Method for producing film, photosensitive resin composition, method for producing cured product, cured product, and laminate

Abstract

The present invention provides a method for producing a film, a method for producing a cured product using a photosensitive resin composition, a cured product obtained by curing the photosensitive resin composition, and a laminate comprising the cured product. The method for producing a film comprises: (A) a resin; (C) a photopolymerization initiator; (D) at least one radical polymerization inhibitor selected from the group consisting of (D-1) compounds having radicals in the molecule and (D-2) compounds having no radicals in the molecule and having a molecular weight of 270 or more; and (E) a solvent, after the photosensitive resin composition is applied to a substrate, the method includes a step of drying at a pressure of 5000 Pa or less, or a step of drying at a first temperature; and a step for drying at a second temperature higher than the first temperature at a pressure within the range of + / -10% of the pressure in the step for drying at the first temperature, or a step for drying at 90 DEG C or higher for more than five minutes as a drying step.

Description

Technical Field

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

[0002] As a new packaging technology in the manufacture of semiconductor devices, FOPLP (Fan-Out Panel Level Packaging) has attracted much attention for manufacturing packages on substrates larger than wafers and reducing the manufacturing cost of each package. In the film forming method of a panel such as FOPLP, a composition (coating liquid) for forming a film may be applied by a slit coating method.

[0003] Patent Document 1 describes a method of manufacturing a film by applying a composition containing a polyimide precursor and at least two solvents having different solubility in the polyimide precursor onto a member by a slit coating method.

[0004] In addition, Patent Document 2 describes a lithographic printing plate precursor, which is composed of an image recording layer provided on a support body and containing a free radical polymerization initiator, a free radical polymerizable compound, and a multifunctional polymerization inhibitor having two or more free radical capturing sites in the molecule that directly bond to free radicals to form covalent bonds.

[0005] Previous technical literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2019 / 163860

[0008] Patent Document 2: International Publication No. 2014 / 045783 Summary of the invention

[0009] Technical issues to be solved by the invention

[0010] It is known that in order to reduce the viscosity of the coating liquid in order to impart suitability in slit coating, soft baking is performed after vacuum (reduced pressure) drying in the drying step of the coating film after coating.

[0011] However, the present inventors have studied and found that when a film produced by a conventional film production method is exposed and developed to form a pattern, there is room for improvement in terms of resolution and residues generated in unexposed portions.

[0012] An object of the present invention is to provide a method for producing a film having excellent resolution and in which residues are less likely to be generated in unexposed portions.

[0013] Furthermore, the present invention aims to provide a photosensitive resin composition capable of forming a film having excellent resolution and being less likely to produce residue in unexposed portions, a method for producing a cured product using the photosensitive resin composition, a cured product obtained by curing the photosensitive resin composition, and a laminate containing the cured product.

[0014] Means for solving technical problems

[0015] Hereinafter, examples of representative embodiments of the present invention will be described. [1]

[0017] A method for manufacturing a film, comprising:

[0018] containing (A) a resin;

[0019] (C) a photopolymerization initiator;

[0020] (D) a radical polymerization inhibitor which is at least one compound selected from (D-1) a compound having a free radical in the molecule and (D-2) a compound having no free radical in the molecule and having a molecular weight of 270 or more; and

[0021] (E) Solvent

[0022] After the photosensitive resin composition is coated on the substrate,

[0023] The drying process is performed at a pressure of 5000 Pa or less. [2]

[0025] A method for manufacturing a film, comprising:

[0026] containing (A) a resin;

[0027] (C) a photopolymerization initiator;

[0028] (D) a radical polymerization inhibitor which is at least one compound selected from (D-1) a compound having a free radical in the molecule and (D-2) a compound having no free radical in the molecule and having a molecular weight of 270 or more; and

[0029] (E) Solvent

[0030] After the photosensitive resin composition is coated on the substrate,

[0031] A step of drying at a first temperature; and a step of drying at a second temperature higher than the first temperature at a pressure within a range of ±10% of the pressure in the step of drying at the first temperature. [3]

[0033] A method for producing a film, comprising only:

[0034] containing (A) a resin;

[0035] (C) a photopolymerization initiator;

[0036] (D) a radical polymerization inhibitor which is at least one compound selected from (D-1) a compound having a free radical in the molecule and (D-2) a compound having no free radical in the molecule and having a molecular weight of 270 or more; and

[0037] (E) Solvent

[0038] After the photosensitive resin composition is coated on the substrate,

[0039] The drying step is a step of drying at 90° C. or higher for more than five minutes. [4]

[0041] The method for producing a film according to any one of [1] to [3], wherein

[0042] The photosensitive resin composition satisfies at least one of the following (i) and (ii).

[0043] (i) Containing (B-1) a radical polymerizable compound

[0044] (ii) The above (A) contains a radical polymerizable site [5]

[0046] The method for producing a film according to any one of [1] to [4], wherein

[0047] The above-mentioned (A) is at least one resin selected from the group consisting of polyimide and a polyimide precursor. [6]

[0049] The method for producing a film according to any one of [1] to [5], wherein

[0050] The above-mentioned (A) contains a repeating unit represented by the following formula (2).

[0051] [Chemical formula 1]

[0052]

[0053] In formula (2), A 1 and A 2 Each independently represents an oxygen atom or -NH-, R 111 Represents a divalent organic group, R 115 Represents a 4-valent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group. 113 and R114 At least one of them has a group represented by the following formula (III).

[0054] [Chemical formula 2]

[0055]

[0056] In formula (III), R 200 represents a hydrogen atom, methyl, ethyl or hydroxymethyl, and * represents the bonding position with other structures. 201 It represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group or a polyalkyleneoxy group. [7]

[0058] The method for producing a film according to any one of [1] to [6], wherein

[0059] The molecular weight of the above-mentioned (D-2) is 700 or more. [8]

[0061] The method for producing a film according to any one of [1] to [7], wherein

[0062] The molecular weight of the above-mentioned (D-1) is 160 or more. [9]

[0064] The method for producing a film according to any one of [1] to [8], wherein

[0065] The solid content concentration of the photosensitive resin composition is 35% by mass or less.

[10]

[0067] The method for producing a film according to any one of [1] to [9], wherein

[0068] The surface of the substrate contains Cu.

[11]

[0070] The method for producing a film according to [1], wherein

[0071] The temperature in the step of drying under the pressure of 5000 Pa or less is 35° C. or more and 80° C. or less.

[12]

[0073] A photosensitive resin composition, comprising:

[0074] (A) resin;

[0075] (C) a photopolymerization initiator;

[0076] (D) a radical polymerization inhibitor which is at least one compound selected from (D-1) a compound having a free radical in the molecule and (D-2) a compound having no free radical in the molecule and having a molecular weight of 270 or more; and

[0077] (E) Solvent.

[13]

[0079] The photosensitive resin composition as described in

[12] , wherein

[0080] The photosensitive resin composition satisfies at least one of the following (i) and (ii).

[0081] (i) Containing (B-1) a radical polymerizable compound

[0082] (ii) The above (A) contains a radical polymerizable site

[14]

[0084] The photosensitive resin composition according to

[12] or

[13] , wherein

[0085] The above-mentioned (A) is at least one resin selected from the group consisting of polyimide and a polyimide precursor.

[15]

[0087] The photosensitive resin composition according to any one of

[12] to

[14] , wherein

[0088] The above-mentioned (A) contains a repeating unit represented by the following formula (2).

[0089] [Chemical formula 3]

[0090]

[0091] In formula (2), A 1 and A 2 Each independently represents an oxygen atom or -NH-, R 111 Represents a divalent organic group, R 115 Represents a 4-valent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group. 113 and R 114 At least one of them has a group represented by the following formula (III).

[0092] [Chemical formula 4]

[0093]

[0094] In formula (III), R 200represents a hydrogen atom, methyl, ethyl or hydroxymethyl, and * represents the bonding position with other structures. 201 It represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group or a polyalkyleneoxy group.

[16]

[0096] The photosensitive resin composition according to any one of

[12] to

[15] , wherein

[0097] The molecular weight of the above-mentioned (D-2) is 700 or more.

