Resin composition, cured product, method for producing cured product, laminate, method for producing laminate, semiconductor device, and method for producing semiconductor device

Abstract

Provided are: a resin composition which contains at least one resin that is selected from the group consisting of polyimide precursors and polyimides, a polymerization initiator, and dioxane, wherein the content of the dioxane is 0.1-100 mass ppm relative to the resin; a cured product which is obtained by curing the resin composition; a laminate and a semiconductor device, each of which contains the cured product; a method for producing the cured product; and a method for producing the laminate and a method for producing the semiconductor device, each of which includes the method for producing the cured product.

Description

Resin composition, cured product, method for manufacturing a cured product, laminate, method for manufacturing a laminate, semiconductor device, and method for manufacturing a semiconductor device.

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

[0002] Polyimide precursors and polyimides are used in various fields, such as semiconductor devices and aerospace. Patent Document 1 describes a photosensitive resin composition containing a liquid-repellent material having a specific structural unit, one or more alkali-soluble resins selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors of any of these, and copolymers thereof, and a naphthoquinone diazide compound with an esterification rate of 70% or more and less than 90%.

[0003] Japanese Patent Application Publication No. 2021-135499

[0004] One example of an application for a resin composition containing at least one resin selected from the group consisting of polyimide precursors and polyimides is the formation of films such as interlayer insulating films for redistribution layers used in semiconductor devices. More specifically, a film is formed by coating the resin composition onto a substrate and then exposing and developing the resulting coating. Recently, with the increasing miniaturization and high integration of semiconductor devices, there is a demand for films with fewer defects and less variation in film thickness.

[0005] The present invention aims to provide a resin composition that can suppress the occurrence of defects and variations in film thickness, a cured product obtained by curing the resin composition, a laminate and a semiconductor device containing the cured product, a method for manufacturing the cured product, and a method for manufacturing a laminate and a semiconductor device including the method for manufacturing the cured product.

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

[0007] [1] A resin composition comprising at least one resin selected from the group consisting of a polyimide precursor and a polyimide, a polymerization initiator, and dioxane, wherein the content of the dioxane is 0.1 to 100 ppm by mass with respect to the resin. [2] The resin composition according to [1], wherein the dioxane contains 1,4-dioxane. [3] The resin composition according to [1] or [2], wherein the resin is a polyimide precursor containing a repeating unit represented by the following formula (2-1).

[0008]

[0009] In formula (2-1), R １１１ represents a divalent organic group, R １１５ represents a tetravalent organic group, and R １１３ and R １１４ each independently represent a hydrogen atom or a monovalent organic group. [4] The resin composition according to [3], wherein at least one of R １１３ and R １１４ in the formula (2-1) is a group represented by the following formula (III).

[0010]

[0011] In formula (III), R ２００ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, 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 a bonding site with an oxygen atom. [5] The resin composition according to [3] or [4], wherein R １１５ in the formula (2-1) is represented by the following formula (a) or (b).

[0012]

[0013] In formula (a) or formula (b), * represents a bonding site with a carbonyl group in formula (2-1). [6] The resin composition according to any one of [1] to [5], wherein the resin contains a repeating unit represented by the following formula (3).

[0014]

[0015] In formula (3), G １ This represents a tetravalent organic group containing a structure obtained by removing two or more hydrogen atoms from any of the structures represented by formula (V-1), formula (V-2), formula (V-3), formula (V-5), or formula (V-8), E １ This represents a divalent organic group containing an ethylenically unsaturated bond.

[0016]

[0017] In formula (V-2), R Ｘ１ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halogen, and in formula (V-3), R Ｘ２ and R Ｘ３ Each of these independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３ They may bond to form a ring structure, in formula (V-8), R Ｘ５Each of these is independently a hydrogen atom, an alkyl group, or a halogenated alkyl group. [7] A resin composition according to any one of [1] to [6], comprising a first polymerizable compound. [8] A resin composition according to [7], comprising a second polymerizable compound different from the first polymerizable compound. [9] A resin composition according to [7] or [8], wherein the first polymerizable compound is a polyfunctional (meth)acrylate with three or more functions.

[10] A resin composition according to [8], wherein the second polymerizable compound is a bifunctional (meth)acrylate.

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

[10] , comprising a solvent, wherein the solvent comprises at least one selected from the group consisting of γ-butyrolactone and N-methyl-2-pyrrolidone.

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

[11] , used for forming an interlayer insulating film for a redistribution layer.

[13] A cured product obtained by curing the resin composition according to any one of [1] to

[12] .

[14] A laminate comprising two or more layers made of the cured product described in

[13] , wherein a metal layer is included between any of the layers made of the cured product.

[15] A method for manufacturing a cured product, comprising a film forming step of applying the resin composition described in any one of [1] to

[12] onto a substrate to form a film.

[16] A method for manufacturing a cured product according to

[15] , comprising an exposure step of selectively exposing the film and a developing step of developing the film using a developer to form a pattern.

[17] A method for manufacturing a cured product according to

[15] or

[16] , comprising a heating step of heating the film at 50 to 450°C.

[18] A method for manufacturing a laminate, comprising the method for manufacturing a cured product described in any one of

[15] to

[17] .

[19] A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product described in any one of

[15] to

[18] .

[20] A semiconductor device comprising the cured product described in

[13] .

[0018] According to the present invention, it is possible to provide a resin composition that can suppress the occurrence of defects and variations in film thickness, a cured product obtained by curing the resin composition, a laminate and a semiconductor device containing the cured product, a method for manufacturing the cured product, and a method for manufacturing a laminate and a semiconductor device including the method for manufacturing the cured product.

[0019] A schematic diagram showing the measurement points for film thickness.

[0020] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments explicitly stated. In this specification, numerical ranges represented by the symbol "~" mean a range that includes the numerical values ​​before and after "~" as the lower and upper limits, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes as long as the intended effect of the process is achieved. In the notation of groups (atomic groups) in this specification, notations that do not specify substituted or unsubstituted include both groups (atomic groups) with substituents and groups (atomic groups) without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission line spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic" means both or either "acrylic" and "methacrylic," and "(meth)acryloyl" means both or either "acryloyl" and "methacryloyl." In this specification, Me in structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, total solids means the total mass of all components of the composition excluding the solvent. In this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values, unless otherwise specified.In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and connecting Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series as columns. Unless otherwise specified, these molecular weights shall be measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, if THF is unsuitable as an eluent, such as in cases of low solubility, THF (tetrahydrofuran) may be used. Unless otherwise specified, detection in GPC measurements shall be performed using a UV (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that there are other layers above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to 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 specified, 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 preferred combination of embodiments is a more preferred embodiment. In this specification, "organic group" means a group containing at least one carbon atom.

[0021] [Resin Composition] The resin composition of the present invention is a resin composition comprising at least one resin selected from the group consisting of polyimide precursors and polyimides, a polymerization initiator, and dioxane, wherein the content of the dioxane is 0.1 to 100 ppm by mass relative to the resin.

[0022] The mechanism by which the above effects are obtained by the present invention is not fully understood, but the inventors have hypothesized the following. However, the present invention is not limited in any way by the hypothesized mechanism below. The resin composition of the present invention contains a predetermined amount of dioxane as described above. Dioxane is readily soluble in water and various organic solvents, and it is thought that by adding a predetermined amount to the resin composition, defects can be suppressed by dissolving bubbles and defects. On the other hand, if too much dioxane is added, it is thought that uneven coating will occur and the film thickness within the substrate will vary. This is thought to be because dioxane is a compound with a relatively low boiling point, and some of it volatilizes during coating, resulting in an uneven coating surface.

[0023] <Specific Resin> The resin composition of the present invention comprises at least one resin (also referred to as "specific resin") selected from the group consisting of polyimide precursors and polyimides. In the present invention, "main chain" refers to the relatively longest bonding chain in the resin molecule, and "side chain" refers to the other bonding chains. A polyimide precursor is a resin that undergoes a change in chemical structure to become polyimide upon external stimuli. Resins that undergo a change in chemical structure to become polyimide upon heat are preferred, and resins that undergo a ring-closing reaction upon heat to form a ring structure to become polyimide are more preferred. The specific resin preferably has polymerizable groups, and more preferably contains radical polymerizable groups. If the specific resin has radical polymerizable groups, the resin composition of the present invention preferably contains a radical polymerization initiator, and more preferably contains a radical polymerization initiator and a radical crosslinking agent. Furthermore, a sensitizer may be included as needed. For example, a negative-type photosensitive film can be formed from such a resin composition. The specific resin may also have polarity-converting groups such as acid-degradable groups. If the specific resin has acid-degradable groups, the resin composition preferably contains a photoacid generator. From such resin compositions, for example, a chemically amplified positive-type or negative-type photosensitive film can be formed.

