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

Abstract

A photosensitive resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device. The photosensitive resin composition contains a polyimide precursor having a radically polymerizable group, a photopolymerization initiator, and a compound having a coumarin skeleton.

Description

Technical Field

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

[0002] Nowadays, in various fields, technologies for producing resin materials from resin compositions containing resins are being utilized. For example, polyimide is used in various applications due to its excellent heat resistance and insulation properties. The above-mentioned applications are not particularly limited, but if a semiconductor device for mounting is used as an example, it can be used as an insulating film, a sealing material, or a protective film. In addition, it can also be used as a base film, a cover layer, etc. of a flexible substrate.

[0003] For example, in the above-mentioned applications, polyimide is used in the form of a resin composition containing a polyimide precursor. For example, such a resin composition is applied to a substrate 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 is cyclized by, for example, heating, and becomes a polyimide in a cured product. The resin composition can be applied by a known coating method, etc., and therefore, it can be said that the resin composition has excellent manufacturing adaptability, such as high degree of freedom in designing the shape, size, and application position when applied. From the perspective of excellent manufacturing adaptability in addition to the high performance of polyimide, the expansion of industrial application of the resin composition is increasingly expected.

[0004] For example, Patent Document 1 describes a novel photosensitive composition comprising a polymer having a repeating unit of a specific structure, an oxime compound of a specific structure, and a coumarin compound of a specific structure. Patent Document 2 describes a photosensitive resin composition comprising a compound having a specific structure, a polyimide precursor, a photopolymerization initiator, and a compound selected from the group consisting of a benzoquinone compound, a phenol compound, a catechol compound, a resorcinol compound, and a hydroquinone compound. Previous technical literature Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 01-048857 Patent Document 2: Japanese Patent Application Publication No. 2000-131838 Summary of the invention Technical issues to be solved by the invention

[0006] A resin composition for obtaining a cured product is required to have excellent chemical resistance. For example, when another photosensitive resin composition is further laminated on the cured product, the cured product may be exposed to chemicals such as solvents and developers contained in the photosensitive resin composition. In such cases, it is desirable to use a cured product having excellent chemical resistance.

[0007] An object of the present invention is to provide a photosensitive resin composition that can produce a cured product having excellent chemical resistance, a cured product obtained by curing the photosensitive resin composition, a laminate containing the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device containing the cured product. Means for solving technical problems

[0008] Hereinafter, examples of representative embodiments of the present invention will be described. <1> A photosensitive resin composition comprising: A polyimide precursor having a free radical polymerizable group; photopolymerization initiator; and Compounds with a coumarin skeleton. <2> The photosensitive resin composition according to <1>, comprising a compound represented by the following formula (C-1) as the compound having the coumarin skeleton. [Chemical formula 1] <3> The photosensitive resin composition according to <1> or <2>, comprising an oxime ester group-containing compound as the photopolymerization initiator. <4> The photosensitive resin composition according to any one of <1> to <3>, further comprising a compound D represented by the following formula (D). [Chemical formula 2] In formula (D), Ar represents a monovalent aromatic group which may have a substituent, and L D1 Each independently represents a divalent linking group, n1 represents 1 or 2, R D1 Each independently represents a hydrogen atom or a monovalent organic group, n2 represents 0 or 1, and the total of n1 and n2 is 2. <5> The photosensitive resin composition according to <4>, comprising, as the compound D, a compound represented by the following (D-1). [Chemical formula 3] <6> The photosensitive resin composition according to any one of <1> to <5>, further comprising an organic titanium compound. <7> The photosensitive resin composition according to <6>, comprising di(n-butoxide)bis(2,4-pentanedione)titanium or diisopropyloxide bis(ethyl acetoacetate)titanium as the organic titanium compound. <8> The photosensitive resin composition according to any one of <1> to <7>, wherein The total content of the compound represented by the following formula (UR-1), formula (UR-2) or formula (UR-3) is 1 to 500 ppm relative to the content of the polyimide precursor. [Chemical formula 4]

[0009] In formula (UR-1), formula (UR-2) or formula (UR-3), R 11 and R 12 Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R 21 and R 22 Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R 31 and R 32 Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R 33 It represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent. <9> The photosensitive resin composition according to any one of <1> to <8>, further comprising a base generating agent. <10> The photosensitive resin composition according to <9>, comprising a compound represented by the following formula (F-1) or a compound represented by the following formula (F-2) as the base generator. [Chemical formula 5] <11> The photosensitive resin composition according to any one of <1> to <10>, further comprising a compound G containing at least one bond selected from the group consisting of a urea bond and a urethane bond. <12> The photosensitive resin composition according to <11>, further comprising, as the compound G, at least one compound selected from the group consisting of compounds represented by any one of Formula (G-1) to Formula (G-3). [Chemical formula 6] <13> The photosensitive resin composition according to any one of <1> to <12>, wherein The polyimide precursor includes a structure represented by the following formula (X-1) or formula (X-2). [Chemical formula 7] <14> The photosensitive resin composition according to any one of <1> to <13>, wherein The polyimide precursor includes a structure represented by any one of the following formulas (Y-1) to (Y-4). [Chemical formula 8] <15> The photosensitive resin composition according to any one of <1> to <14>, wherein The polyimide precursor includes a structure represented by the following formula (X-2) and a structure represented by the following formula (Y-4). [Chemical formula 9] <16> The photosensitive resin composition according to any one of <1> to <15>, which is used for forming an interlayer insulating film for a redistribution layer. <17> A cured product obtained by curing the resin composition according to any one of <1> to <16>. <18> A laminate comprising two or more layers consisting of the cured product according to <17>, and comprising a metal layer between any of the layers consisting of the cured product. <19> A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of <1> to <16> to a substrate to form a film. <20> The method for producing a cured product according to <19>, comprising: An exposure step of selectively exposing the film; and In the development step, the film is developed using a developer to form a pattern. <21> The method for producing a cured product according to <19> or <20>, comprising a heating step of heating the film at 50 to 450°C. <22> A method for producing a laminate, comprising the method for producing a cured product according to any one of <19> to <21>. <23> A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to any one of <19> to <21>. <24> A semiconductor device comprising the cured product according to <17>. Effects of the Invention

[0010] According to the present invention, there are provided a photosensitive resin composition capable of obtaining a cured product having excellent chemical resistance, a cured product obtained by curing the photosensitive resin composition, a laminate containing the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device containing the cured product. DETAILED DESCRIPTION

[0011] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described above. In the present specification, a numerical range expressed using the symbol “to” means a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit, respectively. In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended effect of the process can be achieved. In the marking of groups (atomic groups) in this specification, the marking not indicating substitution and unsubstituted includes not only groups (atomic groups) without substitution but also groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include active light or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams. In this specification, “(meth)acrylate” means both or either “acrylate” and “methacrylate”, “(meth)acrylic acid” means both or either “acrylic acid” and “methacrylic acid”, and “(meth)acryloyl” means both or either “acryloyl” and “methacryloyl”. In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of the components after removing the solvent from all the components of the composition. In addition, in this specification, the solid content concentration refers to the mass percentage of the other components excluding the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. In this specification, for example, using HLC-8220GPC (TOSOH CORPORATION manufacture), guard column HZ-L, TSKgel Super HZM-M, TSKgelSuper HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (more than TOSOH CORPORATION manufacture) are connected in series and used as tubing column, thus weight average molecular weight (Mw) and number average molecular weight (Mn) can be obtained. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as eluent. Wherein, the situation where solubility is relatively low, in the case where THF is not suitable as eluent, NMP (N- methyl -2- pyrrolidone) can also be used. Furthermore, unless otherwise specifically stated, detection in GPC measurement uses a UV ray (ultraviolet) detector having a wavelength of 254 nm. In this specification, regarding the positional relationship of each layer constituting the laminate, when recorded as "up" or "down", other layers can be located on the upper side or lower side of the layer that becomes the benchmark in the multiple layers of interest. That is, the third layer or element can also be sandwiched between the layer that becomes the benchmark and the above-mentioned other layers, and the layer that becomes the benchmark does not need to contact the above-mentioned other layers. Unless otherwise specified, the direction of the substrate stacking layer is referred to as "up", or, when there is a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "up", and the opposite direction is referred to as "down". In addition, the setting of this up and down direction is for the convenience of explaining this specification, and in a practical manner, the "up" direction in this specification can also be different from the vertical upward direction. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to the component as each component contained in the composition. Also, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to the component. In this specification, unless otherwise specifically stated, the temperature is 23° C., the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In the present specification, a combination of preferred embodiments is a more preferred embodiment.

[0012] (Photosensitive resin composition) The photosensitive resin composition of the present invention (hereinafter, also simply referred to as "resin composition") contains a polyimide precursor having a radical polymerizable group (hereinafter, also referred to as "specific resin"), a photopolymerization initiator, and a compound having a coumarin skeleton (hereinafter, also referred to as "specific compound").

[0013] The resin composition of the present invention is preferably used to form a photosensitive film (subject to exposure and development), and is preferably used to form a film (subject to exposure and development using a developer containing an organic solvent). The resin composition of the present invention can be used to form, for example, an insulating film of a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer. In particular, it is also one of the preferred embodiments of the present invention that the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer. Furthermore, the resin composition of the present invention is preferably used to form a photosensitive film for negative-tone development. In the present invention, among exposure and development, negative-tone development refers to development in which non-exposed areas are removed by development, and positive-tone development refers to development in which exposed areas are removed by development. As the exposure method, the developer, and the developing method, for example, the exposure method described in the exposure step in the description of the method for producing a cured product described later, and the developer and the developing method described in the developing step can be used.

[0014] According to the photosensitive resin composition of the present invention, a cured product having excellent chemical resistance can be obtained. The mechanism by which the above effects are obtained is not clear, but is presumed as follows.

[0015] The resin composition of the present invention contains a compound (specific compound) having a coumarin skeleton. Because the planarity of the coumarin skeleton is high, therefore, in the cured product, together with the specific resin and the polyimide obtained by the specific resin, it is arranged in a plane to form a dense structure. Therefore, when exposed and heat cured, in this state, the sensitization effect of the specific compound is used to promote free radical polymerization, thus efficiently forming the polymerization of the free radical polymerizable groups of the polyimide each other and the polymerization between the polyimide and the polymerizable compound contained as required, so as to form a film with a high crosslinking density and a high film density. In this way, it is believed that the film with a high crosslinking density and a high film density has low solubility in solvents, etc. and excellent chemical resistance.

[0016] Here, Patent Documents 1 and 2 do not describe a composition containing a specific resin, a specific compound, and a photopolymerization initiator.

[0017] Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

[0018] <Specified resin> The resin composition of the present invention contains a polyimide precursor (specific resin) having a radical polymerizable group. As the free radical polymerizable group in the specific resin, a group having an ethylenically unsaturated bond is preferred, and examples thereof include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl, etc.), a (meth)acrylamide group, a (meth)acryloyloxy group, and the like. Preferred are vinylphenyl group, (meth)acrylamide group, or (meth)acryloyloxy group, and more preferred are (meth)acrylamide group, or (meth)acryloyloxy group. The specific resin is preferably present in R in the formula (2) described below. 113 and R 114 At least one of the compounds contains a radical polymerizable group.

[0019] The radical polymerizable group value in the specific resin (the molar amount of the radical polymerizable group per 1 g of the compound) is preferably 1.0 to 3.0 mmol / g, more preferably 1.5 to 2.8 mmol / g, and even more preferably 2.0 to 2.7 mmol / g.

[0020] Furthermore, the specific resin preferably contains a structure represented by formula (X-1) or formula (X-2), and more preferably contains a structure represented by formula (X-2). Furthermore, the specific resin preferably contains a structure represented by formula (X-1) or formula (X-2) as R in formula (2) described later. 115 . The specific resin also preferably contains a structure represented by Formula (X-1) or Formula (X-2) as a structure derived from a carboxylic dianhydride. [Chemical formula 10]

[0021] Furthermore, the specific resin preferably contains a structure represented by any one of the following formulas (Y-1) to (Y-4), and more preferably contains a structure represented by formula (Y-4). The structure represented by the formula (Y-4) has high mobility, and it is considered that the inclusion of this structure increases the imidization ratio of the polyimide during curing and increases the elongation at break. Furthermore, the specific resin preferably contains a structure represented by any one of formulas (Y-1) to (Y-4) as R in formula (2) described below. 111 . It is also preferred that the specific resin contains a structure represented by any one of Formula (Y-1) to Formula (Y-4) as a structure derived from a diamine. [Chemical formula 11]

[0022] Furthermore, it is preferred that the polyimide precursor include a structure represented by the above formula (X-2) and a structure represented by the above formula (Y-4).

[0023] The polyimide precursor used in the present invention is not particularly limited in its type and the like, but preferably contains a repeating unit represented by the following formula (2). [Chemical formula 12] In formula (2), A 1 and A 2 Each independently represents an oxygen atom or -NR z -, 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, R z represents a hydrogen atom or a monovalent organic group.

[0024] A in formula (2) 1 and A 2 Each independently represents an oxygen atom or -NR z -, preferably an oxygen atom. R z represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom. R in formula (2) 111 Represents a divalent organic group. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, preferably linear or branched aliphatic groups having 2 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 3 to 20 carbon atoms or groups consisting of a combination thereof, and more preferably groups containing aromatic groups having 6 to 20 carbon atoms. The hydrocarbon groups in the chains of the linear or branched aliphatic groups may be substituted with groups containing heteroatoms, and the hydrocarbon groups of the ring members of the cyclic aliphatic groups and aromatic groups may be substituted with groups containing heteroatoms. As R in formula (2) 111 Examples include groups represented by -Ar- and -Ar-L-Ar-, preferably groups represented by -Ar-L-Ar-. Ar is independently an aromatic group, L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2- or -NHCO-, or a group consisting of a combination of two or more of the above. Their preferred ranges are as described above.

[0025] R 111It is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cycloaliphatic or aromatic diamines. The diamine may be used alone or in combination of two or more. Specifically, R 111 Preferred are diamines containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably diamines containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the linear or branched aliphatic group may be substituted with a group containing a heteroatom, and the hydrocarbon group of the ring member of the cyclic aliphatic group and the aromatic group may be substituted with a group containing a heteroatom. Examples of the group containing an aromatic group include the following groups.

[0026] [Chemical formula 13] In the formula, A represents a single bond or a divalent linking group, preferably a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO- or a combination of these, more preferably a single bond or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S- or -SO2-, further preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2- or -C(CH3)2-. In the formula, * indicates the bonding site with other structures.

[0027] Specific examples of the diamine 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-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2, 2-Bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene , 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4' -Dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 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, At least one diamine selected from 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotoluidine or 4,4'-diaminoquaterphenyl.

[0028] Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0029] Furthermore, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 can also be preferably used.

[0030] From the viewpoint of the flexibility of the obtained organic film, R 111 Preferably, it is represented by -Ar-L-Ar-. Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO2- or -NHCO-, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S- or -SO2-. The aliphatic hydrocarbon group here is preferably an alkylene group.

[0031] Furthermore, from the perspective of i-ray transmittance, R 111 Preferred are divalent organic groups represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, divalent organic groups represented by formula (61) are more preferred. Formula (51) [Chemical formula 14] In formula (51), R 50 ~R 57 are independently a hydrogen atom, a fluorine atom or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to a nitrogen atom in formula (2). As 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). [Chemical formula 15] In formula (61), R 58 and R 59 Each independently represents a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to a nitrogen atom in formula (2). Examples of the diamine that imparts the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

[0032] And, R 111 It preferably contains a structure represented by any one of the above formulae (Y-1) to (Y-4), and more preferably contains a structure represented by formula (Y-4). Examples of the diamine that imparts such a structure include 4,4′-diaminodiphenyl ether, 2,2′-dimethylbenzidine, 1,4-diaminobenzene, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

[0033] R in formula (2) 115 The tetravalent organic group is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6). In formula (5) or (6), * each independently represents a bonding site with another structure. [Chemical formula 16] In formula (5), R 112It is a single bond or a divalent linking group, preferably a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO2- and -NHCO-, and a combination of these, more preferably a single bond or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S- and -SO2-, further preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0034] Specifically, R 115 Examples include a tetracarboxylic acid residue remaining after the anhydride group is removed from tetracarboxylic dianhydride. 115 The polyimide precursor may contain only one tetracarboxylic dianhydride residue or two or more tetracarboxylic dianhydride residues. It is preferable that tetracarboxylic dianhydride is represented by the following formula (O). [Chemical formula 17] In formula (O), R 115 Represents a tetravalent organic group. 115 The preferred range of R in formula (2) 115 The preferred range is the same.

[0035] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride. , 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 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 alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms thereof.

[0036] And, R 115 It preferably contains the structure represented by the above formula (X-1) or formula (X-2), and more preferably contains the structure represented by formula (X-2). Examples of the carboxylic acid dianhydride that imparts such a structure include 4,4′-oxydiphthalic dianhydride and 3,3′,4,4′-biphenyltetracarboxylic dianhydride.

[0037] Furthermore, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can also be mentioned as preferred examples.

[0038] In formula (2), R 111 and R 115 At least one of R may have an OH group. 111 , for example, residues of bisaminophenol derivatives can be mentioned.

[0039] R in formula (2) 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, it is preferred to contain a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkyleneoxy group. And, preferably R113 and R 114 At least one of them contains a radical polymerizable group, and more preferably both contain a radical polymerizable group. Preferred embodiments of the radical polymerizable group are as described above. When R 113 or R 114 When containing a free radical polymerizable group, one R 113 or R 114 The number of radical polymerizable groups contained in the ester is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 or 2. Furthermore, an embodiment in which the number of radical polymerizable groups is 1 is also one of the preferred embodiments of the present invention. And, R 113 or R 114 It is also preferred that other polymerizable groups be contained that are different from the radical polymerizable group. Specific examples of other polymerizable groups include alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy, oxetanyl, benzoxazolyl, blocked isocyanate, and amino groups. When R 113 or R 114 When containing a radical polymerizable group, R 113 or R 114 It is a group represented by the following formula (III).

[0040] [Chemical formula 18]

[0041] In formula (III), R 200 It represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and is preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site with other structures. In formula (III), R 201 It represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group or a polyalkyleneoxy group. R 201 Preferred examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH2CH(OH)CH2-, and polyalkyleneoxy groups. More preferred examples include alkylene groups such as ethylene and propylene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkyleneoxy groups. Further preferred examples include alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups. In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, an alternating arrangement, or the like. The number of carbon atoms of the alkylene group (including the carbon atoms of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, further preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2. Furthermore, the above-mentioned alkylene group may have a substituent, and preferred substituents include an alkyl group, an aryl group, a halogen atom, and the like. Furthermore, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2-20, more preferably 2-10, and even more preferably 2-6. As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded is preferred, polyethyleneoxy or polypropyleneoxy is more preferred, and polyethyleneoxy is further preferred. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in alternating patterns. The preferred form of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

[0042] In formula (2), when R 113 When it is a hydrogen atom or R 114 When it is a hydrogen atom, the polyimide precursor can form a salt pair 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.

