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

Abstract

To provide a cured product which is excellent in adhesion to a metal layer and is obtained by curing a photosensitive resin composition.SOLUTION: There are provided: a photosensitive resin composition which contains at least one resin selected from the group consisting of polyimides, polyamide-imides, polyimide precursors, and polyamide-imide precursors, and a photopolymerization initiator, the resin having a group capable of photodimerization reaction; a cured product obtained by curing the photosensitive 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.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Polyimide or polyamideimide is used in various applications due to its excellent heat resistance and insulating properties. The applications are not particularly limited, but for example, in the case of semiconductor devices for mounting, it can be used as an insulating film or sealing material, or as a protective film. It is also used as a base film or coverlay for flexible substrates.

[0003] For example, in the above-mentioned applications, polyimide or polyamideimide is used in the form of a photosensitive resin composition containing at least one resin selected from the group consisting of polyimide, polyimide precursor, polyamideimide, and polyamideimide precursor. Such a photosensitive resin composition is applied to a substrate by, for example, coating to form a resin film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate. The polyimide precursor and the polyamideimide precursor are cyclized, for example, by heating, to become polyimide and polyamideimide, respectively, in the cured product. Since the photosensitive resin composition can be applied by a known coating method, etc., it can be said to have excellent adaptability in manufacturing, for example, high degree of freedom in designing the shape, size, application position, etc., of the applied photosensitive resin composition. In addition to the high performance of polyimide, polyamideimide, etc., from the viewpoint of such excellent adaptability in manufacturing, the industrial application development of the above-mentioned photosensitive resin composition is expected to continue.

[0004] For example, Patent Document 1 describes a liquid crystal alignment agent for photo-alignment, which contains at least two polymers that are reaction products from raw materials containing tetracarboxylic dianhydride and diamine; the polymers include a specific polymer (A) and a specific polymer (B); the raw materials used to synthesize polymer (A) include at least one compound having a photoreactive structure and do not include a specific compound; and the raw materials used to synthesize polymer (B) include at least one specific compound and do not include a compound having a photoreactive structure. Patent Document 2 describes a liquid crystal aligning agent that is characterized by containing a polymer having a specific structure in its side chain. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2018-180227 A [Patent Document 2] JP 2007-224273 A Summary of the Invention [Problem to be solved by the invention]

[0006] It is desirable for a cured product obtained by curing a photosensitive resin composition to have excellent adhesion to a metal layer.

[0007] The present invention aims to provide a photosensitive resin composition that can give a cured product having excellent adhesion to metal, a cured product obtained by curing the photosensitive 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]

[0008] Examples of typical embodiments of the present invention are given below. <1> At least one resin selected from the group consisting of polyimide, polyamideimide, polyimide precursor, and polyamideimide precursor; and a photopolymerization initiator, The resin has a group capable of undergoing a photodimerization reaction. Photosensitive resin composition. <2> The photodimerization reactive group is a group having a cinnamoyl structure. <1> The photosensitive resin composition according to claim 1. <3> The resin contains a radical polymerizable group. <1> or <2> The photosensitive resin composition according to claim 1. <4> Further comprising a compound B having an alkoxysilyl group, <1> ~ <3> 10. The photosensitive resin composition according to claim 9 . <5> the compound B having an alkoxysilyl group has at least one group selected from the group consisting of a photodimerization reactive group and a radical polymerizable group; <4> The photosensitive resin composition according to claim 1. <6> The compound B having an alkoxysilyl group has an azole group. <4> or <5> The photosensitive resin composition according to claim 1. <7> Further comprising a compound C having an azole group and at least one group selected from the group consisting of a radical polymerizable group and a photodimerization reactive group, <1> ~ <6> 10. The photosensitive resin composition according to claim 9 . <8> Compound D further includes an azole group and does not include an alkoxysilyl group, a radical polymerizable group, or a photodimerization reactive group. <1> ~ <7> 10. The photosensitive resin composition according to claim 9 . <9> Used to form an interlayer insulating film for a redistribution layer, <1> ~ <8> 10. The photosensitive resin composition according to claim 9 . <10> <1> ~ <9> 2. A cured product obtained by curing the photosensitive resin composition according to claim 1. <11> <10> 1. A laminate comprising two or more layers of the cured product according to claim 1, and a metal layer between any two of the layers of the cured product. <12> <1> ~ <9> 13. A method for producing a cured product, comprising a film formation step of applying the photosensitive resin composition according to any one of the above items 1 to 6 on a substrate to form a film. <13> The method includes 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. <12> A method for producing the cured product according to claim 1. <14> The method further includes a second exposure step of exposing the pattern obtained by the development step after the development step. <13> A method for producing the cured product according to claim 1. <15> The method includes a heating step of heating the film at 50 to 450 ° C. <12> ~ <14> 13. A method for producing the cured product according to any one of the above items. <16> <10> or <11> A semiconductor device comprising the stack according to claim 1. Effect of the Invention

[0009] According to the present invention, there are provided a photosensitive resin composition which can give a cured product having excellent adhesion to metal, a cured product obtained by curing the photosensitive 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 PREFERRED EMBODIMENTS

[0010] The main embodiments of the present invention will be described below, however, 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 "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, so long as the process can achieve its intended effect. In the description of groups (atomic groups) in this specification, when there is no indication of whether they are substituted or unsubstituted, the term encompasses both groups (atomic groups) that have no substituents and groups (atomic groups) that have a substituent. For example, the term "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have a substituent (substituted alkyl groups). In this specification, unless otherwise specified, the term "exposure" 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 represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic" means both or either of "acrylic" and "methacrylic", and "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, Me in the structural formulae represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent, and in this specification, the solid content concentration refers to the mass percentage of the other components excluding the solvent with respect to the total mass of the composition. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) unless otherwise specified, and are defined as polystyrene equivalent values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and using 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 as columns. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as an eluent. However, when THF is not suitable as an eluent, such as when the solubility is low, NMP (N-methyl-2-pyrrolidone) can also be used. In addition, unless otherwise specified, detection in GPC measurement is performed using a UV (ultraviolet) light detector with a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", it is sufficient that there is another layer above or below the reference layer among the multiple layers being noted. That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer. In addition, unless otherwise specified, the direction in which the layers are stacked on the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "upper", and the opposite direction is referred to as "lower". Note that such a vertical direction is set for the convenience of this specification, and in an actual embodiment, the "upper" direction in this specification may be different from the vertical upward direction. In this specification, unless otherwise specified, the 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 atm), and the relative humidity is 50% RH. As used herein, combinations of preferred aspects are more preferred aspects.

[0011] (Photosensitive resin composition) The photosensitive resin composition of the present invention (hereinafter also simply referred to as "resin composition") contains at least one resin selected from the group consisting of polyimide, polyamideimide, polyimide precursor, and polyamideimide precursor, and a photopolymerization initiator, and the resin has a group capable of undergoing a photodimerization reaction. Hereinafter, at least one resin selected from the group consisting of polyimide, polyamideimide, polyimide precursor, and polyamideimide precursor, and having a group capable of undergoing a photodimerization reaction, is also referred to as a "specific resin".

[0012] The photosensitive resin composition of the present invention may be either a negative-type photosensitive resin composition or a positive-type photosensitive resin composition, but is preferably a negative-type photosensitive resin composition. The negative photosensitive resin composition refers to a composition in which, when a layer formed from the photosensitive resin composition is exposed to light, the unexposed portions (non-exposed portions) are removed by a developer. The positive photosensitive resin composition refers to a composition in which, when a layer formed from the photosensitive resin composition is exposed to light, the exposed portion (exposed area) is removed by a developer.

[0013] The cured product obtained from the photosensitive resin composition of the present invention has excellent adhesion to metals. The mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.

[0014] The photosensitive resin composition of the present invention contains a resin having a photodimerization reactive group and a photopolymerization initiator. It has been found that by using such a resin, both reactions, polymerization by a photopolymerization initiator and dimerization of photodimerizable groups, can be utilized for curing upon exposure to light, and therefore strong bonds are formed between the resins, resulting in excellent adhesion between the cured product and metal. In particular, when at least one of the following conditions is satisfied: the resin has a polymerizable group or the photosensitive resin composition contains a crosslinking agent described below, or when re-exposure is performed before heat curing after development, after heat curing, or during heating, dimerization of photodimerization reactive groups in the resin is promoted, and adhesion to the metal is considered to be further improved. It is believed that the above-mentioned effects can be obtained in both positive and negative types by utilizing the re-exposure.

[0015] Furthermore, in the case of a conventional photosensitive resin composition containing a photopolymerization initiator, curing may be insufficient, particularly on the surface of the film facing the air interface, resulting in poor chemical resistance. This is presumably because the polymerization does not proceed sufficiently on the air interface side due to the influence of oxygen, moisture, etc. However, since the resin contained in the photosensitive resin composition of the present invention has a group capable of photodimerization, the photodimerization reaction proceeds on the surface on the air interface side of the film, and therefore the film is sufficiently cured even on the air interface side, and the resulting cured product is considered to have excellent chemical resistance. Because the cured product has excellent chemical resistance, it is considered that, for example, when a photosensitive resin composition containing a solvent is further applied and cured on a cured product made of the photosensitive resin composition of the present invention to produce a laminate, dissolution of the cured product is suppressed even if the cured product comes into contact with a developer or the photosensitive resin composition. According to the present invention, it is believed that a cured product having excellent chemical resistance can be obtained, in which the solubility in polar solvents such as dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP), alkaline aqueous solutions such as an aqueous tetramethylammonium hydroxide (TMAH) solution, or mixed solutions of the above polar solvents and the above alkaline aqueous solutions is suppressed.

[0016] However, Patent Documents 1 and 2 do not disclose a photosensitive resin composition containing a resin having a group capable of photodimerization and a photopolymerization initiator.

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

[0018] <Specific resin> The photosensitive resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polyamideimide, polyimide precursor, and polyamideimide precursor, and having a group capable of photodimerization reaction. The photosensitive resin composition of the present invention preferably contains a polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.

[0019] [Photodimerization Reaction Capable Group] The specific resin may have a photodimerization reactive group in the main chain or in a side chain of the resin, but it is preferable that the group be in the side chain. In this specification, the term "main chain" refers to the relatively longest bonding chain in the molecule of the polymer compound constituting the resin, and the term "side chain" refers to any other bonding chain. The photodimerizable group is not particularly limited, but is preferably a group capable of undergoing a dimerizable reaction by ultraviolet light. The photodimerization reactive group is preferably a group having a cinnamoyl structure, a coumarin structure, a naphthalene structure, or an anthracene structure, and more preferably a group having a cinnamoyl structure.

[0020] Moreover, the photodimerization reactive group is preferably a group represented by the following formula (P-1). [ka] In formula (P-1), T 1 and T 2 each independently represents a hydrogen atom or a monovalent organic group, j represents 1 or 2, R 1 each independently represents a monovalent organic group or a bonding site to another structure; R 2 each independently represents a monovalent organic group or a bonding site with another structure, i represents an integer of 0 or more, i+j is 6 or less, and when j is 2, two T 1 may be the same or different, and when j is 2, two T 2 may be the same or different, and at least one of the structures contains a binding site to another structure.

[0021] In formula (P-1), R 1 R each independently represents a monovalent organic group or a bonding site with another structure. 1 When represents a monovalent organic group, it is preferably a hydrocarbon group, more preferably an alkyl group having 1 to 12 carbon atoms, a phenyl group or a biphenyl group. The above-mentioned hydrocarbon group may be substituted with a known substituent, such as a halogen atom or a cyano group. In formula (P-1), R 2 R each independently represents a monovalent organic group or a bonding site with another structure. 2 When represents a monovalent organic group, R 2is preferably a carboxy group, an alkylcarbonyloxy group, an alkenylcarbonyloxy group, or an arylcarbonyloxy group. The number of carbon atoms in the alkyl group in the alkylcarbonyloxy group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4. The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkenyl group in the alkenylcarbonyloxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 4. The alkenyl group may be linear, branched, or cyclic. The aryl group in the arylcarbonyloxy group is preferably an aromatic hydrocarbon group, and more preferably a phenyl group. In formula (P-1), T 1 and T 2 each independently represents a hydrogen atom or a monovalent organic group, is preferably a hydrogen atom, a cyano group, or a halogen atom, and is more preferably a hydrogen atom. Also, T 1 and T 2 are all hydrogen atoms, or T 1 is a hydrogen atom, and T 2 An embodiment in which is a cyano group or a halogen atom is also one of the preferred embodiments. In formula (P-1), i represents an integer of 0 or more, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 0. In formula (P-1), j represents 1 or 2, and is preferably 1.

[0022] The group represented by formula (P-1) contains at least one bonding site with another structure in the structure, and preferably contains only one bonding site with another structure in the structure. Also, R 2 At least one of R is preferably a binding site to another structure. 2 It is more preferred that one of them is the binding site for the other structure. In addition, in the group represented by formula (P-1), all of R 2is a monovalent organic group, and R 1 An embodiment in which at least one of the above is a binding site for another structure is also one of the preferred embodiments of the present invention.

[0023] In addition, the specific resin preferably contains a structure represented by the following formula (P-2) as a structure containing a group capable of undergoing a photodimerization reaction. [ka] In formula (P-2), T 1 and T 2 each independently represents a hydrogen atom or a monovalent organic group, n represents 0 or 1, j represents 1 or 2, R 1 each independently represents a monovalent organic group or a bonding site to another structure; R 2 each independently represents a monovalent organic group or a bonding site with another structure, i represents an integer of 0 or more, i+j is 6 or less, and when j is 2, T 1 may be the same or different, and when j is 2, there are 2 or more T 2 may be the same or different, and two n's may be the same or different. In formula (P-2), T 1 , T 2 , R 1 , R 2 Preferred embodiments of i, j are the same as those in formula (P-1) above. In formula (P-3), n is 0 or 1, and 0 is more preferable.

[0024] [Polymerizable Group] In addition, the specific resin preferably has a polymerizable group. Examples of the polymerizable group in the specific resin include known polymerizable groups such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group, and an alkoxymethyl group. The radically 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 (meth)acrylamide group, or a (meth)acryloyloxy group, with a (meth)acryloyloxy group being preferred.

[0025] Among these, the specific resin preferably contains a radical polymerizable group. When the specific resin has a radical polymerizable group, the photosensitive resin composition preferably contains a photoradical polymerization initiator described later as a photopolymerization initiator, more preferably contains a photoradical polymerization initiator described later as a photopolymerization initiator and a radical crosslinking agent described later, and further preferably contains a photoradical polymerization initiator described later as a photopolymerization initiator, a radical crosslinking agent described later, and a sensitizer described later. For example, a negative type photosensitive layer is formed from such a photosensitive resin composition. The specific resin may also have a polarity conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the photosensitive resin composition preferably contains a photoacid generator described later. For example, a chemically amplified positive-type photosensitive layer or negative-type photosensitive layer is formed from such a photosensitive resin composition.