[17]

[0099] The photosensitive resin composition according to any one of

[12] to

[16] , wherein

[0100] The molecular weight of the above-mentioned (D-1) is 160 or more.

[18]

[0102] The photosensitive resin composition according to any one of

[12] to

[17] , wherein

[0103] The solid content concentration of the photosensitive resin composition is 35% by mass or less.

[19]

[0105] The photosensitive resin composition according to any one of

[12] to

[18] , which is used for forming an interlayer insulating film for a redistribution layer.

[20]

[0107] A method for manufacturing a solidified product, comprising:

[0108] A step of applying the photosensitive resin composition described in any one of

[12] to

[19] on a substrate and drying the composition under reduced pressure to form a film;

[0109] An exposure step of selectively exposing the film; and

[0110] In the development step, the film exposed in the exposure step is developed using a developer to form a pattern. [twenty one]

[0112] A cured product obtained by curing the photosensitive resin composition according to any one of

[12] to

[19] . [twenty two]

[0114] A laminate comprising two or more layers consisting of the cured product according to

[21] , wherein a metal layer is provided between any of the layers consisting of the cured product.

[0115] Effects of the Invention

[0116] According to the present invention, it is possible to provide a method for producing a film having excellent resolution and in which residues are less likely to be generated in unexposed portions.

[0117] Furthermore, according to the present invention, there can be provided a photosensitive resin composition capable of forming a film having excellent resolution and being less likely to produce residue in unexposed portions, a method for producing a cured product using the photosensitive resin composition, a cured product formed by curing the photosensitive resin composition, and a laminate containing the cured product. DETAILED DESCRIPTION

[0118] Hereinafter, the main embodiments of the present invention will be described. In addition, the present invention is not limited to the embodiments explicitly described.

[0119] In the present specification, a numerical range expressed by the symbol “to” means a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit, respectively.

[0120] In the present specification, the term "step" includes not only independent steps but also steps that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.

[0121] In the marking of groups (atomic groups) in this specification, the marking not marked with substitution and unsubstituted includes groups (atomic groups) without substitution and also includes 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).

[0122] 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 rays represented by excimer lasers, extreme ultraviolet rays (EUV rays), X-rays, and electron beams.

[0123] 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”.

[0124] 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.

[0125] In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent. In addition, in this specification, the solid content concentration refers to the mass percentage of other components excluding the solvent relative to the total mass of the composition.

[0126] In this specification, as long as there is no special description, weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC) method, defined as polystyrene conversion value. In this specification, about weight average molecular weight (Mw) and number average molecular weight (Mn), for example, can be obtained by using HLC-8220GPC (TOSOH CORPORATION system), and guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgelSuper HZ2000 (more than TOSOH CORPORATION system) are connected in series and used as column. As long as there is no special description, these molecular weights are measured using THF (tetrahydrofuran) as eluent. Wherein, when solubility is low, when THF is not suitable as eluent, NMP (N- methyl -2- pyrrolidone) can also be used. Furthermore, unless otherwise specified, a UV ray (ultraviolet ray) detector with a wavelength of 254 nm was used for detection in GPC measurement.

[0127] In this specification, about the positional relationship of each layer constituting the laminate, when it is recorded as "up" or "down", as long as there are other layers on the upper side or lower side of the layer that becomes the benchmark in the multiple layers concerned. That is, the third layer or the third element can be further 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 these up and down directions is for convenience in this specification, and in a practical manner, the "up" direction in this specification can also be different from the vertical direction.

[0128] In this specification, as each component contained in the composition, the composition may contain two or more compounds belonging to the component unless otherwise specified. In addition, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds belonging to the component.

[0129] In this specification, unless otherwise specified, the temperature is 23° C., the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0130] In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0131] [Photosensitive resin composition]

[0132] First, the photosensitive resin composition (also referred to as “resin composition”) of the present invention will be described.

[0133] The photosensitive resin composition of the present invention contains:

[0134] Containing (A) resin;

[0135] (C) a photopolymerization initiator;

[0136] (D) a radical polymerization inhibitor which is at least one compound selected from (D-1) a compound having a free radical in the molecule and (D-2) a compound having no free radical in the molecule and having a molecular weight of 270 or more; and

[0137] (E) Solvent.

[0138] The resin composition of the present invention is preferably used to form a photosensitive film for exposure and development, and is preferably used to form a film for exposure and development using a developer containing an organic solvent.

[0139] 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.

[0140] The resin composition of the present invention is preferably a negative photosensitive resin composition. The negative photosensitive resin composition is a photosensitive resin composition for forming a negative developing photosensitive film.

[0141] 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.

[0142] 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.

[0143] According to the resin composition of the present invention, a film having excellent resolution and hardly generating residue in unexposed portions can be formed.

[0144] The mechanism by which the above effects are obtained is not clear, but is presumed to be as follows.

[0145] In conventional resin compositions, it is believed that the polymerization inhibitor contained in the resin composition is easily volatilized under reduced pressure, and thus is likely to cause dark polymerization of the polymerizable compound, resulting in reduced resolution or residues in the unexposed portion. In the present invention, it is believed that a compound that is not easily volatilized and has an effect even under reduced pressure is used as a polymerization inhibitor, thereby being able to form a film with excellent resolution and less likely to generate residues in the unexposed portion.

[0146] Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

[0147] <(A) Resin>

[0148] The resin composition of the present invention contains (A) a resin (also simply referred to as “resin”).

[0149] The resin is not particularly limited, but is preferably at least one resin (specific resin) selected from cyclized resins and precursors thereof.

[0150] The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.

[0151] In the present invention, the "main chain" refers to the relatively longest bond chain in the resin molecule, and the "side chain" refers to the bond chains other than the main chain.

[0152] Examples of the cyclized resin include polyimide, polybenzoxazole, and polyamideimide.

[0153] The precursor of the cyclized resin is a resin whose chemical structure changes by external stimulation to become a cyclized resin, preferably a resin whose chemical structure changes by heat to become a cyclized resin, and more preferably a resin that forms a ring structure by a ring-closing reaction using heat.

[0154] Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor.

[0155] That is, the resin composition preferably contains, as the specific resin, at least one resin selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, a polybenzoxazole precursor, polyamideimide, and a polyamideimide precursor.

[0156] The resin composition preferably contains at least one resin selected from the group consisting of polyimide and a polyimide precursor.

[0157] The specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group.

[0158] When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator, more preferably contains a radical polymerization initiator and a radical crosslinking agent. A sensitizer may be further contained as needed. For example, a negative photosensitive film is formed from such a resin composition.

[0159] Furthermore, the specific resin may have a polarity conversion group such as an acid-decomposable group.

[0160] When the specific resin has an acid-decomposable group, the resin composition preferably contains a photoacid generator. For example, a chemically amplified positive photosensitive film or a negative photosensitive film is formed from such a resin composition.

[0161] 〔Polyimide precursor〕

[0162] The type and the like of the polyimide precursor are not particularly limited, but it is preferred that the polyimide precursor contain a repeating unit represented by the following formula (2).

[0163] [Chemical formula 5]

[0164]

[0165] 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 4-valent 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.

[0166] A in formula (2) 1 and A 2 Each independently represents an oxygen atom or -NR z -.

[0167] R z represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.

[0168] A 1 and A 2 It is preferably an oxygen atom or -NH-, and more preferably an oxygen atom.

[0169] R in formula (2) 111Represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, preferably an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a group 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 in the ring member of the cyclic aliphatic group and the aromatic group may be substituted with a group containing a heteroatom. 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. The preferred ranges are as described above.

[0170] R 111 It 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.

[0171] 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 in 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.

[0172] [Chemical formula 6]

[0173]

[0174] In the formula, A represents a single bond or a divalent connecting 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-.

[0175] In the formula, * indicates the bonding site with other structures.

[0176] Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 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;

[0177] 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.

[0178] Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0179] 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.

[0180] From the viewpoint of the flexibility of the obtained organic film, R 111 Preferably, it is represented by -Ar-L-Ar-. Wherein, 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.

[0181] 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.

[0182] [Chemical formula 7]

[0183]

[0184] 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 position to a nitrogen atom in formula (2).

[0185] 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).

[0186] [Chemical formula 8]

[0187]

[0188] In formula (61), R 57 and R 59 Each independently represents a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding position to a nitrogen atom in formula (2).

