obtained by dividing the imidization index A by the imidization index B was calculated as the imidization rate of the resin.

Chemical formula

[0255] 〔Synthesis Examples P-2 to P-26: Synthesis of Resins (P-2) to (P-26)〕 Resins (P-2) to (P-26) were synthesized in the same manner as resin (P-1), except that the types and charging ratios of the acid anhydride and diamine, which are the raw materials used in Synthesis Example P-1, were appropriately changed. Resins (P-2) to (P-26) are resins having repeating units represented by the following formulas (P-2) to (P-26), respectively. The structure of each repeating unit was determined from the 1 1H-NMR spectrum. In the following structures, the symbols in parentheses are the values described in the table below and represent the molar ratio of each structure. For resins (P-3) to (P-20), the values of A and B, which are the molar ratios of each structure, are described in the table below. Also, the weight average molecular weight (Mw) and imidization rate (%) of these resins are described in the table below. Resins having the same structure but different Mw were obtained by appropriately changing the equivalent amount of diamine. Also, resins having the same structure but different imidization rates were obtained by appropriately changing the reaction temperature. [Chemical formula] [Chemical formula] [Chemical formula]

[0256] [Synthesis Example P-27: Synthesis of Resin (P-27)] 19.8 g (63.8 mmol) of 4,4'-oxydiphthalic dianhydride, 12.4 g (57.4 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl, and 1.39 g (12.8 mmol) of 4-aminophenol were dissolved in 125 mL of NMP. The solution was stirred at 200 °C for 3 hours under a nitrogen atmosphere to obtain a polyimide. Then, 0.1 g of TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical) and 29.7 g (191.2 mmol) of 2-isocyanatoethyl methacrylate were added at room temperature. After raising the temperature to 60 °C, 0.1 g of Neostan U-600 (manufactured by Nitto Kasei Co., Ltd., inorganic bismuth) was added, and the mixture was stirred for 3 hours. 375 mL of tetrahydrofuran was added to the obtained polyimide solution, and the solution was dropped into 1500 mL of methanol to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40 °C for 1 day to obtain a resin (P-27) which is a polyimide as a powder.

Chemical formula

[0257] 〔Synthesis Examples P-28 to P-29: Synthesis of Resins (P-28) to (P-29)〕 Resins (P-28) to (P-29) were synthesized in the same manner as resin (P-27), except that the types of acid anhydrides, diamines, charging ratios, and compounds having polymerizable groups used in Synthesis Example P-1 were appropriately changed. Resins (P-28) to (P-29) are resins having repeating units represented by the following formulas (P-28) to (P-29), respectively. The structures of the respective repeating units were determined from the 1 H-NMR spectrum. In the following structures, the symbols in parentheses are the values described in the table below, representing the molar ratio of each structure. The weight average molecular weight (Mw) and imidization rate (%) of these resins are described in the table below.

Chemical formula

Chemical formula

[0258] [Synthesis Examples P-30 to P-32: Synthesis of Resins (P-30) to (P-32)] Resins (P-30) to (P-32) were synthesized in the same manner as resin (P-1), except that the types and charging ratios of the acid anhydride and diamine, which are the raw materials used in Synthesis Example P-1, were appropriately changed. Resins (P-30) to (P-32) are resins having repeating units represented by the following formulas (P-30) to (P-32), respectively. The structure of each repeating unit was 1 determined from the H-NMR spectrum. In the following structures, the symbols in parentheses are the values described in the table below and represent the molar ratio of each structure. For resins (P-30) to (P-32), A and B, which are the molar ratios of each structure, are described in the table below. Also, the weight average molecular weight (Mw) and imidization rate (%) of these resins are described in the table below. [Chemical Formula]

[0259] [Table 1]

[0260] [Examples and Comparative Examples] In each example, the components described in the following table were mixed to obtain each resin composition. Also, in each comparative example, the components described in the following table were mixed to obtain each comparative composition. Specifically, the content of each component described in the table was the amount (parts by mass) described in the "parts by mass" column of each column of the table. The amount of the solvent used was such that the solid content concentration of the composition was the value in the "solid content concentration (mass%)" column of the table, and a mixture obtained by mixing at the mixing ratio (mass ratio) described in the "ratio" column of each solvent was used. The obtained resin compositions and comparative compositions were pressure-filtered using a polytetrafluoroethylene filter with a pore size of 0.8 μm. Also, in the table, the description "-" indicates that the composition does not contain the corresponding component.