[0026] [Polyimide precursor] The polyimide precursor used in the present invention is not particularly limited in terms of its type, but it preferably contains a repeating unit represented by the following formula (2). 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, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group.

[0027] In addition, the polyimide precursor used in the present invention preferably contains a photodimerizable group in the repeating unit represented by the above formula (2), and R 115 and R 111 It is more preferable that at least one of R 111 It is more preferable that the compound contains a group capable of photodimerization. The preferred embodiments of the photodimerization reaction capable group are as described above.

[0028] A in Equation (2) 1 and A 2 each independently represents an oxygen atom or -NH-, and an oxygen atom is preferable. R in Equation (2) 111 represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing 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 hetero atom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a hetero atom. As a preferred embodiment of the present invention, a group represented by -Ar- and -Ar-L-Ar- is exemplified, and a group represented by -Ar-L-Ar- is particularly preferred. Here, 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-, -SO 2 - or -NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges of these are as described above.

[0029] R 111 is preferably derived from a diamine. Examples of diamines used in the production of 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, it is preferable that the diamine 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 it is more preferable that the diamine contains 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 hetero atom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a hetero atom. Examples of groups containing an aromatic group include the following.

[0030] [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-, or -SO 2 -, -NHCO-, or a combination thereof is preferably a group selected from a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO 2 -, more preferably a group selected from -CH 2 -, -O-, -S-, -SO 2 -, -C(CF 3 ) 2 - or -C(CH 3 ) 2 It is even more preferable that In the formula, * represents a bonding site with another structure.

[0031] 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'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'- Diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4 ,4'-Diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-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 , 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine , bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-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 can be mentioned.

[0032] Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017 / 038598.

[0033] In addition, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of WO 2017 / 038598 are also preferably used.

[0034] R 111 From the viewpoint of flexibility of the obtained organic film, it is preferably represented by -Ar-L-Ar-, where 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-, -SO 2 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 -SO 2 The aliphatic hydrocarbon group here is preferably an alkylene group.

[0035] Also, R 111From the viewpoint of i-line transmittance, it is preferable that the divalent organic group represented by the following formula (51) or formula (61) is used. In particular, from the viewpoints of i-line transmittance and ease of availability, it is more preferable that the divalent organic group represented by the formula (61) is used. Formula (51) [ka] In formula (51), R 50 ~R 57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group; R 50 ~R 57 At least one of these is a fluorine atom, a methyl group or a trifluoromethyl group, and each * independently represents a bonding site with 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 each independently represents 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.

[0036] Also, R 111 may be a structure containing a photodimerization group. Preferred embodiments of the photodimerization group are as described above. For example, R 111 can also be a structure derived from a diamine compound having a photodimerization reactive group. R 111 When R contains a group capable of photodimerization, 111 It is preferable that the compound contains an aromatic hydrocarbon group and a structure in which the group containing the photodimerization reactive group is directly bonded to the aromatic hydrocarbon group. The aromatic hydrocarbon group is not particularly limited, but a benzene ring structure is preferred.

[0037] Also, R 111 When R contains the above-mentioned photodimerization reactive group, 111 is preferably a structure represented by the following formula (LD-1). [ka] In formula (LD-1), Y D1 represents an n+2 valent group containing an aromatic hydrocarbon group, P D1 represents a group having a group capable of photodimerization, n represents an integer of 1 or more, and * represents R 111 represents the bonding site with the nitrogen atom to which it is bonded.

[0038] -Y D1 - In formula (LD-1), Y D1 represents an (n+2) valent group containing an aromatic hydrocarbon group. Y D1 The aromatic hydrocarbon group in is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, still more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring, and particularly preferably a group in which three or more hydrogen atoms have been removed from a benzene ring. In formula (LD-1), Y D1 In the formula (1-1), it is preferable that the bonding sites to the two * in the formula (LD-1) are both aromatic hydrocarbon groups. 1 It is preferable that the aromatic hydrocarbon ring structure be directly bonded to the aromatic hydrocarbon ring structure contained in the above. In addition, in formula (LD-1), Y D1 In P D1It is preferable that the bonding sites with P are all aromatic hydrocarbon groups. D1 is Y D1 It is preferable that the aromatic hydrocarbon ring structure be directly bonded to the aromatic hydrocarbon ring structure contained in the above.

[0039] Y D1 It is preferable that the compound contains at least one structure selected from the group consisting of the structures represented by the following formulas (A2-1) to (A2-5), and it is more preferable that the compound contains at least one structure selected from the group consisting of the structures represented by the above formulas (A2-1) to (A2-5). [ka] In formulas (A2-1) to (A2-5), R A211 ~R A214 , R A221 ~R A224 , R A231 ~R A238 , R A241 ~R A248 and R A251 ~R A258 each independently represents a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group, or a halogen atom; L A231 and L A241 each independently represents a single bond, a carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a heteroatom, a heterocyclic group, or a halogenated alkylene group; R A211 ~R A214 At least one of R A221 ~R A224 At least one of R A231 ~R A238 At least one of R A241 ~R A248 At least one of, and R A251 ~R A258 At least one of the above is P in formula (1-1). 1 Each * independently represents a binding site to another structure.

[0040] Among these, Y 1 preferably contains a structure represented by any one of formulas (A2-1) to (A2-4), and more preferably contains a structure represented by formula (A2-1) or formula (A2-4).

[0041] In formulas (A2-1) to (A2-5), R A211 ~R A214 , R A221 ~R A224 , R A231 ~R A238 , R A241 ~R A248 and R A251 ~R A258 does not contain a bonding site with the carbonyl group in the above formula (1-1), and R A211 ~R A214 At least one of R A221 ~R A224 At least one of R A231 ~R A238 At least one of R A241 ~R A248 At least one of, and R A251 ~R A258 At least one of the above is P in formula (LD-1). D1 It may be a binding site to In formula (A2-1), R A211 ~R A214 P D1 If it is not a binding site for R A211 ~R A214 each independently preferably represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom, and from the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferable. Above R A211 ~R A214The halogen atom in the halogenated alkyl group in the above formula (I) or the above halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom or a bromine atom is preferred. In formula (A2-2), R A221 ~R A224 is R in formula (A2-1) A211 ~R A214 and preferred embodiments are also the same. In formula (A2-3), R A231 ~R A238 each independently preferably represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom, and from the viewpoint of solvent solubility, more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Above R A231 ~R A238 The halogen atom in the halogenated alkyl group in the above formula (I) or the above halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom or a bromine atom is preferred. In formula (A2-3), L A231 is a single bond, a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, a divalent unsaturated hydrocarbon group having 5 to 24 carbon atoms, -O-, -S-, -NR N It is preferable that the alkyl group represents -, a heterocyclic group, or a halogenated alkylene group having 1 to 6 carbon atoms, and it is more preferable that the alkyl group represents a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, -O-, or a heterocyclic group, and it is more preferable that the alkyl group represents a single bond or -O-. Above R N 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. The divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group, but is preferably a divalent aromatic hydrocarbon group. The heterocyclic group is preferably, for example, a group in which two hydrogen atoms have been removed from an aliphatic or aromatic heterocycle, more preferably a group in which two hydrogen atoms have been removed from an aliphatic or aromatic heterocycle, and more preferably a group in which two hydrogen atoms have been removed from a ring structure such as a pyrrolidine ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, a piperidine ring, a tetrahydropyran ring, a pyridine ring, a morpholine ring, etc. These heterocycles may further form a condensed ring with another heterocycle or a hydrocarbon ring. The heterocycle preferably has 5 to 10 ring members, and more preferably 5 or 6 ring members. The heteroatom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom. 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 chlorine atom or a bromine atom being preferred. In formula (A2-4), R A241 ~R A248 , L A241 is R in formula (A2-3) A231 ~R A238 , L A231 and preferred embodiments are also the same. In formula (A2-5), R A251 ~R A258 is R in formula (A2-1) A211 ~R A214 and preferred embodiments are also the same.

[0042] In formula (A2-1), R A211 ~R A214 At least one of the groups is P in formula (LD-1). D1 Preferably, the binding site is R A211 ~R A214 One of the above P D1 More preferably, the binding site is R A213 The above P D1 It is preferred that the binding site is In formula (A2-2), R A221 ~R A224At least one of the groups is P in formula (LD-1). D1 Preferably, the binding site is R A221 ~R A224 One of the above P D1 More preferably, the binding site is R A223 The above P D1 It is preferred that the binding site is In formula (A2-3), R A231 ~R A238 At least one of the groups is P in formula (LD-1). D1 Preferably, the binding site is R A231 ~R A238 Two of them are listed above. D1 More preferably, the binding site is R A231 ~R A234 One of them and R A235 ~R A238 One of the two is the above P D1 More preferably, R A231 and R A238 The above two are D1 It is particularly preferred that the binding site is In formula (A2-4), R A241 ~R A248 At least one of the groups is P in formula (LD-1). D1 Preferably, the binding site is R A241 ~R A248 Two of them are listed above. D1 More preferably, the binding site is R A241 ~R A244 One of them and R A245 ~R A248 One of the two is the above P D1 More preferably, R A241 and R A248 The above two are D1 It is particularly preferred that the binding site is In formula (A2-5), R A251 ~R A258 At least one of the groups is P in formula (LD-1). D1 Preferably, the binding site is R A251 ~RA258 Two of them are listed above. D1 More preferably, the binding site is R A251 ~R A254 One of them and R A255 ~R A258 One of the two is the above P D1 More preferably, R A253 and R A257 The above two are D1 It is particularly preferred that the binding site is

[0043] In the formulas (A2-1) to (A2-5), each of the two * is preferably * in the formula (LD-1). 111 The two nitrogen atoms to which are bonded are preferably directly bonded to the positions represented by the two * in formulae (A2-1) to (A2-5).

[0044] Among these, Y D1 is preferably a group represented by the following formula (Y-1) or (Y-2). [ka] In formula (Y-1), R Y11 , R Y12 , R Y13 are R in formula (A2-1), A211 , R A212 and R A214 The same applies to the preferred embodiments. In formula (Y-2), R Y21 ~R Y26 are R in formula (A2-4), A242 ~R A247 The same applies to the preferred embodiments. In formula (Y-1) or formula (Y-2), * represents R in formula (2). 111 The two nitrogen atoms to which the #'s bond are bonded, and the P's bond to the #'s bond to the P's bond to the D1 The binding sites for each are shown.

[0045] -P D1 - In formula (LD-1), P D1 represents a group having a photodimerization group. Preferred embodiments of the photodimerization group are the same as the preferred embodiments of the photodimerization group in the specific resin described above. PD1 is preferably a group represented by the following formula (PD-1). [ka] In formula (PD-1), L PD1 represents a single bond or a linking group having a valence of m+1; X PD1 represents a group capable of photodimerization, m represents an integer of 1 or more, * represents Y in formula (LD-1). D1 It represents the binding site with

[0046] In formula (PD-1), L PD1 is a single bond, or a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N - or a group in which two or more of these are bonded is preferred, and a single bond, a hydrocarbon group, an ether bond, a carbonyl group, -NR N - or a group in which two or more of these are bonded together is more preferred. Above R N 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. The above L PD1 The hydrocarbon group in is 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 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.

[0047] In formula (PD-1), X PD1 The preferred embodiments of the photodimerization reactive group in the specific resin are the same as those of the photodimerization reactive group in the specific resin described above.

[0048] In formula (PD-1), m is preferably an integer of 1 to 4, more preferably 1 or 2, and particularly preferably 1.

[0049] -n- In formula (LD-1), n ​​represents an integer of 1 or more, preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.

[0050] The structure represented by the above formula (LD-1) can be obtained, for example, as a structure derived from a diamine represented by the following formula (LDA-1). [ka] In the above formula (LDA-1), Y D1 , P D1 , n is Y in the above formula (LD-1), D1 , P D1 , n, and the preferred embodiments are also the same.

[0051] Also, R 111 may be a structure containing a polymerizable group. For example, R 111 can also be a structure derived from a diamine compound having a polymerizable group. The diamine compound having a polymerizable group is not particularly limited, but is preferably a compound containing an aromatic ring structure, and more preferably a compound having a structure in which a structure containing an amino group and a polymerizable group is directly bonded to the aromatic ring structure. As the polymerizable group, a group containing an ethylenically unsaturated bond, a cyclic ether group, a group containing a methylol group or an alkoxymethyl group is preferred, a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group is more preferred, and a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a methylol group or an alkoxymethyl group is even more preferred.

[0052] Also, R 111When R is a structure containing a polymerizable group, 111 is preferably a structure represented by the following formula (1-1). [ka] In formula (1-1), Y 1 represents an n+2 valent group containing an aromatic hydrocarbon group, P 1 represents a group containing a polymerizable group, n represents an integer of 1 or more, and * represents R 111 represents the bonding site with the nitrogen atom to which it is bonded.

[0053] -Y 1 - In formula (1-1), Y 1 represents an (n+2) valent group containing an aromatic hydrocarbon group. Y 1 The aromatic hydrocarbon group in is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, still more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring, and particularly preferably a group in which three or more hydrogen atoms have been removed from a benzene ring. In formula (1-1), Y 1 In the formula (1-1), each of the bonding sites to the two *'s in the formula is preferably an aromatic hydrocarbon group. 1 It is preferable that the aromatic hydrocarbon ring structure be directly bonded to the aromatic hydrocarbon ring structure contained in the above. In addition, in formula (1-1), Y 1 In P 1 It is preferable that the bonding sites with P are all aromatic hydrocarbon groups. 1 is Y 1 It is preferable that the aromatic hydrocarbon ring structure be directly bonded to the aromatic hydrocarbon ring structure contained in the above.

[0054] Y 1It is preferable that the compound contains at least one structure selected from the group consisting of the structures represented by the above formulas (A2-1) to (A2-5), and it is more preferable that the compound is at least one structure selected from the group consisting of the structures represented by the above formulas (A2-1) to (A2-5). However, in the explanation of the above formulas (A2-1) to (A2-5), “P in formula (LD-1)” D1 The description of "bonding site with" is "P in formula (1-1) 1 "binding site with the In addition, Y 1 A preferred embodiment of the present invention is Y D1 This is similar to the preferred embodiment of the above.