[0189] 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 can be used alone or in combination of two or more.

[0190] R in formula (2) 115 represents a tetravalent organic group. 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 formula (6), * independently represents a bonding site with other structures.

[0191] [Chemical formula 9]

[0192]

[0193] In formula (5), R 112It is a single bond or a divalent connecting 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-.

[0194] 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.

[0195] It is preferable that tetracarboxylic dianhydride is represented by the following formula (O).

[0196] [Chemical formula 10]

[0197]

[0198] In formula (O), R 115 represents a tetravalent organic group. 115 The preferred range of R in formula (2) 115 The meanings are the same and the preferred ranges are also the same.

[0199] Specific examples of tetracarboxylic dianhydrides include pyromelitic acid dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-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, 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 groups having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms thereof.

[0200] 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.

[0201] In formula (2), R 111 and R 115 At least one of R may also have an OH group. More specifically, 111 , for example, residues of bisaminophenol derivatives can be mentioned.

[0202] 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 include a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkyleneoxy group. 113 and R 114 At least one of them contains a polymerizable group, and more preferably both contain a polymerizable group. 113 and R 114At least one of them contains more than two polymerizable groups. As a polymerizable group, it is a group that can undergo crosslinking reaction by the action of heat, free radicals, etc., preferably a free radical polymerizable group. As a specific example of a polymerizable group, a group with an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group can be cited. As a free radical polymerizable group possessed by a polyimide precursor, a group with an ethylenically unsaturated bond is preferably present.

[0203] Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl, etc.), a (meth)acrylamide group, a (meth)acryloyloxy group, a group represented by the following formula (III), and the like. Preferably, the group represented by the following formula (III) is included.

[0204] However, R 113 and R 114 At least one of them preferably has a group represented by the following formula (III).

[0205] [Chemical formula 11]

[0206]

[0207] 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.

[0208] In formula (III), * represents a bonding site with other structures.

[0209] 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.

[0210] Preferred R 201 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. Alkylene groups such as ethylene and propylene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkyleneoxy groups are more preferred. Alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups are further preferred.

[0211] 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 included in the polyalkyleneoxy group may be the same or different.

[0212] When the polyalkyleneoxy group includes 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, an arrangement having blocks, an arrangement having an alternating pattern, or the like.

[0213] 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.

[0214] 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.

[0215] Furthermore, the number of the 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.

[0216] As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and further preferably a polyethyleneoxy group. 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 an alternating pattern. The preferred form of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

[0217] 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.

[0218] In formula (2), R 113 and R 114 At least one of the groups 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 produce 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.

[0219] 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.

[0220] 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.

[0221] 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, examples of the diamine include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0222] 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.

[0223] Formula (2-A)

[0224] [Chemical formula 12]

[0225]

[0226] 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.

[0227] 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. 112The meaning of is the same as R in formula (5) 112 The meanings are the same, and the preferred ranges are also the same.

[0228] 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.

[0229] 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 precursor except the terminal can be repeating units represented by formula (2).

[0230] 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.

[0231] 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, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0232] In this specification, the molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.

[0233] 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. In addition, 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.

[0234] 〔Polyimide〕

[0235] The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer mainly composed of an organic solvent.

[0236] In this specification, the alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more in 100 g of a 2.38 mass % tetramethylammonium aqueous solution at 23° C., preferably a polyimide that dissolves 0.5 g or more, and more preferably a polyimide that dissolves 1.0 g or more from the viewpoint of pattern formation. The upper limit of the above-mentioned dissolution amount is not particularly limited, but is preferably 100 g or less.

[0237] From the viewpoint of film strength and insulation properties of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.

[0238] -Fluorine atom-

[0239] From the viewpoint of the film strength of the obtained organic film, it is also preferred that the polyimide has fluorine atoms.

[0240] The fluorine atom is preferably present in R contained in the repeating unit represented by the formula (4) described below. 132 or R in the repeating unit represented by the formula (4) described below 131 Among them, R contained in the repeating unit represented by the formula (4) described later as a fluorinated alkyl group is more preferably 132 or R in the repeating unit represented by the formula (4) described below 131 middle.

[0241] The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and preferably 20% by mass or less.

[0242] -Silicon Atoms-

[0243] From the viewpoint of the film strength of the obtained organic film, it is also preferred that the polyimide has a silicon atom.

[0244] For example, the silicon atom is preferably contained in R in the repeating unit represented by the formula (4) described below. 131 Among them, R in the repeating unit represented by the formula (4) described below is more preferably included as the organo-modified (poly)siloxane structure described below. 131 middle.

[0245] The silicon atom or the organo-modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in a main chain of the polyimide.

[0246] The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0247] -Ethylenically unsaturated bond-

[0248] From the viewpoint of film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond.

[0249] The polyimide may have an ethylenically unsaturated bond at a main chain terminal or at a side chain, and preferably has an ethylenically unsaturated bond at a side chain.

[0250] The ethylenically unsaturated bond preferably has radical polymerizability.

[0251] The ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (4) described below. 132 or R 131 It is more preferred that the group having an ethylenically unsaturated bond is contained in R 132 or R 131 middle.

[0252] Among these, the ethylenically unsaturated bond is preferably contained in R 131 It is more preferred that the group having an ethylenically unsaturated bond is contained in R 131 middle.

[0253] Examples of the group having an ethylenically unsaturated bond include groups having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, and a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

[0254] [Chemical formula 13]

[0255]

[0256] In formula (IV), R 20 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.

[0257] In formula (IV), R 21 It represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 or 3, and the number of repetitions of the alkyleneoxy group is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), or a group consisting of two or more of these groups in combination.

[0258] The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, cyclic, or a combination thereof.

[0259] The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0260] Among these, R 21The group is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1).

[0261] [Chemical formula 14]

[0262]

[0263] In formulas (R1) to (R3), L represents a single bond or an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these groups, X represents an oxygen atom or a sulfur atom, * represents a bonding position with other structures, and ● represents the bonding position with R in formula (IV). 21 The bonding position of the bonded oxygen atom.

[0264] In formulae (R1) to (R3), the preferred embodiment of L being an alkylene group having 2 to 12 carbon atoms or a (poly)alkyleneoxy group having 2 to 30 carbon atoms is the same as that of R in formula (IV). 21 The preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms are the same.

[0265] In formula (R1), X is preferably an oxygen atom.

[0266] In formulae (R1) to (R3), * has the same meaning as * in formula (IV), and preferred aspects are also the same.

[0267] The structure represented by formula (R1) can be obtained by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).

[0268] The structure represented by the formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate).

[0269] The structure represented by the formula (R3) can be obtained by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate).

[0270] In formula (IV), * represents a bonding site to other structures, and is preferably a bonding site to the main chain of the polyimide.

[0271] The amount of the ethylenically unsaturated bonds is preferably 0.0001 to 0.1 mol / g, more preferably 0.0005 to 0.05 mol / g, based on the total mass of the polyimide.

[0272] -Polymerizable groups other than groups having ethylenically unsaturated bonds-

[0273] The polyimide may contain a polymerizable group other than the group having an ethylenically unsaturated bond.

[0274] Examples of the polymerizable group other than the group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetane group, an alkoxymethyl group such as a methoxymethyl group, and a hydroxymethyl group.

[0275] For example, a polymerizable group other than a group having an ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (4) described later. 131 .

[0276] The amount of the polymerizable groups other than the groups having an ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0277] -Polarity conversion group-

[0278] The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide and R in the above formula (2) 113 and R 114 The acid-decomposable groups described in , and the preferred embodiments are also the same.

[0279] The polarity conversion group is, for example, contained in R in the repeating unit represented by the formula (4) described below. 131 , R 132 , the end of polyimide, etc.

[0280] -Acid value-

[0281] When the polyimide is used for alkali development, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more from the viewpoint of improving developability.

[0282] The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.

[0283] When the polyimide is used for development using a developer containing an organic solvent as the main component (eg, "solvent development"), the acid value of the polyimide is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g.

[0284] The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0285] As the acid group contained in the polyimide, from the viewpoint of achieving both storage stability and developability, an acid group having a pKa of 0 to 10 is preferred, and an acid group having a pKa of 3 to 8 is more preferred.

