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

Abstract

A resin composition which comprises a cyclization resin or a precursor thereof, a free-radical polymerization initiator, and one or more radical-polymerizable compounds, wherein the radical-polymerizable compounds include a compound A having a urea bond and having no axis of symmetry, the compound A satisfying requirement 1 and / or requirement 2; a cured object obtained by curing the resin composition; a layered object including the cured object; a method for producing the cured object; and a semiconductor device including the cured object or the layered object. Requirement 1: The compound A has two or more radical- polymerizable groups. Requirement 2: The compound A has at least one group selected from the group consisting of hydroxy, alkyleneoxy, amide, and cyano groups.

Description

[Technical Field]

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

[0002] Cyclized resins such as polyimides have excellent heat resistance and insulating properties and are therefore used in a variety of applications. Examples of such applications include, but are not limited to, insulating films, sealing materials, and protective films for semiconductor devices used for packaging. They are also used as base films and coverlays for flexible substrates.

[0003] For example, in the above-mentioned applications, the cyclized resin such as polyimide is used in the form of a resin composition containing at least one of the cyclized resin such as polyimide and a precursor of the cyclized resin. Such a resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are carried out to form a cured product on the substrate. The precursor of the cyclized resin, such as a polyimide precursor, is cyclized, for example, by heating, and becomes a cyclized resin, such as a polyimide, in the cured product. The resin composition can be applied by known coating methods, etc., and therefore can be said to have excellent adaptability in manufacturing, for example, a high degree of freedom in designing the shape, size, application position, etc. of the resin composition when applied. In addition to the high performance of cyclized resins such as polyimides, from the viewpoint of such excellent adaptability in manufacturing, there are increasing expectations for the industrial application and development of the above-mentioned resin composition.

[0004] For example, Patent Document 1 describes a photosensitive polyimide precursor composition that contains (a) a polymer (A) mainly composed of a specific structural unit, (b) a compound (B) having a specific structure, and (c) a photoinitiator and / or a sensitizer and / or a photoreactive monomer. Patent Document 2 describes a negative photosensitive resin composition containing (A) 100 parts by mass of a polyimide precursor having a specific structural unit, (B) 1 to 20 parts by mass of a photopolymerization initiator, and (C) 0.1 to 30 parts by mass of at least one compound selected from the group consisting of a compound represented by a specific structure or a polymer thereof and a compound represented by a specific structure or a polymer thereof, or a polymer thereof. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 6-332178 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-059656 Summary of the Invention [Problem to be solved by the invention]

[0006] Resin compositions containing at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin are required to produce cured products with excellent chemical resistance. The present invention aims to provide a resin composition that can give a cured product having excellent chemical resistance, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, and a semiconductor device including the cured product or the laminate. [Means for solving the problem]

[0007] Examples of typical embodiments of the present invention are given below. <1> cyclized resin or a precursor thereof, a radical polymerization initiator, and Contains a radical polymerizable compound, The radical polymerizable compound includes a compound A having a urea bond and not having an axis of symmetry, The compound A satisfies at least one of the following conditions 1 and 2: resin composition; Condition 1: Compound A has two or more radically polymerizable groups; Condition 2: Compound A has at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group. <2> The cyclized resin or its precursor is at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor. <1> The resin composition according to claim 1. <3> The acid value of the cyclized resin or its precursor is 0 mmol / g to 1.2 mmol / g. <1> or <2> The resin composition according to claim 1. <4> wherein compound A contains an aromatic group; <1> ~ <3> The resin composition according to any one of the above. <5> The radical polymerizable compound further includes a compound different from the compound A. <1> ~ <4> The resin composition according to any one of the above. <6> The compound A is a compound represented by the following formula (1-1) or formula (1-2): <1> ~ <5> The resin composition according to any one of the above. [ka] In formula (1-1), R P1 and R P2 each independently represents a group containing at least one radically polymerizable group; In formula (1-2), R P1 represents a group containing at least one radically polymerizable group, and L 3 represents a divalent linking group. <7> Used to form an interlayer insulating film for a rewiring layer, <1> ~ <5> The resin composition according to any one of the above. <8> <1> ~ <7> A cured product obtained by curing the resin composition according to any one of the above items. <9> <8> 1. A laminate comprising two or more layers each made of the cured product according to claim 1, and a metal layer between any two adjacent layers made of the cured product. <10> <1> ~ <7> 10. A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of the above items onto a substrate to form a film. <11> an exposure step of selectively exposing the film to light and a development step of developing the film with a developer to form a pattern, <10> A method for producing the cured product described in <12> A heating step of heating the film at 50 to 450 ° C. <10> or <11> A method for producing the cured product described in <13> <8> or a cured product according to <9> A semiconductor device comprising the stack described in claim 1. [Effects of the Invention]

[0008] According to the present invention, there are provided a resin composition that can give a cured product having excellent chemical resistance, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, and a semiconductor device including the cured product or the laminate. DETAILED DESCRIPTION OF THE INVENTION

[0009] The main embodiments of the present invention will be described below, but the present invention is not limited to the embodiments explicitly described. In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values ​​before and after "to" as the lower limit and upper limit, respectively. In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps, so long as the intended effect of the step can be achieved. In the description of groups (atomic groups) in this specification, when a notation does not specify whether they are substituted or unsubstituted, it encompasses both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents. For example, the term "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups). Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation. In this specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", "(meth)acrylic" means either or both of "acrylic" and "methacrylic", and "(meth)acryloyl" means either or both of "acryloyl" and "methacryloyl". In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the term "total solids content" refers to the total mass of all components of the composition excluding the solvent, and the term "solids concentration" refers to the mass percentage of the components excluding the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220GPC (manufactured by Tosoh Corporation) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, when THF is not suitable as the eluent, such as when the solubility is low, NMP (N-methyl-2-pyrrolidone) can also be used. Unless otherwise specified, detection in GPC measurements is performed using a UV (ultraviolet) ray (ultraviolet) detector at a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting a laminate is described as "above" or "below," it is sufficient that there is another layer above or below the reference layer among the multiple layers being considered. In other words, 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 "above," or, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as "above," and the opposite direction is referred to as "below." Note that such vertical directions are defined for convenience in this specification, and in actual embodiments, the "above" direction in this specification may differ from the vertically upward direction. In this specification, unless otherwise specified, a composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23° C., the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. As used herein, combinations of preferred embodiments are more preferred embodiments.

[0010] (Resin composition) The resin composition of the present invention comprises a cyclized resin or a precursor thereof, a radical polymerization initiator, and a radical polymerizable compound, wherein the radical polymerizable compound comprises a compound A having a urea bond and no axis of symmetry, and the compound A satisfies at least one of the following conditions 1 and 2: Condition 1: Compound A has two or more radically polymerizable groups. Condition 2: Compound A has at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group.

[0011] The resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and more preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent. The resin composition of the present invention can be used to form, for example, an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a rewiring layer. The resin composition of the present invention may also be used to form a photosensitive film that is subjected to negative development. In the present invention, negative development refers to development in which the unexposed areas are removed by development, and positive development refers to development in which the exposed areas are removed by development. As the exposure method, the developer, and the development method, for example, the exposure method described in the exposure step and the developer and development method described in the development step in the description of the method for producing a cured product described below can be used.

[0012] According to the resin composition of the present invention, a cured product having excellent chemical resistance can be obtained. The mechanism by which the above effects are obtained is unknown, but is speculated as follows.

[0013] Regarding compositions containing cyclized resins or precursors thereof, prior art documents have investigated the use of radically polymerizable compounds having urea bonds. However, when a radical polymerizable compound having a urea bond is used in a resin composition containing a cyclized resin or a precursor thereof, the radical polymerizable compounds tend to aggregate with each other, which may result in a decrease in chemical resistance. In particular, polymerizable compounds having two or more radically polymerizable groups and a urea bond, or polymerizable compounds having a polar group such as a hydroxy group, an alkyleneoxy group, an amide group, or a cyano group and a urea bond, tend to aggregate easily, and when polymerized after being formed into a composition film, unevenness occurs in the density of the polymer in the film, which can result in reduced chemical resistance. Therefore, the present inventors have conducted extensive studies and found that chemical resistance can be improved by using Compound A, which is a compound having no axis of symmetry, as a polymerizable compound having two or more radically polymerizable groups and a urea bond, or a polymerizable compound having a polar group such as a hydroxy group, an alkyleneoxy group, an amide group, or a cyano group and a urea bond. This is presumably because the aggregation of the polymerizable compound is suppressed due to the absence of an axis of symmetry in compound A, and therefore, when compound A is polymerized, compound A is present in the film in a relatively uniform state. Furthermore, polymers of compounds having two or more radically polymerizable groups and polymers of compounds having polar groups such as hydroxy groups, alkyleneoxy groups, amide groups, and cyano groups are less likely to dissolve in organic solvents, etc., and it is presumed that the chemical resistance of the resulting cured film is greatly improved when such polymers are present in a relatively uniform state in the film.

[0014] Furthermore, since compound A does not have an axis of symmetry, aggregation is suppressed as described above, and it is thought that the solubility in a developer of the unexposed areas of the film is improved, resulting in excellent developability. Furthermore, since aggregation of compound A is suppressed as described above, it is presumed that, for example, inhibition of ring closure of a precursor of a cyclized resin by a polymer of the aggregated polymerizable compound is suppressed, and the resulting cured film also has excellent elongation at break.

[0015] Here, Patent Documents 1 and 2 do not describe the use of Compound A.

[0016] The components contained in the resin composition of the present invention will be described in detail below.

[0017] <Specific resin> The resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof. The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure. In the present invention, the main chain refers to the relatively longest connecting chain in the resin molecule. Examples of the cyclized resin include polyimide, polybenzoxazole, and polyamideimide. The precursor of a cyclized resin refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a cyclized resin. A resin that undergoes a change in chemical structure due to heat to become a cyclized resin is preferred, and a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a cyclized resin is more preferred. Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor. That is, 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 a polyimide or a polyimide precursor as the specific resin. The specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group. When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical crosslinking agent described below. If necessary, the resin composition of the present invention may further contain a sensitizer described below. For example, a negative-tone photosensitive film can be formed from the resin composition of the present invention. When the specific resin has a polymerizable group, it is also preferable that the resin has a molecular chain containing the polymerizable group and a urea bond. The molecular chain is preferably bonded to the main chain of the resin as a side chain, for example. When the specific resin contains a repeating unit represented by formula (2) described later, the molecular chain may be, for example, R 111 , R 115 , R 113 and R 114 It is preferable that the compound is included in at least one of the above. When the specific resin contains a repeating unit represented by formula (4) described later, the molecular chain may be, for example, R 131 and R 132 It is preferable that the compound is included in at least one of the above. When the specific resin contains a repeating unit represented by formula (3) described later, the molecular chain may be, for example, R 121 , R 122 , R 123 and R 124 It is preferable that the compound is included in at least one of the above. When the specific resin contains a repeating unit represented by formula (X) described later, the molecular chain may be, for example, R 133 and R 134 It is preferable that the compound is included in at least one of the above. When the specific resin contains a repeating unit represented by formula (PAI-2) described later, the molecular chain may be, for example, R 111 , R 117 and R 113 It is preferable that the compound is included in at least one of the above. When the specific resin contains a repeating unit represented by formula (PAI-3) described later, the molecular chain may be, for example, R 111 and R 117 It is preferable that the compound is included in at least one of the above.

[0018] From the viewpoint of chemical resistance, the acid value of the specific resin is preferably 0 mmol / g to 1.2 mmol / g, more preferably 0 mmol / g to 0.8 mmol / g, and even more preferably 0 mmol / g to 0.6 mmol / g. The acid value is measured, for example, by the method described in JIS K 0070:1992.

[0019] [Polyimide precursor] The polyimide precursor used in the present invention is not particularly limited in type, but preferably contains a repeating unit represented by the following formula (2). [ka] In formula (2), A 1 and A 2 each independently represents an oxygen atom or -NH-; R 111 represents a divalent organic group, and R 115 represents a tetravalent organic group, and R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group.

[0020] A in equation (2) 1 and A 2 each independently represents an oxygen atom or —NH—, and preferably an oxygen atom. R in Equation (2) 111 represents a divalent organic group. Examples of the divalent organic group include groups containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group. 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 group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Preferred embodiments of the present invention include groups represented by -Ar- and -Ar-L-Ar-, and particularly preferred is a group represented by -Ar-L-Ar-. wherein each Ar is independently an aromatic group, 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 a combination of two or more of the above. The preferred ranges for these are as described above.

[0021] R 111is preferably derived from a diamine. Examples of diamines used in producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, the diamine preferably contains 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 group consisting of 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 a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Examples of groups containing an aromatic group include the following.

[0022] [ka] In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or a group selected from combinations thereof; more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, or a group selected from -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.

[0023] Specific examples of diamines 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'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 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-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-Bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether fluorene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- or 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine methyldisiloxane, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters 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,At least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 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'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl may be mentioned.

[0024] Additionally, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017 / 038598 are also preferred.

[0025] Also preferably used are diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of WO 2017 / 038598.

[0026] R 111 is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the obtained organic film. Here, each Ar is independently an aromatic group, and L is 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 a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO2-. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

[0027] Also, R 111From the viewpoint of i-line transmittance, is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-line transmittance and ease of availability, it is more preferably a divalent organic group represented by formula (61). Formula (51) [ka] In formula (51), R 50 ~R 57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R 50 ~R 57 At least one of the above is a fluorine atom, a methyl group or a trifluoromethyl group, and each * independently represents a bonding site to the nitrogen atom in formula (2). R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [ka] In formula (61), R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site to 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, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.