[0261]

Table 2

[0262]

Table 3

[0263]

Table 4

[0264]

Table 5

[0265]

Table 6

[0266]

Table 7

[0267]

Table 8

[0268]

Table 9

[0269] 〔Resin〕 ·P-1 to P-32: Resins (P-1) to (P-32) synthesized above

[0270] 〔Polymerizable Compound〕 ·C-1: NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.) ·C-2: NK Ester TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) ·C-3: Compound with the following structure ·C-4: Compound with the following structure ·C-5: Biscuit #802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) ·C-6: A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.) ·C-7: NK Ester A-9300S (manufactured by Shin-Nakamura Chemical Co., Ltd.) ·C-8: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

Chemical formula

[0271] 〔Photoinitiator〕 ·D-1: Compound with the following structure ·D-2: IRGACURE OXE 01 (manufactured by BASF) ·D-3: TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) ·D-4: TR-PBG-3057 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) ·D-5: Compound with the following structure ·D-6: Compound with the following structure

Chemical formula

[0272] 〔Compound A〕 ·(A-1)-1 to (A-1)-31: Compounds with the following structure ·(A-2)-1 to (A-2)-3: Compounds with the following structure

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0273] -Synthesis of Compound (A-1)-1- In a flask, 5.00 g of 4,4'-diaminodiphenylmethane, 23.1 g of ethyl bromoacetate, 17.4 g of potassium carbonate, 10.5 g of potassium iodide, and 79.0 g of acetonitrile were mixed and stirred under heating and reflux for 5 hours. After cooling to room temperature, 500 mL of ethyl acetate was added. After removing the solid by filtration, the filtrate was concentrated under heating and reduced pressure. After diluting the concentrate with 100 mL of ethyl acetate, 400 mL of hexane was added, and 9.8 g of ester X-1 was obtained by recrystallization (yield 80%). 1 H-NMR, 400 MHz, δ (DMSO-d6) ppm: 3.63 (12H, s), 3.65 (2H, s), 4.16 (8H, s), 6.43 (4H, d, J = 8.7 Hz), 6.96 (4H, d, J = 8.6 Hz). In a flask, 10.0 g of ester X-1, 4.7 g of lithium aluminum hydride, and 364.0 g of tetrahydrofuran were mixed and stirred under heating and reflux for 3 hours. After cooling to 0 °C, 13.3 g of water was added and stirred at room temperature for 1 hour. After removing the solid by filtration, the filtrate was concentrated under heating and reduced pressure. The obtained solid was suspended in 50 mL of water and stirred at 50 °C for 1 hour, and then the solution and the solid were separated by filtration. By air-drying the obtained solid, 2.4 g of compound (A-1)-1 was obtained (yield 31%). 1 H-NMR, 400 MHz, δ (DMSO-d6) ppm: 3.30 - 3.40 (8H, m), 3.50 (8H, q, J = 6.06 Hz), 3.62 (2H, s), 4.71 (4H, t, J = 5.44 Hz), 6.56 (4H, d, J = 8.76 Hz), 6.93 (4H, d, J = 8.68 Hz). Also, in the same manner, compounds (A-1)-2 to (A-1)-31 and (A-2)-1 to (A-2)-3 were synthesized.

Chemical Structure

Chemical Structure

[0274] Compound B ·(B-1)-1 to (B-1)-10: Compounds with the following structure

Chemical formula

[0275] Sensitizer ·E-1 to E-6: Compounds represented by the following formulas (E-1) to (E-6)

Chemical formula

[0276] Antioxidant ·F-1: Compound with the following structure ·F-2: Adeka Stab CDA-10 (manufactured by ADEKA) ·F-3: Compound with the following structure

Chemical formula

[0277] Metal adhesion improver ·G-1: Compound with the following structure ·G-2: X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.) ·G-3: KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.) ·G-4: Compound with the following structure ·G-5: Compound with the following structure

Chemical formula

[0278] Migration inhibitor ·H-1 to H-5: Compounds with the following structure

Chemical formula

[0279] Metal complex ·I-1 to I-2: Compounds with the following structure

Chemical formula

[0280] 〔Photoabsorbent〕 ·J-1: Ester of 2,2’,3,3’-tetrahydro-3,3,3’,3’-tetramethyl-1,1’-spirobi(1H-indene)-5,5’,6,6’,7,7’ hexanol and 1,2-naphthoquinone-(2)-diazido-5-sulfonic acid (NQD (naphthoquinone diazide)) ·J-2: Compounds with the following structure ·J-3: Compounds with the following structure