[0286] pKa is a value that takes into account the dissociation reaction of releasing hydrogen ions from an acid and represents its equilibrium constant Ka by its negative common logarithm pKa. In this specification, unless otherwise specified, pKa is set to a calculated value based on ACD / ChemSketch (registered trademark). pKa can refer to the values ​​recorded in "Revised 5th Edition of Chemistry Handbook Basics" compiled by the Chemical Society of Japan.

[0287] When the acid group is a polyacid such as phosphoric acid, the pKa is the first dissociation constant.

[0288] As such an acid group, the polyimide preferably contains at least one selected from a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0289] -Phenolic hydroxyl group-

[0290] From the viewpoint of making the development speed with an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxyl group.

[0291] The polyimide may have a phenolic hydroxyl group at a main chain terminal or may have a phenolic hydroxyl group in a side chain.

[0292] The phenolic hydroxyl group is preferably contained in R in the repeating unit represented by the formula (4) described below. 132 or R 131 .

[0293] The amount of the phenolic hydroxyl group is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g, based on the total mass of the polyimide.

[0294] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but preferably contains a repeating unit represented by the following formula (4).

[0295] [Chemical formula 15]

[0296]

[0297] In formula (4), R 131 represents a divalent organic group, R 132 It represents a tetravalent organic group.

[0298] In the case of having a polymerizable group, the polymerizable group may be located at R 131 and R 132At least one of them may be located at a terminal of the polyimide as shown in the following formula (4-1) or formula (4-2).

[0299] Formula (4-1)

[0300] [Chemical formula 16]

[0301]

[0302] In formula (4-1), R 133 is a polymerizable group, and the other groups have the same meanings as in formula (4).

[0303] Formula (4-2)

[0304] [Chemical formula 17]

[0305]

[0306] R 134 and R 135 At least one of them is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups have the same meaning as in formula (4).

[0307] Examples of the polymerizable group include a group containing the above-mentioned ethylenically unsaturated bond or a crosslinkable group other than a group having the above-mentioned ethylenically unsaturated bond.

[0308] R 131 The divalent organic group includes the following: 111 The preferred ranges are the same.

[0309] As R 131 , and the diamine residue remaining after removing the amino group of the diamine can be cited. As the diamine, aliphatic, cycloaliphatic or aromatic diamine can be cited. As a specific example, R in the formula (2) of the polyimide precursor can be cited. 111 Example.

[0310] From the perspective of more effectively suppressing the warping during calcination, R 131 Preferably, the diamine residue has at least two alkylene glycol units in the main chain. More preferably, the diamine residue contains two or more ethylene glycol chains or propylene glycol chains or both in total in one molecule. Still more preferably, the diamine residue contains no aromatic ring.

[0311] Examples of the diamine containing two or more ethylene glycol chains or propylene glycol chains or both in total in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (these are trade names, manufactured by Huntsman Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0312] R 132 represents a tetravalent organic group. Examples of the tetravalent organic group include 115 The preferred ranges are the same.

[0313] For example, as R 115 The four bonds of the exemplified tetravalent organic group are bonded to the four -C(=0)- moieties in the formula (4) to form a condensed ring.

[0314] R 132 Examples thereof include tetracarboxylic acid residues remaining after the anhydride groups are removed from tetracarboxylic dianhydride. Specific examples thereof include R in the formula (2) of the polyimide precursor. 115 From the perspective of the strength of the organic film, R 132 An aromatic diamine residue having 1 to 4 aromatic rings is preferred.

[0315] It is also preferred that R 131 and R 132 More specifically, as R 131 As preferred examples, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, the above (DA-1) to (DA-18) can be cited as R 132 As more preferred examples, the above-mentioned (DAA-1) to (DAA-5) can be mentioned.

[0316] The polyimide also preferably has fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0317] In order to improve the adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be mentioned.

[0318] In order to improve the storage stability of the resin composition, the main chain terminal of the polyimide is preferably blocked with a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, an active monoester compound, etc. Among these, monoamines are more preferably used, and preferred compounds of the monoamines 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 2-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

[0319] -Imidization rate (ring closure rate)-

[0320] From the viewpoint of film strength, insulation properties, etc. of the obtained organic film, the imidization ratio (also referred to as “ring closure ratio”) of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0321] The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

[0322] The imidization ratio can be measured, for example, by the following method.

[0323] Measure the infrared absorption spectrum of polyimide and find the absorption peak at 1377 cm-1 derived from the imide structure. -1 Next, the polyimide was heat treated at 350°C for 1 hour, and the infrared absorption spectrum was measured again to obtain the peak intensity P1 at 1377 cm -1 The imidization ratio of the polyimide can be determined from the following formula using the obtained peak intensities P1 and P2.

[0324] Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0325] Polyimide may contain repeating units with all R 131 and R 132 The repeating unit represented by the above formula (4) may also contain R 131 and R 132 The polyimide may contain two or more different repeating units represented by the above formula (4). In addition to the repeating unit represented by the above formula (4), the polyimide may also contain other types of repeating units. As other types of repeating units, for example, the repeating unit represented by the above formula (2) can be cited.

[0326] For example, polyimide can be obtained by a method of reacting tetracarboxylic dianhydride with diamine (partially substituted with monoamine, i.e., end-capping agent) at low temperature, a method of reacting tetracarboxylic dianhydride (partially substituted with acid anhydride or monoacyl chloride compound or active monoester compound, i.e., end-capping agent) with diamine at low temperature, a method of reacting a diester by tetracarboxylic dianhydride and alcohol in the presence of diamine (partially substituted with monoamine, i.e., end-capping agent) and a condensing agent, a method of chlorinating the remaining dicarboxylic acid after obtaining a diester by tetracarboxylic dianhydride and alcohol and reacting it with diamine (partially substituted with monoamine, i.e., end-capping agent), and the like, and a method of completely imidizing it by a conventional imidization reaction method or stopping the imidization reaction midway and introducing a part of the imide structure, and a method of further mixing a completely imidized polymer and its polyimide precursor to introduce a part of the imide structure. In addition, other known methods of synthesizing polyimides can also be applied.

[0327] The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), the weight average molecular weight is particularly preferably 15,000 or more.

[0328] The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and further preferably 4,000 to 20,000.

[0329] The molecular weight dispersion of the polyimide 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 is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0330] When the resin composition contains multiple polyimides as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion degree of at least one polyimide are within the above ranges. It is also preferred that the weight average molecular weight, number average molecular weight and dispersion degree calculated for the multiple polyimides as one resin are within the above ranges.

[0331] 〔Polybenzoxazole precursor〕

[0332] The structure of the polybenzoxazole precursor used in the present invention is not particularly limited, but it preferably contains a repeating unit represented by the following formula (3).

[0333] [Chemical formula 18]

[0334]

[0335] In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, R 123 and R 124 Each independently represents a hydrogen atom or a monovalent organic group.

[0336] In formula (3), R 123 and R 124 Respectively with R in formula (2) 113 The meanings of are the same and the preferred ranges are also the same. That is, at least one is preferably a polymerizable group.

[0337] In formula (3), R 121 R represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferred. As the aliphatic group, a straight-chain aliphatic group is preferred. 121 A dicarboxylic acid residue is preferred. The dicarboxylic acid residue may be used alone or in combination of two or more.

[0338] As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferred, and a dicarboxylic acid residue containing an aromatic group is more preferred.

[0339] As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferred, and a dicarboxylic acid composed of a linear or branched (preferably linear) aliphatic group and two -COOH groups is more preferred. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, further preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.

[0340] Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethyl Pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid acid, behenedioic acid, triacontanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, dicarboxylic acid represented by the following formula, etc.

[0341] [Chemical formula 19]

[0342]

[0343] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

[0344] As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic group is preferred, and a dicarboxylic acid consisting only of a group having the following aromatic group and two -COOH groups is more preferred.

[0345] [Chemical formula 20]

[0346]

[0347] In the formula, A represents a divalent group selected from -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2- and -C(CH3)2-, and * independently represents a bonding site with other structures.

[0348] Specific examples of the dicarboxylic acid containing an aromatic group include 4,4′-carbonyldibenzoic acid, 4,4′-dicarboxydiphenyl ether, and terephthalic acid.