[0024] [Polyimide Precursor] The polyimide precursor that can be used in the present invention is not particularly limited in terms of type, but it is preferable that it contains repeating units represented by the following formula (2).

[0025]

[0026] In formula (2), A １ and A ２ Each is independently an oxygen atom or -NR ｚ - represents R １１１ represents a divalent organic group, R １１５ represents a tetravalent organic group, R １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group, R ｚ represents a hydrogen atom or a monovalent organic group.

[0027] A in equation (2) １ and A２ Each is independently an oxygen atom or -NR ｚ R represents a negative sign, and an oxygen atom is preferred. ｚ represents a hydrogen atom or a monovalent organic group, with a hydrogen atom being preferred.

[0028] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-1) below. The specific resin preferably contains the repeating unit represented by formula (2-1) below.

[0029]

[0030] In formula (2-1), R １１１ represents a divalent organic group, R １１５ represents a tetravalent organic group, R １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group.

[0031] R in equations (2) and (2-1) １１１ R represents a divalent organic group. １１１ It is preferable that the base is one of the bases described in paragraphs 0042 to 0053 of Japanese Patent Publication No. 2023-003421.

[0032] Also, R １１１ From the viewpoint of i-ray transmittance, it is preferable that the group is a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, it is more preferable that the group is a divalent organic group represented by formula (61).

[0033]

[0034] In formula (51), R ５０ ~R ５７ Each of these is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R ５０ ~R ５７ At least one of them is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents the bonding site with the nitrogen atom in formula (2) and formula (2-1). ５０ ~R ５７Examples of monovalent organic groups include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0035]

[0036] In formula (61), R ５８ and R ５９ Each of these is independently a fluorine atom, a methyl group, or a trifluoromethyl group, and each of these independently represents a bonding site with the nitrogen atom in formula (2) and formula (2-1). Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used individually or in combination of two or more.

[0037] R in equations (2) and (2-1) １１５ * represents a tetravalent organic group. A tetravalent organic group containing an aromatic ring is preferred, and a group represented by formula (5) or formula (6) below is more preferred. In formula (5) or formula (6), * independently represents a bonding site with another structure.

[0038]

[0039] In formula (5), R １１２ The linking group is a single bond or a divalent linking group, and may be a single bond or a carbon-1 to carbon-10 aliphatic hydrocarbon group, -O-, -CO-, -S-, -SO- which may be substituted with a fluorine atom. ２ Preferably, the group is selected from -, -NHCO-, and combinations thereof, and is a C1- to C3 alkylene group, -O-, -CO-, -S-, and -SO- which may be single-bonded or substituted with a fluorine atom. ２ - More preferably, the group is selected from -CH ２ -, -C(CF ３ ) ２ -, -C(CH ３ ) ２ -, -O-, -CO-, -S-, and -SO２ It is even more preferable that the group is a divalent group selected from the group consisting of -.

[0040] R １１５ Preferably, this is a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride described in paragraphs 0055 to 0057 of Japanese Patent Publication No. 2023-003421.

[0041] R in equations (2) and (2-1) １１５ It is preferable that it is represented by the following formula (a) or (b).

[0042]

[0043] In formula (a) or formula (b), * represents the bonding site with the carbonyl group in formula (2) and formula (2-1).

[0044] In equations (2) and (2-1), R １１１ and R １１５ It is also possible that at least one of them has an OH group. More specifically, R １１１ Examples include residues of bisaminophenol derivatives.

[0045] R in equations (2) and (2-1) １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxy group. Also, R １１３ and R １１４ It is preferable that at least one of them contains a polymerizable group, and more preferably that both contain a polymerizable group. １１３ and R １１４It is also preferable that at least one of the components contains two or more polymerizable groups. The polymerizable groups are groups that can undergo crosslinking reactions by the action of heat, radicals, etc., and radical polymerizable groups are preferred. Specific examples of polymerizable groups include groups having an ethylenically unsaturated bond, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As radical polymerizable groups of the polyimide precursor, groups having an ethylenically unsaturated bond are preferred. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl groups), (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (III), with groups represented by the following formula (III) being preferred.

[0046]

[0047] In equation (III), R ２００ R represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred. In formula (III), * represents a bonding site with other structures. In formula (2-1), R １１３ and R １１４ When is a group represented by formula (III), * represents the bonding site with the oxygen atom. In formula (III), R ２０１ This is an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ - represents a cycloalkylene group or a polyalkylene oxy group. Preferred R ２０１ Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, as well as 1,2-butanediyl, 1,3-butanediyl, and -CH ２ CH(OH)CH ２ -Polyalkylene oxy groups are examples, including alkylene groups such as ethylene groups and propylene groups, and -CH ２ CH(OH)CH ２-, cyclohexyl groups, polyalkylene oxy groups are more preferred, alkylene groups such as ethylene groups and propylene groups, or polyalkylene oxy groups are even more preferred. In the present invention, a polyalkylene oxy group refers to a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When the polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of the alkylene oxy groups in the polyalkylene oxy group may be random, have blocks, or have alternating patterns. The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituents if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. The alkylene group may also have substituents. Preferred substituents include alkyl groups, aryl groups, halogen atoms, etc. The number of alkylene oxy groups contained in the polyalkylene oxy group (number of repeating polyalkylene oxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkylene oxy group is preferably a polyethylene oxy group, a polypropylene oxy group, a polytrimethylene oxy group, a polytetramethylene oxy group, or a group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, more preferably a polyethylene oxy group or a polypropylene oxy group, and even more preferably a polyethylene oxy group. In the group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, the ethylene oxy groups and propylene oxy groups may be arranged randomly, in blocks, or in alternating patterns. The preferred configurations for the number of repeating ethylene oxy groups in these groups are as described above.

[0048] In equations (2) and (2-1), R１１３ If R is a hydrogen atom, １１４ If the atom is a hydrogen atom, the polyimide precursor may form a pair salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0049] In equations (2) and (2-1), R １１３ and R １１４ At least one of the groups may be a polarity-converting group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes under the action of acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups, but acetal groups, ketal groups, silyl groups, silyl ether groups, and tertiary alkyl ester groups are preferred, and from the viewpoint of exposure sensitivity, acetal groups or ketal groups are more preferred. Specific examples of acid-degradable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, and trimethylsilyl ether group. From the viewpoint of exposure sensitivity, ethoxyethyl groups or tetrahydrofuranyl groups are preferred.

[0050] The polyimide precursor may also preferably contain fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0051] Furthermore, to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane as the diamine.

[0052] The repeating unit represented by the formula (2) is preferably a repeating unit represented by the formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by the formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the exposure latitude.

[0053] Formula (2-A)

[0054]

[0055] In the formula (2-A), A １ and A ２ represent an oxygen atom, and R １１１ and R １１２ each independently represent a divalent organic group, and R １１３ and R １１４ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R １１３ and R １１４ is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.

[0056] A １ 、A ２ 、R １１１ 、R １１３ and R １１４ each independently have the same meaning as A １ 、A ２ 、R １１１ 、R １１３ and R １１４ in the formula (2), and the preferable ranges are also the same. R １１２ has the same meaning as R １１２ in the formula (5), and the preferable ranges are also the same.

[0057] The polyimide precursor may contain one kind of the repeating unit represented by the formula (2), or may contain two or more kinds. Further, it may contain a structural isomer of the repeating unit represented by the formula (2). The polyimide precursor may contain other types of repeating units in addition to the repeating unit of the above formula (2).

[0058] One embodiment of the polyimide precursor in the present invention is one in which the content of repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).

[0059] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersion of the above polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no particular upper limit for the molecular weight dispersion of the polyimide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. In this specification, molecular weight dispersion is a value calculated by weight-average molecular weight / number-average molecular weight. When a resin composition contains multiple types of polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polyimide precursors as a single resin are, respectively, within the above ranges.

[0060] [Polyimide] The polyimide that can be used in the present invention may be an alkali-soluble polyimide, or a polyimide that is soluble in a developer mainly composed of an organic solvent. In this specification, an alkali-soluble polyimide means a polyimide that dissolves at 23°C in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium, and from the viewpoint of pattern formation, it is preferable that the polyimide dissolves at a rate of 0.5 g or more, and more preferably at a rate of 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited, but it is preferably 100 g or less. From the viewpoint of film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having multiple imide structures in its main chain.

