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

Abstract

Provided are: a resin composition from which a cured object having excellent adhesiveness with respect to a metal can be obtained; a cured object obtained by curing the resin composition; a laminate including the cured object; a cured object manufacturing method; a laminate manufacturing method; a semiconductor device manufacturing method including a laminate manufacturing method; and a semiconductor device including the laminate or the cured object. This resin composition contains a resin and a base generating agent. The base generating agent is a compound represented by formula (1-1). L1 represents a linkage group having a valence of n+m. Each R1 independently represents a monovalent organic group. Each R2 independently represents a monovalent organic group or a hydrogen atom. R1s may be linked to each other to form a ring structure. m represents an integer of 1 or more, and n represents an integer of 1 or more.

Description

[Technical Field]

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

[0002] In modern times, resin materials are being utilized in various fields using resin compositions that contain resins. For example, cyclopolymer resins such as polyimide are used in a variety of applications due to their excellent heat resistance and insulation properties. While not limited to these applications, examples of such applications include their use as insulating films, encapsulants, or protective films in semiconductor devices for packaging. They are also used as base films and coverlays for flexible substrates.

[0003] For example, in the applications described above, cyclized resins such as polyimide are used in the form of a resin composition containing a precursor of the cyclized resin, such as a polyimide precursor. Such a resin composition can be applied to a substrate, for example by coating, to form a photosensitive film, and then, if necessary, exposure, development, heating, etc., can be performed to form a cured product on the substrate. The precursors of the cyclized resin, such as polyimide precursors, are cyclized, for example, by heating, and become cyclized resins such as polyimide in the cured product. Since the resin composition can be applied by known coating methods, it can be said to have excellent manufacturing adaptability, such as a high degree of freedom in designing the shape, size, and application location of the resin composition when applied. In addition to the high performance of cyclized resins such as polyimides, the industrial application development of the above-mentioned resin composition is increasingly expected from the standpoint of such excellent manufacturing adaptability.

[0004] For example, Patent Document 1 describes a photosensitive resin composition containing a polyimide precursor having a specific structure and a photobase generator. Furthermore, Patent Document 2 describes a photosensitive resin composition containing a polyimide precursor having a specific structure different from that described in Patent Document 1, and a photobase generator. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2016-021068 [Patent Document 2] Japanese Patent Publication No. 2012-093746 [Overview of the project] [Problems that the invention aims to solve]

[0006] In resin compositions for obtaining cured products, excellent adhesion between the resulting cured product and metal is required.

[0007] The present invention aims to provide a resin composition that yields a cured product with excellent adhesion to metals, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the laminate, and a semiconductor device containing the cured product or the laminate. [Means for solving the problem]

[0008] Examples of typical embodiments of the present invention are shown below. <1> Resin, and Contains a base generator, A resin composition in which the base generator is a compound represented by the following formula (1-1). [ka] In formula (1-1), L 1 represents a linking group with n+m valence, R 1 Each of these independently represents a monovalent organic group, R 2 Each of these independently represents a monovalent organic group or hydrogen atom, and R 1The groups may be linked together to form a ring structure, m represents an integer of 1 or greater, and n represents an integer of 1 or greater. <2> The L in formula (1-1) 1 The resin composition according to <1>, wherein L comprises at least one aromatic ring structure. <3> The L in formula (1-1) 1 The resin composition according to <1> or <2>, wherein the bonding sites between L and the m+n carbonyl groups in formula (1-1) are all carbon atoms. <4> The R in formula (1-1) 1 each R is independently a hydrocarbon group which may have a substituent, or the R groups in formula (1-1) 1 The resin composition according to any one of <1> to <3>, wherein the R groups are bonded to each other to form a nitrogen-containing aliphatic heterocyclic structure which may have a substituent. <5> The R in formula (1-1) 2 The resin composition according to any one of <1> to <4>, wherein each R is independently a hydrogen atom or a hydrocarbon group which may have a substituent. <6> The resin composition according to any one of <1> to <5>, wherein the resin is at least one resin selected from the group consisting of cyclized resins and precursors thereof. <7> The resin composition according to any one of <1> to <6>, wherein the resin comprises at least one group selected from the group consisting of an ethylenically unsaturated bond-containing group, epoxide, oxetane, aldehyde and ketone. <8> The resin composition according to any one of <1> to <7>, further comprising a photopolymerization initiator. <9> The resin composition according to any one of <1> to <8>, further comprising a polymerizable compound. <10> The resin composition according to any one of <1> to <9>, further comprising an organometallic complex. <11> The resin composition according to any one of <1> to <10>, which comprises a cyclized resin or a precursor thereof as said resin and is used for forming an interlayer dielectric film for a redistribution layer. <12> A cured product obtained by curing the resin composition according to any one of <1> to <11>. <13> <12> A laminate comprising two or more layers made of the cured material described above, with a metal layer between the layers made of the cured material. <14> <1> ~ <11> A method for producing a cured product, comprising a film-forming step of applying a resin composition described in any one of the above onto a substrate to form a film. <15> The process includes an exposure step of selectively exposing the above film and a developing step of developing the above film using a developer to form a pattern. <14> A method for producing the cured product described above. <16> The process includes a heating step of heating the above film to 50-450°C. <14> or <15> A method for producing the cured product described above. <17> <14> ~ <16> A method for manufacturing a laminate, comprising a method for manufacturing a cured product as described in any one of the following. <18> <14> ~ <16> A method for producing a cured product as described in any one of the following, <17> A method for manufacturing a semiconductor device, including a method for manufacturing a laminate described above. <19> <12> The cured product described above or <13> A semiconductor device including the laminate described above. [Effects of the Invention]

[0009] The present invention provides a resin composition that yields a cured product with excellent adhesion to metal, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the laminate, and a semiconductor device containing the cured product or the laminate. [Modes for carrying out the invention]

[0010] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments specified. In this specification, a numerical range represented by the symbol "~" means a range that includes the numbers written before and after "~" as the lower limit and upper limit, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes insofar as they achieve their intended function. In this specification, when groups (atomic groups) are not specified as substituted or unsubstituted, the notation includes both groups (atomic groups) with and without substituents. For example, "alkyl group" includes not only unsubstituted alkyl groups but also 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 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 the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, total solids refers to the total mass of all components of the composition excluding the solvent. In this specification, solids concentration refers to 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 defined as polystyrene equivalent values, unless otherwise specified, and are measured using gel permeation chromatography (GPC). 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 are measured using THF (tetrahydrofuran) as the eluent. However, if THF is unsuitable as an eluent, such as in cases of low solubility, NMP (N-methyl-2-pyrrolidone) may be used. Furthermore, unless otherwise specified, detection in GPC measurements will be performed using a UV (ultraviolet) wavelength 254nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that the other layer is 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 layer, and the reference layer and the other layer do not need to be in contact. Furthermore, 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. Furthermore, unless otherwise specified, the content of each component in a composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, a preferred combination of embodiments is a more preferred embodiment.

[0011] (Resin composition) The resin composition of the present invention comprises a resin and a base generating agent, wherein the base generating agent is a compound represented by the following formula (1-1). Hereinafter, the base-generating agent represented by the following formula (1-1) will also be referred to as a "specific base-generating agent." [ka] In formula (1-1), L 1 represents a linking group with n+m valence, R 1 Each of these independently represents a monovalent organic group, R 2 Each of these independently represents a monovalent organic group or hydrogen atom, and R 1 The elements may be linked together to form a ring structure, where m represents an integer greater than or equal to 1, and n represents an integer greater than or equal to 1.

[0012] The resin composition of the present invention is preferably used to form a photosensitive film subjected to exposure and development, and more preferably used to form a film subjected to exposure and development using a developer solution containing an organic solvent. The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for redistribution layers. In particular, one preferred embodiment of the present invention is that the resin composition of the present invention includes a cyclized resin or its precursor as the resin and is used for forming an interlayer insulating film for a redistribution layer. Furthermore, the resin composition of the present invention may be used to form a photosensitive film for positive-type development, or for forming a photosensitive film for negative-type development. In the present invention, negative development refers to development in which unexposed areas are removed by development, and positive development refers to development in which exposed areas are removed by development. As the above-mentioned exposure method, developer, and developing method, for example, the exposure method, developer, and developing method described in the exposure step, developing step, and developing steps described in the description of the manufacturing method of the cured product described later may be used.

[0013] According to the resin composition of the present invention, a cured film with excellent adhesion to metal can be obtained. The mechanism by which the above effects are achieved is unknown, but it is speculated to be as follows.

[0014] According to the specific base generator in the resin composition of the present invention, base generation occurs simultaneously with -C(=O)-NR 2 It is thought that a compound containing the structure -C(=O)- will be formed. 2 R in equation (1-1) above is 2 This is synonymous with the following. For example, from the compound represented by A-1 below, heating will generate a compound with the following structure and piperidine as a base. [ka] Since the above compound is a near-neutral compound, it is believed that when the layer formed from the resin composition comes into contact with the metal layer, the migration of metal ions from the metal layer to the layer formed from the resin composition is suppressed. As a result of this suppression of migration, the cured product obtained from the resin composition of the present invention is expected to have excellent adhesion to metal.

[0015] Furthermore, since compounds containing the above structure, which are generated simultaneously with the generation of the base, are highly polar, it is believed that the solvent solubility of the cured product can be reduced, thereby improving its chemical resistance. Furthermore, since specific base-generating agents have near-neutral structures both before and after base generation, they are considered less likely to inhibit the action of bases compared to, for example, base-generating agents whose pre-base-generation structure is more acidic. For example, when a precursor of a cyclized resin is used as the resin, the promotion of cyclization by the action of a base is less likely to be inhibited, so cyclization proceeds more easily, and the elongation at break of the resulting cured product may increase even further. In addition, if a precursor of a cyclized resin is used as the resin, for example, the cyclization process will proceed more easily as described above, resulting in a higher cyclization rate of the resin in the resulting cured product. Therefore, compounds generated during the cyclization of the resin (for example, R in formula (2) described later) 113 , R 114 Compounds derived from structures containing the above can be sufficiently volatilized from the cured product during curing. Therefore, it is thought that outgassing during use of the cured product (for example, outgassing when the cured product is used for a long period of time, or when the cured product is used under high-temperature conditions) will also be suppressed. Furthermore, when using resins with a structure similar to the base generator of the present invention (for example, both having amide groups), such as cyclized resins or their precursors, the compatibility between the base generator and the resin increases, resulting in nearly uniform base generation in the resin film. This can also improve the pattern shape of the resulting cured product. Furthermore, as mentioned above, by increasing the compatibility between the base-generating agent and the resin, it may be possible to increase the amount of base-generating agent contained, thereby improving the design flexibility of the composition. Furthermore, in the past, organometallic complexes such as organotitanium compounds have sometimes been used to improve chemical resistance. However, depending on their structure, these organometallic complexes may decompose or denature when used in combination with conventional base generators that have acidic structures such as carboxylic acids and phenolic hydroxyl groups. However, since the specific base generator in this invention has a structure close to neutral, it is thought that such decomposition and modification of organometallic complexes are less likely to occur. As a result, it is thought that a cured product with excellent lithoactivity and chemical resistance can be obtained.

[0016] However, Patent Documents 1 and 2 do not describe resin compositions containing specific base-generating agents.

[0017] The components included in the resin composition of the present invention will be described in detail below.

[0018] <Resin> The resin composition of the present invention contains a resin. The resin is not particularly limited, and examples include resins used in conventional pattern-forming compositions. However, it is preferable to include at least one resin (specific resin) selected from the group consisting of cyclized resins and their precursors, and it is more preferable to include a precursor of a cyclized resin. Furthermore, it is preferable that the resin of the present invention contains at least one group selected from the group consisting of a group having an ethylenically unsaturated bond, an epoxide, an oxetane, an aldehyde, and a ketone. In particular, when a specific resin is a precursor of a cyclized resin, an addition or insertion reaction occurs between the base generated from the specific base generator and these groups. This suppresses the reaction of the cyclization site in the specific resin with the base, and is thought to improve the cyclization rate of the specific resin. 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 (e.g., vinylphenyl group), (meth)acrylamide groups, (meth)acryloyloxy groups, etc. Groups having an aromatic ring directly bonded to a vinyl group, (meth)acrylamide groups, or (meth)acryloyloxy groups are preferred, and (meth)acryloyloxy groups are more preferred.

[0019] Here, it is preferable that the resin composition of the present invention satisfies at least one of the following conditions 1 and 2. Furthermore, it is also a preferred embodiment of the present invention that both conditions 1 and 2 are satisfied. Condition 1: The resin has radical polymerizable groups. Condition 2: Further comprises a polymerizable compound having a radical polymerizable group.

[0020] The cyclized resin is preferably a resin that contains an imide ring structure or an oxazole ring structure in its main chain structure. In this invention, the main chain refers to the relatively longest bonding chain within the resin molecule. Examples of cyclized resins include polyimide, polybenzoxazole, and polyamideimide. A precursor of a cyclized resin is a resin that undergoes a change in chemical structure due to external stimuli to become a cyclized resin. Resins that undergo a change in chemical structure due to heat to become a cyclized resin are preferred, and resins that undergo a ring-closing reaction due to heat to form a ring structure to become a cyclized resin are more preferred. Examples of precursors for cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors. In other words, the resin composition of the present invention preferably contains, as a specific resin, at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor. The resin composition of the present invention preferably contains polyimide or a polyimide precursor as a specific resin. Furthermore, the specific resin preferably has polymerizable groups, and more preferably contains radical polymerizable groups. When a specific resin has radical polymerizable groups, the resin composition of the present invention preferably contains a radical polymerization initiator as described below, and more preferably contains a radical polymerization initiator as described below and a radical crosslinking agent as described below. Furthermore, it may optionally contain a sensitizer as described below. A negative-type photosensitive film can be formed from such a resin composition of the present invention. Furthermore, the specific resin may have polarity-converting groups such as acid-degradable groups. When a specific resin has an acid-degradable group, the resin composition of the present invention preferably contains a photoacid generator as described below. From such a resin composition of the present invention, for example, a chemically amplified positive-type or negative-type photosensitive film can be formed.

[0021] [Polyimide precursor] The polyimide precursor used in this invention is not particularly limited in type, but it is preferable that it contains repeating units represented by the following formula (2). [ka] In formula (2), A 1 and A 2Each of these independently represents an oxygen atom or -NH-, and R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 Each of these independently represents either a hydrogen atom or a monovalent organic group.