[0349] In formula (3), R 122 represents a tetravalent organic group. As a tetravalent organic group, R in the above formula (2) 115 The meanings are the same, and the preferred ranges are also the same.

[0350] R122 The group derived from a bisaminophenol derivative is preferably a group derived from a bisaminophenol derivative. Examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis -(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

[0351] Among the bisaminophenol derivatives, those having the following aromatic groups are preferred.

[0352] [Chemical formula 21]

[0353]

[0354] In the formula, X3 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, -NHCO-, * and # represent the bonding sites with other structures respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. And, R 122 The structure represented by the above formula is also preferred. 122 In the case of the structure represented by the above formula, among the total of 4 * and #, it is preferred that any two of them are the same as R in formula (3). 122 The bonding site of the nitrogen atom to which the bond is attached and the other two are R in formula (3) 122 The bonding site of the oxygen atom to which the bond is attached is preferably 2 * to R in formula (3). 122 The bonding site of the oxygen atom to which the bond is attached and the two # are the same as R in formula (3) 122 The bonding site of the nitrogen atom to which it is bonded, or the two * are R in formula (3) 122 The bonding site of the nitrogen atom to which it is bonded and the two # are the same as R in formula (3) 122 The bonding site of the oxygen atom to which the bond is attached is preferably 2 * which is the same as R in formula (3).122 The bonding site of the oxygen atom to which the bond is attached and the two # are the same as R in formula (3) 122 The bonding site of the bonded nitrogen atom.

[0355] The bisaminophenol derivative is also preferably a compound represented by formula (As).

[0356] [Chemical formula 22]

[0357]

[0358] In formula (As), R1 is an organic group selected from the group consisting of a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, -SO2-, -CO-, -NHCO-, a single bond, or the following formula (A-sc). R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different. R3 is any one of a hydrogen atom, a straight-chain or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different.

[0359] [Chemical formula 23]

[0360]

[0361] In the organic group selected from the group of formula (A-sc), * represents a bond to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).

[0362] In formula (As), having a substituent at the ortho position of the phenolic hydroxyl group, i.e., R3, is particularly preferred because it is believed that this brings the carbonyl carbon of the amide bond and the hydroxyl group closer together and further increases the cyclization rate during curing at low temperatures.

[0363] In the formula (As), when R2 is an alkyl group and R3 is an alkyl group, it is preferable because high transparency to i-rays and a high cyclization rate can be maintained during curing at a low temperature.

[0364] In formula (As), R1 is further preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group involved in R1 include a linear or branched alkyl group having 1 to 8 carbon atoms, wherein -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferred in terms of obtaining a polybenzoxazole precursor having an excellent balance while maintaining high transparency to i-rays and a high cyclization rate when cured at low temperatures and having sufficient solubility in solvents.

[0365] As a method for producing the bisaminophenol derivative represented by the formula (As), for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A-2013-256506 can be referred to, and the contents thereof are incorporated herein.

[0366] Specific examples of the structure of the bisaminophenol derivative represented by formula (As) include those described in paragraphs 0070 to 0080 of JP-A-2013-256506, which are incorporated herein. Specific examples of the structure of the bisaminophenol derivative represented by formula (As) are not limited to these.

[0367] The polybenzoxazole precursor may contain other types of repeating units in addition to the repeating unit of the above formula (3).

[0368] From the viewpoint of being able to suppress warpage caused by ring closure, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[0369] [Chemical formula 24]

[0370]

[0371] In formula (SL), Z has structure a and structure b, and R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 2s is a hydrocarbon group having 1 to 10 carbon atoms, R 3s , R 4s , R 5s , R 6s At least one of them is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. Regarding the mole % of the Z part, structure a is 5 to 95 mole %, structure b is 95 to 5 mole %, and a+b is 100 mole %.

[0372] In formula (SL), preferred Z includes R in structure b. 5s and R 6s The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight to the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be more effectively reduced, and the effect of suppressing warping and the effect of improving solvent solubility can be achieved.

[0373] When the diamine residue represented by the formula (SL) is included as another type of repeating unit, it is also preferred to further include a tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride as a repeating unit. Examples of such a tetracarboxylic acid residue include R in the formula (2): 115 Example.

[0374] The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and further preferably 9,200 to 11,200.

[0375] The molecular weight dispersion of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the molecular weight dispersion of the polybenzoxazole precursor is not particularly limited, for example, preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and further preferably 2.2 or less.

[0376] When the resin composition contains a plurality of polybenzoxazole precursors as specific resins, it is preferred that at least one polybenzoxazole precursor has a weight average molecular weight, a number average molecular weight, and a dispersion degree within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, the number average molecular weight, and the dispersion degree calculated by treating the plurality of polybenzoxazole precursors as one resin are within the above ranges.

[0377] 〔Polybenzoxazole〕

[0378] As polybenzoxazole, as long as it is a polymer compound having a benzoxazole ring, it is not particularly limited, preferably a compound represented by the following formula (X), more preferably a compound represented by the following formula (X) and having a polymerizable group. As the above-mentioned polymerizable group, a free radical polymerizable group is preferred. In addition, it can be a compound represented by the following formula (X) and having a polar conversion group such as an acid decomposable group.

[0379] [Chemical formula 25]

[0380]

[0381] In formula (X), R 133 Represents a divalent organic group, R 134 It represents a tetravalent organic group.

[0382] When there is a polarity conversion group such as a polymerizable group or an acid-decomposable group, the polymerizable group or the acid-decomposable group may be located at R 133 and R 134At least one of them may be located at a terminal of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2).

[0383] Formula (X-1)

[0384] [Chemical formula 26]

[0385]

[0386] In formula (X-1), R 135 and R 136 At least one of them is a polarity converting group such as a polymerizable group or an acid-decomposable group, and when it is not a polymerizable group or an acid-decomposable group, it is an organic group, and the other groups have the same meanings as in formula (X).

[0387] Formula (X-2)

[0388] [Chemical formula 27]

[0389]

[0390] In formula (X-2), R 137 is a polar conversion group such as a polymerizable group or an acid-decomposable group, and the rest are substituents. The other groups have the same meanings as in formula (X).

[0391] The polarity converting group such as the polymerizable group or the acid-decomposable group has the same meaning as the polymerizable group explained in the polymerizable group of the above-mentioned polyimide precursor.

[0392] R 133 represents a divalent organic group. Examples of the divalent organic group include an aliphatic group and an aromatic group. As a specific example, R in the formula (3) of the polybenzoxazole precursor may be 121 Examples, preferably examples with R 121 same.

[0393] R 134 represents a tetravalent organic group. Examples of the tetravalent organic group include R in the formula (3) of the polybenzoxazole precursor: 122 Examples, preferably examples with R 122 same.

[0394] For example, as R 122 The four bonds of the exemplified tetravalent organic group are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. 134 When it is the following organic group, the following structure is formed. In the following structure, * represents the bonding site to the nitrogen atom or oxygen atom in formula (X).

[0395] [Chemical formula 28]

[0396]

[0397] The oxazolidinylation rate of the polybenzoxazole is preferably 85% or more, more preferably 90% or more. The upper limit is not particularly limited, and may be 100%. When the oxazolidinylation rate is 85% or more, the shrinkage of the film caused by ring closure during oxazolidinylation by heating is reduced, and warping can be effectively suppressed.

[0398] For example, the above-mentioned oxazolylation rate can be measured by the following method.

[0399] The infrared absorption spectrum of polybenzoxazole was measured to find the absorption peak at 1650 cm-1 derived from the amide structure of the precursor. -1 Next, using the peak intensity Q1 near 1490 cm -1 The polybenzoxazole was heat treated at 350°C for 1 hour, and then the infrared absorption spectrum was measured again to determine the absorption intensity of the aromatic ring at 1650cm -1 The peak intensity near Q2 is at 1490 cm -1 The absorption intensity of the aromatic ring observed in the vicinity is normalized. The oxazolylation rate of the polybenzoxazole can be determined from the following formula using the obtained standard values ​​of the peak intensities Q1 and Q2.