[0061] -Fluorine Atoms- From the viewpoint of the film strength of the resulting organic film, it is also preferable for the polyimide to have fluorine atoms. Fluorine atoms are, for example, in the repeating unit represented by formula (4) described later, R １３２ , or R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in the repeating unit R represented by formula (4) described later. １３２ , or R in the repeating unit represented by formula (4) described later. １３１ It is more preferable that it be included as an alkyl fluoride. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and more preferably 20% by mass or less.

[0062] -Silicon atoms- From the viewpoint of the film strength of the resulting organic film, it is also preferable for the polyimide to have silicon atoms. For example, silicon atoms are R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in the repeating unit R represented by formula (4) described later. １３１ It is more preferable that the silicon atoms or the organically modified (poly)siloxane structure described later be included. The silicon atoms or the organically modified (poly)siloxane structure may be included in the side chains of the polyimide, but it is preferable that they be included in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0063] - Ethylene-unsaturated bond - From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide has an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain or in the side chains, but it is preferable that it has one in the side chains. It is preferable that the above ethylenically unsaturated bond has radical polymerizability. The ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. １３２ or R １３１ Preferably, it is included in R １３２ or R １３１ It is more preferable that it be included as a group having an ethylenically unsaturated bond. Among these, the ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in R １３１ It is more preferable that the group contains an ethylenically unsaturated bond. Examples of groups containing an ethylenically unsaturated bond include vinyl groups, allyl groups, vinylphenyl groups, and other groups containing a vinyl group that is directly bonded to an aromatic ring and may be substituted, (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (IV).

[0064]

[0065] In formula (IV), R ２０ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred.

[0066] In formula (IV), R ２１ This is an alkylene group having 2 to 12 carbon atoms, -O-CH ２ CH(OH)CH ２The characters represent -, -C(=O)O-, -O(C=O)NH-, a (poly)alkylene oxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and particularly preferably 2 or 3; the repeating number of the alkylene oxy group preferably has 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group formed by combining two or more of these. The alkylene group having 2 to 12 carbon atoms may be linear, branched, cyclic, or a combination thereof. The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0067] Among these, R ２１ It is preferable that the group is represented by any of the following formulas (R1) to (R3), and more preferably by the group represented by formula (R1).

[0068]

[0069] In formulas (R1) to (R3), L represents a single bond, or an alkylene group having 2 to 12 carbon atoms, a (poly)alkylene oxy group having 2 to 30 carbon atoms, or a group having two or more of these bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R in formula (IV). ２１ This represents the bonding site with the oxygen atom to which it is bonded. In formulas (R1) to (R3), a preferred embodiment of L is an alkylene group having 2 to 12 carbon atoms, or a (poly)alkylene oxy group having 2 to 30 carbon atoms, as shown in formula (IV) R ２１The preferred embodiment is the same as that of an alkylene group having 2 to 12 carbon atoms, or a (poly)alkylene oxy group having 2 to 30 carbon atoms. In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * is the same as * in formula (IV), and the preferred embodiment is the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate).

[0070] In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the polyimide main chain.

[0071] The amount of ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0072] -Polymerizable groups other than those having ethylenically unsaturated bonds- Polyimide may have polymerizable groups other than those having ethylenically unsaturated bonds. Examples of polymerizable groups other than those having ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. Polymerizable groups other than those having ethylenically unsaturated bonds include, for example, R in the repeating unit represented by formula (4) described later. １３１ It is preferable that it be included in the following. The amount of polymerizable groups other than those having ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0073] -Polarity-Converting Group- Polyimides may have polarity-converting groups such as acid-degradable groups. Acid-degradable groups in polyimides are R in formula (2) above. １１３ and R １１４ The acid-degradable group is the same as described above, and the preferred embodiment is also the same. The polarity-converting group is, for example, R in the repeating unit represented by formula (4) described later. １３１ , R １３２ It is found at the ends of polyimides, etc.

[0074] - Acid Value - When polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of polyimide is preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, and even more preferably 70 mg KOH / g or more. The above acid value is preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. When polyimide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development"), the acid value of polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. From the viewpoint of achieving both storage stability and developability, the acid groups contained in polyimides are preferably acid groups with a pKa of 0 to 10, and more preferably acid groups with a pKa of 3 to 8. pKa is the negative common logarithm of the equilibrium constant Ka, considering the dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa is the value calculated by ACD / ChemSketch®. The value of pKa may also be referenced from the value published in the "Revised 5th Edition Chemical Handbook Basic Edition" edited by the Chemical Society of Japan. When the acid group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant. As such acid groups, polyimides preferably contain at least one selected from the group consisting of carboxyl groups and phenolic hydroxyl groups, and more preferably contain phenolic hydroxyl groups.

[0075] -Phenolenic Hydroxyl Group- From the viewpoint of ensuring an appropriate development rate with an alkaline developer, it is preferable that the polyimide has a phenolic hydroxyl group. The polyimide may have a phenolic hydroxyl group at the end of the main chain or in the side chain. The phenolic hydroxyl group is, for example, R in the repeating unit represented by formula (4) described later. １３２ or R １３１ It is preferable that it be included in [the polyimide]. The amount of phenolic hydroxyl groups relative to the total mass of the polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0076] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains repeating units represented by the following formula (4).

[0077]

[0078] In formula (4), R １３１ represents a divalent organic group, R １３２ R represents a tetravalent organic group. If it has a polymerizable group, the polymerizable group is R １３１ and R １３２ It may be located at least one of the two, or it may be located at the end of the polyimide as shown in formula (4-1) or formula (4-2) below.

[0079] Formula (4-1)

[0080]

[0081] In formula (4-1), R １３３ is a polymerizable group, and the other groups are equivalent to formula (4).

[0082] Formula (4-2)

[0083]

[0084] R １３４ and R １３５ At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group is equivalent to formula (4).

[0085] Examples of polymerizable groups include groups containing the ethylenically unsaturated bond described above, or crosslinkable groups other than those having the ethylenically unsaturated bond described above. １３１ R represents a divalent organic group. As an example of a divalent organic group, R in formula (2) is １１１ Similar examples are given, and the preferred range is also similar. １３１ Examples include diamine residues remaining after the removal of the amino group of a diamine. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. A specific example is R in formula (2) of the polyimide precursor. １１１ Examples include:

[0086] R １３１ It is preferable that the diamine residue has at least two alkylene glycol units in its main chain, as this more effectively suppresses warping during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule, and even more preferably, it is the above-mentioned diamine residue that does not contain an aromatic ring.

[0087] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule include, but are not limited to, Jeffermin® KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0088] R １３２ R represents a tetravalent organic group. As an example of a tetravalent organic group, R in formula (2) is １１５ Similar examples are given, and the preferred range is also similar. For example, R １１５ The four bonders of the tetravalent organic group, as exemplified, bond with the four -C(=O)- parts in formula (4) to form a fused ring.

[0089] R １３２ Examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. A specific example is R in formula (2) of the polyimide precursor. １１５ Examples include: From the standpoint of the strength of the organic film, R １３２ It is preferable that it is an aromatic diamine residue having 1 to 4 aromatic rings.

[0090] R １３１ and R １３２ It is also preferable that at least one of them has an OH group. More specifically, R １３１ As examples, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) are listed as preferred examples, R １３２ As such, (DAA-1) to (DAA-5) above can be cited as more preferred examples.

[0091] The polyimide preferably contains repeating units represented by the following formula (3). The specific resin preferably contains repeating units represented by the following formula (3).

[0092]

[0093] In formula (3), G １ This represents a tetravalent organic group containing a structure obtained by removing two or more hydrogen atoms from any of the structures represented by formula (V-1), formula (V-2), formula (V-3), formula (V-5), or formula (V-8), E １ This represents a divalent organic group containing an ethylenically unsaturated bond.

[0094]

[0095] In formula (V-2), R Ｘ１ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halogen, and in formula (V-3), R Ｘ２ and R Ｘ３ Each of these independently represents a hydrogen atom or a substituent, RＸ２ and R Ｘ３ They may bond to form a ring structure, in formula (V-8), R Ｘ５ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halogen.

[0096] It is also preferable that the polyimide contains fluorine atoms in its structure. The fluorine atom content in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0097] To improve adhesion to the substrate, the polyimide may be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0098] To improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide are encapsulated with end-capturing agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. Of these, the use of monoamines is more preferable, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy Examples include -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end encapsulants.

[0099] Polyimide is a material in which all repeating units are R １３１ and R １３２ The combination of R may include the repeating unit represented by the above formula (4), which is the same. １３１ and R １３２ The polyimide may contain repeating units represented by formula (4) above, which include two or more different combinations of elements. In addition to the repeating units represented by formula (4) above, the polyimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by formula (2) above.