[0043] In formula (2), R 113 and R 114 At least one of them may be a polar 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 hydroxyl group or a carboxyl group, but is preferably an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc., and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, trimethylsilyl ether, etc. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0044] The polyimide precursor also preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and preferably 20% by mass or less.

[0045] Furthermore, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate. Specifically, as the diamine, there can be mentioned an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

[0046] 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 containing a repeating unit represented by formula (2-A) in the polyimide precursor, the exposure latitude can be further increased. Formula (2-A) [Chemical formula 19] In formula (2-A), A 1 and A 2 represents 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 them is a group containing a polymerizable group, and preferably both of them are groups containing a polymerizable group.

[0047] A 1 , A 2 , R 111 , R 113 and R 114 The meanings of are independent of A in formula (2) 1 , A 2 , R 111 , R 113 and R 114 has the same meaning and the preferred range is also the same. 112 The meaning of is the same as R in formula (5) 112 The meanings are the same, and the preferred ranges are also the same.

[0048] The polyimide precursor may contain one or more repeating units represented by formula (2). Furthermore, the polyimide precursor may contain structural isomers of the repeating units represented by formula (2). In addition to the repeating units represented by the above formula (2), the polyimide precursor may also contain other types of repeating units.

[0049] As one embodiment of the polyimide precursor in the present invention, the content of the repeating unit represented by formula (2) can be cited as 50 mol% or more of the total repeating units. The above-mentioned total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above-mentioned total content is not particularly limited, and all repeating units in the polyimide except the terminal can be repeating units represented by formula (2).

[0050] The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. The number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and further preferably 4,000 to 20,000. The molecular weight dispersion of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less. In this specification, the molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight. Furthermore, when the resin composition contains a plurality of polyimide precursors as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion degree of at least one polyimide precursor are within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight and dispersion degree calculated using the plurality of polyimide precursors as one resin are within the above ranges, respectively.

[0051] [Method for producing polyimide precursor] The polyimide precursor can be obtained, for example, by the following methods: a method of reacting tetracarboxylic dianhydride with diamine at low temperature, a method of reacting tetracarboxylic dianhydride with diamine at low temperature to obtain polyamic acid and esterifying it with a condensing agent or an alkylating agent, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then reacting it in the presence of a diamine and a condensing agent, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine, etc. Among the above production methods, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine is more preferred. Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N′-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, and the like. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like. In the method for producing a polyimide precursor, it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one kind or two or more kinds. The organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing a polyimide precursor, it is preferred to add a basic compound during the reaction. The basic compound may be one kind or two or more kinds. The basic compound can be appropriately determined depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0052] -Capping agent- In the manufacture method of polyimide precursor, in order to further improve storage stability, preferably the carboxylic acid anhydride, anhydride derivative or amino group remaining in the resin end of polyimide precursor is blocked. When the carboxylic acid anhydride and anhydride derivative remaining in the resin end are blocked, as end-capping agent, monoalcohol, phenol, mercaptan, thiophenol, monoamine etc. can be cited, and from the perspective of reactivity and film stability, monoalcohol, phenols, monoamine are more preferably used. As the preferred compound of monoalcohol, methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, primary alcohols such as furfuryl alcohol, isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, tertiary alcohols such as ... Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene. , 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 can be used, and a variety of different terminal groups can be introduced by reacting a variety of end-capping agents. In addition, when the amino group at the end of the resin is blocked, it can be blocked with a compound having a functional group that can react with the amino group. The preferred end-capping agent for the amino group is preferably carboxylic anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonyl chloride, sulfonic acid anhydride, sulfonic acid carboxylic anhydride, etc., and more preferably carboxylic acid anhydride and carboxylic acid chloride. As preferred compounds of carboxylic anhydride, acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. can be mentioned. In addition, as preferred compounds of carboxylic acid chloride, acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearyl chloride, benzoyl chloride, etc. can be mentioned.

[0053] -Solid Precipitation- In the manufacture method of polyimide precursor, the process of solid precipitation can be included. Specifically, after filtering the water absorption byproduct of the dehydration condensation agent coexisting in the reaction solution as required, the obtained polymer component is put into poor solvents such as water, aliphatic lower alcohol or its mixed solution and the polymer component is precipitated, so that it can be precipitated with solid and dried to obtain the polyimide precursor. In order to improve the degree of purification, the polyimide precursor can be repeatedly dissolved, reprecipitated, dried and other operations. In addition, the process of using ion exchange resin to remove ionic impurities can also be included.

[0054] 〔content〕 The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and further preferably 50% by mass or more relative to the total solid content of the resin composition. In addition, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, further preferably 97% by mass or less, and further preferably 95% by mass or less relative to the total solid content of the resin composition. The resin composition of the present invention may contain only one specific resin or two or more specific resins. When containing two or more specific resins, the total amount is preferably within the above range.

[0055] The resin composition of the present invention also preferably contains at least two types of resins. Specifically, the resin composition of the present invention may contain two or more specific resins in total and other resins described below, or may contain two or more specific resins, but preferably contains two or more specific resins. When the resin composition of the present invention contains two or more specific resins, for example, it preferably contains a structure derived from a dianhydride (R in the above formula (2)) as a polyimide precursor. 115 ) Two or more different polyimide precursors.

[0056] <Other resins> The resin composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also simply referred to as "other resins"). As other resins, there can be mentioned polyimide precursors having no free radical polymerizable groups, polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, polyamideimides, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styrene-based resins, polyether resins, polyester resins, and the like. For example, by further adding a (meth)acrylic resin, a resin composition having excellent coating properties can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained. For example, by adding a (meth)acrylic resin to the resin composition instead of or in addition to the polymerizable compound described below, the coating properties of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved. The (meth)acrylic resin has a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, the molar amount of the polymerizable group in 1 g of the resin is 1×10 -3 mol / g or more).

[0057] When the resin composition of the present invention contains other resins, the content of other resins is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, further preferably 1 mass % or more, further preferably 2 mass % or more, further preferably 5 mass % or more, and further preferably 10 mass % or more, relative to the total solid content of the resin composition. The content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and further preferably 50% by mass or less, relative to the total solid content of the resin composition. As a preferred mode of the resin composition of the present invention, it is also possible to set it as a mode in which the content of other resins is low. In the above-mentioned mode, relative to the total solid content of the resin composition, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less. The lower limit of the above-mentioned content is not particularly limited, and 0% by mass or more is sufficient. The resin composition of the present invention may contain only one other resin or two or more other resins. When containing two or more specific resins, the total amount is preferably within the above range.

[0058] <Specified compounds> The resin composition of the present invention contains a compound (specific compound) having a coumarin skeleton.

[0059] The coumarin skeleton is a structure represented by the following formula (C). [Chemical formula 20] In formula (C), * represents a bonding site with other structures.

[0060] The specific compound is preferably a compound that functions as a sensitizer for radical polymerization. The specific compound is preferably a compound having a maximum absorption wavelength at a wavelength of 330 to 450 nm.

[0061] As the specific compound, a compound represented by the following formula (S-1) or formula (S-2) is particularly preferred. In the following structure, the hydrogen atom may be further substituted by another substituent. [Chemical formula 21] In formula (S-1), R S1 ~R S3 Each independently represents a monovalent organic group. In formula (S-2), R S4 ~R S7 Each independently represents a monovalent organic group.

[0062] In formula (S-1), R S1 It is preferably an alkyl group, an alkoxy group or an aromatic hydrocarbon group, more preferably an alkoxy group having 1 to 4 carbon atoms, and still more preferably a methoxy group or an ethoxy group. The above-mentioned alkyl group, alkoxy group or aromatic hydrocarbon group may further have a substituent, for example, it may be a benzyloxy group. In formula (S-1), R S2 An alkyl group or an aromatic hydrocarbon group is more preferred, an alkyl group is more preferred, an alkyl group having 1 to 4 carbon atoms is further preferred, and a methyl group or an ethyl group is further preferred. In formula (S-1), R S3 The preferred method and R S2 The preferred method is the same.

[0063] In formula (S-2), R S4 ~R S7 The preferred method is respectively S2 The preferred method is the same.

[0064] Preferred specific compounds include 3,3′-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, and 3-ethoxycarbonyl-7-diethylaminocoumarin.

[0065] The resin composition of the present invention preferably contains a compound represented by the following formula (C-1) as a specific compound. [Chemical formula 22]

[0066] 〔Molecular weight〕 The molecular weight of the specific compound is preferably 160 to 1,000, more preferably 170 to 800, and even more preferably 180 to 600.

[0067] 〔content〕 The content of the specific compound is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 0.2% by mass or more, further preferably 0.4% by mass or more, and particularly preferably 0.6% by mass or more. The upper limit is more preferably 8% by mass or less, further preferably 6% by mass or less, and particularly preferably 4% by mass or less. Furthermore, the content of the specific compound in the resin composition of the present invention is preferably 0.05 to 8 parts by mass, and more preferably 0.10 to 5 parts by mass, based on 100 parts by mass of the specific resin. The specific compound may be used alone or in combination of two or more. When two or more are used in combination, the total amount thereof is preferably within the above range.

[0068] <Compound D> The resin composition of the present invention preferably further contains a compound D represented by the following formula (D). When the resin composition contains the compound D, radical polymerization can be promoted, and thus the sensitivity can be further improved. [Chemical formula 23] In formula (D), Ar represents a monovalent aromatic group which may have a substituent, and L D1 Each independently represents a divalent linking group, n1 represents 1 or 2, R D1 Each independently represents a hydrogen atom or a monovalent organic group, n2 represents 0 or 1, and the total of n1 and n2 is 2.

[0069] In formula (D), Ar is preferably a monovalent aromatic group having 6 to 20 carbon atoms, more preferably a monovalent aromatic group having 6 to 10 carbon atoms, and further preferably a phenyl group. These groups may have a substituent. As the substituent in Ar, a known substituent can be used without limitation within the range where the effects of the present invention can be obtained, and examples thereof include an alkyl group and the like. L D1 Each of them is independently preferably a hydrocarbon group, more preferably an alkylene group, further preferably an alkylene group having 2 to 10 carbon atoms, and particularly preferably an alkylene group having 2 to 4 carbon atoms. Furthermore, ethylene group is also one of the preferred embodiments of the present invention. R D1 Each of them independently is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and still more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n1 is preferably 2.

[0070] Examples of the compound D include N-phenyl-N′-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, and N-phenylethanolamine.

[0071] The resin composition of the present invention preferably contains, as compound D, a compound represented by the following formula (D-1). [Chemical formula 24]

[0072] 〔Molecular weight〕 The molecular weight of compound D is preferably 100 to 1,000, preferably 120 to 800, and more preferably 150 to 400.

[0073] 〔content〕 The content of compound D is preferably 0.1 to 20% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 0.2% by mass or more, further preferably 0.4% by mass or more, and particularly preferably 0.6% by mass or more. The upper limit is more preferably 15% by mass or less, further preferably 12% by mass or less, and particularly preferably 10% by mass or less. Furthermore, the content of the compound D in the resin composition of the present invention is preferably 0.05 to 15 parts by mass, and more preferably 0.10 to 8 parts by mass, based on 100 parts by mass of the specific resin. Compound D may be used alone or in combination of two or more. When two or more are used in combination, the total amount thereof is preferably within the above range.

[0074] 〔Organotitanium compounds〕 The resin composition preferably contains an organic titanium compound. It is believed that by coordinating the polyimide and the organic titanium compound in the cured product, a film with a high crosslinking density and film density can be formed, thereby improving the chemical resistance of the cured product. In particular, by containing the organic titanium compound in the resin composition, a cured product with excellent chemical resistance can be formed even when cured at a low temperature. Furthermore, by using the organic titanium compound and the specific compound in combination, light energy can be efficiently transferred to the photopolymerization initiator, thereby improving the rectangularity of the developed pattern after standing.

[0075] Examples of the organic titanium compound that can be used include compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organic titanium compound are shown in the following I) to VII). I) Titanium chelate compound: From the perspective of excellent storage stability of the resin composition and the ability to obtain a good cured pattern, a titanium chelate compound having two or more alkoxy groups is more preferred. Specific examples include titanium diisopropylate bis(triethanolamine), titanium di(n-butyl alcohol) bis(2,4-pentanedione), titanium diisopropylate bis(2,4-pentanedione), titanium diisopropylate bis(tetramethylheptanedione), titanium diisopropylate bis(ethyl acetoacetate), 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 tetramethylphenol, titanium tetra(n-nonoxide), titanium tetra(n-propoxide), titanium tetrastearylate, titanium tetra[bis{2,2-(allyloxymethyl)butoxide}], and the like. III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compound: for example, tris(dioctyl phosphate)titanium isopropoxide, tris(dodecylbenzene sulfonate)titanium isopropoxide, and the like. V) Titanium oxide compound: for example, bis(pentanedione)titanium oxide, bis(tetramethylheptanedione)titanium oxide, titanium phthalocyanine oxide, and the like. VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate. VII) Titanate coupling agent: for example, isopropyl tri(dodecyl)benzenesulfonyl titanate.

[0076] 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 better chemical resistance. Among these, in particular, the resin composition of the present invention preferably contains di(n-butyloxide)bis(2,4-pentanedione)titanium or diisopropyloxide bis(ethyl acetoacetate)titanium as the organic titanium compound.

[0077] When an organic titanium compound is contained, the content is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the obtained cured pattern are better, and when it is 10 parts by mass or less, the storage stability of the composition is better. The resin composition of the present invention may contain only one organic titanium compound or two or more organic titanium compounds. When containing two or more specific resins, the total amount is preferably within the above range.

[0078] <Compound G> The resin composition of the present invention preferably further contains a compound G containing at least one bond selected from the group consisting of a urea bond and a urethane bond. Compound G does not include a compound represented by formula (UR-1) described later. Furthermore, compound G does not include a compound corresponding to a base generating agent described later. In the present invention, the urea bond refers to the bond consisting of *-NR N -C(=O)-NR N -* indicates a key, R N Each independently represents a hydrogen atom or a monovalent organic group, and * each represents a bonding site to a carbon atom. In the present invention, a urethane bond refers to a bond consisting of *-OC(=O)-NR N -* indicates a key, R N represents a hydrogen atom or a monovalent organic group, and * represents a bonding site to a carbon atom.

[0079] The urea bond or urethane bond in the compound G increases the interaction between the components by hydrogen bonding with the carbonyl group of the polyimide or specific compound contained in the cured product. As a result, it is believed that by coexisting the polyimide precursor, the specific compound and the compound G in the resin composition, the film density is further increased, thereby improving chemical resistance and moisture resistance. In addition, it is believed that the elongation at break is also improved by improving the intermolecular force. In particular, when the compound G has a polymerizable group, it is considered that it can contribute to an increase in crosslinking density, thereby further improving chemical resistance and the like.

[0080] The compound G may have only one urea bond or one urethane bond, one or more urea bonds and one or more urethane bonds, no urethane bond but two or more urea bonds, or no urea bond but two or more urethane bonds. The total number of urea bonds and urethane bonds in compound G is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When the compound G does not have a urethane bond, the number of urea bonds in the compound G is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When the compound G does not have a urea bond, the number of urethane bonds in the compound G is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0081] Compound G preferably has a polymerizable group, and more preferably has a radical polymerizable group. The free radical polymerizable group in compound G is not particularly limited and examples thereof include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamide, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamide, vinylphenyl or maleimide, and more preferably (meth)acryloyloxy. When compound G has two or more radical polymerizable groups, the structures of the respective radical polymerizable groups may be the same or different. The number of radical polymerizable groups in compound G may be only one or two or more, and is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. The radical polymerizable group value (the mass of the radical polymerizable group per 1 mol of the compound) in the compound G is preferably 150 to 400 g / mol. From the viewpoint of chemical resistance of the cured product, the lower limit of the free radical polymerizable group value is more preferably 200 g / mol or more, further preferably 210 g / mol or more, further preferably 220 g / mol or more, further preferably 230 g / mol or more, further preferably 240 g / mol or more, and particularly preferably 250 g / mol or more.

[0082] From the viewpoint of developability, the upper limit of the radical polymerizable group value is more preferably 350 g / mol or less, further preferably 330 g / mol or less, particularly preferably 300 g / mol or less. The polymerizable group value of compound G is preferably 210 to 400 g / mol, more preferably 220 to 400 g / mol.

[0083] It is also preferred that the compound G has at least one of a hydroxyl group, an alkyleneoxy group, an amide group, and a cyano group. From the viewpoint of chemical resistance of the obtained cured film, the hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group, but an alcoholic hydroxyl group is preferred. In particular, when the resin composition of the present invention contains the organic titanium compound and the compound G having a hydroxyl group, it is considered that the film density is further increased due to the coordination with titanium of the compound G, thereby further improving chemical resistance and the like.

