Photosensitive resin composition, method for producing pattern, photosensitive film, cured product, laminate, and device

Abstract

To provide a photosensitive resin composition and the like giving a pattern excellent in resolution and chemical resistance.SOLUTION: The photosensitive resin composition contains: at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide, and a polybenzoxazole; an organometallic complex; and a sensitizer having a condensed ring structure.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Polyimide or polybenzoxazole is applied to 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 polybenzoxazole is used in the form of a photosensitive resin composition containing at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor. Such a photosensitive resin composition is applied to a substrate, for example by coating, to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate. The polyimide precursor and the polybenzoxazole precursor are cyclized, for example, by heating, to become polyimide and polybenzoxazole, 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 photosensitive resin composition to be applied. In addition to the high performance of polyimide, polybenzoxazole, etc., from the viewpoint of such excellent adaptability in manufacturing, industrial application development of the above-mentioned photosensitive resin composition is expected to continue.

[0004] For example, Patent Document 1 describes a photosensitive resin composition that is characterized by comprising a polyimide precursor having a specific structure, a photopolymerization initiator, a sensitizer, an inhibitor for the purpose of storage stability, and a solvent containing a photosensitizer. Patent Document 2 describes a positive photosensitive resin composition comprising a polyimide precursor having a specific structure, a vinyloxy group-containing compound having a specific structure, a photosensitizer that decomposes in response to actinic rays such as ultraviolet light to generate an acid, a sensitizer that promotes the decomposition of the photosensitizer, and a solvent. Patent Document 3 describes a polyamic acid ester composition comprising (A) a polyamic acid ester having a specific structure, (B) an organotitanium compound in an amount of 0.3 to 10% by weight based on the weight of the polyamic acid ester (A), and (C) a solvent. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2003-186187 A [Patent Document 2] JP 2001-290270 A [Patent Document 3] JP 2004-91572 A Summary of the Invention [Problem to be solved by the invention]

[0006] In forming a pattern from a photosensitive resin composition, there is a demand for improving the resolution and chemical resistance of the resulting pattern.

[0007] The present invention aims to provide a photosensitive resin composition which gives a pattern excellent in resolution and chemical resistance, a method for producing a pattern comprising the photosensitive resin composition, a photosensitive film formed from the photosensitive resin composition, a cured product of the photosensitive film, a laminate including a layer comprising the cured product, and a 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 a polyimide precursor, a polybenzoxazole precursor, a polyimide, and a polybenzoxazole; Organometallic complexes, and Sensitizers having fused ring structures Photosensitive resin composition. <2> The sensitizer contains at least one atom selected from the group consisting of a nitrogen atom and a sulfur atom as a ring member in a fused ring structure. <1> The photosensitive resin composition according to claim 1. <3> the sensitizer contains, as a condensed ring structure, at least one structure selected from the group consisting of an acridone structure, a thioxanthone structure, and an acridine structure; <1> or <2> The photosensitive resin composition according to claim 1. <4> the content of the sensitizer is 0.5 to 5.0 parts by mass per part by mass of the organometallic complex; <1> ~ <3> 10. The photosensitive resin composition according to claim 9 . <5> The organometallic complex is a metallocene compound. <1> ~ <4> 10. The photosensitive resin composition according to claim 9 . <6> The metal contained in the organometallic complex is at least one metal selected from the group consisting of titanium, zirconium, and hafnium. <1> ~ <5> 10. The photosensitive resin composition according to claim 9 . <7> The organometallic complex has a photoradical polymerization initiation ability. <1> ~ <6> 10. The photosensitive resin composition according to claim 9 . <8> <1> ~ <7> a film-forming step of applying the photosensitive resin composition according to any one of the above to a substrate to form a photosensitive film; an exposure step of exposing the photosensitive film to light; and A development step of developing the photosensitive film after the exposure to obtain a pattern. A method for manufacturing a pattern. <9> The exposure light used in the exposure step includes light having a wavelength of 150 to 450 nm. <8> A method for producing the pattern according to claim 1. <10> The method further includes a heating step of curing the pattern obtained by the developing step by heating the pattern. <8> or <9> A method for producing the pattern according to claim 1. <11> <1> ~ <7> 13. A photosensitive film formed from the photosensitive resin composition according to claim 12. <12> <11> A cured product of the photosensitive film described in 1. <13> Used as an interlayer insulating film for rewiring layers, <12> The cured product according to claim 1. <14> <12> or <13> 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. <15> <12> or <13> or <14> A device comprising the laminate according to claim 1. Effect of the Invention

[0009] According to the present invention, there are provided a photosensitive resin composition which gives a pattern excellent in resolution and chemical resistance, a method for producing a pattern comprising the photosensitive resin composition, a photosensitive film formed from the photosensitive resin composition, a cured product of the photosensitive film, a laminate including a layer comprising the cured product, and a 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 defined as polystyrene equivalent values ​​according to gel permeation chromatography (GPC measurement) unless otherwise specified. 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 guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as an eluent. In addition, detection in GPC measurement is performed using a UV ray (ultraviolet ray) detector at a wavelength of 254 nm unless otherwise specified. 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. In other words, 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 photosensitive film, the direction from the substrate to the photosensitive film 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 actual embodiments, 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 contains at least one resin (hereinafter also referred to as a "specific resin") selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide, and a polybenzoxazole, an organometallic complex, and a sensitizer having a condensed ring structure.

[0012] The photosensitive resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to exposure and development, and is preferably used for forming a film to be subjected to exposure and development using a developer containing an organic solvent. As the exposure method, the developer, and the development method, for example, the exposure method described in the exposure step and the developer and development method described in the development step in the description of the pattern manufacturing method described below are used.

[0013] The photosensitive resin composition of the present invention provides patterns that are excellent in resolution and chemical resistance. The mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.

[0014] For example, as described in Patent Documents 1 and 2, a sensitizer is used in a photosensitive resin composition containing a specific resin for the purpose of improving exposure sensitivity. Furthermore, Patent Document 3 describes that the use of an organic titanium compound in the composition improves chemical resistance. As a result of extensive investigations, the present inventors have found that the resolution of the resulting pattern can be improved by using an organometallic complex in combination with a sensitizer having a condensed ring structure in a photosensitive resin composition. Although the mechanism by which the above-mentioned effect is obtained is not clear, it is speculated that the photosensitive resin composition contains an organometallic complex and a sensitizer having a specific structure, and thus the electronic state of the sensitizer changes, for example, the LUMO (Lowest Unoccupied Molecular Orbital) decreases, improving the sensitivity of the sensitizer and thereby improving the resolution of the obtained pattern. This is believed to be because the interaction between the metal site contained in the organometallic complex and the sensitizer improves the planarity of the structure of the sensitizer having a condensed ring structure and changes the electronic state. Furthermore, they have found that by using an organometallic complex in combination with a sensitizer having a condensed ring structure in a photosensitive resin composition, the chemical resistance of the resulting pattern is improved. Although the mechanism by which the above-mentioned effects are obtained is not clear, it is speculated that the chemical resistance is improved due to the interaction between the specific resin, the organometallic complex, and the sensitizer having a fused ring structure within the obtained pattern. Because the pattern has excellent chemical resistance, it is believed that, for example, when another photosensitive resin composition containing a solvent is further applied onto a pattern formed from the photosensitive resin composition of the present invention to create a laminate, dissolution of the pattern is suppressed even if the pattern comes into contact with a developer or another photosensitive resin composition. Furthermore, according to the present invention, it is considered that a pattern having excellent chemical resistance can be obtained in which the solubility in a polar solvent such as dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP), an alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, an acidic aqueous solution such as a dilute sulfuric acid aqueous solution or a dilute hydrochloric acid aqueous solution, a mixture of the above polar solvent and the above alkaline aqueous solution, or a mixture of the above polar solvent and the above acidic aqueous solution is suppressed. Furthermore, due to the reduction in LUMO resulting from the improvement in planarity, etc., the photosensitive film formed from the photosensitive resin composition of the present invention tends to have excellent exposure sensitivity when exposure is performed using a photomask or exposure by laser direct imaging, etc.

[0015] The components contained in the photosensitive resin composition of the present invention will be described in detail below.

[0016] <Specific resin> The photosensitive resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor. 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. In addition, the specific resin preferably has 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 photosensitizer, more preferably contains a photoradical polymerization initiator described later as a photosensitizer and a radical crosslinking agent described later, and further preferably contains a photoradical polymerization initiator described later as a photosensitizer, a radical crosslinking agent described later, and a sensitizer described later. For example, a negative photosensitive film 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 as described below as a photosensitizer. For example, a chemically amplified positive-type photosensitive layer or negative-type photosensitive layer is formed from such a photosensitive resin composition.

[0017] [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.

[0018] A in Equation (2) 1 and A 2 each independently represents an oxygen atom or NH, and an oxygen atom is preferred. 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 6 to 20 carbon atoms, an aromatic group having 6 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. A particularly preferred embodiment of the present invention is a group 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 - 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.

[0019] 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 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof, and it is more preferable that the diamine contains a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following.

[0020] [ka] In the formula, A is 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-, -SO 2 -, NHCO-, or a combination thereof, and is preferably 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.

[0021] 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, 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, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,At least one diamine selected from 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.

[0022] Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017 / 038598.

[0023] 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.

[0024] 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.

[0025] 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 is a fluorine atom, a methyl group, or a trifluoromethyl group. R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [ka] In formula (61), R 58 and R 59 are each independently a fluorine atom or a trifluoromethyl group. Examples of the diamine compound giving 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.

[0026] In addition, the following diamines can also be suitably used. [ka]

[0027] R in Equation (2) 115represents 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 represents 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 -, 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 -.

[0028] R 115 Specifically, the tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic acid dianhydride can be mentioned. Only one type of tetracarboxylic acid dianhydride may be used, or two or more types of tetracarboxylic acid dianhydrides may be used. 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.

[0029] 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.

[0030] Further, preferred examples include the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598.

[0031] R 111 and R 115 It is also preferable that at least one of R111 Examples of the residue include residues of bisaminophenol derivatives.

[0032] R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group; R 113 and R 114 It is preferable that at least one of the above contains a polymerizable group, and it is more preferable that both of the above contain a polymerizable group. 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, a methylol group, and an amino group. As the radically polymerizable group possessed by the polyimide precursor or the like, a group having an ethylenically unsaturated bond is preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a group represented by the following formula (III), with the group represented by the following formula (III) being preferred.

[0033] [ka]

[0034] In formula (III), R 200 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. 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 - or a polyalkyleneoxy group. Suitable R 201 Examples of the alkyl group include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, -CH 2 CH(OH)CH2 -, and polyalkyleneoxy groups, such as an ethylene group, a propylene group, a trimethylene group, -CH 2 CH(OH)CH 2 A polyalkyleneoxy group is more preferable, and a polyalkyleneoxy group is even more preferable. In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. The alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, and even more preferably 2-6. As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy group, polypropyleneoxy group, polytrimethyleneoxy group, polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded is preferred, polyethyleneoxy group or polypropyleneoxy group is more preferred, and polyethyleneoxy group is even more preferred.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 groups etc. in these groups is as described above.

[0035] R 113 and R 114 are each independently a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include aromatic groups and aralkyl groups in which an acidic group is bonded to one, two or three, preferably one, of the carbon atoms constituting the aryl group. Specific examples include aromatic groups having 6 to 20 carbon atoms and having an acidic group, and aralkyl groups having 7 to 25 carbon atoms and having an acidic group. More specific examples include a phenyl group having an acidic group and a benzyl group having an acidic group. The acidic group is preferably an OH group. R 113 or R 114 It is also more preferable that is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, or 4-hydroxybenzyl.

[0036] From the viewpoint of solubility in organic solvents, R 113 or R 114 is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group. The number of carbon atoms of the alkyl group is preferably 1 to 30. The alkyl group may be linear, branched, or cyclic. Examples of the linear or branched 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, a dodecyl group, a tetradecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a 1-ethylpentyl group, a 2-ethylhexyl group, a 2-(2-(2-methoxyethoxy)ethoxy)ethoxy group, a 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy group, a 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy group, and a 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a campholoyl group, a dicyclohexyl group, and a pinenyl group. Among them, the cyclohexyl group is the most preferable from the viewpoint of compatibility with high sensitivity. In addition, the alkyl group substituted with an aromatic group is preferably a linear alkyl group substituted with an aromatic group as described below. Specific examples of the aromatic group include a substituted or unsubstituted benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, a triphenylene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, A pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, or a phenazine ring. A benzene ring is most preferred.

[0037] 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.

[0038] 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 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.

[0039] It is also preferable that the polyimide precursor has a fluorine atom in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0040] In order to improve adhesion to the substrate, the polyimide precursor 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.

[0041] 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 adopting such a structure, it is possible to further expand 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 114 At least one of the groups is a group containing a polymerizable group, and it is preferable that both of the groups are polymerizable groups.

[0042] 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.

[0043] The polyimide precursor may contain one type of repeating structural 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 structural units in addition to the repeating unit of formula (2).

[0044] One embodiment of the polyimide precursor in the present invention is a polyimide precursor in which 50 mol % or more, further 70 mol % or more, and particularly 90 mol % or more of all repeating units are repeating units represented by formula (2).

[0045] The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000.The number average molecular weight (Mn) of the polyimide precursor is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. The polyimide precursor has a molecular weight dispersity of preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly specified, but is, for example, preferably 4.5 or less, more preferably 4.0 or less, even more preferably 3.8 or less, even more preferably 3.2 or less, even more preferably 3.1 or less, even more preferably 3.0 or less, and particularly preferably 2.95 or less. In this specification, the dispersity of molecular weight is a value calculated by weight average molecular weight / number average molecular weight.

[0046] [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.