[0100] Polyimides can be synthesized by obtaining polyimide precursors using methods such as: reacting tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-captive) at low temperatures; reacting tetracarboxylic dianhydride (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-captive) with a diamine at low temperatures; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then reacting it with a diamine (partially substituted with a monoamine end-captive) in the presence of a condensing agent; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then acid-chloridizing the remaining dicarboxylic acid and reacting it with a diamine (partially substituted with a monoamine end-captive); completely imidizing the precursor using a known imidation reaction method; stopping the imidation reaction midway to introduce a partial imide structure; or introducing a partial imide structure by blending a fully imidized polymer with its polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0101] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the flexural resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), the weight-average molecular weight is particularly preferably 15,000 or more. The number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The degree of dispersion of the molecular weight of the above polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no specific upper limit for the degree of dispersion of the molecular weight of polyimide, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When the resin composition contains multiple types of polyimide as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyimide are treated as a single resin are each within the above range.

[0102] [Polybenzoxazole precursors] Examples of polybenzoxazole precursors include the compounds described in paragraphs 0073-0095 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0103] [Polybenzoxazoles] Examples of polybenzoxazoles include the compounds described in paragraphs 0101-0108 of International Publication No. 2022 / 145355. The foregoing description is incorporated herein by reference.

[0104] [Polyamide-imide precursors] Examples of polyamide-imide precursors include the compounds described in paragraphs 0104-0119 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0105] [Polyamideimides] Examples of polyamideimides include the compounds described in paragraphs 0125-0138 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0106] [Method for producing polyimide precursors, etc.] Polyimide precursors, etc., are produced, for example, by the method described in paragraphs 0134 to 0136 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0107] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of specific resin, or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.

[0108] The resin composition of the present invention may also preferably contain at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more types of specific resins and other resins described later, or it may contain two or more specific resins, but it is preferable to contain two or more specific resins. When the resin composition of the present invention contains two or more specific resins, for example, a polyimide precursor with a structure derived from a dianhydride (R in formula (2) above) １１５ Preferably, the polyimide precursor contains two or more different types of polyimide precursors.

[0109] <Other Resins> The resin composition of the present invention may contain the specified resin described above and other resins different from the specified resin (hereinafter also simply referred to as "other resins"). Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, etc. For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, in place of the polymerizable compound described later, or in addition to the polymerizable compound described later, a resin with a high polymerizability value and a weight-average molecular weight of 20,000 or less (for example, the molar amount of polymerizable groups per 1 g of resin is 1 × 10) may be used. －３ By adding (meth)acrylic resin (in a quantity of mol / g or more) to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), and other properties can be improved.

[0110] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. In the resin composition of the present invention, the content of other resins is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. In one preferred embodiment of the resin composition of the present invention, the content of other resins is also low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the above content is not particularly limited and may be 0% by mass or more. The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, it is preferable that the total amount is within the above range.

[0111] <Dioxane> The resin composition of the present invention contains dioxane. The dioxane may be 1,2-dioxane, 1,3-dioxane, or 1,4-dioxane. It is preferable that the dioxane contains 1,4-dioxane. That is, it is preferable that the resin composition of the present invention contains at least 1,4-dioxane.

[0112] The dioxane content in the resin composition of the present invention is 0.1 to 100 ppm by mass (parts per million) relative to a specific resin, more preferably 0.5 to 50 ppm by mass, even more preferably 1 to 10 ppm by mass, and particularly preferably 1 to 2 ppm by mass. The dioxane contained in the resin composition of the present invention may be one type or two or more types. When the resin composition of the present invention contains two or more types of dioxane, it is preferable that the total amount is within the above range. The ratio of 1,4-dioxane to the total amount of dioxane contained in the resin composition of the present invention is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, and particularly preferably 100% by mass (i.e., all dioxane contained in the resin composition of the present invention is 1,4-dioxane). The dioxane content in the resin composition is quantified by GC / MS (gas chromatography-mass spectrometry) after pre-treating the sample by headspace method. The measurement method conforms to US EPA Methods 5021 and 8260.

[0113] <Polymerizable Compounds> The resin composition of the present invention preferably contains polymerizable compounds. Examples of polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0114] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the above-mentioned groups containing an ethylenically unsaturated bond include vinyl group, allyl group, vinylphenyl group, (meth)acryloyl group, maleimide group, and (meth)acrylamide group. Among these, (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred, and from the viewpoint of reactivity, the (meth)acryloyl group is more preferred.

[0115] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compound having two or more ethylenically unsaturated bonds, it is preferable that it has 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6. 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.

[0116] 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.

[0117] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. For specific examples, refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0118] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0119] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204-0208 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0120] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0121] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethylene oxy chains; SR-209, 231, and 239, difunctional methacrylates having four ethylene oxy chains (all manufactured by Sartomer Co., Ltd.); DPCA-60, a hexafunctional acrylate having six pentylene oxy chains; and TPA-330, a trifunctional acrylate having three isobutylene oxy chains (both manufactured by Nippon Kayaku Co., Ltd.); and urethane oligomers. Examples include UAS-10, UAB-140 (both manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0122] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Compounds having an amino or sulfide structure within the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0123] The radical crosslinking agent may be a radical crosslinking agent having an acidic group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acidic group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. Particularly preferred is a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0124] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mg KOH / g, and more preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing and excellent developability. It also exhibits good polymerizability. The above acid value is measured in accordance with the description in JIS K 0070:1992. As a radical crosslinking agent, a radical crosslinking agent having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") is also preferred. Examples of crosslinking agent U include compounds described in paragraphs 0133 to 0143 of International Publication No. 2023 / 190064. This content is incorporated herein.

[0125] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6- Hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, ethylene oxide (EO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the formula weight of the polyethylene glycol chain is about 200. From the viewpoint of suppressing warping of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent in the resin composition of the present invention.Preferably used as monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. To suppress volatilization before exposure, compounds with a boiling point of 100°C or higher under normal pressure are also preferred as monofunctional radical crosslinking agents. Other examples of bifunctional or more functional radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0126] If a radical crosslinking agent is included, the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less, relative to 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.

[0127] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more agents are used in combination, it is preferable that their total amount be within the above range.

[0128] [Other Crosslinking Agents] The resin composition of the present invention may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. Other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by photosensitization with the photoacid generator or photobase generator described above, and are preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or base. The acid or base is preferably an acid or base generated from the photoacid generator or photobase generator in the exposure step. Examples of other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0129] The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. The other crosslinking agents may be present as one type or as two or more types. If two or more other crosslinking agents are present, it is preferable that their total amount is within the above range.

[0130] A preferred embodiment of the resin composition of the present invention is one which comprises a first polymerizable compound and a second polymerizable compound different from the first polymerizable compound. The polymerizable compounds mentioned above are examples of the first polymerizable compound and the second polymerizable compound. It is preferable that the first polymerizable compound is a polyfunctional (meth)acrylate with three or more functions. It is preferable that the second polymerizable compound is a bifunctional (meth)acrylate. The ratio of the first polymerizable compound to the second polymerizable compound is not particularly limited, but it is preferable that the mass ratio of the first polymerizable compound to the second polymerizable compound is 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1.

[0131] [Polymerization Initiator] The resin composition of the present invention contains a polymerization initiator (also called "initiator"). The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.

[0132] The photoradical polymerization initiator is present in an amount of at least about 50 L / mol with a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１ It is preferable that the compound contains 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 it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0133] Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For further details, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in International Publication No. 2018 / 221177, the photopolymerization initiators described in International Publication No. 2018 / 110179, the photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, the photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are incorporated herein by reference.

[0134] Examples of ketone compounds include the compounds described in paragraph 0087 of Japanese Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

[0135] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

[0136] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0137] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0138] As aminoacetophenone initiators, acylphosphine oxide initiators, and metallocene compounds, for example, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be suitably used. This is incorporated herein by reference.

[0139] More preferably, oxime compounds are used as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0140] Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 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), and Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, and others, the contents of which are incorporated herein by reference.

[0141] Preferred oxime compounds include, for example, compounds with the following structures, as well as 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-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In resin compositions, it is particularly preferable to use oxime compounds as photoradical polymerization initiators. Oxime compounds used as photoradical polymerization initiators have a >C=N-O-C(=O)- linking group in their molecule.

[0142]

[0143] 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, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-730, NCI-831, and ADEKA Arclus NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure PDO (SARTOMER Examples include those manufactured by ARKEMA. Additionally, oxime compounds with the following structures can also be used.