[0084] From the viewpoint of chemical resistance of the obtained cured film, the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, further preferably an alkyleneoxy group having 2 to 4 carbon atoms, further preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. The alkyleneoxy group may be contained as a polyalkyleneoxy group in the compound G. In this case, the number of repetitions of the alkyleneoxy group is preferably 2 to 10, more preferably 2 to 6. Amide refers to -C(=O)-NR N - indicates a bond. N As described above, when compound G has an amide group, compound G can contain an amide group as, for example, RC(=O)-NR N -* or a group represented by *-C(=O)-NR N - A group represented by R. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. The compound G may have two or more structures selected from the group consisting of a hydroxyl group, an alkyleneoxy group (in the case of a polyalkyleneoxy group, a polyalkyleneoxy group), an amide group, and a cyano group in the molecule, but preferably has only one structure in the molecule. The above-mentioned hydroxyl group, alkyleneoxy group, amide group and cyano group may be present at any position in compound G, but from the viewpoint of chemical resistance, it is also preferred that at least one selected from the group consisting of the above-mentioned hydroxyl group, alkyleneoxy group and cyano group is connected to at least one free radical polymerizable group contained in compound G via a connecting group containing a urea bond or a urethane bond (hereinafter also referred to as "connecting group L2-1"). In particular, when compound G contains only one free radical polymerizing group, the free radical polymerizing group contained in compound G is preferably connected to at least one of the group consisting of a hydroxyl group, an alkylene oxide group, an amide group and a cyano group via a connecting group containing a urea bond or a carbamate bond (hereinafter also referred to as "connecting group L2-2"). When compound G contains alkyleneoxy (wherein, when constituting polyalkyleneoxy, it is polyalkyleneoxy) and has the above-mentioned linking group L2-1 or the above-mentioned linking group L2-2, the structure of the linking group L2-1 or the linking group L2-2 opposite to the alkyleneoxy (wherein, when constituting polyalkyleneoxy) is not particularly limited, but is preferably a group represented by a hydrocarbon group, a free radical polymerizable group or a combination thereof. As the above-mentioned hydrocarbon group, a hydrocarbon group with a carbon number of 20 or less is preferred, a hydrocarbon group with a carbon number of 18 or less is more preferred, and a hydrocarbon group with a carbon number of 16 or less is further preferred. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group or a group represented by their bonds can be cited. In addition, the preferred mode of the free radical polymerizable group is the same as the preferred mode of the free radical polymerizable group in the above-mentioned compound G. When compound G contains amide group and has above-mentioned linking group L2-1 or above-mentioned linking group L2-2, the structure bonded to the linking group L2-1 or linking group L2-2 opposite to the amide group is not particularly limited, but preferably a group represented by a hydrocarbon group, a free radical polymerizable group or a combination thereof. As the above-mentioned hydrocarbon group, a hydrocarbon group with a carbon number of 20 or less is preferred, a hydrocarbon group with a carbon number of 18 or less is more preferred, and a hydrocarbon group with a carbon number of 16 or less is further preferred. In addition, as the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group or a group represented by their bond can be cited. The preferred mode of the free radical polymerizable group is the same as the preferred mode of the free radical polymerizable group in the above-mentioned compound G. In addition, in the above-mentioned mode, the carbon atom side of the amide group can be bonded to the linking group L2-1 or the linking group L2-2, and the nitrogen atom side of the amide group can be bonded to the linking group L2-1 or the linking group L2-2. Among these, it is preferred that the compound G has a hydroxyl group from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids.

[0085] From the viewpoint of compatibility with a specific resin, etc., it is preferred that the compound G contains an aromatic group. The aromatic group is preferably directly bonded to the urea bond or urethane bond contained in the compound G. When the compound G contains two or more urea bonds or urethane bonds, it is preferred that one of the urea bonds or urethane bonds is directly bonded to the aromatic group. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may be a condensed ring structure formed by these groups, but is preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and still more preferably a group obtained by removing two or more hydrogen atoms from a benzene ring structure. As the above-mentioned aromatic heterocyclic group, a 5-membered or 6-membered aromatic heterocyclic group is preferred. As the aromatic heterocyclic ring in such an aromatic heterocyclic group, pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. can be cited. These rings can be further condensed with other rings, such as indole and benzimidazole. As the hetero atom contained in the above aromatic heterocyclic group, a nitrogen atom, an oxygen atom or a sulfur atom is preferred. The above-mentioned aromatic group is preferably included in the following connecting group, for example: a connecting group connecting two or more free radical polymerizing groups and containing a urea bond or a carbamate bond; or a connecting group connecting at least one selected from the group consisting of the above-mentioned hydroxyl group, alkylene oxide group, amide group and cyano group and at least one free radical polymerizing group contained in compound G.

[0086] The compound G preferably has a structure represented by the following formula (U-1), for example. [Chemical formula 25] In formula (U-1), R U1 is a hydrogen atom or a monovalent organic group, A is -O- or -NR N -, R N is a hydrogen atom or a monovalent organic group, Z U1 is an m-valent organic group, Z U2 is an n+1-valent organic group, X is a radical polymerizable group, n is an integer of 1 or more, and m is an integer of 1 or more.

[0087] R U1 A hydrogen atom, an alkyl group or an aromatic hydrocarbon group is preferred, and a hydrogen atom is more preferred. R N A hydrogen atom, an alkyl group or an aromatic hydrocarbon group is preferred, and a hydrogen atom is more preferred. Z U1 Preferred are hydrocarbon, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group formed by bonding two or more of them, more preferably a hydrocarbon group or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N -A group formed by bonding at least one group in the group consisting of The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and still more preferably a hydrocarbon group having 16 or less carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by bonds thereof. N It represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or a methyl group. Z U2 Preferred are hydrocarbon, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group formed by bonding two or more of them, more preferably a hydrocarbon group or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N -A group formed by bonding at least one group in the group consisting of Examples of the hydrocarbon group include U1 The same hydrocarbon groups as those mentioned above are preferred in the same manner. X is not particularly limited and examples thereof include vinyl, allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamide, vinylphenyl, maleimide, etc., preferably (meth)acryloyloxy, (meth)acrylamide, vinylphenyl or maleimide, and more preferably (meth)acryloyloxy. n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1. m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

[0088] The number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group in the radical polymerizable group-containing compound G is not particularly limited, but is preferably 30 or less, more preferably 2-20, and further preferably 2-10. When compound G contains a total of more than 2 urea bonds or carbamate bonds, when it contains more than 2 free radical polymerizing groups, or when it contains more than 2 urea bonds or carbamate bonds and more than 2 free radical polymerizing groups, the minimum number of atoms (connection chain length) between the urea bond or carbamate bond and the free radical polymerizing group can be within the above range. In this specification, "the number of atoms (connection chain length) between the urea bond or urethane bond and the polymerizable group" means that in the atomic chain on the path connecting two atoms or atomic groups as the connection objects, these connection objects are connected by the shortest (smallest number of atoms) path. For example, in the structure represented by the following formula, the number of atoms (connection chain length) between the urea bond and the free radical polymerizable group (methacryloyloxy) is 2. [Chemical formula 26]

[0089] The method for producing the compound G having a polymerizable group is not particularly limited, and for example, the compound G can be obtained by reacting a compound having a radical polymerizable group and an isocyanate group with a compound having at least one of a hydroxyl group and an amino group.

[0090] Specific examples of the compound G having a polymerizable group are shown below, but the compound G is not limited thereto. [Chemical formula 27] [Chemical formula 28] [Chemical formula 29]

[0091] When the compound G does not have a polymerizable group, the compound G is preferably a compound represented by the following formula (U-2). [Chemical formula 30] In formula (U-2), A is -O- or -NR N -, R N is a hydrogen atom or a monovalent organic group, Z U3 is an m-valent organic group, R U2 Each independently represents a monovalent organic group, R U3 Each independently represents a monovalent organic group, and m is an integer of 1 or greater.

[0092] In formula (U-2), A is preferably -NR N -. R N A hydrogen atom, an alkyl group or a phenyl group is preferred, and a hydrogen atom is more preferred.

[0093] In formula (U-2), Z U3 Preferred are hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O) 2 -、-NR N - or a group formed by bonding two or more of them, more preferably a hydrocarbon group or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N -a group formed by bonding at least one group selected from the group consisting of -, more preferably a hydrocarbon group. The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and still more preferably a hydrocarbon group having 16 or less carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by bonds thereof. N It represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or a methyl group.

[0094] In formula (U-2), R U2 Each of them independently is preferably a hydrocarbon group, more preferably an alkyl group, more preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The above-mentioned hydrocarbon group may have a substituent. An embodiment in which the hydrocarbon group has a hydroxyl group, an alkyleneoxy group, an amide group, or a cyano group as a substituent is also one of the preferred embodiments of the present invention. Preferred embodiments of these groups are as described above.

[0095] In formula (U-2), R U3 The preferred method and R U2 The preferred method is the same.

[0096] In formula (U-2), m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

[0097] 〔Axis of symmetry〕 Compound G is also preferably a compound having a structure without a symmetry axis. Compound G does not have an axis of symmetry, which means that it is a bilaterally asymmetric compound and does not have an axis that produces a molecule identical to the original molecule by rotating the entire compound. In addition, when the structural formula of compound G is written on paper, compound G does not have an axis of symmetry, which means that the structural formula of compound G cannot be written in a form with an axis of symmetry. It is considered that since compound G has no symmetry axis, aggregation of compounds G is suppressed in the composition film.

[0098] The resin composition of the present invention preferably contains, as compound G, at least one compound selected from the group consisting of compounds represented by any one of formula (G-1) to formula (G-3). [Chemical formula 31]

[0099] 〔Molecular weight〕 The molecular weight of compound G is preferably 100 to 2,000, more preferably 150 to 1,500, and more preferably 200 to 900.

[0100] The content of compound G relative to the total solid content of the resin composition of the present invention is preferably 0.1 to 20% by mass. The lower limit is more preferably 0.2% by mass or more, further preferably 0.4% by mass or more, and particularly preferably 0.6% by mass or more. The upper limit is more preferably 15% by mass or less, further preferably 12% by mass or less, and particularly preferably 10% by mass or less. Furthermore, the content of the compound G in the resin composition of the present invention is preferably 0.05 to 15 parts by mass, and more preferably 0.10 to 8 parts by mass, relative to 100 parts by mass of the specific resin. Compound G may be used alone or in combination of two or more. When two or more are used in combination, the total amount thereof is preferably within the above range.

[0101] <Compound represented by any one of formula (UR-1) to formula (UR-3)> The resin composition of the present invention preferably contains a compound represented by any one of Formula (UR-1) to Formula (UR-3). It is considered that the inclusion of these compounds improves the compatibility between the specific compound and the specific resin, and the crosslinking structure in the cured product becomes close to a uniform state, thereby improving moisture resistance. Furthermore, it is considered that by using these compounds in combination with an organic titanium compound, the dispersibility of the organic titanium compound is improved, and since the organic titanium compound exists in a nearly uniform state in the film, the resolution is improved. [Chemical formula 32]

[0102] In formula (UR-1), formula (UR-2) or formula (UR-3), R 11 and R 12 Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R 21 and R 22 Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R 31 and R 32 Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R 33 It represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent. In formula (UR-1), R 11 and R 12 Preferably, each is independently an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms having, as a substituent, at least one substituent selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amine group, a tertiary amine salt structure and a quaternary ammonium group, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms. As R 11 and R 12 The unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms is preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms, and more preferably ethyl, isopropyl, tert-butyl or cyclohexyl.

[0103] In formula (UR-1), R 11 and R 12 Each of the above groups may independently be an aliphatic hydrocarbon group having 2 to 7 carbon atoms and having at least one substituent selected from the group consisting of a hydroxyl group, an alkoxy group, a thiol group, and an alkylthio group. The aliphatic hydrocarbon group having 2 to 7 carbon atoms may have two or more substituents, but preferably has only one substituent.

[0104] In formula (UR-2), R 21 and R 22 Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent. In formula (UR-2), R 21 and R 22An unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or an aliphatic hydrocarbon group having 1 to 7 carbon atoms having an amino group or a quaternary ammonium group as a substituent is preferred, and an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferred. In formula (UR-2), R 21 and R 22 The preferred embodiments of the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the aliphatic hydrocarbon group having 1 to 7 carbon atoms having the above-mentioned substituent are respectively the same as R 11 and R 12 The same way as shown in the instructions.

[0105] In formula (UR-3), R 31 and R 32 An unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or an aliphatic hydrocarbon group having 1 to 7 carbon atoms having an amino group or a quaternary ammonium group as a substituent is preferred, and an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferred. In formula (UR-3), R 31 and R 32 The preferred embodiments of the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the aliphatic hydrocarbon group having 1 to 7 carbon atoms having the above-mentioned substituent are respectively the same as R 11 and R 12 The same way as shown in the instructions.

[0106] In formula (UR-3), R 33 It represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, and more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. In formula (UR-3), R 33 , preferably methyl, ethyl, propyl, isopropyl, butyl or tert-butyl, more preferably ethyl.

[0107] Specific examples of the compound represented by any one of Formula (UR-1) to Formula (UR-3) include dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, diisopropylisourea, etc., but are not limited thereto.

[0108] The total content of the compound represented by any one of formula (UR-1) to formula (UR-3) is preferably 1 to 500 ppm, more preferably 10 to 300 ppm, and further preferably 20 to 200 ppm relative to the total mass of the solid content. In this specification, ppm is parts per million of mass / mass unless otherwise specified. The total content of the compound represented by any one of Formula (UR-1) to Formula (UR-3) is preferably 1 to 500 ppm, more preferably 10 to 300 ppm, and further preferably 20 to 200 ppm relative to the content of the specific resin. The compound represented by any one of formula (UR-1) to formula (UR-3) may be used alone or in combination of two or more. When two or more are used in combination, the total content thereof is preferably within the above range.

[0109] <Polymerizable compounds> The resin composition of the present invention preferably contains a polymerizable compound. The polymerizable compound mentioned here does not include a compound corresponding to the above-mentioned compound G. Examples of the polymerizable compound include radical crosslinking agents and other crosslinking agents.

[0110] 〔Free radical crosslinking agent〕 The resin composition of the present invention preferably contains a radical crosslinking agent. The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenically unsaturated bond is preferred. As the above-mentioned group containing an ethylenically unsaturated bond, vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, (meth)acrylamide, etc. can be cited. Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and a (meth)acryloyl group is more preferred from the viewpoint of reactivity.

[0111] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferred, a compound having 2 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 2 to 6 ethylenically unsaturated bonds is further preferred. From the viewpoint of film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0112] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0113] As a specific example of a free radical crosslinking agent, unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides can be cited, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, and sulfanyl groups and monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups and epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are preferred, and substitution reaction products of unsaturated carboxylic acid esters or amides with leaving substituents such as halogen groups and tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, the above unsaturated carboxylic acid can be replaced with a compound group substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, and allyl ether. As a specific example, reference can be made to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, which is incorporated into this specification.

[0114] The radical crosslinking agent is also preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples of the compound having a boiling point of 100° C. or higher under normal pressure include compounds described in paragraph 0203 of International Publication No. 2021 / 112189, etc. This content is incorporated into this specification.

[0115] Preferred radical crosslinking agents other than those described above include radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189, etc. The contents are incorporated into the present specification.

[0116] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.)), A-TMMT (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)), A-DPH (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), and structures in which (meth)acryloyl groups thereof are bonded via an ethylene glycol residue or a propylene glycol residue. Oligomer types of these can also be used.

[0117] Commercially available products of the radical crosslinking agent include, for example, tetrafunctional acrylate SR-494 having four vinyloxy chains, bifunctional methacrylate SR-209, 231, 239 having four vinyloxy chains (all manufactured by Sartomer Company, Inc.), hexafunctional acrylate DPCA-60 having six pentyleneoxy chains, trifunctional acrylate TPA-330 having three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), urethane oligomers UAS-10 and UAB-140 (all 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 (all manufactured by SHIN-NAKAMURA Chemical Co., Ltd.), DPHA-40H (all manufactured by Nippon Kayaku Co., Ltd.), and NK ESTER 4G. Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMERPME400 (manufactured by NOF CORPORATION), etc.

[0118] As the radical crosslinking agent, urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. As the radical crosslinking agent, compounds having an amino structure or a thioether structure in the molecule described in Japanese Patent Publication No. 63-277653, Japanese Patent Publication No. 63-260909, and Japanese Patent Publication No. 01-105238 can also be used.

[0119] The free radical crosslinking agent may be a free radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. The free 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 free radical crosslinking agent having an acid group by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. Particularly preferred are the following compounds: in the free radical crosslinking agent having an acid group by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. As commercially available products, for example, polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO., LTD. can be cited.

[0120] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, more preferably 1 to 100 mgKOH / g. As long as the acid value of the radical crosslinking agent is within the above range, the workability in production and the developability are excellent. In addition, the polymerizability is good. The above acid value is measured according to the description of JIS K 0070:1992.

[0121] From the viewpoint of pattern resolution and film stretchability, it is preferred to use a bifunctional methacrylate or acrylate as the resin composition. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-Hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid EO modified dimethacrylate, other bifunctional acrylates having a urethane bond, bifunctional methacrylates having a urethane bond. These can be used in combination of two or more as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a polyethylene glycol chain with a formula weight of about 200. From the viewpoint of suppressing the warping of the pattern (cured product), the resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as a radical crosslinking agent. As a 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-hydroxymethyl (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, allyl glycidyl ether, etc. can be preferably used. As a monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of more than 100°C at normal pressure is also preferred. Examples of the bifunctional or higher-functional radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0122] When a free radical crosslinking agent is contained, the content of the free radical crosslinking agent is preferably more than 0% by mass and less than 60% by mass relative to the total solid content of the resin composition. The lower limit is more preferably more than 5% by mass. The upper limit is more preferably less than 50% by mass, and further preferably less than 30% by mass.

[0123] The radical crosslinking agent may be used alone or in combination of two or more. When two or more radical crosslinking agents are used in combination, the total amount thereof is preferably within the above range.

[0124] 〔Other cross-linking agents〕 The resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent. Other crosslinking agents refer to crosslinking agents other than the above-mentioned free radical crosslinking agents, and are preferably compounds having multiple groups in the molecule that promote the reaction (form covalent bonds with other compounds in the composition or their reaction products) by the photosensitization of a photoacid generator or a photobase generator, and are preferably compounds having multiple groups in the molecule that promote the reaction (form covalent bonds with other compounds in the composition or their reaction products) by the action of an acid or a base. The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step. As other crosslinking agents, compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355 can be mentioned. The above description is incorporated into the present specification.

[0125] 〔Photopolymerization initiator〕 The resin composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. In addition, it can also be an activator that acts with a photoexcited sensitizer to generate active free radicals.

[0126] The photoradical polymerization initiator preferably contains at least one having a photopolymerization activity of at least about 50 L·mol in a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). -1 cm -1 The molar absorption coefficient of a compound can be measured by a known method. For example, it is preferably measured by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.

[0127] As a photo-radical polymerization initiator, known compounds can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic complexes, etc. can be cited. For details of these, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, and the content is incorporated into this specification. In addition, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, and these contents are incorporated into this specification.

[0128] Examples of the ketone compound include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

[0129] In one embodiment of the present invention, as the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can be preferably used. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and the contents are incorporated into this specification.

[0130] As the α-hydroxyketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (all manufactured by BASF) can be used.

[0131] As the α-aminoketone initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0132] As the aminoacetophenone-based initiator, the acylphosphine oxide-based initiator, and the metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be preferably used. The contents are incorporated into the present specification.

[0133] From the viewpoint of improving exposure sensitivity, oxime compounds are more preferably used as photoradical polymerization initiators. By using oxime compounds, the exposure latitude can be further effectively improved. Oxime compounds have a wide exposure latitude (exposure margin) and also act as photocuring accelerators, so they are particularly preferred. Examples of the oxime compound include compounds having an oxime ester group. The oxime ester group refers to a group represented by >C═NOC(═O)-. That is, the resin composition of the present invention preferably contains an oxime ester group-containing compound as a photopolymerization initiator.