[0022] A in equation (2) 1 and A 2 Each of these independently represents either an oxygen atom or -NH-, with the oxygen atom being preferred. R in equation (2) 111 -Ar- and -Ar-L-Ar- are examples of divalent organic groups. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, the group consists of a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, and more preferably, a group containing an aromatic group having 6 to 20 carbon atoms. In the linear or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and aromatic group, the hydrocarbon group of the ring member may be substituted with a group containing a heteroatom. As a preferred embodiment of the present invention, the group is exemplified by groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably by groups represented by -Ar-L-Ar-. However, Ar is an aromatic group independently, and L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2- or -NHCO-, or a group consisting of two or more of the above. The preferred ranges for these are as described above.

[0023] R 111 It is preferable that the polyimide precursor is derived from a diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. One type of diamine may be used, or two or more types may be used. Specifically, the diamine is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have hydrocarbon groups in the chain substituted with groups containing heteroatoms, and the cyclic aliphatic group and aromatic group may have hydrocarbon groups in the ring members substituted with groups containing heteroatoms. Examples of groups containing aromatic groups are listed below.

[0024] [ka] In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond or a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or a group selected from a combination thereof; more preferably a single bond or a C1-C3 alkylene group which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO2-; and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-. In the formula, * represents a bonding site with another structure.

[0025] Diamines specifically include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4- (Aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-A Minophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-Diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl Fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-dia Minopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis [4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,Examples include at least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotidine, and 4,4'-diaminoquaterphenyl.

[0026] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0027] Furthermore, diamines having two or more alkylene glycol units as the main chain, as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598, are also preferably used.

[0028] R 111 From the viewpoint of the flexibility of the resulting organic film, it is preferable that it be represented as -Ar-L-Ar-. However, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO2-. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

[0029] 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). Formula (51) [ka] 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 these is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents a bonding site with the nitrogen atom in formula (2). R 50 ~R 57 Examples 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). [ka] 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). Examples of diamines that give the structure of formula (51) or (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.

[0030] R in equation (2) 115 represents a tetravalent organic group. Preferably, the tetravalent organic group is one containing an aromatic ring, and more preferably, a group represented by formula (5) or formula (6) below. In formula (5) or formula (6), * independently represents a bonding site with another structure. [ka] In formula (5), R 112The linking group is a single bond or a divalent linking group, preferably a single bond or a group selected from a C1-C10 aliphatic hydrocarbon group, -O-, -CO-, -S-, -SO2-, and -NHCO-, which may be substituted with a fluorine atom, and combinations thereof; more preferably a group selected from a single bond or a C1-C3 alkylene group, -O-, -CO-, -S-, and -SO2-, which may be substituted with a fluorine atom; and even more preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S-, and -SO2-.

[0031] R 115 Specifically, examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. Polyimide precursors are R 115 The structure may contain only one tetracarboxylic dianhydride residue, or it may contain two or more. Tetracarboxylic acid dianhydrides are preferably represented by the following formula (O). [ka] In formula (O), R 115 R represents a tetravalent organic group. 115 The preferred range of R in equation (2) is 115 This is synonymous with the same thing, and the preferred range is also similar.

[0032] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, and 2,2 ',3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, Examples include 3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl and alkoxy derivatives of these having 1 to 6 carbon atoms.

[0033] Furthermore, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 are also preferred examples.

[0034] In equation (2), R 111 and R 115It is also possible that at least one of them has an OH group. More specifically, R 111 Examples include residues of bisaminophenol derivatives.

[0035] R in equation (2) 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 114 It 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 ethylenically unsaturated bonds, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As radical polymerizable groups in the polyimide precursor, groups having ethylenically unsaturated bonds are preferred. 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.

[0036] [ka]

[0037] In equation (III), R 200 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 equation (III), * represents a bonding site with another structure. In equation (III), R 201 This represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkylene oxy group. Suitable 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, -CH2CH(OH)CH2-, and polyalkylene oxy groups. More preferably, alkylene groups such as ethylene and propylene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkylene oxy groups are preferred, and even more preferably, alkylene groups such as ethylene and propylene, or polyalkylene oxy groups. 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 a polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of alkylene oxy groups in the polyalkylene oxy group may be random, block-like, 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, even more preferably 2 to 6, still more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. Furthermore, the alkylene group may have substituents. Preferred substituents include alkyl groups, aryl groups, halogen atoms, and the like. Furthermore, 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 above-mentioned 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 or other patterned arrangements. The preferred configuration of the number of repeating ethylene oxy groups in these groups is as described above.

[0038] In equation (2), R 113 If R is a hydrogen atom, 114 If the atom is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0039] In equation (2), 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 an acid to produce an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but acetal groups, ketal groups, silyl groups, silyl ether groups, tertiary alkyl ester groups, etc. 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 group or tetrahydrofuranyl group are preferred.

[0040] Furthermore, the polyimide precursor preferably contains fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

[0041] 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 or bis(p-aminophenyl)octamethylpentasiloxane as the diamine.

[0042] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to broaden the exposure latitude. Formula (2-A) [ka] In formula (2-A), A 1 and A 2 represents an oxygen atom, R 111 and R 112 Each of these independently represents a divalent organic group, R 113 and R 114 Each of these independently represents a hydrogen atom or a monovalent organic group, R 113 and R 114 Preferably, at least one of the groups is a polymerizable group, and both are polymerizable groups.

[0043] A 1 , A 2 , R 111 , R 113 and R 114 These are, independently of A in equation (2), 1 , A 2 , R 111 , R 113 and R114 This is synonymous with the same thing, and the preferred range is also similar. R 112 R in equation (5) is 112 This is synonymous with the same thing, and the preferred range is also similar.

[0044] The polyimide precursor may contain one type of repeating unit represented by formula (2), or it may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). Furthermore, it goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).

[0045] 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).

[0046] 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) 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 molecular weight dispersion of the 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 upper limit to the degree of 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, the degree of molecular weight dispersion is the value calculated by dividing the weight-average molecular weight by the number-average molecular weight. Furthermore, if the 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.

[0047] [Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or a polyimide soluble in a developer mainly composed of an organic solvent. In this specification, alkali-soluble polyimide refers to a polyimide that dissolves at a rate of 0.1 g or more in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium at 23°C. 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. Furthermore, from the viewpoint of the film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having multiple imide structures in its main chain. In this specification, "main chain" refers to the relatively longest bonding chain in the polymer compound molecule constituting the resin, and "side chain" refers to the other bonding chains.

[0048] -Fluorine atom- From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains fluorine atoms. Fluorine atoms are, for example, R in the repeating unit represented by formula (4) described later. 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.

[0049] -Silicon atom- From the viewpoint of the film strength of the obtained organic film, the polyimide preferably also has a silicon atom. The silicon atom is, for example, contained in R in the repeating unit represented by formula (4) described later 131 and is preferably contained in R in the repeating unit represented by formula (4) described later 131 , more preferably contained as the organically modified (poly)siloxane structure described later in said R. Further, the above-mentioned silicon atom or the above-mentioned organically modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0050] -Ethylenically unsaturated bond- From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at a main chain terminal or in a side chain, but preferably has the ethylenically unsaturated bond in a side chain. The ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is contained in R in the repeating unit represented by formula (4) described later 132 , or is contained in R in the repeating unit represented by formula (4) described later 131 and is preferably contained in R in the repeating unit represented by formula (4) described later 132 , or is contained in R in the repeating unit represented by formula (4) described later 131 , more preferably contained as a group having an ethylenically unsaturated bond in said R. Among these, the ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by formula (4) described later 131 and is preferably contained in R in the repeating unit represented by formula (4) described later131 It is more preferable that it be included as a group having an ethylenically unsaturated bond. Groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, vinylphenyl groups, and other groups having 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).

[0051] [ka]

[0052] 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.

[0053] In formula (IV), R 21 This represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkylene oxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group formed by combining two or more of these. Furthermore, the alkylene group having 2 to 12 carbon atoms may be a linear, branched, cyclic, or a combination thereof. Of the alkylene groups having 2 to 12 carbon atoms, alkylene groups having 2 to 8 carbon atoms are preferred, and alkylene groups having 2 to 4 carbon atoms are more preferred.

[0054] 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). [ka] In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these groups; X represents an oxygen atom or a sulfur atom; * represents a bonding site to another structure; and ● represents R in formula (IV) 21 represents a bonding site to the oxygen atom to which it bonds. In formulas (R1) to (R3), the preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms for L are the same as the above-mentioned R 21 for the preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms. In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * has the same definition as * in formula (IV), and the preferred embodiments are also the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate, etc.). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate, etc.). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate, etc.).

[0055] In formula (IV), * represents a bonding site to another structure, and is preferably a bonding site to the main chain of the polyimide.

[0056] The content of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0057] -Polymerizable groups other than those having ethylenically unsaturated bonds- Polyimides may have polymerizable groups other than those having ethylenically unsaturated bonds. 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 an ethylenically unsaturated bond include, for example, R in the repeating unit represented by formula (4) described later. 131 It is preferable that it be included in 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.

[0058] -Polar Conversion Group- Polyimides may have polarity-changing groups such as acid-degradable groups. The acid-degradable group in polyimides is 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 conversion 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.

[0059] - Acid Value - When polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mg KOH / g or higher, more preferably 50 mg KOH / g or higher, and even more preferably 70 mg KOH / g or higher. Furthermore, 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. Furthermore, when polyimide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of the 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. Furthermore, regarding the acid groups contained in polyimide, from the viewpoint of achieving both storage stability and developability, acid groups with a pKa of 0 to 10 are preferred, and acid groups with a pKa of 3 to 8 are more preferred. pKa is the negative common logarithm of the equilibrium constant Ka, expressed as pKa, when considering a dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa values ​​shall be those calculated using ACD / ChemSketch®. Alternatively, values ​​published in the "Revised 5th Edition Chemical Handbook, Basic Edition" edited by the Chemical Society of Japan may be referred to. Furthermore, if the acidic group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant. The polyimide preferably contains at least one of the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0060] -Phenolenic hydroxyl group- From the viewpoint of ensuring an appropriate development speed with an alkaline developer, it is preferable that the polyimide has a phenolic hydroxyl group. Polyimides may have phenolic hydroxyl groups at the ends of their main chains or in their side chains. The phenolic hydroxyl group is, for example, R in the repeating unit represented by formula (4) described later. 132 , or R in the repeating unit represented by formula (4) described later. 131 It is preferable that it be included in The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0061] 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). [ka] In formula (4), R 131 represents a divalent organic group, R 132 This represents a tetravalent organic group. If it has polymerizable groups, the polymerizable groups are 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. Formula (4-1) [ka] In formula (4-1), R 133 is a polymerizable group, and the other groups are equivalent to formula (4). Formula (4-2) [ka] 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).

[0062] 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. R 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. Also, R 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:

[0063] 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 that does not contain an aromatic ring.

[0064] 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.

[0065] 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 bonds of the tetravalent organic group, as exemplified above, bond with the four -C(=O)- parts in formula (4) above to form a fused ring.

[0066] Also, 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.

[0067] R131 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 preferable examples.

[0068] Furthermore, it is 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 preferably 20% by mass or less.

[0069] Furthermore, 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.

[0070] Furthermore, in order to improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide are encapsulated with end-captives 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.

[0071] -Imidization rate (ring closure rate)- The imidization rate (also called the "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength and insulating properties of the resulting organic film. There is no particular upper limit to the imidization rate mentioned above; it is acceptable as long as it is 100% or less. The above imidization rate can be measured, for example, by the following method. The infrared absorption spectrum of polyimide was measured, and the absorption peak originating from the imide structure was found at 1377 cm⁻¹. -1 The peak intensity P1 in the vicinity is determined. Next, the polyimide is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again, at 1377 cm⁻¹. -1 Determine the nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be determined based on the following formula. Imidization rate (%) = (Peak intensity P1 / Peak intensity P2) × 100

[0072] Polyimides are all of the same type R 131 or R 132 It may include the repeating unit represented by the above formula (4), and may include two or more different types of R 131 or R 132 The polyimide may also contain repeating units represented by the above formula (4). In addition to the repeating units represented by the above formula (4), the polyimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by the above formula (2).

[0073] 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.

[0074] 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 cured film can be improved. To obtain an organic film with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or more is particularly preferred. Furthermore, 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 molecular weight dispersion of the polyimide is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit set for the degree of molecular weight dispersion of the polyimide, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. Furthermore, if the resin composition contains multiple types of polyimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimides are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyimides are treated as a single resin are, respectively, within the above ranges.

[0075] [Polybenzoxazole precursor] As polybenzoxazole precursors, compounds described in paragraphs 0049-0074 of International Publication No. 2021 / 172420 can be used. This information is incorporated herein.

[0076] [Method for producing polyimide precursors, etc.] Polyimide precursors can be obtained by methods such as reacting tetracarboxylic dianhydride with a diamine at low temperature, reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and esterifying it with a condensing agent or alkylating agent, obtaining a diester from tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine in the presence of a condensing agent, or obtaining a diester from tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine. Of the above production methods, the method of obtaining a diester from tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine is more preferred. Examples of the condensing agents mentioned above include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agents mentioned above include N,N-dimethylformamide dimethylacetal, N,N-dimethylformamide diethylacetal, N,N-dialkylformamide dialkylacetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the method for producing polyimide precursors, it is preferable to use an organic solvent during the reaction. One organic solvent may be used, or two or more may be used. The organic solvent can be appropriately determined depending on the raw materials, but examples include pyridine, diethylene glycol dimethyl ether (diglym), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing polyimide precursors, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types. The basic compound can be appropriately determined depending on the raw materials, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, and N,N-dimethyl-4-aminopyridine.

[0077] -End-capturing agent- In the production method of polyimide precursors, etc., it is preferable to encapsulate the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin ends of the polyimide precursors, etc., in order to further improve storage stability. When encapsulating the carboxylic acid anhydride and acid anhydride derivative remaining at the resin ends, an example of an end encapsulant is the end encapsulant described in paragraph 0131 of International Publication No. 2021 / 100768. This content is incorporated herein by reference.

[0078] -Solid precipitation- The production of polyimide precursors may include a step for precipitating a solid. Specifically, after filtering out the water-absorbing by-products of the dehydrating condensation agent present in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid. The resulting solid is then dried to obtain the polyimide precursor. To improve the degree of purity, the polyimide precursor may be repeatedly redissolved, reprecipitation, and dried. Furthermore, the process may include a step for removing ionic impurities using an ion exchange resin.

[0079] [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 specific resin or may contain two or more specific resins. When it contains two or more specific resins, it is preferable that the total amount is within the above range.

[0080] Furthermore, the resin composition of the present invention preferably contains at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more 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.