[0047] -Fluorine atom- From the viewpoint of the film strength of the resulting organic film, the polyimide preferably contains fluorine atoms. The fluorine atom can be, for example, R 132 or R in the repeating unit represented by formula (4) described below 131 R in the repeating unit represented by formula (4) described later is preferably included. 132or R in the repeating unit represented by formula (4) described below 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 from 1 to 50 mol / g, and more preferably from 5 to 30 mol / g.

[0048] -Silicon atom- From the viewpoint of the film strength of the resulting organic film, it is 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 0.01 to 5 mol / g, and more preferably 0.05 to 1 mol / g.

[0049] - 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 131 R 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 131It 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).

[0050] [ka]

[0051] In formula (IV), R 20 represents a hydrogen atom or a methyl group, and a methyl group is preferable.

[0052] In formula (IV), R 21 is an alkylene group having 2 to 12 carbon atoms, -O-CH 2 CH(OH)CH 2 It represents -, -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.

[0053] 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 201 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.). As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy group, polypropyleneoxy group, polytrimethyleneoxy group, polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded is preferred, polyethyleneoxy group or polypropyleneoxy group is more preferred, and polyethyleneoxy group is even more preferred.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 groups etc. in these groups is as described above.

[0054] In formula (IV), * represents a bonding site to another structure, and is preferably a bonding site to the main chain of a polyimide.

[0055] The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.05 to 10 mol / g, and more preferably 0.1 to 5 mol / g. From the viewpoint of manufacturability, 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.

[0056] -Crosslinking group other than ethylenically unsaturated bond- The polyimide may have a crosslinkable group other than the ethylenically unsaturated bond. Examples of crosslinkable groups other than ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. The crosslinkable group other than the 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 crosslinkable groups other than ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g. From the viewpoint of production suitability, the amount of crosslinkable groups other than ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0057] - 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.

[0058] -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, "solvent development" described later), the acid value of the polyimide is preferably from 2 to 35 mgKOH / g, more preferably from 3 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.

[0059] -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.

[0060] The polyimide used in the present invention is not particularly limited as long as it is a polymeric compound having an imide ring, but it preferably contains a repeating unit represented by the following formula (4), and more preferably is a compound containing a repeating unit represented by formula (4) and having a polymerizable group. 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).

[0061] The polymerizable group has the same meaning as the polymerizable group described above in relation to the polymerizable group contained in the polyimide precursor or the like. 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:

[0062] R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain in order to more effectively suppress the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue not containing an aromatic ring.

[0063] 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.

[0064] 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 115 The 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.

[0065] 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.

[0066] 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. 132As the above, the above (DAA-1) to (DAA-5) are more preferred examples.

[0067] It is also preferable that the polyimide has fluorine atoms in its structural units. The content of fluorine atoms in the polyimide is preferably 10% by mass or more and 20% by mass or less.

[0068] 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.

[0069] In order to improve the storage stability of the composition, it is preferable to cap the main chain end of the polyimide with a terminal capping 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 monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-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.

[0070] -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

[0071] All polyimides are of the same type R 131 or R 132 and may contain a repeating structural unit of the above formula (4) containing two or more different types of R 131 or R 132 The polyimide may contain a repeating unit of the above formula (4) including: Furthermore, in addition to the repeating unit of the above formula (4), the polyimide may also contain other types of repeating structural units.

[0072] Polyimides can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine compound (partially substituted with a terminal blocking agent that is a monoamine) at low temperature, by reacting a tetracarboxylic dianhydride (partially substituted with a terminal blocking agent that is an acid anhydride, a monoacid chloride compound, or a monoactive ester compound) with a diamine compound at low temperature, by obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then reacting it with a diamine (partially substituted with a terminal blocking agent that is a monoamine) in the presence of a condensing agent, by obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with a diamine (partially substituted with a terminal blocking agent that is a monoamine), or by using a method in which a polyimide precursor is obtained and then completely imidized by a known imidization reaction method, or by stopping the imidization reaction midway and partially introducing an imide structure, or by blending a completely imidized polymer with the polyimide precursor to partially introduce an imide structure. Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by Fujifilm Corporation) and Matrimide 5218 (manufactured by HUNTSMAN Corporation).

[0073] The weight average molecular weight (Mw) of the polyimide is 4,000 to 100,000, 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. In addition, when two or more types of polyimides are contained, it is preferable that the weight average molecular weight of at least one type of polyimide is in the above range.

[0074] [Polybenzoxazole precursor] The polybenzoxazole precursor used in the present invention is not particularly limited with respect to its structure, but preferably contains a repeating unit represented by the following formula (3). Formula (3) [ka] In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, R 123 and R 124 each independently represents a hydrogen atom or a monovalent organic group.

[0075] In formula (3), R 123 and R 124 are R in Eq. (2), 113 In other words, it is preferable that at least one of them is a polymerizable group. In formula (3), R 121 R represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. The aliphatic group is preferably a linear aliphatic group. 121The dicarboxylic acid residue is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types of dicarboxylic acid residues may be used.

[0076] As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferred, and a dicarboxylic acid residue containing an aromatic group is more preferred. The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and more preferably a dicarboxylic acid consisting of a linear or branched (preferably linear) aliphatic group and two -COOH. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. Dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetramethylpimelic acid. , suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanediacid, heneicosanediacid, docosanediacid, tricosanediacid, tetracosanediacid, pentacosanediacid, hexacosanediacid, heptacosanediacid, octacosanediacid, nonacosanediacid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and further dicarboxylic acids represented by the following formula.

[0077] [ka] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

[0078] As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids consisting of only an aromatic group and two -COOH groups are more preferred.

[0079] [ka] In the formula, A is -CH 2 -, -O-, -S-, -SO 2 -, -CO-, -NHCO-, -C(CF 3 ) 2 - and -C(CH 3 ) 2 -, and each * independently represents a bonding site to another structure.

[0080] Specific examples of dicarboxylic acids containing an aromatic group include 4,4'-carbonyldibenzoic acid and 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

[0081] In formula (3), R 122 represents a tetravalent organic group. The tetravalent organic group is R 115 The same definition and preferred range are also the same. R 122is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These bisaminophenols may be used alone or in combination.

[0082] Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferred.

[0083] [ka] In the formula, X 1 -O-, -S-, -C(CF 3 ) 2 -, -CH 2 -, -SO 2 R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. 122It is also preferable that R is a structure represented by the above formula. 122 is a structure represented by the above formula, any two of the four * and # are R 122 is a bonding site with the nitrogen atom to which it is bonded, and the other two are R 122 is preferably a bonding site with the oxygen atom to which the bond is bonded, and the two * are preferably R 122 is a bonding site with the oxygen atom to which it is bonded, and the two #'s are R 122 is a bonding site with the nitrogen atom to which it is bonded, or two * are R 122 is a bonding site with the nitrogen atom to which it is bonded, and the two #'s are R 122 is more preferably a bonding site with the oxygen atom to which the bond is bonded, and two * are 122 is a bonding site with the oxygen atom to which it is bonded, and the two #'s are R 122 It is more preferable that the nitrogen atom to which the group is bonded is the bonding site.

[0084] [ka]

[0085] In formula (As), R 1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO 2 R is -, -CO-, -NHCO-, a single bond, or an organic group selected from the group represented by the following formula (A-sc). 2 R is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different. 3 are either a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.

[0086] [ka] (In formula (A-sc), * indicates bonding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

[0087] In the above formula (As), the ortho position of the phenolic hydroxyl group, i.e., R 3 It is believed that the distance between the carbonyl carbon of the amide bond and the hydroxyl group is made shorter, and this is particularly preferred in that the effect of achieving a high cyclization rate when cured at low temperatures is further enhanced.

[0088] In addition, in the above formula (As), R 2 is an alkyl group, and R 3 It is preferable that the alkyl group is used since the effects of high transparency to i-line and a high cyclization rate when cured at a low temperature can be maintained.

[0089] In addition, in the above formula (As), R 1 It is more preferred that R is alkylene or substituted alkylene. 1 Specific examples of the alkylene and substituted alkylene include linear or branched alkyl groups having 1 to 8 carbon atoms. 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 is more preferable in that it is possible to obtain a polybenzoxazole precursor having a good balance between high transparency to i-line and a high cyclization rate when cured at a low temperature and sufficient solubility in a solvent.

[0090] For the production method of the bisaminophenol derivative represented by the above formula (As), reference can be made to, for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP 2013-256506 A, the contents of which are incorporated herein by reference.

[0091] Specific examples of the structure of the bisaminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of JP 2013-256506 A, the contents of which are incorporated herein by reference. Of course, it goes without saying that the present invention is not limited to these.

[0092] The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of formula (3) above. In terms of being able to suppress the occurrence of warping due to ring closure, it is preferable that the resin contains a diamine residue represented by the following formula (SL) as another type of repeating structural unit.

[0093] [ka] In formula (SL), Z has an a structure and a b structure, and R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 2s is a hydrocarbon group having 1 to 10 carbon atoms, R 3s , R 4s , R 5s , R 6s At least one of them is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. The molar percentage of the Z portion is 5 to 95 mol % for the a structure, 95 to 5 mol % for the b structure, and a+b is 100 mol %.

[0094] In formula (SL), preferred Z is R in the b structure. 5s and R 6s is a phenyl group. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight within the above range, it is possible to more effectively reduce the elastic modulus of the polybenzoxazole precursor after dehydration ring closure, and to simultaneously achieve the effect of suppressing warpage and the effect of improving solvent solubility.

[0095] When the diamine residue represented by formula (SL) is contained as another type of repeating structural unit, it is also preferable that the diamine residue represented by formula (SL) further contains, as a repeating structural unit, a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride. 115 Examples include:

[0096] When used in a composition described later, the polybenzoxazole precursor has a weight average molecular weight (Mw) of preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. The polybenzoxazole precursor has a molecular weight dispersity of preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly specified, but is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less.

[0097] [Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymeric compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) having a polymerizable group. The polymerizable group is preferably a radical polymerizable group. Alternatively, it may be a compound represented by the following formula (X) having a polarity conversion group such as an acid decomposable group. [ka] In formula (X), R 133 represents a divalent organic group, R 134 represents a tetravalent organic group. In the case where a polarity conversion group such as a polymerizable group or an acid-decomposable group is present, the polarity conversion group such as a polymerizable group or an acid-decomposable group is R 133 and R 134 or may be located at an end of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2). Formula (X-1) [ka] In formula (X-1), R 135 and R 136 At least one of the groups is a polarity conversion group such as a polymerizable group or an acid-decomposable group, and if it is not a polarity conversion group such as a polymerizable group or an acid-decomposable group, it is an organic group, and the other group has the same meaning as in formula (X). Formula (X-2) [ka] In formula (X-2), R 137 is a polarity conversion group such as a polymerizable group or an acid-decomposable group, and the others are substituents, and the other groups are the same as those in formula (X).

[0098] The polarity conversion group such as a polymerizable group or an acid-decomposable group has the same meaning as the polarity conversion group such as a polymerizable group or an acid-decomposable group described above in relation to the polymerizable group contained in the polyimide precursor or the like.

[0099] R 133 represents a divalent organic group. Examples of the divalent organic group include an aliphatic or aromatic group. A specific example is R 121 Examples of the preferred examples include R 121 is the same as:

[0100] R 134 represents a tetravalent organic group. The tetravalent organic group is R 122 Examples of the preferred examples include R 122 is the same as: For example, R 122The four bonds of the tetravalent organic group exemplified by R 134 When is an organic group, the following structure is formed: [ka]

[0101] The polybenzoxazole preferably has an oxazolization rate of 85% or more, more preferably 90% or more. By having an oxazolization rate of 85% or more, film shrinkage due to ring closure that occurs when oxazolized by heating is reduced, and the occurrence of warping can be more effectively suppressed.

[0102] Polybenzoxazoles are all of the same type R 131 or R 132 and may contain repeating structural units of the above formula (X) including two or more different types of R 131 or R 132 The polybenzoxazole may contain a repeating unit of the above formula (X) including: In addition to the repeating unit of the above formula (X), the polybenzoxazole may also contain other types of repeating structural units.

[0103] Polybenzoxazole is, for example, a bisaminophenol derivative and R 133 or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor, which is then converted into an oxazole by a known oxazole conversion reaction method. In the case of dicarboxylic acids, in order to increase the reaction yield, etc., it is also possible to use an active ester type dicarboxylic acid derivative which has been reacted in advance with 1-hydroxy-1,2,3-benzotriazole or the like.

[0104] The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By 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. In addition, when two or more types of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one type of polybenzoxazole is within the above range.

[0105] [Method for producing polyimide precursor, etc.] The polyimide precursor or the like can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine, preferably by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting the halogenated dicarboxylic acid or a dicarboxylic acid derivative with a diamine. 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 materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone. Polyimide may be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (e.g., promoting the cyclization reaction by the action of a catalyst), or polyimide may be synthesized directly.

[0106] It is also preferable to synthesize using a non-halogen catalyst without using the halogenating agent. As the non-halogen catalyst, a known amidation catalyst that does not contain a halogen atom can be used without any particular limitation, and examples thereof include boroxine compounds, N-hydroxy compounds, tertiary amines, phosphoric acid esters, amine salts, urea compounds, and carbodiimide compounds. As the carbodiimide compounds, N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, and the like can be mentioned.

[0107] -End capping agent- In the method for producing a polyimide precursor or the like, in order to further improve storage stability, it is preferable to cap the ends of the polyimide precursor or the like with an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactive ester compound, etc. As the end-capping agent, it is more preferable to use a monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 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 ... Examples of the amino acid ester include 5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

[0108] -Solid precipitation- The production of the polyimide precursor or the like may include a step of precipitating a solid. Specifically, the polyimide precursor or the like in the reaction solution is precipitated in water, and then dissolved in a solvent in which the polyimide precursor or the like is soluble, such as tetrahydrofuran, to precipitate the solid. Thereafter, the polyimide precursor or the like is dried to obtain a powdered polyimide precursor or the like.