[0055] -P 1 - In formula (1-1), P 1 represents a group containing a polymerizable group. As the polymerizable group, a group containing an ethylenically unsaturated bond, a cyclic ether group, a group containing a methylol group or an alkoxymethyl group is preferred, a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group is more preferred, and a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a methylol group or an alkoxymethyl group is even more preferred. P 1 The number of polymerizable groups contained in is 1 or more, preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.

[0056] Also, P 1 is preferably a group represented by the following formula (P-1). [ka] In formula (P-1), L 1 represents a single bond or a linking group having a valence of m+1; A 2represents a polymerizable group, m represents an integer of 1 or more, * represents Y 1 It represents the binding site with In formula (P-1), L 1 is a single bond, or a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N - or a group in which two or more of these are bonded is preferred, and a single bond, a hydrocarbon group, an ether bond, a carbonyl group, -NR N - or a group in which two or more of these are bonded together is more preferred. Above R N is as described above. The above L 1 The hydrocarbon group in is 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 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.

[0057] In formula (P-1), A 2 is preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group, and more preferably a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a methylol group or an alkoxymethyl group.

[0058] In formula (P-1), m is preferably an integer of 1 to 15, more preferably an integer of 1 to 10, even more preferably an integer of 1 to 5, particularly preferably 1 or 2, and most preferably 1.

[0059] Also, P 1 is preferably a group represented by the following formula (P-2) or formula (P-3). [ka] In formula (P-2), A 2 represents a polymerizable group, and * represents Y 1It represents the binding site with In formula (P-2), A 2 is A in formula (P-1) 2 The same applies to the preferred embodiments. In formula (P-3), A 2 represents a polymerizable group, L 2 is a hydrocarbon group, or a hydrocarbon group and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N - or a group in which two or more of these are bonded together; Z 1 represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond, or a carbonate bond, and * represents Y 1 R represents the binding site. N is as described above. In formula (P-3), A 2 is A in formula (P-1) 2 The same applies to the preferred embodiments. In formula (P-3), L 2 is preferably a hydrocarbon group, a (poly)alkyleneoxy group, or a group represented by a combination thereof. The above-mentioned hydrocarbon group is preferably an alkylene group, a divalent aromatic hydrocarbon group, or a group represented by a combination thereof, and more preferably an alkylene group. In this specification, the term "(poly)alkyleneoxy group" refers to an alkyleneoxy group or a polyalkyleneoxy group. In addition, in the present invention, the term "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 with 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 alkylene group is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, and even more preferably an alkylene 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, further preferably a phenylene group or naphthylene group, and particularly preferably a phenylene group. The alkylene group in the (poly)alkyleneoxy group is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group or propylene group, and even more preferably an ethylene group. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, further preferably 2-5, and particularly preferably 2-4. In formula (P-3), Z 1 represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond, or a carbonate bond, and is more preferably an ester bond, a urethane bond, a urea bond, or an amide bond. In the present invention, when simply referring to an "ester bond", "urethane bond", "amide bond", etc., the orientation of these bonds is not limited. For example, 1 is an ester bond, Z 1 L in 2 The bonding site with may be a carbon atom or an oxygen atom in the ester bond.

[0060] -n- In formula (1-1), n ​​represents an integer of 1 or more, preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.

[0061] R in Equation (2) 115 represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), each * independently represents a bonding site to another structure. [ka] In formula (5), R 112 is a single bond or a divalent linking group, and is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 -, -NHCO-, and combinations thereof are preferred, and examples thereof include a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO 2 -, more preferably a group selected from -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -O-, -CO-, -S- and -SO 2 It is more preferably a divalent group selected from the group consisting of -.

[0062] 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 R represents a tetravalent organic group. 115 The preferred range of R in formula (2) is 115 The same definition and preferred range are also the same.

[0063] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic 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 their alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

[0064] Further, preferred examples include the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598.

[0065] In formula (2), R 111 and R 115At least one of R may have an OH group. 111 Examples of the residue include residues of bisaminophenol derivatives.

[0066] 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 It is preferable that at least one of R contains a polymerizable group, and it is more preferable that both of R contain a polymerizable group. 113 and R 114 It is also preferable that at least one of the above 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 is preferably a radically polymerizable group. 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 of 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 (e.g., 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.

[0067] [ka]

[0068] 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 is an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 represents a cycloalkylene group or a polyalkyleneoxy group. Suitable R 201 Examples of the alkylene group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, and the like; a 1,2-butanediyl group, a 1,3-butanediyl group, a -CH 2 CH(OH)CH 2 -, and polyalkyleneoxy groups; alkylene groups such as ethylene and propylene groups; -CH 2 CH(OH)CH 2 More preferred are alkylene groups such as ethylene and propylene, and polyalkyleneoxy groups. 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 repetitions of the polyalkyleneoxy group) is preferably 2-20, more preferably 2-10, and even more preferably 2-6. From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group.In the group in which multiple ethyleneoxy groups and multiple 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 embodiment of the number of repetitions of the ethyleneoxy group in these groups is as described above.

[0069] In formula (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.

[0070] In formula (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.

[0071] It is also preferable that the polyimide precursor has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0072] In order to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be used as the diamine.

[0073] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it is 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, 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 114At least one of the groups is a group containing a polymerizable group, and it is preferable that both of the groups are groups containing a polymerizable group.

[0074] A 1 , A 2 , R 111 , R 113 and R 114 Each independently represents A in formula (2). 1 , A 2 , R 111 , R 113 and R 114 The same definition and preferred range are also the same. R 112 is R in Eq. (5). 112 The same definition and preferred range are also the same.

[0075] The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. In addition, it may 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).

[0076] 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 terminals may be the repeating unit represented by formula (2).

[0077] 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 has a molecular weight dispersity of 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 polyimide precursor is not particularly specified, 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 dispersity of molecular weight is a value calculated by weight average molecular weight / number average molecular weight. In addition, 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 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 one resin are each within the above ranges.

[0078] [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, the alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous solution of tetramethylammonium at 23° C., and from the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferable, and a polyimide that dissolves at 1.0 g or more is more preferable. The upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less. 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 bonding chain in the molecule of the polymer compound constituting the resin, and the term "side chain" refers to any other bonding chain.

[0079] -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 is, for example, R in the repeating unit represented by formula (4) described later, or R 131 It is preferable that R132 in the repeating unit represented by formula (4) described later is included in the repeating unit represented by formula (4) described later. 131 It is more preferable that the fluorinated alkyl group is contained in the above-mentioned formula (I). 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.

[0080] -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 later. 131 R in the repeating unit represented by formula (4) described later is preferably included. 131 It is more preferable that the organic modified (poly)siloxane structure described below is contained in the above. Furthermore, the silicon atom or the organic 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 mass % or more, and more preferably 20 mass % or less.

[0081] - 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 the side chain. The ethylenically unsaturated bond is preferably radically polymerizable. The ethylenically unsaturated bond is represented by R 132 or R in the repeating unit represented by formula (4) described below 131R in the repeating unit represented by formula (4) described later is preferably included. 132 or R in the repeating unit represented by formula (4) described below 131 It is more preferable that the ethylenically unsaturated bond-containing group is included in the formula (I). Among these, the ethylenically unsaturated bond is represented by R 131 R in the repeating unit represented by formula (4) described later is preferably included. 131 It is more preferable that the ethylenically unsaturated bond-containing group is included in the formula (I). Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

[0082] [ka]

[0083] 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.

[0084] In formula (IV), R 21 is an alkylene group having 2 to 12 carbon atoms, -O-CH 2 CH(OH)CH 2 -, -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 consisting of a combination of 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 any 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.

[0085] 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 formulae (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 formula (1). 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, etc.). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.).

[0086] In formula (IV), * represents a bonding site to another structure, and is preferably a bonding site to the main chain of a polyimide.

[0087] 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.

[0088] -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 the polymerizable group 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 131 It is preferred that the fluorine-containing compound 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.

[0089] - 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 group is the same as that described above, and preferred embodiments are also the same. The polarity conversion group is, for example, R 131 , R 132 , and are contained in the ends of polyimides.

[0090] -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. When the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, the "solvent development" described later), the acid value of the polyimide is preferably from 1 to 35 mgKOH / g, more preferably from 2 to 30 mgKOH / g, and further preferably from 5 to 20 mgKOH / 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 polyimide preferably has a pKa of 0 to 10, and more preferably has a pKa of 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 "Revised 5th Edition Chemistry Handbook: Basics" edited by the Chemical Society of Japan may be referenced. Furthermore, when the acid group is a polyacid such as phosphoric acid, the pKa is the first dissociation constant. As such an acid group, the polyimide preferably contains at least one type selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.

[0091] -Phenol hydroxy group- From the viewpoint of ensuring an appropriate development speed 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 132 or R in the repeating unit represented by formula (4) described below 131 It is preferred that the fluorine-containing compound 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, and more preferably 1 to 20 mol / g.

[0092] The polyimide used in the present invention is not particularly limited as long as it is a polymeric 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, 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 an 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 are the same as those 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).

[0093] 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 111 The same are exemplified, 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. The diamine may be an aliphatic, cycloaliphatic or aromatic diamine. Specific examples include R 111 Examples include:

[0094] R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain, from the viewpoint of more effectively suppressing 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.

[0095] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both 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 Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0096] R 132 represents a tetravalent organic group. The tetravalent organic group is R 115 The same are exemplified, and the preferred ranges are also the same. For example, R 115The four bonds of the tetravalent organic group exemplified by the following formula (4) are bonded to the four -C(=O)- portions in the above formula (4) to form a condensed ring.

[0097] Also, R 132 Examples of R include tetracarboxylic acid residues remaining after removal of the anhydride groups from tetracarboxylic dianhydride. 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.

[0098] R 131 and R 132 It is also preferable that at least one of R 131 Preferred examples of the 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) are mentioned. 132 As the above, the above (DAA-1) to (DAA-5) are more preferred examples.

[0099] It is also preferable that the polyimide has fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more and 20% by mass or less.

[0100] In order 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.

[0101] In order to improve the storage stability of the resin composition, the main chain end of the polyimide is preferably 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. Of these, it is more preferable to use a monoamine, and preferred compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-9-aminonaphthalene, 1-carboxy-10-aminonaphthalene, 1-carboxy-11-aminonaphthalene, 1-carboxy-12-aminonaphthalene, 1-carboxy-13-aminonaphthalene, 1-carboxy-14-aminonaphthalene, 1-carboxy-15-aminonaphthalene, 1-carboxy-16-aminonaphthalene, 1-carboxy-17-aminonaphthalene, 1-carboxy-18-aminonaphthalene, 1-carboxy-19 ... 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 blocking agents.

[0102] -Imidization rate (ring closure rate)- From the viewpoints of the film strength, insulating properties, etc. of the resulting organic film, the imidization rate of the polyimide (also referred to as the "ring closure rate") 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 -1 Next, the polyimide is heat-treated at 350°C for 1 hour, and the infrared absorption spectrum is measured again to obtain the peak intensity P1 around 1377cm. -1 Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be calculated based on the following formula. Imidization rate (%) = (peak intensity P1 / peak intensity P2) x 100

[0103] All polyimides are of the same type R 131 or R 132 The repeating unit 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) including: 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).

[0104] Polyimide can be synthesized by, for example, reacting tetracarboxylic dianhydride with diamine (partially substituted with a terminal blocking agent that is a monoamine) at low temperature, reacting tetracarboxylic dianhydride (partially substituted with a terminal blocking agent that is an acid anhydride, a monoacid chloride compound, or a monoactive ester compound) with diamine at low temperature, obtaining a diester from tetracarboxylic dianhydride with alcohol, and then reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine) in the presence of a condensing agent, obtaining a diester from tetracarboxylic dianhydride with alcohol, and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine), and then completely imidizing the polyimide precursor using a known imidization reaction method, or by stopping the imidization reaction midway and introducing a partial imide structure, or by blending a completely imidized polymer with the polyimide precursor to introduce a partial imide structure. Other known polyimide synthesis methods can also be applied.

[0105] The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. By making the weight average molecular weight 5,000 or more, it is possible to improve the folding resistance of the film after curing. In order to obtain an organic film having 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 further 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. The upper limit of the polyimide molecular weight dispersity is not particularly limited, but is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In addition, when the resin composition contains multiple types of polyimides as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyimide are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple types of polyimides as one resin are each within the above ranges.

[0106] [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, R 111 represents a divalent organic group, A 2 represents an oxygen atom or -NH-; R 113 represents a hydrogen atom or a monovalent organic group. The polyamide-imide precursor is R 111 It is preferable that the compound has a group capable of photodimerization.

[0107] 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 by 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 by 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 by a single bond or a linking group. The linking group includes, for example, -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 is preferred, and -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these is more preferred. 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 more preferably a halogenated alkylene group having 1 to 4 carbon atoms. In addition, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are 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 further preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0108] 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. Of the three carboxy groups of the tricarboxylic acid compound, two of the carboxy groups may be converted into acid anhydrides. The optionally halogenated tricarboxylic acid compound used in the production of the polyamideimide precursor includes branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0109] 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.

[0110] 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 bonded with a single bond, -O-, -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -SO 2 - or a compound linked via a phenylene group. These compounds may be compounds in which two carboxy groups are anhydridized (e.g., trimellitic anhydride) or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride).

[0111] In formula (PAI-2), R 111 , A 2 , R 113 are R in the above formula (2), 111 , A 2 , R 113 The same applies to the preferred embodiments.

[0112] The polyamideimide precursor may further comprise other repeat 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]

[0113] In formula (PAI-1), R 116 represents a divalent organic group, R 111 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 by 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 by 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 by a single bond or a linking group. The linking group includes, for example, -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 is preferred, and -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these is more preferred. 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 more preferably a halogenated alkylene group having 1 to 4 carbon atoms. In addition, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are 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 further preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0114] Also, R 116 is 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.

[0115] 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.

[0116] 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 hexadecafluorosuccinic acid. Examples of the fluorosebacic acid include fluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanediacid, heneicosanediacid, docosanediacid, tricosanediacid, tetracosanediacid, pentacosanediacid, hexacosanediacid, heptacosanediacid, octacosanediacid, nonacosanediacid, 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.

[0117] In formula (PAI-1), R 111 is R in the above formula (2). 111 The same applies to the preferred embodiments.

[0118] It is also preferable that the polyamideimide precursor has fluorine atoms in its structure. The fluorine atom content in the polyamideimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0119] In order 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 the diamine component.