[0134] Specific examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science. and Technology (1995, pp. 202-232), compounds described in Japanese Patent Application Publication No. 2000-066385, compounds described in Japanese Patent Application Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Application Publication No. 2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, etc., the contents of which are incorporated into this specification.

[0135] Preferred oxime compounds include, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferred to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group >C=NOC(=O)- in the molecule.

[0136] [Chemical formula 33]

[0137] Commercially available products of oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in JP-A-2012-014052), TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemix Corporation), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). In addition, oxime compounds of the following structures can also be used. [Chemical formula 34]

[0138] As the photoradical polymerization initiator, for example, an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of International Publication No. 2021 / 112189, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, and an oxime compound having a fluorine atom can also be used. Furthermore, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a substituent having a hydroxyl group bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359 can also be used. These contents are incorporated into this specification.

[0139] As the photopolymerization initiator, an aromatic ring group Ar having an electron-withdrawing group introduced into the aromatic ring can also be used. OX1 As the aromatic ring group Ar OX1The electron withdrawing group may include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano. Acyl and nitro are preferred. Acyl is more preferred because it is easy to form a film with excellent light resistance, and benzoyl is further preferred. The benzoyl may have a substituent. As a substituent, a halogen atom, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic group, heterocyclicoxy, alkenyl, alkylsulfanyl, arylsulfanyl, acyl or amino is preferred. An alkyl, alkoxy, aryl, aryloxy, heterocyclicoxy, alkylsulfanyl, arylsulfanyl or amino is more preferred. An alkoxy, alkylsulfanyl or amino is further preferred.

[0140] The oxime compound OX is preferably at least one selected from the group consisting of a compound represented by the formula (OX1) and a compound represented by the formula (OX2), and is more preferably a compound represented by the formula (OX2). [Chemical formula 35] In the formula, R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphonyl group, a carbamoyl group or a sulfamoyl group, R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group or an amino group, R X3 ~R X14 Each independently represents a hydrogen atom or a substituent. Among them, R X10 ~R X14 At least one of them is an electron withdrawing group.

[0141] In the above formula, preferably R X12 is an electron-withdrawing group and R X10 , R X11 , R X13 , R X14 A hydrogen atom.

[0142] Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.

[0143] Particularly preferred oxime compounds include oxime compounds having specific substituents described in Japanese Patent Application Laid-Open No. 2007-269779 and oxime compounds having thioaryl groups described in Japanese Patent Application Laid-Open No. 2009-191061, and the like, and the contents thereof are incorporated into the present specification.

[0144] 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.

[0145] Furthermore, the photoradical polymerization initiator is a trihalomethyl triazine compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound, more preferably at least one compound selected from the group consisting of a trihalomethyl triazine compound, an α-amino ketone compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, and a benzophenone compound, and further preferably a metallocene compound or an oxime compound.

[0146] As the photoradical polymerization initiator, the compounds described in paragraphs 0175 to 0179 of International Publication No. 2021 / 020359 and the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used, and the contents are incorporated into the present specification.

[0147] As the photo-radical polymerization initiator, a photo-radical polymerization initiator of difunctional or trifunctional or more can be used. By using this type of photo-radical polymerization initiator, more than two free radicals are generated from one molecule of the photo-radical polymerization initiator, so good sensitivity can be obtained. And, in the case of using a compound of asymmetric structure, crystallinity decreases and the solubility in solvents etc. becomes higher, becomes difficult to separate out over time, and can thus improve the stability over time of resin combination. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include dimers of oxime compounds described in paragraphs 0407 to 0412 of JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015 / 004565, JP-A-2016-532675, and paragraphs 0039 to 0055 of International Publication No. 2017 / 033680, and compounds (E) and ( G), Cmpd1 to 7 described in International Publication No. 2016 / 034963, the oxime ester photoinitiator described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of Japanese Patent Publication No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Patent Publication No. 2017-151342, the oxime ester photoinitiator described in Japanese Patent No. 6469669, etc., the contents of which are incorporated into this specification.

[0148] When the resin composition contains a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and further preferably 1.0 to 10% by mass relative to the total solid content of the resin composition. The photopolymerization initiator may contain only one or more. When containing more than two photopolymerization initiators, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

[0149] 〔Sensitizer〕 The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state contacts with a thermal free radical polymerization initiator, a photo free radical polymerization initiator, etc., and generates electron transfer, energy transfer, heat generation, etc. As a result, the thermal free radical polymerization initiator and the photo free radical polymerization initiator cause chemical changes and decompose, and generate free radicals, acids or bases. The sensitizer mentioned here does not include compounds corresponding to the above-mentioned specific compound and the above-mentioned compound D. As sensitizers that can be used, compounds such as benzophenone, Michler's ketone, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzal, oxocyanine, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo can be used. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, and 2-(p-dimethylaminophenylvinylene)isonaphthylthiazole. azole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 4-morpholinobenzophenone, isopentyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminophenylvinyl)benzoxazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)naphthalene(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. Furthermore, other sensitizing pigments may also be used. For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and the contents are incorporated into this specification.

[0150] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and further preferably 0.5 to 10% by mass relative to the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more.

[0151] 〔Chain transfer agent〕 The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005) pages 683-684. As chain transfer agents, for example, a compound group having -SS-, -SO2-S-, -NO-, SH, PH, SiH and GeH in the molecule, dithiobenzoates, trithiocarbonates, dithiocarbamates, xanthate compounds having thiocarbonylthio groups for RAFT (Reversible Addition Fragmentation chain Transfer) polymerization, etc. can be used. These can generate free radicals by supplying hydrogen to low-activity free radicals, or can generate free radicals by deprotonating after oxidation. In particular, thiol compounds can be preferably used.

[0152] Furthermore, as the chain transfer agent, compounds described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219 can also be used, and the contents are incorporated into the present specification.

[0153] When the resin composition has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the total solid content of the resin composition. The chain transfer agent may be only one or more. When there are two or more chain transfer agents, it is preferred that the total is within the above range.

[0154] <Alkali-generating agent> The resin composition of the present invention preferably further contains an alkali generator. It is considered that even when a base generator is used, the crosslinking density increases during exposure due to the sensitization of the specific compound, but imidization of the specific resin easily proceeds during subsequent heating. Furthermore, the resin composition of the present invention preferably contains a base generator and the above-mentioned organic titanium compound. Even if the polyimide and the organic titanium compound are coordinated to increase the film density by containing the organic titanium compound, a base is generated during subsequent heating, so that imidization of the specific resin is easily carried out. Here, the base generator refers to a compound that can generate a base by physical action or chemical action. Preferred base generators include thermal base generators and photobase generators. When the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be promoted by heating, so that the cured product has good mechanical properties and chemical resistance, and the performance as an interlayer insulating film for a redistribution layer included in a semiconductor package is improved. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generating agent is not particularly limited, and a known base generating agent can be used. Examples of known base generating agents include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, imide salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like. Specific examples of the nonionic base generator include compounds described in paragraphs 0249 to 0275 of International Publication No. 2022 / 145355. The above description is incorporated into the present specification.

[0155] Furthermore, from the viewpoint of storage stability and generation of a base by deprotection during curing, the base generator is preferably an amine in which the amino group is protected by a tert-butoxycarbonyl group.

[0156] Examples of the amine compound protected by a tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl The present invention also includes, but is not limited to, alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidinyl)-2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetrahydrotetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxoundecane, or a compound in which the amino group of an amino acid and a derivative thereof is protected by a tert-butoxycarbonyl group.

[0157] Examples of the base generating agent include the following compounds, but the base generating agent is not limited to these compounds.

[0158] [Chemical formula 36]

[0159] The molecular weight of the nonionic base generating agent is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

[0160] Specific examples of preferred compounds of the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0161] Specific examples of the ammonium salt include the following compounds, but are not limited to these. [Chemical formula 37]

[0162] Specific examples of the imide salt include the following compounds, but are not limited to these. [Chemical formula 38]

[0163] Among these, the resin composition of the present invention preferably contains a compound represented by the following formula (F-1) or a compound represented by the formula (F-2) as the above-mentioned base generator. [Chemical formula 39]

[0164] When the resin composition contains an alkali generator, the content of the alkali generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. The base generating agent can be used alone or in combination. When two or more base generating agents are used, the total amount is preferably within the above range.

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

[0166] Examples of the 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, γ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.) Preferred esters include 2-alkoxy alkyl propionates (e.g., 2-alkoxy methyl propionate, 2-alkoxy ethyl propionate, 2-alkoxy propyl propionate, etc. (e.g., 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-methoxy propyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate), 2-alkoxy-2-methyl methyl propionate and 2-alkoxy-2-methyl ethyl propionate (e.g., 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

[0167] As the ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether and the like are preferred ethers.

[0168] Examples of the ketones preferably include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0169] Examples of the cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene. Preferred cyclic hydrocarbons include these.

[0170] As the sulfoxides, for example, dimethyl sulfoxide can be mentioned as a preferred sulfoxide.

[0171] As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like are preferred amides.

[0172] As the urea, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like are mentioned as preferred ureas.

[0173] Examples of the alcohol 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, methylbenzyl alcohol, n-pentanol, methylpentanol and diacetone alcohol.

[0174] From the viewpoint of improving the properties of the coated surface, etc., a mode in which two or more solvents are mixed is also preferred.

[0175] In the present invention, preferably, it is a 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, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levulose ketone and dihydrolevulose ketone, or a mixed solvent consisting of two or more thereof. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone in combination, dimethyl sulfoxide and γ-valerolactone in combination, 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone in combination, 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide in combination, or N-methyl-2-pyrrolidone and ethyl lactate in combination. In addition, one preferred embodiment of the present invention is to further add about 1 to 10% by mass of toluene to the total mass of the solvent to these solvents used in combination. Particularly, from the viewpoint of the storage stability of resin combination etc., the mode containing gamma-valerolactone as solvent is also one of preferred modes of the present invention. In this mode, the content of gamma-valerolactone relative to the gross mass of solvent is preferably more than 50 mass %, more preferably more than 60 mass %, further preferably more than 70 mass %. And, the upper limit of above-mentioned content is not particularly limited, can be 100 mass %. Above-mentioned content considers the solubility of the composition such as the specific resin contained in the resin combination etc. to determine. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and still more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide, relative to the total mass of the solvent.

[0176] From the viewpoint of coating property, the content of solvent is preferably set to the amount of 5 to 80 mass % of the total solid content concentration of the resin composition of the present invention, more preferably set to the amount of 5 to 75 mass % of the total solid content concentration, further preferably set to the amount of 10 to 70 mass % of the total solid content concentration, and further preferably set to the amount of 20 to 70 mass % of the total solid content concentration. The solvent content can be adjusted according to the thickness and coating method required for the coating film. When containing two or more solvents, it is preferred that the total is within the above range.

[0177] <Metal Adhesion Improver> From the viewpoint of improving the adhesion to the metal material used in electrodes or wiring, the resin composition of the present invention preferably contains a metal adhesion improver. Examples of the metal adhesion improver include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0178] 〔Silane coupling agent〕 As a silane coupling agent, for example, the compounds described in paragraph 0316 of International Publication No. 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Publication No. 2018-173573 can be cited, and these contents are incorporated into this specification. In addition, as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358, it is also preferred to use two or more different silane coupling agents. The following compounds are also preferably used as silane coupling agents. In the following formula, Me represents a methyl group and Et represents an ethyl group. In addition, the following R can cite the structure of a blocking agent derived from a blocked isocyanate group. As a blocking agent, it can be selected according to the desorption temperature, and alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, active methylene compounds, etc. can be cited. For example, from the viewpoint of setting the desorption temperature to 160 to 180°C, caprolactam is preferred. Examples of commercially available products of such a compound include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0179] [Chemical formula 40]

[0180] Examples of other silane coupling agents include vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, 3-glycidoxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3- Acryloxypropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyl trimethoxysilane, tris-(trimethoxysilylpropyl) isocyanurate, 3-ureidopropyl trialkoxysilane, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used alone or in combination of two or more. Furthermore, as the silane coupling agent, an oligomer type compound having a plurality of alkoxysilyl groups can also be used. Examples of such oligomer-type compounds include compounds containing a repeating unit represented by the following formula (S-1). [Chemical formula 41] In formula (S-1), R S1 Represents a monovalent organic group, R S2 represents a hydrogen atom, a hydroxyl group or an alkoxy group, and n represents an integer of 0 to 2. R S1 It is preferred to have a structure containing a polymerizable group. As a polymerizable group, a group with an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, an amino group, etc. can be cited. As a group with an ethylenically unsaturated bond, a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group with an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl, etc.), a (methyl) acrylamide group, a (methyl) acryloxy group, etc. can be cited, preferably vinylphenyl, (methyl) acrylamide group or (methyl) acryloxy group, more preferably vinylphenyl or (methyl) acryloxy group, further preferably (methyl) acryloxy group. R S2 It is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. n represents an integer of 0 to 2, and is preferably 1. Here, the structures of the plurality of repeating units represented by the formula (S-1) contained in the oligomer type compound may be the same. Here, among the multiple repeating units represented by formula (S-1) contained in the oligomer type compound, n is preferably 1 or 2 in at least one, more preferably 1 or 2 in at least two, and even more preferably 1 in at least two. As such an oligomer type compound, a commercially available product can be used, and examples of the commercially available product include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0181] 〔Aluminum-based adhesive additive〕 Examples of the aluminum-based adhesion promoter include tris(ethyl acetoacetate)aluminum, tris(acetylacetonate)aluminum, and ethyl acetoacetate aluminum diisopropoxide.

[0182] As other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used, and these contents are incorporated into the present specification.

[0183] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the specific resin. By setting it to above the above lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it to below the above upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver may be only one or more. When two or more are used, it is preferred that the total is within the above range.

[0184] <Migration inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0185] The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic 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 pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring, a 6H-pyran ring, a triazine ring), compounds having a thiourea or sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0186] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions may also be used.

[0187] As other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Laid-Open No. 2011-059656, the compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015 / 199219, etc. can be used, and the contents are incorporated into this specification.

[0188] Specific examples of the migration inhibitor include the following compounds.

[0189] [Chemical formula 42]

[0190] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass based on the total solid content of the resin composition.

[0191] The migration inhibitor may be one or two or more. When the migration inhibitor is two or more, the total amount thereof is preferably within the above range.

[0192] <Polymerization inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0193] Specific examples of the polymerization inhibitor include compounds described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc. This content is incorporated into this specification.

[0194] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition.

[0195] The polymerization inhibitor may be used alone or in combination of two or more. When the polymerization inhibitor is used in combination of two or more, the total amount thereof is preferably within the above range.

[0196] <Light absorber> The resin composition of the present invention also preferably contains a compound (light absorber) whose absorbance at an exposure wavelength is reduced by exposure.

[0197] Whether the compound a contained in the resin composition functions as a light absorber (that is, whether the absorbance at the exposure wavelength is reduced by exposure) can be determined by the following method. First, a solution of compound a having the same concentration as that contained in the resin composition is prepared, and the molar absorption coefficient (mol -1 ·L·cm -1, also called "molar absorption coefficient 1". ). In order to reduce the influence of changes such as the decrease in the molar absorption coefficient of compound a, the above measurement is performed quickly. Regarding the solvent in the above solution, when the resin composition contains a solvent, the solvent is used, and when the resin composition does not contain a solvent, N-methyl-2-pyrrolidone is used. Next, the solution of the compound a was irradiated with exposure light, and the accumulated exposure amount was set to 500 mJ per 1 mol of the compound a. Then, the molar absorption coefficient (mol -1 ·L·cm -1 , also called the "molar absorption coefficient 2". ). The attenuation rate (%) is calculated from the above-mentioned molar absorption coefficient 1 and molar absorption coefficient 2 according to the following formula. When the attenuation rate (%) is greater than 5%, compound a is judged to be a compound whose absorbance at the exposure wavelength decreases due to exposure (i.e., a light absorber). Attenuation rate (%) = 1-molar absorption coefficient 2 / molar absorption coefficient 1×100 The attenuation rate is preferably 10% or more, and more preferably 20% or more. The lower limit of the attenuation rate is not particularly limited, and may be 0% or more. The wavelength of the exposure light may be any wavelength to which the photosensitive film is exposed when the resin composition is used to form a photosensitive film. The wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition has sensitivity. The photopolymerization initiator having sensitivity to a certain wavelength means that polymerization initiating species are generated when the photopolymerization initiator is exposed to light at a certain wavelength. As for the wavelength of the above-mentioned exposure light, in relation to the light source, there can be cited (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), broadband (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6nm), (6) electron beams, (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm, etc. The wavelength of the exposure light may be, for example, a wavelength to which the photopolymerization initiator has sensitivity, but h-rays (wavelength 405 nm) or i-rays (wavelength 365 nm) are preferred, and i-rays (wavelength 365 nm) are more preferred.

[0198] The light absorber may be a compound that generates a radical polymerization initiating species upon exposure, but is preferably a compound that does not generate a radical polymerization initiating species upon exposure from the viewpoint of resolution and chemical resistance. Whether the light absorber is a compound that generates a radical polymerization initiating species upon exposure can be determined by the following method. A solution containing a light absorber and a free radical crosslinking agent at the same concentration as that contained in the resin composition is prepared. When the resin composition contains a free radical crosslinking agent, the same compound as the free radical crosslinking agent contained in the resin composition is used as the free radical crosslinking agent in the above solution at the same concentration. When the resin composition does not contain a free radical crosslinking agent, methyl methacrylate is used at a concentration 5 times that of the light absorber. Thereafter, exposure light was irradiated, and the accumulated amount of exposure light was set to 500 mJ. After exposure, the polymerization of the polymerizable compound is determined by, for example, high performance liquid chromatography. When the molar ratio of the polymerized polymerizable compound relative to the total molar ratio of the polymerizable compound is 10% or less, the light absorber is determined to be a compound that does not generate free radical polymerization initiating species due to exposure. The above molar ratio is preferably 5% or less, and more preferably 3% or less. The lower limit of the above molar ratio is not particularly limited, and may be 0%. The wavelength of the exposure light may be any wavelength to which the photosensitive film is exposed when the resin composition is used to form a photosensitive film. Furthermore, the wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition has sensitivity.

[0199] As compounds that generate free radical polymerization initiating species upon exposure, the same compounds as the above-mentioned photo radical polymerization initiators can be cited. When the composition contains a photo radical polymerization initiator as a light absorber, the one with the lowest polymerization initiating ability of the generated free radical species is used as the light absorber, and the others are used as photopolymerization initiators. Examples of the compound that does not generate radical polymerization initiating species by light exposure include, in addition to photoacid generators and photobase generators, pigments whose absorption wavelength changes by light exposure. Among these, the light absorber is preferably a naphthoquinonediazide compound or a dye whose absorbance changes upon exposure, and more preferably a naphthoquinonediazide compound. Furthermore, as the light absorber, for example, it is also conceivable to use a photoacid generator or a photobase generator in combination with a compound whose absorbance at the exposure wavelength decreases depending on pH.