[0109] [Content] The content of the specific resin in the 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 composition. The content of the resin in the 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 composition. The 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.

[0110] The photosensitive resin composition of the present invention also preferably contains at least two types of resins. Specifically, the photosensitive resin composition of the present invention may contain a total of two or more types of the specific resin and the other resin described below, or may contain two or more types of specific resins, but it is preferable that the photosensitive resin composition contains two or more types of specific resins. When the photosensitive 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.

[0111] <Organometallic complexes> The photosensitive resin composition of the present invention contains an organometallic complex. The organometallic complex may be an organic complex compound containing a metal atom, but is preferably a complex compound containing a metal atom and an organic group, more preferably a compound in which an organic group is coordinated to a metal atom, and further preferably a metallocene compound. In the present invention, the metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives, which may have a substituent, as η5-ligands. The organic group is not particularly limited, but is preferably a hydrocarbon group or a group consisting of a combination of a hydrocarbon group and a heteroatom, preferably an oxygen atom, a sulfur atom, or a nitrogen atom. In the present invention, it is preferred that at least one of the organic groups is a cyclic group, and more preferred that at least two of the organic groups are cyclic groups. The cyclic group is preferably selected from a 5-membered ring group and a 6-membered ring group, and more preferably a 5-membered ring group. The cyclic group may be a hydrocarbon ring or a heterocyclic ring, with a hydrocarbon ring being preferred. The five-membered cyclic group is preferably a cyclopentadienyl group. In addition, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

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

[0113] The organometallic complex may contain two or more metal atoms or may contain only one metal atom, but preferably contains only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one type of metal atom or may contain two or more types of metal atoms.

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

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

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

[0117] Preferred examples of the organometallic complex include compounds represented by the following formula (P). [ka] In formula (P), M is a metal element, and each R is independently a substituent. It is preferable that each R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

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

[0119] Specific examples of organometallic complexes include, but are not limited to, tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonato)titanium, and the following compounds. [ka]

[0120] In addition, compounds described in paragraphs 0078 to 0088 of WO 2018 / 025738 can also be used, but are not limited thereto.

[0121] The content of the organometallic complex is preferably 0.1 to 30% by mass based on the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less. The organometallic complexes 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.

[0122] <Sensitizers Having a Fused Ring Structure> The photosensitive resin composition of the present invention contains a sensitizer having a condensed ring structure (hereinafter also referred to as a "specific sensitizer"). In the present invention, the term "fused ring structure" refers to a structure in which two ring structures share two atoms and one bond. One or both of the two ring structures may further form a fused ring structure with another ring structure. The specific sensitizer needs to have at least one fused ring structure, and may have a plurality of fused ring structures. In addition, the fused ring structure in the specific sensitizer may be a structure in which a plurality of ring structures are linearly fused, such as an acene hydrocarbon, a structure in which a plurality of ring structures are non-linearly fused, such as a phenanthrene structure, or a structure in which a plurality of ring structures are each fused with a plurality of other ring structures, such as a pyrene structure. Among these, the fused ring structure is preferably a structure formed by condensing 2 to 6 ring structures, more preferably a ring structure formed by condensing 2 to 4 ring structures, still more preferably a ring structure formed by condensing 2 or 3 ring structures, and particularly preferably a ring structure formed by condensing 3 ring structures. The ring structure is not particularly limited, but is preferably a 5-membered ring structure or a 6-membered ring structure. In addition, at least one of the ring structures is preferably a ring structure containing a nitrogen atom or a ring structure containing a sulfur atom, as described below.

[0123] The specific sensitizer may be any sensitizer for the photosensitizer described later, but is preferably a compound which is an organometallic complex as described above and has photoradical polymerization initiation ability, or a sensitizer which has a sensitizing effect on the radical polymerization initiator described later.

[0124] The specific sensitizer preferably has a maximum absorption wavelength in the wavelength range of 250 nm to 550 nm, and more preferably has a maximum absorption wavelength in the wavelength range of 300 nm to 450 nm. The maximum absorption wavelength is measured by a known method using, for example, a spectrophotometer.

[0125] The fused ring structure in the specific sensitizer preferably contains at least one atom selected from the group consisting of a nitrogen atom and a sulfur atom as a ring member in the fused ring structure. The phrase "containing at least one atom selected from the group consisting of a nitrogen atom and a sulfur atom" as a ring member in a fused ring structure means that at least one ring structure of at least two ring structures forming the fused ring structure contains at least one atom selected from the group consisting of a nitrogen atom and a sulfur atom as a ring member. Examples of ring structures containing a nitrogen atom as a ring member include a pyrrolidine ring, a pyrrole ring, an imidazolidine ring, an oxazolidine ring, a thiazolidine ring, an isothiazolidine ring, a triazole ring, a tetrazole ring, a piperidine ring, a piperazine ring, a pyridine ring, a diazine ring, a triazine ring, and a 4-piperidone ring. Examples of the ring structure containing a sulfur atom as a ring member include a thiophene ring, a tetrahydrothiophene ring, a thiazolidine ring, an isothiazolidine ring, a dithiolane ring, and a 4-oxothiane ring. The ring that forms the fused ring structure and the ring structure containing at least one atom selected from the group consisting of a nitrogen atom and a sulfur atom as a ring member is not particularly limited and may be a ring structure containing at least one atom selected from the group consisting of a nitrogen atom and a sulfur atom as a ring member, but is preferably a hydrocarbon ring structure, more preferably an aromatic hydrocarbon ring structure, and even more preferably a benzene ring structure.

[0126] From the viewpoints of resolution, exposure sensitivity, and chemical resistance, the specific sensitizer preferably contains, as a fused ring structure, at least one structure selected from the group consisting of an acridone structure, a thioxanthone structure, and an acridine structure. The specific sensitizer may contain at least one structure selected from the group consisting of an acridone structure, a thioxanthone structure, and an acridine structure, or may contain two or more of them. When the specific sensitizer contains two or more structures, the structures may be the same or different. The specific sensitizer is preferably a compound represented by any one of the following formulas (1-1), (2-1), and (3-1). [ka] In the formula (1-1), the formula (2-1) or the formula (3-1), R 11 ~R 19 each independently represents a hydrogen atom or a substituent; R 11 ~R 19 At least two of R may be bonded to form a ring structure; 21 ~R 28 each independently represents a hydrogen atom or a substituent; R 21 ~R 28 At least two of R may be bonded to form a ring structure; 31 ~R 39 each independently represents a hydrogen atom or a substituent; R 31 ~R 39At least two of these may be bonded to form a ring structure.

[0127] In formula (1-1), R 11 ~R 18 each independently represents a hydrogen atom or a substituent, and is preferably a hydrogen atom, a hydrocarbon group or a halogen atom. The above-mentioned hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but is preferably an alkyl group or an aromatic hydrocarbon group, and more preferably an alkyl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom or a bromine atom. In formula (1-1), R 19 represents a hydrogen atom or a substituent, preferably a hydrogen atom, a hydrocarbon group or a halogen atom, more preferably a hydrogen atom or a hydrocarbon group. In formula (1-1), R 19 Preferred embodiments of the hydrocarbon group and halogen atom in R 11 ~R 18 The preferred embodiments of the hydrocarbon group and halogen atom in are the same as those in the above. In the present invention, R 11 ~R 19 At least two of the groups may be bonded to form a ring structure, but R 11 ~R 19 An embodiment in which none of the above forms a ring structure is also a preferred embodiment.

[0128] In formula (2-1), R 21 ~R 28 each independently represents a hydrogen atom or a substituent, preferably a hydrogen atom, a hydrocarbon group, or a halogen atom, more preferably a hydrogen atom or a halogen atom, and particularly preferably a hydrogen atom. The above-mentioned hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but is preferably an alkyl group or an aromatic hydrocarbon group, and more preferably an alkyl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom or a bromine atom. In the present invention, R 21 ~R 28 At least two of the groups may be bonded to form a ring structure, but R 21 ~R 28 An embodiment in which none of the above forms a ring structure is also a preferred embodiment.

[0129] In formula (3-1), R 31 ~R 38 each independently represents a hydrogen atom or a substituent, and is preferably a hydrogen atom, a hydrocarbon group or a halogen atom. The above-mentioned hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but is preferably an alkyl group or an aromatic hydrocarbon group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom or a bromine atom. In formula (3-1), R 39 represents a hydrogen atom or a substituent, preferably a hydrogen atom, a hydrocarbon group or a halogen atom, more preferably a hydrogen atom or a hydrocarbon group. In formula (3-1), R 39Preferred embodiments of the hydrocarbon group and halogen atom in R 31 ~R 38 The preferred embodiments of the hydrocarbon group and halogen atom in are the same as those in the above. In the present invention, R 31 ~R 39 At least two of the groups may be bonded to form a ring structure, but R 31 ~R 39 An embodiment in which none of the above forms a ring structure is also a preferred embodiment.

[0130] The specific sensitizer is a compound represented by any one of formulas (1-1), (2-1), and (3-1), in which R 11 ~R 19 , R 21 ~R 28 , R 31 ~R 39 The compound may also be a compound containing, as a partial structure, a structure in which at least one of the following structures serves as a binding site to another structure. For example, as shown in the following formula (3-2), in the structure represented by formula (3-1), R 39 as a binding site to another structure. [ka] In formula (3-2), R 31 ~R 38 are each independently R in the above formula (3-1). 31 ~R 38 The same applies to the preferred embodiments. In formula (3-2), L represents an m-valent linking group, and is preferably an m-valent hydrocarbon group which may have a substituent. Examples of L include a hydrocarbon group, -O-, C(=O)-, -S-, -S(=O) 2 -, or a combination of two or more of these. A group containing at least a hydrocarbon group is preferred, and a hydrocarbon group is more preferred. The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof, but is preferably a saturated aliphatic hydrocarbon group. In formula (3-2), m represents an integer of 2 or more, and is preferably an integer of 2 to 10.

[0131] The molecular weight of the specific sensitizer is preferably from 100 to 2,000, and more preferably from 150 to 1,000.

[0132] Specific examples of the specific sensitizer include, but are not limited to, 2,4-dimethylthioxanthone, N-phenyldiethanolamine, 7-(diethylamino)coumarin-3-carboxylate ethyl, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, acridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, 9-phenylacridine, 1,7-bis(9,9'-acridinyl)heptane, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, Examples of the 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, dibenzothiophene, benzo[b]naphtho[1,2-d]thiophene, benzo[b]naphtho[1,2-d]thiophene, 4-phenyldibenzothiophene, and the like.

[0133] The content of the specific sensitizer is preferably 0.1 to 30% by mass based on the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 0.2% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1.0% by mass or more. The upper limit is more preferably 25% by mass or less. The organometallic complexes 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.

[0134] Furthermore, the content of the specific sensitizer relative to 1 part by mass of the organometallic complex is preferably 0.5 to 5.0 parts by mass, more preferably 0.6 to 3.0 parts by mass, and even more preferably 0.75 to 2.0 parts by mass.

[0135] <Other resins> The composition of the present invention may contain the above-mentioned specific resin and another resin (hereinafter, simply referred to as "another resin") different from the specific resin. Examples of other resins include polyamideimide, polyamideimide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, and acrylic resins. For example, by further adding an acrylic resin, a composition with excellent coatability can be obtained, and an organic film with excellent solvent resistance can be obtained. For example, by adding an acrylic resin having a high polymerizable group value and a weight-average molecular weight of 20,000 or less to the composition in place of or in addition to the crosslinking agent described later, the coatability of the composition and the solvent resistance of the organic film can be improved.

[0136] When the 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 composition. In addition, the content of other resins in the composition of the present invention is preferably 80 mass % or less, more preferably 75 mass % or less, even more preferably 70 mass % or less, still more preferably 60 mass % or less, and even more preferably 50 mass % or less, based on the total solid content of the composition. In addition, as a preferred embodiment of the 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 composition. The lower limit of the content is not particularly limited, and may be 0% by mass or more. The 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.

[0137] <Solvent> The photosensitive resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0138] 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.

[0139] Suitable examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.

[0140] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0141] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0142] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0143] Preferred examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-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.

[0144] Preferred examples of the ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0145] 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.

[0146] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0147] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or a mixed solvent composed of two or more of them, is preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred. Also preferred are combinations of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, and cyclopentanone and γ-butyrolactone.

[0148] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solids concentration of the photosensitive 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 40 to 70 mass%. The content of the solvent may be adjusted according to the desired thickness of the coating film and the coating method.

[0149] The composition may contain only one type of solvent, or two or more types of solvents. When two or more types of solvents are contained, the total content thereof is preferably within the above range.

[0150] <Photosensitizer> The composition of the present invention preferably contains a photosensitizer. The photosensitizer is the above-mentioned organometallic complex, but does not include a compound having photoradical polymerization initiation ability. The photosensitizer is preferably a photopolymerization initiator.

[0151] [Photopolymerization initiator] The composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer. 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.

[0152] In the present invention, the compound corresponding to the organometallic complex does not correspond to the photosensitizer and the photoradical polymerization initiator.

[0153] When the composition of the present invention has photoradical polymerization initiation ability, it is also preferable that the composition of the present invention is substantially free of radical polymerization initiators other than the above-mentioned organometallic complex. Substantially free of radical polymerization initiators other than the above-mentioned organometallic complex means that the content of the radical polymerization initiator other than the above-mentioned organometallic complex in the composition of the present invention is 5 mass% or less, preferably 3 mass% or less, more preferably 1 mass% or less, and even more preferably 0.1 mass% based on the total mass of the above-mentioned organometallic complex. When the composition of the present invention contains an organometallic complex having radical polymerization initiation ability, it is also preferable that the composition of the present invention contains the above-mentioned organometallic complex and another photoradical polymerization initiator. When the composition of the present invention contains an organometallic complex and another photoradical polymerization initiator, the content of the organometallic complex relative to the total content of the organometallic complex and the other photoradical polymerization initiator is preferably 20 to 80 mass%, and more preferably 30 to 70 mass%. As the other photoradical polymerization initiator, an oxime compound described later is preferable.