[0120] An embodiment of the polyamideimide precursor of the present invention is one in which 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 the total 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 of the repeating units in the polyamideimide precursor except for the terminals 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 the repeating units represented by formula (PAI-2) and the repeating units represented by formula (PAI-1) 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 polyamideimide precursor except for the terminals may be either the repeating units represented by formula (PAI-2) or the repeating units represented by formula (PAI-1).

[0121] The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number average molecular weight (Mn) is 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 specified, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In addition, when the resin composition contains multiple types of polyamideimide precursors as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyamideimide precursor are within the above range. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple types of polyamideimide precursors as one resin are each within the above range.

[0122] [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, the alkali-soluble polyamideimide refers to a polyamideimide that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous solution of tetramethylammonium at 23° C., and from the viewpoint of pattern formability, it is preferable that the polyamideimide dissolves at 0.5 g or more, and more preferably that the polyamideimide dissolves at 1.0 g or more. The upper limit of the dissolution amount is not particularly limited, but it is preferable that it is 100 g or less. 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.

[0123] -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 R in the repeating unit represented by formula (PAI-3) described later is preferably included.117 , or R 111 It is more preferable that the fluorinated alkyl group is contained in the above-mentioned formula (I). 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.

[0124] - 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 the side chain. The ethylenically unsaturated bond is preferably radically polymerizable. The ethylenically unsaturated bond is represented by R 117 , or R 111 R in the repeating unit represented by formula (PAI-3) described later is preferably included. 117 , or R 111 It is more preferable that the ethylenically unsaturated bond-containing group is included in the formula (I). Preferred embodiments of the group having an ethylenically unsaturated bond are the same as those of the group having an ethylenically unsaturated bond in the above-mentioned polyimide.

[0125] 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.

[0126] -Polymerizable group other than ethylenically unsaturated bond- The polyamideimide may have a polymerizable group other than the 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 above-mentioned polyimide. The polymerizable group other than the ethylenically unsaturated bond is, for example, R111 It is preferred that the fluorine-containing compound 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, and more preferably 0.1 to 5 mol / g.

[0127] - 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 group is the same as that described above, and preferred embodiments are also the same.

[0128] -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, the "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. The acid value is measured by a known method, for example, the method described in JIS K 0070:1992. In addition, examples of the acid group contained in the polyamideimide include the same groups as the acid groups in the above-mentioned polyimides, and the preferred embodiments are also the same.

[0129] -Phenol hydroxy group- From the viewpoint of ensuring an appropriate development speed 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 fluorine-containing compound 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, and more preferably 1 to 20 mol / g.

[0130] The polyamideimide used in the present invention is not particularly limited as long as it is a polymeric 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), 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 an end of the polyamideimide.

[0131] 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. The preferred aspects of the terminal capping agent are the same as the preferred aspects of the terminal capping agent for the polyimide described above.

[0132] -Imidization rate (ring closure rate)- From the viewpoints of the film strength, insulating properties, etc. of the resulting organic film, the imidization rate of polyamideimide (also referred to as the "ring closure rate") 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 in the same manner as the ring closure rate of the polyimide described above.

[0133] The polyamideimide may contain repeat units represented by the above formula (PAI-3) all containing one type of R111 or R117, or may contain 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) including the repeating unit represented by the above formula (PAI-3). The polyamideimide may also contain other types of repeating units in addition to the repeating unit represented by the above formula (PAI-3). Examples of other types of repeating units include the repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0134] Polyamideimide can be synthesized, for example, by obtaining a polyamideimide precursor by a known method and completely imidizing the precursor by 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.

[0135] 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 folding resistance of the film after curing can be improved. In order to obtain an organic film having 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 further preferably 4,000 to 25,000. The polyamideimide has a molecular weight dispersity of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the polyamideimide molecular weight dispersity 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 addition, when the resin composition contains multiple types of polyamideimides as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyamideimide are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple types of polyamideimides as one resin are each within the above ranges.

[0136] [Method for producing polyimide precursor, 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 diamine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the diamine, etc. Among the above-mentioned production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the diamine, is more preferable. 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, phosphorus oxychloride, and the like. In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent during the reaction. The organic solvent may be one type or two or more types. The organic solvent can be appropriately selected depending on the raw material, and examples thereof 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 or the like, 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.

[0137] -End capping agent- In the method for producing 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 in order to further improve storage stability. When capping the carboxylic acid anhydride and acid anhydride derivative remaining at the resin terminal, examples of the terminal capping agent include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and it is more preferable to use monoalcohols, phenols, or monoamines in terms of reactivity and film stability. Preferred examples of monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, 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.Preferred examples of the monoamine compound 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 of the amino groups 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, and 4-aminothiophenol. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents. In addition, when the amino group at the resin end is blocked, it can be blocked with a compound having a functional group capable of reacting with the amino group. Preferred blocking agents for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, and the like, and more preferably carboxylic acid anhydrides and carboxylic acid chlorides. Preferred compounds of carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like. Preferred examples of the carboxylic acid chloride 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.

[0138] -Solid precipitation- The production of polyimide precursors and the like may include a step of precipitating a solid. Specifically, after filtering off the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction liquid as necessary, the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid, and then dried to obtain polyimide precursors and the like. In order to improve the degree of purification, the polyimide precursors and the like may be repeatedly subjected to operations such as redissolving, reprecipitating, and drying. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.

[0139] [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 type of specific resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0140] 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 It is preferable that the polyimide precursor contains two or more different polyimide precursors.

[0141] <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, simply referred to as "another resin"). Examples of other resins include phenol 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 high polymerizable group value and a weight average molecular weight of 20,000 or less (for example, a polymerizable group content of 1×10 per 1 g of resin) may be used. -3 By adding a (meth)acrylic resin having a molecular weight of at least 100 mol / g to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0142] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the resin composition. In addition, the content of other resins in the resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, even more preferably 60 mass% or less, and even more preferably 50 mass% or less, based on the total solid content of the resin composition. In addition, as a preferred embodiment of the resin composition of the present invention, the content of the other resin may be low. In the above 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 within the above range.

[0143] <Compounds having an alkoxysilyl group> The photosensitive resin composition of the present invention preferably contains compound B which is a compound having an alkoxysilyl group. The compounds corresponding to the above-mentioned specific resins are not considered to be compound B.

[0144] [Alkoxysilyl group] The alkoxysilyl group may be any one of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group. From the viewpoints of pattern formability and adhesion of the cured product to metal, a trialkoxysilyl group is preferred. The alkoxy group in the alkoxysilyl group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably an ethoxy group.

[0145] [Photodimerization Reaction Capable Group] Compound B preferably has at least one group selected from the group consisting of a photodimerization reactive group and a radically polymerizable group, and more preferably has at least one group selected from the group consisting of a group having a cinnamoyl structure and a radically polymerizable group. The preferred embodiments of the photodimerization reaction group contained in the compound B are the same as the preferred embodiments of the photodimerization reaction group contained in the specific resin described above. The radical polymerizable group contained in compound B 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 (meth)acrylamide group, or a (meth)acryloyloxy group, with a (meth)acryloyloxy group being preferred.

[0146] [Formula (B1-1), Formula (B1-2)] Compound B is preferably a compound represented by the following formula (B1-1) or (B1-2). Moreover, the compound represented by the following formula (B1-1) or (B1-2) is preferably a compound corresponding to the low molecular weight compound B described below. [ka] In formula (B1-1), R 1 each independently represents a monovalent organic group, n represents an integer of 0 to 5, T 1 and T 2 each independently represents a hydrogen atom or a monovalent organic group; X 1 represents a divalent linking group; Z 1 represents an alkoxysilyl group. In formula (B1-2), R 1 each independently represents a monovalent organic group, m represents an integer of 0 to 4, T 3 ~T 6 each independently represents a hydrogen atom or a monovalent organic group; X 2 and X 3 each independently represents a divalent linking group; Z 2 and Z 3 each independently represents an alkoxysilyl group.

[0147] In formula (B1-1), R 1 R each independently represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom. 1 When represents a monovalent organic group, it is preferably a hydrocarbon group, more preferably an alkyl group having 1 to 12 carbon atoms, a phenyl group or a biphenyl group. The above-mentioned hydrocarbon group may be substituted with a known substituent, such as a halogen atom or a cyano group. In formula (B1-1), n ​​represents an integer of 0 to 5, is preferably an integer of 0 to 3, more preferably 0 or 1, and particularly preferably 0. Also, when n is 1, R 1 is T 1 is preferably in the para position relative to the carbon atom to which it is attached. In formula (B1-1), T 1 and T 2 each independently represents a hydrogen atom or a monovalent organic group, is preferably a hydrogen atom, a cyano group, or a halogen atom, and is more preferably a hydrogen atom. Also, T 1 and T 2 are all hydrogen atoms, or T1 is a hydrogen atom, and T 2 An embodiment in which is a cyano group or a halogen atom is also one of the preferred embodiments. In formula (B1-1), X 1 represents a divalent linking group, and is a hydrocarbon group or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O) 2 - and -NR N - is preferably a group represented by a bond to at least one group selected from the group consisting of: Above R N 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. Also, X 1 is a group represented by the following formula (X-1) is also a preferred embodiment. [ka] In formula (X-1), L X1 represents a single bond or a divalent linking group; A X -O- or -NR N - represents L X2 represents a divalent linking group, * represents T in formula (B1-1). 1 represents the bonding site with the carbon atom to which Z is bonded, and # represents the bonding site with the carbon atom to which Z is bonded in formula (B1-1). 1 It represents the binding site with Above R N is as mentioned above. In formula (X-1), L X1 is preferably a single bond or a hydrocarbon group, more preferably a single bond or an optionally substituted ethylene group, and even more preferably a single bond or an unsubstituted ethylene group. Examples of the substituent on the ethylene group include a cyano group and a halogen atom. In formula (X-1), A X Ha-NR N - is preferred, and -NH- is more preferred. In formula (X-1), L X2 is a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2 - and -NR N A group represented by a bond to at least one group selected from the group consisting of - is preferred, a hydrocarbon group is more preferred, and an alkylene group is even more preferred. The number of carbon atoms in the hydrocarbon group or alkylene group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 3 to 6. In formula (B1-1), Z 1 The preferred embodiments of are the same as the preferred embodiments of the alkoxysilyl group in compound B described above.

[0148] In formula (B1-2), R 1 A preferred embodiment of the formula (B1-1) is R 1 This is similar to the preferred embodiment of the above. In formula (B1-2), T 3 ~T 6 each independently represents a hydrogen atom or a monovalent organic group, is preferably a hydrogen atom, a cyano group, or a halogen atom, and is more preferably a hydrogen atom. Also, T 1 and T 2 are all hydrogen atoms, or T 4 and T 5 is a hydrogen atom, and T 3 and T 6 An embodiment in which is a cyano group or a halogen atom is also one of the preferred embodiments. In formula (B1-2), X 2 and X 3 each independently represents a divalent linking group, and is a hydrocarbon group or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O) 2 - and -NR N - is preferably a group represented by a bond to at least one group selected from the group consisting of: Above R N is as mentioned above. In formula (B1-2), X 2 and X 3 In another preferred embodiment, one or both of the following is a group represented by the above formula (X-1). However, X 2is a group represented by the above formula (X-1), * in formula (X-1) represents T 3 represents the bonding site with the carbon atom to which Z is bonded, and # represents the bonding site with the carbon atom to which Z is bonded in formula (1-2). 2 It represents the binding site with Also, X 3 is a group represented by the above formula (X-1), * in formula (X-1) represents T 6 represents the bonding site with the carbon atom to which Z is bonded, and # represents the bonding site with the carbon atom to which Z is bonded in formula (B1-2). 3 It represents the binding site with In formula (B1-2), Z 2 and Z 3 The preferred embodiments of the alkoxysilyl group in the compound B are the same as the preferred embodiments of the alkoxysilyl group in the compound B described above.

[0149] [Azole group] It is also preferable that compound B has an azole group. According to the above embodiment, it is believed that the azole group coordinates with a metal such as copper, thereby further improving the adhesion of the cured product to the metal. The azole group in compound B may be a five-membered heterocyclic compound containing one or more nitrogen atoms as ring members and having a structure in which one or more hydrogen atoms have been removed from a five-membered heterocyclic compound which may have a substituent or a fused ring structure, but is preferably a five-membered heterocyclic compound containing only one or more nitrogen atoms and one or more carbon atoms as ring members and having a structure in which one or more hydrogen atoms have been removed from a five-membered heterocyclic compound which may have a substituent. From the viewpoint of adhesion of the cured product to metal, the azole group is preferably a group having a structure in which one or more hydrogen atoms have been removed from a pyrrole ring, a pyrazole ring, an indazole ring, an imidazole ring, a benzimidazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring, a benzotriazole ring, or a tetrazole ring, and more preferably a group having a structure in which one or more hydrogen atoms have been removed from an imidazole ring, a benzimidazole ring, a 1,2,4-triazole ring, or a benzotriazole ring.

[0150] The azole group in compound B is preferably a group represented by the following formula (B-1) or (B-2). [ka] In formula (B-1), R B1 represents a bonding site with other structures, a hydrogen atom or a monovalent organic group, Z B1 ~Z B4 are independent of each other, =CR B7 - or a nitrogen atom, R B7 represents a bonding site with other structures, a hydrogen atom, or a monovalent organic group, and R B1 and R B7 of which at least one represents a binding site with other structures; In formula (B-2), R B2 ~R B6 each independently represents a bonding site to another structure, a hydrogen atom or a monovalent organic group; Z B5 and Z B6 are independent of each other, =CR B8 - or a nitrogen atom, R B8 represents a bonding site with other structures, a hydrogen atom, or a monovalent organic group, and R B2 ~R B6 and R B8 At least one of these represents a binding site for other structures.

[0151] In formula (B-1), R B1 represents a bonding site to another structure, a hydrogen atom or a monovalent organic group, and more preferably a bonding site to another structure. Above R B1 The monovalent organic group in is not particularly limited, and any known organic group can be used as long as the effects of the present invention can be obtained, but is preferably a hydrocarbon group or an amino group, and more preferably an alkyl group or an amino group. The number of carbon atoms in the hydrocarbon group or alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 4. The amino group may be a substituted or unsubstituted amino group.