[0028] R in Equation (2) 115 represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In formula (5) or formula (6), * each independently represents a bonding site to another structure. [ka] In formula (5), R 112 represents a single bond or a divalent linking group, and is preferably 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-, -NHCO-, or a group selected from combinations thereof; more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO2-; 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-.

[0029] R 115 Specifically, R may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. 115 As a structure corresponding to the above, only one type of tetracarboxylic dianhydride residue may be contained, or two or more types may be contained. The tetracarboxylic dianhydride is preferably represented by the following formula (O). [ka] In formula (O), R 115 represents a tetravalent organic group. 115 The preferred range of R in formula (2) 115 The same applies to the preferred range.

[0030] 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, 2,2 ',3,3'-Diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-C6 alkyl and C1-C6 alkoxy derivatives thereof.

[0031] Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598 are also preferred examples.

[0032] In equation (2), R 111 and R 115At least one of R may have an OH group. 111 Examples of the amino acid residue include residues of bisaminophenol derivatives.

[0033] R in Equation (2) 113 and R 114 Each of R independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. 113 and R 114 Preferably, at least one of R contains a polymerizable group, and more preferably, both of R contain a polymerizable group. 113 and R 114 It is also preferable that at least one of the groups contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and a radically polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radically polymerizable group contained in the polyimide precursor is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.

[0034] [ka]

[0035] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site to another structure. In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkyleneoxy group. Suitable R 201 Examples of the alkylene group include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene; 1,2-butanediyl, 1,3-butanediyl, -CHCH(OH)CH-; and polyalkyleneoxy groups. Of these, alkylene groups such as ethylene and propylene, -CHCH(OH)CH-, cyclohexyl, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups are even more preferred. In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. The alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, and even more preferably 2-6. As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded is preferred, a polyethyleneoxy group or a polypropyleneoxy group is more preferred, and a polyethyleneoxy group is even more preferred. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating. The preferred embodiments of the number of repetitions of the ethyleneoxy groups etc. in these groups are as described above.

[0036] In equation (2), R 113 is a hydrogen atom, or R 114 When 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.

[0037] In equation (2), R 113 and R 114 At least one of the groups may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

[0038] The polyimide precursor also preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0039] To improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as diamines.

[0040] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). When the polyimide precursor contains a repeating unit represented by formula (2-A), it becomes possible to further widen the width of the exposure latitude. Formula (2-A) [ka] In formula (2-A), A 1 and A 2 represents an oxygen atom, and R 111 and R 112 each independently represents a divalent organic group, R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group, R 113 and R 114 At least one of the groups is a group containing a polymerizable group, and it is preferred that both of the groups are groups containing a polymerizable group.

[0041] A 1 , A 2 , R 111 , R 113 and R 114 are each independently A in formula (2). 1 , A 2 , R 111 , R113 and R 114 The same applies to the preferred range. R 112 is R in Equation (5). 112 The same applies to the preferred range.

[0042] The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).

[0043] In one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. The 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 total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminal repeating units may be repeating units represented by formula (2).

[0044] 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 polyimide precursor preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the molecular weight dispersity is a value calculated by weight average molecular weight / number average molecular weight. When the resin composition contains multiple polyimide precursors as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as a single resin are within the above-mentioned ranges.

[0045] [Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide that is soluble in a developer containing an organic solvent as a main component. In this specification, alkali-soluble polyimide refers to a polyimide that dissolves at least 0.1 g in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C. From the viewpoint of pattern formability, a polyimide that dissolves at least 0.5 g is preferred, and a polyimide that dissolves at least 1.0 g is more preferred. The upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less. In addition, from the viewpoint of the film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain. In this specification, the term "main chain" refers to the relatively longest bonded chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to any other bonded chain.

[0046] -Fluorine atom- From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains fluorine atoms. The fluorine atom can be, for example, R 132 or R in the repeating unit represented by formula (4) described below 131 and R in the repeating unit represented by formula (4) described below is preferably included. 132 or R in the repeating unit represented by formula (4) described below 131 It is more preferable that the alkyl group is contained as a fluorinated alkyl group. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and 20% by mass or less.

[0047] -Silicon atom- From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains a silicon atom. The silicon atom is, for example, R in the repeating unit represented by formula (4) described below. 131 and R in the repeating unit represented by formula (4) described below is preferably included. 131 It is more preferable that the organic modified (poly)siloxane structure described below is contained in the above. The silicon atom or the 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.

[0048] -Ethylenically unsaturated bond- From the viewpoint of the film strength of the resulting organic film, the polyimide preferably has an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but preferably in a side chain. The ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is represented by R in the repeating unit represented by formula (4) described below. 132 or R in the repeating unit represented by formula (4) described below 131 and R in the repeating unit represented by formula (4) described below is preferably included. 132 or R in the repeating unit represented by formula (4) described below 131 It is more preferable that the group having an ethylenically unsaturated bond is contained in the formula (I). Among these, the ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described below. 131 and R in the repeating unit represented by formula (4) described below is preferably included.131 It is more preferable that the group having an ethylenically unsaturated bond is contained in the formula (I). Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring, such as a vinyl group, an allyl group, or a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV):

[0049] [ka]

[0050] In formula (IV), R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.

[0051] In formula (IV), R 21 represents an alkylene group having 2 to 12 carbon atoms, -O-CHCH(OH)CH-, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy 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. The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, and alkylene groups represented by a combination thereof. The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0052] Among these, R 21 is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a 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 in which two or more of these are bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R 21 represents the bonding site with the oxygen atom to which it is bonded. In the formulas (R1) to (R3), preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms in L are the same as those of the above-mentioned R 21 The preferred embodiments are the same as those of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms in the above. In formula (R1), X is preferably an oxygen atom. In the formulae (R1) to (R3), * has the same meaning as * in the 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 (for example, 2-isocyanatoethyl methacrylate). 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 (for example, 2-hydroxyethyl methacrylate). 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 (for example, glycidyl methacrylate).

[0053] In formula (IV), * represents a bonding site to another structure, and is preferably a bonding site to the main chain of the polyimide.

[0054] The amount 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.

[0055] -Polymerizable group other than a group having an ethylenically unsaturated bond- The polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond. Examples of polymerizable groups other than the group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group. The polymerizable group other than the group having an ethylenically unsaturated bond is, for example, R in the repeating unit represented by formula (4) described below. 131 It is preferred that the hydroxyl group is included in the formula (I). The amount of polymerizable groups other than groups having ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0056] -Polarity conversion group- The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is represented by R 113 and R 114 The acid-decomposable groups are the same as those described above, and preferred embodiments are also the same. The polarity conversion group is, for example, R in the repeating unit represented by formula (4) described below. 131 , R 132 , contained in the terminals of polyimides, etc.

[0057] -Acid value- When the polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more. The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. Furthermore, when the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g. The acid value is measured by a known method, for example, the method described in JIS K 0070:1992. From the viewpoint of chemical resistance, the acid value of the polyimide is preferably 0 mmol / g to 1.2 mmol / g, more preferably 0 mmol / g to 0.8 mmol / g, and even more preferably 0 mmol / g to 0.6 mmol / g. The acid group contained in the polyimide preferably has a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of achieving both storage stability and developability. pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm, pKa. In this specification, pKa is a value calculated using ACD / ChemSketch (registered trademark) unless otherwise specified. Alternatively, values ​​listed in the "Revised 5th Edition Chemistry Handbook: Basics" edited by the Chemical Society of Japan may be referenced. Furthermore, when the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant. As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.

[0058] -Phenol hydroxy group- From the viewpoint of ensuring an appropriate development rate with an alkaline developer, the polyimide preferably has a phenolic hydroxy group. The polyimide may have a phenolic hydroxy group at the end of the main chain or on a side chain. The phenolic hydroxy group is, for example, R in the repeating unit represented by formula (4) described below. 132 or R in the repeating unit represented by formula (4) described below131 It is preferred that the hydroxyl group is included in the formula (I). The amount of phenolic hydroxy groups relative to the total mass of the polyimide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0059] 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 a repeating unit represented by the following formula (4). [ka] In formula (4), R 131 represents a divalent organic group, and R 132 represents a tetravalent organic group. In the case where the polymerizable group is present, the polymerizable group is R 131 and R 132 or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2). Formula (4-1) [ka] In formula (4-1), R 133 is a polymerizable group, and the other groups have the same meanings as in formula (4). Formula (4-2) [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 has the same meaning as in formula (4).

[0060] Examples of the polymerizable group include the above-mentioned group containing an ethylenically unsaturated bond, and crosslinkable groups other than the above-mentioned group having an ethylenically unsaturated bond. R 131 represents a divalent organic group. The divalent organic group is R in formula (2). 111The same examples are given, and the preferred ranges are also the same. Also, R 131 Examples of the diamine include a diamine residue remaining after removal of the amino group of the diamine. Examples of the diamine include aliphatic, cycloaliphatic, and aromatic diamines. Specific examples include R in the formula (2) of the polyimide precursor. 111 Examples include:

[0061] R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain, in order to more effectively suppress the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue of the above diamine that does not contain an aromatic ring.

[0062] Examples of diamines containing two or more ethylene glycol chains, two or more propylene glycol chains in one molecule include, but are not limited to, JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (all trade names, manufactured by HUNTSMAN Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0063] R 132 represents a tetravalent organic group. The tetravalent organic group is R 115 The same examples are given, and the preferred ranges are also the same. For example, R 115 The four bonds of the tetravalent organic group exemplified by the following are bonded to the four -C(=O)- moieties in the above formula (4) to form a fused ring.

[0064] Also, R 132The R tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride is an example. 115 From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

[0065] R 131 and R 132 It is also preferable that at least one of R 131 Preferred examples of R include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18). 132 As such, the above (DAA-1) to (DAA-5) are more preferred examples.

[0066] The polyimide preferably has fluorine atoms in its structure, and the content of fluorine atoms in the polyimide is preferably 10% by mass or more and 20% by mass or less.

[0067] To improve adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0068] In order to improve the storage stability of the resin composition, it is preferable that the main chain terminals of the polyimide are blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. Among these, it is more preferable to use a monoamine, 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-8-aminonaphthalene. 2-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different terminal groups may be introduced by reacting multiple terminal-capping agents.

[0069] -Imidization rate (ring closure rate)- From the viewpoint of the film strength, insulating properties, etc. of the resulting organic film, the imidization rate (also referred to as the "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less. The imidization rate is measured, for example, by the following method. The infrared absorption spectrum of polyimide was measured, and the absorption peak at 1377 cm due to the imide structure was observed. -1 Next, the polyimide was heat-treated at 350°C for 1 hour, and the infrared absorption spectrum was measured again to determine the peak intensity P1 around 1377cm. -1 The peak intensity P2 around the peak intensity P1 is then measured. The imidization rate of the polyimide can be calculated using the obtained peak intensities P1 and P2 based on the following formula: Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0070] All polyimides are of the same type R 131 or R 132 and may contain a repeating unit represented by the above formula (4) containing two or more different types of R 131 or R 132 The polyimide may contain a repeating unit represented by the above formula (4), which includes: In addition to the repeating unit 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 unit represented by the above formula (2).

[0071] Polyimides can be synthesized by, for example, reacting a tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-capping agent) at low temperature, reacting a tetracarboxylic dianhydride with a diamine (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-capping agent) at low temperature, obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine (partially substituted with a monoamine end-capping agent) in the presence of a condensing agent, or obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then converting the remaining dicarboxylic acid into an acid chloride and reacting it with a diamine (partially substituted with a monoamine end-capping agent), or by completely imidizing the polyimide precursor using a known imidization reaction method, or by terminating the imidization reaction midway to introduce a partial imide structure, or by blending a fully imidized polymer with the polyimide precursor to introduce a partial imide structure. Other known polyimide synthesis methods can also be used.

[0072] 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 fold resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties (for example, breaking elongation), the weight-average molecular weight is particularly preferably 15,000 or more. The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The polyimide preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersity of the polyimide, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When the resin composition contains multiple polyimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyimides as a single resin are each within the above-mentioned ranges.

[0073] [Polybenzoxazole precursor] The polybenzoxazole precursor used in the present invention is not particularly limited with respect to its structure, but preferably contains a repeating unit represented by the following formula (3). [ka] In formula (3), R 121 represents a divalent organic group, and R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represents a hydrogen atom or a monovalent organic group.

[0074] In equation (3), R 123 and R 124 are R in Eq. (2), respectively. 113 In other words, it is preferable that at least one of them is a polymerizable group. In equation (3), R 121 represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. The aliphatic group is preferably a linear aliphatic group. R 121 The dicarboxylic acid residue is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

[0075] As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferred, and a dicarboxylic acid residue containing an aromatic group is more preferred. The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and more preferably a dicarboxylic acid consisting of a linear or branched (preferably linear) aliphatic group and two -COOH groups. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, still more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. Dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetramethylpimelic acid. , suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedicarboxylic acid, heneicosanedicarboxylic acid, docosanedicarboxylic acid, tricosanedicarboxylic acid, tetracosanedicarboxylic acid, pentacosanedicarboxylic acid, hexacosanedicarboxylic acid, heptacosanedicarboxylic acid, octacosanedicarboxylic acid, nonacosanedicarboxylic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and further dicarboxylic acids represented by the following formula:

[0076] [ka] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

[0077] As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids consisting of only a group having an aromatic group and two -COOH groups are more preferred.

[0078] [ka] In the formula, A represents a divalent group selected from the group consisting of -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2-, and -C(CH3)2-, and each * independently represents a bonding site to another structure.

[0079] Specific examples of dicarboxylic acids containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

[0080] In equation (3), R 122 represents a tetravalent organic group. The tetravalent organic group is R 115 The same applies to the preferred range. R 122is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino Examples of suitable bisaminophenols include 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.