[0154] The photoradical polymerization initiator has a wavelength of about 300 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.

[0155] 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 oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide 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.

[0156] 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 (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0157] In one embodiment of the present invention, as the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine oxide-based initiator described in JP-A-4225898 can be used.

[0158] As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

[0159] As the aminoacetophenone initiator, commercially available products such as IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all manufactured by BASF) can be used.

[0160] As the aminoacetophenone-based initiator, the compounds described in JP-A-2009-191179, which have an absorption maximum wavelength matching a light source with a wavelength of 365 nm or 405 nm, can also be used.

[0161] Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. In addition, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

[0162] 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.

[0163] Specific examples of the oxime compound that can be used include the compounds described in JP-A-2001-233842, JP-A-2000-080068, and JP-A-2006-342166.

[0164] Examples of preferred oxime compounds include 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 composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of >C=NOC(=O)- in the molecule.

[0165] [ka]

[0166] 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 Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A). TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831, and Adeka Arcles NCI-930 (manufactured by ADEKA Corporation) can also be used. DFI-091 (manufactured by Daito Chemistry Co., Ltd.) can also be used. Oxime compounds having the following structure can also be used. [ka]

[0167] As the photopolymerization 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 the compounds described in JP-A-06636081.

[0168] As the photopolymerization 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 the compounds described in WO 2013 / 083505.

[0169] 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.

[0170] Most preferred examples of the oxime compound 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.

[0171] 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.

[0172] 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, oxime compounds, triarylimidazole dimers, and benzophenone compounds is even more preferred. It is even more preferred to use a metallocene compound or an oxime compound, and even more preferred is an oxime compound.

[0173] 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.

[0174] [ka]

[0175] 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, 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 a phenyl group substituted with at least one of an alkyl group having 1 to 4 carbon atoms, or a biphenyl; 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.

[0176] [ka]

[0177] In the formula, R I05 ~R I07 is R in the above formula (I). I02 ~R I04 is the same as:

[0178] In addition, the compounds described in paragraphs 0048 to 0055 of WO 2015 / 125469 can also be used as the photoradical polymerization initiator.

[0179] When a photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30 mass% based on the total solid content of the 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.

[0180] [Photoacid generator] The composition of the present invention also preferably contains a photoacid generator as a photosensitizer. By including a photoacid generator, for example, acid is generated in exposed areas of the photosensitive film, increasing the solubility of the exposed areas in a developer (e.g., an alkaline aqueous solution), and a positive pattern can be obtained in which the exposed areas are removed by the developer. In addition, by containing a photoacid generator and a crosslinking agent other than the radical crosslinking agent described later, for example, the crosslinking reaction of the crosslinking agent is promoted by the acid generated in the exposed area, and the exposed area is more difficult to remove by a developer than the non-exposed area. According to such an embodiment, a negative pattern can be obtained.

[0181] The photoacid generator is not particularly limited as long as it generates an acid upon exposure to light, and examples of the photoacid generator include quinone diazide compounds, onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts, and sulfonate compounds such as imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonate.

[0182] Examples of the quinone diazide compound include a polyhydroxy compound to which a sulfonic acid of quinone diazide is bonded via an ester bond, a polyamino compound to which a sulfonic acid of quinone diazide is bonded via a sulfonamide bond, a polyhydroxypolyamino compound to which a sulfonic acid of quinone diazide is bonded via at least one of an ester bond and a sulfonamide bond, etc. In the present invention, for example, it is preferable that 50 mol % or more of the total functional groups of these polyhydroxy compounds or polyamino compounds are substituted with quinone diazide.

[0183] In the present invention, either 5-naphthoquinone diazide sulfonyl group or 4-naphthoquinone diazide sulfonyl group is preferably used as the quinone diazide. 4-naphthoquinone diazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. 5-naphthoquinone diazide sulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure. In addition, naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be contained.

[0184] The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized by a known method. The use of these naphthoquinone diazide compounds improves the resolution, sensitivity, and film remaining rate. Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, salts or esters of these compounds.

[0185] Examples of the onium salt compound or sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A No. 2008-013646.

[0186] The photoacid generator is also 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).

[0187] [ka]

[0188] In formula (OS-1), X 3 represents an alkyl group, an alkoxyl 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 alkoxyl group in X is preferably a linear or branched alkoxyl 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 alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxyl 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 alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxyl 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.

[0189] 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.

[0190] 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.

[0191] [ka]

[0192] 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 substituent T.

[0193] In formula (OS-103) ~ formula (OS-105), R s2is 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 (I) may have a substituent T. 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.

[0194] 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.

[0195] 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]

[0196] 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.

[0197] 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.

[0198] 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.

[0199] 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).

[0200] [ka]

[0201] In formula (OS-101) or formula (OS-102), R u9 R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl 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.

[0202] In formula (OS-101) or formula (OS-102), R u1 ~R u4R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxyl 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 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. Each of the above-mentioned substituents may further have a substituent.

[0203] 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, b-9, b-16, b-31 and b-33 are preferred.

[0204] In addition, commercially available photoacid generators may be used. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-699 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Omnicat 250 and Omnicat 270 (all manufactured by IGM Resins BV), Irgacure 250, Irgacure 270, and Irgacure 290 (all manufactured by BASF), and MBZ-101 (manufactured by Midori Chemical Industry Co., Ltd.).

[0205] Further, compounds represented by the following structural formulas are also preferred examples. [ka]

[0206] As the photoacid generator, an organic halogenated compound can also be used. 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, JP-A-48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, and M.P. Hutt, Journal of Heterocyclic Chemistry, Vol. 1 (No. 3), (1970), and in particular, 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, riazine, 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-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 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.

[0207] As the photoacid generator, an organic borate compound can also be used. Examples of the organic borate compound 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, and Japanese Patent Application No. 2000-310808, and those described in Kunz, Martin, "Rad Tech'98. Proceedings of April 1999, Vol. 1, No. 2, pp. 1111-1115, 1999. 19-22, 1998, Chicago", etc.; organoboron sulfonium complexes or organoboron oxosulfonium complexes described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561; organoboron iodonium complexes described in JP-A-6-175554 and JP-A-6-175553; 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, etc., are specifically exemplified.

[0208] As the photoacid generator, a disulfone compound can also be used. Examples of the disulfone compound include compounds described in JP-A-61-166544 and JP-A-2001-132318, and diazodisulfone compounds.

[0209] 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; and iodonium 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 the specifications of 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, p478, Tokyo, Oct. (1988); and onium salts such as pyridinium salts.

[0210] 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 1 to 12 carbon atoms, an alkynyl group having 1 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, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl 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 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 1 to 12 carbon atoms, an alkynyl group having 1 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, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl 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 21 - 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 20 or less 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 1 to 12 carbon atoms, an alkynyl group having 1 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, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl 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.

[0211] Specific examples include the following: [ka] [ka] [ka] [ka]

[0212] When a photoacid generator is contained, its content is preferably 0.1 to 30 mass % based on the total solid content of the composition of the present invention, more preferably 0.1 to 20 mass %, and even more preferably 2 to 15 mass %. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more types of photoacid generators are contained, the total content is preferably within the above range.

[0213] [Photobase Generator] The photosensitive resin composition of the present invention may contain a photobase generator as a photosensitizer. By containing a photobase generator and a crosslinking agent described later, the photosensitive resin composition can be configured such that the exposed portion is more difficult to remove by a developer than the non-exposed portion due to, for example, the action of promoting cyclization of a specific resin by the base generated in the exposed portion, promoting the crosslinking reaction of the crosslinking agent, etc. According to such an embodiment, a negative relief pattern can be obtained.

[0214] The photobase generator is not particularly limited as long as it generates a base upon exposure to light, and any known photobase generator can be used. For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Kadooka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol., 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and As described in S. Yoshitaka, J. Photopolym. Sci. Technol., 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol., 19, 81 (2006), examples of the compound include ionic compounds in which the base component is neutralized by forming a salt, such as transition metal compound complexes, compounds having an ammonium salt structure, and compounds in which the amidine moiety is rendered latent by forming a salt with a carboxylic acid, and nonionic compounds in which the base component is rendered latent by a urethane bond or oxime bond, such as carbamate derivatives, oxime ester derivatives, and acyl compounds. In the present invention, preferred examples of the photobase generator include carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, and oxime derivatives.

[0215] The basic substance generated from the photobase generator is not particularly limited, but examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines. From the viewpoint of the imidization rate, the basic substance preferably has a large pKa in DMSO (dimethyl sulfoxide) of the conjugate acid. The pKa is preferably 1 or more, more preferably 3 or more. The upper limit of the pKa is not particularly limited, but is preferably 20 or less. Here, the pKa refers to the logarithm of the reciprocal of the first dissociation constant of an acid, and can be found in Determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; editors: Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (authors: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using ACD / pKa (ACD / Labs) software is used as the pKa.

[0216] From the viewpoint of storage stability of the photosensitive resin composition, the photobase generator is preferably a photobase generator that does not contain a salt in the structure, and preferably has no charge on the nitrogen atom of the base portion generated in the photobase generator. The photobase generator is preferably one in which the base generated is made latent using a covalent bond, and the base generation mechanism is preferably one in which the covalent bond between the nitrogen atom of the base portion generated and the adjacent atom is broken to generate the base. If the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is better and the pot life is improved. For these reasons, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine. From the viewpoint of the chemical resistance of the pattern, the photobase generator is preferably a photobase generator containing a salt in its structure.

[0217] For the reasons mentioned above, it is preferable that the photobase generator generates a base in a latent form using a covalent bond as described above, and it is preferable that the generated base is latent using an amide bond, a carbamate bond, or an oxime bond. Examples of the photobase generator according to the present invention include photobase generators having a cinnamic acid amide structure as disclosed in JP 2009-080452 A and WO 2009 / 123122 A, photobase generators having a carbamate structure as disclosed in JP 2006-189591 A and JP 2008-247747 A, photobase generators having an oxime structure or a carbamoyloxime structure as disclosed in JP 2007-249013 A and JP 2008-003581 A, but are not limited to these, and other known photobase generator structures can also be used.

[0218] Other examples of the photobase generator include the compounds described in JP2012-093746A, paragraphs

[0185] to

[0188] ,

[0199] to

[0200] , and

[0202] , the compounds described in JP2013-194205A, paragraphs

[0022] to

[0069] , the compounds described in JP2013-204019A, paragraphs

[0026] to

[0074] , and the compound described in WO2010 / 064631A, paragraph

[0052] .

[0219] In addition, commercially available products may be used as the photobase generator. Commercially available products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), A2502, B5085, N0528, N1052, O0396, O0447, and O0448 (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0220] When a photobase generator is contained, its content is preferably 0.1 to 30 mass%, more preferably 0.1 to 20 mass%, and even more preferably 2 to 15 mass% based on the total solid content of the photosensitive resin composition of the present invention. Only one type of photobase generator may be contained, or two or more types may be contained. When two or more types of photobase generators are contained, the total content is preferably within the above range.

[0221] <Thermal polymerization initiator> The 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. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the crosslinking agent can also be advanced in the heating step described below, so that the solvent resistance can be further improved.

[0222] Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554.

[0223] When a thermal polymerization initiator is contained, the content is preferably 0.1 to 30 mass% based on the total solid content of the composition of the present invention, more preferably 0.1 to 20 mass%, and even more preferably 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.

[0224] <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.

[0225] 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).

[0226] 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.

[0227] 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.

[0228] In addition, the compounds described in paragraph 0059 of JP-A-2013-167742 are also preferred as thermal acid generators.

[0229] 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.

[0230] <Onium salt> The photosensitive resin composition of the present invention may further contain an onium salt. In particular, when the photosensitive resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it preferably contains an onium salt. The type of onium salt is not particularly limited, but preferred examples include ammonium salts, iminium salts, sulfonium salts, iodonium salts and phosphonium salts. Among these, ammonium salts or iminium salts are preferred from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts or phosphonium salts are preferred from the viewpoint of compatibility with the polymer.

[0231] Furthermore, an onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bonded via a covalent bond. That is, the onium salt may be an intramolecular salt having a cationic moiety and an anionic moiety in the same molecular structure, or an intermolecular salt in which a cationic molecule and an anionic molecule, which are separate molecules, are ionic-bonded, but an intermolecular salt is preferable. In the photosensitive resin composition of the present invention, the cationic moiety or cationic molecule and the anionic moiety or anionic molecule may be ionic-bonded or dissociated. The cation in the onium salt is preferably an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation, and more preferably at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation.

[0232] The onium salt used in the present invention may be a thermal base generator, which will be described later. The thermal base generator refers to a compound that generates a base when heated, and examples thereof include compounds that generate a base when heated to 40° C. or higher. Examples of the onium salt include the onium salts described in paragraphs 0122 to 0138 of WO 2018 / 043262. In addition, onium salts used in the field of polyimide precursors can be used without particular limitation.

[0233] When the photosensitive resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50 mass% based on the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 0.5 mass% or more, even more preferably 0.85 mass% or more, and even more preferably 1 mass% or more. The upper limit is more preferably 30 mass% or less, even more preferably 20 mass% or less, and even more preferably 10 mass% or less, and may be 5 mass% or less, or may be 4 mass% or less. The onium salt 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.