[0081] <Other resins> The resin composition of the present invention may contain, in addition to or in place of the specified resin described above, other resins different from the specified resin (hereinafter also simply referred to as "other resins"). Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. In particular, by using a (meth)acrylic resin having an acid-degradable group, the resin composition can be used as a pattern-forming composition. Examples of such an (meth)acrylic resin having an acid-degradable group include resin (B) described in paragraphs 0069 to 0170 of Japanese Patent Application Publication No. 2019-174549. Furthermore, by adding, for example, (meth)acrylic resin, a resin composition with excellent coatability can be obtained, as well as a pattern (cured product) with excellent solvent resistance. For example, instead of the polymerizable compounds described later, or in addition to the polymerizable compounds described later, a polymerizable compound with a high polymerizable value of 20,000 or less weight-average molecular weight (for example, the molar amount of polymerizable groups in 1g of resin is 1 × 10⁻⁶) -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.

[0082] If 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. Furthermore, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. Furthermore, in a preferred embodiment of the resin composition of the present invention, the content of other resins may be 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.

[0083] <Specific base-generating agent> The resin composition of the present invention contains a specific base generator.

[0084] The specific base generator of the present invention is a compound represented by the following formula (1-1). [ka] In formula (1-1), L 1 represents a linking group with n+m valence, R 1 Each of these independently represents a monovalent organic group, R 2 Each of these independently represents a monovalent organic group or hydrogen atom, and R 1 The elements may be linked together to form a ring structure, where m represents an integer greater than or equal to 1, and n represents an integer greater than or equal to 1. Here, for the compound represented by formula (1-1), if the structural formulas are identical, there are no limitations regarding stereoisomers such as geometric isomers and optical isomers.

[0085] [L 1 ] L 1These are hydrocarbon groups, or hydrocarbon groups and -O-, -C(=O)-, -S-, -S(=O)2-, and -NR N - Preferably, the group is represented by a combination of at least one structure selected from the group consisting of -, a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)- and -NR N - More preferably, the group is represented by a combination with at least one structure selected from the group consisting of - and even more preferably, it is a hydrocarbon group.

[0086] The above R N Each of these independently represents a hydrogen atom or a monovalent organic group, with a hydrogen atom or a hydrocarbon group being preferred, a hydrogen atom, an alkyl group or an aromatic hydrocarbon group being preferred, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group being more preferred, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group being even more preferred, and a hydrogen atom being particularly preferred.

[0087] The above hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. Furthermore, the hydrocarbon group may have substituents. The substituents are not particularly limited, but examples include groups having polymerizable properties. As for groups having polymerizable properties, groups having radical polymerizable properties are preferred. Examples of radical polymerizable properties include vinyl groups, allyl groups, vinylphenyl groups, (meth)acryloyloxy groups, maleimide groups, and (meth)acrylamide groups, with (meth)acryloxy groups, (meth)acrylamide groups, or vinylphenyl groups being preferred, and (meth)acryloxy groups being more preferred from the viewpoint of reactivity. Also, L 1 If the material has radical polymerizable groups, it is preferable that at least one of the following conditions is met: the resin has radical polymerizable groups, or the resin composition contains a radical crosslinking agent as described later. In this embodiment, since the base generator is incorporated into the polymer formed by polymerization, the distribution of the base generator within the composition becomes nearly uniform, and the rectangular pattern is expected to be further improved.

[0088] From the perspective of facilitating base generation and adhesion, L 1 It is preferable that it contains an aromatic ring structure. The aromatic ring structure is not particularly limited, but an aromatic hydrocarbon ring structure is preferred, a naphthalene ring structure or a benzene ring structure is more preferred, and a benzene ring structure is even more preferred.

[0089] From the perspective of facilitating base generation and chemical resistance, L 1 In L 1 and R in equation (1-1) 2 It is preferable that the bonding sites between the nitrogen atom directly bonded to L and the carbonyl group directly bonded to L are both carbon atoms, 1 Furthermore, it is more preferable that all of the bonding sites with the m+n carbonyl groups in formula (1-1) are carbon atoms.

[0090] L 1 In equation (1-1), R 2 A carbonyl group directly bonded to the nitrogen atom directly bonded to and R in formula (1-1) 1 The number of atoms on the shortest path of the linking chain between the nitrogen atom directly bonded to the carbonyl group (linking chain length) is preferably 2 to 5, and more preferably 2 or 3. If at least one of m and n is 2 or more, then the R in m equations (1-1) 2 One of the carbonyl groups directly bonded to the nitrogen atom directly bonded to and n R groups in formula (1-1) 1 The length of the chain connecting to one of the carbonyl groups directly bonded to the nitrogen atom directly bonded to it is within the above range. For example, in compound A-1 below, the above linkage chain length is 2. [ka]

[0091] L 1 Specific examples are shown below, but the present invention is not limited thereto. In the following specific examples, * represents R in formula (1-1).2 # represents the bond site between the nitrogen atom directly bonded to the carbonyl group and the nitrogen atom directly bonded to the carbonyl group in formula (1-1). 1 These represent the bonding sites between a nitrogen atom directly bonded to a carbonyl group and a nitrogen atom directly bonded to a carbonyl group. In this specification, a bond intersecting the edge of a ring structure means that it substitutes for any hydrogen atom in that ring structure that is not explicitly described. [ka]

[0092] [R 1 ] In formula (1-1), R 1 Each of these is independently a hydrocarbon group which may have substituents, or R in formula (1-1) 1 It is preferable that the molecules bond together to form a nitrogen-containing aliphatic heterocyclic structure, which may have substituents. R 1 When the hydrocarbon group may have substituents, the hydrocarbon group is more preferably an alkyl group, an aromatic hydrocarbon group, or a combination thereof, even more preferably an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof, and particularly preferably an alkyl group having 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic, but from the viewpoint of improving elongation at break, a branched alkyl group (e.g., isopropyl group, isobutyl group, 2-ethylhexyl group, etc.) or a cyclic alkyl group (e.g., cyclohexyl group, etc.) is preferred. The substituents on the hydrocarbon group mentioned above are not particularly limited, but include halogen atoms, alkoxy groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, hydroxyl groups, and the like.

[0093] Also, R in equation (1-1) 1 They may be linked together to form a ring structure. In the above embodiment, R bonded to the same nitrogen atom 1 It is preferable that they are connected to each other to form a ring structure. The ring structure formed is preferably a nitrogen-containing aliphatic heterocyclic structure, for example, the above R 1 Examples include pyrrolidine rings, piperidine rings, morpholine rings, and nortropine rings, which have a nitrogen atom directly bonded to them as a ring member. These ring structures may further have substituents. Examples of substituents include those similar to those in the hydrocarbon groups described above.

[0094] Also, in equation (1-1), R 1 It is also preferable that at least one of them is a structure represented by equation (R-1). R 1 Because at least one of the structures is represented by formula (R-1), the area around the nitrogen atom of the amino group in the generated base becomes bulkier, which suppresses the reaction with the resin in the film due to steric hindrance. As a result, the base diffuses more uniformly in the film. Therefore, it is thought that differences in the degree of film shrinkage between the surface side and the substrate side are suppressed, and the rectangularity of the resulting pattern is excellent. [ka] In formula (R-1), R 11 Each of these independently represents a monovalent organic group, and the two R 11 or R 11 and R in equation (1-1) 1 Of the other R 1 (That is, the two R in equation (1-1) 1 When one of them is represented by equation (R-1), the other R in equation (1-1) 1 The other R 1 (The structure may also be represented by formula (R-1)) and may be linked together to form a ring structure. In formula (R-1), R 11 The group is preferably a hydrocarbon group, more preferably an alkyl group, an aromatic hydrocarbon group, or a combination thereof, even more preferably an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof, and particularly preferably an alkyl group having 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic, but from the viewpoint of improving elongation at break, a branched alkyl group (e.g., isopropyl group, isobutyl group, 2-ethylhexyl group, etc.) or a cyclic alkyl group (e.g., cyclohexyl group, etc.) is preferred. Two R's 11 Mutual or R 11 and R in equation (1-1) 1 Of the other R 1 The ring structure formed by the linkage of the above R is, for example, 1 Examples include pyrrolidine rings, piperidine rings, morpholine rings, and nortropine rings, which have a nitrogen atom directly bonded to them as a ring member. These ring structures may further have substituents. Examples of substituents include those similar to those in the hydrocarbon groups described above.

[0095] Furthermore, R 1 At least one of them is a structure represented by the above formula (R-1), and the structure represented by formula (R-1) and R in formula (1-1) 1 Of the other R 1 Preferably, one of them has at least one of a heteroatom and an aromatic group. Examples of the above heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, etc., with oxygen atoms being preferred. The above aromatic group may be a heteroaromatic group or an aromatic hydrocarbon group, but an aromatic hydrocarbon group is preferred. The above aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably an aromatic hydrocarbon group having 6 carbon atoms. Examples of heteroatoms in the above-mentioned heteroaromatic group include oxygen atoms, sulfur atoms, nitrogen atoms, etc., with oxygen atoms being preferred. The above heteroaromatic group is preferably a 5-membered ring, a 6-membered ring, or a fused ring of a 5-membered ring and a 6-membered ring.

[0096] R 1 Examples of preferred embodiments include, but are not limited to, the following structures. The nitrogen atoms included in the structure of the specific example below are R in formula (1-1). 1This refers to a nitrogen atom directly bonded to the carbonyl group. In the specific examples below, * indicates the bonding site with the carbonyl group. [ka] Furthermore, both cis and trans isomers exist for the dimethylpiperidine ring and dimethylmorpholine ring in the above structure, and either is acceptable. However, from the viewpoint of the fracture elongation of the resulting cured product, the cis isomer is preferred. The trans isomer has a slightly higher bulk around the nitrogen atom compared to the cis isomer. This is thought to allow the substrate compound to approach the nitrogen atom of the active site in the generated base more easily, thus improving the imidation-promoting effect. On the other hand, it is thought to have sufficient bulk to avoid reaction with the resin, thus maintaining the rectangular pattern. Therefore, it is presumed that the cis isomer maintains other properties while having superior elongation at break compared to the trans isomer. Furthermore, even for structures not included in the above specific examples, if geometric isomers exist, the cis form is preferable for the same reasons if the area around the nitrogen atom is bulkier in the cis form.

[0097] [R 2 ] R 2 Hydrogen atoms or hydrocarbon groups which may have substituents are preferred, and from the viewpoint of adhesion, hydrocarbon groups which may have substituents are more preferred. The hydrocarbon groups mentioned above are preferably saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination of saturated aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The saturated aliphatic hydrocarbon group described above is preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and even more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. Examples of the above-mentioned aromatic hydrocarbon groups include aromatic hydrocarbon groups having 6 to 20 carbon atoms, and groups obtained by removing one or more hydrogen atoms from a benzene ring or a naphthalene ring are preferred, with groups obtained by removing one or more hydrogen atoms from a benzene ring being more preferred. As the group represented by a combination of a saturated aliphatic hydrocarbon group and an aromatic hydrocarbon group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 10 carbon atoms is more preferable. Preferred embodiments of the saturated aliphatic hydrocarbon group and the aromatic hydrocarbon group in the group represented by a combination of a saturated aliphatic hydrocarbon group and an aromatic hydrocarbon group are the same as those for R 2 when R is a saturated aliphatic hydrocarbon group, and for R 2 when R is an aromatic hydrocarbon group, respectively. Further, the above hydrocarbon group may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, and a hydroxy group.

[0098] R 2 Examples of preferred embodiments of R include, but are not limited to, the following structures. In the following specific examples, * represents a binding site to a nitrogen atom.

Chemical Formula

[0099] [m] m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, still more preferably 1 or 2, and particularly preferably 1.

[0100] [n] n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, still more preferably 1 or 2, and particularly preferably 1. An embodiment in which m and n are the same number is also one of the preferred embodiments of the present invention.

[0101] [Base Generation Conditions] The specific base generator preferably cleaves between the nitrogen atom directly bonded to R 1 and the carbonyl group directly bonded to said nitrogen atom to generate a base having an amino group. Furthermore, the specific base generator of the present invention preferably generates a base when heated to 250°C, more preferably generates a base when heated to 220°C, still more preferably generates a base when heated to 200°C, particularly preferably generates a base when heated to 190°C, and most preferably generates a base when heated to 180°C. The lower limit of the temperature at which the base is generated is not particularly limited, but from the viewpoint of storage stability of the composition, for example, the temperature is preferably 100°C or higher. Whether a given compound A exhibits the property of generating a base at a temperature X°C is determined by the following method. 1 mol of compound A is heated in a sealed container at 1 atm and the aforementioned X°C for 3 hours, then the amount of decomposition is quantified by a method such as HPLC (high performance liquid chromatography). When 0.01 mol or more of a base is generated, it is determined that compound A generates a base upon heating at X°C. Whether the generated compound is a base can be determined, for example, by 1 confirmation using 1H-NMR. The amount of the base generated is preferably 0.1 mol or more, and more preferably 0.5 mol or more. The upper limit of the amount of the base generated is not particularly limited, and can be, for example, 1000 mol or less.

[0102] [Base] The base generated from the specific base generator is preferably a compound having an amino group. The base may be a compound having two or more amino groups, but is preferably a compound having only one amino group. The amino group is preferably a secondary amino group. Furthermore, the base that is the compound having an amino group may be an aliphatic amine or an aromatic amine, but is preferably an aliphatic amine. Since aliphatic amines have higher basicity than aromatic amines, they are considered to have a greater curing acceleration effect. It is also preferable that the base is a cyclic aliphatic amine such as pyrrolidine, piperidine, morpholine, nortropine, or those in which some of the hydrogen atoms thereof are substituted with substituents. The substituents are not particularly limited, but alkyl groups, aromatic hydrocarbon groups, and hydroxyalkyl groups are preferred, alkyl groups having 1 to 10 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, and hydroxyalkyl groups having 1 to 10 carbon atoms are more preferred, and alkyl groups having 1 to 4 carbon atoms, phenyl groups, or hydroxyalkyl groups having 2 to 4 carbon atoms are even more preferred. An aliphatic amine is one in which all carbon atoms bonded to the nitrogen atom of the amino group are carbon atoms included in the aliphatic hydrocarbon group. An aromatic amine is one in which at least one carbon atom bonded to the nitrogen atom of the amino group is a carbon atom included as a ring member in the aromatic group. A cyclic aliphatic amine is an aliphatic amine in which the nitrogen atom of the amino group is included in the aliphatic ring structure.