[0081] Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferred.

[0082] [ka] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, or -NHCO-, and * and # each represent a bonding site with another structure. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. 122 It is also preferable that R is a structure represented by the above formula. 122is a structure represented by the above formula, any two of the four * and # are R 122 are the bonding sites with the nitrogen atom to which R is bonded, and the other two are R in formula (3) 122 is preferably a bonding site with the oxygen atom to which the two * are bonded, and 122 is the bonding site with the oxygen atom to which it is bonded, and the two #s are R 122 is a bonding site with the nitrogen atom to which the bond is attached, or two * are R 122 is a bonding site with the nitrogen atom to which the bond is made, and two #s are R 122 is more preferably a bonding site with the oxygen atom to which the two * are bonded, and 122 is the bonding site with the oxygen atom to which it is bonded, and the two #s are R 122 is more preferably the bonding site with the nitrogen atom to which is bonded.

[0083] The bisaminophenol derivative is also preferably a compound represented by formula (As). [ka]

[0084] In formula (As), R1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO2-, -CO-, -NHCO-, a single bond, or an organic group selected from the group represented by the following formula (A-sc). R2 is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different. R3 is a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.

[0085] [ka] (In formula (A-sc), * indicates bonding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by formula (As) above.)

[0086] In the above formula (As), having a substituent at the ortho position of the phenolic hydroxy group, i.e., at R3, is thought to bring the distance between the carbonyl carbon of the amide bond and the hydroxy group closer, which is particularly preferred in that it further enhances the effect of achieving a high cyclization rate when cured at low temperatures.

[0087] In addition, in the above formula (As), it is preferable that R2 is an alkyl group and R3 is an alkyl group, since this maintains the effects of high transparency to i-line and a high cyclization rate when cured at low temperature.

[0088] In the formula (As), R1 is more preferably alkylene or substituted alkylene. Specific examples of the alkylene and substituted alkylene groups for R1 include linear or branched alkyl groups having 1 to 8 carbon atoms, of which -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferred in that they can provide a well-balanced polybenzoxazole precursor that has sufficient solubility in solvents while maintaining the effects of high transparency to i-line and a high cyclization rate when cured at low temperature.

[0089] For the production method of the bisaminophenol derivative represented by the above formula (As), reference can be made to, for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP 2013-256506 A, the contents of which are incorporated herein by reference.

[0090] Specific examples of the structure of the bisaminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of JP 2013-256506 A, the contents of which are incorporated herein by reference, but needless to say, are not limited thereto.

[0091] The polybenzoxazole precursor may contain other types of repeating units in addition to the repeating unit of formula (3) above. The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit, in that warping due to ring closure can be suppressed.

[0092] [ka] In formula (SL), Z has an a structure and a b structure, and R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R 2s is a hydrocarbon group having 1 to 10 carbon atoms, and R 3s , R 4s , R 5s , R 6s At least one of them is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, and they may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. The mole percentages of the Z portion are 5 to 95 mole% for the a structure, 95 to 5 mole% for the b structure, and a+b is 100 mole%.

[0093] In formula (SL), preferred Z is R in the b structure. 5s and R 6s is a phenyl group. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, it is possible to more effectively reduce the elastic modulus of the polybenzoxazole precursor after dehydration ring closure, thereby achieving both the effect of suppressing warpage and the effect of improving solvent solubility.

[0094] When the diamine residue represented by formula (SL) is contained as another type of repeating unit, it is also preferable to further contain, as a repeating unit, a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Examples of such a tetracarboxylic acid residue include R 115 Examples include:

[0095] The polybenzoxazole precursor has a weight-average molecular weight (Mw) of, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000, and a number-average molecular weight (Mn) of, for example, preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. The polybenzoxazole precursor preferably has a molecular weight dispersity of 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly limited, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less. When the resin composition contains multiple polybenzoxazole precursors as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polybenzoxazole precursor are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polybenzoxazole precursors as a single resin are within the above-mentioned ranges.

[0096] [Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymeric compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) having a polymerizable group. The polymerizable group is preferably a radically polymerizable group. [ka] In formula (X), R 133 represents a divalent organic group, and R 134 represents a tetravalent organic group. In the case where the polymerizable group is present, the polymerizable group is R 133 and R 134or may be located at the end of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2). Formula (X-1) [ka] In formula (X-1), R 135 and R 136 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 has the same meaning as in formula (X). Formula (X-2) [ka] In formula (X-2), R 137 is a polymerizable group, and the others are substituents, and the other groups have the same meanings as in formula (X).

[0097] The polymerizable group has the same meaning as the polymerizable group described above as the polymerizable group contained in the polyimide precursor.

[0098] R 133 represents a divalent organic group. Examples of the divalent organic group include an aliphatic group and an aromatic group. Specific examples include R in formula (3) of the polybenzoxazole precursor. 121 Examples of the preferred examples include R 121 is the same as:

[0099] R 134 represents a tetravalent organic group. The tetravalent organic group is R in formula (3) of the polybenzoxazole precursor. 122 Examples of the preferred examples include R 122 is the same as: For example, R 122 The four bonds of the tetravalent organic group exemplified by R 134 When is the following organic group, the following structure is formed: In the following structure, * represents the bonding site with the nitrogen atom or oxygen atom in formula (X), respectively. [ka]

[0100] The polybenzoxazole preferably has an oxazolization rate of 85% or more, more preferably 90% or more. The upper limit is not particularly limited and may be 100%. When the oxazolization rate is 85% or more, film shrinkage due to ring closure that occurs when oxazolized by heating is reduced, and warpage can be more effectively suppressed. The oxazole ratio is measured, for example, by the following method. The infrared absorption spectrum of polybenzoxazole was measured, and the absorption peak at 1650 cm was identified, which is derived from the amide structure of the precursor. -1 Next, calculate the peak intensity Q1 around 1490cm -1 The polybenzoxazole was heat-treated at 350°C for 1 hour, and the infrared absorption spectrum was measured again. -1 The peak intensity Q2 near 1490 cm -1 The absorption intensity of the aromatic ring observed near the peak is normalized. The normalized values ​​of the obtained peak intensities Q1 and Q2 can be used to calculate the oxazole ratio of polybenzoxazole based on the following formula: Oxazolization rate (%) = (standard value of peak intensity Q1 / standard value of peak intensity Q2) × 100

[0101] All polybenzoxazoles are of the same type R 131 or R 132 and may contain repeating units of the above formula (X) containing two or more different types of R 131 or R 132 The polybenzoxazole may contain a repeating unit of the above formula (X) including: In addition to the repeating unit of the above formula (X), the polybenzoxazole may also contain other types of repeating units.

[0102] Polybenzoxazole is, for example, a compound obtained by combining a bisaminophenol derivative with R 133or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor, which is then oxazolized using a known oxazolization reaction method. In the case of dicarboxylic acids, in order to increase the reaction yield, etc., it is also possible to use an activated ester type dicarboxylic acid derivative which has been previously reacted with 1-hydroxy-1,2,3-benzotriazole or the like.

[0103] The weight-average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By adjusting the weight-average molecular weight to 5,000 or more, the crease resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or more. Furthermore, when two or more types of polybenzoxazoles are contained, it is preferable that the weight-average molecular weight of at least one type of polybenzoxazole is within the above range. The number average molecular weight (Mn) of the polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. The polybenzoxazole preferably has a molecular weight dispersity of 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole is not particularly limited, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less. When the resin composition contains multiple polybenzoxazoles as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polybenzoxazole are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polybenzoxazoles as a single resin are within the above-mentioned ranges.

[0104] [Polyamide-imide precursor] The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2). [ka] In formula (PAI-2), R 117 represents a trivalent organic group, and R 111 represents a divalent organic group, and A 2 represents an oxygen atom or -NH-, and R 113 represents a hydrogen atom or a monovalent organic group.

[0105] In formula (PAI-2), R 117 is exemplified by a straight-chain or branched-chain aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked together via a single bond or a linking group, and is preferably a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined together via a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined together via a single bond or a linking group. The linking group is preferably -O-, -S-, -C(=O)-, -S(=O)2-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. The halogenated alkylene group may contain hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group. The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0106] Also, R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. The halogenation is preferably chlorination. In the present invention, a compound having three carboxy groups is called a tricarboxylic acid compound. Two of the three carboxy groups of the tricarboxylic acid compound may be converted into acid anhydrides. Examples of the tricarboxylic acid compound which may be halogenated and is used in the production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic, and aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0107] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group, and more preferably a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0108] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked via a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or a phenylene group. These compounds may be compounds in which two carboxy groups are anhydrides (for example, trimellitic anhydride), or may be compounds in which at least one carboxy group is halogenated (for example, trimellitic anhydride chloride).

[0109] In formula (PAI-2), R 111 , A 2 , R 113 are the R in the above formula (2), 111 , A 2 , R 113 The same applies to the preferred embodiments.

[0110] The polyamideimide precursor may further comprise other repeating units. Examples of other repeating units include the repeating unit represented by the above formula (2) and the repeating unit represented by the following formula (PAI-1). [ka]

[0111] In formula (PAI-1), R 116 represents a divalent organic group, and R111 represents a divalent organic group. In formula (PAI-1), R 116 is exemplified by a straight-chain or branched-chain aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked together via a single bond or a linking group, and is preferably a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined together via a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined together via a single bond or a linking group. The linking group is preferably -O-, -S-, -C(=O)-, -S(=O)2-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. The halogenated alkylene group may contain hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group. The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0112] Also, R 116is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present invention, a compound having two carboxy groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound. The carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example, i.e., the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. Examples of the optionally halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic dicarboxylic acid compound or dicarboxylic acid dihalide compound. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

[0113] Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group, and more preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0114] Specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, and hexadecafluoroadipic acid. Examples of the carboxylic acid include fluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedicarboxylic acid, heneicosanedicarboxylic acid, docosanedicarboxylic acid, tricosanedicarboxylic acid, tetracosanedicarboxylic acid, pentacosanedicarboxylic acid, hexacosanedicarboxylic acid, heptacosanedicarboxylic acid, octacosanedicarboxylic acid, nonacosanedicarboxylic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, and benzophenone-4,4'-dicarboxylic acid. Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxy groups in the specific examples of the dicarboxylic acid compound are halogenated.

[0115] In formula (PAI-1), R 111 is R in the above equation (2) 111 The same applies to the preferred embodiments.

[0116] The polyamideimide precursor preferably has fluorine atoms in its structure, and the fluorine atom content in the polyamideimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0117] To improve adhesion to the substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, the polyamide-imide precursor may be copolymerized with bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as a diamine component.

[0118] In one embodiment of the polyamideimide precursor of the present invention, the total content of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2) is 50 mol% or more of all repeating units. This total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular upper limit to this total content, and all repeating units in the polyamideimide precursor excluding the terminal repeating units may be any of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2). Another embodiment of the polyamideimide precursor of the present invention is one in which the total content of repeating units represented by formula (PAI-2) and repeating units represented by formula (PAI-1) is 50 mol% or more of all repeating units. This total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular upper limit to this total content, and all repeating units in the polyamideimide precursor except for the terminal repeating units may be either repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1).

[0119] The polyamideimide precursor has a weight-average molecular weight (Mw) of preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000, and a number-average molecular weight (Mn) of preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The molecular weight dispersity of the polyamideimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. Furthermore, when the resin composition contains multiple polyamideimide precursors as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyamideimide precursor are within the above-mentioned ranges. Furthermore, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyamideimide precursors as a single resin are each within the above-mentioned ranges.

[0120] [Polyamide-imide] The polyamideimide used in the present invention may be an alkali-soluble polyamideimide, or may be a polyamideimide that is soluble in a developer containing an organic solvent as a main component. In this specification, alkali-soluble polyamideimide refers to a polyamideimide that dissolves 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C. From the viewpoint of pattern formability, a polyamideimide that dissolves 0.5 g or more is preferred, and a polyamideimide that dissolves 1.0 g or more is more preferred. There is no particular upper limit to the amount of dissolution, 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 polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain.

[0121] -Fluorine atom- From the viewpoint of the film strength of the resulting organic film, the polyamideimide preferably contains a fluorine atom. The fluorine atom can be, for example, R 117 , or R 111 and R in the repeating unit represented by formula (PAI-3) described below is preferably included.117 , or R 111 It is more preferable that the alkyl group is contained as a fluorinated alkyl group. The amount of fluorine atoms relative to the total mass of the polyamideimide is preferably 5% by mass or more and 20% by mass or less.

[0122] -Ethylenically unsaturated bond- From the viewpoint of the film strength of the resulting organic film, the polyamideimide may have an ethylenically unsaturated bond. The polyamideimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but preferably in a side chain. The ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is represented by R in the repeating unit represented by formula (PAI-3) described later. 117 , or R 111 and R in the repeating unit represented by formula (PAI-3) described below is preferably included. 117 , or R 111 It is more preferable that the group having an ethylenically unsaturated bond is contained in the formula (I). Preferred embodiments of the group having an ethylenically unsaturated bond are the same as the preferred embodiments of the group having an ethylenically unsaturated bond in the polyimide described above.

[0123] The amount of ethylenically unsaturated bonds relative to the total mass of the polyamideimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0124] -Polymerizable group other than ethylenically unsaturated bond- The polyamideimide may have a polymerizable group other than an ethylenically unsaturated bond. Examples of the polymerizable group other than the ethylenically unsaturated bond in the polyamideimide include the same groups as the polymerizable group other than the ethylenically unsaturated bond in the polyimide described above. The polymerizable group other than the ethylenically unsaturated bond is, for example, R in the repeating unit represented by formula (PAI-3) described later.111 It is preferred that the hydroxyl group is included in the formula (I). The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of the polyamideimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.