[0234] <Thermal base generator> The photosensitive resin composition of the present invention may further contain a thermal base generator. In particular, when the photosensitive resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it preferably contains a thermal base generator. The other thermal base generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermal base generator other than the above-mentioned onium salt. Examples of thermal base generators other than the above-mentioned onium salts include nonionic thermal base generators. Examples of the nonionic thermal base generator include compounds represented by formula (B1) or formula (B2). [ka]

[0235] 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. 1and 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.

[0236] 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.

[0237] More specifically, Rb 1 and Rb 2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). These groups may have a substituent within the range in which the effects of the present invention are exhibited. Rb 1 and Rb 2 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 2is particularly preferably a linear, branched or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, more preferably a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, and even more preferably a cyclohexyl group which may have a substituent.

[0238] Rb 3 Examples of the group include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and more preferably having 2 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 12 carbon atoms), an arylalkenyl group (preferably having 8 to 24 carbon atoms, more preferably having 8 to 20 carbon atoms, and more preferably having 8 to 16 carbon atoms), an 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.

[0239] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or (B1-2). [ka]

[0240] In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb32 respectively represent Rb in formula (B1). 1 and Rb 2 is the same as: Rb 13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and may have a substituent within the range in which the effects of the present invention can be achieved. 13 is preferably an arylalkyl group.

[0241] 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.

[0242] 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.

[0243] The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a). [ka]

[0244] Rb 11 and Rb 12 is Rb in formula (B1-1). 11 and Rb 12 is synonymous with. Rb 15 and Rb 16 represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and 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.

[0245] The molecular weight of the nonionic thermal 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.

[0246] Among the above-mentioned onium salts, specific examples of compounds that are thermal base generators, or specific examples of thermal base generators other than the above-mentioned onium salts, include the following compounds.

[0247] [ka]

[0248] [ka]

[0249] [ka]

[0250] The content of the other thermal base generator is preferably 0.1 to 50% by mass based on the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less. One or more types of thermal base generators can be used. When two or more types are used, the total amount is preferably within the above range.

[0251] <Crosslinking agent> The photosensitive resin composition of the present invention preferably contains a crosslinking agent. The crosslinking agent may be a radical crosslinking agent or other crosslinking agent.

[0252] <Radical crosslinking agent> The photosensitive resin composition of the present invention preferably further 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 group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth)acryloyl group. Among these, the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, and from the viewpoint of reactivity, a (meth)acryloxy group is more preferable.

[0253] The radical crosslinking agent may be a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more ethylenically unsaturated bonds. The compound having two ethylenically unsaturated bonds is preferably a compound having two of the above groups containing an ethylenically unsaturated bond. From the viewpoint of the film strength of the obtained pattern, the photosensitive resin composition of the present invention preferably contains a compound having 3 or more ethylenically unsaturated bonds as a radical crosslinking agent. The compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 to 15 ethylenically unsaturated bonds, more preferably a compound having 3 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 3 to 6 ethylenically unsaturated bonds. Furthermore, the compound having three or more ethylenically unsaturated bonds is preferably a compound having three or more groups containing the ethylenically unsaturated bonds, more preferably a compound having 3 to 15 such bonds, even more preferably a compound having 3 to 10 such bonds, and particularly preferably a compound having 3 to 6 such bonds. From the viewpoint of the film strength of the obtained pattern, it is also preferable that the photosensitive resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.

[0254] 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.

[0255] 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.

[0256] In addition, the radical crosslinking agent is preferably a compound having a boiling point of 100° C. or more 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 (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.

[0257] 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.

[0258] 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.

[0259] 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.

[0260] 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.

[0261] 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.

[0262] 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.

[0263] 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).

[0264] 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.

[0265] 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.

[0266] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. If the acid value of the radical crosslinking agent is within the above range, the handling property during production is excellent, and furthermore, the developability is excellent. Also, the polymerizability is good. On the other hand, from the viewpoint of the development speed in the case of alkali development, 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. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0267] In terms of pattern resolution and film stretchability, the photosensitive resin composition of the present invention preferably uses a bifunctional methacrylate or acrylate. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, and 1,6-hexanediol diacrylate. , 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as necessary. In addition, from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the pattern, 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 pyrrolidone, N-vinyl caprolactam, and other N-vinyl compounds, and allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, and other allyl compounds 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.

[0268] When the radical crosslinking agent is contained, the content thereof is preferably more than 0% by mass and not more than 60% by mass based on the total solid content of the photosensitive 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.

[0269] 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.

[0270] <Other crosslinking agents> The photosensitive resin composition of the present invention preferably contains a crosslinking agent other than the above-mentioned radical crosslinking agent. In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that 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 photosensitizer, 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 the action of an acid or a base. The acid or base is preferably an acid or base generated from a photoacid generator or photobase generator, which is a photosensitizer, in the exposure step. As the other crosslinking agent, a compound having at least one group selected from the group consisting of 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 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 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 photosensitive 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.

[0271] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0272] 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, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated 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, monodiethoxymethylated 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.

[0273] Specific examples of benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0274] 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.

[0275] 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.

[0276] The photosensitive 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.

[0277] [Epoxy compounds (compounds having an epoxy group)] 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 film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in curing the photosensitive resin composition at low temperatures and suppressing warping.

[0278] 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.

[0279] 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) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-15 0, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822, 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, Likaresin (registered trademark) BEO-20E (all trade names, manufactured by DIC Corporation), Likaresin (registered trademark) (registered trademark) BEO-60E, Likaresin (registered trademark) HBE-100, Likaresin (registered trademark) DME-100, Likaresin (registered trademark) L-200 (product name, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (all product names, manufactured by ADEKA Corporation), Celoxide 2021P, 2081, 2000, 3000, EHPE3150, Epolead GT400, Cellvinars B0134, B0177 (all product names, manufactured by Daicel Corporation), NC-300 0, 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.).

[0280] [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 the Aron Oxetane series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd., which may be used alone or in combination of two or more kinds.

[0281] [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 degassing does not occur during curing, and further, they reduce thermal shrinkage and suppress the occurrence of warping.

[0282] Preferred examples of benzoxazine compounds include Ba-type benzoxazine, Bm-type benzoxazine, 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.

[0283] The content of the other crosslinking agent is preferably 0.1 to 30 mass% based on the total solid content of the photosensitive 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.

[0284] <Compounds having a sulfonamide structure, compounds having a thiourea structure> From the viewpoint of improving the adhesion of the obtained pattern to a substrate, it is preferable that the photosensitive resin composition of the present invention further contains at least one compound selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure.

[0285] [Compounds having a sulfonamide structure] The sulfonamide structure is a structure represented by the following formula (S-1). [ka] In formula (S-1), R represents a hydrogen atom or an organic group, R may bond to another structure to form a ring structure, and each * independently represents a bonding site to another structure. The above R is R in the following formula (S-2): 2 It is preferable that the group is the same as the following group. The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but is preferably a compound having one sulfonamide structure.

[0286] The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2). [ka] In formula (S-2), R 1 , R 2 and R 3 each independently represents a hydrogen atom or a monovalent organic group; R 1 , R 2 and R 3 Two or more of these may be bonded to each other to form a ring structure. R 1 , R 2 and R 3 is preferably each independently a monovalent organic group. R 1 , R 2 and R 3Examples of the alkyl group include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a combination of two or more of these groups. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, and a 2-ethylhexyl group. The above cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the above cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The above alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the above alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group. The above alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, and more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the above alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Examples of the heterocyclic group include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimididine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran group, and a group in which one hydrogen atom has been removed from a heterocyclic structure such as a triazine ring.

[0287] Among these, R 1 is an aryl group, and R 2 and R 3 are each independently a hydrogen atom or an alkyl group.

[0288] Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanilamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1-sulfonamide, naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethanesulfonamide.

[0289] [Compounds having a thiourea structure] The thiourea structure is a structure represented by the following formula (T-1). [ka] In formula (T-1), R 4 and R 5 each independently represents a hydrogen atom or a monovalent organic group; R 4 and R 5 may be bonded to form a ring structure, R4 may combine with another structure to which * is bonded to form a ring structure, R 5 may bond to another structure to which the * is bonded to form a ring structure, and each * independently represents a bonding site to another structure.

[0290] R 4 and R 5 are each preferably independently a hydrogen atom. R 4 and R 5 Examples of the alkyl group include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a combination of two or more of these groups. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, and a 2-ethylhexyl group. The above cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the above cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The above alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the above alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group. The above alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, and more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the above alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Examples of the heterocyclic group include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimididine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran group, and a group in which one hydrogen atom has been removed from a heterocyclic structure such as a triazine ring. The compound having a thiourea structure may be a compound having two or more thiourea structures, but is preferably a compound having one thiourea structure.

[0291] The compound having a thiourea structure is preferably a compound represented by the following formula (T-2). [ka] In formula (T-2), R 4 ~R 7 each independently represents a hydrogen atom or a monovalent organic group; R 4 ~R 7 At least two of these may be bonded to each other to form a ring structure.

[0292] In formula (T-2), R 4 and R 5 is R in formula (T-1) 4 and R 5 The same applies to the preferred embodiments. In formula (T-2), R 6 and R 7 is preferably each independently a monovalent organic group. In formula (T-2), R 6 and R 7 A preferred embodiment of the monovalent organic group in formula (T-1) is 4and R 5 The preferred embodiments are the same as those of the monovalent organic group in the above.

[0293] Examples of compounds having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1-adamantylthiourea, N-benzoylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea, N,N-diphenylthiourea, ethylenethiourea (2-imidazolinethione), carbimazole, and 1,3-dimethyl-2-thiohydantoin.

[0294] [Content] The total content of the compound having a sulfonamide structure and the compound having a thiourea structure relative to the total mass of the photosensitive resin composition of the present invention is preferably 0.05 to 10 mass%, more preferably 0.1 to 5 mass%, and even more preferably 0.2 to 3 mass%. The photosensitive resin composition of the present invention may contain only one compound selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure, or may contain two or more compounds. When only one compound is contained, the content of the compound is preferably within the above range, and when two or more compounds are contained, the total amount is preferably within the above range.

[0295] <Migration inhibitor> The photosensitive resin composition of the present invention preferably further contains a migration inhibitor, which makes it possible to effectively inhibit migration of metal ions originating from the metal layer (metal wiring) into the photosensitive film.

[0296] The migration inhibitor is not particularly limited, but includes compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

[0297] Alternatively, an ion trapping agent that traps anions such as halogen ions can be used.

[0298] Other examples of the migration inhibitor include the rust inhibitor described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compounds described in paragraph 0052 of JP-A-2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, and the compounds described in paragraph 0166 of WO 2015 / 199219.

[0299] Specific examples of the migration inhibitor include the following compounds.

[0300] [ka]

[0301] When the photosensitive resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass %, based on the total solid content of the photosensitive resin composition.

[0302] The migration inhibitor may be one type or two or more types. When two or more types of migration inhibitors are used, the total amount is preferably within the above range.

[0303] <Polymerization inhibitor> The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.

[0304] Examples of the polymerization inhibitor include hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol (t-butylcatechol), 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrophenyl-p-benzoquinone, and the like. Nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, 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-sulfopropionate), (p-amino)phenol, N-nitrosophenylhydroxyamine cerium salt, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxygen Syl free radical, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbamate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N,N'-diphenyl-p-phenylenediamine, 2,4-di-tert-butylphenol, di-t-butylhydroxytoluene, 1,4-naphthoquinone, etc. can be suitably used. In addition, the polymerization inhibitor described in paragraph 0060 of JP2015-127817A and the compounds described in paragraphs 0031 to 0046 of WO2015 / 125469A can also be used.

[0305] Additionally, the following compound can be used (Me is a methyl group):

[0306] [ka]

[0307] When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is, for example, 0.01 to 20.0 mass%, preferably 0.01 to 5 mass%, more preferably 0.02 to 3 mass%, and even more preferably 0.05 to 2.5 mass%, relative to the total solid content of the photosensitive resin composition of the present invention.

[0308] 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.

[0309] <Metal adhesion improver> The photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents, 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.

[0310] Examples of the silane coupling agent include the compounds described in paragraph 0167 of WO 2015 / 199219, the compounds described in paragraphs 0062-0073 of JP 2014-191002 A, the compounds described in paragraphs 0063-0071 of WO 2011 / 080992 A, the compounds described in paragraphs 0060-0061 of JP 2014-191252 A, the compounds described in paragraphs 0045-0052 of JP 2014-041264 A, and the compounds described in paragraph 0055 of WO 2014 / 097594 A. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050-0058 of JP 2011-128358 A. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

[0311] [ka] 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-methacryloxypropyl Examples of the silane include pyryltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-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, and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0312] [Aluminum-based adhesion promoter] Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0313] As the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP-A No. 2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A No. 2013-072935 can also be used.

[0314] The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 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 of only one type, or of two or more types. When two or more types are used, the total is preferably within the above range.

[0315] <Metal adhesion improver> The photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes, wiring, etc. As the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP2013-072935A can also be used.

[0316] The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the heterocycle-containing polymer precursor. By making it equal to or more than the lower limit, the adhesion between the pattern and the metal layer after the heating step is improved, and by making it equal to or less than the upper limit, the heat resistance and mechanical properties of the cured product after the heating step are improved. 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.

[0317] <Other additives> The photosensitive resin composition of the present invention may contain various additives, such as sensitizers, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc., as necessary, within the range in which the effects of the present invention can be obtained. When these additives are added, the total amount of the additives is preferably 3% by mass or less of the solid content of the photosensitive resin composition.

[0318] [Sensitizer] The photosensitive resin composition of the present invention may contain a sensitizer (also referred to as "other sensitizer") different from the specific sensitizer described above. The sensitizer absorbs specific active radiation and becomes electronically excited. The sensitizer in the electronically excited state comes into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal curing accelerator, thermal radical polymerization initiator, and photoradical polymerization initiator undergo a chemical change and decompose, generating a radical, an acid, or a base. Other sensitizers include, for example, 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, 1,3-bis(4'-dimethylaminobenzal)acet ... Examples of such amines include (4'-diethylaminobenzal)acetone, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 1-phenyl-5-mercaptotetrazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. As the sensitizer, a sensitizing dye may 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.