Chemical formula

[0281] 〔Base generator〕 ·K-1 to K-4: Compounds with the following structure

Chemical formula

[0282] 〔Compound X〕 ·X-1 to X-3: Compounds with the following structure

Chemical formula

[0283] 〔Compound Y〕 ·Y-1 to Y-7: Compounds with the following structure

Chemical formula

[0284] 〔Solvent〕 ·L-1: γ-Butyrolactone ·L-2: Dimethyl sulfoxide ·L-3: Ethyl lactate ·L-4: N-Methyl-2-pyrrolidone ·L-5: γ-Valerolactone ·L-6: 3-Methoxy-N,N-dimethylpropanamide ·L-7: 3-Butoxy-N,N-dimethylpropanamide

[0285] [Surfactant] ·M-1: F-554 (manufactured by DIC Corporation) ·M-2: BYK-333 (manufactured by BYK)

[0286] <Evaluation> [Evaluation of Resolution] The resin composition or comparative composition prepared in each example or comparative example was applied layer by layer on the surface of the copper thin layer of a resin substrate with a copper thin layer formed on its surface by spin coating, dried at 110 °C for 5 minutes, and after forming a resin composition layer with a film thickness of 4 μm after film formation, the obtained resin composition layer was formed using a square via mask with a pattern formed in increments of 0.5 μm from 0.5 to 10 μm, and exposed at each exposure dose in the range of 100 to 800 mJ / cm 2 in increments of 50 mJ / cm 2 of each exposure dose. Subsequently, development was carried out until the unexposed portion was removed with cyclopentanone, rinsed with PGMEA for 30 seconds, and further heated in a nitrogen atmosphere at a heating rate of 10 °C / min to 230 °C for 1 hour. The minimum opening mask diameter of the obtained cured product was determined by observing the cross-section of the opening pattern part with a scanning microscope S-4800 (manufactured by Hitachi High-Technologies Corporation) and evaluated according to the following evaluation criteria. The minimum opening mask diameter was the smallest among the mask diameters for which an opening pattern was formed at at least one of the above exposure doses. Also, the remaining film ratio (%: film thickness after development / film thickness before development × 100) was calculated from the film thickness before and after development when exposed at 400 mJ / cm 2 . When the remaining film ratio is less than 80%, it is not preferable for forming a rewiring layer regardless of the opening mask size. (Evaluation Criteria) A: The minimum opening mask diameter was 3 μm or less and the remaining film ratio after development was 90% or more. B: The minimum opening mask diameter exceeded 3 μm and was 4 μm or less, and the development residue film ratio was 90% or more. C: The minimum opening mask diameter exceeded 4 μm and was 5 μm or less, and the development residue film ratio was 90% or more. D: The minimum opening mask diameter exceeded 5 μm or the development residue film ratio was less than 80%.

[0287] 〔Chemical resistance〕 The resin composition or comparative composition prepared in each example or comparative example was applied layer by layer on a silicon wafer by spin coating, dried at 110 °C for 5 minutes, and a resin composition layer with a film thickness of 15 μm after film formation was formed. Next, for the resin composition layer, using a broad-band exposure machine (manufactured by Ushio Electric Co., Ltd.: UX-1000SN-EH01), full-surface exposure was performed at 400 mJ / cm 2 Then, heat treatment was performed at 230 °C for 1 hour in an N2 atmosphere using a clean oven (manufactured by Koyo, CLH-21) to obtain a cured film of the resin composition or comparative composition. The obtained cured film was immersed in the following chemicals under the following immersion conditions, and the residue film ratio (immersion after film thickness / immersion before film thickness × 100 (%)) was calculated from the film thickness before and after immersion. Evaluation was performed according to the following evaluation criteria, and the evaluation results were described in the column of "chemical resistance". The higher the residue film ratio, the better the chemical resistance. · Chemical: A 90:10 mixture of dimethyl sulfoxide (DMSO) and an aqueous solution of 2.38 mass% tetramethylammonium hydroxide (TMAH) · Immersion conditions: 60 °C for 30 minutes - Evaluation criteria - A: The above residue film ratio was 95% or more. B: The above residue film ratio was 80% or more and less than 95%.