[0125] -Polarity conversion group- The polyamideimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyamideimide is represented by R 113 and R 114 The acid-decomposable groups are the same as those described above, and preferred embodiments are also the same.

[0126] -Acid value- When the polyamideimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyamideimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more. The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. Furthermore, when the polyamideimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyamideimide is preferably 2 to 35 mgKOH / g, more preferably 3 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g. From the viewpoint of chemical resistance, the acid value of the polyamideimide is preferably 0 mmol / g to 1.2 mmol / g, more preferably 0 mmol / g to 0.8 mmol / g, and even more preferably 0 mmol / g to 0.6 mmol / g. The acid value is measured by a known method, for example, the method described in JIS K 0070:1992. The acid group contained in the polyamideimide may be the same as the acid group in the polyimide described above, and the preferred embodiments are also the same.

[0127] -Phenol hydroxy group- From the viewpoint of ensuring an appropriate development rate with an alkaline developer, the polyamideimide preferably has a phenolic hydroxy group. The polyamideimide may have a phenolic hydroxy group at the end of the main chain or on a side chain. The phenolic hydroxy group is, for example, R 117 , or R 111 It is preferred that the hydroxyl group is included in the formula (I). The amount of phenolic hydroxy groups relative to the total mass of the polyamideimide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0128] The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it is preferable that it contains a repeating unit represented by the following formula (PAI-3). [ka] In formula (PAI-3), R 111 and R 117 are R in formula (PAI-2), respectively. 111 and R 117 The same applies to the preferred embodiments. In the case where the polymerizable group is present, the polymerizable group is R 111 and R 117 or may be located at the end of the polyamideimide.

[0129] In order to improve the storage stability of the resin composition, it is preferable to cap the main chain ends of the polyamideimide with a terminal capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactive ester compound, etc. Preferred embodiments of the terminal capping agent are the same as those of the terminal capping agent for the polyimide described above.

[0130] -Imidization rate (ring closure rate)- The imidization rate (also called "ring closure rate") of polyamideimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less. The imidization rate is measured in the same manner as the ring closure rate of the polyimide.

[0131] All polyamide-imides are of the same type R 111 or R 117 and may contain a repeating unit represented by the above formula (PAI-3) containing two or more different types of R 131 or R 132 The polyamideimide may contain a repeating unit represented by the above formula (PAI-3), which includes: In addition to the repeating unit represented by the above formula (PAI-3), the polyamideimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0132] Polyamideimide can be synthesized, for example, by obtaining a polyamideimide precursor by a known method and completely imidizing it using a known imidization reaction method, or by terminating the imidization reaction midway and introducing a partial imide structure, or by blending a completely imidized polymer with the polyamideimide precursor to introduce a partial imide structure.

[0133] The weight-average molecular weight (Mw) of the polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By making the weight-average molecular weight 5,000 or more, the fold resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or more. The number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polyamideimide preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersity of the polyamideimide, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When the resin composition contains multiple polyamideimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamideimide are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyamideimides as a single resin are each within the above-mentioned ranges.

[0134] [Method for producing polyimide precursors, etc.] The polyimide precursor or the like can be obtained by, for example, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and then esterifying the polyamic acid using a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting the diester with a diamine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine, etc. Among the above production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine is more preferred. Examples of the condensing agent 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 agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the method for producing a polyimide precursor, etc., it is preferable to use an organic solvent during the reaction. The organic solvent may be one kind or two or more kinds. The organic solvent can be appropriately determined depending on the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing a polyimide precursor, etc., 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 selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0135] -End-capping agent- In the production method of a polyimide precursor or the like, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like to further improve storage stability. When capping the carboxylic acid anhydride or acid anhydride derivative remaining at the resin terminal, examples of end-capping agents include monoalcohols, phenols, thiols, thiophenols, and monoamines. From the perspective of reactivity and film stability, it is more preferable to use monoalcohols, phenols, or monoamines. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecynol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.Furthermore, preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end-capping agents. Furthermore, when capping the amino group at the resin terminal, it is possible to cap it with a compound having a functional group capable of reacting with the amino group. Preferred capping agents for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, etc., and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides. Preferred carboxylic acid anhydride compounds include acetic anhydride, propionic acid anhydride, oxalic acid anhydride, succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, benzoic acid anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride. Preferred examples of carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.

[0136] -Solid precipitation- The method for producing a polyimide precursor or the like may include a step of precipitating a solid. Specifically, after filtering out water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution as needed, the resulting polymer component is added to a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof to precipitate the polymer component as a solid, which is then dried to obtain a polyimide precursor or the like. To improve the degree of purification, the polyimide precursor or the like may be repeatedly subjected to operations such as redissolution, reprecipitation, and drying. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.

[0137] [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. 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 two or more specific resins are contained, the total amount is preferably within the above range.

[0138] The resin composition of the present invention also preferably contains at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more types of the specific resin and the other resins described below, or may contain two or more types of specific resins, but it is preferable that the resin composition contains two or more types of specific resins. When the resin composition of the present invention contains two or more specific resins, for example, a polyimide precursor having a structure derived from a dianhydride (R 115 ) preferably contains two or more kinds of polyimide precursors with different

[0139] <Other resins> The resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as "another resin"). Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described later, a polymerizable compound having a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, a polymerizable compound having a molar content of 1×10 per 1 g of resin) may be used. -3 By adding a (meth)acrylic resin (having a molecular weight of 1000 to 1000 mol / g or more) to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0140] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, still more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to 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. In addition, a preferred embodiment of the resin composition of the present invention may be an embodiment in which the content of the other resin is low. In this embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, still 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 content is not particularly limited, and may be 0% by mass or more. The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0141] <Compound A> The resin composition of the present invention contains, as a radically polymerizable compound, a compound A having a urea bond and no axis of symmetry, and the compound A satisfies at least one of the following conditions 1 and 2. Condition 1: Compound A has two or more radically polymerizable groups. Condition 2: Compound A has at least one of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group.

[0142] [Axis of symmetry] Compound A is a compound with a structure that does not have an axis of symmetry. "Compound A does not have an axis of symmetry" means that the compound is asymmetric and does not have an axis that would produce a molecule identical to the original molecule when the entire compound is rotated. Also, "Compound A does not have an axis of symmetry" means that when the structural formula of compound A is written on paper, the structural formula of compound A cannot be written in a form that has an axis of symmetry. It is believed that the absence of an axis of symmetry in compound A prevents aggregation of compounds A within the composition film.

[0143] [Urea bond] The urea bond in compound A is -NR N -C(=O)-NR N - refers to a bond represented by R N each independently represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group, or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. Compound A may contain two or more urea bonds, but an embodiment containing only one urea bond is also one of the preferred embodiments of the present invention.

[0144] [Radical polymerizable group] Compound A has a radical polymerizable group. The radical polymerizable group is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring, such as a vinyl group, an allyl group, or a vinylphenyl group, a maleimide group, a (meth)acrylamide group, or a (meth)acryloyloxy group, with a (meth)acryloyloxy group being preferred. When the above-mentioned condition 1 is satisfied, compound A has two or more radical polymerizable groups. In this case, the two or more radical polymerizable groups may have the same structure or different structures. In addition, an embodiment in which all of the radical polymerizable groups contained in compound A have the same structure is also one of the preferred embodiments of the present invention. In condition 1, the number of radically polymerizable groups is preferably 2 to 10, more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2. When the above-mentioned condition 2 is satisfied, compound A contains a radical polymerizable group and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group. In condition 2, the number of radical polymerizable groups contained in compound A may be 1 or more, and is preferably 1 to 10, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 1 or 2.

[0145] From the viewpoint of chemical resistance, when compound A has two or more radical polymerizable groups, one preferred embodiment of the present invention is one in which compound A has a structure in which at least one of the two or more radical polymerizable groups and at least another of the two or more radical polymerizable groups are linked by a linking group containing a urea bond (hereinafter also referred to as "linking group L"). The linking group L may be any group as long as it contains a urea bond, but it is also preferred that the linking group L is a group containing a urea bond and a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N It is preferable that the structure is a structure in which at least two selected from the group consisting of R N is as described above. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof. The saturated aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and even more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring structure. Among these, it is preferable that both ends of the urea bond are directly bonded to carbon atoms, more preferably that both ends of the urea bond are directly bonded to a hydrocarbon group, more preferably that one of the ends of the urea bond is directly bonded to an aromatic hydrocarbon group and the other is directly bonded to a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof, and even more preferably that one of the ends of the urea bond is directly bonded to an aromatic hydrocarbon group and the other is directly bonded to a saturated aliphatic hydrocarbon group. The preferred number of carbon atoms in the saturated aliphatic hydrocarbon group or the aromatic hydrocarbon group is as described above.

[0146] Specific examples of the linking group L are given below, but the present invention is not limited thereto. In the following specific examples, * and # each represent a bonding site with the radical polymerizable group. [ka] [ka]

[0147] [Hydroxy group, alkyleneoxy group, amide group, or cyano group] When the above-mentioned condition 2 is satisfied, the compound A has at least one group selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group. From the viewpoint of the chemical resistance of the resulting cured film, the hydroxy group may be either an alcoholic hydroxy group or a phenolic hydroxy group, but is preferably an alcoholic hydroxy group. From the viewpoint of the chemical resistance of the resulting cured film, the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, still more preferably an alkyleneoxy group having 2 to 4 carbon atoms, still more preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. The alkyleneoxy group may be contained as a polyalkyleneoxy group in the compound A. In this case, the number of repeating units of the alkyleneoxy group is preferably 2 to 10, and more preferably 2 to 6. The amide group is -C(=O)-NR N - refers to a bond represented by R N When compound A has an amide group, compound A may be, for example, RC(═O)—NR N A group represented by -* or *-C(=O)-NR N The compound A may contain, in the molecule, two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (when a polyalkyleneoxy group is formed, the group is a polyalkyleneoxy group), an amide group, and a cyano group. However, an embodiment in which the compound A contains only one structure in the molecule is also one of the preferred embodiments of the present invention. The hydroxy group, alkyleneoxy group, amide group, and cyano group may be present at any position in compound A. However, from the viewpoint of chemical resistance, when the above-mentioned condition 2 is satisfied, compound A has at least one selected from the group consisting of the hydroxy group, alkyleneoxy group, amide group, and cyano group linked to at least one radically polymerizable group contained in compound A via a linking group containing a urea bond (hereinafter also referred to as "linking group L2-1"). This is also a preferred embodiment of the present invention. In particular, when compound A contains only one radically polymerizable group, it is preferable that the radically polymerizable group contained in compound A and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group are linked via a linking group containing a urea bond (hereinafter also referred to as "linking group L2-2"). When compound A contains an alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2, the structure bonded to the side of the alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. Preferred embodiments of the hydrocarbon group are the same as the preferred embodiments of the hydrocarbon group in the linking group L described above. Furthermore, preferred embodiments of the radically polymerizable group are the same as the preferred embodiments of the radically polymerizable group in compound A described above. When compound A contains an amide group and has the linking group L2-1 or L2-2, the structure bonded to the side of the amide group opposite to the linking group L2-1 or L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. Preferred embodiments of the hydrocarbon group are the same as the preferred embodiments of the hydrocarbon group in the linking group L described above. Preferred embodiments of the radically polymerizable group are the same as the preferred embodiments of the radically polymerizable group in compound A described above. In the above embodiments, the carbon atom side of the amide group may be bonded to the linking group L2-1 or L2-2, or the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or L2-2. Specific examples of the linking group L2-1 or L2-2 include the same groups as the above-mentioned linking group L. However, * represents a bonding site with the radical polymerizable group, and when the structures shown as specific examples do not contain an alkyleneoxy group, # represents a bonding site with a structure containing at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group, and when the structures shown as specific examples contain an alkyleneoxy group, # represents a structure containing at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group, or a bonding site with the radical polymerizable group.

[0148] [Aromatic group] From the viewpoint of compatibility with the specific resin, the compound A preferably contains an aromatic group. The aromatic group is preferably directly bonded to a urea bond contained in compound A. When compound A contains two or more urea bonds, one of the urea bonds is preferably directly bonded to the aromatic group. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring structure. The aromatic heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocyclic ring in such an aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. These rings may be further condensed with other rings, such as indole and benzimidazole. The heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The aromatic group is preferably contained in, for example, the above-mentioned linking group L or a linking group that links at least one selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, amide group, and cyano group to at least one radically polymerizable group contained in compound A.

[0149] [Number of atoms between the urea bond and the radical polymerizable group (linking chain length)] The number of atoms (linking chain length) between the urea bond and the radical polymerizable group in compound A is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10. When compound A contains two or more urea bonds, when it contains two or more radically polymerizable groups, or when it contains two or more urea bonds and two or more radically polymerizable groups, the minimum number of atoms (linking chain length) between the urea bond and the radically polymerizable group may be within the above range. In this specification, the "number of atoms (linking chain length) between the urea bond and the polymerizable group" refers to the atomic chain on the path connecting the two atoms or atomic groups to be linked that connects these objects with the shortest length (minimum number of atoms). For example, in the structure represented by the following formula, the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2. [ka]

[0150] [Formula (1-1) or Formula (1-2)] Compound A is preferably a compound represented by the following formula (1-1) or formula (1-2). [ka] In formula (1-1), R P1 and R P2 each independently represents a group containing at least one radically polymerizable group; In formula (1-2), R P1 represents a group containing at least one radically polymerizable group, and L 3 represents a divalent linking group.