[0152] In formula (B-1), Z B1 ~Z B4 are independent of each other, =CR B7 - or a nitrogen atom. Among them, Z B1 ~Z B4 Two of them are nitrogen atoms and two are =CR B7 -Z B1 ~Z B4 One of them is a nitrogen atom and three are =CR B7 or Z B1 ~Z B4 Three of them are nitrogen atoms and one is =CR B7 - is preferred. Among these, Z B1 and Z B3 is a nitrogen atom, and Z B2 and Z B4 GA=CR B7 -Z B1 and Z B2 is a nitrogen atom, and Z B3 and Z B4 GA=CR B7 -Z B2 is a nitrogen atom, and Z B1 , Z B3 and Z B4 GA=CR B7 or Z B1 , Z B2 and Z B3 is a nitrogen atom, and Z B4 GA=CR B7 - is preferred, and Z B1 and Z B3 is a nitrogen atom, and Z B2 and Z B4 GA=CR B7 The more preferred embodiment is -. Above R B7 is preferably a hydrogen atom or a monovalent organic group. Also, Z B1 , Z B2 and Z B3 is a nitrogen atom, and Z B4 GA=CR B7 -If RB7 is preferably a binding site for another structure. R B7 Preferred embodiments of the monovalent organic group in the above R B1 The preferred embodiments are the same as those of the monovalent organic group in the above.

[0153] R contained in formula (B-1) B1 and R B7 At least one of these represents a binding site with another structure, and at least R B1 It is preferable that R represents a bonding site with another structure. B1 Only represents the binding site with other structures, and R B7 Each of the groups independently represents a hydrogen atom or a monovalent organic group, which is also one of the preferred embodiments of the present invention.

[0154] In formula (B-2), Z B5 and Z B6 are independent of each other, =CR B8 - or a nitrogen atom. Among them, Z B5 and Z B6 each represents a nitrogen atom, or Z B5 The nitrogen atom is Z B6 GA=CR B8 - is preferred. In formula (B-2), Z B5 and Z B6 When both represent nitrogen atoms, R B6 In formula (B-2), Z preferably represents a bonding site with another structure. B5 and Z B6 each represents a nitrogen atom, and R B6 An embodiment in which only represents a binding site to another structure is also one of the preferred embodiments of the present invention. In formula (B-2), Z B5 The nitrogen atom is Z B6 GA=CR B8 -, R B8 In formula (B-2), Z preferably represents a bonding site with another structure. B5 The nitrogen atom is ZB6 GA=CR B8 -, and R B8 An embodiment in which only represents a binding site to another structure is also one of the preferred embodiments of the present invention.

[0155] In formula (B-2), R B2 ~R B5 Each of R independently preferably represents a hydrogen atom or a monovalent organic group. B2 ~R B5 Preferred embodiments of the monovalent organic group in the above R B1 The preferred embodiments are the same as those of the monovalent organic group in the above. In formula (B-2), Z B5 The nitrogen atom is Z B6 GA=CR B8 -, R B6 R preferably represents a hydrogen atom or a monovalent organic group. B6 Preferred embodiments of the monovalent organic group in the above R B1 The preferred embodiments are the same as those of the monovalent organic group in the above. In other cases, R B6 It is preferred that Z represents a binding site with another structure. B5 The nitrogen atom is Z B6 GA=CR B8 -, R B8 It is preferred that represents a binding site to another structure. In formula (B-2), R B8 preferably represents a binding site to another structure. Z B5 and Z B6 Both are =CR B8 When expressing -, one R B8 It is preferable that R represents a bonding site with another structure, and the other represents a hydrogen atom or a monovalent organic group. B8 Preferred embodiments of the monovalent organic group in the above R B1 The preferred embodiments are the same as those of the monovalent organic group in the above.

[0156] R included in formula (B-2) B2 ~R B6 and R B8At least one of these represents a binding site with another structure, and at least R B6 or R B8 It is preferable that R represents a bonding site with another structure. B6 and R B8 Only one of the two represents the binding site with the other structure, and R B6 and R B8 The other of and R B2 ~R B5 Each of the groups independently represents a hydrogen atom or a monovalent organic group, which is also one of the preferred embodiments of the present invention.

[0157] Among these, the azole group is preferably a group represented by any one of the following formulas (B-3) to (B-6). [ka]

[0158] In formulas (B-3) to (B-6), R B9 ~R B20 each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site to another structure. In formulas (B-3) to (B-6), R B9 ~R B20 is preferably a hydrocarbon group, an amino group, or a nitro group. In formulas (B-3) to (B-6), R B9 ~R B20 Preferred embodiments of the hydrocarbon group in the above R B1 The preferred embodiments are the same as those of the hydrocarbon group in the above. Also, R B9 ~R B20 The amino group in may be a substituted amino group or an unsubstituted amino group.

[0159] [Other silane coupling agents] Compound B may also be a compound (another silane coupling agent) that does not have a photodimerization reactive group and an azole group but has an alkoxysilyl group. Examples of other silane coupling agents include, for example, compounds described in paragraph 0167 of International Publication No. 2015 / 199219, compounds described in paragraphs 0062-0073 of JP-A-2014-191002, compounds described in paragraphs 0063-0071 of International Publication No. 2011 / 080992, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, compounds described in paragraphs 0055 of International Publication No. 2014 / 097594, and compounds described in paragraphs 0067-0078 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.

[0160] [ka]

[0161] 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- (Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0162] Compound B may be a compound having a molecular weight of less than 2,000 (hereinafter also referred to as "low molecular compound B"), or may be a resin (hereinafter also referred to as "resin B"). From the viewpoint of adhesion of the cured product to metal, it is also preferable that the photosensitive resin composition contains both the low molecular weight compound B and the resin B. From the viewpoint of adhesion, compound B is preferably a resin.

[0163] [Low molecular compound B] The molecular weight of the low molecular weight compound B is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.

[0164] The number of photodimerization reactive groups in the low molecular weight compound B is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1. The number of alkoxysilyl groups in the low molecular weight compound B is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.

[0165] The low molecular weight compound B is preferably a compound represented by the above formula (B1-1) or (B1-2). The low molecular weight compound B may also be another silane coupling agent as described above.

[0166] [Resin B] The weight average molecular weight of Resin B is preferably from 2,000 to 100,000, more preferably from 3,000 to 70,000, and further preferably from 5,000 to 50,000.

[0167] The molar amount of the photodimerization reactive group in 1 g of Resin B is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and further preferably 0.005 to 0.1 mmol / g.

[0168] The molar amount of the polymerizable group in 1 g of Resin B is preferably from 0.001 to 1 mmol / g, more preferably from 0.002 to 0.3 mmol / g, and further preferably from 0.005 to 0.1 mmol / g.

[0169] The molar amount of the alkoxysilyl group in 1 g of Resin B is preferably from 0.001 to 1 mmol / g, more preferably from 0.002 to 0.3 mmol / g, and further preferably from 0.005 to 0.1 mmol / g.

[0170] Resin B is preferably a resin having a repeating unit containing a photodimerization group, a repeating unit containing a radically polymerizable group, and a repeating unit containing an alkoxysilyl group, and is more preferably a resin having a repeating unit containing a photodimerization group, and a repeating unit containing an alkoxysilyl group. Resin B may contain one type of these repeating units alone, or may contain two or more types.

[0171] -Repeating unit containing a photodimerization group- Resin B preferably contains a repeating unit represented by the following formula (BL-1) as a repeating unit containing a photodimerization reactive group. [ka] In formula (BL-1), L L1 represents a single bond or a divalent linking group; X L1 represents a group capable of photodimerization, and R represents a hydrogen atom or a methyl group. In formula (BL-1), L L1 represents a single bond or a divalent linking group, and a divalent linking group is preferable. The divalent linking group is a hydrocarbon group, or a combination of a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O) 2 - and -NR N A group represented by a bond to at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. Above R N is as mentioned above. The above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group. The above hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. Among these, L L1 is preferably a group represented by the following formula (BL-1-1). [ka] In formula (BL-1-1), L L4represents a divalent linking group, L L5 represents a single bond or a divalent linking group, * represents a bonding site with the carbonyl group in formula (BL-1), A L1 and A L2 -O- or -NR N -, and # is X in (BL-1). L1 It represents the binding site with R N is as mentioned above.

[0172] In formula (BL-1-1), L L4 is a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O) 2 - and -NR N A group represented by a bond to at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. Above R N is as mentioned above. The above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group. The above hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms.

[0173] In formula (BL-1-1), L L5 is preferably a single bond. L5 In the case where is a divalent linking group, the preferred embodiment is the above-mentioned L L4 This is similar to the preferred embodiment of the above.

[0174] In formula (BL-1-1), A L1 and A L2 -O- or -NR N -, preferably -O-. Above R N is as mentioned above.

[0175] In formula (BL-1), X L1 The preferred embodiments of are the same as the preferred embodiments of the photodimerization reactive group in compound B described above.

[0176] -Repeating unit containing a radically polymerizable group- Resin B preferably contains a repeating unit represented by the following formula (BP-1) as a repeating unit containing a radically polymerizable group. [ka] In formula (BP-1), A P -O- or -NR N - represents L P represents a n+1-valent linking group, X P represents a radically polymerizable group, R represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more.

[0177] In formula (BP-1), A P -O- or -NR N -, with -O- being preferred. N is as mentioned above.

[0178] In formula (BP-1), L P represents a linking group having a valence of n+1, which is a hydrocarbon group or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O) 2 - and -NR N A group represented by a bond to at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. Above R N is as mentioned above. The above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group. The above hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms.

[0179] In formula (BP-1), X P The preferred embodiments of are the same as the preferred embodiments of the radical polymerizable group in compound B described above.

[0180] In formula (BP-1), n ​​represents an integer of 1 or greater, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, particularly preferably 1 or 2, and most preferably 1.

[0181] -Repeating unit containing an alkoxysilyl group- Resin B preferably contains a repeating unit represented by the following formula (BA-2) as a repeating unit containing an alkoxysilyl group. [ka] In formula (BA-2), A 3 -O- or -NR N - represents L P1 represents a divalent linking group; X P1 represents an alkoxysilyl group, and R represents a hydrogen atom or a methyl group.

[0182] In formula (BA-2), A 3 -O- or -NR N -, with -O- being preferred. N is as mentioned above.

[0183] In formula (BA-2), L P1 represents a divalent linking group, and is a hydrocarbon group or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O) 2 - and -NR N A group represented by a bond to at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. Above R N is as mentioned above. The above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group. The above hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms.

[0184] In formula (BA-2), X P1 The preferred embodiments of are the same as the preferred embodiments of the alkoxysilyl group in compound B described above.

[0185] -Repeating unit containing an azole group- It is also preferable that Resin B contains a repeating unit represented by the following formula (BA-1) as a repeating unit containing an azole group. [ka] In formula (BA-1), L 3 represents a single bond or a divalent linking group; X 3 represents an azole group, and R represents a hydrogen atom or a methyl group. In formula (BA-1), L 3 represents a single bond or a divalent linking group. The divalent linking group is a hydrocarbon group, or a combination of a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O) 2 - and -NR N A group represented by a bond to at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. Above R N is as mentioned above. The above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group. The above hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. Among these, L 3 is preferably a single bond, a group represented by the following formula (BA-1-1) or a group represented by the following formula (BA-1-2). [ka] In formula (BA-1-1) or formula (BA-1-2), L 4 represents a divalent linking group, L 5 represents a single bond or a divalent linking group; L 6 represents a divalent linking group, L 7 represents a single bond or a divalent linking group, * represents a bonding site with the carbonyl group in formula (BA-1), A 1 and A 2 -O- or -NR N -, and # is X in (BA-1).3 It represents the binding site with

[0186] In formula (BA-1-1), L 4 is a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O) 2 - and -NR N A group represented by a bond to at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. Above R N is as mentioned above. The above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group. The above hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms.

[0187] In formula (BA-1-1), L 5 is preferably a single bond. 5 When L is a divalent linking group, 5 is a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O) 2 - and -NR N A group represented by a bond to at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred.

[0188] In formula (BA-1-2), L 6 is L in formula (BA-1-1) 4 The same applies to the preferred embodiments.

[0189] In formula (BA-1-2), L 7 is preferably a divalent linking group. 7 When L is a divalent linking group, 7 A preferred embodiment of the present invention is L in the above formula (BA-1-1). 5 is the same as the preferred embodiment when is a divalent linking group.

[0190] In formula (BA-1-1) or formula (BA-1-2), A 1 and A 2 -O- or -NRN -, with -O- being preferred. N is as mentioned above.

[0191] In formula (BA-1), X 3 The preferred embodiment of the azole group in formula (BA-1) is as described above. The bonding site of the azole group to other structures is L 3 This corresponds to the binding site for

[0192] Resin B may contain only one type of repeating unit represented by formula (BA-1), or may contain two or more types. When Resin B contains a repeating unit containing an azole group, the molar amount of the azole group per 1 g of Resin B is preferably 0.001 to 5 mmol / g, and more preferably 0.01 to 1 mmol / g.

[0193] -Other repeating units- Resin B may further have a repeating unit other than the repeating unit represented by the above formula (BL-1), formula (BP-1), formula (BA-2) or formula (BA-1).

[0194] [Specific examples] Specific examples of compound B include the compounds used in the Examples, but are not limited thereto.

[0195] [Content] The content of compound B is preferably from 0.05 to 10 mass %, more preferably from 0.10 to 5 mass %, and further preferably from 0.15 to 2 mass %, based on the total solid content of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention may contain only one type or two or more types of compound B. When two or more types of compound B are contained, the total amount is preferably within the above range.

[0196] <Compound C Having an Azole Group and at Least One Group Selected from the Group Consisting of a Radical Polymerizable Group and a Photodimerization Reactive Group> The photosensitive resin composition of the present invention preferably further contains a compound C having an azole group and at least one group selected from the group consisting of a radically polymerizable group and a photodimerization reactive group. Compound C is a compound that does not contain an alkoxysilyl group. The above-mentioned specific resin or compound B does not fall under compound C.

[0197] The azole group, radical polymerizable group, and photodimerization group in compound C are the same as the azole group, radical polymerizable group, and photodimerization group in compound B, respectively, and preferred embodiments are also the same.

[0198] Compound C may be a compound having a molecular weight of less than 2,000 (hereinafter also referred to as "low molecular compound C"), or may be a resin (hereinafter also referred to as "resin C"). From the viewpoint of adhesion of the cured product to metal, it is also preferable that the photosensitive resin composition contains both the low molecular weight compound C and the resin C. From the viewpoint of adhesion, compound C is preferably a resin.

[0199] [Low molecular compound C] The molecular weight of the low molecular weight compound C is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.

[0200] The number of azole groups in the low molecular weight compound C is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1. The number of photodimerization reactive groups in the low molecular weight compound C is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1. The number of radically polymerizable groups in the low molecular weight compound C is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.

[0201] [Resin C] The weight average molecular weight of Resin C is preferably from 2,000 to 100,000, more preferably from 3,000 to 70,000, and further preferably from 5,000 to 50,000.