[0103] Furthermore, it is preferable that the base generated from the specific base generator has at least two organic groups bonded to at least one of the carbon atoms that are directly bonded to the nitrogen atom of at least one of the amino groups contained in the amine, and that the molecule excluding the amino group has at least one heteroatom and at least one aromatic group. The above organic group is preferably an organic group in which the bonding site with the above carbon atom is a carbon atom, and may have substituents, a hydrocarbon group or -C(=O)-R C A base represented by is more preferable. Furthermore, the heteroatoms mentioned above include oxygen atoms, sulfur atoms, nitrogen atoms, etc., with oxygen atoms being preferred. The hydrocarbon group in the above organic group is more preferably an alkyl group, an aromatic hydrocarbon group, or a combination thereof, even more preferably an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof, and particularly preferably an alkyl group having 1 to 10 carbon atoms. The substituents in the hydrocarbon group described above are not particularly limited, but include hydroxyl groups, carboxyl groups, groups containing keto groups (-C(=O)-), groups containing ester groups (-C(=O)O-), groups containing ether groups (-O-), and amide groups (-C(=O)NR N -) groups containing imide groups (-C(=O)NR NExamples include groups containing a C(=O)- group, a thioether group (-S-), and a ketoxime group (-C(=N(-OH)-). N represents a hydrogen atom or a monovalent organic group, with a hydrogen atom or a hydrocarbon group being more preferred. In the present invention, when simply referring to an ester group, amide group, etc., the orientation of the bond is not particularly limited. For example, in an ester group, the oxygen atom may be directly bonded to the hydrocarbon group, or the carbonyl group may be directly bonded to the hydrocarbon group. -C(=O)-R in the above organic group C R in the group represented by C Examples of alkyl groups include alkyl groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 10), alkoxy groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 10), aryl groups (preferably having 4 to 20 carbon atoms, more preferably 4 to 10), and aryloxy groups (preferably having 6 to 20 carbon atoms, more preferably 6 to 10), with alkoxy groups being more preferred.

[0104] Furthermore, the base generated from a specific base generator may form a ring structure in which the nitrogen atom contained in the amino group serves as a ring member. The above ring structure may be an aliphatic ring structure or an aromatic ring structure, but it is preferably an aliphatic ring structure, and more preferably a saturated aliphatic ring structure. The above ring structure is preferably a five-membered or six-membered ring. Furthermore, the above ring structure may be a single ring or a double ring. Examples of double rings include fused rings, bridging rings, and spiro rings. The above ring structure may also preferably be a ring structure containing at least one group selected from the group consisting of keto groups, ester groups, ether groups, amide groups, imide groups, thioether groups, and ketoxime groups, or a ring structure to which a hydroxyl group or carboxyl group is bonded. Furthermore, if geometric isomers exist in the above-mentioned ring structure, the cis isomer is preferable from the viewpoint of the fracture elongation of the resulting cured product. The trans isomer has a slightly higher bulk around the nitrogen atom compared to the cis isomer. This is thought to allow the substrate compound to approach the nitrogen atom of the active site in the generated base more easily, thus improving the imidation-promoting effect. On the other hand, it is thought to have sufficient bulk to avoid reaction with the resin, thus maintaining the rectangular pattern. Therefore, it is presumed that the cis isomer maintains other properties while having superior elongation at break compared to the trans isomer.

[0105] The molecular weight of the base generated from the specific base generator is preferably 70 to 1,000, more preferably 80 to 800, and even more preferably 85 to 500. The base generated from the specific base generator is preferably a base whose conjugate acid has a pKa of 0 or greater, more preferably a base with a pKa of 3 or greater, and even more preferably a base with a pKa of 6 or greater. The upper limit of the pKa of the conjugate acid is not particularly limited, but it is preferably 30 or less. pKa is the negative common logarithm of the equilibrium constant Ka, expressed as pKa, when considering a dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa values ​​are calculated using ACD / ChemSketch®. If there are multiple pKa values ​​for the above-mentioned conjugate acids, it is preferable that at least one of them falls within the above range.

[0106] Specific examples of the bases that are generated are not limited to the following, but include, for example, bases with the following structure. [ka] Furthermore, both cis and trans isomers of dimethylpiperidine and dimethylmorpholine exist in the above structure, and either is acceptable. However, from the viewpoint of the fracture elongation of the resulting cured product, the cis isomer is preferred. The trans isomer has a slightly higher bulk around the nitrogen atom compared to the cis isomer. This is thought to allow the substrate compound to approach the nitrogen atom at the active site more easily in the cis isomer, thus improving the imidation-promoting effect. On the other hand, it is thought to have sufficient bulk to avoid reaction with the resin, thus maintaining the rectangular pattern. Therefore, the cis isomer is considered to have superior elongation at break while maintaining other properties compared to the trans isomer. Furthermore, even for structures not included in the above specific examples, if geometric isomers exist, the cis form is preferable for the same reasons if the area around the nitrogen atom is bulkier in the cis form.

[0107] [Molecular weight] The molecular weight of the specific base generator is preferably 150 to 1,500, more preferably 180 to 1,000, and even more preferably 200 to 800.

[0108] [Synthesis method] Specific base generators can be synthesized, for example, by reacting a monocarboxylic acid-monoamide compound obtained by reacting a carboxylic acid anhydride with an amine, and then reacting that compound with a condensing agent such as a carbodiimide and an amine. Alternatively, they may be synthesized using other known synthesis methods, and the synthesis method is not particularly limited.

[0109] Specific examples of specific base-generating agents include, but are not limited to, A-1 to A-34 used in the examples.

[0110] The content of the specific base generating agent relative to the total solid content of the resin composition of the present invention is preferably 0.1 to 30% by mass. The lower limit is more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, and particularly preferably 2% by mass or more. The upper limit is more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less. A specific base-generating agent may be used alone, or two or more may be used in combination. When two or more are used in combination, it is preferable that their total amount falls within the above range. When the resin composition of the present invention contains a specific base generator and a base generator described below (a base generator different from the specific base generator), the total content of the specific base generator and the base generator (the base generator different from the specific base generator) is preferably 0.1 to 30% by mass. The lower limit is more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 2% by mass or more. The upper limit is more preferably 20% by mass or less, still more preferably 15% by mass or less, and particularly preferably 10% by mass or less. In the resin composition of the present invention, the content of the specific base generator relative to 100 parts by mass of the specific resin is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass.

[0111] <Organometallic Complex> From the viewpoint of chemical resistance, the resin composition of the present invention preferably also contains an organometallic complex. The organometallic complex may be any organic complex compound containing a metal atom, but is preferably a complex compound containing a metal atom and an organic group, more preferably a compound in which an organic group is coordinated to a metal atom, and still more preferably a metallocene compound. In the present invention, the metallocene compound refers to an organometallic complex having two optionally substituted cyclopentadienyl anion derivatives as η5-ligands. The organic group is not particularly limited, but is preferably a hydrocarbon group or a group composed of a combination of a hydrocarbon group and a heteroatom. As the heteroatom, an oxygen atom, a sulfur atom and a nitrogen atom are preferred. In the present invention, at least one of the organic groups is preferably a cyclic group, and more preferably at least two are cyclic groups. The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably a 5-membered cyclic group. The cyclic group may be a hydrocarbon ring or a heterocyclic ring, but a hydrocarbon ring is preferred. As the 5-membered cyclic group, a cyclopentadienyl group is preferred. Furthermore, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

[0112] The metal included in the organometallic complex is not particularly limited, but it is preferably a metal belonging to Group 4 elements, more preferably at least one metal selected from the group consisting of titanium, zirconium, and hafnium, even more preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.

[0113] Organometallic complexes may contain two or more metal atoms, or only one metal atom, but it is preferable that they contain only one metal atom. When organometallic complexes contain two or more metal atoms, they may contain only one type of metal atom, or two or more types of metal atoms.

[0114] The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound, or a hafnocene compound; more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound; even more preferably a titanocene compound or a zirconocene compound; and particularly preferably a titanocene compound.

[0115] An embodiment in which the organometallic complex has the ability to initiate photoradical polymerization is also one of the preferred embodiments of the present invention. In the present invention, having photo-radical polymerization initiation ability means being able to generate free radicals that can initiate radical polymerization upon irradiation with light. For example, the presence or absence of photo-radical polymerization initiation ability can be confirmed by irradiating a composition containing a radical crosslinking agent and an organometallic complex with light in a wavelength range in which the organometallic complex absorbs light and the radical crosslinking agent does not absorb light, and then checking whether or not the radical crosslinking agent disappears. An appropriate method can be selected depending on the type of radical crosslinking agent to check whether or not it disappears, but for example, it can be confirmed by IR measurement (infrared spectroscopy) or HPLC measurement (high-performance liquid chromatography). When the organometallic complex has photoradical polymerization initiation ability, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, even more preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound. If the organometallic complex does not have photoradical polymerization initiation ability, the organometallic complex is preferably at least one compound selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds and hafnocene compounds, more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds and hafnocene compounds, even more preferably at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds, and particularly preferably a titanocene compound.

[0116] The molecular weight of the organometallic complex is preferably 50 to 2,000, and more preferably 100 to 1,000.

[0117] Preferred organometallic complexes include compounds represented by the following formula (P). [ka] In formula (P), M is a metal atom, and R is a substituent, independently of each other. Preferably, each of the above R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

[0118] In formula (P), the metal atom represented by M is preferably an iron atom, a titanium atom, a zirconium atom, or a hafnium atom; more preferably a titanium atom, a zirconium atom, or a hafnium atom; even more preferably a titanium atom or a zirconium atom; and particularly preferably a titanium atom. Examples of aromatic groups in formula (P) include aromatic groups having 6 to 20 carbon atoms, with aromatic hydrocarbon groups having 6 to 20 carbon atoms being preferred, such as phenyl groups, 1-naphthyl groups, or 2-naphthyl groups. The alkyl group in R in formula (P) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples include methyl group, ethyl group, propyl group, octyl group, isopropyl group, t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, etc. Examples of halogen atoms in R include F, Cl, Br, and I. The alkyl group constituting the alkylsulfonyloxy group in R above is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples include methyl group, ethyl group, propyl group, octyl group, isopropyl group, t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, etc. The above R may have further substituents. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, monoalkylamino groups, dialkylamino groups, monoarylamino groups, and diarylamino groups.

[0119] Specific examples of organometallic complexes, though not limited to them, include tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonate)titanium, tetraacetylacetonate titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and the following compounds. [ka]

[0120] Other compounds described in paragraphs 0078-0088 of International Publication No. 2018 / 025738 may also be used, but are not limited to these.

[0121] The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 1.0% by mass or more, even more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less. One or more organometallic complexes can be used. When using two or more, it is preferable that the total amount is within the above range.

[0122] <Polymerizable compound> The resin composition of the present invention preferably contains a polymerizable compound. Polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0123] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. Radical crosslinking agents are compounds having radical polymerizable groups. Preferred radical polymerizable groups are those containing ethylenically unsaturated bonds. Examples of such groups include vinyl groups, allyl groups, vinylphenyl groups, (meth)acryloyl groups, maleimide groups, and (meth)acrylamide groups. Among these, the (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred as groups containing the ethylenically unsaturated bond, and the (meth)acryloyl group is more preferred from the viewpoint of reactivity.

[0124] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compounds having two or more ethylenically unsaturated bonds, compounds having 2 to 15 ethylenically unsaturated bonds are preferred, compounds having 2 to 10 ethylenically unsaturated bonds are more preferred, and compounds having 2 to 6 ethylenically unsaturated bonds are even more preferred. Furthermore, 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 of the above-mentioned ethylenically unsaturated bonds.

[0125] 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.

[0126] 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.

[0127] Furthermore, radical crosslinking agents that have a boiling point of 100°C or higher under normal pressure are also preferred. Examples of compounds with a boiling point of 100°C or higher under normal pressure include those described in paragraph 0203 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0128] Other preferred radical crosslinking agents include radical polymerizable compounds described in paragraphs 0204-0208 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0129] 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., 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., 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.

[0130] Examples of commercially available radical crosslinking agents include the compounds described in paragraph 0211 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0131] As radical crosslinking agents, compounds described in paragraph 0211 of International Publication No. 2021 / 112189 may also be used. This content is incorporated herein by reference. Urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese 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 are also suitable. Furthermore, as radical crosslinking agents, compounds having an amino structure or a sulfide structure within the molecule, as described in Japanese Patent Publication No. 63-277653, Japanese Patent Publication No. 63-260909, and Japanese Patent Publication No. 01-105238, can also be used.

[0132] 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.

[0133] The preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 300 mg KOH / g, and particularly 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, as well as excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0134] 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, 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, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, and other difunctional acrylates and difunctional 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 molecular weight of the polyethylene glycol chain is approximately 200. From the viewpoint of suppressing warping associated with controlling the elastic modulus of the pattern (cured product), the resin composition of the present invention preferably uses a monofunctional radical crosslinking agent. Preferred 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, as well as N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether. As a monofunctional radical crosslinking agent, compounds with a boiling point of 100°C or higher under normal pressure are also preferred in order to suppress volatilization before exposure. Other examples of bifunctional or more radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0135] If a radical crosslinking agent is included, its content is preferably more than 0% by mass and 60% by mass or less, relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0136] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more are used in combination, it is preferable that their total amount be within the above range.

[0137] [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. In the present invention, other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon exposure to the photoacid generator or photobase generator described above, and are preferably compounds having multiple groups in their 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 a base. The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or photobase generator during the exposure process. Other preferred crosslinking agents include compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups, and alkoxymethyl groups, and more preferably compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl groups, methylol groups, and alkoxymethyl groups is directly bonded to a nitrogen atom. Other crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluryl, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and an alcohol, and the hydrogen atoms of the amino group are replaced with acyloxymethyl groups, methylol groups, or alkoxymethyl groups. The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compounds produced by the above method is acceptable. Furthermore, oligomers formed by the self-condensation of methylol groups of these compounds may also be used. As for the amino group-containing compounds mentioned above, crosslinking agents using melamine are called melamine-based crosslinking agents, crosslinking agents using glycoluryl, urea, or alkylene urea are called urea-based crosslinking agents, crosslinking agents using alkylene urea are called alkylene urea-based crosslinking agents, and crosslinking agents using benzoguanamine are called benzoguanamine-based crosslinking agents. Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluryl-based crosslinking agents and melamine-based crosslinking agents, as described later.

[0138] Examples of compounds containing at least one alkoxymethyl group and acyloxymethyl group in the present invention include compounds in which the alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic group, a nitrogen atom of the urea structure described below, or on a triazine. The alkoxymethyl group or acyloxymethyl group in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the above compound is preferably 1500 or less, and more preferably 180 to 1200.