[0151] In formula (1-1), R P1 and R P2 The number of radical polymerizable groups in each of the formulas is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. R P1 and R P2 The preferred embodiments of the radical polymerizable group in are the same as the preferred embodiments of the radical polymerizable group in compound A described above.

[0152] R P1and R P2 are each independently a group represented by the following formula (RP-1): [ka] In formula (RP-1), L RP1 represents a single bond or an (m+1)-valent linking group, and X RP1 represents a radical polymerizable group, m represents an integer of 1 or more, and * represents the bonding site with the urea bond in formula (1-1).

[0153] In formula (RP-1), L RP1 is a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group in which two or more of these are bonded is preferred, and a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O)2-, or -NR N A group bonded to at least one group selected from the group consisting of R N is as described above. Also, L RP1 In the above formula, the structure adjacent to *, which is the bonding site with the urea bond, is preferably a hydrocarbon group. The above L RP1 The hydrocarbon group in is preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof, more preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group represented by a combination thereof, and even more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a group in which two or more hydrogen atoms have been removed from a benzene ring, or a group represented by a bond thereof. Among these, L RP1 When m is a divalent linking group (m=1), L RP1 is preferably an alkylene group, an arylene group, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbamate group, or a group formed by combining two or more of these. The alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. The arylene group is preferably an aromatic hydrocarbon group. The arylene group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably a phenylene group. The alkylene group contained in the alkyleneoxy group, alkyleneoxycarbonyl group, or alkylenecarbamate group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms.

[0154] In formula (RP-1), X RP1 The preferred embodiments of are the same as the preferred embodiments of the radical polymerizable group in compound A described above.

[0155] In formula (RP-1), m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably 1 or 2, and particularly preferably 1.

[0156] In formula (1-2), R P1 A preferred embodiment of the formula (1-1) is P1 This is the same as the preferred embodiment of the above. In formula (1-2), L 3 A preferred embodiment of the formula (RP-1) is RP1 is a divalent linking group (m=1).

[0157] [Molecular weight] The molecular weight of compound A is preferably 100 to 2,000, more preferably 150 to 1500, and even more preferably 200 to 900.

[0158] Specific examples of compound A include, but are not limited to, the following compounds: In the specific examples below, the subscripts in parentheses indicate the number of repetitions. [ka] [ka]

[0159] The content of compound A relative to the total solid content of the resin composition of the present invention is preferably 1 to 40% by mass. The lower limit is more preferably 2% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less, even more preferably 20% by mass or less. One compound A may be used alone, or two or more compounds may be used in combination. When two or more compounds are used in combination, the total amount thereof is preferably within the above range.

[0160] <Other polymerizable compounds> The resin composition of the present invention preferably further contains a polymerizable compound different from the above-mentioned compound A (hereinafter also referred to as "another polymerizable compound"). In particular, it is preferable that the radical polymerizable compound further contains a compound different from the compound A (a radical crosslinking agent, which will be described later). The other polymerizable compounds are compounds having a polymerizable group and do not fall under the category of compound A described above. Specifically, the other polymerizable compounds include compounds having a radical polymerizable group but no urea bond, compounds having a radical polymerizable group and a urea bond but having an axis of symmetry, and compounds having one radical polymerizable group and a urea bond but no hydroxy group, alkyleneoxy group, amide group, or cyano group. The other polymerizable compound may be a radical crosslinking agent or another crosslinking agent, and preferably contains a radical crosslinking agent.

[0161] [Radical crosslinking agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group. Among these, the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

[0162] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds, and may also have three or more ethylenically unsaturated bonds. The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds. In addition, 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 the compound having three or more ethylenically unsaturated bonds.

[0163] 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.

[0164] 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.), their esters, and amides. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, amino group, or sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogeno group or a tosyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a compound group in which the above-mentioned unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, etc. For specific examples, see paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0165] Furthermore, the radical crosslinking agent is preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, trimethylolethane, and many other compounds. Examples of suitable compounds include compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylating the resulting compound, urethane (meth)acrylates as described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates as described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, and polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. Compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also suitable. Further examples include polyfunctional (meth)acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate.

[0166] In addition, as preferred radical crosslinking agents other than those described above, compounds having a fluorene ring and two or more groups having an ethylenically unsaturated bond, as described in JP-A No. 2010-160418, JP-A No. 2010-129825, Japanese Patent No. 4364216, etc., and cardo resins can also be used.

[0167] Other examples include the specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, and the vinylphosphonic acid compounds described in Japanese Patent Laid-Open No. 02-025493. Compounds containing perfluoroalkyl groups described in Japanese Patent Laid-Open No. 61-022048 can also be used. Furthermore, compounds introduced as photopolymerizable monomers and oligomers in the Journal of the Japan Adhesion Association, Vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0168] In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP 2015-034964 A and the compounds described in paragraphs 0087 to 0131 of WO 2015 / 199219 A can also be preferably used, the contents of which are incorporated herein by reference.

[0169] In addition, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the resulting compound, which are described in JP-A-10-062986 as formula (1) and formula (2) together with specific examples thereof, can also be used as radical crosslinking agents.

[0170] Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as radical crosslinking agents, the contents of which are incorporated herein by reference.

[0171] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), and dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), as well as compounds in which the (meth)acryloyl groups are bonded via an ethylene glycol residue or a propylene glycol residue. Oligomers of these compounds can also be used.

[0172] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer Corporation; SR-209, 231, and 239, difunctional methacrylates having four ethyleneoxy chains, manufactured by Sartomer Corporation; DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, TPA-330, a trifunctional acrylate having three isobutyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd.; and urethane Examples of such oligomers include Oligomer UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corporation).

[0173] Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418. Furthermore, compounds having an amino structure or a sulfide structure in the molecule, such as those described in JP-A No. 63-277653, JP-A No. 63-260909, and JP-A No. 01-105238, can also be used as radical crosslinking agents.

[0174] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is provided by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound. Particularly preferred is a radical crosslinking agent in which an acid group is provided by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers such as M-510 and M-520 manufactured by Toagosei Co., Ltd.

[0175] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. When the acid value of the radical crosslinking agent is within the above range, the agent has excellent handleability in production and developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0176] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a difunctional methacrylate or acrylate for 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, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 for the polyethylene glycol chain. In the resin composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the pattern (cured product). Examples of the monofunctional radical crosslinking agent include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. To suppress volatilization before exposure, compounds having a boiling point of 100°C or higher at normal pressure are also preferred as the monofunctional radical crosslinking agent. Other examples of the bifunctional or higher functional radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0177] When a radical crosslinking agent is contained, its content is preferably more than 0% by mass and not more than 60% by mass, based on 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.

[0178] The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount thereof is preferably within the above range.

[0179] [Other crosslinking agents] The resin composition of the present invention preferably contains a crosslinking agent other than the above-mentioned radical crosslinking agent. In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that, upon exposure to light such as a photoacid generator or a photobase generator, promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof, and is preferably a compound having, in its molecule, a plurality of groups that, upon the action of an acid or a base, promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof. The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step. As the other crosslinking agent, a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an alkoxymethyl group is preferred, and a compound having a structure in which at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferred. Other crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and an alcohol, and the hydrogen atom of the amino group is substituted with an acyloxymethyl group, a methylol group, or an alkoxymethyl group.The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compound produced by the above method may be used.In addition, oligomers formed by self-condensation of the methylol groups of these compounds may also be used. As the amino group-containing compound, a crosslinking agent using melamine is called a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. Among 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 glycoluril-based crosslinking agents and melamine-based crosslinking agents, which will be described later.

[0180] Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the following urea structure, or on a triazine. The alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups contained in the compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the compound is preferably 1,500 or less, and more preferably 180 to 1,200.

[0181] [ka]

[0182] R 100 represents an alkyl group or an acyl group. R 101 and R 102 each independently represents a monovalent organic group, and may be bonded to each other to form a ring.

[0183] Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula:

[0184] [ka]

[0185] 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, and R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes under the action of an acid to generate an alkali-soluble group (for example, a group that is eliminated by the action of an acid, -C(R4 )2COOR 5 A group represented by (R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that is eliminated by the action of an acid. R 105 each independently represents an alkyl group or an alkenyl group, a, b, and c each independently represent 1 to 3, d represents 0 to 4, e represents 0 to 3, f represents 0 to 3, a+d represents 5 or less, b+e represents 4 or less, and c+f represents 4 or less. A group that decomposes under the action of an acid to generate an alkali-soluble group, a group that is eliminated under the action of an 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 ) etc. In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 may be bonded to each other to form a ring. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may be either linear or branched. The 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 cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. The 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 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 the preferred embodiments of the alkyl and aryl groups described above. The 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. These groups may further have known substituents within the range in which the effects of the present invention can be obtained.

[0186] R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0187] The group that decomposes under the action of an acid to generate an alkali-soluble group or the group that is eliminated under the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. More preferably, it is a tertiary alkyl ester group or an acetal group.

[0188] Specific examples of compounds having an alkoxymethyl group include the following structures: Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group in the following compounds is replaced with an acyloxymethyl group: Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds:

[0189] [ka]

[0190] [ka]

[0191] The compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be commercially available or may be synthesized by a known method. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

[0192] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0193] Specific examples of the urea-based crosslinking agent include glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril; urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; ethyleneurea-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.

[0194] Specific examples of benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0195] In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferably 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''-ethylidenetris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], and 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol.

[0196] As other crosslinking agents, commercially available products may be used, and suitable commercially available products include 46DMOC, 46DMOEP (all 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. , 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.), Nikalac (registered trademark, the same applies hereinafter) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), and the like.

[0197] The resin composition of the present invention also preferably contains, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0198] -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 200°C or less, and since dehydration reactions resulting from crosslinking do not occur, film shrinkage is unlikely to occur. Therefore, the inclusion of an epoxy compound is effective in low-temperature curing of the resin composition of the present invention and suppressing warpage.

[0199] The epoxy compound preferably contains a polyethylene oxide group, which further reduces the elastic modulus and suppresses warpage. The polyethylene oxide group refers to a group having 2 or more repeating ethylene oxide units, and preferably has 2 to 15 repeating units.

[0200] 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, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-830LVP, Epicron (registered trademark) EXA-8183, Epicron (registered trademark) EXA-8169, Epicron (registered trademark) N- 660, Epicron (registered trademark) N-665-EXP-S, Epicron (registered trademark) N-740 (all trade names, manufactured by DIC Corporation), Likaresin (registered trademark) BEO-20E, Likaresin (registered trademark) BEO-60E, Likaresin (registered trademark) HBE-100, Likaresin (registered trademark) DME-100, Likaresin (registered trademark) L-200 (trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088 S, EP-3950S (all trade names, manufactured by ADEKA Corporation), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (all trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-300 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, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds are also preferably used.

[0201] [ka]

[0202] In the formula, n is an integer of 1 to 5, and m is an integer of 1 to 20.

[0203] Among the above structures, n is preferably 1 to 2 and m is preferably 3 to 7 in order to achieve both improved heat resistance and improved elongation.

[0204] -Oxetane compounds (compounds containing an oxetanyl group)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, such as 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 that can be suitably used include the Aron Oxetane series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd., and these may be used alone or in combination of two or more.

[0205] -Benzoxazine compounds (compounds having a benzoxazolyl group)- Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that no degassing occurs during curing, and furthermore, they reduce thermal shrinkage and suppress the occurrence of warping.

[0206] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds, which may be used alone or in combination of two or more.

[0207] The content of the other crosslinking agent is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, even more preferably 0.5 to 15 mass %, and particularly preferably 1.0 to 10 mass %, based on the total solid content of the resin composition of the present invention. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total content thereof is preferably within the above range.

[0208] [Polymerization initiator] The resin composition of the present invention contains a radical polymerization initiator. The radical polymerization initiator is preferably a radical polymerization initiator that can initiate polymerization by light and / or heat. In particular, it is preferable to contain a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and 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 reacts with a photoexcited sensitizer to generate active radicals.

[0209] The photoradical polymerization initiator has a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm) and a concentration of at least about 50 L·mol -1 ·cm -1 Preferably, the composition contains at least one compound having a molar absorption coefficient of 0.01 g / L. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0210] Any known photoradical polymerization initiator can be used. 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, hexaarylbiimidazoles, oxime compounds such as 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, organic boron compounds, and iron arene complexes. For details, see paragraphs

[0165] to

[0182] of JP 2016-027357 A and paragraphs

[0138] to

[0151] of WO 2015 / 199219 A, the contents of which are incorporated herein by reference. Further, paragraphs 0065 to 0111 of JP 2014-130173 A, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol.19, No.3,2019 described peroxide-based photopolymerization initiators, photopolymerization initiators described in WO 2018 / 221177, photopolymerization initiators described in WO 2018 / 110179, photopolymerization initiators described in JP 2019-043864 A, photopolymerization initiators described in JP 2019-044030 A, peroxide-based initiators described in JP 2019-167313 A are mentioned, the contents of which are also incorporated herein.

[0211] Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0212] In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, or an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 or an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

[0213] Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, and 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).

[0214] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF).

[0215] As the aminoacetophenone initiator, compounds described in JP-A-2009-191179, whose maximum absorption wavelength matches a wavelength light source such as 365 nm or 405 nm, can also be used, the contents of which are incorporated herein by reference.

[0216] Examples of acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. Also usable are Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, and IRGACURE-TPO (trade names: all manufactured by BASF).

[0217] Examples of metallocene compounds include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0218] As the photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. An oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0219] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232) compounds described in, compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017 / 164127, compounds described in WO 2013 / 167515, and the like, the contents of which are incorporated herein by reference.

[0220] Preferred oxime compounds include, for example, compounds having the following structure: 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. Oxime-based photoradical polymerization initiators have a linking group of >C=NOC(=O)- within the molecule.