[0144]

[0145]

[0146]

[0147] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring as described in paragraphs 0169-0171 of International Publication No. 2021 / 112189, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring, and oxime compounds having a fluorine atom can be used. Also, oxime compounds having a nitro group as described in paragraphs 0208-0210 of International Publication No. 2021 / 020359, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxyl group is attached to the carbazole skeleton can be used. These contents are incorporated herein by reference.

[0148] In addition, compounds described in paragraphs 0113 to 0117 of Japanese Patent Publication No. 2023-058585 may be used as photopolymerization initiators. This description is incorporated into the present specification.

[0149] If the resin composition contains a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. The resin composition may contain only one type of photopolymerization initiator or two or more types. If two or more types of photopolymerization initiators are contained, it is preferable that the total amount is within the above range. In addition, since photopolymerization initiators may also function as thermal polymerization initiators, crosslinking by the photopolymerization initiator may be further advanced by heating with an oven or hot plate, etc.

[0150] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. When the sensitizer enters an electronically excited state, it comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases. Suitable sensitizers include compounds such as benzophenone, Michlaz ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.Examples of sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, and p-dimethylaminobenzylideneindanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylaminobenzoate Examples include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. Other sensitizing dyes may also be used. For details on sensitizing dyes, refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which are incorporated herein by reference.

[0151] If the resin composition contains a sensitizer, the sensitizer content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even 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 types.

[0152] [Chain Transfer Agents] The resin compositions of the present invention may contain chain transfer agents. Chain transfer agents are defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005). Examples of chain transfer agents include -S-S- and -SO2 molecules. ２ Compounds containing -S-, -N-O-, SH, PH, SiH, and GeH, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization, are used. These can generate radicals by donating hydrogen to low-activity radicals, or by generating radicals after oxidation and deprotonation. Thiol compounds are particularly preferred.

[0153] Furthermore, the chain transfer agent may be a compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0154] If the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition. There may be only one type of chain transfer agent, or there may be two or more types. If there are two or more types of chain transfer agents, it is preferable that their total content is within the above range.

[0155] <Base Generator> The resin composition of the present invention may contain a base generator. Here, a base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted by heating, for example, resulting in good mechanical properties and chemical resistance of the cured product, and thus good performance as an interlayer insulating film for redistribution layers contained in semiconductor packages, for example. The base generator may be an ionic base generator or a nonionic base generator. Examples of bases 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. Known base-generating agents include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of nonionic base-generating agents include the compounds described in paragraphs 0249-0275 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0156] Examples of base-generating agents include, but are not limited to, the following compounds.

[0157]

[0158] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0159] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018 / 038002.

[0160] Specific examples of ammonium salts include, but are not limited to, the following compounds.

[0161]

[0162] Specific examples of iminium salts include, but are not limited to, the following compounds.

[0163]

[0164] When the resin composition contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generating agents can be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0165] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used. An organic solvent is preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0166] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 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.)), and 2-alkyloxy Suitable examples include alkyl cypropionates (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.).

[0167] Suitable ethers include, 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 monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0168] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0169] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0170] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0171] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0172] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0173] 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, methylamyl alcohol, and diacetone alcohol.

[0174] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0175] 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, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The resin composition of the present invention preferably contains a solvent, and it is preferable that the solvent contains at least one selected from the group consisting of γ-butyrolactone and N-methyl-2-pyrrolidone. As the solvent, a combination of dimethyl sulfoxide and γ-butyrolactone, or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0176] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method. If two or more solvents are included, it is preferable that their total is within the above range.

[0177] <Metal Adhesion Enhancers> From the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc., the resin composition preferably contains a metal adhesion enhancer. Examples of metal adhesion enhancers 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.

[0178] [Silane Coupling Agents] Examples of silane coupling agents include the compounds described in paragraph 0316 of International Publication No. 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358. The following compounds are also preferable as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group. R below represents a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent can be selected according to the elimination temperature, but examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of wanting to set the elimination temperature to 160 to 180°C, caprolactam is preferred. Examples of commercially available compounds of this type include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0179]

[0180] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups can also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing repeating units represented by the following formula (S-1).

[0181]

[0182] In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ R represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer between 0 and 2. Ｓ１It is preferable that the structure includes polymerizable groups. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, amino groups, etc. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), (meth)acrylamide groups, (meth)acryloyloxy groups, etc., with vinylphenyl groups, (meth)acrylamide groups, or (meth)acryloyloxy groups being preferred, vinylphenyl groups or (meth)acryloyloxy groups being more preferred, and (meth)acryloyloxy groups being even more preferred. Ｓ２ n is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. n represents an integer from 0 to 2, and is preferably 1. Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound may all be the same. Here, it is preferable that n is 1 or 2 in at least one of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. Commercially available products can be used as such oligomer-type compounds, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0183] [Aluminum-based adhesive aids] Examples of aluminum-based adhesive aids include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0184] Other metal adhesion modifiers that can be used include the compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0185] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. A value above the lower limit ensures good adhesion between the pattern and the metal layer, while a value below the upper limit ensures good heat resistance and mechanical properties of the pattern. Only one type of metal adhesion improver may be used, or two or more types may be used. If two or more types are used, it is preferable that their total value is within the above range.

[0186] <Migration Inhibitor> The resin composition preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0187] While there are no particular limitations on the migration inhibitors, examples include compounds having heterocyclic rings (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 sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0188] As migration inhibitors, ion trapping agents that capture anions such as halogen ions can also be used.

[0189] Other migration inhibitors that can be used include the rust inhibitor described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, the details of which are incorporated herein by reference.

[0190] Specific examples of migration inhibitors include the following compounds.

[0191]

[0192] If the resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition.

[0193] There may be only one type of migration inhibitor, or there may be two or more types. If there are two or more types of migration inhibitors, it is preferable that their total number is within the above range.

[0194] <Polymerization Inhibitors> The resin composition preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0195] Specific examples of polymerization inhibitors include the compounds described in paragraph 0310 of International Publication No. 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]nona-2-ene-N,N-dioxide, and the like. This information is incorporated herein by reference.

[0196] If the resin composition contains 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 even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition.

[0197] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0198] <Light Absorbers> The resin composition may also preferably contain a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure. Examples of light absorbers include the compounds described in paragraphs 0159 to 0183 of International Publication No. 2022 / 202647 and the compounds described in paragraphs 0088 to 0108 of Japanese Patent Publication No. 2019-206689. These contents are incorporated herein by reference.

[0199] The content of the light absorber relative to the total solid content of the resin composition is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass.

[0200] [Surfactants] The resin composition preferably contains a surfactant. Various surfactants can be used, such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0201] By incorporating a surfactant into the resin composition, the liquid properties (especially fluidity) of the composition are improved, leading to improved uniformity of coating thickness and reduced liquid consumption, as well as increased conformability of the composition to uneven surfaces. Specifically, when forming a film using a coating solution containing a surfactant, the interfacial tension between the surface to be coated and the coating solution decreases, improving wettability to the surface and enhancing coatability. As a result, air bubbles are less likely to be incorporated into uneven areas, and a more uniform film with less thickness variation can be formed more effectively.

[0202] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329-0334 of International Publication No. 2021 / 112189, respectively, which are incorporated herein by reference.

[0203] One type of surfactant may be used, or two or more types may be used in combination. The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition. This will be incorporated into the specification.

[0204] <Other Additives> The resin composition may optionally contain various additives, such as higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.), to the extent that the effects of the present invention can be obtained. By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, and the contents of these are incorporated herein. When these additives are included, their total content is preferably 3% by mass or less of the solid content of the resin composition.

[0205] <Characteristics of the Resin Composition> The viscosity of the resin composition can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000 mm ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, 2,500 mm ２ / s~8,000mm ２ / s is even more preferable. Within the above range, it becomes easier to obtain a highly uniform coating film. 1,000 mm ２If the temperature is 1 / s or higher, it is easy to coat the film with the required thickness, for example, as an insulating film for rewiring, and 12,000 mm ２ If the rate is less than or equal to / s, a coating with excellent properties can be obtained on the coated surface.

[0206] <Restrictions on the substances contained in the resin composition> The water content of the resin composition is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0207] From the viewpoint of insulating properties, the metal content of the resin composition is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excludes metals included as complexes between organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range.

[0208] Furthermore, methods for reducing metal impurities unintentionally included in resin compositions include selecting raw materials with low metal content as components of the resin composition, filtering the raw materials of the resin composition, and performing distillation under conditions that suppress contamination as much as possible by lining the apparatus with polytetrafluoroethylene or the like.