[0200] 〔Naphthoquinone diazide compounds〕 Examples of the naphthoquinonediazide compound include compounds that generate indene carboxylic acid upon exposure to light and reduce the absorbance at the exposure wavelength, and compounds having a 1,2-naphthoquinonediazide structure are preferred. The naphthoquinonediazide compound is preferably a naphthoquinonediazidesulfonic acid ester of a hydroxy compound. As the hydroxy compound, a compound represented by any one of the following formulae (H1) to (H6) is preferred. [Chemical formula 43] In formula (H1), R 1 and R 2 Each independently represents a monovalent organic group, R 3 and R 4 Each independently represents a hydrogen atom or a monovalent organic group; n1, n2, m1 and m2 each independently represent an integer of 0 to 5; and at least one of m1 and m2 represents an integer of 1 to 5. In formula (H2), Z represents a tetravalent organic group, L 1 , L 2 , L 3 and L 4 Each independently represents a single bond or a divalent organic group, R 5 , R 6 , R 7 and R 8 Each independently represents a monovalent organic group, n3, n4, n5 and n6 each independently represent an integer of 0 to 3, m3, m4, m5 and m6 each independently represent an integer of 0 to 2, and at least one of m3, m4, m5 and m6 is 1 or 2. In formula (H3), R 9 and R 10 Each independently represents a hydrogen atom or a monovalent organic group, L 5 Each independently represents a divalent organic group, and n7 represents an integer of 3-8. In formula (H4), L 6 Represents a divalent organic group, L 7 and L 8 Each independently represents a divalent organic group containing an aliphatic tertiary carbon or a quaternary carbon. In formula (H5), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 Each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, L9 , L 10 and L 11 Each independently represents a single bond or a divalent organic group; m7, m8, m9, and m10 each independently represent an integer of 0 to 2; and at least one of m7, m8, m9, and m10 is 1 or 2. In formula (H6), R 42 , R 43 , R 44 and R 45 Each independently represents a hydrogen atom or a monovalent organic group, R 46 and R 47 Each independently represents a monovalent organic group, n16 and n17 each independently represent an integer of 0 to 4, m11 and m12 each independently represent an integer of 0 to 4, and at least one of m11 and m12 is an integer of 1 to 4.

[0201] In formula (H1), R 1 and R 2 Each of R is independently preferably a monovalent organic group having 1 to 60 carbon atoms, and more preferably a monovalent organic group having 1 to 30 carbon atoms. 1 and R 2 The monovalent organic group in the amine group may be a hydrocarbon group which may have a substituent, for example, an aromatic hydrocarbon group which may have a substituent such as a hydroxyl group. In formula (H1), R 3 and R 4 Each of R is independently preferably a monovalent organic group having 1 to 60 carbon atoms, and more preferably a monovalent organic group having 1 to 30 carbon atoms. 3 and R 4 The monovalent organic group in the alkyl group may be a hydrocarbon group which may have a substituent, for example, a hydrocarbon group which may have a substituent such as a hydroxyl group. In formula (H1), n1 and n2 are each independently preferably 0 or 1, and more preferably 0. In formula (H1), it is preferred that both m1 and m2 are 1.

[0202] The compound represented by formula (H1) is preferably a compound represented by any one of formula (H1-1) to formula (H1-5). [Chemical formula 44] In formula (H1-1), R 21 , R 22 and R 23 Each independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a group represented by the following formula (R-1). [Chemical formula 45] In formula (R-1), R 29 represents a hydrogen atom, an alkyl group or an alkoxy group, n13 represents an integer of 0 to 2, and * represents a bonding site with other structures. In (H1-1), n8, n9 and n10 each independently represent an integer of 0 to 2, and preferably 0 or 1.

[0203] In formula (H1-2), R 24 represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. n14, n15, and n16 each independently represent an integer of 0 to 2. 30 represents a hydrogen atom or an alkyl group.

[0204] In formula (H1-3), R 25 , R 26 , R 27 and R 28 Each independently represents a monovalent organic group, preferably a hydrogen atom, an alkyl group or a group represented by the above formula (R-1). In formula (H1-3), n11, n12 and n13 each independently represent an integer of 0 to 2, and preferably 0 or 1.

[0205] As the compound represented by the formula (H1-1), a compound represented by any one of the following formulas (H1-1-1) to (H1-1-4) is preferred. As the compound represented by the formula (H1-2), a compound represented by the following formula (H1-2-1) or (H1-2-2) is preferred. As the compound represented by the formula (H1-3), compounds represented by the following formulas (H1-3-1) to (H1-3-3) are preferred. [Chemical formula 46]

[0206] In formula (H2), Z is preferably a tetravalent group having 1 to 20 carbon atoms, and more preferably a group represented by any one of the following formulae (Z-1) to (Z-4). In the following formulae (Z-1) to (Z-4), * represents a bonding site to another structure. [Chemical formula 47] In formula (H2), L 1 , L 2 , L 3 and L 4 Each independently is preferably a single bond or a methylene group. In formula (H2), R5 , R 6 , R 7 and R 8 Each independently is preferably an organic group having 1 to 30 carbon atoms. In formula (H2), n3, n4, n5 and n6 are each independently preferably an integer of 0 to 2, more preferably 0 or 1. In formula (H2), m3, m4, m5 and m6 are each independently preferably 1 or 2, more preferably 1. As the compound represented by the formula (H2), compounds of the following structures can be exemplified. [Chemical formula 48]

[0207] In formula (H3), R 9 and R 10 Each independently preferably represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. In formula (H3), L 5 Each independently preferably is a group represented by the following formula (L-1). [Chemical formula 49] In formula (L-1), R 30 represents a monovalent organic group having 1 to 20 carbon atoms, n14 represents an integer of 1 to 5, and * represents a bonding site with other structures. In formula (H3), n7 is preferably an integer of 4-6. Examples of the compound represented by the formula (H3) include the following compounds. In the following formula, n each independently represents an integer of 0 to 9. [Chemical formula 50]

[0208] In formula (H4), L 6 Preferred is -C(CF3)2-, -S(=O)2- or -C(=O)-. In formula (H4), L 7 and L 8 Each independently is preferably a divalent organic group having 2 to 20 carbon atoms. Examples of the compound represented by formula (H4) include the following compounds. [Chemical formula 51]

[0209] In formula (H5), R 11 , R 12 , R 13 , R 14, R 15 , R 16 , R 17 , R 18 , R 19 and R 20 Each independently preferably is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group or an acyl group. In formula (H5), L 9 , L 10 and L 11 Each of them is independently preferably a single bond, -O-, -S-, -S(=O)2-, -C(=O)-, -C(=O)O-, cyclopentylene, cyclohexylene, phenylene or a divalent organic group having 1 to 20 carbon atoms, and is more preferably a group represented by any one of the following formulas (L-2) to (L-4). [Chemical formula 52] In formula (L-2) to formula (L-4), R 31 and R 32 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, and R 34 , R 35 , R 36 and R 37 Each independently represents a hydrogen atom or an alkyl group, n15 is an integer from 1 to 5, and R 38 , R 39 , R 40 and R 41 Each independently represents a hydrogen atom or an alkyl group, and * represents a bonding site to other structures. Examples of the compound represented by formula (H5) include the following compounds. [Chemical formula 53]

[0210] In formula (H6), R 42 , R 43 , R 44 and R 45 Each independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms. In formula (H6), R 46 and R 47 An alkyl group, an alkoxy group or an aryl group is respectively and independently preferred, and an alkyl group is more preferred. In formula (H6), n16 and n17 are each independently preferably an integer of 0 to 2, more preferably 0 or 1. In formula (H6), n16 and n17 are each independently preferably an integer of 1 to 3, and more preferably 2 or 3. Examples of the compound represented by formula (H6) include the following compounds. [Chemical formula 54]

[0211] Examples of the hydroxy compound include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2′-methylbenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,4,6,3′,4′-pentahydroxybenzophenone, 2,3,4,2′,4′-pentahydroxybenzophenone, 2,3,4,2′,5′-pentahydroxybenzophenone, 2,4,6,3′,4′,5′-hexahydroxybenzophenone and 2,3,4,3′,4′,5′-hexahydroxybenzophenone; Polyhydroxyphenyl alkyl ketones such as 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyphenylpentanone, 2,3,4-trihydroxyphenylhexanone, Bis((poly)hydroxyphenyl)alkanes such as bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)propane-1, bis(2,3,4-trihydroxyphenyl)propane-1, nordihydroguaiaretic acid, 1,1-bis(4-hydroxyphenyl)cyclohexane, Polyhydroxybenzoic acid esters such as propyl 3,4,5-trihydroxybenzoate, phenyl 2,3,4-trihydroxybenzoate, phenyl 3,4,5-trihydroxybenzoate, Bis(2,3,4-trihydroxybenzoyl)methane, bis(3-acetyl-4,5,6-trihydroxyphenyl)methane, bis(2,3,4-trihydroxybenzoyl)benzene, bis(2,4,6-trihydroxybenzoyl)benzene and other bis(polyhydroxybenzoyl)alkanes or bis(polyhydroxybenzoyl)aryls, Alkylene-di(polyhydroxybenzoates) such as ethylene glycol-di(3,5-dihydroxybenzoate) and ethylene glycol-di(3,4,5-trihydroxybenzoate), 2,3,4-biphenyltriol, 3,4,5-biphenyltriol, 3,5,3′,5′-biphenyltetraol, 2,4,2′,4′-biphenyltetraol, 2,4,6,3′,5′-biphenylpentaol, 2,4,6,2′,4′,6′-biphenylhexanol, 2,3,4,2′,3′,4′-biphenylhexanol and other polyhydroxy biphenyls, 4,4'-thiobis(1,3-dihydroxy)benzene and other bis(polyhydroxy)sulfides, 2,2',4,4'-Tetrahydroxydiphenyl ether and other bis(polyhydroxyphenyl) ethers, 2,2',4,4'-Tetrahydroxydiphenyl sulfoxide and other bis(polyhydroxyphenyl) sulfoxides, 2,2',4,4'-diphenyl sulfone and other bis(polyhydroxyphenyl) sulfones, tris(4-hydroxyphenyl)methane, 4,4′,4″-trihydroxy-3,5,3′,5′-tetramethyltriphenylmethane, 4,4′,3″,4″-tetrahydroxy-3,5,3′,5′-tetramethyltriphenylmethane, 4-[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]-2-methoxy-phenol, 4,4′-(3,4-diol-benzylidene)bis[2,6-dimethylphenol], 4,4′-[(2-hydroxy-phenyl)methylene]bis[2-cyclohexyl-5-methylphenol, 4,4′,2″,3″,4″-pentahydroxy-3,5,3 ',5'-tetramethyltriphenylmethane, 2,3,4,2',3',4'-hexahydroxy-5,5'-diacetyltriphenylmethane, 2,3,4,2',3',4',3",4"-octahydroxy-5,5'-diacetyltriphenylmethane, 2,4,6,2',4',6'-hexahydroxy-5,5'-dipropionyltriphenylmethane and other polyhydroxytriphenylmethanes, 4,4'-(phenylmethylene)bisphenol, 4,4'-(1-phenyl-ethylidene)bis[2-methylphenol], 4,4',4"-ethylidene-triphenol and other polyhydroxytriphenylethanes, 3,3,3′,3′-tetramethyl-1,1′-spirobi-indane-5,6,5′,6′-tetrol, 3,3,3′,3′-tetramethyl-1,1′-spirobi-indane-5,6,7,5′,6′,7′-hexol, 3,3,3′,3′-tetramethyl-1,1′-spirobi-indane-4,5,6,4′,5′,6′-hexol, 3,3,3′,3′-tetramethyl-1,1′-spirobi-indane-4,5,6,5′,6′,7′-hexol and other polyhydroxy spirobi-indanes, 2,4,4-trimethyl-2′,4′,7′-trihydroxyflavane and other polyhydroxy flavanes, Polyhydroxyphthalides such as 3,3-bis(3,4-dihydroxyphenyl)phthalide, 3,3-bis(2,3,4-trihydroxyphenyl)phthalide, 3′,4′,5′,6′-tetrahydroxyspiro[phthalide-3,9′-xanthene], flavonoid pigments such as morin, quercetin, and rutin, α,α',α"-Tris(4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-Tris(3,5-dimethyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-Tris(3,5-diethyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-Tris(3,5-di-n-propyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-Tris(3,5-di-n-butyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-Tris(3-methyl-4 α,α',α"-tris(3-methoxy-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α',α"-tris(2,4-dihydroxyphenyl)1,3,5-triisopropylbenzene, 1,3,5-tris(3,5-dimethyl-4-hydroxyphenyl)benzene, 1,3,5-tris(5-methyl-2-hydroxyphenyl)benzene, 2,4,6-tris(3,5-dimethyl-4-hydroxyphenylthiomethyl)mesitylene, 1-[α-methyl-α-(4'-hydroxyphenyl)ethyl]-4-[α,α'-bis(4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(4'-hydroxyphenyl)ethyl]-3-[α, α'-bis(4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3',5'-dimethyl-4'-hydroxyphenyl)ethyl]-4-[α,α'-bis(3",5"-dimethyl-4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(3'-methyl-4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(3"-methyl-4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3'-methoxy-4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(3"-methoxy-4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(2',4'-dihydroxyphenyl)ethyl]-4-[α' ,α'-bis(4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(2',4'-dihydroxyphenyl)ethyl]-3-[α',α'-bis(4"-hydroxyphenyl)ethyl]benzene and the like polyhydroxy compounds described in Japanese Patent Laid-Open No. 4-253058, α,α,α',α',α",α"-hexa-(4-hydroxyphenyl)-1,3,5-triethylbenzene and the like polyhydroxy compounds described in Japanese Patent Laid-Open No. 5-224410, 1,2,2,3-tetra(p-hydroxyphenyl)propane, 1,3,3,5-tetra(p-hydroxyphenyl)pentane and the like poly(hydroxyphenyl)alkanes described in Japanese Patent Laid-Open No. 5-303200 and EP-530148, p-Bis(2,3,4-trihydroxybenzoyl)benzene, p-Bis(2,4,6-trihydroxybenzoyl)benzene, m-Bis(2,3,4-trihydroxybenzoyl)benzene, m-Bis(2,4,6-trihydroxybenzoyl)benzene, p-Bis(2,5-dihydroxy-3-bromobenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5-methylbenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5-methoxybenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5-nitrobenzoyl)benzene, p-Bis(2,3,4-trihydroxy-5 -cyanobenzoyl)benzene, 1,3,5-tris(2,5-dihydroxybenzoyl)benzene, 1,3,5-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,3-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,4-tris(2,3,4-trihydroxybenzoyl)benzene, 1,2,4,5-tetrakis(2,3,4-trihydroxybenzoyl)benzene, α,α'-bis(2,3,4-trihydroxybenzoyl)p-xylene, α,α',α'-tris(2,3,4-trihydroxybenzoyl)mesitylene, 2,6-bis-(2-hydroxy-3,5-dimethylbenzyl)-p-cresol, 2,6-bis-(2-hydroxy-5′-methylbenzyl)-p-cresol, 2,6-bis-(2,4,6-trihydroxybenzyl)-p-cresol, 2,6-bis-(2,3,4-trihydroxybenzyl)-p-cresol, 2,6-bis-(2,3,4-trihydroxybenzyl)-p-cresol, 2,6-bis-(2,3,4-trihydroxybenzyl)-3,5-dimethyl-phenol, 4,6-bis-(4-hydroxy-3,5-dimethylbenzyl)-pyrogallol, 2,6-bis-( 4-hydroxy-3,5-dimethylbenzyl)-1,3,4-trihydroxy-phenol, 4,6-bis-(2,4,6-trihydroxybenzyl)-2,4-dimethyl-phenol, 4,6-bis-(2,3,4-trihydroxybenzyl)-2,5-dimethyl-phenol, 2,6-bis-(4-hydroxybenzyl)-p-cresol, 2,6-bis(4-hydroxybenzyl)-4-cyclohexylphenol, 2,6-bis(4-hydroxy-3-methylbenzyl)-p-cresol, 2,6-bis(4-hydroxy -3,5-dimethylbenzyl)-p-cresol, 2,6-bis(4-hydroxy-2,5-dimethylbenzyl)-p-cresol, 2,6-bis(4-hydroxy-3-methylbenzyl)-4-phenyl-phenol, 2,2′,6,6′-tetrakis[(4-hydroxyphenyl)methyl]-4,4′-methylenediphenol, 2,2′,6,6′-tetrakis[(4-hydroxy-3,5-dimethylphenyl)methyl]-4,4′-methylenediphenol, 2,2′,6,6′-tetrakis[(4-hydroxy-3,5-dimethylphenyl)methyl]-4,4′-methylenediphenol, 2,2'-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]6,6'-dimethyl-4,4'-methylenediphenol, 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol, bis(4-hydroxy-3,5-dimethylphenyl)methyl]-(4-hydroxy-3-methoxyphenyl)methane, etc. Furthermore, low-nuclear forms of phenolic resins such as novolac resins can also be used.

[0212] Examples of the naphthoquinonediazidesulfonic acid include 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid, and these may be used in combination.

[0213] The method for producing the naphthoquinonediazidesulfonic acid ester of a hydroxy compound is not particularly limited, and the ester can be obtained, for example, by subjecting naphthoquinonediazidesulfonic acid to sulfonylation with chlorosulfonic acid or thionyl chloride, and subjecting the obtained naphthoquinonediazidesulfonyl chloride to a condensation reaction with a hydroxy compound. For example, it can be obtained by reacting a hydroxy compound with a predetermined amount of naphthoquinonediazidesulfonyl chloride in a solvent such as dioxane, acetone or tetrahydrofuran in the presence of a basic catalyst such as triethylamine to carry out esterification, and then washing the obtained product with water and drying it.

[0214] The esterification rate of naphthoquinone diazide sulfonic acid ester is not particularly limited, but is preferably 10% or more, and more preferably 20% or more. The upper limit of the esterification rate is not particularly limited, and may be 100%. The above esterification rate can be obtained by 1 It can be confirmed by H-NMR or the like as the ratio of esterified groups among the hydroxyl groups in the hydroxyl compound.

[0215] Furthermore, as the light absorber, the compounds described in paragraphs 0088 to 0108 of JP-A-2019-206689 can also be used.