[0221] [ka]

[0222] Commercially available products such as IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF) and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A) are also suitable. TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation) can also be used. DFI-091 (manufactured by Daito ChemiX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can also be used. Oxime compounds having the following structure can also be used. [ka]

[0223] As the photoradical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP 2014-137466 A and Japanese Patent No. 6636081 A, the contents of which are incorporated herein by reference.

[0224] As the photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in WO 2013 / 083505, the contents of which are incorporated herein by reference.

[0225] It is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include the compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and compound (C-3) described in paragraph 0101 of JP 2013-164471 A, the contents of which are incorporated herein by reference.

[0226] As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012 and 0070 to 0079 of JP 2014-137466 A, and the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 A, the contents of which are incorporated herein by reference. Another example of the oxime compound having a nitro group is ADEKA ARCLES NCI-831 (manufactured by ADEKA Corporation).

[0227] The photoradical polymerization initiator may also be an oxime compound having a benzofuran skeleton, specific examples of which include OE-01 to OE-75 described in WO 2015 / 036910.

[0228] The photo-radical polymerization initiator may be an oxime compound having a carbazole skeleton to which a hydroxyl-containing substituent is bonded. Examples of such photo-polymerization initiators include compounds described in WO 2019 / 088055, the contents of which are incorporated herein by reference.

[0229] As a photopolymerization initiator, an aromatic ring group Ar in which an electron-withdrawing group is introduced into the aromatic ring is used. OX1 It is also possible to use an oxime compound having the aromatic ring group Ar OX1 Examples of the electron-withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. Acyl and nitro groups are preferred, and an acyl group is more preferred because it is easier to form a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group. An alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group is more preferred, and an alkoxy group, an alkylsulfanyl group, or an amino group is even more preferred.

[0230] 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 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group, R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group, R X3 ~R X14 each independently represents a hydrogen atom or a substituent. However, R X10 ~R X14 At least one of the groups is an electron-withdrawing group.

[0231] In the above formula, R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 , R X14 is preferably a hydrogen atom.

[0232] Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.

[0233] Most preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP-A-2007-269779 and oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, the contents of which are incorporated herein by reference.

[0234] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

[0235] More 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, and at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is even more preferred, and it is even more preferred to use a metallocene compound or an oxime compound.

[0236] In addition, the photoradical polymerization initiator may be benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, quinones fused with an aromatic ring such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzil dimethyl ketal, etc. Compounds represented by the following formula (I) may also be used.

[0237] [ka]

[0238] In formula (I), R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, or a biphenyl group; R I01 is a group represented by formula (II), or R I00 is the same group as R I02 ~R I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0239] [ka]

[0240] In the formula, R I05 ~R I07 is R in the above formula (I). I02 ~R I04 is the same as

[0241] Furthermore, the photoradical polymerization initiator may also be the compounds described in paragraphs 0048 to 0055 of WO 2015 / 125469, the contents of which are incorporated herein by reference.

[0242] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional 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, resulting in good sensitivity. Furthermore, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, thereby improving the stability of the resin composition over time. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, WO-A-2015 / 004565, WO-A-2016-532675, paragraphs 0407 to 0412, and WO-A-2017 / 033680, paragraphs 0039 to 0055; compounds (E) and (G) described in JP-A-2013-522445; Examples of such initiators include Cmpd1 to 7 described in Japanese Patent Application Publication No. 34963, the oxime ester photoinitiators described in paragraph 0007 of JP-T-2017-523465, the photoinitiators described in paragraphs 0020 to 0033 of JP-A-2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, and the oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0243] The content of the radical polymerization initiator is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

[0244] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator or the photoradical polymerization initiator undergoes a chemical change and decomposes, generating a radical, an acid, or a base. Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds. Examples of sensitizers include Michler'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-dimethylaminocinnamylideneindanone, 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 (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isodiethylaminobenzoate amyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, and the like. Other sensitizing dyes may also be used. For details about the sensitizing dye, please refer to the description in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein by reference.

[0245] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0246] [Chain transfer agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of chain transfer agents include compounds having -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can donate hydrogen to low-activity radicals to generate radicals, or can generate radicals by being oxidized and then deprotonated. Thiol compounds are particularly preferred.

[0247] In addition, the chain transfer agent may be a compound described in paragraphs 0152 to 0153 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0248] When 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, relative to 100 parts by mass of the total solid content of the resin composition of the present invention. The chain transfer agent may be one type, or two or more types. When two or more types of chain transfer agents are used, the total amount thereof is preferably within the above range.

[0249] <Base generator> The resin composition of the present invention may contain a base generator. Here, the base generator is a compound that can generate a base by physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators. In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator. By containing the thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in good performance as an interlayer insulating film for a rewiring layer included in, for example, a semiconductor package. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator according to the present invention is not particularly limited, and known base generators can be used. Examples of known base generators that can be used include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of the non-ionic base generator include compounds represented by formula (B1), formula (B2), and formula (B3). [ka]

[0250] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3are each independently an organic group not having a tertiary amine structure, a halogen atom, or a hydrogen atom, provided that Rb 1 and Rb 2 cannot be hydrogen atoms at the same time. 1 , Rb 2 and Rb 3 None of these has a carboxy group. In this specification, the term "tertiary amine structure" refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, this does not apply to cases in which the bonded carbon atom is a carbon atom that forms a carbonyl group, that is, a case in which the bonded carbon atom forms an amide group together with the nitrogen atom.

[0251] In formulas (B1) and (B2), Rb 1 , Rb 2 and Rb 3 Preferably, at least one of these contains a cyclic structure, and more preferably, at least two contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a fused ring, and a monocyclic ring or a fused ring formed by condensing two monocyclic rings is preferred. The monocyclic ring is preferably a 5- or 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably a cyclohexane ring.

[0252] More specifically, Rb 1 and Rb 2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). These groups may have a substituent within the range in which the effects of the present invention are exhibited. Rb 1 and Rb 2 may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. 1 and Rb 2is particularly preferably a linear, branched, or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, more preferably a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, and even more preferably a cyclohexyl group which may have a substituent.

[0253] Rb 3 Examples of the group include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and more preferably having 2 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 12 carbon atoms), an arylalkenyl group (preferably having 8 to 24 carbon atoms, more preferably having 8 to 20 carbon atoms, and more preferably having 8 to 16 carbon atoms), an alkoxyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and more preferably having 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 12 carbon atoms), and an arylalkyloxy group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 12 carbon atoms). Among these, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferred. 3 may further have a substituent within the range in which the effects of the present invention are exhibited.

[0254] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or (B1-2). [ka]

[0255] In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb32 respectively represent Rb in formula (B1). 1 and Rb 2 is the same as Rb 13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and may have a substituent within the range in which the effects of the present invention are exhibited. 13 is preferably an arylalkyl group.

[0256] Rb 33 and Rb 34 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and still more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 8 carbon atoms, and still more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and still more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and still more preferably having 7 to 11 carbon atoms), and a hydrogen atom is preferred.

[0257] Rb 35 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and still more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and still more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and still more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and still more preferably having 7 to 12 carbon atoms), and an aryl group is preferred.

[0258] The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a). [ka]

[0259] Rb 11 and Rb 12 is Rb in formula (B1-1) 11 and Rb 12 is synonymous with. Rb 15 and Rb 16 represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and still more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and still more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and still more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and still more preferably having 7 to 11 carbon atoms), and preferably a hydrogen atom or a methyl group. Rb 17 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and among these, an aryl group is preferred.

[0260] [ka]

[0261] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the linking chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the linking chain is 3 or more. N1 and R N2 each independently represents a monovalent organic group.

[0262] In this specification, the term "linking chain" refers to the chain of atoms on the path connecting two atoms or groups of atoms to be linked, which links these atoms to be linked in the shortest possible manner (with the smallest number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group and has an ethylene group as the saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length" or "length of the linking chain") is 4. [ka]

[0263] The number of carbon atoms in L in formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly progressing the intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds for the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of WO 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of WO 2018 / 038002.

[0264] The base generator also preferably contains a compound represented by the following formula (N1). [ka]

[0265] In formula (N1), R N1 and R N2 each independently represents a monovalent organic group, R C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0266] L is a divalent linking group, and is preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms present in the atomic sequence that forms the shortest path between the two carbonyl groups in the formula.

[0267] In formula (N1), R N1 and R N2 R each independently represents a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), and is preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms). Specific examples include an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), and an aliphatic hydrocarbon group is preferred. N1 and R N2 When an aliphatic hydrocarbon group is used as the base, the basicity of the generated base is high, and this is preferable. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain, in the aromatic ring, or in the substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

[0268] R N1 and R N2Examples of the aliphatic hydrocarbon group constituting the formula (I) include a linear or branched chain alkyl group, a cyclic alkyl group, a group formed by combining a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an isopropyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group. The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The group representing the combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. Examples of the group representing the combination of a chain alkyl group and a cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group. The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. Among these, from the viewpoint of increasing the boiling point of the decomposition product base described later, R N1 and R N2 is preferably an alkyl group having 5 to 12 carbon atoms. However, in a formulation where importance is placed on adhesion when laminating with a metal (for example, copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

[0269] R N1 and R N2may be linked to each other to form a cyclic structure. When forming a cyclic structure, an oxygen atom or the like may be included in the chain. N1 and R N2 The cyclic structure formed by may be a monocyclic ring or a fused ring, but is preferably a monocyclic ring. The cyclic structure formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), such as a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, or a morpholine ring, and is preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, or a morpholine ring.

[0270] R C1 represents a hydrogen atom or a protecting group, and is preferably a hydrogen atom.

[0271] The protecting group is preferably a protecting group that is decomposed by the action of an acid or a base, and a protecting group that is decomposed by an acid is preferred.

[0272] Specific examples of the protecting group include linear or cyclic alkyl groups, and linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a cyclohexyl group. Specific examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and more specific examples include a methyloxymethyl (MOM) group and an ethyloxyethyl (EE) group. Examples of cyclic alkyl groups having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl (THP) group.

[0273] The divalent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent and may have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linking group which may have an oxygen atom in the chain is preferred, and a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a group relating to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group is more preferred, and a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is even more preferred. It is preferable that these groups do not have an oxygen atom. The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. The group (e.g., an arylene alkyl group) formed by combining a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and even more preferably 7 to 10 carbon atoms.

[0274] Specific examples of the linking group L include linear or branched chain alkylene groups, cyclic alkylene groups, groups relating to a combination of a linear alkylene group and a cyclic alkylene group, alkylene groups having an oxygen atom in the chain, linear or branched chain alkenylene groups, cyclic alkenylene groups, arylene groups, and arylene alkylene groups. The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. The group relating to the combination of the chain alkylene group and the cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms. The alkylene group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0275] The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The linear or branched chain alkenylene group preferably has 1 to 10 C=C bonds, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenylene group preferably has 1 to 6 C═C bonds, more preferably 1 to 4, and even more preferably 1 or 2. The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms. Among these, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferred, and a 1,2-ethylene group, a propanediyl group (particularly a 1,3-propanediyl group), a cyclohexanediyl group (particularly a 1,2-cyclohexanediyl group), a vinylene group (particularly a cis-vinylene group), a phenylene group (1,2-phenylene group), a phenylenemethylene group (particularly a 1,2-phenylenemethylene group), and an ethyleneoxyethylene group (particularly a 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.

[0276] Examples of the base generator include the following, but the present invention is not limited thereto.

[0277] [ka]

[0278] 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.

[0279] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0280] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [ka]

[0281] Specific examples of iminium salts include the following compounds, but the present invention is not limited to these. [ka]

[0282] When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the 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, and even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less. The base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

[0283] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0284] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionates, Preferred examples of the alkyl cypropionate include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

[0285] Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0286] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0287] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0288] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0289] Preferred examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0290] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0291] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

[0292] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0293] In the present invention, preferred are solvents selected from the group consisting of 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, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or mixed solvents composed of two or more of these solvents. A combination of dimethyl sulfoxide and γ-butyrolactone, or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0294] From the viewpoint of coatability, the content of the solvent is preferably an amount that makes the total solids concentration of the resin composition of the present invention 5 to 80 mass %, more preferably an amount that makes it 5 to 75 mass %, even more preferably an amount that makes it 10 to 70 mass %, and even more preferably an amount that makes it 20 to 70 mass %. The content of the solvent may be adjusted depending on the desired thickness of the coating film and the coating method.

[0295] The resin composition of the present invention may contain only one solvent or two or more solvents. When two or more solvents are contained, the total amount thereof is preferably within the above range.

[0296] <Metal adhesion improver> The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0297] [Silane coupling agent] Examples of silane coupling agents include compounds described in paragraph 0167 of International Publication No. 2015 / 199219, compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, compounds described in paragraphs 0063 to 0071 of WO 2011 / 080992, compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, compounds described in paragraphs 0045 to 0052 of JP-A-2014-041264, compounds described in paragraph 0055 of WO 2014 / 097594, compounds described in paragraphs 0067 to 0078 of JP-A-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 JP 2011-128358 A. It is also preferable to use the following compound as the silane coupling agent: In the following formula, Me represents a methyl group, and Et represents an ethyl group.

[0298] [ka]

[0299] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples of such silanes include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These silanes can be used alone or in combination of two or more.

[0300] [Aluminum-based adhesion promoter] Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0301] In addition, other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP-A No. 2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A No. 2013-072935, the contents of which are incorporated herein by reference.