[0319] When the photosensitive resin composition of the present invention 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 photosensitive resin composition of the present invention. The sensitizer may be used alone or in combination of two or more kinds.

[0320] [Chain transfer agent] The photosensitive resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is 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, a thiol compound can be preferably used.

[0321] In addition, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of WO 2015 / 199219 can also be used.

[0322] When the photosensitive resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive 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.

[0323] [Surfactant] A surfactant may be added to the photosensitive resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. The following surfactants are also preferred. In the following formula, the parentheses indicating the repeating unit of the main chain indicate the content (mol %) of each repeating unit, and the parentheses indicating the repeating unit of the side chain indicate the number of repeats of each repeating unit. [ka] In addition, the compounds described in paragraphs 0159 to 0165 of WO 2015 / 199219 can also be used as the surfactant. The fluorine-containing surfactant may be a fluorine-containing polymer having an ethylenically unsaturated group in the side chain. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of JP2010-164965A, such as Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0324] 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.

[0325] 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.), KP341, KF6001, KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie Co., Ltd.), and the like.

[0326] 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.).

[0327] 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, sorbitan fatty acid ether, and the like. Examples of such compounds include Stel, 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.).

[0328] Specific examples of cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0329] 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.

[0330] When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass% and more preferably 0.005 to 1.0 mass% based on the total solid content of the photosensitive resin composition of the present invention. The surfactant may be one type or two or more types. When two or more types of surfactants are used, the total is preferably within the above range.

[0331] [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 photosensitive resin composition of the present invention and distributed unevenly on the surface of the photosensitive resin composition during drying after coating.

[0332] In addition, the higher fatty acid derivative may be a compound described in paragraph 0155 of WO 2015 / 199219.

[0333] When the photosensitive 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 photosensitive 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.

[0334] [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. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also be promoted, so that the solvent resistance can be further improved.

[0335] Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554.

[0336] 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.

[0337] [Inorganic particles] The resin composition of the present invention may contain inorganic fine particles, specifically, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

[0338] 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. When the inorganic particles have a large average particle size, the mechanical properties of the cured film may deteriorate, and when the average particle size of the inorganic particles exceeds 2.0 μm, the resolution may decrease due to scattering of the exposure light.

[0339] [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.

[0340] 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(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine.

[0341] In the present invention, the above-mentioned various ultraviolet absorbents may be used alone or in combination of two or more. The composition of the present invention may or may not contain an ultraviolet absorber. When the composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably from 0.001% by mass to 1% by mass, and more preferably from 0.01% by mass to 0.1% by mass, relative to the total solid mass of the composition of the present invention.

[0342] [Organotitanium Compounds] The resin composition of the present embodiment may contain an organotitanium compound. By containing an organotitanium compound in the resin composition, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

[0343] Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the negative photosensitive resin composition and provide a good cured pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like. II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], and the like. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like. IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: For example, isopropyl tridodecylbenzenesulfonyl titanate.

[0344] Among them, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0345] When an organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the cyclized resin precursor. When the blending amount is 0.05 parts by mass or more, the obtained cured pattern exhibits good heat resistance and chemical resistance, while when it is 10 parts by mass or less, the composition has excellent storage stability.

[0346] [Antioxidants] The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, it is possible to improve the elongation properties of the film after curing and the adhesion to metal materials. Examples of the antioxidant include phenolic compounds, phosphite compounds, and thioether compounds. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, a hindered phenolic compound can be mentioned. A compound having a substituent at the site (ortho position) adjacent to the phenolic hydroxyl group is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, as the antioxidant, a compound having a phenolic group and a phosphite group in the same molecule is also preferred. In addition, as the antioxidant, a phosphorus-based antioxidant can also be suitably used. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite. Examples of commercially available antioxidants include ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, and ADK STAB AO-330 (all manufactured by ADEKA CORPORATION). In addition, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as the antioxidant. In addition, the composition of the present invention may contain a latent antioxidant as necessary. Examples of latent antioxidants include compounds in which the site functioning as an antioxidant is protected with a protecting group, and which function as an antioxidant when heated at 100 to 250° C. or heated at 80 to 200° C. in the presence of an acid / base catalyst, causing the protecting group to be eliminated.Examples of latent antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and JP-A-2017-008219. Examples of commercially available latent antioxidants include Adeka Arcles GPA-5001 (manufactured by ADEKA Corporation). Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and a compound represented by the general formula (3).

[0347] [ka]

[0348] In general formula (3), R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, R6 represents an alkylene group having 2 or more carbon atoms, R7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom, and k represents an integer of 1 to 4.

[0349] The compound represented by the general formula (3) suppresses the oxidative deterioration of the aliphatic groups and phenolic hydroxyl groups of the resin, and also suppresses the oxidation of metals by its rust-preventing effect on metal materials.

[0350] Since it can act simultaneously on resin and metal materials, k is more preferably an integer of 2 to 4. Examples of R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among these, it is preferable to have an alkyl ether or -NH- from the viewpoint of solubility in a developer and metal adhesion, and -NH- is more preferable from the viewpoint of interaction with a resin and metal adhesion due to metal complex formation.

[0351] Examples of the compound represented by the following general formula (3) include, but are not limited to, the following structures.

[0352] [ka]

[0353] [ka]

[0354] [ka]

[0355] [ka]

[0356] The amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. If the amount added is less than 0.1 part by mass, it is difficult to obtain the effect of improving the elongation characteristics after reliability and the adhesion to metal materials, and if it is more than 10 parts by mass, there is a risk of causing a decrease in the sensitivity of the resin composition due to interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

[0357] <Restrictions on other substances> The water content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass, from the viewpoint of the properties of the coated surface. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container.

[0358] The metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulation. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are contained, the total of these metals is preferably within the above range.

[0359] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the photosensitive resin composition of the present invention include selecting raw materials having a low metal content as raw materials constituting the photosensitive resin composition of the present invention, filtering the raw materials constituting the photosensitive resin composition of the present invention through a filter, and lining the inside of an apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that suppress contamination as much as possible.

[0360] Considering the use of the photosensitive resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosion. Among them, those existing in the form of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range. A preferred method for adjusting the content of halogen atoms is ion exchange treatment.

[0361] A conventionally known container can be used as the container for the photosensitive resin composition of the present invention. In addition, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six-layer resins or a bottle with a seven-layer structure made of six types of resins as the container for the purpose of suppressing impurities from being mixed into the raw materials or the photosensitive resin composition. Examples of such containers include the container described in JP 2015-123351 A.

[0362] <Applications of photosensitive resin composition> The photosensitive resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer. Furthermore, the present invention can also be used for forming an insulating film for a semiconductor device, a stress buffer film, or the like.

[0363] <Preparation of Photosensitive Resin Composition> The photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be a conventionally known method.

[0364] In addition, it is preferable to perform filtration using a filter in order to remove foreign matter such as dust and fine particles in the photosensitive resin composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, it is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. The filter may be used after being washed in advance with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. In addition, various materials may be filtered multiple times. When filtering multiple times, circulation filtration may be performed. In addition, filtration may be performed under pressure. When filtering under pressure, the pressure applied is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, the pressure is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, and even more preferably 0.05 MPa or more and 0.7 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent may be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be used.

[0365] (Photosensitive film, cured product, laminate, device, and manufacturing method thereof) Next, the photosensitive film, the cured product, the laminate, the device, and the methods for producing them will be described.

[0366] The photosensitive film of the present invention is a film formed from the photosensitive resin composition of the present invention. The photosensitive film of the present invention is formed, for example, by applying the photosensitive resin composition of the present invention to a substrate. The application method and the type of substrate are not particularly limited, but preferred examples include the application method and substrate in the film formation step described below. The thickness of the photosensitive film may be set so that the thickness of the cured product described below falls within the range described below. For example, the thickness of the photosensitive film may be determined in consideration of shrinkage due to curing when forming the cured product.

[0367] The cured product of the present invention is a cured product of the photosensitive resin composition of the present invention, or a cured product of the photosensitive film of the present invention. The cured product of the present invention is preferably a pattern obtained by the pattern forming method of the present invention described below. The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention or the photosensitive film of the present invention. The thickness of the cured product of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. The upper limit can be 100 μm or less, and can be 30 μm or less. The cured product of the present invention is preferably used as an interlayer insulating film for a rewiring layer.

[0368] The layer of the cured product of the present invention may be laminated to two or more layers, or even three to seven layers. The laminate of the present invention preferably includes two or more layers of the cured product, and includes a metal layer between any of the layers of the cured product. For example, a laminate including at least a layer structure in which three layers, a layer of a first cured product, a metal layer, and a layer of a second cured product, are laminated in this order, is preferred. The layer of the first cured product and the layer of the second cured product are both layers of the cured product of the present invention, and for example, both the layer of the first cured product and the layer of the second cured product are films formed by curing the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention used to form the layer of the first cured product and the photosensitive resin composition of the present invention used to form the layer of the second cured product may be compositions having the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

[0369] The fields in which the cured product of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), and the formation of patterns by etching of insulating films for mounting applications such as those described above. For these applications, reference can be made to, for example, Science & Technology Co., Ltd., "High-performance and Applied Technology of Polyimides," April 2008, supervised by Masaaki Kakimoto, CMC Technical Library, "Basics and Development of Polyimide Materials," published in November 2011, and Japan Polyimide and Aromatic Polymer Research Association, "Latest Polyimides: Basics and Applications," NTS, August 2010.

[0370] The cured products according to the invention can also be used for the production of printing plates, such as offset printing plates or screen printing plates, for etching molded parts, for the production of protective lacquers and dielectric layers in electronics, especially microelectronics, etc.

[0371] The method for producing a pattern of the present invention (hereinafter also simply referred to as the "production method of the present invention") preferably includes a film formation step of applying the photosensitive resin composition of the present invention to a substrate to form a film (photosensitive film). The method for producing a pattern of the present invention preferably includes the film forming step, an exposure step of exposing the film to light, and a development step of developing the exposed film to obtain a pattern. Furthermore, the method for producing a pattern of the present invention preferably includes the above-mentioned film forming step and, if necessary, the above-mentioned developing step, and more preferably includes a heating step of curing the pattern by heating the pattern obtained by the developing step. Specifically, the method preferably includes the following steps (a) to (c), and more preferably includes the following steps (a) to (d). (a) A film-forming step of applying a photosensitive resin composition to a substrate to form a film (photosensitive film) (b) an exposure step of exposing the film to light (c) a development step for developing the exposed film to obtain a pattern. (d) a heating step of curing the pattern obtained by the developing step by heating the pattern. By heating in the heating step, the photosensitive film can be further cured.

[0372] A laminate manufacturing method according to a preferred embodiment of the present invention includes a pattern manufacturing method according to the present invention. In the laminate manufacturing method of this embodiment, after forming a pattern according to the above pattern manufacturing method, step (a), or steps (a) to (c), or steps (a) to (d) are performed again. In particular, it is preferable to perform each of the above steps in order multiple times, for example, 2 to 5 times (i.e., 3 to 6 times in total). By stacking the patterns in this way, a laminate can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the patterned portion or between the patterns, or both. In addition, in the manufacture of the laminate, it is not necessary to repeat all of the steps (a) to (d), and as described above, a patterned laminate can be obtained by performing at least (a), preferably steps (a) to (c) or (a) to (d) multiple times.

[0373] <Film formation process (layer formation process)> The production method according to a preferred embodiment of the present invention includes a film-forming step (layer-forming step) of applying a photosensitive resin composition to a substrate to form a film (layer).

[0374] The type of substrate can be appropriately determined depending on the application, but is not particularly limited to substrates for semiconductor production such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, and electrode plates for plasma display panels (PDPs). In addition, these substrates may have layers such as an adhesion layer and an oxide layer on the surface. In the present invention, substrates for semiconductor production are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred. Furthermore, these substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface. As the base material, for example, a plate-shaped base material (substrate) is used. The shape of the substrate is not particularly limited and may be circular or rectangular, but is preferably rectangular. The size of the substrate is, for example, a diameter of 100 to 450 mm, preferably 200 to 450 mm, if it is circular, and, for example, a length of a short side of 100 to 1000 mm, preferably 200 to 700 mm, if it is rectangular.

[0375] When a photosensitive film is formed on the surface of a resin layer (a layer made of a cured product) or on the surface of a metal layer, the resin layer or the metal layer serves as the base material.

[0376] The photosensitive resin composition is preferably applied to a substrate by coating.

[0377] Specifically, examples of the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, a slit coating method, and an inkjet method. From the viewpoint of uniformity of the thickness of the photosensitive film, more preferred are a spin coating method, a slit coating method, a spray coating method, and an inkjet method. By adjusting the solid content concentration and the coating conditions appropriately according to the method, a resin layer of a desired thickness can be obtained. In addition, the coating method can be appropriately selected depending on the shape of the substrate, and if the substrate is a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, and the like are preferred, and if the substrate is a rectangular substrate, a slit coating method, a spray coating method, an inkjet method, and the like are preferred. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. Depending on the viscosity of the photosensitive resin composition and the film thickness to be set, it is also preferable to apply the film at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. In order to obtain a uniform film thickness, a combination of multiple rotation speeds can also be used for coating. Alternatively, a coating film formed by applying the coating material to a temporary support in advance using the above-mentioned application method may be transferred onto the substrate. Regarding the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used in the present invention. Additionally, a process may be performed to remove excess film from the edges of the substrate, such as edge bead rinse (EBR), air knife, back rinse, etc. Furthermore, a pre-wetting step may be employed in which, before applying the resin composition to the substrate, the substrate is coated with various solvents to improve the wettability of the substrate, and then the resin composition is applied.