[0400] Oxazolylation rate (%) = (specification value of peak intensity Q1 / specification value of peak intensity Q2) × 100

[0401] Polybenzoxazole may contain R 133 and R 134 The repeating unit of the above formula (X) may also contain R 133 and R 134 In addition to the repeating unit of the above formula (X), the polybenzoxazole may also contain other types of repeating units.

[0402] For example, a bisaminophenol derivative is reacted with a 133 A polybenzoxazole precursor is obtained by reacting a dicarboxylic acid or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acids, and then oxazolidinylating the precursor by a conventional oxazolidinylating reaction method to obtain polybenzoxazole.

[0403] In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative which has been reacted with 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to improve the reaction yield or the like.

[0404] The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and further preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When containing two or more polybenzoxazoles, it is preferred that the weight average molecular weight of at least one polybenzoxazole is within the above range.

[0405] The number average molecular weight (Mn) of the polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.

[0406] The molecular weight dispersion of the polybenzoxazole is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the molecular weight dispersion of the polybenzoxazole is not particularly limited, for example, preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and further preferably 2.2 or less.

[0407] When the resin composition contains multiple polybenzoxazoles as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersity of at least one polybenzoxazole are within the above ranges. In addition, it is also preferred that the weight average molecular weight, number average molecular weight and dispersity calculated as one resin of the multiple polybenzoxazoles are within the above ranges.

[0408] 〔Polyamide-imide precursor〕

[0409] The polyamideimide precursor preferably includes a repeating unit represented by the following formula (PAI-2).

[0410] [Chemical formula 29]

[0411]

[0412] In the formula (PAI-2), R 117 Represents a trivalent organic group, R 111 Represents a divalent organic group, A 2 represents an oxygen atom or -NH-, R 113 represents a hydrogen atom or a monovalent organic group.

[0413] In the formula (PAI-2), R 117Examples include a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked via a single bond or a linking group. Preferably, it is a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0414] As the above-mentioned connecting group, preferred are -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, halogenated alkylene, arylene or connecting groups formed by bonding two or more of these, more preferred are -O-, -S-, alkylene, halogenated alkylene, arylene or connecting groups formed by bonding two or more of these.

[0415] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

[0416] As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferred, a halogenated alkylene group having 1 to 10 carbon atoms is more preferred, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferred. In addition, as the halogen atom in the above-mentioned halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be mentioned, and a fluorine atom is preferred. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted by halogen atoms, but preferably all hydrogen atoms are substituted by halogen atoms. As examples of preferred halogenated alkylene groups, (ditrifluoromethyl)methylene and the like can be mentioned.

[0417] The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0418] And, R 117 It is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As the halogenation, chlorination is preferred.

[0419] In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound.

[0420] Two of the three carboxyl groups of the above tricarboxylic acid compound may be converted to anhydride.

[0421] Examples of the tricarboxylic acid compound which may be halogenated and is used for producing the polyamideimide precursor include branched aliphatic, cycloaliphatic or aromatic tricarboxylic acid compounds.

[0422] These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0423] Specifically, as the tricarboxylic acid compound, a tricarboxylic acid compound containing a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these groups are combined via a single bond or a linking group is preferred, and a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group is more preferred.

[0424] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked by a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2- or a phenylene group.

[0425] These compounds may be compounds in which two carboxyl groups are anhydrified (for example, trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (for example, trimellitic anhydride chloride).

[0426] In the formula (PAI-2), R 111 , A 2 , R 113 The meanings of are respectively the same as those of R in the above formula (2) 111 , A 2 , R 113 The meanings are the same and the preferred aspects are also the same.

[0427] The polyamideimide precursor may further comprise other repeating units.

[0428] Examples of other repeating units include repeating units represented by the above formula (2) and repeating units represented by the following formula (PAI-1).

[0429] [Chemical formula 30]

[0430]

[0431] In the formula (PAI-1), R 116 represents a divalent organic group, R 111 It represents a divalent organic group.

[0432] In the formula (PAI-1), R 116Examples include a linear or branched aliphatic group, a cyclic aliphatic group and an aromatic group, a heteroaromatic group, or a group obtained by connecting two or more of these groups via a single bond or a linking group. Preferably, it is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups via a single bond or a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

[0433] As the above-mentioned connecting group, preferred are -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, halogenated alkylene, arylene or connecting groups formed by bonding two or more of these, more preferred are -O-, -S-, alkylene, halogenated alkylene, arylene or connecting groups formed by bonding two or more of these.

[0434] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

[0435] As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferred, a halogenated alkylene group having 1 to 10 carbon atoms is more preferred, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferred. In addition, as the halogen atom in the above-mentioned halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be mentioned, and a fluorine atom is preferred. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted by halogen atoms, but preferably all hydrogen atoms are substituted by halogen atoms. As examples of preferred halogenated alkylene groups, (ditrifluoromethyl)methylene and the like can be mentioned.

[0436] The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0437] And, R 116 It is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide.

[0438] In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide compound.

[0439] The carboxyl group in the dicarboxylic acid dihalide compound may be halogenated, and is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.

[0440] Examples of the dicarboxylic acid compound or dicarboxylic acid dihalide compound which may be halogenated and is used for producing the polyamideimide precursor include linear or branched aliphatic, cycloaliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds.

[0441] These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

[0442] Specifically, as the dicarboxylic acid compound or dicarboxylic acid dihalide compound, a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups via a single bond or a linking group is preferred, and a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group is more preferred.

[0443] Specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecanoic acid, Fluorosebacic acid, 1,9-azeladic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, henodecanedioic acid, dohenedioic acid, tetracosanedioic acid, tetracosanedioic acid, pentadecanedioic acid, hexadecanedioic acid, Heptadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxyl diphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc.

[0444] Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxyl groups are halogenated among the specific examples of the dicarboxylic acid compound described above.

[0445] In the formula (PAI-1), R 111 With R in the above formula (2) 111The meanings are the same and the preferred aspects are also the same.

[0446] Furthermore, it is also preferred that the polyamide-imide precursor has fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more and preferably 20% by mass or less.

[0447] Furthermore, the polyamideimide 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 component, there can be mentioned an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

[0448] As one embodiment of the polyamideimide precursor in the present invention, a method containing a repeating unit represented by formula (PAI-2), a repeating unit represented by formula (PAI-1), and a repeating unit represented by formula (2) can be listed. The total content of the above repeating units is preferably 50 mol% or more of the total repeating units, 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 total content is not particularly limited and is 100 mol% or less. All repeating units in the polyamideimide precursor except the terminal can be any one of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2).

[0449] Furthermore, as another embodiment of the polyamideimide precursor in the present invention, a method containing a repeating unit represented by formula (PAI-2) and a repeating unit represented by formula (PAI-1) can be cited. The total content of the above repeating units is preferably 50 mol% or more of the total repeating units, 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 total content is not particularly limited and is 100 mol% or less. All repeating units in the polyamideimide precursor except the terminal can be any one of the repeating units represented by formula (PAI-2) or the repeating units represented by formula (PAI-1).

[0450] The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

[0451] The molecular weight dispersion of the polyamideimide 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 polyamideimide precursor is not particularly limited, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less. When the resin composition includes a plurality of polyamideimide precursors as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion of at least one polyamideimide precursor are within the above range. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight and dispersion calculated using the plurality of polyamideimide precursors as one resin are within the above range, respectively.

[0452] 〔Polyamide-imide〕

[0453] The polyamideimide used in the present invention may be an alkali-soluble polyamideimide or a polyamideimide soluble in a developer mainly composed of an organic solvent.

[0454] In this specification, the alkali-soluble polyamide-imide refers to a polyamide-imide that dissolves 0.1 g or more in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23° C., preferably 0.5 g or more, and more preferably 1.0 g or more, from the viewpoint of pattern formation. The upper limit of the above-mentioned dissolution amount is not particularly limited, but is preferably 100 g or less.

[0455] Furthermore, from the viewpoint of film strength and insulation properties of the obtained organic film, the polyamide-imide is preferably a polyamide-imide having a plurality of amide bonds and a plurality of imide structures in the main chain.

[0456] -Fluorine atom-

[0457] From the viewpoint of the film strength of the obtained organic film, the polyamideimide preferably has fluorine atoms.