[0302] The content of the metal adhesion improver is preferably 0.1 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, relative to 100 parts by mass of the specific resin. By ensuring that the content is equal to or greater than the lower limit, the adhesion between the pattern and the metal layer is improved, and by ensuring that the content is equal to or less than the upper limit, the heat resistance and mechanical properties of the pattern are improved. The metal adhesion improver may be one type, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0303] <Migration inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor, which makes it possible to effectively inhibit metal ions derived from the metal layer (metal wiring) from migrating into the film.

[0304] The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (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, 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, 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 are preferably used.

[0305] Alternatively, an ion trapping agent that traps anions such as halogen ions can also be used.

[0306] Other migration inhibitors include the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compounds described in paragraph 0052 of JP-A-2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, and the compounds described in paragraph 0166 of WO 2015 / 199219. The contents of these compounds are incorporated herein by reference.

[0307] Specific examples of the migration inhibitor include the following compounds.

[0308] [ka]

[0309] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, relative to the total solid content of the resin composition of the present invention.

[0310] The migration inhibitor may be one type only, or two or more types may be used. When two or more types of migration inhibitors are used, the total amount thereof is preferably within the above range.

[0311] <Polymerization inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.

[0312] Specific compounds of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso 1-Naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbonate copper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, and the like are preferably used. Additionally, the polymerization inhibitors described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of WO 2015 / 125469 A can also be used, the contents of which are incorporated herein by reference.

[0313] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass %, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %, relative to the total solid content of the resin composition of the present invention.

[0314] The polymerization inhibitor may be one kind or two or more kinds. When two or more kinds of polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0315] <Other additives> The resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, UV absorbers, organotitanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), as needed, provided that the effects of the present invention are achieved. By appropriately incorporating these components, film properties and other characteristics can be adjusted. For details of these components, please refer to, for example, paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104 and 0107-0109 of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are incorporated, the total amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0316] [Surfactant] As the surfactant, various surfactants can be used, such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0317] By incorporating a surfactant into the resin composition of the present invention, the liquid properties (particularly fluidity) of the coating liquid prepared therefrom are further improved, and the uniformity of the coating thickness and the liquid saving can be further improved. That is, when a film is formed using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and the coatability of the surface to be coated. Therefore, it is possible to more suitably form a film of uniform thickness with little thickness unevenness.

[0318] Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, and RS-72-K (all manufactured by DIC Corporation), Fluorad FC430, FC431, FC171, Novec FC4430, and FC4432 (all manufactured by 3M Corporation). Examples of suitable surfactants include Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, and Surflon KH-40 (all manufactured by Asahi Glass Co., Ltd.), and PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA). The fluorine-based surfactants may also be compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A and compounds described in paragraphs 0117 to 0132 of JP 2011-132503 A, the contents of which are incorporated herein by reference. A block polymer can also be used as the fluorine-based surfactant, and specific examples include compounds described in JP-A-2011-89090, the contents of which are incorporated herein by reference. As the fluorosurfactant, a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used, and the following compounds are also exemplified as the fluorosurfactant used in the present invention. [ka]

[0319] The weight average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. The fluorine-containing surfactant may be a fluorine-containing polymer having an ethylenically unsaturated group in the side chain. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of JP 2010-164965 A, the contents of which are incorporated herein by reference. Commercially available products include Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0320] The fluorine content in the fluorine-containing surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-containing surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and also has good solubility in the composition.

[0321] Examples of silicone surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF6001, and KF6002 (all manufactured by Shin-Etsu Silicones Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK-Chemie Co., Ltd.).

[0322] Examples of hydrocarbon surfactants include Paionin A-76, Newkalgen FS-3PG, Paionin B-709, Paionin B-811-N, Paionin D-1004, Paionin D-3104, Paionin D-3605, Paionin D-6112, Paionin D-2104-D, Paionin D-212, Paionin D-931, Paionin D-941, Paionin D-951, Paionin E-5310, Paionin P-1050-B, Paionin P-1028-P, and Paionin P-4050-T (all manufactured by Takemoto Oil & Fat Co., Ltd.).

[0323] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0324] Specific examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 77, No. 90, and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0325] Specific examples of anionic surfactants include W004, W005, and W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.).

[0326] The surfactant may be used alone or in combination of two or more kinds. The content of the surfactant is preferably from 0.001 to 2.0 mass %, more preferably from 0.005 to 1.0 mass %, based on the total solid content of the composition.

[0327] [Higher fatty acid derivative] In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention, and the higher fatty acid derivative may be unevenly distributed on the surface of the resin composition of the present invention during drying after application.

[0328] In addition, the higher fatty acid derivative may be a compound described in paragraph 0155 of International Publication No. 2015 / 199219, the contents of which are incorporated herein by reference.

[0329] 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 mass% based on the total solid content of the resin composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more types of higher fatty acid derivatives are used, the total content thereof is preferably within the above range.

[0330] [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 by thermal energy and initiates or accelerates the polymerization reaction of a polymerizable compound. Adding a thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance. In addition, the above-mentioned photopolymerization initiator may also have the function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

[0331] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554, the contents of which are incorporated herein by reference.

[0332] When a thermal polymerization initiator is contained, its content is preferably 0.1 to 30 mass % relative to the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass %, and even more preferably 0.5 to 15 mass %. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, the total amount is preferably within the above range.

[0333] [Inorganic particles] The resin composition of the present invention may contain inorganic particles, such as calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0334] The average particle size of the inorganic particles is preferably from 0.01 to 2.0 μm, more preferably from 0.02 to 1.5 μm, even more preferably from 0.03 to 1.0 μm, and particularly preferably from 0.04 to 0.5 μm. The above average particle size of the fine particles is the primary particle size and also the volume average particle size, which can be measured by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurements are difficult, centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction / scattering method can also be used.

[0335] [Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber, such as a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based ultraviolet absorber. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and pt-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of the benzotriazole-based ultraviolet absorber include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0336] Examples of the substituted acrylonitrile ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Further, examples of the triazine-based ultraviolet absorber include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; bis(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-3-methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; and tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine.

[0337] In the present invention, the above-mentioned various ultraviolet absorbents may be used singly or in combination of two or more. The composition of the present invention may or may not contain an ultraviolet absorber. When the composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably from 0.001% by mass to 1% by mass, and more preferably from 0.01% by mass to 0.1% by mass, relative to the total solid mass of the composition of the present invention.

[0338] [Organotitanium Compounds] The resin composition of the present embodiment may contain an organotitanium compound. When the resin composition contains an organotitanium compound, a resin layer having excellent chemical resistance can be formed even when cured at low temperatures.

[0339] Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide resin compositions with good storage stability and a good curing pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), etc. II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc. III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like. IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0340] Among these, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds is preferred as the organic titanium compound from the viewpoint of exhibiting better chemical resistance. Titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are particularly preferred.

[0341] When an organotitanium compound is added, the amount added is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the amount added is 0.05 part by mass or more, the obtained cured pattern more effectively exhibits good heat resistance and chemical resistance, while when the amount is 10 parts by mass or less, the composition has better storage stability.

[0342] [Antioxidants] The composition of the present invention may contain an antioxidant. By including an antioxidant as an additive, the elongation properties of the cured film and adhesion to metal materials can be improved. Examples of antioxidants include phenolic compounds, phosphite ester compounds, and thioether compounds. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Examples of preferred phenolic compounds include hindered phenolic compounds. Compounds having a substituent at the position adjacent to the phenolic hydroxy group (ortho position) are preferred. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. Furthermore, compounds having a phenol group and a phosphite ester group in the same molecule are also preferred. Furthermore, phosphorus-based antioxidants can also be suitably used as the antioxidant. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite. Commercially available antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, and ADK STAB AO-330 (all manufactured by ADEKA Corporation). The antioxidant may also be a compound described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, the contents of which are incorporated herein by reference. The composition of the present invention may also contain a latent antioxidant, if necessary. Examples of latent antioxidants include compounds in which the moiety functioning as an antioxidant is protected with a protecting group, and which function as an antioxidant upon heating at 100 to 250°C or at 80 to 200°C in the presence of an acid / base catalyst, whereby the protecting group is eliminated.Examples of latent antioxidants include compounds described in International Publication Nos. 2014 / 021023, 2017 / 030005, and JP-A-2017-008219, the contents of which are incorporated herein by reference. Commercially available latent antioxidants include ADEKA ARCLES GPA-5001 (manufactured by ADEKA Corporation). Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and the compound represented by formula (3).

[0343] [ka]

[0344] In general formula (3), R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R 6 represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). 7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer of 1 to 4.

[0345] The compound represented by formula (3) inhibits the oxidative degradation of aliphatic groups and phenolic hydroxyl groups in resins, and also inhibits metal oxidation by its rust-preventing effect on metal materials.

[0346] Since it can act simultaneously on resins and metal materials, k is more preferably an integer of 2 to 4. Examples of R7 include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among these, an alkyl ether group or -NH- is preferred from the viewpoints of solubility in a developer and metal adhesion, and -NH- is more preferred from the viewpoints of interaction with resins and metal adhesion due to metal complex formation.

[0347] Examples of the compound represented by general formula (3) include, but are not limited to, the following structures.

[0348] [ka]

[0349] [ka]

[0350] [ka]

[0351] [ka]

[0352] The amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. By adding an amount of 0.1 part by mass or more, it is easy to obtain the effect of improving elongation properties and adhesion to metal materials even in a high-temperature, high-humidity environment, while by adding an amount of 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, by interaction with the photosensitizer. 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 the total amount thereof is within the above range.

[0353] [Anti-aggregating agent] The resin composition of the present embodiment may contain an anti-aggregation agent, if necessary. Examples of the anti-aggregation agent include sodium polyacrylate.

[0354] In the present invention, the anti-aggregating agent may be used alone or in combination of two or more. The composition of the present invention may or may not contain an anti-agglomerating agent. When the composition of the present invention contains an anti-agglomerating agent, the content of the anti-agglomerating agent is preferably from 0.01% by mass to 10% by mass, and more preferably from 0.02% by mass to 5% by mass, relative to the total solid content by mass of the composition of the present invention.

[0355] [Phenol compounds] The resin composition of this embodiment may contain a phenolic compound as needed. Examples of the phenolic compound 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, Methylenetrith-FR-CR, and BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0356] In the present invention, the phenolic compounds may be used singly or in combination of two or more. The composition of the present invention may or may not contain a phenolic compound. When the composition of the present invention contains a phenolic compound, the content of the phenolic compound is preferably from 0.01% by mass to 30% by mass, and more preferably from 0.02% by mass to 20% by mass, relative to the total solid mass of the composition of the present invention.

[0357] [Other polymer compounds] Examples of other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. The other polymer compounds may be modified by introducing crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups.

[0358] In the present invention, the other polymer compounds may be used singly or in combination of two or more. The composition of the present invention may or may not contain other polymer compounds. When the composition of the present invention contains other polymer compounds, 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, relative to the total solid mass of the composition of the present invention.

[0359] <Characteristics of resin composition> The viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content of the resin composition. 2 / s~12,000mm 2 / s is preferred, 2,000 mm 2 / s~10,000mm 2 / s is more preferable, 2,500 mm 2 / s~8,000mm 2 / s is more preferable. Within the above range, it is easy to obtain a highly uniform coating film. 2 / s or more, it is easy to apply it to a thickness required for an insulating film for rewiring, for example, and it is 12,000 mm 2 If the viscosity is less than / s, a coating film with excellent surface condition can be obtained.

[0360] <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 the water content is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.

[0361] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, the total amount of these metals is preferably within the above range.

[0362] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as raw materials for constituting the resin composition of the present invention, filtering the raw materials for constituting the resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.

[0363] Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms 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. Among these, the content 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 preferred that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above-mentioned range. A preferred method for adjusting the content of halogen atoms is ion exchange treatment.

[0364] A conventionally known container can be used as a container for storing the resin composition of the present invention. Furthermore, in order to prevent impurities from being mixed into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six resin layers, or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

[0365] <Cured product of resin composition> By curing the resin composition of the present invention, a cured product of this resin composition can be obtained. The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. The resin composition is preferably cured by heating, with the heating temperature being 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. The form of the cured product of the resin composition is not particularly limited, and can be selected depending on the application, such as film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. Furthermore, by patterning the resin composition, the shape of the cured product can be selected depending on the application, such as forming a protective film on the wall surface, forming via holes for electrical connection, adjusting impedance, capacitance, or internal stress, or imparting heat dissipation functionality. 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 percentage 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 percentage refers to the percentage of volume change before and after curing of the resin composition, and can be calculated using the following formula. Shrinkage rate [%] = 100 - (volume after curing / volume before curing) x 100

[0366] <Characteristics of the cured resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and 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 product of the 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.

[0367] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be carried out by a conventionally known method. The mixing can be performed by using a stirring blade, a ball mill, or by rotating the tank itself. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0368] Furthermore, filtration using a filter is preferably performed to remove foreign matter such as dust and fine particles from the resin composition of the present invention. The filter pore size may 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. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferable. The filter may be pre-washed with an organic solvent. In the filter filtration step, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. Examples of connection modes include connecting an HDPE filter with a pore size of 1 μm in the first stage and an HDPE filter with a pore size of 0.2 μm in the second stage in series. Various materials may also be filtered multiple times. When filtration is performed multiple times, circulating filtration may be used. Filtration may also be performed under pressure. When filtration is performed under pressure, the pressure applied is, for example, 0.01 MPa to 1.0 MPa, preferably 0.03 MPa to 0.9 MPa, more preferably 0.05 MPa to 0.7 MPa, and even more preferably 0.05 MPa to 0.5 MPa. In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal using an adsorbent may be combined. Known adsorbents can be used as the adsorbent. Examples of the adsorbent 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 in the bottle may be subjected to a degassing step by placing it under reduced pressure.