[0378] <Drying process> The manufacturing method of the present invention may include a drying step to remove the solvent after the film forming step (layer forming step). The drying temperature is preferably 50 to 150° C., more preferably 70 to 130° C., and further preferably 90 to 110° C. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 3 to 7 minutes.

[0379] <Exposure process> The production method of the present invention may include an exposure step of exposing the film (photosensitive film) to light. The amount of exposure is not particularly limited as long as the photosensitive resin composition can be cured. For example, the amount of exposure is 100 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. 2 It is preferable to irradiate with 200 to 8,000 mJ / cm 2 Irradiation is more preferred.

[0380] The exposure light used in the exposure step preferably contains light having a wavelength of 150 to 1,000 nm, more preferably contains light having a wavelength of 150 to 450 nm, and even more preferably contains light having a wavelength of 240 to 550 nm.

[0381] In terms of the light source, the exposure wavelength may be, in terms of the relationship with the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet ray; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser second harmonic 532nm, third harmonic 355nm, etc. can be mentioned. For the photosensitive resin composition of the present invention, exposure by a high pressure mercury lamp is particularly preferred, and among them, exposure by i-line is preferred. This can provide particularly high exposure sensitivity. From the viewpoint of ease of handling and productivity, a broad (three wavelengths of g, h, and i lines) light source of a high-pressure mercury lamp or a semiconductor laser of 405 nm is also suitable.

[0382] <Developing process> The manufacturing method of the present invention may include a development step in which the exposed film (photosensitive film) is developed (the film is developed). By carrying out development, the unexposed portion (non-exposed portion) is removed. The development method is not particularly limited as long as the desired pattern can be formed, and examples thereof include discharging the developer from a nozzle, spraying, and immersing the substrate in the developer, with discharging from a nozzle being preferably used. The development step may include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept substantially stationary on the substrate, a step in which the developer is vibrated by ultrasonic waves or the like, and a combination of these steps.

[0383] The development is carried out using a developer. There are no particular limitations on the developer that can be used as long as it can remove the unexposed areas. As the developer, a developer containing an organic solvent or an alkaline aqueous solution can be used.

[0384] In the present invention, the developer preferably contains an organic solvent having a ClogP value of −1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be calculated by inputting a structural formula into ChemBioDraw.

[0385] When the developer is a developer containing an organic solvent, the organic solvent may be, for example, an ester, such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate), ethyl 3-alkyloxypropionate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., 2-methoxypropionate, ethyl 2-alkyloxypropionate, Methyl cypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2-oxobutanoic acid Ethyl and the like, and ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate,Suitable examples of the organic solvent include propylene glycol monopropyl ether acetate, ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone, cyclic hydrocarbons such as toluene, xylene, anisole, and limonene, and sulfoxides such as dimethyl sulfoxide. Mixtures of these organic solvents are also suitable.

[0386] When the developer contains an organic solvent, in the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. When the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more kinds.

[0387] When the developer contains an organic solvent, the developer preferably contains 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and even more preferably 90% by mass or more of the organic solvent. The developer may also contain 100% by mass of the organic solvent.

[0388] The developer may further comprise other components. Examples of other components include known surfactants and known defoamers.

[0389] When the developer is an alkaline aqueous solution, examples of the basic compound that the alkaline aqueous solution may contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate, etc., and preferably TMAH. When TMAH is used, the content of the basic compound in the developer is preferably 0.01 to 10 mass % of the total mass of the developer, more preferably 0.1 to 5 mass %, and even more preferably 0.3 to 3 mass %.

[0390] [Method of Supplying Developer] The method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and includes a method of immersing the substrate in the developer, a method of supplying the developer onto the substrate using a nozzle for paddle development, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, a method of supplying the developer through a spray nozzle is more preferred. Alternatively, a process may be adopted in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate. This process may be repeated multiple times. As a method of supplying the developer in the development process, a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept substantially stationary on the substrate, a process in which the developer is vibrated on the substrate by ultrasonic waves or the like, or a combination of these processes can be used.

[0391] The development time is preferably 5 seconds to 10 minutes, and more preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is usually 10 to 45°C, and preferably 20 to 40°C.

[0392] After the treatment using the developer, rinsing may be further performed. Alternatively, a method of supplying a rinsing liquid before the developer in contact with the pattern is completely dried may be adopted. Rinsing is preferably performed with a solvent different from the developer. For example, rinsing can be performed with a solvent contained in the photosensitive resin composition. When the developer contains an organic solvent, the rinse liquid may be PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), etc., and is preferably PGMEA. In addition, the rinse liquid for development using a developer containing an alkaline aqueous solution is preferably water. The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 5 seconds to 1 minute. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0393] When the rinse solution contains an organic solvent, examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetate), ethyl butyl methoxyacetate, ... ethyl dimethylacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and ethyl Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate,Suitable examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; suitable examples of the aromatic hydrocarbons include toluene, xylene, anisole, and limonene; suitable examples of the sulfoxides include dimethyl sulfoxide; suitable examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol; and suitable examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0394] When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethylsulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are even more preferred.

[0395] When the rinse liquid contains an organic solvent, the rinse liquid preferably contains 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and even more preferably 90% by mass or more of the organic solvent. Alternatively, the rinse liquid may contain 100% by mass of the organic solvent.

[0396] The rinse solution may further contain other ingredients. Examples of other components include known surfactants and known defoamers.

[0397] [Method of Supplying Rinse Liquid] The method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples of the method include a method of immersing the substrate in the rinse liquid, a method of forming a liquid film of the rinse liquid on the substrate, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like. From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, the rinse liquid may be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, while from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc. That is, the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle. As a method of supplying the rinsing liquid in the rinsing step, a step in which the rinsing liquid is continuously supplied to the substrate, a step in which the rinsing liquid is kept substantially stationary on the substrate, a step in which the rinsing liquid is vibrated on the substrate by ultrasonic waves or the like, or a combination of these steps can be used.

[0398] <Heating process> The production method of the present invention preferably includes a step of heating the developed film at 50 to 450° C. (heating step). The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step. In the heating step, for example, the above-mentioned thermal base generator is decomposed to generate a base, and the cyclization reaction of the precursor of the specific resin proceeds. In addition, the photosensitive resin composition of the present invention may contain a radical crosslinking agent other than the precursor of the specific resin, but the curing of the radical crosslinking agent other than the unreacted precursor of the specific resin can also proceed in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50°C or higher, more preferably 80°C or higher, even more preferably 140°C or higher, even more preferably 150°C or higher, even more preferably 160°C or higher, and even more preferably 170°C or higher. The upper limit is preferably 500°C or lower, more preferably 450°C or lower, even more preferably 350°C or lower, even more preferably 250°C or lower, and even more preferably 220°C or lower.

[0399] The heating is preferably performed at a temperature rise rate of 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. By setting the temperature rise rate at 1°C / min or more, it is possible to prevent excessive volatilization of the amine while ensuring productivity, and by setting the temperature rise rate at 12°C / min or less, it is possible to alleviate the residual stress of the pattern. In addition, in the case of an oven capable of rapid heating, it is preferable to perform the heating from the temperature at the start of heating to the maximum heating temperature at a temperature rise rate of 1 to 8°C / sec, more preferably 2 to 7°C / sec, and even more preferably 3 to 6°C / sec.

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

[0401] The heating time (heating time at the maximum heating temperature) is preferably from 10 to 360 minutes, more preferably from 20 to 300 minutes, and further preferably from 30 to 240 minutes. Furthermore, by using the photosensitive resin composition of the present invention, the heating time can be reduced to 15 minutes or less.

[0402] In particular, when forming a multi-layer laminate, from the viewpoint of adhesion between the layers of the pattern, the heating temperature is preferably 180° C. to 320° C., and more preferably 180° C. to 260° C. The reason for this is unclear, but it is thought that by setting the temperature at this level, a crosslinking reaction between ethynyl groups of the specific resin between the layers proceeds.

[0403] Heating may be performed stepwise. For example, a pretreatment step may be performed in which the temperature is raised from 25°C to 180°C at 3°C / min, held at 180°C for 60 minutes, raised from 180°C to 200°C at 2°C / min, and held at 200°C for 120 minutes. The heating temperature in the pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and even more preferably 120 to 185°C. In this pretreatment step, it is also preferable to treat while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment step can improve the properties of the film. The pretreatment step is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, pretreatment step 1 may be performed in the range of 100 to 150°C, and then pretreatment step 2 may be performed in the range of 150 to 200°C.

[0404] Furthermore, after heating, the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C. / min.

[0405] The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, argon, etc., in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less. The heating means is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, and a hot air oven.

[0406] <Metal layer formation process> The manufacturing method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (photosensitive film).

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

[0408] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP-A-2007-157879, JP-T-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and combinations of these methods can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned.

[0409] The thickness of the metal layer at its thickest portion is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, and even more preferably 1 to 10 μm.

[0410] <Lamination process> The manufacturing method of the present invention preferably further includes a lamination step.

[0411] The lamination process is a series of processes including (a) a film forming process (layer forming process), (b) an exposure process, (c) a development process, and (d) a heating process, which are carried out again on the surface of the pattern (layer made of a cured product) or the metal layer in this order. However, it is also possible to repeat only the film forming process (a). In addition, the heating process (d) may be carried out collectively at the end or in the middle of the lamination. That is, it is also possible to carry out the processes (a) to (c) a predetermined number of times repeatedly, and then carry out the heating process (d) to cure the laminated photosensitive film collectively. In addition, after the development process (c), a metal layer forming process (e) may be included, and the heating process (d) may be carried out each time, or the heating process (d) may be carried out collectively after lamination a predetermined number of times. It goes without saying that the lamination process may further include the drying process, heating process, etc., as appropriate.

[0412] In the case where a further lamination step is performed after the lamination step, a surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. An example of the surface activation treatment is a plasma treatment.

[0413] The lamination step is preferably carried out 2 to 20 times, more preferably 2 to 5 times, and further preferably 3 to 5 times. Moreover, the layers in the lamination step may be layers having the same composition, shape, film thickness, etc., or may be layers having different compositions.

[0414] For example, a structure having 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, a structure having 3 to 7 layers is more preferred, and a structure having 3 to 5 layers is even more preferred.

[0415] In the present invention, a particularly preferred embodiment is to form a pattern (resin layer) of the photosensitive resin composition so as to cover the metal layer after providing the metal layer. Specifically, the steps may be repeated in the order of (a) film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, and (d) heating step, or the steps may be repeated in the order of (a) film formation step, (b) exposure step, (c) development step, and (e) metal layer formation step, with (d) heating step being provided at the end or in the middle. By alternately performing the lamination step of laminating the photosensitive film and the metal layer formation step, the cured product (pattern) and the metal layer can be laminated alternately.

[0416] (Surface activation treatment process) The method for producing a laminate of the present invention may include a surface activation treatment step of subjecting at least a part of the metal layer and the photosensitive resin composition layer to a surface activation treatment. The surface activation treatment step is usually carried out after the metal layer formation step, but after the exposure and development step, the photosensitive resin composition layer may be subjected to the surface activation treatment step before the metal layer formation step. The surface activation treatment may be performed on at least a part of the metal layer, or on at least a part of the photosensitive resin composition layer after exposure, or on at least a part of both the metal layer and the photosensitive resin composition layer after exposure. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the area of ​​the metal layer on which the photosensitive resin composition layer is formed. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin layer provided on the surface can be improved. In addition, the surface activation treatment is preferably performed on a part or the whole of the photosensitive resin composition layer (resin layer) after exposure. By performing the surface activation treatment on the surface of the photosensitive resin composition layer in this manner, the adhesion between the metal layer or the resin layer provided on the surface that has been subjected to the surface activation treatment can be improved. Specifically, surface activation treatments include plasma treatments using various raw gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatments, and CF4 / O 2 , N.F. 3 / O 2 ,SCIENCE FICTION 6 , N.F. 3 , N.F. 3 / O 2 The treatment is selected from the group consisting of etching treatment using a UV ozone method, surface treatment using an ultraviolet (UV) ozone method, immersion treatment in an organic surface treatment agent containing a compound having at least one amino group and thiol group after immersion in an aqueous hydrochloric acid solution to remove the oxide film, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw gas is particularly preferred. In the case of corona discharge treatment, the energy is 500 to 200,000 J / m 2 is preferable, and 1000 to 100,000 J / m 2 More preferably, 10,000 to 50,000 J / m 2 is most preferred.

[0417] The present invention also discloses a device (e.g., a semiconductor device) including the cured product or laminate of the present invention. Specific examples of devices using the photosensitive resin composition of the present invention for forming an interlayer insulating film for a rewiring layer can be found in paragraphs 0213 to 0218 and FIG. 1 of JP2016-027357A, the contents of which are incorporated herein by reference. EXAMPLES

[0418] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are by weight unless otherwise specified.