[0202] The molar amount of the azole group in 1 g of Resin C is preferably from 0.001 to 1 mmol / g, more preferably from 0.002 to 0.3 mmol / g, and further preferably from 0.005 to 0.1 mmol / g.

[0203] The molar amount of the photodimerization reactive group in 1 g of resin C is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and further preferably 0.005 to 0.1 mmol / g.

[0204] The molar amount of the radically polymerizable group in 1 g of Resin C is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and further preferably 0.005 to 0.1 mmol / g.

[0205] Resin C is preferably a resin having a repeating unit having an azole group, and at least one repeating unit selected from the group consisting of a repeating unit containing a photodimerization group and a repeating unit containing a radically polymerizable group, and more preferably a resin having a repeating unit having an azole group, and a repeating unit containing a photodimerization group. Resin C may contain one kind of these repeating units alone or two or more kinds of them. Preferred embodiments of these repeating units are the same as those of the repeating units in Resin B. Furthermore, resin C may further include other repeating units.

[0206] [Specific examples] Specific examples of compound C include the compounds used in the Examples, but are not limited thereto.

[0207] [Content] The content of compound C is preferably from 0.05 to 10 mass %, more preferably from 0.10 to 5 mass %, and further preferably from 0.15 to 2 mass %, based on the total solid content of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention may contain only one type of compound C, or may contain two or more types of compound C. When two or more types of compound C are contained, the total amount is preferably within the above range.

[0208] <Compound D having an azole group and no alkoxysilyl group, no radical polymerizable group, and no photodimerization group> From the viewpoint of adhesion to metal of the obtained cured product, the photosensitive resin composition of the present invention preferably contains a compound D that has an azole group and does not have an alkoxysilyl group, a radically polymerizable group, or a group capable of photodimerization.

[0209] Compound D is preferably a compound represented by the following formula (D1-1) or (D1-2). [ka] In formula (D1-1), Z 1 ~Z 4 are independent of each other, =CR 7 - or a nitrogen atom, R 1 represents a hydrogen atom or a monovalent organic group, R 7 represents a hydrogen atom or a monovalent organic group, and the structure represented by formula (D1-1) does not contain an alkoxysilyl group, a radically polymerizable group, or a group capable of photodimerization; In formula (D1-2), Z 5 ~Z 6 are independent of each other, =CR 8 - or a nitrogen atom, R 2 ~R 6 each independently represents a hydrogen atom or a monovalent organic group; R 8 represents a hydrogen atom or a monovalent organic group, and the structure represented by formula (D1-2) does not include an alkoxysilyl group, a radically polymerizable group, or a group capable of photodimerization.

[0210] In formula (D1-1), Z 1 ~Z 4 are independent of each other, =CR 7 - or a nitrogen atom. Among them, Z 1 ~Z 4 One of them is a nitrogen atom and three are =CR 7 -Z 1 ~Z 4 Two of them are nitrogen atoms and two are =CR 7 or Z 1 ~Z 4 Three of them are nitrogen atoms and one is =CR 7 - is preferred. Among these, Z 1 and Z 3 is a nitrogen atom, and Z 2 and Z 4 GA=CR 7 -Z 1 and Z 2 is a nitrogen atom, and Z 3 and Z 4 GA=CR 7 or Z 1 , Z 2 and Z 3 is a nitrogen atom, and Z 4 GA=CR 7 - is preferred, and Z 1 and Z 3 is a nitrogen atom, and Z 2 and Z 4 GA=CR B7 or Z 1 , Z 2 and Z 3 is a nitrogen atom, and Z 4 GA=CR 7 The more preferred embodiment is -.

[0211] In formula (D1-1), R 1 is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. The above hydrocarbon group or alkyl group preferably has 1-20 carbon atoms, more preferably 1-10 carbon atoms, and even more preferably 1-4 carbon atoms.

[0212] In formula (D1-1), R 7 A preferred embodiment of R 1 is the same as:

[0213] In formula (D1-2), Z 5 and Z 6 are independent of each other, =CR 8 - or a nitrogen atom. Among them, Z 5 and Z 6 each represents a nitrogen atom, or Z 5 The nitrogen atom is Z 6 GA=CR 8 - is preferred.

[0214] In formula (D1-2), R 2 ~R 6 , R 8 are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

[0215] [Specific examples] Specific examples of compound D include the compounds used in the Examples, but are not limited thereto.

[0216] [Content] The content of compound D is preferably from 0.05 to 10 mass %, more preferably from 0.10 to 5 mass %, and further preferably from 0.15 to 2 mass %, based on the total solid content of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention may contain only one type or two or more types of compound D. When two or more types of compound D are contained, the total amount is preferably within the above range.

[0217] <Solvent> The resin composition of the present invention preferably contains a solvent. The solvent may be any known 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.

[0218] 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.)), 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 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 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 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-eth Preferred examples of the cypropionic acid alkyl esters include 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, 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.

[0219] Suitable examples of the 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.

[0220] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0221] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0222] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0223] 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.

[0224] Preferred examples of the ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0225] 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, methylamyl alcohol, and diacetone alcohol.

[0226] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0227] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more of them, is preferred. A combination of dimethyl sulfoxide and γ-butyrolactone, or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0228] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solids concentration of the resin composition of the present invention is 5 to 80 mass%, more preferably an amount such that the total solids concentration is 5 to 75 mass%, even more preferably an amount such that the total solids concentration is 10 to 70 mass%, and even more preferably an amount such that the total solids concentration is 20 to 70 mass%. The content of the solvent may be adjusted according to the desired thickness of the coating film and the coating method.

[0229] The resin composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more types of solvents are contained, the total amount thereof is preferably within the above range.

[0230] [Photopolymerization initiator] The composition of the present invention includes a photopolymerization initiator. The photopolymerization initiator is preferably 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 having photosensitivity to light rays in the ultraviolet to visible regions is preferable. Alternatively, it may be an activator that generates active radicals by reacting with a photoexcited sensitizer.

[0231] 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 It is preferable that 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 the molar absorption coefficient at a concentration of 0.01 g / L using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) using ethyl acetate as a solvent.

[0232] Any known compound can be used as the photoradical polymerization initiator. For example, 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 oxide, hexaarylbiimidazole, 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, iron arene complexes, etc. For details of these, refer to the descriptions in 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, the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A and JP Patent No. 6301489 A, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in WO 2018 / 221177 A, the photopolymerization initiators described in WO 2018 / 110179 A, ​​the photopolymerization initiators described in JP 2019-043864 A, the photopolymerization initiators described in JP 2019-044030 A, and the peroxide-based initiators described in JP 2019-167313 A are mentioned, and the contents of these are also incorporated herein.

[0233] Examples of the ketone compound include the compounds described in paragraph 0087 of JP2015-087611A, the contents of which are incorporated herein by reference. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0234] In one embodiment of the present invention, as the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in JP-A-4225898 can be used, the contents of which are incorporated herein by reference.

[0235] Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names: all manufactured by BASF).

[0236] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all manufactured by BASF).

[0237] As the aminoacetophenone-based initiator, compounds having a maximum absorption wavelength matching a light source having a wavelength of 365 nm or 405 nm, etc., as described in JP-A-2009-191179 can also be used, the contents of which are incorporated herein by reference.

[0238] Examples of the acylphosphine oxide initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. In addition, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.

[0239] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0240] As the photoradical polymerization initiator, more preferably, an oxime compound is used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. The oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0241] 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 JP 2000-066385 A, compounds described in JP-T-2004-534797 A, compounds described in JP-A-2017-019766 A, compounds described in Japanese Patent No. 6065596 A, compounds described in WO 2015 / 152153 A, compounds described in WO 2017 / 051680 A, compounds described in JP-A-2017-198865 A, compounds described in paragraphs 0025-0038 of WO 2017 / 164127 A, compounds described in WO 2013 / 167515 A, and the like, the contents of which are incorporated herein by reference.

[0242] Preferred oxime compounds include, for example, compounds having the following structure, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. The oxime-based photoradical polymerization initiator has a linking group of >C=NOC(=O)- in the molecule.

[0243] [ka]

[0244] Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), and Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., photoradical polymerization initiator 2 described in JP-A-2012-014052). In addition, 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 Co., Ltd.) can also be used. In addition, DFI-091 (manufactured by Daito Chemistry Co., Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can also be used. In addition, an oxime compound having the following structure can also be used. [ka]

[0245] 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-A-2014-137466 and JP-A-06636081, the contents of which are incorporated herein by reference.

[0246] 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 International Publication No. 2013 / 083505, the contents of which are incorporated herein by reference.

[0247] In addition, 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-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, paragraph 0345, and compound (C-3) described in JP-A-2013-164471, paragraph 0101, the contents of which are incorporated herein by reference.

[0248] 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. In addition, an example of the oxime compound having a nitro group is Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).

[0249] As the photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can be used. Specific examples include OE-01 to OE-75 described in WO 2015 / 036910.

[0250] As the photoradical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019 / 088055, the contents of which are incorporated herein by reference.

[0251] 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 OX1Examples of the electron-withdrawing group of 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. An acyl group and a nitro group are preferred, and an acyl group is more preferred because it is easy 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, more preferably 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, and even more preferably an alkoxy group, an alkylsulfanyl group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group.

[0252] The oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), and is more preferably the compound represented by the 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 heterocyclic oxy 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, RX3 ~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.

[0253] 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.

[0254] 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.

[0255] 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.

[0256] 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.

[0257] 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. 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.

[0258] 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 ketone such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, quinones condensed with aromatic rings such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoins, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, a compound represented by the following formula (I) may be used.

[0259] [ka]

[0260] In formula (I), R I00is 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 each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0261] [ka]

[0262] In the formula, R I05 ~R I07 is R in the above formula (I). I02 ~R I04 is the same as:

[0263] In addition, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of WO 2015 / 125469 can also be used, the contents of which are incorporated herein by reference.

[0264] 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, so good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity is reduced and the solubility in a solvent or the like is improved, so that precipitation is less likely to occur over time, and the stability over time of the resin composition can be improved. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-2015 / 004565, WO-2016-532675, paragraphs 0407 to 0412, and WO-2017 / 033680, paragraphs 0039 to 0055; compounds (E) and (G) described in JP-T-2013-522445; compounds (C) and (D) described in WO-2016 / 033680; Examples of the photoinitiator include Cmpd1 to 7 described in Japanese Patent Publication No. 34963, the oxime ester photoinitiator described in paragraph 0007 of JP-T-2017-523465, the photoinitiator 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 photoinitiator described in Japanese Patent Publication No. 6469669, the contents of which are incorporated herein by reference.

[0265] When a photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30 mass% based on the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass%, further 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 caused by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

[0266] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The sensitizer in the electronically excited state 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 and the photoradical polymerization initiator undergo a chemical change and are decomposed to generate 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, indigo-based compounds, and the like. Examples of the sensitizer 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-dimethylaminocinnamylidene indanone, and p-dimethylaminobenzylidene indanone. 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, isoethylaminobenzoate 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, reference can be made to paragraphs 0161 to 0163 of JP2016-027357A, the contents of which are incorporated herein by reference.

[0267] 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 further 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 kinds.

[0268] [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 those having -SS-, -SO 2 Compounds having -S-, -NO-, SH, PH, SiH, and GeH, dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization, etc. can be used. These can donate hydrogen to a low activity radical to generate a radical, or can generate a radical by being oxidized and then deprotonated. In particular, thiol compounds can be preferably used.

[0269] In addition, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of WO 2015 / 199219 can also be used, the contents of which are incorporated herein by reference.

[0270] 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, based on 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 is preferably within the above range.

[0271] [Photoacid generator] The resin composition of the present invention preferably contains a photoacid generator. The photoacid generator refers to a compound that generates at least one of a Bronsted acid and a Lewis acid when irradiated with light of 200 nm to 900 nm. The light to be irradiated is preferably light having a wavelength of 300 nm to 450 nm, more preferably light having a wavelength of 330 nm to 420 nm. The photoacid generator is preferably a photoacid generator that can generate an acid by being exposed to light, either alone or in combination with a sensitizer. Preferred examples of the acid to be generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acids, phosphoric acid monoesters, phosphoric acid diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.

[0272] Examples of the photoacid generator used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halide compounds, organic borate compounds, disulfone compounds, onium salt compounds, and the like. From the viewpoints of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the viewpoints of the mechanical properties of the film to be formed, oxime esters are preferred.

[0273] Examples of the quinone diazide compound include a monovalent or polyvalent hydroxy compound to which the sulfonic acid of quinone diazide is ester-bonded, a monovalent or polyvalent amino compound to which the sulfonic acid of quinone diazide is sulfonamide-bonded, and a polyhydroxy polyamino compound to which the sulfonic acid of quinone diazide is ester-bonded and / or sulfonamide-bonded. All functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxy polyamino compounds do not have to be substituted with quinone diazide, but it is preferable that on average 40 mol% or more of the total functional groups are substituted with quinone diazide. By including such a quinone diazide compound, it is possible to obtain a resin composition that is sensitive to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which are common ultraviolet rays.

[0274] Specific examples of hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, and BisO CP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML -PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, T riML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all product names, manufactured by Honshu Chemical Industries), BIR-OC, BI P-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (product names, Examples of suitable tertiary phenols include, but are not limited to, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and novolak resins.

[0275] Specific examples of the amino compound include, but are not limited to, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0276] Specific examples of the polyhydroxypolyamino compound include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

[0277] Among these, it is preferable that the quinone diazide compound contains a phenol compound and an ester of 4-naphthoquinone diazide sulfonyl group, which can provide higher sensitivity to i-line exposure and higher resolution.

[0278] The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the resin. By setting the content of the quinone diazide compound within this range, it is possible to obtain a contrast between the exposed and unexposed parts, thereby achieving higher sensitivity, which is preferable. Furthermore, a sensitizer or the like may be added as necessary.

[0279] The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as an "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably an oxime sulfonate compound represented by the following formula (OS-1), or the below-described formula (OS-103), formula (OS-104), or formula (OS-105).

[0280] [ka]

[0281] In formula (OS-1), X 3 represents an alkyl group, an alkoxy group, or a halogen atom. 3 When there are a plurality of X's, they may be the same or different. 3 The alkyl group and alkoxy group in the above formula (X) may have a substituent.3 The alkyl group in the above formula (X) is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. 3 The alkoxy group in the above formula (I) is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. 3 The halogen atom in is preferably a chlorine atom or a fluorine atom. In formula (OS-1), m3 represents an integer of 0 to 3, and is preferably 0 or 1. When m3 is 2 or 3, a plurality of X 3 may be the same or different. In formula (OS-1), R 34 represents an alkyl group or an aryl group, and is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

[0282] In formula (OS-1), m3 is 3, and X 3 is a methyl group, and X 3 The substitution position of is the ortho position, and R 34 Particularly preferred are compounds in which R is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group, or a p-tolyl group.