[0458] The fluorine atom is preferably contained in R 117 or R 111 , more preferably R contained in the repeating unit represented by the formula (PAI-3) described later as a fluorinated alkyl group 117 or R 111 .

[0459] The amount of fluorine atoms relative to the total mass of the polyamide-imide is preferably 5% by mass or more and preferably 20% by mass or less.

[0460] -Ethylenically unsaturated bond-

[0461] From the viewpoint of the film strength of the obtained organic film, the polyamideimide may have an ethylenically unsaturated bond.

[0462] The polyamideimide may have an ethylenically unsaturated bond at a main chain terminal or in a side chain, and preferably has an ethylenically unsaturated bond in a side chain.

[0463] The ethylenically unsaturated bond preferably has radical polymerizability.

[0464] The ethylenically unsaturated bond is preferably contained in R in the repeating unit represented by the formula (PAI-3) described later. 117 or R 111 More preferably, R is included in the repeating unit represented by the formula (PAI-3) described later as a group having an ethylenically unsaturated bond. 117 or R 111 .

[0465] Preferred embodiments of the group having an ethylenically unsaturated bond are the same as preferred embodiments of the group having an ethylenically unsaturated bond in the above-mentioned polyimide.

[0466] The amount of ethylenically unsaturated bonds relative to the total mass of the polyamide-imide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.

[0467] -Polymerizable groups other than ethylenically unsaturated bonds-

[0468] The polyamideimide may have a polymerizable group other than the ethylenically unsaturated bond.

[0469] Examples of the polymerizable groups other than the ethylenically unsaturated bond in the polyamideimide include the same polymerizable groups other than the ethylenically unsaturated bond in the above-mentioned polyimide.

[0470] For example, it is preferable that a polymerizable group other than an ethylenically unsaturated bond is contained in R in a repeating unit represented by the formula (PAI-3) described later. 111 .

[0471] The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of the polyamide-imide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.

[0472] -Polarity conversion group-

[0473] The polyamideimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyamideimide and R in the above formula (2) 113 and R 114 The acid-decomposable groups described in , and the preferred embodiments are also the same.

[0474] -Acid value-

[0475] When the polyamideimide is used for alkali development, the acid value of the polyamideimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more, from the viewpoint of improving developability.

[0476] Furthermore, the acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.

[0477] When the polyamideimide is used for development using a developer containing an organic solvent as the main component (eg, "solvent development"), the acid value of the polyamideimide is preferably 2 to 35 mgKOH / g, more preferably 3 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g.

[0478] The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0479] Furthermore, examples of the acid group contained in the polyamide-imide include the same groups as the acid groups in the above-mentioned polyimide, and preferred aspects are also the same.

[0480] -Phenolic hydroxyl group-

[0481] From the viewpoint of making the development speed with an alkaline developer appropriate, the polyamideimide preferably has a phenolic hydroxyl group.

[0482] The polyamide-imide may have a phenolic hydroxyl group at a main chain terminal or may have a phenolic hydroxyl group at a side chain.

[0483] The phenolic hydroxyl group is preferably contained in R in the repeating unit represented by the formula (PAI-3) described below. 117 or R 111 .

[0484] The amount of the phenolic hydroxyl group relative to the total mass of the polyamide-imide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0485] The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but preferably contains a repeating unit represented by the following formula (PAI-3).

[0486] [Chemical formula 31]

[0487]

[0488] In the formula (PAI-3), R 111 and R 117Respectively with R in formula (PAI-2) 111 and R 117 The meanings are the same and the preferred aspects are also the same.

[0489] When there is a polymerizable group, the polymerizable group may be located at R 111 and R 117 At least one of them may be located at a terminal of the polyamideimide.

[0490] In order to improve the storage stability of the resin composition, the main chain terminal of the polyamide-imide is preferably blocked with a blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacyl chloride compound, active monoester compound, etc. The preferred embodiment of the blocking agent is the same as the preferred embodiment of the blocking agent in the above-mentioned polyimide.

[0491] -Imidization rate (ring closure rate)-

[0492] From the viewpoint of film strength and insulation properties of the obtained organic film, the imidization ratio (also referred to as "ring closure ratio") of the polyamideimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0493] The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

[0494] The imidization ratio is measured by the same method as the ring closure ratio of the polyimide.

[0495] Polyamideimide may contain R 111 and R 117 The repeating unit represented by the above formula (PAI-3) may also contain R 111 and R 117 The polyamide-imide may contain not only the repeating unit represented by the above formula (PAI-3) but also other types of repeating units. Examples of other types of repeating units include repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0496] Polyamideimide can be synthesized, for example, by a method in which a polyamideimide precursor is obtained by a known method and completely imidized by a conventional imidization reaction method, or by a method in which the imidization reaction is stopped midway and a partial imide structure is introduced, or by a method in which a fully imidized polymer is further mixed with the polyamideimide precursor to introduce a partial imide structure.

[0497] The weight average molecular weight (Mw) of the polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and further preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more.

[0498] Furthermore, the number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

[0499] The molecular weight dispersion of polyamideimide 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 polyamideimide is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0500] Furthermore, when the resin composition contains a plurality of polyamide-imides as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersity of at least one polyamide-imide are within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight and dispersity calculated using the plurality of polyamide-imides as one resin are within the above ranges, respectively.

[0501] [Method for producing polyimide precursor, etc.]

[0502] For example, the polyimide precursor can be obtained 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 with a condensing agent or an alkylating agent, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then reacting the diester 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 the diester with a 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 the diester with a diamine is more preferred.

[0503] 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.

[0504] 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.

[0505] Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.

[0506] In the method for producing a polyimide precursor, etc., it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one kind or two or more kinds.

[0507] 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.

[0508] In the method for producing a polyimide precursor, etc., it is preferred to add a basic compound during the reaction. The basic compound may be one kind or two or more kinds.

[0509] 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.

[0510] -Capping agent-

[0511] In the manufacturing method of polyimide precursor etc., in order to further improve storage stability, it is preferred to seal the carboxylic anhydride, anhydride derivative or amino group remaining at the resin end of polyimide precursor etc. When the carboxylic anhydride and anhydride derivative remaining at the resin end are blocked, as the end-blocking agent, monoalcohol, phenol, mercaptan, thiophenol, monoamine etc. can be cited. From the perspective of reactivity and film stability, monoalcohol, phenols and monoamines are more preferably used. As the preferred compound of monoalcohol, primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, 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 may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

[0512] Moreover, 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 blocking agent for the amino group is preferably carboxylic anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic anhydride, etc., and more preferably carboxylic anhydride and carboxylic acid chloride. As the preferred compound 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. And, as the preferred compound of carboxylic acid chloride, acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, valeryl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearyl chloride, benzoyl chloride, etc. can be mentioned.

[0513] -Solid Precipitation-

[0514] In the manufacturing method of polyimide precursor etc., 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 a poor solvent such as water, aliphatic lower alcohol or its mixed solution and the polymer component is precipitated, thereby making it precipitate with solid and dry to obtain polyimide precursor etc. In order to improve the degree of purification, operations such as redissolution, reprecipitation, precipitation, and drying can be repeatedly performed on polyimide precursor etc. It is also possible to further include a process of removing ionic impurities using an ion exchange resin.

[0515] 〔content〕

[0516] The content of the resin (A) 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 (A) 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.

[0517] The resin composition of the present invention may contain only one type of (A) resin, or may contain two or more types of other resins. When two or more types are contained, the total amount is preferably within the above range.

[0518] The (A) resin is a specific resin and the content of the specific resin is particularly preferably within the above range.

[0519] It is also preferred that the resin composition of the present invention contains at least two types of resins.

[0520] Specifically, the resin composition of the present invention may contain two or more specific resins in total of the specific resin and other resins described below, or may contain two or more specific resins, and preferably contains two or more specific resins.

[0521] When the resin composition of the present invention contains two or more specific resins, for example, it is preferred to contain a structure derived from a dianhydride (R represented by the above formula (2)) which is a polyimide precursor. 115 ) Two or more different polyimide precursors.

[0522] 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").

[0523] Examples of other resins include phenolic resins, polyamides, epoxy resins, silanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styrene resins, polyether resins, and polyester resins.