[0419] <Synthesis Example 1: Synthesis of Polymer A-1> 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol), and 100 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to −10° C., and 16.12 g (135.5 mmol) of SOCl was added while maintaining the temperature at −10±4° C. 2 was added over 10 min. 2 The viscosity increased during the addition. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution of 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was dropped into the reaction mixture over 20 minutes at -5 to 0 ° C. Then, the reaction mixture was reacted at 0 ° C. for 1 hour, after which 70 g of ethanol was added and stirred at room temperature overnight. Then, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at a speed of 5,000 rpm (revolutions per minute) for 15 minutes. The polyimide precursor was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at 45 ° C. for 3 days to obtain polymer A-1. The weight average molecular weight of this polymer A-1 was 19,000. The obtained polymer A-1 is presumed to contain a repeating unit represented by the following formula (A-1). [ka]

[0420] <Synthesis Example 2: Synthesis of Polymer A-2> Polymer A-2 was obtained by synthesizing in the same manner as in Synthesis Example 1, except that 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140° C. for 12 hours) was replaced with 20.0 g (64.5 mmol) of 3,3',4,4'-biphenyltetracarboxylic anhydride (dried at 140° C. for 12 hours). The weight average molecular weight of polymer A-2 was 22,000. The obtained polymer A-2 is presumed to contain a repeating unit represented by the following formula (A-2). In the repeating unit represented by formula (A-2), the single bond contained in the biphenyl structure derived from 3,3',4,4'-biphenyltetracarboxylic anhydride and the ester structure formed by 3,3',4,4'-biphenyltetracarboxylic anhydride and 2-hydroxyethyl methacrylate may be present at the meta position on the benzene ring or at the para position (for example, the repeating unit represented by formula (A-2-2) below), and it is believed that these structures are mixed in the polyimide precursor A-2. Similarly, in the chemical formulas showing the repeating units contained in the polyimide precursors produced in the synthesis examples using 3,3',4,4'-biphenyltetracarboxylic anhydride or 4,4'-oxydiphthalic anhydride as the acid dianhydride, the positional relationship on the benzene ring between the single bond contained in the biphenyl structure derived from 3,3',4,4'-biphenyltetracarboxylic anhydride or the ether bond contained in 4,4'-oxydiphthalic anhydride and the ester bond and amide bond bonded to the benzene ring contained in each repeating unit is not limited to the structure shown as the chemical formula, and repeating units with different positional relationships are also included. [ka]

[0421] <Synthesis Example 3: Synthesis of Polymer A-3> Polymer A-3 was obtained by synthesizing in the same manner as in Synthesis Example 1, except that 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140° C. for 12 hours) was replaced with 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140° C. for 12 hours). The weight average molecular weight of polymer A-3 was 19,300. The obtained polymer A-3 is presumed to contain a repeating unit represented by the following formula (A-3). [ka]

[0422] <Synthesis Example 4: Synthesis of Polymer A-4> In Synthesis Example 1, 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours) was replaced with 9.49 g (32.25 mmol) of 4,4'-biphthalic dianhydride and 10.0 g (32.25 mmol) of oxydiphthalic dianhydride (both dried at 140 ° C. for 12 hours), and the same synthesis method as Synthesis Example 1 was used to obtain polymer A-4. The weight average molecular weight of polymer A-4 was 18,000. The obtained polymer A-4 is presumed to contain two types of repeating units represented by the following formula (A-4). [ka]

[0423] <Synthesis Example 5: Synthesis of Polymer A-5> 28.0g (76.4mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 200g of N-methylpyrrolidone with stirring to prepare solution A. Next, 12.1g (153mmol) of pyridine was added to solution A, and while keeping the temperature at -10 to 0°C, a solution in which 1.38g (70.1mmol) of pimelic acid dichloride was dissolved in 75g of N-methylpyrrolidone was added dropwise to solution A over 1 hour. After stirring for 30 minutes, 1.00g (12.7mmol) of acetyl chloride was added and stirred for another 60 minutes. After the reaction solution was cooled to 25° C., 0.005 g of p-methoxyphenol was added and dissolved. To this solution, 16.75 g (160 mmol) of methacrylic acid chloride was added dropwise, and the mixture was stirred at 25° C. for 2 hours and then further stirred at 60° C. for 3 hours. The polybenzoxazole precursor resin was then precipitated in 6 liters of water, and the water-polybenzoxazole precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polybenzoxazole precursor resin was obtained by filtration, stirred again in 6 liters of water for 30 minutes, and filtered again. The obtained polybenzoxazole precursor resin was then dried under reduced pressure at 45°C for 3 days to obtain polymer A-5. The weight average molecular weight of the obtained polymer A-5 was 20,000. The obtained polymer A-5 is presumed to contain a repeating unit represented by the following formula (A-5). [ka]

[0424] <Synthesis Example 6: Synthesis of Polymer A-6> 43.25 g (200 mmol) of 2-hydroxy-4,4'-diaminodiphenyl ether was dissolved in 300 g of N-methylpyrrolidone (NMP) with the removal of moisture in a dry reactor equipped with a flat-bottom joint equipped with a stirrer, a condenser and an internal thermometer. Subsequently, 88.85 g (200 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride was added, and the mixture was stirred for 2 hours at a temperature of 40° C. Then, 50 mL of toluene and 2.18 g (10 mmol) of 3-aminophenol were added, and the mixture was stirred for 2 hours at 40° C. After stirring, the temperature was raised to 180° C. while flowing nitrogen at a flow rate of 200 ml / min, and the mixture was stirred for 6 hours. After cooling the reaction solution to 25°C, 0.005g of p-methoxyphenol was added and dissolved. 16.75g (160mmol) of methacrylic acid chloride was added dropwise to this solution, and the solution was stirred at 25°C for 2 hours, and then further stirred at 60°C for 3 hours. This was cooled to 25°C, and 10g of acetic acid was added and stirred at 25°C for 1 hour. After stirring, the solution was precipitated in 2 liters of water / methanol = 75 / 25 (volume ratio) and stirred at a speed of 2,000 rpm for 30 minutes. The precipitated polyimide resin was collected by filtration, washed with 1.5 liters of water, and then mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again. The obtained polyimide was dried under reduced pressure at 40°C for 1 day to obtain polymer A-6. The weight average molecular weight of the polymer A-6 was 18500. The obtained polymer A-6 is presumed to contain a repeating unit represented by the following formula (A-6). [ka]

[0425] <Synthesis Example 7: Synthesis of Polymer A-7> 28.0g (76.4mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 200g of N-methylpyrrolidone with stirring to prepare solution A. Then, 12.1g (153mmol) of pyridine was added to solution A, and while keeping the temperature at -10 to 0°C, a solution in which 1.38g (70.1mmol, synthetic product) of 2,5-dihydroxyterephthalic acid dichloride was dissolved in 75g of N-methylpyrrolidone was dropped into solution A over 1 hour. After stirring for 30 minutes, 1.00g (12.7mmol) of acetyl chloride was added and stirred for another 60 minutes. After stirring, the temperature was raised to 180°C while flowing nitrogen at a flow rate of 200ml / min, and the mixture was stirred for 6 hours. After the reaction solution was cooled to 25° C., 0.005 g of p-methoxyphenol was added and dissolved. To this solution, 16.75 g (160 mmol) of methacrylic acid chloride was added dropwise, and the mixture was stirred at 25° C. for 2 hours and then further stirred at 60° C. for 3 hours. The polybenzoxazole resin was then precipitated in 6 liters of water, and the water-polybenzoxazole resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polybenzoxazole resin was obtained by filtration, stirred again in 6 liters of water for 30 minutes, and filtered again. The resulting polybenzoxazole resin was then dried under reduced pressure at 45°C for 3 days to obtain polymer A-7. The weight average molecular weight of the resulting polymer A-7 was 19,200. The resulting polymer A-7 is presumed to contain a repeating unit represented by the following formula (A-7). [ka]

[0426] <Synthesis Example 8: Synthesis of Polymer A'-1> 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol), and 200 g of γ-butyrolactone were mixed and stirred at room temperature for 36 hours to produce a diester of pyromellitic dianhydride and 2-hydroxyethyl methacrylate. Next, under ice cooling, a solution in which 26.6 g of dicyclohexylcarbodiimide (DCC) was dissolved in 25 g of γ-butyrolactone was added dropwise with stirring. Then, 12.0 g of 4,4'-diaminodiphenyl ether suspended in 45 ml of γ-butyrolactone was added simultaneously over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 100 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. Next, a polyimide precursor was precipitated in 3 liters of water, and the water-polyimide precursor mixture was stirred at a speed of 5,000 rpm (revolutions per minute) for 15 minutes. The polyimide precursor was obtained by filtration, dissolved in 300 mL of tetrahydrofuran, and then the polyimide precursor was obtained again as a precipitate in 2 liters of water. The obtained polyimide precursor was dried under reduced pressure at 45°C for 3 days to obtain polymer A'-1. The weight average molecular weight of this polymer A'-1 was 21000. The obtained polymer A'-1 is presumed to contain a repeating unit represented by the above formula (A-1).

[0427] <Synthesis Example 9: Synthesis of Polymer A'-2> Polymer A'-2 was obtained by synthesizing in the same manner as in Synthesis Example 8, except that 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140° C. for 12 hours) was replaced with 20.0 g (64.5 mmol) of 3,3',4,4'-biphenyltetracarboxylic anhydride (dried at 140° C. for 12 hours). The weight average molecular weight of polymer A'-2 was 22,500. The obtained polymer A'-2 is presumed to contain a repeating unit represented by the above formula (A-2).

[0428] <Synthesis Example 10: Synthesis of Polymer A'-3> Polymer A'-3 was obtained by synthesizing in the same manner as in Synthesis Example 8, except that 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140° C. for 12 hours) was replaced with 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140° C. for 12 hours). The weight average molecular weight of polymer A'-3 was 21,200. The obtained polymer A'-3 is presumed to contain a repeating unit represented by the above formula (A-3).

[0429] <Synthesis Example 11: Synthesis of Polymer A'-4> Polymer A'-4 was obtained by synthesizing in the same manner as in Synthesis Example 8, except that 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours) was replaced with 9.49 g (32.25 mmol) of 4,4'-biphthalic dianhydride and 10.0 g (32.25 mmol) of oxydiphthalic dianhydride (both dried at 140 ° C. for 12 hours). The weight average molecular weight of polymer A'-4 was 21,000. The obtained polymer A'-4 is presumed to contain two types of repeating units represented by the above formula (A-4).

[0430] <Examples and Comparative Examples> I...

Claims

1. A resin that is a polyimide precursor; Organometallic complexes, A sensitizer having a fused ring structure, and containing a photoradical polymerization initiator different from the organometallic complex, The polyimide precursor contains at least one of a repeating unit represented by the following formula (PI-1) and a repeating unit represented by the following formula (PI-2), and the photoradical polymerization initiator is an oxime compound. Photosensitive resin composition. 【Chemistry 1】 In formula (PI-1) and formula (PI-2), A 1 and A 2 each independently represent an oxygen atom or NH, R 111 represents a divalent organic group, and R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.

2. The photosensitive resin composition according to claim 1, wherein the polyimide precursor contains at least one of a repeating unit represented by the following formula (PI-3) and a repeating unit represented by the following formula (PI-4): 【Chemistry 2】 In formulae (PI-3) and (PI-4), R 111 represents a divalent organic group.

3. The photosensitive resin composition according to claim 1, comprising at least one of a repeating unit represented by formula (PI-1), in which R 111 is a structure represented by the following formula (51), and a repeating unit represented by formula (PI-2), in which R 111 is a structure represented by the following formula (51): 【Chemistry 3】 In formula (51), R 50 to R 57 each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, or a trifluoromethyl group.

4. A photosensitive resin composition described in any one of claims 1 to 3, further comprising an organic solvent.

5. The photosensitive resin composition described in claim 4, wherein the organic solvent contains two or more types of organic solvents.

6. The photosensitive resin composition according to claim 4 or 5, wherein the organic solvent comprises gamma-butyrolactone.

7. The photosensitive resin composition of claim 6, wherein the organic solvent comprises gamma-butyrolactone and dimethylsulfoxide.

8. The photosensitive resin composition according to claim 1, wherein the resin comprises the polyimide precursor, comprises a photoradical polymerization initiator different from the organometallic complex, and comprises an organic solvent, the polyimide precursor comprises at least one of a repeating unit represented by the following formula (PI-5) and a repeating unit represented by the following formula (PI-6), the photoradical polymerization initiator is an oxime compound, and the organic solvent comprises γ-butyrolactone and dimethyl sulfoxide. 【Chemistry 4】 In formula (PI-5) and formula (PI-6), R 111 is a structure represented by the following formula (51). 【Chemistry 5】 In formula (51), R 50 to R 57 each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, or a trifluoromethyl group.

9. The photosensitive resin composition described in any one of claims 1 to 8, further comprising N-phenyldiethanolamine.

10. The photosensitive resin composition described in any one of claims 1 to 9, further comprising a silane coupling agent.

11. The photosensitive resin composition according to claim 10, wherein the silane coupling agent comprises a compound having a structure represented by the following formula (I-1): 【Chemistry 6】

12. The photosensitive resin composition according to any one of claims 1 to 11, further comprising a compound represented by the following formula (H-1): 【Chemistry 7】

13. The photosensitive resin composition according to claim 8, further comprising N-phenyldiethanolamine, a compound having a structure represented by the following formula (I-1), and a compound represented by the following formula (H-1): 【Chemistry 8】 【Chemistry 9】

14. The photosensitive resin composition according to any one of claims 1 to 13, wherein the content of the sensitizer is 0.5 to 5.0 parts by mass per part by mass of the organometallic complex.

15. A film-forming step of applying the photosensitive resin composition according to any one of claims 1 to 14 to a substrate to form a photosensitive film; an exposure step of exposing the photosensitive film to light; and a developing step of developing the photosensitive film after the exposure to obtain a pattern; A method for manufacturing a pattern.

16. The method for producing a pattern according to claim 15, wherein the exposure light used in the exposure step contains light having a wavelength of 150 to 450 nm.

17. The method for producing a pattern according to claim 15 or 16, further comprising a heating step of curing the pattern by heating the pattern obtained in the developing step.

18. A photosensitive film formed from the photosensitive resin composition according to any one of claims 1 to 14.

19. A cured product of the photosensitive film according to claim 18.

20. The cured product according to claim 19, which is used as an interlayer insulating film for a rewiring layer.

21. A laminate comprising two or more layers of the cured product according to claim 19 or 20, and a metal layer between any two of the layers of the cured product.

22. A device comprising the cured product according to claim 19 or 20, or the laminate according to claim 21.

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