[0209] When considering the application of the resin composition as a semiconductor material, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of preventing wiring corrosion. In particular, the halogen atoms present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chloride ions and bromine ions, is within the above ranges. A preferred method for adjusting the halogen atom content is ion exchange treatment.

[0210] Conventional containers can be used as containers for the resin composition. To suppress the incorporation of impurities into the raw materials and resin composition, it is also preferable to use multilayer bottles with an inner wall constructed of six types of resin in six layers, or bottles with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

[0211] <Preparation of 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 conventionally known methods. Mixing methods include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, and more preferably 15 to 25°C.

[0212] For the purpose of removing foreign matter such as dirt and fine particles from the resin composition of the present invention, filtration using a filter is preferable. Paragraph 0287 of International Publication No. 2023 / 190064 is incorporated herein by reference as part of this specification.

[0213] (Cured product) The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.

[0214] (Method for Manufacturing Cured Products) The method for manufacturing cured products 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 manufacturing cured products more preferably includes the film-forming step, an exposure step of selectively exposing the film formed in the film-forming step, and a developing step of developing the film exposed in the exposure step using a developer to form a pattern. The method for manufacturing cured products particularly preferably includes the film-forming step, the exposure step, the developing step, and at least one of a heating step of heating the pattern obtained in the developing step and a post-development exposure step of exposing the pattern obtained in the developing step. Furthermore, the method for manufacturing cured products may also preferably include the film-forming step and a step of heating the film. Details of each step will be described below.

[0215] <Membrane Formation Process> The resin composition of the present invention can be used in a membrane formation process in which it is applied to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a membrane formation process in which the resin composition is applied to a substrate to form a film.

[0216] [Substrate] The type of substrate can be appropriately determined according to the application and is not particularly limited. Examples of substrates include semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal, and substrates in which a metal layer is formed by, for example, plating or vapor deposition); paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, molded substrates, and electrode plates for plasma display panels (PDPs). Semiconductor manufacturing substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred. These substrates may have layers such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) on their surface. The shape of the substrate is not particularly limited and may be circular or rectangular. If the substrate is circular, for example, a diameter of 100 to 450 mm is preferred, and 200 to 450 mm is more preferred. If it is rectangular, for example, the length of the shorter side is preferred to be 100 to 1000 mm, and 200 to 700 mm is more preferred. As the substrate, for example, a plate-shaped, preferably panel-shaped, substrate (substrate) is used.

[0217] When a resin composition is applied to the surface of a resin layer (for example, a layer made of cured material) or a metal layer to form a film, the resin layer or metal layer serves as the substrate.

[0218] Coating is a preferred method for applying the resin composition onto a substrate. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating are preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the application method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected depending on the shape of the substrate; for circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Furthermore, a method can be applied in which a coating film, which has been previously applied and formed on a temporary support using the above application method, is transferred onto the substrate. Regarding the transfer method, the manufacturing methods described in paragraphs 0023, 0036-0051 of Japanese Patent Application Publication No. 2006-023696 and paragraphs 0096-0108 of Japanese Patent Application Publication No. 2006-047592 can be suitably used. In addition, a step of removing excess film at the edges of the substrate may be performed. Examples of such steps include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may be employed in which the substrate is coated with various solvents to improve the wettability of the substrate before applying the resin composition to the substrate, and then the resin composition is applied.

[0219] <Drying Process> After the film formation process (layer formation process), the film may be subjected to a drying process to remove the solvent from the formed film (layer). That is, the method for producing a cured product of the present invention may include a drying process for drying the film formed in the film formation process. The drying process is preferably performed 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 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is exemplified as 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0220] <Exposure Process> The above film may be subjected to an exposure process in which the film is selectively exposed. The method for manufacturing the cured product may include an exposure process in which the film formed by the film formation process is selectively exposed. Selective exposure means exposing a part of the film. By selective exposure, exposed areas (exposed parts) and unexposed areas (unexposed parts) are formed in the film. The amount of exposure is not particularly limited as long as the resin composition of the present invention can be cured, but for example, it may be 50 to 10,000 mJ / cm in terms of exposure energy at a wavelength of 365 nm. ２ Preferably, 200 to 8,000 mJ / cm² ２ This is preferable.

[0221] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0222] In relation to the light source, the exposure wavelength can be found in: (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (three wavelengths: g, h, i), (4) excimer lasers, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ２Examples of exposures include (5) excimer laser (wavelength 157 nm), (6) extreme ultraviolet light; EUV (wavelength 13.6 nm), (7) YAG laser with second harmonic 532 nm and third harmonic 355 nm. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with the i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited, and any method in which at least a part of the film made of the resin composition of the present invention is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0223] <Post-exposure heating step> The above film may be subjected to a heating step after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step in which the film exposed in the exposure step is heated. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heating step 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. The heating rate may also be changed as appropriate during heating. The heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters, etc., can be used. Furthermore, it is preferable to carry out the heating process in a low-oxygen atmosphere by flowing inert gases such as nitrogen, helium, or argon through the system.

[0224] <Development Process> The film after exposure may be subjected to a development process in which a pattern is formed by developing it with a developer. That is, the method for manufacturing a cured product of the present invention may include a development process in which a pattern is formed by developing the film exposed in the exposure process with a developer. By developing, one of the exposed and unexposed parts of the film is removed, and a pattern is formed. Here, development in which the unexposed part of the film is removed by the development process is called negative development, and development in which the exposed part of the film is removed by the development process is called positive development.

[0225] [Developer] Developers used in the developing process include alkaline aqueous solutions or developers containing organic solvents.

[0226] When the developer is an alkaline aqueous solution, the basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Specific examples of these include the compounds described in paragraph 0300 of International Publication No. 2023 / 190064. The above description is incorporated herein by reference. More preferably, the basic compound that the alkaline aqueous solution may contain is TMAH. 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 even more preferably 0.3 to 3% by mass, based on the total mass of the developer.

[0227] If the developer contains an organic solvent, the organic solvent may be one of the compounds described in paragraph 0387 of International Publication No. 2021 / 112189. This is incorporated herein by reference. Suitable alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, triethylene glycol, etc., and suitable amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

[0228] When the developer contains an organic solvent, one or more organic solvents can be used in mixture form. 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.

[0229] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Alternatively, the above content may be 100% by mass.

[0230] The developing solution may further contain other components. Examples of other components include known surfactants and known defoamers.

[0231] In the developing process, after processing with the developer, the pattern may be further washed (rinsed) with a rinsing solution. Alternatively, methods such as supplying the rinsing solution before the developer in contact with the pattern dries completely may be employed.

[0232] [Rinsing Solution] If the developer is an alkaline aqueous solution, water can be used as the rinsing solution. If the developer contains an organic solvent, a solvent different from the solvent contained in the developer (for example, water, or an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0233] When the rinsing solution contains an organic solvent, the organic solvent can be the same as the organic solvent exemplified above when the developer contains an organic solvent. Preferably, the organic solvent in the rinsing solution is different from the organic solvent in the developer, and more preferably, it is an organic solvent with lower pattern solubility than the organic solvent in the developer.

[0234] If the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. Preferred organic solvents are cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monomethyl ether (PGME). More preferred are cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME, and even more preferred are cyclohexanone and PGMEA.

[0235] When the rinsing solution contains an organic solvent, the amount of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the total mass of the rinsing solution. Alternatively, the amount of the organic solvent may be 100% by mass, relative to the total mass of the rinsing solution.

[0236] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0237] [Method of supplying rinsing solution] There are no particular restrictions on the method of supplying the rinsing solution as long as a desired pattern can be formed. These include immersing the substrate in the rinsing solution, supplying the rinsing solution to the substrate by pouring the solution, supplying the rinsing solution to the substrate with a shower, and continuously supplying the rinsing solution onto the substrate using means such as a straight nozzle. From the viewpoint of the penetration of the rinsing solution, the removal of non-image areas, and manufacturing efficiency, there are methods of supplying the rinsing solution with a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuous supply with a spray nozzle is preferred, and from the viewpoint of the penetration of the rinsing solution into the image area, the method of supplying with a spray nozzle is more preferred. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc. That is, the rinsing process is preferably a process of supplying the rinsing solution to the film after exposure using a straight nozzle or continuously supplying it, and it is more preferable to supply the rinsing solution using a spray nozzle. Possible methods for supplying the rinsing solution in the rinsing process include a process in which the rinsing solution is continuously supplied to the substrate, a process in which the rinsing solution is kept in a nearly stationary state on the substrate, a process in which the rinsing solution is vibrated on the substrate using ultrasound or the like, and a process that combines these methods.