[0139] [ka]

[0140] R 100 This represents an alkyl group or acyl group. R 101 and R 102 Each of these independently represents a monovalent organic group and may be bonded to each other to form a ring.

[0141] Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted for an aromatic group include compounds with the following general formula.

[0142] [ka]

[0143] In the formula, X represents a single bond or a divalent organic group, and each R 104 Each independently represents an alkyl group or an acyl group, R 103 This includes hydrogen atoms, alkyl groups, alkenyl groups, aryl groups, aralkyl groups, or groups that decompose upon the action of an acid to produce alkali-soluble groups (for example, groups that are eliminated by the action of an acid, -C(R4 ) 2COOR 5 The group represented by (R 4 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 The symbol indicates a group that is removed by the action of an acid. R 105 Each independently represents an alkyl group or an alkenyl group, a, b, and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. Groups that decompose under the action of acid to produce alkali-soluble groups, groups that are eliminated under the action of acid, -C(R 4 ) 2COOR 5 R in the group represented by 5 For example, -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(R 01 )(R 02 )(OR 39 Examples include: In the formula, R 36 ~R 39 Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 These elements may be joined together to form a ring. The alkyl group described above is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group described above may be linear or branched. The above cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms. The above cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. The above aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms. The above-mentioned aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those described above for preferred embodiments of alkyl and aryl groups. The above alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Furthermore, these groups may have known substituents within the range that the effects of the present invention can be obtained.

[0144] R 01 and R 02 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0145] Groups that decompose upon the action of an acid to produce alkali-soluble groups, or groups that are eliminated upon the action of an acid, are preferably tertiary alkyl ester groups, acetal groups, cumyl ester groups, enol ester groups, etc. More preferably, tertiary alkyl ester groups and acetal groups.

[0146] The following structures are examples of compounds containing an alkoxymethyl group. Compounds containing an acyloxymethyl group are examples of compounds obtained by changing the alkoxymethyl group in the following compounds to an acyloxymethyl group. The following compounds are examples of compounds containing an alkoxymethyl group or acyloxymethyl group in the molecule, but are not limited to these.

[0147] [ka]

[0148] [ka]

[0149] The compound containing at least one alkoxymethyl group and acyloxymethyl group may be a commercially available product or one synthesized by a known method. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or triazine ring are preferred.

[0150] Specific examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexasubtoxicbutylmelamine.

[0151] Specific examples of urea-based crosslinking agents include, for example, glycoluryl-based crosslinking agents such as monohydroxymethylated glycoluryl, dihydroxymethylated glycoluryl, trihydroxymethylated glycoluryl, tetrahydroxymethylated glycoluryl, monomethoxymethylated glycoluryl, dimethoxymethylated glycoluryl, trimethoxymethylated glycoluryl, tetramethoxymethylated glycoluryl, monoethoxymethylated glycoluryl, diethoxymethylated glycoluryl, triethoxymethylated glycoluryl, tetraethoxymethylated glycoluryl, monopropoxymethylated glycoluryl, dipropoxymethylated glycoluryl, trippropoxymethylated glycoluryl, tetrapropoxymethylated glycoluryl, monobutoxymethylated glycoluryl, dibutoxymethylated glycoluryl, tripbutoxymethylated glycoluryl, or tetrabutoxymethylated glycoluryl; Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea. Ethylene urea-based crosslinking agents such as monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethylated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea. Propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea. Examples include 1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

[0152] Specific examples of benzoguanamine crosslinking agents include, for example, monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, Examples include diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, trippropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tripbutoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0153] In addition, as compounds having at least one group selected from the group consisting of methylol groups and alkoxymethyl groups, compounds in which at least one group selected from the group consisting of methylol groups and alkoxymethyl groups is directly bonded to an aromatic ring (preferably a benzene ring) are also suitably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidentris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, and the like.

[0154] Other crosslinking agents may be commercially available, and suitable commercially available products include 46DMOC, 46DMOEP (both manufactured by Asahi Organic Chemicals Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, and TriML-35XL. Examples include TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), Nikarac (registered trademark, hereinafter the same) MX-290, Nikarac MX-280, Nikarac MX-270, Nikarac MX-279, Nikarac MW-100LM, Nikarac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.).

[0155] Furthermore, the resin composition of the present invention may also preferably contain, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0156] - Epoxy compounds (compounds containing epoxy groups) - The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at temperatures below 200°C, and since dehydration reactions resulting from crosslinking do not occur, film shrinkage is less likely to occur. Therefore, including an epoxy compound is effective in suppressing low-temperature curing and warping of the resin composition of the present invention.

[0157] The epoxy compound preferably contains polyethylene oxide groups. This further reduces the modulus of elasticity and suppresses warping. A polyethylene oxide group refers to a group with two or more repeating units of ethylene oxide, and preferably with 2 to 15 repeating units.

[0158] Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane.Specifically, Epiclon® 850-S, Epiclon® HP-4032, Epiclon® HP-7200, Epiclon® HP-820, Epiclon® HP-4700, Epiclon® HP-4770, Epiclon® EXA-830LVP, Epiclon® EXA-8183, Epiclon® EXA-8169, Epiclon® N- 660, Epiclon® N-665-EXP-S, Epiclon® N-740 (all product names, manufactured by DIC Corporation), Licaresin® BEO-20E, Licaresin® BEO-60E, Licaresin® HBE-100, Licaresin® DME-100, Licaresin® L-200 (product names, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088 S, EP-3950S (product names, manufactured by ADEKA Corporation), Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2081, Celoxide (registered trademark) 2000, EHPE3150, Epolid (registered trademark) GT401, Epolid (registered trademark) PB4700, Epolid (registered trademark) PB3600 (product names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-300 Examples include 0-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, and BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds are also suitably used.

[0159] [ka]

[0160] In the formula, n is an integer between 1 and 5, and m is an integer between 1 and 20.

[0161] Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7, in order to achieve both heat resistance and improved elongation.

[0162] -Oxetane compounds (compounds containing an oxetanyl group)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. Specific examples include the Aronoxetane series manufactured by Toagosei Co., Ltd. (e.g., OXT-121, OXT-221), which can be used individually or in combination of two or more.

[0163] -Benzoxazine compounds (compounds containing a benzoxazolyl group)- Benzoxazine compounds are preferred because, due to the crosslinking reaction resulting from a ring-opening addition reaction, degassing does not occur during curing, and furthermore, thermal shrinkage is reduced, suppressing warping.

[0164] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (both trade names, manufactured by Shikoku Chemicals Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resin, and phenol novolac-type dihydrobenzoxazine compounds. These may be used individually or in combination of two or more.

[0165] 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 of the present invention. The other crosslinking agents may be present by one type or by 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.

[0166] [Photopolymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator that can initiate polymerization by light and / or heat. It is particularly preferable that it contains 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 interacts with a photoexcited sensitizer to generate active radicals.

[0167] The photoradical polymerization initiator is present in a wavelength range of approximately 240-800 nm (preferably 330-500 nm) at a concentration of at least approximately 50 L·mol. -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 (Cary-5 spectrophotometer, Varian) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0168] 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 0165-0182 of Japanese Patent Publication No. 2016-027357 and paragraphs 0138-0151 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, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are also incorporated herein.

[0169] 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.

[0170] 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 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.

[0171] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

[0172] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

[0173] As aminoacetophenone initiators, acylphosphine oxide initiators, and metallocene compounds, for example, compounds described in paragraphs 0161-0163 of International Publication No. 2021 / 112189 can also be suitably used. This information is incorporated herein.

[0174] 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.

[0175] 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 JCSPerkin II (1979, pp. 1653-1660), the compounds described in JCSPerkin II (1979, pp. 156-162), and the 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 Publication 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, and compounds described in International Publication No. 2013 / 167515, the contents of which are incorporated herein by reference.

[0176] Preferred oxime compounds include, for example, compounds with the following structures, as well as 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as a photoradical polymerization initiator. Oxime-based photoradical polymerization initiators have a >C=NOC(=O)- linking group in their molecule.

[0177] [ka]

[0178] Commercially available options include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), and ADEKA optomer N-1919 (manufactured by ADEKA Corporation, a 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 Arcules NCI-730, NCI-831, and ADEKA Arcules NCI-930 (manufactured by ADEKA Corporation). Additionally, DFI-091 (manufactured by Daito Chemix Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Furthermore, oxime compounds with the following structures can also be used. [ka]

[0179] 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 may be used. These are incorporated herein by reference.

[0180] Furthermore, as photopolymerization initiators, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl group substituent attached to a carbazole skeleton, as described in paragraphs 0208-0210 of International Publication No. 2021 / 020359, can also be used. These contents are incorporated herein by reference.

[0181] As a photopolymerization initiator, an aromatic ring group Ar, in which an electron-withdrawing group is introduced to the aromatic ring, is used. OX1 An oxime compound having the above aromatic ring group Ar (hereinafter also referred to as oxime compound OX) can also be used. OX1Examples of electron-withdrawing groups include acyl groups, nitro groups, trifluoromethyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and cyano groups. Acyl and nitro groups are preferred, acyl groups are more preferred because they easily form films with excellent light resistance, and benzoyl groups are even more preferred. The benzoyl group may have substituents. Preferred substituents are halogen atoms, cyano groups, nitro groups, hydroxyl groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, acyl groups, or amino groups. More preferred substituents are alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic oxy groups, alkylsulfanyl groups, arylsulfanyl groups, or amino groups. Even more preferred substituents are alkoxy groups, alkylsulfanyl groups, or amino groups.

[0182] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2). [ka] In the formula, R X1 This represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group, or sulfamoyl group. R X2 This represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, or amino group. RX3 ~R X14 Each of these independently represents a hydrogen atom or a substituent. However, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0183] In the above formula, R X12 R is an electron-withdrawing group, X10 , R X11 , R X13 , R X14 It is preferable that it is a hydrogen atom.

[0184] Specific examples of oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent Publication No. 4600600, which are incorporated herein by reference.

[0185] The most preferred oxime compounds include oxime compounds having specific substituents as described in Japanese Patent Publication No. 2007-269779 and oxime compounds having a thioaryl group as described in Japanese Patent Publication No. 2009-191061, the details of which are incorporated herein by reference.

[0186] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-arylsubstituted coumarin compounds.

[0187] Further preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds, with at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds being even more preferred, and the use of a metallocene compound or an oxime compound being even more preferred.

[0188] Furthermore, as photoradical polymerization initiators, compounds described in paragraphs 0175-0179 of International Publication No. 2021 / 020359 may also be used. This is incorporated herein by reference.

[0189] Furthermore, the photoradical polymerization initiator may be a compound described in paragraphs 0048-0055 of International Publication No. 2015 / 125469, which is incorporated herein by reference.

[0190] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thus providing good sensitivity. Furthermore, when an asymmetric compound is used, the crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time and improving the long-term stability of the resin composition. Specific examples of bifunctional or trifunctional or more photoradical polymerization initiators include dimers of oxime compounds described in JP 2010-527339, JP 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of JP 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680, as well as compounds (E) and (G) described in JP 2013-522445, and International Publication No. 2016 / 0 Examples include Cmpd1-7 described in Patent No. 34963, oxime ester photoinitiators described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators described in paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators (A) described in paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0191] If a photopolymerization initiator is included, 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, relative to the total solid content of the resin composition of the present invention. Only one type of photopolymerization initiator may be included, or two or more types may be included. If two or more types of photopolymerization initiators are included, it is preferable that the total amount is within the above range. Furthermore, since photopolymerization initiators can also function as thermal polymerization initiators, heating with an oven or hot plate may further accelerate the crosslinking process by the photopolymerization initiator.

[0192] [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 benzophenones, Michlar's ketones, coumarins, pyrazole azos, anilino azos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, pyrazolotriazole azos, pyridone azos, cyanines, phenothiazines, pyrrolopyrazole azomethine, xanthenes, phthalocyanines, benzopyranes, and indigos. 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, Np-Tolyldiethanolamine, N-phenylethanolamine, 4-Morpholinobenzophenone, Isoamyl dimethylaminobenzoate, Isoamyl diethylaminobenzoate Examples include amyl, 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, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details regarding the sensitizing dye, please refer to paragraphs 0161 to 0163 of Japanese Patent Publication No. 2016-027357, which are incorporated herein by reference.

[0193] 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.

[0194] [Chain transfer agent] The resin composition of the present invention may contain a chain transfer agent. A chain transfer agent is 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 compounds having -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH in their molecules, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These can generate radicals by donating hydrogen to low-activity radicals, or by generating radicals after oxidation and deprotonation. Thiol compounds are particularly preferred.

[0195] 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.

[0196] If the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 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 of the present invention. 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.

[0197] <Base Generator> The resin composition of the present invention may contain a base-generating agent. Here, a base-generating agent is a compound that can generate a base by physical or chemical action. Preferred base-generating agents for the resin composition of the present invention include thermal base-generating agents and photobase-generating agents. However, base-generating agents that fall under the category of specific base-generating agents as described above are not included in the definition of base-generating agents used herein. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition also contains a base generator. By including a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example by heating, resulting in a cured product with good mechanical properties and chemical resistance, and thus good performance as an interlayer insulating film for redistribution layers included in semiconductor packages. The base generator can be either an ionic or nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines. There are no particular restrictions on the base-generating agent according to the present invention, and known base-generating agents can be used. Examples of known base-generating agents include 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, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like. As nonionic base generators, for example, compounds represented by formula (B1) or formula (B2) described in paragraphs 0275 to 0285 of International Publication No. 2021 / 112189, compounds represented by formula (N1) described in paragraphs 0102 to 00162 of International Publication No. 2020 / 066416, or as base generators, the thermobase generators described in paragraphs 0013 to 0041 of International Publication No. 2020 / 054226 are preferred. These contents are incorporated herein.

[0198] Examples of base-generating agents are listed below, but the present invention is not intended to be limited thereto.

[0199] [ka]

[0200] 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.

[0201] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018 / 038002.

[0202] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [ka]

[0203] Specific examples of iminium salts include the following compounds, but the present invention is not limited to these. [ka]

[0204] If the resin composition of the present invention 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 of the present invention. 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, and may be 5 parts by mass or less, or 4 parts by mass or less. One or more types of base-generating agents may be used. When using two or more types, it is preferable that the total amount is within the above range. Furthermore, the resin composition of the present invention may also be configured in a manner that substantially does not contain base-generating agents other than the specified base-generating agent. Specifically, the content of base-generating agents other than the specified base-generating agent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less, relative to the total mass of the resin composition. The lower limit is not particularly limited and may be 0% by mass.