[0288] 〔Reliability〕 In each of the examples and comparative examples, a resin composition or a comparative composition was applied onto a silicon wafer on which Cu 2-μm line-and-space wiring was formed by spin coating to form a resin composition layer. The silicon wafer coated with the obtained resin composition layer was dried on a hot plate at 110°C for 5 minutes to obtain a uniform resin composition layer with a thickness of about 15 μm after film formation on the silicon wafer. With respect to the obtained resin composition layer, the entire surface of the silicon wafer was exposed with an exposure energy of 400 mJ / cm 2 using a USHIO exposure machine (light source: 500 W / m 2 ultra-high pressure mercury lamp). After the above exposure, the resin composition layer was heated under a nitrogen atmosphere at a heating rate of 10°C / min and heated at 230°C for 1 hour to obtain a cured product. With respect to the obtained cured product, 150°C / 1000 hours was carried out, and the film thickness of copper oxide at the interface between the Cu wiring and the cured product was observed with a scanning electron microscope (S-4800) (manufactured by Hitachi High-Technologies Corporation). The measurement was calculated as the average value of observing 10 locations. (Evaluation Criteria) A: The film thickness of copper oxide was less than 150 nm. B: The film thickness of copper oxide was 150 nm or more and less than 200 nm.

[0289] 〔Film Formability〕 The resin composition or the comparative composition prepared in each example or comparative example was applied onto a silicon wafer by spin coating at 3000 rpm in an environment of a temperature of 23°C and a humidity of 50%, and the film surface immediately after spin coating and after standing for 5 minutes after spin coating was visually observed. -Evaluation Criteria- A: No film turbidity was observed immediately after spin coating and after standing. B: No film turbidity was observed immediately after spin coating, but film turbidity was observed after standing.

[0290] 〔Storage Stability〕 The presence or absence of precipitation and the viscosity change rate = |((viscosity after storage / viscosity before storage) × 100)| were evaluated when the resin composition or comparative composition prepared in each example or comparative example was stored in a constant temperature bath at 23°C for 168 hours. Viscosity measurement was performed using a TV-100E viscometer (manufactured by Toki Sangyo Co., Ltd.). (Evaluation criteria) A: The viscosity change rate was less than 2%, and no precipitation was observed. B: The viscosity change rate was 2% or more and less than 5%, and no precipitation was observed. C: The viscosity change rate was 5% or more and less than 10%, and no precipitation was observed.

[0291] From the above results, it can be seen that the resolution is improved by using the resin composition according to the present invention. In comparison, when the composition according to Comparative Example 1 that does not contain Compound A is used, it can be seen that the resolution is inferior.

Claims

1. A resin selected from the group consisting of a polyimide precursor and a polyimide, a photoinitiator, and a compound A represented by the following formula (A-1) or formula (A-2), satisfying at least one of the following Condition 1 and Condition 2 photosensitive resin composition. Condition 1: The resin has a polymerizable group. Condition 2: The photosensitive resin composition further contains a polymerizable compound. 【Chemical 1】 In formula (A-1), R １１ and R １２ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R １１ and R １２ contains a group represented by formula (R-1), Ar １ represents an aromatic ring structure which may have a substituent or a condensed ring, n1 represents an integer of 2 or more, when n1 is 2, X represents a single bond or a divalent linking group, and when n1 is 3 or more, X represents an n1-valent linking group. In formula (A-2), R ２１ and R ２２ each independently represents a hydrogen atom or a monovalent organic group, and at least one of R ２１ and R ２２ contains a group represented by formula (R-1), Ar ２ represents an aromatic ring structure which may have a substituent or a condensed ring, and n2 represents an integer of 2 or more. 【Chemical 2】 In formula (R-1), R Ｒ１ and R Ｒ２ each independently represents a hydrogen atom or a monovalent organic group, and m R Ｒ１ may be the same or different from each other, and m R Ｒ２ may be the same or different from each other, m represents an integer of 2 or more, and * represents a bonding site with other structures.

2. The compound A is a compound represented by the formula (A-1), and R in the formula (A-1) １１ and R １２ are both groups represented by the formula (R-1), and m in the formula (R-1) is 2. The photosensitive resin composition according to claim 1.

3. The photosensitive resin composition according to claim 1 or 2, wherein the compound A is a compound represented by the following formula (AA-1), formula (AA-2), or formula (AA-3). [Chemical 3]

4. The photosensitive resin composition according to claim 1 or 2, containing a compound X represented by the following formula (X-1), formula (X-2), or formula (X-3). 【Chemical 4】

5. The photosensitive resin composition according to claim 4, wherein the content of the compound X is 0.001 to 10 parts by mass when the content of the compound A is 100 parts by mass.

6. The photosensitive resin composition according to claim 3, containing a compound represented by formula (AA-1) as the compound A and containing a compound represented by the following formula (Y-1-1). 【Chemical Formula 5】

7. The photosensitive resin composition according to claim 1 or 2, wherein the resin is a polyimide precursor containing a repeating unit represented by the following formula (1-1). 【Chemical Formula 6】 In formula (1-1), X is a tetravalent organic group, Y is a divalent organic group, and R １ and R ２ are each independently a hydrogen atom or a group represented by the following formula (III). 【Chemical Formula 7】 In formula (III), R ２００ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and R ２０１ represents an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ -, a cycloalkylene group, or a polyalkyleneoxy group, and * represents the bonding site with an oxygen atom.