[0238] The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0239] <Heating Step> The pattern obtained by the developing step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a heating step in which the pattern obtained by the developing step is heated. That is, the method for producing a cured product of the present invention may include a heating step in which the pattern obtained by the developing step is heated. Furthermore, the method for producing a cured product of the present invention may include a heating step in which a pattern obtained by another method without performing a developing step, or a film obtained by a film formation step is heated. In the heating step, resins such as polyimide precursors are cyclized to become resins such as polyimide. In addition, crosslinking of unreacted crosslinkable groups in specific resins or crosslinking agents other than specific resins also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C. Paragraphs 0326 to 0332 of International Publication No. 2023 / 190064 are incorporated herein by reference as part of this specification.

[0240] <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 in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer formation process in which a metal layer is formed 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).

[0241] The metal layer is not particularly limited, and existing metal species can be used, with examples including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.

[0242] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7888181B2, and U.S. 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, patterning methods combining sputtering, photolithography and etching, and patterning methods combining photolithography and electroplating can be mentioned. Preferred embodiments of the plating include electroplating using copper sulfate or copper cyanide plating solutions.

[0243] The thickness of the metal layer is preferably 0.01 to 50 μm at the thickest part, and more preferably 1 to 10 μm.

[0244] <Applications> The manufacturing method of the cured product of the present invention, or the fields in which the cured product can be applied, include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffer films. Other applications include sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or etching to form patterns on insulating films for the above-mentioned mounting applications. For more information on these applications, please refer to, for example, Science & Technology Co., Ltd., "High-Functionality and Application Technologies of Polyimides," April 2008, supervised by Masaaki Kakimoto; CMC Technical Library, "Fundamentals and Development of Polyimide Materials," November 2011; and the Japan Polyimide and Aromatic Polymer Research Association, ed., "Latest Polyimide Fundamentals and Applications," NTS, August 2010.

[0245] The method for manufacturing the cured product of the present invention, or the cured product of the present invention, can also be used for manufacturing printing plates such as offset plates or screen printing plates, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, particularly microelectronics.

[0246] (Laminate and Method for Manufacturing a Laminate) The laminate of the present invention refers to a structure having multiple layers made of the cured product of the present invention. The laminate is a laminate containing two or more layers made of the cured product, and may be a laminate with three or more layers. Of the two or more layers made of the cured product included in the above laminate, at least one is made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product due to the above shrinkage, it is also preferable that all the layers made of the cured product included in the above laminate are made of the cured product of the present invention.

[0247] In other words, the method for manufacturing the laminate of the present invention preferably includes a method for manufacturing the cured product of the present invention, and more preferably includes repeating the method for manufacturing the cured product of the present invention multiple times.

[0248] The laminate of the present invention preferably comprises two or more layers made of cured material, with a metal layer preferably included between any of the layers made of cured material. The metal layer is preferably formed by the metal layer formation step described above. That is, the method for manufacturing the laminate of the present invention preferably further includes a metal layer formation step of forming a metal layer on a layer made of cured material, which is performed multiple times during the manufacturing process of the cured material. The preferred embodiment of the metal layer formation step is as described above. As the laminate, for example, a laminate is preferred that includes at least three layers in which a first layer made of cured material, a metal layer, and a second layer made of cured material are laminated in this order. It is preferable that both the first layer made of cured material and the second layer made of cured material are layers made of cured material of the present invention. The resin composition of the present invention used to form the first layer made of cured material and the resin composition of the present invention used to form the second layer made of cured material may have the same composition or may have different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

[0249] <Lamination Process> The method for manufacturing a laminate of the present invention preferably includes a lamination process. The lamination process is a series of steps that include performing, in this order, at least one of the following on the surface of a pattern (resin layer) or metal layer: (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process, and post-development exposure process. However, the method may also involve repeating at least one of the following: (a) film formation process and (d) heating process and post-development exposure process. Furthermore, at least one of the following: (d) heating process and post-development exposure process may be followed by (e) metal layer formation process. Needless to say, the lamination process may further include the above-mentioned drying process and the like as appropriate.

[0250] If a further lamination process is performed after the lamination process, a surface activation treatment process may be performed after the exposure process, the heating process, or the metal layer formation process. Plasma treatment is an example of a surface activation treatment. Details of the surface activation treatment will be described later.

[0251] The above lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times. For example, a configuration with 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a configuration with 2 to 9 resin layers is even more preferred. Each of the above layers may have the same composition, shape, film thickness, etc., or they may be different.

[0252] In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after providing the metal layer. Specifically, examples include repeating the steps in the order of (a) film formation, (b) exposure, (c) development, (d) heating and post-development exposure, and (e) metal layer formation, or repeating the steps in the order of (a) film formation, (d) heating and post-development exposure, and (e) metal layer formation. By alternately performing the lamination step of stacking the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately stacked.

[0253] (Surface Activation Treatment Step) The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the resin composition layer is surface activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the surface activation treatment step may be performed on the resin composition layer before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the post-exposure resin composition layer. It is preferable to perform the surface activation treatment on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on a portion or all of the area on the surface of the metal layer where the resin composition layer is formed. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin composition layer (film) provided on its surface can be improved. It is also preferable to perform the surface activation treatment on a portion or all of the post-exposure resin composition layer (resin layer). By performing the surface activation treatment on the surface of the resin composition layer in this way, the adhesion to the metal layer and resin layer provided on the surface-activated surface can be improved. In particular, when developing negative film, if the resin composition layer is cured, it is less susceptible to damage from surface treatment and adhesion is easily improved. Surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This is incorporated herein by reference.

[0254] (Semiconductor Devices and Methods for Manufacturing the Same) The present invention also discloses semiconductor devices including a cured product or a laminate of the present invention. Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured product or a laminate of the present invention. Specific examples of semiconductor devices in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer can be found in paragraphs 0213 to 0218 and Figure 1 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0255] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0256] <Examples and Comparative Examples> In each example and comparative example, the components listed in Table 1 below were mixed to obtain a resin composition. The content of each component other than dioxane listed in the table was the amount (parts by mass) indicated in the "Content" column. When two or more compounds were used as each component, the "Type" and "Content" were listed separated by " / ". In these columns, the order of the entries separated by " / " corresponds to each other. In the table, "-" indicates that the resin composition does not contain the corresponding component. In the table, the content of "Dioxane" is the ratio (ppm by mass) to the resin in each resin composition. "1,4-D" represents 1,4-dioxane, "1,3-D" represents 1,3-dioxane, and "1,2-D" represents 1,2-dioxane. The obtained resin composition was pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.5 μm before use.

[0257]

[0258] Details of each component listed in the table above are as follows:

[0259] <Resins> The structural formulas of the compounds used as resins are shown below. For resins that have two or more repeating units enclosed in brackets [ ], the molar ratio (mol%) of each repeating unit relative to the total number of repeating units is indicated as a subscript to the right of the brackets [ ].

[0260]

[0261]

[0262] The terminal structure of resin A-2 (resin terminal structure) is the group represented by RT-1. * indicates a bonding site.

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270] The weight-average molecular weight (Mw) of each resin is shown in Table 2 below.

[0271]

[0272] [Synthesis Example: Synthesis of A-1] 30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride is dissolved in 120 g of N-methylpyrrolidone (NMP). Subsequently, 5.138 g (24.2 mmol) of 4,4'-diamino-2,2'-dimethylbiphenyl and 5.235 g (24.2 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl are dissolved in 100 g of NMP and added dropwise over 1 hour at a temperature of 10°C to 25°C. After stirring at 25°C for 30 minutes, 10 g of toluene is added, and the mixture is reacted at 200°C for 4 hours while flowing nitrogen, and then cooled to 25°C. Next, 13.2 g (86.4 mmol) of 4-(chloromethyl)styrene, 16.6 g (120 mmol) of potassium carbonate, 1.66 g (12 mmol) of potassium iodide, and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were added, and the mixture was reacted at 95°C for 15 hours. After cooling to 25°C, the mixture was diluted with 200 g of tetrahydrofuran. Subsequently, the reaction mixture was added dropwise to a mixture of 2.0 L of methanol and 0.5 L of water, stirred for 15 minutes, and the polyimide resin was filtered. Next, the resin was re-slurred with 1 L of water, filtered, re-slurred again with 1 L of methanol, filtered, and dried under reduced pressure at 40°C for 10 hours. Next, the dried resin is dissolved in 250 g of tetrahydrofuran, 40 g of ion exchange resin (MB-1: manufactured by Organo), and the mixture is stirred for 4 hours. After removing the ion exchange resin by filtration, the polyimide resin is precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin is obtained by filtration and dried under reduced pressure at 45°C for 1 day to obtain resin (A-1).