[0216] <Other additives> Resin combination of the present invention can contain various additives as required within the scope of obtaining the effect of the present invention, for example, surfactant, higher fatty acid derivative, thermal polymerization initiator, inorganic particles, ultraviolet light absorber, antioxidant, light acid generator, anti-agglomeration agent, phenolic compound, other polymer compounds, plasticizer and other auxiliary agents (for example, defoamer, flame retardant, etc.) etc. By suitably containing these components, properties such as film properties can be adjusted. About these components, for example, can refer to the record of 0183 paragraphs after (0237 paragraphs of corresponding U.S. Patent Application Publication No. 2013 / 0034812 specification) of Japanese Patent Application Publication No. 2008-250074, the record of paragraphs 0101~0104, 0107~0109 etc., these contents are incorporated in this specification. When allocating these additives, it is preferred that its total content is set to less than 3% by mass of the solid component of resin combination of the present invention.

[0217] Examples of these other additives include compounds described in paragraphs 0316 to 0358 of International Publication No. 2022 / 145355. The above description is incorporated into the present specification.

[0218] <Characteristics of resin composition> The viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm 2 / s~12,000mm 2 / s, more preferably 2,000 mm 2 / s~10,000mm 2 / s, more preferably 2,500mm 2 / s~8,000mm 2 / s. As long as it is within the above range, it is easy to obtain a coating film with high uniformity. For example, if it is 1,000mm 2 / s or more, it is easy to apply the film thickness required as a redistribution insulating film. If it is 12,000mm 2 / s or less, a coating film having an excellent coating surface shape can be obtained.

[0219] <Regarding restrictions on substances contained in resin compositions> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and further preferably less than 1.0% by mass. When the water content is less than 2.0%, the storage stability of the resin composition is improved. Examples of methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0220] From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., except for metals contained as complexes of organic compounds and metals. When multiple metals are contained, the total amount of these metals is preferably within the above range.

[0221] In addition, as a method for reducing metal impurities accidentally contained in the resin composition of the present invention, the following methods can be cited: selecting raw materials with a low metal content as raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention, lining the inside of the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible, etc.

[0222] Regarding the resin composition of the present invention, if the use as a semiconductor material is considered, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and further preferably less than 200 mass ppm from the viewpoint of wiring corrosion. Among them, the halogen atoms present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be cited. The total of chlorine atoms and bromine atoms or chlorine ions and bromide ions is preferably within the above range, respectively. As a method for adjusting the content of halogen atoms, ion exchange treatment or the like is preferably mentioned.

[0223] As a storage container for the resin composition of the present invention, a conventionally known storage container can be used. As a storage container, for the purpose of suppressing the mixing of impurities into the raw materials or the resin composition of the present invention, a multilayer bottle having an inner wall of the container composed of six kinds of six layers of resins or a bottle having a seven-layer structure composed of six kinds of resins is preferably used. As such a container, for example, a container described in Japanese Patent Publication No. 2015-123351 can be cited.

[0224] <Cured product of resin composition> By curing the resin composition of the present invention, a cured product of the resin composition can be obtained. The cured product of the present invention is a cured product obtained by curing the resin composition. The curing of the resin composition is preferably carried out by heating, and the heating temperature is more preferably 120°C to 400°C, further preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited, and a film, a rod, a sphere, a granular shape, etc. can be selected according to the purpose. In the present invention, the cured product is preferably in a film shape. Through the pattern processing of the resin composition, the shape of the cured product can also be selected according to the purpose of forming a protective film on the wall, forming a conductive through hole, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function. The film thickness of the cured product (film composed of the cured product) is preferably 0.5μm or more and 150μm or less. The shrinkage rate when curing the resin composition of the present invention is preferably 50% or less, more preferably 45% or less, and further preferably 40% or less. Here, the shrinkage rate refers to the percentage of volume change before and after curing of the resin composition, and can be calculated by the following formula. Shrinkage rate [%] = 100-(volume after curing ÷ volume before curing) × 100

[0225] <Characteristics of Cured Product of Resin Composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When it is 70% or more, the cured product may have excellent mechanical properties. The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.

[0226] <Preparation of resin composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be performed by a conventionally known method. Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing while rotating a pot. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0227] For the purpose of removing foreign matter such as dust or particles in the resin composition of the present invention, it is preferred to filter using a filter. Regarding the filter pore size, for example, it is preferably less than 5 μm, more preferably less than 1 μm, further preferably less than 0.5 μm, and further preferably less than 0.1 μm. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferably HDPE (high-density polyethylene). The filter can use a filter pre-cleaned with an organic solvent. In the filter filtering process, multiple filters can be connected in series or in parallel for use. When multiple filters are used, filters with different pore sizes or materials can be used in combination. As a connection method, for example, a method of connecting a HDPE filter with a pore size of 1 μm as the first stage and a HDPE filter with a pore size of 0.2 μm as the second stage in series can be cited. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be a circulation filter. In addition, filtering can also be performed after pressurization. When filtering is performed after pressurization, the pressure applied is preferably 0.01 MPa to 1.0 MPa, more preferably 0.03 MPa to 0.9 MPa, further preferably 0.05 MPa to 0.7 MPa, and still further preferably 0.05 MPa to 0.5 MPa. In addition to filtering using a filter, an impurity removal treatment using an adsorbent may also be performed. Filter filtering and impurity removal treatment using an adsorbent may also 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 cited. After filtering with a filter, the resin composition filled in the bottle may be placed under reduced pressure for degassing.

[0228] (Method for producing cured product) The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film. The method for producing a cured product more preferably includes the film forming step, an exposure step of selectively exposing the film formed in the film forming step, and a developing step of developing the film exposed in the exposure step with a developer to form a pattern. The method for producing a cured product particularly preferably includes the film forming step, the exposure step, the development step, and at least one of a heating step of heating the pattern obtained by the development step and a post-development exposure step of exposing the pattern obtained by the development step. Furthermore, it is also preferable that the method for producing a cured product includes the above-mentioned film forming step and the step of heating the above-mentioned film. Hereinafter, the details of each step will be described.

[0229] <Film formation process> The resin composition of the present invention can be used in a film forming step of applying the composition to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film.

[0230] 〔Base material〕 The type of substrate can be appropriately determined according to the purpose and is not particularly limited. As the substrate, there can be cited semiconductor manufacturing substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor-deposited film, magnetic film, reflective film, Ni, Cu, Cr, Fe and other metal substrates (for example, it can be any one of a substrate formed by a metal and a substrate having a metal layer formed by, for example, plating, vapor deposition, etc.), paper, SOG (Spin On Glass: Spin-on Glass), TFT (Thin Film Transistor) array substrate, mold substrate, plasma display panel (PDP) electrode plate, etc. In particular, the substrate is preferably a semiconductor manufacturing substrate, more preferably a silicon substrate, a Cu substrate and a mold substrate. On the surface of these substrates, a layer such as an adhesive layer or an oxide layer formed of hexamethyldisilazane (HMDS) or the like may be provided. The shape of the substrate is not particularly limited, and may be circular or rectangular. Regarding the size of the substrate, for example, if the substrate is circular, the diameter is preferably 100 to 450 mm, more preferably 200 to 450 mm, and for example, if the substrate is rectangular, the length of the short side is preferably 100 to 1000 mm, more preferably 200 to 700 mm. As the substrate, for example, a plate-shaped substrate (substrate) can be used, and preferably a panel-shaped substrate (substrate) is used.

[0231] When a film is formed by applying the resin composition on the surface of a resin layer (for example, a layer composed of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as a substrate.

[0232] As a method of applying the resin composition to a substrate, coating is preferred. As the method applied, specifically, dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating and inkjet can be cited. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating or inkjet are preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. The solid content concentration or coating conditions of the resin composition are adjusted according to the method applied, thereby obtaining a film of the desired thickness. In addition, the coating method can also be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, spin coating or spray coating, inkjet, etc. are preferred. If it is a rectangular substrate, slit coating, spray coating, inkjet, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Furthermore, a method of transferring a coating film formed on a temporary support in advance by the above-mentioned imparting method to a substrate can also be applied. As for the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used. Furthermore, a process of removing excess film at the edge of the substrate may be performed. Examples of such a process include edge bead rinse (EBR) and backwash. A pre-wetting step may be adopted in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

[0233] <Drying process> After the film forming step (layer forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) in order to remove the solvent. That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step. The drying step is preferably performed after the film forming step and before the exposure step. The drying temperature of the film in the drying step is preferably 50° C. to 150° C., more preferably 70° C. to 130° C., and further preferably 90° C. to 110° C. Furthermore, the drying may be performed by reducing pressure. The drying time may be 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0234] <Exposure process> The film may be subjected to an exposure step of selectively exposing the film. The method for producing a cured product may include an exposure step of selectively exposing the film formed in the film forming step. Selective exposure refers to exposing a portion of the film to light, and by selective exposure, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film. The exposure amount is not particularly limited as long as it can cure the resin composition of the present invention. For example, it is preferably 50 to 10,000 mJ / cm 2 , more preferably 200 to 8,000 mJ / cm 2 .

[0235] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0236] Regarding the exposure wavelength, in relation to the light source, there can be mentioned (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), wide wavelengths (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beams, (7) second harmonics of YAG lasers of 532 nm and third harmonics of 355 nm, etc. For the resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferred, and exposure by i-rays is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited as long as at least a part of the film composed of the resin composition of the present invention is exposed, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0237] <Post-exposure heating process> The film may be subjected to a step of heating after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The temperature increase rate in the post-exposure heating step is preferably 1 to 12° C. / min, more preferably 2 to 10° C. / min, and even more preferably 3 to 10° C. / min from the temperature at the start of heating to the maximum heating temperature. Furthermore, the heating rate can be appropriately changed during the heating process. The heating method in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used. Furthermore, during heating, it is also preferred to conduct the heating in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0238] <Development process> The film after exposure may be subjected to a developing step of developing with a developer to form a pattern. That is, the method for producing a cured product of the present invention may include a developing step of developing the film exposed in the exposing step using a developing solution to form a pattern. By performing development, one of the exposed portion and the non-exposed portion of the film is removed to form a pattern. Here, development in which the non-exposed portion of the film is removed by the development step is referred to as negative development, and development in which the exposed portion of the film is removed by the development step is referred to as positive development.

[0239] 〔Developer〕 As a developer used in the development step, an aqueous alkali solution or a developer containing an organic solvent can be mentioned.

[0240] When the developer is an alkaline aqueous solution, examples of the alkaline compound that the alkaline aqueous solution can contain include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferably TMAH. The content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.3 to 3% by mass, based on the total amount of the developer.

[0241] When the developer contains an organic solvent, the compound described in paragraph 0387 of International Publication No. 2021 / 112189 can be used as the organic solvent. This content is incorporated into this specification. In addition, as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc. can also be preferably mentioned, and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. can also be preferably mentioned.

[0242] Furthermore, when the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0243] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. Furthermore, the above content may also be 100% by mass.

[0244] When the developer contains an organic solvent, the developer may further contain at least one of an alkaline compound and an alkali generator. When at least one of the alkaline compound and the alkali generator in the developer penetrates into the pattern, the properties of the pattern such as elongation at break may be improved.

[0245] As the basic compound, an organic base is preferred from the viewpoint of reliability when remaining in a film after curing (adhesion to a substrate when the cured product is further heated). As the basic compound, a basic compound having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides and the like are preferred. In order to promote the imidization reaction, primary amines, secondary amines, tertiary amines or ammonium salts are preferred, secondary amines, tertiary amines or ammonium salts are more preferred, secondary amines or tertiary amines are further preferred, and tertiary amines are particularly preferred. As the basic compound, from the viewpoint of the mechanical properties (elongation at break) of the cured product, a compound that is not likely to remain in the cured film (the cured product obtained) is preferred, and from the viewpoint of promoting cyclization, a compound whose residual amount is not likely to be reduced by gasification before heating is preferred. Therefore, the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and further preferably 100°C to 230°C at normal pressure (101,325 Pa). The boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer. For example, when the boiling point of the organic solvent is 100° C., the basic compound used preferably has a boiling point of 80° C. or higher, and more preferably has a boiling point of 100° C. or higher. The developer may contain only one kind of basic compound or may contain two or more kinds of basic compounds.

[0246] Specific examples of the basic compound include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butylenediamine, 1,5-diaminopentane, and N-methylhexylamine. , N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-diphenylamineethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propylenediamine, etc.

[0247] Preferred embodiments of the base generator are the same as those of the base generator contained in the above-mentioned composition. In particular, the base generator is preferably a thermal base generator.

[0248] When the developer contains at least one of an alkaline compound and an alkali generator, the content of the alkaline compound or the alkali generator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the developer. The lower limit of the above content is not particularly limited, and is preferably 0.1% by mass or more, for example. When the alkaline compound or the base generator is solid in an environment where a developer is used, the content of the alkaline compound or the base generator is preferably 70 to 100% by mass based on the total solid content of the developer. The developer may contain only one or more of the alkaline compound and the alkali generator. When the alkaline compound and the alkali generator are two or more, the total amount thereof is preferably within the above range.

[0249] The developer may further contain other ingredients. As other components, for example, a known surfactant or a known defoaming agent can be mentioned.

[0250] [Developer supply method] As long as the desired pattern can be formed, the method of supplying the developer is not particularly limited, and there are the following methods: a method of immersing the substrate formed with a film in the developer, a method of supplying the developer to the film formed on the substrate using a nozzle by a capping immersion development, or 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, a spray nozzle, and the like. From the viewpoints of the permeability of the developer, the removability of the non-image area, and the manufacturing efficiency, it is preferred to supply the developer using a straight nozzle or continuously supply the developer using a spray nozzle. From the viewpoint of the permeability of the developer to the image area, it is more preferred to supply the developer using a spray nozzle. In addition, the following process can be adopted: after continuously supplying the developer with a straight nozzle, the substrate is rotated to remove the developer from the substrate, and after spin drying, the developer is continuously supplied with a straight nozzle again, and the substrate is rotated to remove the developer from the substrate. This process can also be repeated multiple times. Examples of a method for supplying the developer in the development step include a step of continuously supplying the developer to the substrate, a step of keeping the developer substantially stationary on the substrate, a step of vibrating the developer on the substrate using ultrasonic waves or the like, and a combination of these steps.

[0251] The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0252] In the development step, the pattern may be cleaned (rinsed) with a rinse liquid after the processing with the developer. Alternatively, a method may be adopted in which the rinse liquid is supplied before the developer in contact with the pattern is completely dried.

[0253] 〔Rinsing fluid〕 When the developer is an alkaline aqueous solution, water can be used as the rinse liquid, and when the developer contains an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[0254] As the organic solvent in the case where the rinse solution contains an organic solvent, the same organic solvents as exemplified in the case where the developer contains an organic solvent can be mentioned. The organic solvent contained in the rinse solution is preferably an organic solvent different from the organic solvent contained in the developer, and more preferably an organic solvent having a lower solubility in the pattern than the organic solvent contained in the developer.

[0255] When the rinse liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, PGME, and further preferably cyclohexanone and PGMEA.

[0256] When the rinse liquid contains an organic solvent, the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more relative to the total mass of the rinse liquid. Furthermore, the organic solvent may be 100% by mass relative to the total mass of the rinse liquid.

[0257] The rinse solution may contain at least one of a basic compound and an alkali generator. Although not particularly limited, when the developer contains an organic solvent, an embodiment in which the rinse solution contains at least one of an organic solvent, an alkaline compound, and an alkali generator is also one of the preferred embodiments of the present invention. Examples of the alkaline compound and the alkaline generator contained in the rinse solution include the alkaline compounds and the compounds exemplified as the alkaline generator that may be contained in the developer containing an organic solvent, and preferred embodiments are also the same. The basic compound and the base generating agent contained in the rinsing liquid may be selected in consideration of their solubility in the solvent in the rinsing liquid.

[0258] When the rinse liquid contains at least one of an alkaline compound and an alkali generator, the content of the alkaline compound or the alkali generator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the rinse liquid. The lower limit of the above content is not particularly limited, for example, preferably 0.1% by mass or more. When the basic compound or base generator is solid in the environment where the rinse liquid is used, the content of the basic compound or base generator is preferably 70 to 100% by mass based on the total solid content of the rinse liquid. When the rinse liquid contains at least one of an alkaline compound and an alkali generator, the rinse liquid may contain only one alkaline compound and at least one of an alkali generator, or may contain two or more alkaline compounds and at least one of an alkali generator. When at least one of the alkaline compound and the alkali generator is two or more, the total amount thereof is preferably within the above range.

[0259] The rinse may also contain other ingredients. As other components, for example, a known surfactant or a known defoaming agent can be mentioned.

[0260] [Method of supplying flushing fluid] As long as the desired pattern can be formed, there is no particular limitation on the method for supplying the rinsing liquid, and the following methods are available: a method of immersing the substrate in the rinsing liquid, a method of supplying the rinsing liquid to the substrate through liquid accumulation, a method of supplying the rinsing liquid to the substrate through spraying, and a method of continuously supplying the rinsing liquid to the substrate through a straight nozzle or the like. From the viewpoint of the permeability of the rinse liquid, the removal of the non-image part, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., preferably a method of continuously supplying using a spray nozzle, and from the viewpoint of the permeability of the rinse liquid to the image part, more preferably a method of supplying using a spray nozzle. 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 or continuously supplying the rinsing liquid to the exposed film using a straight nozzle, and more preferably a step of supplying the rinsing liquid using a spray nozzle. The method for supplying the rinsing liquid in the rinsing step may include continuously supplying the rinsing liquid to the substrate, maintaining the rinsing liquid in a substantially static state on the substrate, vibrating the rinsing liquid on the substrate using ultrasound or the like, and a combination of these.

[0261] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0262] In the development process, after processing with a developer or cleaning the pattern with a rinse solution, a process of bringing the treatment solution into contact with the pattern may be included. In addition, a method of supplying the treatment solution before the developer or rinse solution in contact with the pattern is completely dried may also be adopted.

[0263] Examples of the treatment liquid include a treatment liquid containing at least one of water and an organic solvent and at least one of a basic compound and an alkali generator. Preferred embodiments of the organic solvent, and at least one of the alkaline compound and the base generator are the same as preferred embodiments of the organic solvent, and at least one of the alkaline compound and the base generator used in the rinse solution. The method for supplying the processing liquid to the pattern can be the same method as the method for supplying the rinse liquid, and the preferred aspects are also the same.

[0264] The content of the basic compound or base generating agent in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the treatment liquid. The lower limit of the content is not particularly limited, but is preferably 0.1% by mass or more, for example. Furthermore, when the basic compound or the base generator is solid in the environment where the treatment liquid is used, the content of the basic compound or the base generator is preferably 70 to 100% by mass based on the total solid content of the treatment liquid. When the treatment liquid contains at least one of an alkaline compound and an alkali generator, the treatment liquid may contain only one alkaline compound and at least one of an alkali generator, or may contain two or more alkaline compounds and at least one of an alkali generator. When at least one of the alkaline compound and the alkali generator is two or more, the total amount thereof is preferably within the above range.