[0283] Specific examples of the oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraphs 0064 to 0068 of JP2011-209692A and paragraphs 0158 to 0167 of JP2015-194674A, the contents of which are incorporated herein by reference.

[0284] [ka]

[0285] In formula (OS-103) ~ formula (OS-105), R s1 represents an alkyl group, an aryl group, or a heteroaryl group, and R may be present in plural. s2 R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and may be present in plurality. s6 each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group; Xs represents O or S; ns represents 1 or 2; and ms represents an integer of 0 to 6. In formula (OS-103) ~ formula (OS-105), R s1 The alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms), or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by the following formula may have a known substituent as long as the effects of the present invention can be obtained.

[0286] In formula (OS-103) ~ formula (OS-105), R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), and more preferably a hydrogen atom or an alkyl group. s2 Among R, it is preferable that one or two of them are an alkyl group, an aryl group, or a halogen atom, it is more preferable that one of them is an alkyl group, an aryl group, or a halogen atom, and it is particularly preferable that one of them is an alkyl group and the remaining one is a hydrogen atom. s2 The alkyl group or aryl group represented by the following formula may have a known substituent as long as the effects of the present invention can be obtained. In formula (OS-103), formula (OS-104), or formula (OS-105), Xs represents O or S, and is preferably O. In the above formulae (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered or 6-membered ring.

[0287] In formulae (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1; and when Xs is S, ns is preferably 2. In formula (OS-103) ~ formula (OS-105), R s6 The alkyl group (preferably having 1 to 30 carbon atoms) and alkyloxy group (preferably having 1 to 30 carbon atoms) represented by the following formula may have a substituent. In formulae (OS-103) to (OS-105), ms represents an integer of 0 to 6, is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0288] Furthermore, the compound represented by formula (OS-103) above is particularly preferably a compound represented by formula (OS-106), formula (OS-110) or formula (OS-111) below; the compound represented by formula (OS-104) above is particularly preferably a compound represented by formula (OS-107) below; and the compound represented by formula (OS-105) above is particularly preferably a compound represented by formula (OS-108) or formula (OS-109) below. [ka]

[0289] In formula (OS-106) ~ formula (OS-111), R t1 represents an alkyl group, an aryl group, or a heteroaryl group; R t7 represents a hydrogen atom or a bromine atom, R t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group; R t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group; R t2 represents a hydrogen atom or a methyl group. In formula (OS-106) ~ formula (OS-111), R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

[0290] In formula (OS-106) ~ formula (OS-111), R t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group, and is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0291] In formula (OS-106) ~ formula (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom. R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. In the above oxime sulfonate compound, the stereochemical structure (E, Z) of the oxime may be either one or a mixture. Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include the compounds described in paragraphs 0088 to 0095 of JP-A No. 2011-209692 and paragraphs 0168 to 0194 of JP-A No. 2015-194674, the contents of which are incorporated herein by reference.

[0292] Other preferable embodiments of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formula (OS-101) and formula (OS-102).

[0293] [ka]

[0294] In formula (OS-101) or formula (OS-102), R u9R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. u9 is more preferably a cyano group or an aryl group, u9 More preferably, is a cyano group, a phenyl group, or a naphthyl group. In formula (OS-101) or formula (OS-102), R u2a represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH-, -NR u5 -, -CH 2 -, -CR u6 H- or CR u6 R u7 - represents R u5 ~R u7 each independently represents an alkyl group or an aryl group.

[0295] In formula (OS-101) or formula (OS-102), R u1 ~R u4 R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amido group, a sulfo group, a cyano group, or an aryl group. u1 ~R u4 Two of the rings may be bonded to each other to form a ring. In this case, the rings may be condensed to form a condensed ring together with the benzene ring. u1 ~R u4 is preferably a hydrogen atom, a halogen atom or an alkyl group, and R u1 ~R u4 It is also preferable that at least two of R are bonded to each other to form an aryl group. u1 ~R u4 is preferably a hydrogen atom. Any of the above-mentioned substituents may further have a substituent.

[0296] The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102). In the above oxime sulfonate compound, the stereostructures (E, Z, etc.) of the oxime and benzothiazole rings may each be either one or a mixture. Specific examples of the compound represented by formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of JP-A No. 2011-209692 and paragraphs 0195 to 0207 of JP-A No. 2015-194674, the contents of which are incorporated herein by reference. Among the above compounds, the following b-9, b-16, b-31, and b-33 are preferred. [ka] Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and MBZ-101 (manufactured by Midori Chemical Industries, Ltd.).

[0297] Further, compounds represented by the following structural formulas are also preferred examples. [ka]

[0298] Specific examples of the organic halogenated compounds include those described in Wakabayashi et al., Bull Chem. Soc. Japan, vol. 42, p. 2924 (1969), U.S. Pat. No. 3,905,815, JP-B-4605 / 1971, JP-A-36281 / 1973, JP-A-32070 / 1980, JP-A-239736 / 1985, JP-A-169835 / 1986, JP-A-169837 / 1987, JP-A-58241 / 1987, JP-A-212401 / 1987, JP-A-70243 / 1988, JP-A-298339, and M.P. Hutt, Journal of Heterocyclic Chemistry, vol. 1 (No. 3), (1970), the contents of which are incorporated herein by reference. In particular, preferred examples include oxazole compounds substituted with a trihalomethyl group: S-triazine compounds. More preferably, an s-triazine derivative having at least one mono-, di-, or trihalogen-substituted methyl group bonded to the s-triazine ring, specifically, for example, 2,4,6-tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, Azine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxy phenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(pi-propyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-nathoxynaphthyl)-4,6- Examples of the bis(trichloromethyl)-s-triazine include bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, and 2-methoxy-4,6-bis(tribromomethyl)-s-triazine.

[0299] Examples of the organic borate compounds include those described in JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, JP-A-2000-131837, JP-A-2002-107916, Japanese Patent No. 2764769, JP-A-2002-116539, and Kunz, Martin, "Rad Tech '98. Proceedings of April organic boron sulfonium complexes or organic boron oxosulfonium complexes described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561; organic boron iodine complexes described in JP-A-6-175554 and JP-A-6-175553; Specific examples include organoboron phosphonium complexes described in JP-A-9-188710, and organoboron transition metal coordination complexes described in JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, and the like, the contents of which are incorporated herein by reference.

[0300] Examples of the disulfone compounds include compounds described in JP-A-61-166544 and JP-A-2001-132318, and diazodisulfone compounds.

[0301] Examples of the onium salt compound include diazonium salts described in SI Schlesinger, Photogr. Sci. Eng., 18, 387 (1974) and TSBal et al., Polymer, 21, 423 (1980); ammonium salts described in U.S. Pat. No. 4,069,055 and JP-A-4-365049; phosphonium salts described in U.S. Pat. Nos. 4,069,055 and 4,069,056; iodine salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP-A-2-150848 and JP-A-2-296514. sulfonium salts described in European Patent Nos. 370,693, 390,214, 233,567, 297,443, and 297,442, U.S. Patent Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, and 2,833,827, German Patent Nos. 2,904,626, 3,604,580, and 3,604,581; selenonium salts described in JV Crivello et al., J. Polymer Sci., Polymer Chem. Ed., 17, 1047(1979); arsonium salts described in C.S.Wen et al., Teh., Proc. Conf. Rad. Curing ASIA, p. 478, Tokyo, Oct. (1988); and onium salts such as pyridinium salts, the contents of which are incorporated herein by reference.

[0302] The onium salt includes onium salts represented by the following general formulas (RI-I) to (RI-III). [ka] In formula (RI-I), Ar 11Z represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an alkylamide group having 1 to 12 carbon atoms in the alkyl group or an arylamide group having 6 to 20 carbon atoms in the aryl group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. 11 - represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion. From the viewpoint of stability, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, or a sulfinate ion is preferred. 21 , Ar 22 each independently represents an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group in which the alkyl group each independently has 1 to 12 carbon atoms, an alkylamide group or an arylamide group in which the alkyl group has 1 to 12 carbon atoms, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. -represents a monovalent anion, and is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion. From the standpoint of stability and reactivity, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion is preferred. 31 , R 32 , R 33 each independently represents an aryl group, alkyl group, alkenyl group, or alkynyl group having 6 to 20 carbon atoms, which may have 1 to 6 substituents, and is preferably an aryl group from the viewpoint of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group in which the carbon number of the alkyl group is independently 1 to 12 carbon atoms, an alkylamide group or an arylamide group in which the carbon number of the alkyl group is 1 to 12 carbon atoms, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z 31 - represents a monovalent anion, such as a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, and from the standpoint of stability and reactivity, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion is preferred.

[0303] Specific examples of preferred photoacid generators include the following: [ka] [ka] [ka] [ka]

[0304] The photoacid generator is preferably used in an amount of 0.1 to 20 mass %, more preferably 0.5 to 18 mass %, even more preferably 0.5 to 10 mass %, still more preferably 0.5 to 3 mass %, and even more preferably 0.5 to 1.2 mass %, based on the total solid content of the resin composition. The photoacid generator may be used alone or in combination of two or more kinds. In the case of using a combination of two or more kinds, the total amount thereof is preferably within the above range. It is also preferable to use a sensitizer in combination in order to impart photosensitivity to a desired light source.

[0305] <Thermal acid generator> The compositions of the present invention may also include a thermal acid generator. The thermal acid generator generates an acid upon heating, and has the effect of promoting the crosslinking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound.

[0306] The thermal decomposition starting temperature of the thermal acid generator is preferably 50° C. to 270° C., more preferably 50° C. to 250° C. In addition, it is preferable to select as the thermal acid generator a material that does not generate acid during drying (pre-baking: about 70 to 140° C.) after the composition is applied to a substrate, but generates acid during final heating (cure: about 100 to 400° C.) after patterning by subsequent exposure and development, because this can suppress a decrease in sensitivity during development. The thermal decomposition onset temperature is determined as the lowest exothermic peak temperature when the thermal acid generator is heated to 500° C. at 5° C. / min in a pressure-resistant capsule. An example of an instrument used to measure the thermal decomposition onset temperature is Q2000 (manufactured by TA Instruments).

[0307] The acid generated from the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid, or a haloalkylsulfonic acid such as trifluoromethanesulfonic acid, etc. Examples of such thermal acid generators include those described in paragraph 0055 of JP2013-072935A.

[0308] Among these, from the viewpoint of being less likely to remain in the organic film and being less likely to deteriorate the physical properties of the organic film, those which generate alkylsulfonic acids having 1 to 4 carbon atoms or haloalkylsulfonic acids having 1 to 4 carbon atoms are more preferred, and examples thereof include (4-hydroxyphenyl)dimethylsulfonium methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium methanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium methanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium methanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium methanesulfonate, (4-hydroxyphenyl)dimethylsulfonium trifluoromethanesulfonate, and the like. As the thermal acid generator, preferred are fluorine, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium trifluoromethanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium trifluoromethanesulfonate, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl)propanenitrile, and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

[0309] In addition, the compounds described in paragraph 0059 of JP-A-2013-167742 are also preferred as thermal acid generators.

[0310] The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the specific resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and solvent resistance of the organic film can be further improved. In addition, from the viewpoint of the electrical insulation of the organic film, the content is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

[0311] <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. Examples of base generators that are preferable for the resin composition of the present invention include a thermal base generator and a photobase generator. 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, and the performance as an interlayer insulating film for a rewiring layer contained in a semiconductor package can be improved. 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.Known base generators include, for example, 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, acyloxyimino compounds, etc. Specific examples of the non-ionic base generator include compounds represented by formula (B1), formula (B2), or formula (B3). [ka]

[0312] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 are each independently an organic group not having a tertiary amine structure, a halogen atom, or a hydrogen atom. 1 and Rb 2 cannot be hydrogen atoms at the same time. 1 , Rb 2 and Rb 3 None of the above 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 a hydrocarbon carbon atom. Therefore, this does not apply to cases in which the bonded carbon atom is a carbon atom that forms a carbonyl group, that is, when the bonded carbon atom forms an amide group together with the nitrogen atom.

[0313] In formulas (B1) and (B2), Rb 1 , Rb 2 and Rb 3 At least one of these preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and is preferably a monocyclic ring or a condensed ring in which two monocyclic rings are condensed. The monocyclic ring is preferably a 5-membered 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.

[0314] More specifically, Rb 1 and Rb 2is 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 Rb may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocycle. 1 and Rb 2 is 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.

[0315] Rb 3Examples 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 alkoxy 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 preferable. 3 may further have a substituent within the range in which the effects of the present invention are exhibited.

[0316] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or (B1-2). [ka]

[0317] In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb 32 respectively represent Rb in formula (B1). 1 and Rb 2 is the same as: Rb 13is 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 can be achieved. 13 is preferably an arylalkyl group.

[0318] Rb 33 and Rb 34 each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and 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 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 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 more preferably having 7 to 11 carbon atoms), and a hydrogen atom is preferable.

[0319] Rb 35 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and 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 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 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 more preferably having 7 to 12 carbon atoms), and an aryl group is preferable.

[0320] The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a). [ka]

[0321] Rb 11 and Rb 12is 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 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 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 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 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 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 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 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 more preferably having 7 to 12 carbon atoms), and among these, an aryl group is preferable.

[0322] [ka]

[0323] 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.

[0324] In this specification, the term "linking chain" refers to an atomic chain on a path connecting two atoms or atomic groups to be linked, which links these objects with the shortest distance (the smallest number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group, has an ethylene group as a 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]

[0325] The number of carbon atoms in L in formula (B3) (including carbon atoms other than the carbon atoms 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 proceeding with 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 of 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.

[0326] The base generator also preferably contains a compound represented by the following formula (N1). [ka]

[0327] 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.

[0328] 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 is the shortest path between the two carbonyl groups in the formula.

[0329] 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 alkyl group, the generated base has high basicity, which 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, 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.

[0330] R N1 and R N2Examples of the aliphatic hydrocarbon group constituting the above include a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of 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 a carbon number of 3 to 12, 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 relating to the combination of the chain alkyl group and the cyclic alkyl group preferably has a carbon number of 4 to 24, more preferably 4 to 18, and further preferably 4 to 12. Examples of the group relating to the combination of the chain alkyl group and the 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 them, 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 in which 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.

[0331] R N1 and R N2may be linked together to form a cyclic structure. In forming the 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 single ring or a condensed ring, but is preferably a single ring. The cyclic structure formed is preferably a 5-membered 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.