8. The photosensitive resin composition according to claim 1 or 2, satisfying Condition 2.

9. The photosensitive resin composition according to claim 8, wherein the polymerizable compound contains a compound represented by the following formula (M-1). 【Chemical 8】 In formula (M-1), p represents an integer of 2 or more, and each R independently represents a hydrogen atom or a methyl group.

10. The photosensitive resin composition according to claim 1 or 2, wherein the photoinitiator is an oxime compound.

11. The photosensitive resin composition according to claim 1 or 2, wherein the photoinitiator contains a compound represented by the following formula (P-1). 【Chemical Formula 9】

12. The photosensitive resin composition according to claim 1 or 2, further containing a compound B represented by the following formula (B-1). 【Chemical Formula 10】 In formula (B-1), Ar Ｂ represents an aromatic ring structure which may have a substituent or a fused ring, and R Ｂ１ and R Ｂ２ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R Ｂ１ and R Ｂ２ contains a group represented by the above formula (R-1).

13. The photosensitive resin composition according to claim 12, wherein the total content of the compound A and the compound B is 30 to 200 parts by mass when the total content of the photoinitiator is 100 parts by mass.

14. The resin is a repeating unit represented by the formula (1-1), wherein X in the formula (1-1) is a repeating unit A represented by the following formula (a), and a repeating unit represented by the formula (1-1), wherein X in the formula (1-1) is a repeating unit B represented by the following formula (b). The photosensitive resin composition according to claim 7. 【Chemical 11】 In the formula (a) or the formula (b), * represents a bonding site with the carbonyl group in the formula (1-1).

15. The photosensitive resin composition according to claim 14, wherein the molar amount of the repeating unit A contained relative to the total molar amount of the repeating unit A and the repeating unit B is 50 to 80 mol%.

16. The photosensitive resin composition according to claim 1 or 2, wherein the imidization rate of the resin is 10% or more and less than 30%.

17. The photosensitive resin composition according to claim 1 or 2, wherein the average weight molecular weight of the resin is 8,000 or more and 40,000 or less.

18. The photosensitive resin composition according to claim 1 or 2, further comprising a solvent, wherein the solvent comprises one or more solvents selected from the group consisting of γ-butyrolactone and N-methyl-2-pyrrolidone and ethyl lactate.

19. The photosensitive resin composition according to claim 18, wherein the solvent further comprises dimethyl sulfoxide.

20. The photosensitive resin composition according to claim 1 or 2, further comprising 0.01 to 10 parts by mass of a purine derivative based on 100 parts by mass of the resin.

21. The resin composition according to claim 1 or 2, which is used for forming an interlayer insulating film for a rewiring layer.

22. A cured product obtained by curing the resin composition according to claim 1 or 2.

23. A laminate comprising two or more layers of the cured product according to claim 22, and a metal layer between any two of the layers of the cured product.

24. A method for producing a cured product, comprising a film forming step of applying the resin composition according to claim 1 or 2 onto a substrate to form a film.

25. The method for producing a cured product according to claim 24, comprising an exposure step of selectively exposing the film and a development step of developing the film with a developer to form a pattern.

26. The method for producing a cured product according to claim 25, comprising a heating step of heating the film at 50 to 450 °C.

27. A method for producing a laminate, comprising the method for producing a cured product according to claim 24.

28. A method for producing a semiconductor device, comprising the method for producing a cured product according to claim 24.

29. A semiconductor device comprising the cured product according to claim 22.

30. A compound represented by the following formula (A-1) or formula (A-2). 【Chemical Formula 12】 In formula (A-1), R １１ and R １２ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R １１ and R １２ is a group represented by formula (R-1), Ar １ represents an aromatic ring structure which may have a substituent or a condensed ring, n1 is 2, and X represents a single bond or a divalent linking group. In formula (A-2), R ２１ and R ２２ each independently represents a hydrogen atom or a monovalent organic group, and at least one of R ２１ and R ２２ is a group represented by formula (R-1), Ar ２ represents an aromatic ring structure which may have a substituent or a condensed ring, and n2 is 2. 【Chemical 13】 In formula (R-1), R Ｒ１ and R Ｒ２ each independently represent a hydrogen atom or a monovalent organic group, and m R's Ｒ１ may be the same or different from each other, and m R's Ｒ２ may be the same or different from each other, m represents an integer of 2 or more, and * represents a bonding site with other structures.

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