[0205] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. Organic solvents are preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0206] Specific examples of solvents include those described in International Publication No. 2021 / 112189. Other examples include ethylene 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, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, and N-cyclohexyl-2-pyrrolidone.

[0207] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0208] 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 combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0209] 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.

[0210] The resin composition of the present invention may contain only one solvent or two or more solvents. If two or more solvents are included, it is preferable that their total number is within the above range.

[0211] <Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion modifier to improve adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion modifiers 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.

[0212] [Silane coupling agent] 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 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 Publication No. 2011-128358. Furthermore, it is also preferable to use the following compounds as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group.

[0213] [ka]

[0214] Other silane coupling agents include the compounds described in paragraph 0318 of International Publication No. 2021 / 112189, which are incorporated herein by reference. These can be used individually or in combination of two or more.

[0215] [Aluminum-based adhesive aid] Examples of aluminum-based adhesives include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0216] Furthermore, 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.

[0217] 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 content falls within the above range.

[0218] <Migration inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, it is possible to effectively suppress the movement of metal ions originating from the metal layer (metal wiring) into the film.

[0219] 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.

[0220] Alternatively, an ion trapping agent that captures anions such as halogen ions can be used.

[0221] Other migration inhibitors include, for example, the compounds described in paragraph 0304 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0222] Specific examples of migration inhibitors include the following compounds.

[0223] [ka]

[0224] If the resin composition of the present invention 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 of the present invention.

[0225] 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.

[0226] <Polymerization inhibitor> The resin composition of the present invention 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.

[0227] Specific examples of polymerization inhibitors include the compounds described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, and the like. This information is incorporated herein by reference.

[0228] If the resin composition of the present invention 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 of the present invention.

[0229] 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.

[0230] <Other additives> The resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.), to the extent that the effects of the present invention are obtained. In addition, the resin composition of the present invention may contain urea compounds, carbodiimide compounds, or isourea compounds. 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 0101-0104, 0107-0109, etc., of Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated herein by reference. When these additives are incorporated, it is preferable that their total amount be 3% by mass or less of the solid content of the resin composition of the present invention.

[0231] [Surfactants] Various surfactants can be used, including fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0232] By incorporating a surfactant into the resin composition of the present invention, the liquid properties (especially the fluidity) when prepared as a coating solution are further improved, and the uniformity of the coating thickness and the efficiency of the liquid can be further improved. Specifically, when forming a film using a coating solution to which a surfactant-containing composition has been applied, the interfacial tension between the surface to be coated and the coating solution is reduced, improving the wettability to the surface to be coated and improving the coatability to the surface to be coated. Therefore, it is possible to more favorably form a film of uniform thickness with less thickness variation.

[0233] Examples of fluorinated surfactants include the compounds described in paragraph 0328 of International Publication No. 2021 / 112189. This information is incorporated herein by reference. Fluorine-based surfactants can also preferably be fluorine-containing polymer compounds that include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). The following compounds are also examples of fluorine-based surfactants used in the present invention. [ka]

[0234] The weight-average molecular weight of the above compounds is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. Fluorine-based surfactants can also be obtained by using fluorine-containing polymers having ethylenically unsaturated groups in their side chains. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Commercially available products include, for example, Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0235] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving, and also have good solubility in the composition.

[0236] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include compounds described in paragraphs 0329-0334 of International Publication No. 2021 / 112189, respectively. These contents are incorporated herein by reference.

[0237] 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.

[0238] [Higher fatty acid derivative] In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention may contain a higher fatty acid derivative such as behenic acid or behenic acid amide, which may be unevenly distributed on the surface of the resin composition during the drying process after application.

[0239] Furthermore, higher fatty acid derivatives may also be compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which are incorporated herein by reference.

[0240] When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. There may be only one type of higher fatty acid derivative, or there may be two or more types. If there are two or more types of higher fatty acid derivatives, it is preferable that their total is within the above range.

[0241] [Thermal polymerization initiator] The resin composition of the present invention may contain a thermal polymerization initiator, and in particular may contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals in response to thermal energy, thereby initiating or promoting the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be advanced, thereby further improving solvent resistance. In addition, the photopolymerization initiators mentioned above may also have the function of initiating polymerization in response to heat, and may be added as thermal polymerization initiators.

[0242] Examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Publication No. 2008-063554, the contents of which are incorporated herein by reference.

[0243] If a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass, relative to the total solid content of the resin composition of the present invention. Only one thermal polymerization initiator may be included, or two or more may be included. If two or more thermal polymerization initiators are included, it is preferable that the total amount is within the above range.

[0244] [Inorganic particles] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, boron nitride, and the like.

[0245] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle diameter for inorganic particles is both the primary particle diameter and the volume-average particle diameter. The volume-average particle diameter can be measured by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement methods are difficult, measurements can also be performed using centrifugal sedimentation light transmission, X-ray transmission, or laser diffraction / scattering methods.

[0246] [UV absorber] The composition of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers that can be used include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers. Specific examples of ultraviolet absorbers include the compounds described in paragraphs 0341-0342 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0247] In the present invention, the above-mentioned ultraviolet absorbers may be used individually or in combination of two or more types. The composition of the present invention may or may not contain an ultraviolet absorber, but if it does, the amount of ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less, based on the total solid content mass of the composition of the present invention.

[0248] [Organotitanium compounds] The resin composition of this embodiment may contain an organotitanium compound. By including an organotitanium compound in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0249] Examples of usable organotitanium compounds include those in which an organic group is bonded to a titanium atom via covalent or ionic bonds. Specific examples of organotitanium compounds include those described in paragraphs 0345-0346 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0250] When incorporating an organic titanium compound, the amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are more effectively expressed in the resulting cured pattern, while when it is 10 parts by mass or less, the storage stability of the composition is superior.

[0251] [Antioxidant] The composition of the present invention may contain an antioxidant. Including an antioxidant as an additive can improve the elongation properties of the cured film and its adhesion to metal materials. Examples of antioxidants include phenol compounds, phosphite compounds, and thioether compounds. Specific examples of antioxidants include the compounds described in paragraphs 0348-0357 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0252] The amount of antioxidant added is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, relative to the resin. Adding 0.1 parts by mass or more makes it easier to obtain improved elongation properties and adhesion to metal materials even in high-temperature and high-humidity environments. Adding 10 parts by mass or less improves the sensitivity of the resin composition, for example, through interaction with the photosensitive agent. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.

[0253] [Anti-coagulation agent] The resin composition of this embodiment may optionally contain an anti-flocculation agent. Examples of anti-flocculation agents include sodium polyacrylate.

[0254] In the present invention, one type of anticoagulant may be used alone, or two or more types may be used in combination. The composition of the present invention may or may not contain an anti-flocculation agent. If it does contain an anti-flocculation agent, the amount of the anti-flocculation agent is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less, based on the total solid content mass of the composition of the present invention.

[0255] [Phenol compounds] The resin composition of this embodiment may optionally contain phenolic compounds. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0256] In this invention, a single phenolic compound may be used alone, or two or more compounds may be used in combination. The composition of the present invention may or may not contain a phenolic compound. If it does contain a phenolic compound, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid content of the composition of the present invention.

[0257] [Other polymer compounds] Other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified forms into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups have been introduced.

[0258] In this invention, the other polymer compounds may be used individually or in combination of two or more. The composition of the present invention may or may not contain other polymer compounds. If other polymer compounds are included, the content of the other polymer compounds is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid content mass of the composition of the present invention.

[0259] <Properties of resin compositions> The viscosity of the resin composition of the present invention 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, 2,500mm 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 2 If the rate is 1 / s or higher, it is easy to coat the film thickness required for, for example, as an insulating film for rewiring, and 12,000 mm 2 If the rate is less than or equal to / s, an excellent coating film can be obtained on the coated surface.

[0260] <Restrictions on substances contained in resin compositions> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining moisture content include adjusting humidity during storage and reducing the porosity of the storage container.

[0261] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 ppm (parts per million) by mass, 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.

[0262] Furthermore, methods for reducing metal impurities unintentionally included in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, performing filter filtration on the raw materials constituting the resin composition of the present invention, and performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0263] When considering the application of the resin composition of the present invention 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 wiring corrosion. In particular, the amount of halogen atoms present in the form of halogen ions is 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 chlorine ions and bromine ions, is within the above ranges. Methods for adjusting the halogen atom content include ion exchange treatment.

[0264] Conventional containers can be used as containers for the resin composition of the present invention. Furthermore, to suppress the incorporation of impurities into the raw materials and the resin composition of the present invention, it is also preferable to use a multilayer bottle with an inner wall made of six types of resin in six layers, or a bottle 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.

[0265] <Cured product of resin composition> A cured product of the resin composition of the present invention can be obtained by curing the resin composition. A cured product according to a first aspect of the present invention is a cured product obtained by curing the resin composition of the present invention. The curing of the resin composition is preferably by heating, more preferably within the range of 120°C to 400°C, even more preferably within the range of 140°C to 380°C, and particularly preferably within the range of 170°C to 350°C.

[0266] A cured product according to a second aspect of the present invention comprises a cyclized resin and a carbonate compound. The above-mentioned cyclized resin is preferably a cyclized resin contained in the above-mentioned resin composition, or a precursor of the cyclized resin that has been modified by heating (for example, a precursor of the cyclized resin that has been cyclized, or a polymerizable group contained in the resin that has been polymerized with another resin or polymerizable compound, etc.). The preferred embodiment of the carbonate compound described above is the same as the preferred embodiment of the carbonate compound described in the resin composition according to the first embodiment of the present invention described above. According to this embodiment, the cured product has excellent chemical resistance. As mentioned above, carbonate compounds are highly polar and therefore do not dissolve easily in organic solvents. As a result, cured products containing such carbonate compounds are thought to have excellent chemical resistance. In the present invention, the cured product according to the first embodiment and the cured product according to the second embodiment are collectively referred to simply as "cured product". Furthermore, the cured product according to the first embodiment of the present invention may contain a carbonate compound.

[0267] From the viewpoint of adhesion to metal, the content of the carbonate compound relative to the total mass of the cured product of the present invention is preferably 0.001 to 0.100% by mass, more preferably 0.003 to 0.080% by mass, and even more preferably 0.005 to 0.050% by mass.

[0268] The form of the cured product of the present invention is not particularly limited and can be selected according to the application, such as in the form of a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. Furthermore, by pattern processing of the resin composition, the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming via holes for conductivity, adjusting impedance, capacitance or internal stress, or providing heat dissipation functions. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate of the resin composition of the present invention upon curing is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, and can be calculated using the following formula. Shrinkage rate [%] = 100 - (Volume after hardening ÷ Volume before hardening) × 100

[0269] <Characteristics of cured resin compositions> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties. The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[0270] <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 can be achieved using methods such as mixing with agitators, mixing with a ball mill, or mixing by rotating the tank itself. The mixing temperature is preferably 10-30°C, and more preferably 15-25°C.

[0271] Furthermore, it is preferable to perform filtration using a filter to remove foreign matter such as dirt and fine particles from the resin composition of the present invention. The filter pore size can be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. If the filter material is polyethylene, it is more preferably HDPE (high-density polyethylene). The filter may be one that has been pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. As an example of a connection configuration, an HDPE filter with a pore size of 1 μm may be connected in series as the first stage, and an HDPE filter with a pore size of 0.2 μm may be connected in series as the second stage. In addition, various materials may be filtered multiple times. When filtering multiple times, circulating filtration may be used. In addition, filtration may be performed under pressure. When filtration is performed under pressure, the pressure applied may be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using a filter, impurities may be removed using an adsorbent. A combination of filter filtration and impurity removal using an adsorbent may also be used. As the adsorbent, any known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. Furthermore, after filtration using a filter, the resin composition filled into the bottle may be subjected to a degassing process by placing it under reduced pressure.

[0272] (Method of manufacturing a cured product) The method for producing the cured product of the present invention preferably includes a film-forming step in which a resin composition is applied to a substrate to form a film. Furthermore, the method for producing a cured product of the present invention more preferably includes the above-mentioned film formation step, an exposure step for selectively exposing the film formed in the film formation step, and a developing step for developing the film exposed in the exposure step using a developer to form a pattern. The method for producing a cured product of the present invention is particularly preferably to include at least one of the above-mentioned film formation step, exposure step, development step, and a heating step for heating the pattern obtained in the development step and a post-development exposure step for exposing the pattern obtained in the development step. Furthermore, the manufacturing method of the present invention may also preferably include the above-mentioned film formation step and the step of heating the above-mentioned film. The details of each step are explained below.

[0273] <Film formation process> The resin composition of the present invention can be used in a film-forming process, where it is applied to a substrate to form a film. The method for producing the cured product of the present invention preferably includes a film-forming step in which a resin composition is applied to a substrate to form a film.

[0274] [Base material] The type of substrate can be appropriately determined depending on the application, but examples include semiconductor fabrication 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), and are not particularly limited. In the present invention, semiconductor fabrication substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred. Furthermore, these substrates may have layers on their surface, such as an adhesion layer or an oxidation layer, provided with hexamethyldisilazane (HMDS) or the like. Furthermore, the shape of the base material is not particularly limited and may be circular or rectangular. For the base material, if it is circular, for example, the diameter is 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, for example, the length of the shorter side is 100 to 1000 mm, preferably 200 to 700 mm. Furthermore, as the base material, for example, a plate-shaped, preferably panel-shaped, base material (substrate) is used.

[0275] Furthermore, when a resin composition is applied to the surface of a resin layer (for example, a layer made of a cured material) or a metal layer to form a film, the resin layer or metal layer serves as the substrate.

[0276] As a means of applying the resin composition of the present invention onto a substrate, coating is preferred.

[0277] Specific examples of 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 more preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the 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. Alternatively, a method can be applied in which a coating film, which has been formed in advance on a temporary support using the above application method, is transferred onto a substrate. Regarding the transfer method, the manufacturing methods described in paragraphs 0023, 0036-0051 of Japanese Patent Publication No. 2006-023696 and paragraphs 0096-0108 of Japanese Patent Publication No. 2006-047592 can be suitably used in the present invention as well. Furthermore, a process to remove excess film from the edges of the substrate may be performed. Examples of such processes include edge bead rinsing (EBR) and back rinsing. Alternatively, a pre-wetting process may be employed in which the substrate is coated with various solvents to improve its wettability before applying the resin composition to the substrate.

[0278] <Drying process> The above film may be subjected to a drying step (a process in which the formed film (layer) is dried in order to remove the solvent after the film formation step (layer formation step). In other words, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film formation step. Furthermore, it is preferable that the above drying step be performed after the film formation step and before the exposure step. 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.