[0332] R C1 represents a hydrogen atom or a protecting group, and is preferably a hydrogen atom.

[0333] The protecting group is preferably a protecting group which is decomposed by the action of an acid or a base, and preferably includes a protecting group which is decomposed by an acid.

[0334] Specific examples of the protective group include linear or cyclic alkyl groups, or linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl groups. Specific examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and more specific examples of such groups include methyloxymethyl (MOM) and ethyloxyethyl (EE). Examples of cyclic alkyl groups having an oxygen atom in the chain include epoxy, glycidyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl (THP) groups.

[0335] The divalent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may have an atom other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a group related to a combination of a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, and even more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. It is more 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 relating to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and even more preferably 7 to 10 carbon atoms.

[0336] 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 has 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 further 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 further preferably 1 to 3 carbon atoms.

[0337] The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and still 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 still more preferably 1 to 3. The cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 6. The cyclic alkenylene group preferably has 1 to 6 C═C bonds, and more preferably has 1 to 4 C═C bonds, and even more preferably has 1 or 2 C═C bonds. The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further 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 further 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.

[0338] Examples of the base generator include the following, but the present invention is not limited thereto.

[0339] [ka]

[0340] 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.

[0341] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0342] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [ka]

[0343] Specific examples of iminium salts include the following compounds, but the present invention is not limited to these. [ka]

[0344] 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.

[0345] <Polymerizable compound> The resin composition of the present invention preferably contains a polymerizable compound. The polymerizable compound may include a radical crosslinking agent or other crosslinking agents.

[0346] [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. The group having an ethylenically unsaturated bond includes a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, a (meth)acrylamide group, and the like. Among these, 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 preferable.

[0347] 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 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 obtained 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.

[0348] 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.

[0349] Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids are also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. As another example, it is also possible to use a compound group in which the above unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, etc. As specific examples, the description in paragraphs 0113 to 0122 of JP2016-027357A can be referred to, and the contents of these are incorporated herein by reference.

[0350] In addition, the radical crosslinking agent is preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples of such a compound 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 the compound include polyfunctional acrylates and methacrylates such as compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylating the compound, urethane (meth)acrylates as described in JP-B-48-041708, JP-B-50-006034, and JP-A-51-037193, polyester acrylates as described in JP-A-48-064183, JP-B-49-043191, and JP-A-52-030490, and epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. Compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, there can be mentioned 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.

[0351] 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-2010-160418, JP-A-2010-129825, Japanese Patent No. 4364216, etc., and cardo resins can also be used.

[0352] Other examples include specific unsaturated compounds described in JP-B-46-043946, JP-B-01-040337, and JP-B-01-040336, and vinylphosphonic acid compounds described in JP-A-02-025493. Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in the Journal of the Japan Adhesion Association, Vol. 20, No. 7, pages 300-308 (1984) can also be used.

[0353] 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.

[0354] 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.

[0355] 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.

[0356] As the radical crosslinking agent, 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.), 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.), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. Oligomer types of these may also be used.

[0357] 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 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 Blenmer PME400 (manufactured by NOF Corporation).

[0358] As the radical crosslinking agent, urethane acrylates as described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton as described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418 are also suitable. Furthermore, as the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 can also be used.

[0359] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphoric acid 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 compound in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol in 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. Examples of commercially available products include M-510, M-520, etc., as polybasic acid modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0360] 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. If the acid value of the radical crosslinking agent is within the above range, the agent has excellent handling properties during production and excellent developability. In addition, the agent has good polymerizability. The acid value is measured according to the description of JIS K 0070:1992.

[0361] From the viewpoints 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, EO 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, bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as necessary. 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, from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As the monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether are preferably used. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100° C. or more under normal pressure is also preferred in order to suppress volatilization before exposure. Other examples of the bifunctional or higher radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0362] When the radical crosslinking agent is contained, the 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.

[0363] 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 is preferably within the above range.

[0364] [Other crosslinking agents] The resin composition of the present invention also preferably contains another crosslinking agent different from 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 promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by the above-mentioned photoacid generator or photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof under the action of an acid or a base. 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 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 alcohol, and the hydrogen atom of the amino group is replaced with an acyloxymethyl group, a methylol group, or an alkoxymethyl group.The method for producing these compounds is not particularly limited, and they may be compounds having the same structure as the compounds produced by the above method.In addition, they may be oligomers formed by self-condensation of the methylol groups of these compounds. As the above 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 described below.

[0365] 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 has 2 or 3 carbon atoms, and more preferably has 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6. The molecular weight of the above compound is preferably 1,500 or less, and more preferably 180 to 1,200.

[0366] [ka]

[0367] 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.

[0368] Examples of the compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula:

[0369] [ka]

[0370] In the formula, X represents a single bond or a divalent organic group, and each R 104 each independently represents an alkyl group or an acyl group; R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group which decomposes under the action of an acid to produce an alkali-soluble group (for example, a group which is eliminated under the action of an acid, -C(R4 ) 2 COOR 5 A group represented by R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 5 represents a group which 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 produce an alkali-soluble group, a group that is eliminated under the action of an acid, -C(R 4 ) 2 COOR 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, and more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may be either linear or branched. The above cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms. The cycloalkyl group may be 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 above aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms. The above 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. Furthermore, these groups may further have a known substituent within the range in which the effects of the present invention can be obtained.

[0371] 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.

[0372] The group which is decomposed by the action of an acid to generate an alkali-soluble group, or the group which is eliminated by 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.

[0373] 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 changed to an acyloxymethyl group: Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds:

[0374] [ka]

[0375] [ka]

[0376] The compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be a commercially available compound 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.

[0377] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0378] Specific examples of urea-based crosslinking agents 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.

[0379] 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.

[0380] 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''-ethylidene tris[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.

[0381] As the other crosslinking agent, commercially available products may be used, and suitable commercially available products include 46DMOC, 46DMOEP (both manufactured by Asahi Organic Chemicals Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, and TriML-35XL. , 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 below) 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.

[0382] 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.

[0383] -Epoxy compounds (compounds having epoxy groups)- The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a crosslinking reaction at 200°C or less, and does not undergo a dehydration reaction due to the crosslinking, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in curing the resin composition of the present invention at low temperatures and suppressing warping.

[0384] The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group refers to a group having 2 or more repeating ethylene oxide units, and the number of repeating units is preferably 2 to 15.

[0385] 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 name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S , 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-3000 -FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.), etc. The following compounds are also preferably used.

[0386] [ka]

[0387] In the formula, n is an integer of 1 to 5, and m is an integer of 1 to 20.

[0388] 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.

[0389] -Oxetane compounds (compounds having an oxetanyl group)- Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. Specific examples include Aron Oxetane series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd., which may be used alone or in combination of two or more kinds.

[0390] -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 further, they reduce thermal shrinkage and suppress the occurrence of warping.

[0391] Preferred examples of the benzoxazine compound 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. These may be used alone or in combination of two or more.

[0392] The content of the other crosslinking agent is preferably 0.1 to 30 mass% based on the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass%, further preferably 0.5 to 15 mass%, and particularly preferably 1.0 to 10 mass%. 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 is preferably within the above range.

[0393] <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 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, amino compounds, and the like.

[0394] [Aluminum-based adhesion promoter] Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0395] In addition, other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A, the contents of which are incorporated herein by reference.

[0396] The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.01 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 making it equal to or more than the lower limit, the adhesion between the pattern and the metal layer becomes good, and by making it equal to or less than the upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be one type or two or more types. When two or more types are used, the total is preferably within the above range.

[0397] <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.

[0398] Specific examples 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)hydroxylamine 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, dibutyldithiocarbamate copper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, and the like are preferably used. In addition, the polymerization inhibitors described in paragraph 0060 of JP2015-127817A and the compounds described in paragraphs 0031 to 0046 of WO2015 / 125469A can also be used, the contents of which are incorporated herein by reference.

[0399] 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 %, based on the total solid content of the resin composition of the present invention.

[0400] The polymerization inhibitor may be one type or two or more types. When two or more types of polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0401] <Acid scavenger> The resin composition of the present invention preferably contains an acid scavenger in order to reduce the performance change over time from exposure to heating. Here, the acid scavenger refers to a compound that can capture generated acid by being present in the system, and is preferably a compound with low acidity and high pKa. As the acid scavenger, a compound having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, etc. are preferable, and a primary amine, a secondary amine, a tertiary amine, and an ammonium salt are preferable, and a secondary amine, a tertiary amine, and an ammonium salt are more preferable. Preferred examples of the acid scavenger include compounds having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, aniline derivatives having a hydroxyl group and / or an ether bond, etc. When the acid scavenger has an onium structure, it is preferred that the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid having a lower acidity than the acid generated by the acid generator.

[0402] Examples of acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undeca-7-ene. Examples of acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxides having 2-oxoalkyl groups, specifically triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylsulfonium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers having a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N,N-bis(hydroxyethyl)aniline.

[0403] Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylamine, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, diphenylamine, isobutyl ... ethylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, and the like.

[0404] These acid scavengers may be used alone or in combination of two or more. The composition according to the present invention may or may not contain an acid scavenger. When the composition contains an acid scavenger, the content of the acid scavenger is usually 0.001 to 10 mass %, and preferably 0.01 to 5 mass %, based on the total solid content of the composition.

[0405] The ratio of the acid generator to the acid scavenger is preferably acid generator / acid scavenger (molar ratio) = 2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing a decrease in resolution due to thickening of the relief pattern over time until heat treatment after exposure, the molar ratio is preferably 300 or less. The acid generator / acid scavenger (molar ratio) is more preferably 5.0 to 200, and further preferably 7.0 to 150.

[0406] <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, ultraviolet absorbers, organic titanium compounds, antioxidants, aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope of obtaining the effects of the present invention. By appropriately incorporating these components, it is possible to adjust the properties of the film, etc. These components can be found, for example, in the descriptions in paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of US Patent Application Publication No. 2013 / 0034812), and in paragraphs 0101-0104, 0107-0109, etc. of JP 2008-250074 A, the contents of which are incorporated herein. When these additives are incorporated, the total amount is preferably 3 mass% or less of the solid content of the resin composition of the present invention.

[0407] [Surfactant] As the surfactant, various surfactants 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.

[0408] By adding a surfactant to the photosensitive resin composition of the present invention, the liquid properties (particularly, fluidity) when prepared as a coating liquid can be 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 to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability to the surface to be coated and improving the coatability to the surface to be coated. Therefore, it is possible to more suitably form a film of uniform thickness with little thickness unevenness.

[0409] Examples of fluorine-based surfactants include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, and Megafac R30 (all manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, and Fluorad FC4432 (all manufactured by 3M Corporation). Examples of the fluorine-based surfactant 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, Surflon KH-40 (all manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA). As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP2015-117327A and the compounds described in paragraphs 0117 to 0132 of JP2011-132503A can also be used, the contents of which are incorporated herein by reference. A block polymer can also be used as the fluorine-based surfactant. 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. The following compounds are also exemplified as the fluorosurfactant used in the present invention. [ka]

[0410] 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-based surfactant may be a fluorine-containing polymer having an ethylenically unsaturated group in a 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. In addition, examples of commercially available products include Megafac RS-101, RS-102, RS-718K, etc., manufactured by DIC Corporation.

[0411] The fluorine content in the fluorosurfactant is preferably 3 to 40 mass%, more preferably 5 to 30 mass%, and particularly preferably 7 to 25 mass%. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the coating film thickness and liquid saving properties, and also has good solubility in the composition.

[0412] 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, Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials, Inc.), KP-341, KF6001, KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie Co., Ltd.), and the like.

[0413] 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, Paionin P-4050-T, and the like (all manufactured by Takemoto Oil Co., Ltd.).

[0414] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., 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 Co., Ltd.), Olfin E1010, and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0415] Specific examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0416] Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.), and the like.

[0417] 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.

[0418] [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.

[0419] 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.

[0420] 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. The higher fatty acid derivative may be one type or two or more types. When the higher fatty acid derivative is two or more types, the total is preferably within the above range.

[0421] [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. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. The addition of the thermal radical polymerization initiator can also advance the polymerization reaction of the resin and the polymerizable compound, thereby further improving the 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.

[0422] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein by reference.

[0423] When a thermal polymerization initiator is contained, the content is preferably 0.1 to 30 mass% based on the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass%, and further 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.

[0424] [Inorganic particles] The resin composition of the present invention may contain inorganic particles, specifically, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

[0425] 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, further 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 inorganic particles is the primary particle size and also the volume average particle size. The volume average particle size can be measured by a dynamic light scattering method 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.

[0426] [Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorbing agent. Examples of the ultraviolet absorbing agent that can be used include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbing agents. 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 benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0427] 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 triazine-based ultraviolet absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-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(hydro...

Claims

1. At least one resin selected from the group consisting of polyimide and polyamideimide; a photopolymerization initiator; a radical crosslinker; The resin has a radical polymerizable group and a photodimerization reactive group. Photosensitive resin composition.

2. The photosensitive resin composition according to claim 1 , wherein the photodimerization reactive group is a group having a cinnamoyl structure.

3. The photosensitive resin composition according to claim 1 or 2, further comprising a compound B having an alkoxysilyl group.

4. 4. The photosensitive resin composition according to claim 3, wherein the compound B having an alkoxysilyl group has at least one group selected from the group consisting of a photodimerizable group and a radically polymerizable group.

5. The photosensitive resin composition according to claim 3 or 4, wherein the compound B having an alkoxysilyl group has an azole group.

6. The photosensitive resin composition according to any one of claims 1 to 5, further comprising a compound C having an azole group and at least one group selected from the group consisting of a radically polymerizable group and a photodimerization reactive group.

7. The photosensitive resin composition according to any one of claims 1 to 6, further comprising a compound D having an azole group and not having an alkoxysilyl group, a radically polymerizable group, or a photodimerization reactive group.

8. The photosensitive resin composition according to any one of claims 1 to 7, which is used for forming an interlayer insulating film for a rewiring layer.

9. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 8.

10. A laminate comprising two or more layers each made of the cured product according to claim 9, and a metal layer between any two adjacent layers made of the cured product.

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

12. The method for producing a cured product according to claim 11, 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.

13. The method for producing a cured product according to claim 12 , further comprising, after the developing step, a second exposure step of exposing the pattern obtained by the developing step.

14. The method for producing a cured product according to any one of claims 11 to 13, comprising a heating step of heating the film at 50 to 450°C.

15. A semiconductor device comprising the cured product according to claim 9 or the laminate according to claim 10.