[0369] (Method of producing cured product) The method for producing a cured product of the present invention preferably includes a film-forming step of applying the resin composition onto 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 of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern. It is particularly preferable that the method for producing a cured product of the present invention includes the above-mentioned film-forming step, the above-mentioned exposure step, the above-mentioned development step, and at least one of a heating step of heating the pattern obtained in the development step and a post-development exposure step of exposing the pattern obtained in the development step. The production method of the present invention also preferably includes the film forming step and the step of heating the film. Each step will be described in detail below.

[0370] <Film formation process> The resin composition of the present invention can be used in a film-forming process in which the resin composition is applied to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film-forming step of applying the resin composition onto a substrate to form a film.

[0371] [Base material] The type of substrate can be appropriately determined depending on the application, and includes, but is not limited to, semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, Fe (for example, substrates formed from metal and substrates on which a metal layer is formed by, for example, plating or vapor deposition), paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, mold substrates, plasma display panel (PDP) electrode plates, etc. In the present invention, semiconductor production substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred. Furthermore, these substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface. The shape of the substrate is not particularly limited, and may be circular or rectangular. The size of the substrate is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm, if circular, and 100 to 1000 mm in length, preferably 200 to 700 mm in length, if rectangular. As the substrate, for example, a plate-shaped, preferably a panel-shaped substrate (substrate) is used.

[0372] When a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the substrate.

[0373] The resin composition of the present invention is preferably applied to a substrate by coating.

[0374] Specific examples of the application method 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, and 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 application conditions depending on the method, a film of the desired thickness can be obtained. In addition, the application 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, and 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 coating film may be formed by applying the coating to a temporary support in advance using the above-mentioned application method, and then transferred onto the substrate. Regarding the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used in the present invention. Additionally, a process for removing excess film from the edge of the substrate may be performed, such as edge bead rinsing (EBR) or back rinsing. Furthermore, a pre-wetting step may be employed in which the substrate is coated with various solvents before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

[0375] <Drying process> After the film-forming step (layer-forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) to remove the solvent. That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step. The drying step is preferably carried out after the film-forming step and before the exposure step. The drying temperature of the film in the drying step 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, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0376] <Exposure process> The film may be subjected to an exposure step to selectively expose the film to light. That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed in the film formation step to light. Selective exposure means that only a portion of the film is exposed, resulting in exposed and unexposed areas of the film. The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention. For example, it is 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. 2 is preferred, and 200 to 8,000 mJ / cm 2 is more preferred.

[0377] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0378] Examples of exposure wavelengths, in relation to the light source, include: (1) semiconductor lasers (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps (g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-line), (4) excimer lasers (KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays (EUV) (wavelength 13.6 nm), (6) electron beams, and (7) YAG lasers (second harmonic 532 nm, third harmonic 355 nm). For the resin composition of the present invention, exposure using a high-pressure mercury lamp is particularly preferred, and i-line exposure is particularly preferred. This allows for particularly high exposure sensitivity to be achieved. The exposure method is not particularly limited as long as it is a method that exposes at least a portion of the film made of the resin composition of the present invention, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0379] <Post-exposure baking process> The film may be subjected to a step of heating after exposure (post-exposure baking step). That is, the method for producing a cured product of the present invention may include a post-exposure baking step in which the film exposed in the exposure step is heated. The post-exposure baking step can be carried out after the exposure step and before the development step. The heating temperature in the post-exposure baking step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, more preferably from 1 minute to 10 minutes. The temperature rise rate in the post-exposure heating step from the starting temperature to the maximum heating temperature is preferably 1 to 12°C / min, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The temperature rise rate may be changed during heating as needed. The heating means in the post-exposure baking step is not particularly limited, and known means such as a hot plate, an oven, and an infrared heater can be used. It is also preferable that the heating be carried out in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0380] <Developing process> After exposure, the film may be subjected to a development step in which it is developed with a developer to form a pattern. That is, the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed with a developer to form a pattern. By performing development, one of the exposed and unexposed parts of the film is removed, thereby forming a pattern. Here, development in which the non-exposed portions of the film are removed by the development process is called negative development, and development in which the exposed portions of the film are removed by the development process is called positive development.

[0381] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0382] When the developer is an alkaline aqueous solution, examples of the basic compound that can be contained in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are 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, and more preferred is TMAH. When TMAH is used, for example, the content of the basic compound in the developer is preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, and even more preferably 0.3 to 3 mass %, based on the total mass of the developer.

[0383] When the developer contains an organic solvent, the organic solvent may be an ester, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetic acid), ethyl, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate , ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and acetoacetate. Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate,Suitable examples of the solvent include propylene glycol monopropyl ether acetate, ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone, cyclic hydrocarbons such as aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0384] When the developer contains an organic solvent, the organic solvent may be used alone or in combination. 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.

[0385] 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, and may be 100% by mass.

[0386] The developer may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0387] [Method of Supplying Developer] The method of supplying the developer is not particularly limited as long as it can form a desired pattern, and includes a method of immersing a substrate on which a film has been formed in the developer, puddle development in which the developer is supplied to a film formed on a substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, a method of supplying the developer through a spray nozzle is more preferred. Alternatively, a process may be employed in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate, and this process may be repeated multiple times. As a method for supplying the developer in the development step, a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept substantially stationary on the substrate, a step in which the developer is vibrated on the substrate by ultrasonic waves or the like, or a step in which these are combined can be used.

[0388] The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0389] In the development step, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse liquid. Alternatively, a rinse liquid may be supplied before the developer in contact with the pattern is completely dried.

[0390] [Rinse solution] When the developer is an alkaline aqueous solution, for example, water can be used as the rinse liquid. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[0391] When the rinse solution contains an organic solvent, examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetate), methyl ethoxyacetate, ... ethyl methyl 3-alkyloxypropionate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, methyl, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethoxylated methyl 2-methylpropionate. Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate,Suitable examples of the solvent include propylene glycol monopropyl ether acetate, ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone, cyclic hydrocarbons such as aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0392] When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. 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.

[0393] When the rinse solution contains an organic solvent, the rinse solution preferably contains 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and even more preferably 90% by mass or more of the organic solvent. Alternatively, the rinse solution may contain 100% by mass of the organic solvent.

[0394] The rinse solution may further contain other ingredients. Examples of other components include known surfactants and known defoaming agents.

[0395] [Method of supplying rinse liquid] The method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples thereof include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like. From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, the rinse liquid can be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, and from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, a spray nozzle, etc. That is, the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle. As a method for supplying the rinse liquid in the rinsing step, a step in which the rinse liquid is continuously supplied to the substrate, a step in which the rinse liquid is kept substantially stationary on the substrate, a step in which the rinse liquid is vibrated on the substrate by ultrasonic waves or the like, or a step in which any of these is combined can be used.

[0396] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0397] <Heating process> The pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the development step. The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without performing a development step, or a film obtained in the film-forming step. In the heating step, the resin such as the polyimide precursor is cyclized to form a resin such as a polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in a crosslinking agent other than the specific resin also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, still more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0398] The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of a base or the like generated from the base generator due to heating.

[0399] In the heating step, heating is preferably carried out at a temperature increase rate of 1 to 12°C / min from the initial temperature to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. By setting the temperature increase rate to 1°C / min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature increase rate to 12°C / min or less, it is possible to alleviate residual stress in the cured product. Additionally, in the case of a rapid heating oven, the temperature is preferably increased from the initial temperature to the maximum heating temperature at a rate of 1 to 8°C / sec, more preferably 2 to 7°C / sec, and even more preferably 3 to 6°C / sec.

[0400] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature is the temperature of the film (layer) after this drying, and it is preferable to raise the temperature from, for example, a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

[0401] 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.

[0402] In particular, when forming a multilayer laminate, from the viewpoint of adhesion between layers, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher. The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

[0403] Heating may be performed in stages. For example, the temperature may be increased from 25°C to 120°C at a rate of 3°C / min, held at 120°C for 60 minutes, increased from 120°C to 180°C at a rate of 2°C / min, and held 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. Pat. No. 9,159,547. Such a pretreatment step can improve the film's properties. The pretreatment step is preferably performed for a short period of time, such as 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, a first pretreatment step may be performed at a temperature in the range of 100 to 150°C, followed by a second pretreatment step at a temperature in the range of 150 to 200°C. Furthermore, after heating, the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C. / min.

[0404] The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by carrying out the heating step under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less. The heating means in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0405] <Post-development exposure process> The pattern obtained by the development step (or the pattern after rinsing if a rinsing step is performed) may be subjected to a post-development exposure step in which the pattern after the development step is exposed to light, instead of or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for producing a cured product of the present invention may include both a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. In the post-development exposure step, for example, the photosensitivity of the photobase generator can promote a reaction in which the cyclization of the polyimide precursor or the like progresses. In the post-development exposure step, it is sufficient that at least a part of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed. The exposure dose in the post-development exposure step is 50 to 20,000 mJ / cm, calculated as exposure energy at a wavelength to which the photosensitive compound is sensitive. 2 It is preferable that the concentration is 100 to 15,000 mJ / cm 2 It is more preferable that: The post-development exposure step can be carried out using, for example, the light source used in the exposure step described above, and it is preferable to use broadband light.

[0406] <Metal layer formation process> The pattern obtained by the development step (which is preferably subjected to at least one of the heating step and the post-development exposure step) may be subjected to a metal layer forming step in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained in the development step (preferably subjected to at least one of a heating step and a post-development exposure step).

[0407] The metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

[0408] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP 2007-157879 A, ​​JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used. Examples of suitable methods include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and combinations thereof. More specifically, examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating. Preferred plating methods include electroplating using a copper sulfate or copper cyanide plating solution.

[0409] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0410] <Application> The method for producing the cured product of the present invention or the fields to which the cured product of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), and the etching of insulating films for packaging applications such as those mentioned above. For details of these applications, see, for example, Science & Technology Co., Ltd.'s "High Performance Polyimide and Application Technology" (April 2008), edited by Masaaki Kakimoto, CMC Technical Library's "Fundamentals and Development of Polyimide Materials" (November 2011), and the Japan Polyimide and Aromatic Polymer Research Association's "Latest Polyimides: Fundamentals and Applications" (NTS, August 2010).

[0411] The method for producing the cured product of the present invention or the cured product of the present invention can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, and for producing protective lacquers and dielectric layers in electronics, especially microelectronics.

[0412] (Laminate and method for manufacturing laminate) The laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention. The laminate of the present invention is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers. Of the two or more layers made of the cured product contained in the laminate, at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.

[0413] That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.

[0414] The laminate of the present invention preferably includes two or more layers made of a cured product, and a metal layer between any two of the layers made of the cured product. The metal layer is preferably formed by the metal layer-forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer-forming step of forming a metal layer on the layer made of the cured product, between the steps for producing a cured product that are performed multiple times. Preferred aspects of the metal layer-forming step are as described above. As the laminate, for example, a laminate including at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order, can be mentioned as a preferred example. It is preferable that the layer made of the first cured product and the layer made of the second cured product are both 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 have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

[0415] <Lamination process> The method for producing the laminate of the present invention preferably includes a lamination step. The lamination process is a series of processes including (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) at least one of a heating process and a post-development exposure process, which are carried out again on the surface of the pattern (resin layer) or metal layer in this order. However, it is also possible to repeat the film formation process (a) and at least one of the heating process and the post-development exposure process (d). Furthermore, after at least one of the heating process and the post-development exposure process (d), a metal layer formation process (e) may be included. It goes without saying that the lamination process may further include the drying process and the like as appropriate.

[0416] When a further lamination step is performed after the lamination step, a surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step. An example of the surface activation treatment is a plasma treatment. Details of the surface acti...

Claims

1. cyclized resin or a precursor thereof, a radical polymerization initiator, and Contains a radical polymerizable compound, the radical polymerizable compound includes a compound A having a urea bond and not having an axis of symmetry, The compound A satisfies at least one of the following conditions 1 and 2: said compound A comprises an aromatic group; the aromatic group is directly bonded to the urea bond contained in compound A, The cyclized resin or its precursor is at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor. resin composition; Condition 1: Compound A has two or more radically polymerizable groups; Condition 2: Compound A has at least one group selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group.

2. 2. The resin composition according to claim 1, wherein the cyclized resin or its precursor has an acid value of 0 mmol / g to 1.2 mmol / g.

3. The resin composition according to claim 1 or 2, further comprising a compound different from compound A as the radical polymerizable compound.

4. The resin composition according to any one of claims 1 to 3, wherein the compound A is a compound represented by the following formula (1-1) or formula (1-2): 【Chemistry 1】 In formula (1-1), R Ｐ１ and R Ｐ２ each independently represents a group containing at least one radically polymerizable group, and R N represents a hydrogen atom or a hydrocarbon group; In formula (1-2), R Ｐ１ represents a group containing at least one radically polymerizable group, and L ３ represents a divalent linking group, and R N represents a hydrogen atom or a hydrocarbon group.

5. The resin composition according to any one of claims 1 to 3, which is used for forming an interlayer insulating film for a rewiring layer.

6. A cured product obtained by curing the resin composition according to any one of claims 1 to 5.

7. A laminate comprising two or more layers made of the cured product according to claim 6, and a metal layer between any two adjacent layers made of the cured product.

8. A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of claims 1 to 5 onto a substrate to form a film.

9. The method for producing a cured product according to claim 8 , comprising: an exposure step of selectively exposing the film to light; and a development step of developing the film with a developer to form a pattern.

10. The method for producing a cured product according to claim 8 or 9, comprising a heating step of heating the film at 50 to 450°C.

11. A semiconductor device comprising the cured product according to claim 6 or the laminate according to claim 7.

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