[0279] <Exposure process> The above film may be subjected to an exposure process in which the film is selectively exposed. In other words, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed by the film formation step. Selective exposure means exposing only a portion of a film. Selective exposure creates areas on the film that are exposed (exposed regions) and areas that are not exposed (unexposed regions). The exposure amount is not particularly defined as long as it can cure the resin composition of the present invention, but for example, it is 50 to 10,000 mJ / cm² in terms of exposure energy at a wavelength of 365 nm. 2 Preferably, 200-8,000 mJ / cm² 2 This is preferable.

[0280] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0281] In relation to the light source, the exposure wavelengths include (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 (g, h, i-line wavelengths), (4) excimer lasers, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic 532nm and third harmonic 355nm of YAG lasers. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and among these, exposure with the i-line is preferred. This can result in particularly high exposure sensitivity. Furthermore, the exposure method is not particularly limited, and any method in which at least a portion 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.

[0282] <Post-exposure heating process> The above film may be subjected to a heating step after exposure (post-exposure heating step). In other words, the method for producing a cured product of the present invention may include a post-exposure heating step in which the film exposed by 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 process is preferably 1 to 12°C / min from the initial heating temperature to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. Furthermore, the heating rate may be changed as needed during the heating process. The heating means in the post-exposure heating process 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.

[0283] <Developing process> The film after exposure may be subjected to a developing process in which it is developed using a developing solution to form a pattern. In other words, the method for producing a cured product of the present invention may include a developing step in which the film exposed in the exposure step is developed using a developer to form a pattern. 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 parts of the film are removed by the development process is called negative development, and development in which the exposed parts of the film are removed by the development process is called positive development.

[0284] [Developer] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[0285] 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. Preferably, TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine are preferred, and TMAH is more preferred. The content of basic compounds 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, when using TMAH, for example.

[0286] 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.

[0287] 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 most preferred.

[0288] 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.

[0289] The developing solution may contain other components as well. Other components include, for example, known surfactants and known defoaming agents.

[0290] [Method of supplying developing solution] There are no particular restrictions on the method of supplying the developer, as long as the desired pattern can be formed. These methods include immersing the substrate on which the film has been formed in the developer, paddle development where the developer is supplied to the film formed on the substrate using a nozzle, or a method of continuously supplying the developer. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, and spray nozzles. From the viewpoint of developer penetration, removal of non-image areas, and manufacturing efficiency, a method of supplying the developer with a straight nozzle or a method of continuously supplying it with a spray nozzle is preferred, and from the viewpoint of developer penetration into the image area, the method of supplying with a spray nozzle is more preferred. Alternatively, the process may involve continuously supplying the developer solution through a straight nozzle, spinning the substrate to remove the developer solution from the substrate, spin-drying, and then continuously supplying the developer solution again through a straight nozzle, spinning the substrate to remove the developer solution from the substrate. This process may be repeated multiple times. Furthermore, possible methods for supplying the developer during the developing process include a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a nearly stationary state on the substrate, a process in which the developer is vibrated on the substrate using ultrasound or the like, and a process that combines these methods.

[0291] The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer solution during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0292] 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.

[0293] [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.

[0294] When the rinsing solution contains an organic solvent, the organic solvent can be the same as the organic solvent exemplified above when the developing solution contains an organic solvent.

[0295] If the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are even more preferred.

[0296] If the rinsing solution contains an organic solvent, it is preferable that the rinsing solution contains 50% or more by mass of the organic solvent, more preferably 70% or more by mass of the organic solvent, and even more preferably 90% or more by mass of the organic solvent. Alternatively, the rinsing solution may contain 100% by mass of the organic solvent.

[0297] The rinse solution may contain other ingredients as well. Other components include, for example, known surfactants and known defoaming agents.

[0298] [Method of supplying rinse solution] There are no particular restrictions on the method of supplying the rinsing solution, as long as a desired pattern can be formed. These methods include immersing the substrate in the rinsing solution, supplying the rinsing solution to the substrate by pouring the solution onto it, 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 rinse solution, the removal of non-image areas, and manufacturing efficiency, there are methods for supplying the rinse solution using shower nozzles, straight nozzles, spray nozzles, etc. A method of continuous supply using a spray nozzle is preferred, and from the viewpoint of the penetration of the rinse 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. In other words, the rinsing step is preferably a step of supplying the rinsing solution to the exposed film using a straight nozzle or a continuous supply step, and more preferably a step of supplying the rinsing solution using a spray nozzle. Furthermore, 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.

[0299] 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.

[0300] <Heating process> The pattern obtained by the developing process (or the pattern after rinsing, if a rinsing process is performed) may be subjected to a heating process in which the pattern obtained by the developing process is heated. In other words, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the developing step. Furthermore, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing a developing step, or a film obtained by a film formation step. During the heating process, resins such as polyimide precursors undergo cyclization to become resins such as polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in specific resins or other crosslinking agents also proceeds. The heating temperature (maximum heating temperature) in the heating process 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.

[0301] The heating step is preferably a step in which the heating promotes the cyclization reaction of the polyimide precursor within the pattern by the action of bases generated from the base generating agent.

[0302] In the heating process, heating is preferably carried out at a heating rate of 1 to 12°C / minute from the initial heating temperature to the maximum heating temperature. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. By setting the heating rate to 1°C / minute or more, it is possible to prevent excessive volatilization of acid or solvent while ensuring productivity, and by setting the heating rate to 12°C / minute or less, it is possible to alleviate residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, it is preferable to raise the temperature from the initial temperature to the maximum heating temperature at a rate of 1 to 8°C / second, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0303] The starting temperature for heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The starting temperature for heating refers to the temperature at which the process of heating to the maximum heating temperature is initiated. For example, when the resin composition of the present invention is applied to a substrate and then dried, this is the temperature of the film (layer) after drying. For example, it is preferable to start the heating process from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

[0304] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0305] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and especially preferably 120°C or higher. The upper limit of the above heating temperature is preferably 350°C or less, more preferably 250°C or less, and even more preferably 240°C or less.

[0306] Heating may be carried out in stages. For example, the process may involve raising the temperature from 25°C to 120°C at a rate of 3°C / min, holding at 120°C for 60 minutes, raising the temperature from 120°C to 180°C at a rate of 2°C / min, and holding at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Patent No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment process is best carried out for a short time, from about 10 seconds to 2 hours, with 15 seconds to 30 minutes being more preferable. The pretreatment may consist of two or more steps; for example, the first pretreatment step may be performed in the range of 100 to 150°C, followed by the second pretreatment step in the range of 150 to 200°C. Furthermore, the mixture may be cooled after heating, and in this case, the cooling rate is preferably 1 to 5°C / minute.

[0307] The heating process is preferably carried out in a low-oxygen atmosphere by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure, in order to prevent the decomposition of specific resins. The oxygen concentration is preferably 50 ppm (by volume) or less, and more preferably 20 ppm (by volume) or less. The heating means in the heating process are not particularly limited, but examples include hot plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0308] <Post-development exposure process> The pattern obtained by the development process (or the pattern after rinsing, if a rinsing process is performed) may be subjected to a post-development exposure process in which the pattern after the development process is exposed, either in place of the heating process or in addition to the heating process. In other words, the method for producing a cured product of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or it may include only one of the heating step and the post-development exposure step. In the post-development exposure process, for example, reactions such as the cyclization of polyimide precursors, etc., by exposure to a photobase generator, and the elimination of acid-degradable groups by exposure to a photoacid generator can be accelerated. In the post-development exposure step, it is sufficient for at least a portion of the pattern obtained in the development step to be exposed, but it is preferable for the entire pattern to be exposed. The exposure amount in the post-development exposure step is 50 to 20,000 mJ / cm², converted to exposure energy at the wavelength to which the photosensitive compound is sensitive. 2 Preferably, the concentration is 100 to 15,000 mJ / cm². 2 It is preferable that this be the case. The post-development exposure step can be performed, for example, using the light source from the exposure step described above, and it is preferable to use broadband light.

[0309] <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. In other words, the method for producing a cured product of the present invention preferably includes a metal layer formation step in which a metal layer is formed on a pattern obtained by a developing step (preferably one that has been subjected to a heating step and at least one of a post-development exposure step).

[0310] 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.

[0311] 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 plating include electroplating using copper sulfate or copper cyanide plating solutions.

[0312] The thickness of the metal layer is preferably 0.01 to 50 μm at the thickest part, and more preferably 1 to 10 μm.

[0313] <Application> Examples of applications for the cured product manufacturing method of the present invention, or for the cured product of the present invention, include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffer films. Other applications include etching patterns for sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), or insulating films for the above-mentioned mounting applications. For these applications, see, 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 Japan Polyimide and Aromatic Polymer Research Association, ed., "Latest Polyimides: Fundamentals and Applications," NTS, August 2010.

[0314] Furthermore, the method for manufacturing the cured product of the present invention, or the cured product of the present invention, can also be used in the manufacture of printing plates such as offset plates or screen printing plates, for etching molded parts, and for the manufacture of protective lacquers and dielectric layers in electronics, particularly microelectronics.

[0315] (Laminate and method for manufacturing the 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 of the present invention is a laminate comprising two or more layers made of a cured material, and may be a laminate comprising three or more layers. Of the two or more layers of the cured material contained in the laminate, at least one is made of the cured material of the present invention. From the viewpoint of suppressing shrinkage of the cured material or deformation of the cured material due to such shrinkage, it is also preferable that all layers of the cured material contained in the laminate are made of the cured material of the present invention.

[0316] 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.

[0317] The laminate of the present invention preferably comprises two or more layers made of a cured material, with a metal layer included between any of the layers made of the cured material. The metal layer is preferably formed by the metal layer formation process described above. In other words, the method for manufacturing a laminate of the present invention preferably further includes a metal layer formation step in which a metal layer is formed on a layer made of a cured product during multiple processes for manufacturing a cured product. Preferred embodiments of the metal layer formation step are as described above. As an example of the above-mentioned laminate, a preferred laminate is one that includes at least three layers in which a layer made of a first cured material, a metal layer, and a layer made of a second cured material are laminated in this order. Preferably, both the layer made of the first cured product and the layer made of the second cured product are layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may be compositions with the same composition or compositions with different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a redistribution layer.

[0318] <Lamination process> The method for manufacturing the laminate of the present invention preferably includes a lamination step. The lamination process is a series of steps that include performing, in this order, at least one of the following on the surface of the pattern (resin layer) or metal layer: (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step, and post-development exposure step. However, the film formation step in (a) and at least one of the heating step and post-development exposure step in (d) may be repeated. Furthermore, a metal layer formation step (e) may be included after at least one of the heating step and post-development exposure step. Needless to say, the lamination process may also include the above-mentioned drying step, etc., as appropriate.

[0319] If further lamination is performed after the lamination process, a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step. Plasma treatment is an example of a surface activation treatment. Details of the surface activation treatment will be described later.

[0320] 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 or may not have the same composition, shape, film thickness, etc.

[0321] 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 at least one of the post-development exposure steps, and (e) metal layer formation, or repeating the steps in the order of (a) film formation, (d) heating and at least one of the post-development exposure steps, 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.

[0322] (Surface activation treatment process) The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a portion of the above-mentioned metal layer and resin composition layer. The surface activation treatment step is usually performed after the metal layer formation step, but the surface activation treatment step may be performed on the resin composition layer after the development step (preferably after at least one of the heating step and the post-development exposure step) before the metal layer formation step is performed. The surface activation treatment may be performed on at least a portion of the metal layer, 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 resin composition layer after exposure. 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 that surface can be improved. Furthermore, it is preferable to perform the surface activation treatment on part or all of the resin composition layer (resin layer) after exposure. By performing the surface activation treatment on the surface of the resin composition layer in this way, the adhesion between the surface-activated surface and the metal layer or resin layer can be improved. In particular, when the resin composition layer has hardened, such as when negative type development is performed, it is less susceptible to damage from the surface treatment and adhesion is easily improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This is incorporated herein by reference.

[0323] (Semiconductor devices and methods for manufacturing the same) Furthermore, the present invention also discloses semiconductor devices comprising a cured product of the present invention or a laminate of the present invention. Furthermore, the present invention also discloses a method for manufacturing a cured product of the present invention, or a method for manufacturing a semiconductor device that includes a method for manufacturing 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. [Examples]

[0324] 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.

[0325] <Method for producing precursors of cyclized resins> [Synthesis Example 1: Synthesis of a cyclized resin precursor (resin 1)] 23.48 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) and 22.27 g of bisphthalic acid dianhydride (BPDA) were placed in a separable flask, 39.69 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of tetrahydrofuran were added, and the mixture was stirred at room temperature (25°C). While stirring, 24.66 g of pyridine was added to obtain the reaction mixture. After the exothermic reaction was complete, the mixture was allowed to cool to room temperature and left for 16 hours. Next, under ice cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes with stirring. Subsequently, 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 119.73 g of tetrahydrofuran was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 7.17 g of ethyl alcohol was added and stirred for 1 hour, and then 136.83 g of tetrahydrofuran was added. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution. The resulting reaction solution was added to 716.21 g of ethyl alcohol to produce a precipitate consisting of crude polymer. The crude polymer was filtered off and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain 80.3 g of powdered resin 1. The molecular weight of resin 1 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was found to be 20,000. The structure of resin 1 is presumed to be represented by the following formula (P-1).

[0326] [Synthesis Example 2: Synthesis of a cyclized resin precursor (resin 2)] 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C, and while maintaining the temperature at -10±5°C, 17.0 g of thionyl chloride was added over 60 minutes. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 60 minutes at -10±5°C, and the mixture was stirred at room temperature for 2 hours. Subsequently, 10.0 g of ethanol was added and the mixture was stirred at room temperature for 1 hour. Next, 6000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was filtered and dissolved in 500 g of tetrahydrofuran. 6000 g of water (poor solvent) was added to the resulting solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was filtered again and dried under reduced pressure at 45°C for 3 days. 46.6 g of the dried powder was dissolved in 419.6 g of tetrahydrofuran, and then 2.3 g of triethylamine was added and the mixture was stirred at room temperature for 35 minutes. After that, 3000 g of ethanol was added and the precipitate was filtered off. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTec) were added and the mixture was stirred for 4 hours. The ion exchange resin was then removed by filtration, and the resulting polymer solution was added to 5,600 g of water to obtain a precipitate. The precipitate was filtered off and dried under reduced pressure at 45°C for 24 hours to obtain 45.1 g of resin 2. The structure of resin 2 is presumed to be represented by the following formula (P-2). When the molecular weight of resin 2 was measured by gel permeation chromatography (on a standard polystyrene basis), the weight-average molecular weight (Mw) was found to be 20,000. Furthermore, by appropriately adjusting the equivalent amount of 4,4'-diaminodiphenyl ether, resin 2 with Mw of 5,000, resin 2 with Mw of 10,000, and resin 2 with Mw of 30,000 were also synthesized.