[0273] [Synthesis Example: Synthesis of A-9] Mix 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyclyme (diethylene glycol dimethyl ether), and stir at 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, cool the reaction mixture to -10°C, and while maintaining the temperature at -10±5°C, add 17.0 g of thionyl chloride over 60 minutes. Dilute with 50 mL of N-methylpyrrolidone, then add a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone dropwise to the reaction mixture over 60 minutes at -10±5°C, and stir the mixture at room temperature (25°C) for 2 hours. Next, 10.0 g of ethanol is added and the mixture is stirred at room temperature (25°C) for 1 hour. Then, 6000 g of water is added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) is stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring is filtered and dissolved in 500 g of tetrahydrofuran. 6000 g of water (poor solvent) is added to the resulting solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) is stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring is filtered again and dried under reduced pressure at 45°C for 3 days. 46.6 g of the dried powder is dissolved in 419.6 g of tetrahydrofuran, and then 2.3 g of triethylamine is added and the mixture is stirred at room temperature (25°C) for 35 minutes. Then, 3000 g of ethanol is added and the precipitate is filtered. The resulting precipitate is dissolved in 281.8 g of tetrahydrofuran. To this, 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTec) are added and the mixture is stirred for 4 hours. After that, the ion exchange resin is removed by filtration, and the resulting polymer solution is added to 5,600 g of water to obtain a precipitate. The precipitate is filtered off and dried under reduced pressure at 45°C for 24 hours to obtain 45.1 g of polyimide precursor (A-9).

[0274] <Polymerizable Compounds> The structural formulas of the compounds used as polymerizable compounds are shown below.

[0275]

[0276]

[0277] D-2 is a mixture of the two compounds described above, with a mass ratio of the compound on the left to the compound on the right of 70:30.

[0278]

[0279]

[0280] <Initiator> The structural formula of the compound used as an initiator is shown below.

[0281]

[0282] <Migration Inhibitors> The structural formulas of the compounds used as migration inhibitors are shown below.

[0283]

[0284] <Silane Coupling Agents> The structural formulas of the compounds used as silane coupling agents are shown below. Et represents the ethyl group.

[0285]

[0286] <Light Absorbers> The structural formulas or names of compounds used as light absorbers are shown below.

[0287]

[0288] H-2: 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)-diazo-5-sulfonic acid (NQD (naphthoquinone diazide))

[0289] <Metal Complexes> The structural formulas or product names of the compounds used as metal complexes are shown below.

[0290]

[0291] F-2: TC-750 (manufactured by Matsumoto Fine Chemical)

[0292] <Polymerization Inhibitors> The structural formulas of the compounds used as polymerization inhibitors are shown below.

[0293]

[0294] <Thermal Base Generator> The structural formulas of the compounds used as thermal base generators are shown below.

[0295]

[0296] <Solvents> The names of the compounds used as solvents are listed below. S-1: γ-butyrolactone (GBL) S-2: N-methyl-2-pyrrolidone (NMP) S-3: Dimethyl sulfoxide (DMSO) S-4: Ethyl lactate (EL) S-5: γ-valerolactone (GVL)

[0297] <Evaluation> The evaluation will be conducted as follows.

[0298] [Defect] Each resin composition is dropped onto an 8-inch bare Si substrate and spin-coated at 1500 rpm. A TEL ACT8 coater developer is used. The substrate is heated on a hot plate at 100°C for 5 minutes to obtain a coated film with an average thickness of approximately 10 μm. 400 mJ / cm² is applied to the entire surface of the substrate. ２ i-line exposure is performed. The exposure machine used is a Canon FPA5510iZs. After exposure, the substrate is solvent-developed using a coater developer. Cyclopentanone is used as the developer and PGMEA as the rinse solution. The substrate is heated in a curing oven at 200°C for 2 hours under a nitrogen atmosphere. The substrate is inspected using a defect inspection machine (KLA-Tencor Surfscan SP1) and the number of defects smaller than 0.5 μm in size on the wafer is counted.

[0299] [Variations in film thickness] Each resin composition is dropped onto an 8-inch bare Si substrate and spin-coated at 1500 rpm. A TEL ACT8 coater developer is used. The substrate is heated on a hot plate at 100°C for 5 minutes to obtain a coated film with an average thickness of approximately 10 μm. 400 mJ / cm² is applied to the entire surface of the substrate. ２i-line exposure is performed. The exposure machine used is a Canon FPA5510iZs. After exposure, the substrate is solvent-developed using a coater developer. Cyclopentanone is used as the developer and PGMEA as the rinse solution. The substrate is heated in a cure oven at 200°C for 2 hours under a nitrogen atmosphere. The film thickness of the substrate is measured using an optical interference film thickness analyzer (Screen M-3500). Figure 1 schematically shows the film thickness measurement locations. As shown in Figure 1, the film thickness is measured along a line segment L that passes through the center O of the substrate W and has the same length as the diameter of the substrate W. More specifically, the film thickness at the center O is measured, and the film thickness is measured at 10 locations in the direction X1 away from the center O and in the opposite direction X2, at intervals of 8500 μm from the center O, for a total of 21 locations. The difference between the maximum and minimum values ​​of the obtained 21 film thickness measurements (maximum value - minimum value) is defined as the film thickness variation.

[0300] The results obtained are shown in Table 3 below.

[0301]

[0302] From the above, it can be seen that the resin composition of the example can suppress the occurrence of defects and variations in film thickness compared to the resin composition of the comparative example.

[0303] According to the present invention, it is possible to provide a resin composition that can suppress the occurrence of defects and variations in film thickness, a cured product obtained by curing the resin composition, a laminate and a semiconductor device containing the cured product, a method for manufacturing the cured product, and a method for manufacturing a laminate and a semiconductor device including the method for manufacturing the cured product.

[0304] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2024-206243, filed on 27 November 2024, the contents of which are incorporated herein by reference.

Claims

1. A resin composition comprising at least one resin selected from the group consisting of polyimide precursors and polyimides, a polymerization initiator, and dioxane, wherein the content of the dioxane is 0.1 to 100 ppm by mass relative to the resin.

2. The resin composition according to claim 1, wherein the dioxane comprises 1,4-dioxane.

3. The resin composition according to claim 1, wherein the resin is a polyimide precursor containing repeating units represented by the following formula (2-1). In formula (2-1), R １１１ represents a divalent organic group, R １１５ represents a tetravalent organic group, R １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group.

4. R in the formula (2-1) １１３ and R １１４ At least one of which is a group represented by the following formula (III), The resin composition according to claim 3. In the formula (III), R ２００ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, 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 a bonding site with an oxygen atom.

5. R in formula (2-1) １１５ The resin composition according to claim 3, wherein is represented by the following formula (a) or (b). In formula (a) or formula (b), * represents the bonding site with the carbonyl group in formula (2-1).

6. The resin composition according to claim 1, wherein the resin comprises a repeating unit represented by the following formula (3). In formula (3), G １ This represents a tetravalent organic group containing a structure obtained by removing two or more hydrogen atoms from any of the structures represented by formula (V-1), formula (V-2), formula (V-3), formula (V-5), or formula (V-8), E １ This represents a divalent organic group containing an ethylenically unsaturated bond. In formula (V-2), R Ｘ１ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halogen, and in formula (V-3), R Ｘ２ and R Ｘ３ Each of these independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３ They may bond to form a ring structure, in formula (V-8), R Ｘ５ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halogen.

7. The resin composition according to claim 1 or 2, comprising a first polymerizable compound.

8. The resin composition according to claim 7, comprising a second polymerizable compound different from the first polymerizable compound.

9. The resin composition according to claim 7, wherein the first polymerizable compound is a polyfunctional (meth)acrylate with three or more functions.

10. The resin composition according to claim 8, wherein the second polymerizable compound is a bifunctional (meth)acrylate.

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

12. The resin composition according to claim 1 or 2, used for forming an interlayer insulating film for a redistribution layer.

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

14. A laminate comprising two or more layers made of the cured product described in claim 13, wherein a metal layer is included between any of the layers made of the cured product.

15. 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.

16. A method for producing a cured product according to claim 15, comprising an exposure step of selectively exposing the film, and a developing step of developing the film using a developer to form a pattern.

17. A method for producing a cured product according to claim 15, comprising a heating step of heating the film to 50 to 450°C.

18. A method for manufacturing a laminate, comprising the method for manufacturing a cured product described in claim 15.

19. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to claim 15.

20. A semiconductor device comprising the cured product described in claim 13.

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