[0265] <Heating process> The pattern obtained by the development step (the pattern after the rinsing step when the rinsing step is performed) can be subjected to a heating step of heating the pattern obtained by the development. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the development step. Furthermore, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing a development step or a film obtained by a film forming step. In the heating step, a resin such as a polyimide precursor is cyclized to become a resin such as a polyimide. Furthermore, crosslinking of unreacted crosslinking groups in the specific resin or the crosslinking agent other than the specific resin is also performed. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, further preferably 160 to 250°C, particularly preferably 160 to 230°C.

[0266] The heating step is preferably a step of accelerating the cyclization reaction of the polyimide precursor in the pattern by heating and utilizing the action of a base or the like generated by the base generator.

[0267] Regarding the heating in the heating process, it is preferred to perform the heating at a heating rate of 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature. The heating rate is more preferably 2 to 10°C / min, and further preferably 3 to 10°C / min. By setting the heating rate to be 1°C / min or more, productivity can be ensured and excessive volatilization of the acid or solvent can be prevented. By setting the heating rate to be 12°C / min or less, the residual stress of the cured product can be relaxed. In the case of an oven capable of rapid heating, the heating is preferably performed at a heating rate of 1 to 8°C / sec from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C / sec, and still more preferably 3 to 6°C / sec.

[0268] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and further 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 the resin composition of the present invention is applied to a substrate and then dried, it is the temperature of the dried film (layer), for example, preferably starting from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0269] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and further preferably 15 to 240 minutes.

[0270] In particular, when a multilayer laminate is formed, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, further preferably 100° C. or higher, and particularly preferably 120° C. or higher from the viewpoint of interlayer adhesion. The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and further preferably 240°C or lower.

[0271] Heating can be performed in stages. As an example, the following process can be performed: heating from 25°C to 120°C at 3°C / min and maintaining at 120°C for 60 minutes, heating from 120°C to 180°C at 2°C / min and maintaining at 180°C for 120 minutes. In addition, as described in the specification of U.S. Patent No. 9159547, it is also preferred to treat while irradiating with ultraviolet rays. The properties of the film can be improved by this pretreatment process. The pretreatment process can be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment can be set as a process of more than two stages, for example, the first stage pretreatment process can be performed in the range of 100 to 150°C, and then the second stage pretreatment process can be performed in the range of 150 to 200°C. Furthermore, the heating may be followed by cooling, and the cooling rate at this time is preferably 1 to 5° C. / min.

[0272] The heating step is preferably performed in a low oxygen concentration environment by flowing an inert gas such as nitrogen, helium, or argon under reduced pressure, etc., from the viewpoint of preventing 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 in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0273] <Exposure process after development> The pattern obtained by the development step (the pattern after the rinse step when the rinse step is performed) may be subjected to a post-development exposure step of exposing the pattern after the development step instead of or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include either a heating step or a post-development exposure step. In the post-development exposure step, for example, a cyclization reaction of a polyimide precursor or the like by photosensitization of a photobase generator, a leaving reaction of an acid-decomposable group by photosensitization of a photoacid generator, and the like can be promoted. In the post-development exposure step, at least a portion of the pattern obtained in the development step may be exposed, but it is preferred that the entire pattern be exposed. The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm2 in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity. 2 , more preferably 100 to 15,000 mJ / cm 2 . The post-development exposure step can be performed, for example, using the light source in the above-mentioned exposure step, and preferably using broadband light.

[0274] <Metal layer forming step> The pattern obtained in the development step (preferably the pattern provided to at least one of the heating step and the post-development exposure step) may be provided to the metal layer forming step of forming a metal layer on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern obtained in the development step (preferably a pattern provided for at least one of the heating step and the post-development exposure step).

[0275] The metal layer is not particularly limited, and any existing metal species can be used. Examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is further preferred.

[0276] The formation method of metal layer is not particularly limited, and existing method can be applied.For example, the method described in Japanese Patent Publication No. 2007-157879, Japanese Patent Table No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7888181B2, and U.S. Patent No. 9177926B2 can be used.For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), peeling (lift off), electrolytic plating, electroless plating, etching, printing and combining these methods etc. can be considered.More specifically, the patterning method of combining sputtering, photolithography and etching, the patterning method of combining photolithography and electrolytic plating can be enumerated.As the preferred mode of plating, the electrolytic plating using copper sulfate or copper cyanide plating solution can be enumerated.

[0277] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, based on the thickest portion.

[0278] <Application> As the manufacturing method of the cured product of the present invention or the field of the cured product, the insulating film of the electronic device, the interlayer insulating film for the redistribution layer, the stress buffer film, etc. can be cited. In addition, the sealing film, the substrate material (the base film or cover layer of the flexible printed circuit board, the interlayer insulating film) or the case where a pattern is formed on the insulating film for the installation purpose of the above-mentioned can be cited. For these uses, for example, reference can be made to Science & Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Kakimoto Masaaki / Supervision, CMC Technical Library "Basics and Development of Polyimide Materials" issued in November 2011, Japan Polyimide Aromatic Polymer Research Association / Editor "Latest Polyimide Basics and Applications" NTS, August 2010, etc.

[0279] The method for producing the cured product of the present invention or the cured product of the present invention can also be used in the production of offset printing plates or screen printing plates, the use of etched parts, the production of protective varnishes and dielectric layers in electronic products, especially microelectronic products, etc.

[0280] (Laminate and method for producing laminate) The laminate of the present invention refers to a structure having a plurality of layers composed of the cured product of the present invention. The laminate is a laminate including two or more layers composed of a cured product, and may be a laminate including three or more layers. Among the two or more layers consisting of the above-mentioned cured product contained in the above-mentioned laminate, at least one layer is a layer consisting of the cured product of the present invention. From the viewpoint of suppressing the shrinkage of the cured product or the deformation of the cured product accompanying the above-mentioned shrinkage, it is also preferred that all the layers consisting of the cured product contained in the above-mentioned laminate are layers consisting of the cured product of the present invention.

[0281] That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes a step of repeating the method for producing a cured product of the present invention a plurality of times.

[0282] The laminate of the present invention preferably includes two or more layers consisting of a cured product and includes a metal layer between any of the layers consisting of the cured product. The metal layer is preferably formed by the metal layer forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on the layer composed of the cured product before performing the method for producing a cured product a plurality of times. A preferred embodiment of the metal layer forming step is as described above. As the above-mentioned laminate, for example, a laminate having a layer structure including at least three layers stacked in this order: a layer composed of a first cured product, a metal layer, and a layer composed of a second cured product is preferably used. The layer consisting of the first cured product and the layer consisting of the second cured product are preferably both layers consisting of the cured product of the present invention. The resin composition of the present invention for forming the layer consisting of the first cured product and the resin composition of the present invention for forming the layer consisting of the second cured product may be a composition having the same composition or a composition having different compositions. The metal layer in the laminate of the present invention may be preferably used as a metal wiring such as a redistribution layer.

[0283] <Lamination process> The method for producing a laminated body of the present invention preferably includes a lamination step. The lamination process is a series of processes including performing at least one of (a) a film forming process (layer forming process), (b) an exposure process, (c) a developing process, (d) a heating process, and a post-development exposure process again in sequence on the surface of a pattern (resin layer) or a metal layer. Among them, it can be a method of repeating at least one of (a) a film forming process, (d) a heating process, and a post-development exposure process. In addition, (e) a metal layer forming process can be included after at least one of (d) a heating process and a post-development exposure process. Of course, the above-mentioned drying process, etc., can also be appropriately included in the lamination process.

[0284] When the lamination process is further performed after the lamination process, a surface activation process may be further performed after the exposure process and after the heating process or after the metal layer forming process. As the surface activation process, plasma treatment is exemplified. The details of the surface activation process will be described later.

[0285] The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times. For example, the resin layer has a structure of resin layer / metal layer / resin layer / metal layer / resin layer / metal layer. The resin layer preferably has a structure of 2 or more layers and 20 or less layers, and more preferably has a structure of 2 or more layers and 9 or less layers. The composition, shape, film thickness, etc. of each of the above-mentioned layers may be the same or different.

[0286] In the present invention, it is particularly preferred that the cured product (resin layer) of the resin composition of the present invention is further formed after the metal layer is set to cover the above-mentioned metal layer. Specifically, the method of repeating the order of (a) film forming process, (b) exposure process, (c) developing process, (d) heating process and at least one of the post-exposure process, (e) metal layer forming process, or (a) film forming process, (d) heating process and at least one of the post-exposure process, (e) metal layer forming process can be cited. By alternately stacking the stacking process and the metal layer forming process of the resin composition layer (resin layer) of the present invention, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately stacked.

[0287] (Surface activation treatment process) The method for producing a laminate of the present invention preferably includes a surface activation step of performing surface activation treatment on at least a portion of the metal layer and the resin composition layer. The surface activation treatment step is usually performed after the metal layer forming step, but the metal layer forming step may be performed after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) or after the resin composition layer is subjected to the surface activation treatment step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a portion of the metal layer, and preferably on a portion or all of the region in the metal layer where the resin composition layer is formed on the surface. In this way, by performing a surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) disposed on the surface thereof can be improved. The surface activation treatment is also preferably performed on a part or all of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, the adhesion with the metal layer and the resin layer provided on the surface after the surface activation treatment can be improved. In particular, when the resin composition layer is cured, such as when negative development is performed, it is not easy to be damaged by the surface treatment, and the adhesion is easily improved. The surface activation treatment can be performed by the method described in paragraph 0415 of International Publication No. 2021 / 112189, for example. The contents are incorporated into this specification.

[0288] (Semiconductor device and method of manufacturing the same) The present invention also discloses a semiconductor device comprising the cured product or the laminate of the present invention. Furthermore, the present invention discloses a method for producing a semiconductor device including the method for producing a cured product or a method for producing a laminate according to the present invention. As a specific example of a semiconductor device in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Application Laid-Open No. 2016-027357, the contents of which are incorporated herein. Example

[0289] Hereinafter, the present invention will be further specifically described by giving examples. The materials, usage amounts, ratios, processing contents, processing sequences, etc. shown in the following examples can be appropriately changed without departing from the purpose of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are weight references.

[0290] <Method for producing polyimide precursor> <Synthesis Example 1: Synthesis of polymer A-1> 77.5 g of 4,4'-oxydiphthalic anhydride (ODPA) and 73.5 g of 4,4'-biphenyl dicarboxylic anhydride were added to a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine while stirring at room temperature (25°C). After the heat generated by the reaction ended, the mixture was naturally cooled to room temperature and further left to stand for 16 hours. Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Next, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether suspended in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. After stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour. Then, 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was obtained by filtration, thereby obtaining a reaction solution. The obtained reaction solution was added to 3 liters of ethanol to generate a precipitate consisting of a crude polymer. The generated crude polymer was filtered out and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was filtered out and then vacuum dried to obtain a powdered polymer A-1. The weight average molecular weight (Mw) of the polymer A-1 was measured to be 22,600. 1 H-NMR confirmed that the polymer A-1 contained a repeating unit represented by the following formula (A-1).

[0291] [Synthesis Examples 2 to 6: Synthesis of Polymers A-2 to A-6] Polymers A-2 to A-6 were synthesized by the same method as in Synthesis Example 1 except that the carboxylic acid dianhydride and diamine used were appropriately changed as shown in the following table. The Mw of polymer A-2 was 20,000, the Mw of polymer A-3 was 20,000, the Mw of polymer A-4 was 20,000, the Mw of polymer A-5 was 20,000, and the Mw of polymer A-6 was 20,000. 1 H-NMR confirmed that polymers A-2 to A-6 contained repeating units represented by the following formulae (A-2) to (A-6), respectively. The radical polymerizable group value of each resin is described in the "C=C value (mmol / g)" column of the following table.

[0292] [Table 1] Carboxylic dianhydride Diamine C = C value (mmol / g) A-1 X1 Y1 2.64 A-2 X2 Y4 2.09 A-3 X1 Y1 2.62 A-4 X2 Y1 2.67 A-5 X1 Y2 2.58 A-6 X1 Y3 2.97

[0293] -Carboxylic acid dianhydride- X1 to X2: compounds having the following structures. [Chemical formula 55]

[0294] -Diamine- Y1 to Y4: compounds having the following structures. [Chemical formula 56]

[0295] [Chemical formula 57] [Chemical formula 58]

[0296] <Preparation of resin composition> In each example, the components described in the following table were mixed to obtain each resin composition. In addition, in the comparative example, the components described in the following table were mixed to obtain a comparative composition. Specifically, the amounts of the components described in the table were set to the amounts (parts by mass) described in the "parts by mass" column of the table. In the comparative examples, the components described in the following table were mixed to obtain comparative compositions. In addition, the addition amount of the compound described in "other additives" was set so that the addition amount of other additives with respect to the total mass of the resin composition might become the value (ppm) described in the table. The obtained resin composition or comparative composition was filtered under pressure through a filter made of HDPE (high-density polyethylene) having a pore size of 0.2 μm. In the table, "-" indicates that the composition does not contain the corresponding component.

[0297] [Table 2]

[0298] [Table 3]

[0299] [Table 4]

[0300] The details of each component described in the table are as follows.

[0301] 〔Resin〕 Resin A-1 to Resin A-6: Polymers A-1 to A-6 obtained in the above-mentioned Synthesis Example

[0302] 〔Photopolymerization initiator〕 ·B-1 to B-6: Compounds of the following structures [Chemical formula 59]

[0303] 〔Specific compounds〕 ·C-1~C-2: Compounds of the following structures [Chemical formula 60]

[0304] [Compound D] ·D-1: Compound with the following structure [Chemical formula 61]

[0305] 〔Polymerizable compounds〕 · E-1: A compound having the following structure, wherein the subscript in brackets indicates the number of repetitions. [Chemical formula 62]

[0306] 〔Alkali-generating agent〕 F-1 to F-4: compounds of the following structures (wherein Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group) [Chemical formula 63]

[0307] [Compound G] ·G-1 to G-4: Compounds of the following structures [Chemical formula 64] ·G-5: UA-160TM (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.)

[0308] 〔Titanium compounds〕 H-1: Di(n-butyl)bis(2,4-pentanedione)titanium ·H-2: Titanium diisopropylate bis(ethyl acetoacetate) ·H-3: Isopropyl tri(dodecyl)benzenesulfonyl titanate

[0309] 〔Silane coupling agent〕 ·I-1: A compound having the following structure: wherein Et represents an ethyl group. [Chemical formula 65]

[0310] 〔Inhibitor〕 ·J-1~J-2: Compounds with the following structures [Chemical formula 66]

[0311] 〔Migration inhibitor〕 K-1 to K-4: compounds having the following structures. [Chemical formula 67]

[0312] [Other additives (compounds represented by any one of formula (UR-1) to formula (UR-3))] UR-1 to UR-3: Compounds with the following structures ·L-1: 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol ester with 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid ·L-2: A compound of the following structure. L-2 was synthesized by the method described in paragraph 0184 of Japanese Patent Publication No. 2019-206689. Specifically, in a separable flask equipped with a stirrer, a dropping funnel, and a thermometer, 30 g (0.0707 mol) of 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylene)bisphenol (trade name Tris-PA manufactured by Honshu Chemical Industry Co., Ltd.) and 47.49 g (0.177 mol) of 1,2-naphthoquinonediazide-5-sulfonyl chloride in an amount equivalent to 83.3 mol% of the OH group were stirred and dissolved in 300 g of acetone, and the flask was adjusted to 30°C in a constant temperature bath. Next, 17.9 g of triethylamine was dissolved in 18 g of acetone and placed in a dropping funnel, and then added dropwise to the flask over 30 minutes. After the addition was completed, stirring was continued for 30 minutes, and then hydrochloric acid was added dropwise, and the reaction was completed by stirring for 30 minutes. After that, the reactant was filtered to remove triethylamine hydrochloride. 1640 g of pure water and 30 g of hydrochloric acid were mixed and stirred in a beaker, and the filtrate was added dropwise to the mixture while stirring to obtain a precipitate. After washing and filtering the precipitate, it was dried at 40° C. under reduced pressure for 48 hours to obtain L-2. [Chemical formula 68]

[0313] 〔Solvent〕 ·NMP: N-methyl-2-pyrrolidone EL: Ethyl lactate

[0314] <Chemical resistance test of cured film of resin composition (evaluation of chemical resistance)> A chemical resistance test was carried out using the composition. The resin composition or comparative composition prepared in each embodiment or comparative example was coated on a silicon wafer to form a coating film. In the example recorded as "SP" in the "Coating" column of the table, a spin coating method was used as a coating method. In addition, in the example recorded as "SL" in the "Coating" column of the table, a slit coating method was used as a coating method. The film thickness was adjusted so that the film thickness of the resin composition layer described later reached 15 μm. Next, the silicon wafer formed with each coating film was heated at 100° C. for 300 seconds using a hot plate to form a resin composition layer. Next, the resin composition layer was exposed. For the examples recorded as "i-ray" in the "Exposure" column of the table, exposure was performed using a broadband exposure machine (Ushio Inc. manufactured: UX-1000SN-EH01) and an i-ray filter, and in the examples recorded as "LDI", exposure was performed using a direct exposure device (ADTEC DE-6UH III). Exposure was performed in a manner of full-surface exposure, and the exposure amount was set to 400 mJ / cm 2 . Next, the exposed resin composition layer was developed for 34 seconds at 23°C using cyclopentanone. After the above development, in the example recorded as "PGMEA" in the "Rinsing" column of the table, PGMEA (propylene glycol monomethyl ether acetate) was used, and in the example recorded as "Rinsing Liquid A", a mixed solution of PGMEA:N-[3-(Dimethylamino)propyl]methacrylamide(N-[3-(dimethylamino)propyl]methacrylamide) = 90:10 (mass ratio) was used for rinsing for 30 seconds. In addition, in the example recorded as "Yes" in the "Post-treatment" column of the table, after rinsing, the post-treatment liquid was swirl-covered and immersed in the pattern, and waited for 60 seconds, and then spin-dried to remove the post-treatment liquid. As the post-treatment liquid, a mixed liquid of PGMEA / N-[3-(Dimethylamino)propyl]methacrylamide / GBL=92.5 / 5 / 2.5 (mass ratio) was used. Next, a clean oven (manufactured by Koyo, CLH-21) was used to heat treat for 3 hours at 230°C under N2 environment to obtain a cured film of the resin composition or the comparative composition. The obtained cured film was immersed in the following chemicals under the following immersion conditions, and the residual film rate was calculated from the film thickness before and after immersion (film thickness after immersion / film thickness before immersion × 100 (%)). The evaluation was performed according to the following evaluation criteria, and the evaluation results were recorded in the "Chemical Resistance" column. It can be said that the higher the residual film rate, the better the chemical resistance. Chemical: A 90:10 mixture of dimethyl sulfoxide (DMSO) and a 25 mass % aqueous solution of tetramethylammonium hydroxide (TMAH) Immersion conditions: 15 minutes at 75°C -Evaluation Criteria- A: The residual film rate is 90% or more. B: The residual film ratio is 80% or more and less than 90%. C: The residual film ratio is 60% or more and less than 80%. D: The residual film ratio is 40% or more and less than 60%. E: The residual film ratio is less than 40% or the cured film is peeled off in the chemical resistance test.