[0327] [Synthesis Examples 3-10: Synthesis of Precursors of Cyclic Resins (Resins 3-10)] Resins 3 to 10, each having a structure represented by one of the following formulas (P-3) to (P-10), were synthesized using the same method as in Synthesis Example 2, except that the compounds used were changed as appropriate. The Mw values ​​for resin 3 were 20,000, resin 4 were 20,000, resin 5 were 20,000, resin 6 were 20,000, resin 7 were 20,000, resin 8 were 20,000, resin 9 were 20,000, and resin 10 were 20,000.

[0328] [ka] [ka]

[0329] [Synthesis of resin 11] In a flask equipped with a condenser and stirrer, 18.0 g (40.5 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP) while removing water. Next, 7.95 g (39.7 mmol) of 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25°C for 3 hours, followed by stirring at 45°C for another 3 hours. Then, 12.8 g (160 mmol) of pyridine, 10.3 g (101 mmol) of acetic anhydride, and 40.0 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80°C for 3 hours. Finally, 50 g of N-methylpyrrolidone (NMP) was added to dilute the mixture. This reaction solution was precipitated in 1 liter of methanol and stirred at 3000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. The obtained resin was dried under reduced pressure at 40°C for 1 day to obtain resin 11. The molecular weight of resin 11 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 20,000. The structure of resin 11 is presumed to be represented by the following formula (P-11). [ka]

[0330] [Synthesis of resin 12] 30.78 parts by mass of cyclohexanone was heated to 80°C under a nitrogen stream. While stirring this liquid, a mixed solution of 10.21 parts by mass of 2-oxotetrahydrofuran-3-yl methacrylate, 11.78 parts by mass of 1-isopropylcyclopentyl methacrylate, 57.17 parts by mass of cyclohexanone, and 0.44 parts by mass of 2,2'-aziobisisobutyrate dimethyl [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] was added dropwise over 6 hours. After the addition was complete, the mixture was stirred at 80°C for a further 2 hours. After the reaction solution was allowed to cool, it was reprecipitated with a large amount of methanol / water (mass ratio 9:1), filtered, and the resulting solid was vacuum dried to obtain 18.69 parts by mass of resin 9, an acid-degradable resin. The structure of resin 12 is presumed to be represented by the following formula (P-12). When the molecular weight of resin 12 was measured by gel permeation chromatography (on a standard polystyrene basis), the weight-average molecular weight (Mw) was found to be 20,000. [ka]

[0331] <Examples and Comparative Examples> In each example, the components listed in the table below were mixed to obtain each resin composition. Similarly, in the comparative examples, the components listed in the table below were mixed to obtain comparative compositions. Specifically, the content (amount blended) of each component listed in the table other than the solvent was the amount (parts by mass) indicated in the "parts by mass" column for each column in the table. The solvent content (amount blended) was determined so that the solid content concentration of the composition matched the value (mass %) in the "Solid Content Concentration" column of the table, and the ratio of the content of each solvent to the total mass of the solvent (mass ratio) matched the ratio indicated in the "Ratio" column of the table. The obtained resin composition and comparative composition were subjected to pressure filtration using a polytetrafluoroethylene filter with a pore width of 0.8 μm. In addition, in the table, a "-" indicates that the composition does not contain the corresponding ingredient.

[0332] [Table 1]

[0333] [Table 2]

[0334] [Table 3]

[0335] [Table 4]

[0336] [Table 5]

[0337] [Table 6]

[0338] [Table 7]

[0339] [Table 8]

[0340] [Table 9]

[0341] Details of each component listed in the table are as follows:

[0342] 〔resin〕 • Resins 1 to 12: Resins 1 to 12 obtained by the above synthesis example.

[0343] [Monomers (polymerizable compounds)] • M-1: Compounds with the following structure; the subscript in parentheses indicates the number of repetitions. • DPHA: Dipentaerythritol hexaacrylate [ka]

[0344] [Polymerization initiator or photoacid generator] • I-1 to I-5: Compounds with the following structure [ka]

[0345] [Base Generator] A-1 to A-34: Compounds with the following structure. All of A-1 to A-34 are compounds that fall under the category of specific base generators mentioned above. • AX-1 to AX-3: Compounds with the following structure. None of AX-1 to AX-3 are compounds that fall under the category of the specific base generators mentioned above. • AR-1: A compound with the structure shown below. AR-1 is not a compound that falls under the category of the specific base-generating agents mentioned above. [ka] [ka] [ka]

[0346] [Polymerization inhibitors] • B-1~B-4: Compounds with the following structure [ka]

[0347] [Silane coupling agent (metal adhesion improver)] • C-1 to C-3: Compounds with the following structure. In the following formulas, Et represents the ethyl group. [ka]

[0348] [Migration inhibitors] • D-1~D-4: Compounds with the following structure [ka]

[0349] [Additives] • E-1 to E-7: Compounds with the following structure [ka]

[0350] 〔solvent〕 • NMP: N-methyl-2-pyrrolidone • EL: Ethyl lactate • DMSO: Dimethyl sulfoxide GBL: γ-butyrolactone

[0351] <Rating> [Evaluation of adhesion to copper substrate] The resin composition or comparative composition prepared in each example and comparative example was applied in layers to a copper substrate by spin coating to form a resin composition layer or comparative composition layer. The copper substrate on which the obtained resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes to obtain a resin composition layer or comparative composition layer on the copper substrate with a uniform thickness and the film thickness indicated in the "Film Thickness (μm)" column of the table. The resin composition layer or comparative composition layer on the copper substrate was subjected to a filtration rate of 500 mJ / cm². 2 For the exposure energy, in the example where "Negative" is written in the "Development Conditions" column of the table, a photomask with a 100 μm square non-mask area was formed, and in the example where "Positive" is written in the "Development Conditions" column of the table, a photomask with a 100 μm square mask area was formed, and the images were exposed with light at the exposure wavelength (nm) indicated in the "Exposure Wavelength (nm)" column of the table. In the example where "M" is written in the exposure conditions column, exposure was performed using a stepper as the light source. In the example where "D" is written in the exposure conditions column, a direct exposure system (Adtec DE-6UH III) was used as the light source, and laser direct imaging exposure was performed on a 100 μm square area without using a photomask. Subsequently, the material was developed for 60 seconds using the developer listed in the table to obtain a 100 μm square resin layer. The entry for "TMAH aqueous solution" in the table refers to a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. In the examples where a numerical value is listed in the "Cure Temperature" column, the resin composition layer after exposure was heated using a hot plate under a nitrogen atmosphere at a heating rate of 10°C / min until it reached the temperature indicated in the "Cure Temperature (°C)" column of the table, and then maintained at that temperature for the time indicated in the "Cure Time (min)" column of the table. In the cases where "IR" is written in the "Cure Temperature (°C)" column, the resin films obtained in each example were heated in a nitrogen atmosphere at a heating rate of 10°C / min using an infrared lamp heating device (Advance Riko Co., Ltd., RTP-6), and after reaching 230°C, the above temperature was maintained for the time specified in "Cure Time (min)" in the table. For a 100 μm square resin layer on a copper substrate, the shear force was measured using a bond tester (CondorSigma, XYZTEC) at 25°C and 65% relative humidity (RH), and evaluated according to the evaluation criteria below. The evaluation results are listed in the "Adhesion to Copper Substrate" column of the table. The greater the shear force, the better the metal adhesion (copper adhesion) of the cured film. -Evaluation Criteria- A: The shear force exceeded 30 gf. B: The shear force was greater than 25 gf and less than or equal to 30 gf. C: The shear force was greater than 20 gf and less than or equal to 25 gf. D: The shear force was 20 gf or less. Also, 1 gf is equal to 0.00980665 N.

[0352] [Evaluation of chemical resistance] In each example or comparative example, the prepared resin composition or comparative composition was applied to a silicon wafer by spin coating. The silicon wafer was dried on a hot plate at 100°C for 5 minutes to form a uniform resin composition layer on the silicon wafer with the thickness indicated in the "Film Thickness (μm)" column of the table. In the example where "Negative" was specified for the development conditions and "M" was specified for the exposure conditions, the resin composition layer on the silicon wafer was exposed using a stepper. Exposure was performed on the entire surface of the photosensitive film using light of the wavelength listed in "Exposure Wavelength (nm)" in the table, without using a photomask. The exposure dose was 500 mJ / cm². 2 That's what I decided. In cases where "Negative" was specified in the development conditions and "D" was specified in the exposure conditions, exposure was performed using a direct exposure system (Adtec DE-6UH III). Exposure was performed on the entire surface of the photosensitive film using light of the wavelength listed in "Exposure Wavelength (nm)" in the table. The exposure dose was 500 mJ / cm². 2 That's what I decided. In cases where "positive" was specified in the development conditions, no exposure was performed. Next, in the cases where a numerical value is listed in the "Cure Temperature (°C)" column, a hot plate was used to heat the resin film (resin composition layer) obtained in each example or comparative example at a heating rate of 10°C / min under a nitrogen atmosphere. After reaching the temperature indicated in the "Cure Temperature (°C)" column of the table, the temperature was maintained for the time indicated in the "Cure Time (min)" column to form a cured film. In the cases where "IR" is written in the "Cure Temperature (°C)" column, an infrared lamp heating device (Advance Riko Co., Ltd., RTP-6) was used to heat the resin film obtained in each example in a nitrogen atmosphere at a heating rate of 10°C / min until it reached 230°C, at which point the temperature was maintained for the time indicated in "Cure Time (min)" to form a cured film. The resulting cured film was immersed in the following chemicals under the following conditions, and the dissolution rate was calculated. Chemicals: A mixture of dimethyl sulfoxide (DMSO) and a 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) in a 90:10 (mass ratio) ratio. Evaluation conditions: The above cured film was immersed in the above chemical at 75°C for 15 minutes, and the film thickness of the cured film before and after immersion was compared to calculate the dissolution rate (nm / min). The obtained dissolution rate values ​​were evaluated according to the evaluation criteria below, and the evaluation results are recorded in the "Chemical Resistance Evaluation" column. A lower dissolution rate indicates superior chemical resistance. -Evaluation Criteria- A: The dissolution rate was less than 250 nm / min. B: The dissolution rate was between 250 nm / min and less than 500 nm / min. C: The dissolution rate was between 500 nm / min and less than 750 nm / min. D: The dissolution rate is 750 nm / min or higher.

[0353] From the above results, it can be seen that the cured product formed from the resin composition of the present invention exhibits excellent adhesion to metals. The comparative composition in Comparative Example 1 does not contain a specific base generator. It can be seen that the resulting cured product exhibits poor adhesion to the metal.

[0354] <Example 101> The resin composition used in Example 5 was applied in layers to the copper layer of a resin substrate having a copper layer formed on its surface by spin coating, dried at 100°C for 5 minutes to form a photosensitive film with a thickness of 20 μm, and then exposed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After the above exposure, the film was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain the layer pattern. Next, under a nitrogen atmosphere, the temperature was increased at a rate of 10°C / min until it reached 230°C, and then maintained at 230°C for 180 minutes to form an interlayer insulating film for the redistribution layer. This interlayer insulating film for the redistribution layer exhibited excellent insulating properties. Furthermore, when semiconductor devices were manufactured using these interlayer insulating films for redistribution layers, it was confirmed that they functioned without any problems.

Claims

1. Resin, and Contains a base generator, The base generator is a compound represented by the following formula (1-1), A resin composition in which the content of a base-generating agent other than the compound represented by formula (1-1) is 1% by mass or less relative to the total mass of the resin composition. 【Chemistry 1】 In formula (1-1), L １ R represents an n+m valence linking group with one of the following structures, １ They combine into R １ A dimethylpiperidine structure or R has a nitrogen atom directly bonded to it as a ring member. １ A dimethylmorpholine structure is formed with a nitrogen atom directly bonded to it as a ring member, and the dimethylpiperidine structure and the dimethylmorpholine structure are cis isomers, R ２ R represents a hydrocarbon group which may have substituents, １ They may be linked together to form a ring structure, where m represents 1 or 2, and n represents 1 or 2. 【Chemistry 2】 In the above structure, * represents R in equation (1-1). ２ The bond site between the nitrogen atom directly bonded to the carbonyl group is indicated by # in formula (1-1) R １ These represent the bonding sites between the nitrogen atom directly bonded to the carbonyl group and the carbonyl group directly bonded to the nitrogen atom.

2. L in formula (1-1) above １ The resin composition according to claim 1, wherein L contains at least one aromatic ring structure.

3. The L in equation (1-1) １ The resin composition according to claim 1 or 2, wherein all of the bonding sites with the m+n carbonyl groups in formula (1-1) are carbon atoms.

4. R ２ The resin composition according to claim 1 or 2, wherein the substituent in is a halogen atom, an alkoxy group, an allyloxy group, an alkylcarbonyl group, an arylcarbonyl group, or a hydroxyl group.

5. The resin composition according to claim 1 or 2, wherein the resin is at least one resin selected from the group consisting of cyclized resins and their precursors.

6. The resin composition according to claim 1 or 2, wherein the resin comprises at least one group selected from the group consisting of a group having an ethylenically unsaturated bond, an epoxide, an oxetane, an aldehyde, and a ketone.

7. The resin composition according to claim 1 or 2, further comprising a photopolymerization initiator.

8. The resin composition according to claim 1 or 2, further comprising a polymerizable compound.

9. The resin composition according to claim 1 or 2, further comprising an organometallic complex.

10. The resin composition according to claim 1 or 2, comprising a cyclized resin or a precursor thereof as the resin, and used for forming an interlayer insulating film for a redistribution layer.

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

12. A laminate comprising two or more layers made of the cured material described in claim 11, wherein a metal layer is included between the layers made of the cured material.

13. 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.

14. An exposure step for selectively exposing the aforementioned film, A method for producing a cured product according to claim 13, comprising a developing step of developing the film using a developing solution to form a pattern.

15. A method for producing a cured product according to claim 13, comprising a heating step of heating the film to 50 to 450°C.

16. A method for manufacturing a laminate, comprising the method for manufacturing a cured product described in claim 13.

17. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product described in claim 13.

18. A semiconductor device comprising the cured product described in claim 11.

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