[0315] <Measurement of Tg (Glass Transition Temperature) of Cured Film of Resin Composition (Evaluation of Heat Resistance)> The resin composition or comparative composition prepared in each embodiment or comparative example was coated on a silicon wafer to form a coating film. In the example recorded as "SP" in the "Coating" column of the table, spin coating was used as the coating method. And, in the example recorded as "SL" in the "Coating" column of the table, slit coating was used as the coating method. The film thickness was adjusted so that the film thickness of the resin composition layer described later reached 15μm. Then, a heating plate was used at 100°C for 300 seconds to form a resin composition layer. Then, the resin composition layer was exposed. For the example recorded as "i-ray" in the "Exposure" column of the table, a broadband exposure machine (manufactured by USHIO INC.: UX-1000SN-EH01) and an i-ray filter were used for exposure, and in the example recorded as "LDI", a direct exposure device (ADTEC DE-6UH III) was used for exposure. The exposure amount was set to 400mJ / cm 2. During exposure, a mask with a negative pattern of 2 mm in width and 50 mm in length was used for exposure. Next, the resin composition layer was developed at 23°C for 34 seconds using cyclopentanone. After the above development, in the example recorded as "PGMEA" in the "Rinsing" column of the table, PGMEA (propylene glycol monomethyl ether acetate) was used, and in the example recorded as "Rinsing Liquid A", a mixed liquid of PGMEA:N-[3-(Dimethylamino)propyl]methacrylamide (N-[3-(dimethylamino)propyl]methacrylamide) = 90:10 (mass ratio) was used for rinsing for 30 seconds. In the example recorded as "Yes" in the "Post-treatment" column of the table, after rinsing, the post-treatment liquid was swirl-covered and immersed in the pattern, and waited for 60 seconds, and then spin-dried to remove the post-treatment liquid. As a post-treatment liquid, a mixed solution of PGMEA / N-[3-(Dimethylamino)propyl]methacrylamide / GBL=92.5 / 5 / 2.5 (mass ratio) was used. Next, a clean oven (manufactured by Koyo, CLH-21) was used to perform a heat treatment at 230°C for 3 hours under a N2 environment to obtain a cured film of the resin composition or the comparative composition having a width of 2 mm and a length of 50 mm. The cured film was peeled off by immersing it in a 2% by mass hydrofluoric acid aqueous solution, and a separated cured film thin film having a width of 2 mm and a length of 50 mm was obtained by washing with water. For the cured film thin film, Tg measurement was performed using a dynamic viscoelasticity measuring device (manufactured by TA Instruments: DMA 850). The measurement was carried out under the conditions of chuck distance = 20 mm, frequency 1 Hz, heating rate 5°C / min and heating from room temperature (25°C) to 300°C, and the point where the value of Tanδ(E" / E'), the ratio of the storage modulus E' to the loss modulus E" obtained in the measurement, reached the maximum was defined as Tg. It can be said that the higher the Tg, the less likely the cured film is to deform even at high temperatures, and the better the heat resistance. The heat resistance was evaluated according to the following evaluation criteria, and the evaluation results are recorded in the "Heat Resistance" column of the table. -Evaluation Criteria- A: Tg is 230°C or higher. B: Tg is 200°C or higher and lower than 230°C. C: Tg is less than 200°C.

[0316] <Measurement of elongation at break of cured film of resin composition> In each embodiment or comparative example, a cured film thin film with a width of 2 mm and a length of 50 mm made by the same method as the above-mentioned Tg measurement was used, and a tensile measuring machine (manufactured by INSTRON: INSTRON5965) was used to stretch the cured film thin film along the length direction under the conditions of a measuring temperature of 23°C, a distance between chucks of 20 mm, and a stretching speed of 5 mm / min, and the elongation at break was measured. Six cured film thin films were used for each embodiment or comparative example for measurement, and the arithmetic mean of the elongation at break values ​​(%) of the three points with the largest elongation at break was calculated, and the arithmetic mean was used as the index value. The evaluation results are recorded in the "elongation at break" column of the table. It can be said that the larger the above index value, the better the mechanical properties of the cured product in terms of elongation at break. -Evaluation Criteria- A: The above index value is 60% or more. B: The above index value is 55% or more and less than 60%. C: The above index value is 50% or more and less than 55%. D: The above index value is less than 50%.

[0317] <Humidity resistance reliability test of cured film of resin composition (evaluation of humidity resistance)> For a silicon wafer with wiring formed on the entire surface by plating, a copper wiring with a line and space ratio of 10:10 and a height of 5 μm is formed, and the prepared resin composition is applied to the surface of the silicon wafer with the above wiring to form a coating film. In the example recorded as "SP" in the "Coating" column of the table, a spin coating method is used as a coating method. And, in the example recorded as "SL" in the "Coating" column of the table, a slit coating method is used as a coating method. The film thickness is adjusted so that the film thickness of the resin composition layer described later reaches 15 μm. Next, a heating treatment was performed at 100° C. for 300 seconds using a hot plate to form a resin composition layer. Next, for the resin composition layer, for the example described as "i-ray" in the "Exposure" column of the table, a broadband exposure machine (manufactured by USHIO INC.: UX-1000SN-EH01) and an i-ray filter were used for exposure, and for the example described as "LDI", a direct exposure device (ADTEC DE-6UH III) was used for exposure. The exposure was performed in a manner of full-surface exposure. The exposure amount was set to 400 mJ / cm 2. Next, the exposed resin composition layer was developed for 34 seconds at 23°C using cyclopentanone. After the above development, in the example recorded as "PGMEA" in the "Rinsing" column of the table, PGMEA (propylene glycol monomethyl ether acetate) was used, and in the example recorded as "Rinsing Liquid A", a mixed solution of PGMEA:N-[3-(Dimethylamino)propyl]methacrylamide (N-[3-(dimethylamino)propyl]methacrylamide) = 90:10 (mass ratio) was used for rinsing for 30 seconds. In the example recorded as "Yes" in the "Post-treatment" column of the table, after rinsing, the post-treatment liquid was swirled to immerse the pattern, wait for 60 seconds, and then spin dried to remove the post-treatment liquid. As the post-treatment liquid, a mixed liquid of PGMEA / N-[3-(Dimethylamino)propyl]methacrylamide / GBL=92.5 / 5 / 2.5 (mass ratio) was used. Next, a heat treatment was carried out at 230°C for 3 hours in a clean oven (manufactured by Koyo) under a N2 environment to obtain a cured film of the resin composition. The obtained cured film was placed in an environmental testing device (manufactured by HIRAYAMA Manufacturing Corporation: HASTEST model PC-R8D), and the appearance before and after the humidity resistance reliability test was compared under high temperature and high humidity conditions of temperature = 121°C and humidity = 100% with a treatment time = 250 hours. In addition, a cured film of the resin composition or comparative composition with a width of 2 mm and a length of 50 mm was obtained by the same method as the above-mentioned Tg measurement. The obtained cured film was put into an environmental testing device (manufactured by HIRAYAMA Manufacturing Corporation: HASTEST model PC-R8D), and a humidity resistance reliability test was carried out under high temperature and high humidity conditions of temperature = 121°C and humidity = 100% with a treatment time = 250 hours. The cured film was stripped by immersing it in a 2% by mass hydrofluoric acid aqueous solution, and a separated cured film film with a width of 2 mm and a length of 50 mm was obtained by washing with water. For the cured film after the above-mentioned humidity resistance reliability test, the elongation at break was measured by the method described above. For the elongation at break before and after the humidity resistance reliability test, the change rate of the elongation at break represented by the following formula was calculated and evaluated according to the following evaluation criteria. The evaluation results are recorded in the "humidity resistance" column of the table. No discoloration was found in the copper wiring, and no decrease in insulation between the copper wirings was found. It can be said that the smaller the change rate of the elongation at break, the better the humidity resistance. Change rate of elongation at break (%) = | index value of elongation at break before humidity resistance reliability test − index value of elongation at break after humidity resistance reliability test | / index value of elongation at break before humidity resistance reliability test × 100 -Evaluation Criteria- A: No discoloration was observed in the copper wiring, and the rate of change in the above-mentioned elongation at break was less than 10%. B: No discoloration was observed in the copper wiring, and the rate of change in the elongation at break was 10% or more. C: Discoloration of the copper wiring was observed, a decrease in insulation between the copper wirings was not observed, and the change in elongation at break before and after the humidity resistance test was 10% or more. D: A short circuit of the wiring occurs when the copper wiring is conducted, and the change in the elongation at break before and after the humidity resistance test is 10% or more.

[0318] <Evaluation of sensitivity of resin composition> In each embodiment or comparative example, the prepared resin composition is coated on a silicon wafer to form a coating film. In the example recorded as "SP" in the "Coating" column of the table, spin coating is used as the coating method. And, in the example recorded as "SL" in the "Coating" column of the table, slit coating is used as the coating method. Then, a heating plate was used to perform a heating treatment at 100°C for 300 seconds to form a resin composition layer. Then, the resin composition layer was exposed to a residual pattern of 100 μm square. For the example recorded as "i-ray" in the "Exposure" column of the table, an i-ray stepper (Canon Inc. manufactured: FPR-3000i5) was used for exposure, and in the example recorded as "LDI", a direct exposure device (ADTEC DE-6UH III) was used for exposure. The exposure amount was increased from 50 mJ / cm 2 Up to 800mJ / cm 2 At 50mJ / cm 2The exposure was performed by changing the scale. Next, the resin composition layer was developed for 34 seconds at 23°C using cyclopentanone. After the above development, in the example recorded as "PGMEA" in the "Rinsing" column of the table, PGMEA (propylene glycol monomethyl ether acetate) was used, and for the example recorded as "Rinsing Liquid A", a mixed liquid of PGMEA:N-[3-(Dimethylamino)propyl]methacrylamide(N-[3-(dimethylamino)propyl]methacrylamide)=90:10 (mass ratio) was used for rinsing for 30 seconds. In addition, in the example recorded as "Yes" in the "Post-treatment" column of the table, after rinsing, the post-treatment liquid was swirl-covered and immersed in the pattern, and waited for 60 seconds, and then spin-dried to remove the post-treatment liquid. As the post-treatment liquid, a mixed solution of PGMEA / N-[3-(Dimethylamino)propyl]methacrylamide / GBL=92.5 / 5 / 2.5 (mass ratio) was used. The residual film rate was calculated from the film thickness before and after development (%, film thickness after development / film thickness before development × 100). It can be said that the smaller the exposure amount at which the residual film rate reaches 80% or more, the higher the sensitivity. In addition, the higher the sensitivity, the more capable it is to form a pattern with a low exposure amount, so it is preferred to reduce the lead time during manufacturing. The evaluation is performed according to the following evaluation criteria, and the evaluation results are recorded in the "Sensitivity" column. -Evaluation Criteria- A: The exposure dose for the residual film rate to reach more than 80% is 300mJ / cm 2 the following. B: The exposure dose is greater than 300mJ / cm2 when the residual film rate reaches more than 80% 2 And less than 800mJ / cm 2 . C: The exposure dose for the residual film rate to reach more than 80% is 800mJ / cm 2 above.

[0319] <Pattern forming ability after the resin composition is left to stand> In each example or comparative example, a photomask having a square non-exposure portion of 10 μm square was used, and the coating film formation, heating treatment (drying treatment) and pattern exposure were performed under the same conditions as the above sensitivity evaluation. The exposure amount was set to 400 mJ / cm 2. One week after exposure, the exposed resin composition layer was developed for 34 seconds at 23°C using cyclopentanone. After the above development, in the example recorded as "PGMEA" in the "Rinsing" column of the table, PGMEA (propylene glycol monomethyl ether acetate) was used, and in the example recorded as "Rinsing Liquid A", a mixed liquid of PGMEA:N-[3-(Dimethylamino)propyl]methacrylamide (N-[3-(dimethylamino)propyl]methacrylamide) = 90:10 (mass ratio) was used for rinsing for 30 seconds. In the example recorded as "Yes" in the "Post-treatment" column of the table, after rinsing, the post-treatment liquid was spun on the pattern and waited for 60 seconds, and then spin dried to remove the post-treatment liquid. As a post-treatment liquid, a mixed solution of PGMEA / N-[3-(Dimethylamino)propyl]methacrylamide / GBL=92.5 / 5 / 2.5 (mass ratio) was used. Next, a clean oven (manufactured by Koyo, CLH-21) was used to perform a heat treatment at 230°C for 3 hours under a N2 environment to obtain a cured film of the resin composition or the comparative composition. The hole pattern of the obtained cured film was observed and the rectangularity of the pattern was evaluated. It can be said that the closer each side of each pattern is to a straight line, the better the rectangularity of the pattern. The better the rectangularity of the pattern, the more it can be exposed with good mask reproducibility. Good mask reproducibility in development one week after exposure is related to a good manufacturing margin, so it is preferred. Here, it can be said that the better the rectangularity of the pattern, the better the pattern forming ability after standing. The evaluation is performed according to the following evaluation criteria, and the evaluation results are recorded in the "Pattern forming ability after standing" column of the table. -Evaluation Criteria- A: The base of the pattern is a quadrilateral and the sides remain linear. B: The base of the pattern is roughly a quadrilateral, but there are arcs drawn on each side. C: The bottom of the pattern is round.

[0320] From the above results, it is understood that the cured product formed from the resin composition of the present invention has excellent chemical resistance. The comparative composition of Comparative Example 1 does not contain the specific compound. It is found that the chemical resistance of this comparative composition is poor.

[0321] <Example 101> The resin composition used in Example 1 was applied in layers to the copper thin layer surface of the resin substrate having a copper thin layer formed on the surface by spin coating, and after drying at 100°C for 5 minutes to form a photosensitive film with a film thickness of 20 μm, a stepper (manufactured by NIKON CORPORATION, NSR1505 i6) was used for exposure. Through a mask (a binary mask with a pattern of 1:1 line and space and a line width of 10 μm), exposure was performed at a wavelength of 365 nm. After the above exposure, the layer pattern was obtained by developing with cyclopentanone for 2 minutes and rinsing with PGMEA for 30 seconds. Next, the temperature was raised at a rate of 10° C. / min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 180 minutes to form a redistribution layer interlayer insulating film. The redistribution layer interlayer insulating film had excellent insulation properties. Furthermore, as a result of manufacturing a semiconductor device using the interlayer insulating film for a redistribution layer, it was confirmed that the semiconductor device operated normally.

Claims

1. A photosensitive resin composition comprising: A polyimide precursor having a free radical polymerizable group; photopolymerization initiator; and Compounds with a coumarin skeleton.

2. The photosensitive resin composition according to claim 1, comprising a compound represented by the following formula (C-1) as the compound having a coumarin skeleton, [Chemical formula 1] 3 . The photosensitive resin composition according to claim 1 , comprising an oxime ester group-containing compound as the photopolymerization initiator.

4. The photosensitive resin composition according to claim 1 or 2, further comprising a compound D represented by the following formula (D): [Chemical formula 2] In formula (D), Ar represents a monovalent aromatic group which may have a substituent, and L D1 Each independently represents a divalent linking group, n1 represents 1 or 2, R D1 Each independently represents a hydrogen atom or a monovalent organic group, n2 represents 0 or 1, and the total of n1 and n2 is 2.

5. The photosensitive resin composition according to claim 4, comprising a compound represented by the following (D-1) as the compound D, [Chemical formula 3] The photosensitive resin composition according to claim 1 or 2, further comprising an organic titanium compound. 7 . The photosensitive resin composition according to claim 6 , comprising di(n-butoxide)bis(2,4-pentanedione)titanium or diisopropyloxide bis(ethyl acetoacetate)titanium as the organic titanium compound.

8. The photosensitive resin composition according to claim 1 or 2, wherein The total content of the compounds represented by the following formula (UR-1), formula (UR-2) or formula (UR-3) is 1 to 500 ppm relative to the content of the polyimide precursor. [Chemical formula 4] In formula (UR-1), formula (UR-2) or formula (UR-3), R 11 and R 12 Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R 21 and R 22 Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R 31 and R 32 Each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R 33 It represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent. 9 . The photosensitive resin composition according to claim 1 , further comprising an alkali generator.

10. The photosensitive resin composition according to claim 9, comprising a compound represented by the following formula (F-1) or a compound represented by the following formula (F-2) as the base generator, [Chemical formula 5] 11 . The photosensitive resin composition according to claim 1 , further comprising a compound G containing at least one bond selected from the group consisting of a urea bond and a urethane bond.

12. The photosensitive resin composition according to claim 11, further comprising, as the compound G, at least one compound selected from the group consisting of compounds represented by any one of formulas (G-1) to (G-3), [Chemical formula 6] 13. The photosensitive resin composition according to claim 1 or 2, wherein The polyimide precursor contains a structure represented by the following formula (X-1) or formula (X-2), [Chemical formula 7] 14. The photosensitive resin composition according to claim 1 or 2, wherein The polyimide precursor includes a structure represented by any one of the following formulas (Y-1) to (Y-4), [Chemical formula 8] 15. The photosensitive resin composition according to claim 1 or 2, wherein The polyimide precursor contains a structure represented by the following formula (X-2) and a structure represented by the following formula (Y-4), [Chemical formula 9] 16 . The photosensitive resin composition according to claim 1 , which is used for forming an interlayer insulating film for a redistribution layer.

17. A cured product obtained by curing the resin composition according to claim 1 or 2. 18 . A laminate comprising two or more layers consisting of the cured product according to claim 17 , and comprising a metal layer between any of the layers consisting of the cured product.

19. A method for producing a cured product, comprising a film forming step of applying the resin composition according to claim 1 or 2 to a substrate to form a film.

20. The method for producing a cured product according to claim 19, comprising: An exposure step of selectively exposing the film to light; and In the development step, the film is developed using a developer to form a pattern.

21. The method for producing a cured product according to claim 19, comprising a heating step of heating the film at 50 to 450°C.

22. A method for producing a laminate, comprising the method for producing a cured product according to claim 19.

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

24. A semiconductor device comprising the cured product according to claim 17.

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