[0524] 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.

[0525] For example, by replacing or adding to the polymerizable compound described below, a polymerizable group having a weight average molecular weight of 20,000 or less and having a high value (for example, a polymerizable group content of 1×10 -3 mol / g or more) Adding a (meth)acrylic resin to the resin composition can improve the coating properties of the resin composition, the solvent resistance of the pattern (cured product), and the like.

[0526] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more, relative to the total solid content of the resin composition.

[0527] 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.

[0528] As a preferred embodiment of the resin composition of the present invention, it is also possible to set the content of other resins to be low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less relative to the total solid content of the resin composition. The lower limit of the above content is not particularly limited, and 0% by mass or more is sufficient.

[0529] The resin composition of the present invention may contain only one other resin or two or more other resins. When two or more other resins are contained, the total amount is preferably within the above range.

[0530] The resin composition of the present invention preferably satisfies at least one of the following (i) and (ii).

[0531] (i) Containing (B-1) a radical polymerizable compound

[0532] (ii) (A) The resin contains a free radical polymerizable site

[0533] As an embodiment in which the (A) resin in the above (ii) contains a radical polymerizable site, there can be mentioned an embodiment in which the (A) resin contains a radical polymerizable group. The radical polymerizable group is as described above.

[0534] <(B-1) Radically polymerizable compound>

[0535] (B-1) The radical polymerizable compound (also referred to as a "radical crosslinking agent") is described below.

[0536] 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.

[0537] 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.

[0538] 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.

[0539] 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.

[0540] 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.

[0541] 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.

[0542] As the specific example of free radical crosslinking agent, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or its esters, amides can be cited, preferably esters of unsaturated carboxylic acid and polyol compounds and amides of unsaturated carboxylic acid and polyamine compounds. In addition, unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, thiohydrin and the like and addition reaction products of 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, unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups and epoxy groups and monofunctional or polyfunctional alcohols, amines, thiols are preferably added, and then unsaturated carboxylic acid esters or amides with leaving substituents such as halogen, p-toluenesulfonyloxy (tosyloxy group) and monofunctional or polyfunctional alcohols, amines, thiols are preferably substituted reaction products. In addition, as another example, the above unsaturated carboxylic acid can be replaced with a compound group substituted with unsaturated phosphonic acid, styrene, etc., vinylbenzene derivatives, vinyl ethers, and allyl ethers. 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.

[0543] 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. This content is incorporated into this specification.

[0544] 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. This content is incorporated into the present specification.

[0545] As the radical crosslinking agent, 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 these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

[0546] Commercially available products of the radical crosslinking agent include, for example, tetrafunctional acrylate SR-494 having four vinyloxy chains, bifunctional methacrylate SR-209, 205, 214, 231, 239 having four vinyloxy chains, bifunctional methacrylate SR-268, 213, 230, 238F, 272, 306H, 508 having four vinyloxy chains (all manufactured by Sartomer Company, Inc.), TPGDA, DPGDA, HDDA (all manufactured by DAICEL-ALLNEX LTD.), hexafunctional acrylate DPCA-60 having six oxypentylene 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 PAPERINDUSTRIES CO., LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LIGHT ESTER 3EG, LIGHT ESTER NP, LIGHT ESTER 1.6HX, LIGHT ESTER 1.9ND (all manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME-400, PDE-200, 400 (all manufactured by NOF CORPORATION), etc.

[0547] 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.

[0548] 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. Preferably, the free radical crosslinking agent having an acid group is 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 is the following compound: 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.

[0549] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and 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.

[0550] As the radical crosslinking agent, a radical crosslinking agent having at least one selected from a urea bond and a urethane bond (hereinafter also referred to as “crosslinking agent U”) is also preferred.

[0551] 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 position to a carbon atom.

[0552] In the present invention, the urethane bond refers to the 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 position to a carbon atom.

[0553] When the resin composition contains the crosslinking agent U, chemical resistance, resolution, etc. may be improved.

[0554] The mechanism by which the above effect can be obtained is not clear, but it is considered that, for example, a part of the crosslinking agent U is thermally decomposed during curing by heating or the like to generate amines or the like, and the amines or the like promote the cyclization of the precursor of the cyclized resin such as the polyimide precursor.

[0555] The crosslinking agent U may have only one urea bond or one urethane bond, may have one or more urea bonds and one or more urethane bonds, may have two or more urea bonds without a urethane bond, or may have two or more urethane bonds without a urea bond.

[0556] The total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0557] When the crosslinking agent U does not have a urethane bond, the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0558] When the crosslinking agent U does not have a urea bond, the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0559] The free radical polymerizable group in the crosslinking agent U 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.

[0560] When the crosslinking agent U has two or more radical polymerizable groups, the structures of the respective radical polymerizable groups may be the same or different.

[0561] The number of radical polymerizable groups in the crosslinking agent U 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.

[0562] The radical polymerizable group value (mass of the radical polymerizable group per 1 mol of the compound) in the crosslinking agent U is preferably 150 to 400 g / mol.

[0563] 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.

[0564] 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.

[0565] The polymerizable group value of the crosslinking agent U is preferably 210 to 400 g / mol, more preferably 220 to 400 g / mol.

[0566] The crosslinking agent U is preferably a structure represented by the following formula (U-1), for example.

[0567] [Chemical formula 32]

[0568]

[0569] In formula (U-1), R U1 is a hydrogen atom or a monovalent organic group, and 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.

[0570] R U1 A hydrogen atom, an alkyl group or an aromatic hydrocarbon group is preferred, and a hydrogen atom is more preferred.

[0571] R N A hydrogen atom, an alkyl group or an aromatic hydrocarbon group is preferred, and a hydrogen atom is more preferred.

[0572] 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

[0573] 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 of these. 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 still more preferably a hydrogen atom or a methyl group.

[0574] 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

[0575] Examples of the hydrocarbon group include U1 The same groups as those mentioned above have the same preferred embodiments.

[0576] 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.

[0577] 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.

[0578] m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

[0579] The crosslinking agent U also preferably has at least one of a hydroxyl group, an alkyleneoxy group, an amide group, and a cyano group.

[0580] The hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group, and is preferably an alcoholic hydroxyl group, from the viewpoint of chemical resistance of the obtained cured film.

[0581] 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.

[0582] The alkyleneoxy group may be contained as a polyalkyleneoxy group in the crosslinking agent U. In this case, the number of repetitions of the alkyleneoxy group is preferably 2 to 10, and more preferably 2 to 6.

[0583] Amide refers to -C(=O)-NR N - represents the bond. N As described above, when the crosslinking agent U has an amide group, the crosslinking agent U can contain an amide group as a 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.

[0584] The crosslinking agent U 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.

[0585] The above-mentioned hydroxyl group, alkyleneoxy group, amide group and cyano group may be present at any position of the crosslinking agent U, 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, amide group and cyano group is linked to at least one free radical polymerizable group contained in the crosslinking agent U via a connecting group containing a urea bond or a urethane bond (hereinafter also referred to as "connecting group L2-1").

[0586] In particular, when the crosslinking agent U contains only one free radical polymerizable group, it is preferred that the free radical polymerizable group contained in the crosslinking agent U is linked to at least one selected from a hydroxyl group, an alkyleneoxy group, an amide group and a cyano group via a linking group containing a urea bond or a carbamate bond (hereinafter also referred to as "linking group L2-2").

[0587] When the crosslinking agent U contains an alkyleneoxy group (wherein, when constituting a polyalkyleneoxy group, it is a polyalkyleneoxy group) and has the above-mentioned linking group L2-1 or the above-mentioned linking group L2-2, the structure bonded to the linking group L2-1 or the linking group L2-2 opposite to the alkyleneoxy group (wherein, when constituting a polyalkyleneoxy group, it is a polyalkyleneoxy group) is not particularly limited, and is preferably a hydrocarbon group, a free radical polymerizable group, or a group represented by a combination of these. 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 a bond of these can be cited. In addition, the preferred embodiment of the free radical polymerizable group is the same as the preferred embodiment of the free radical polymerizable group in the above-mentioned crosslinking agent U.

[0588] When the crosslinking agent U contains an amide group and has the above-mentioned linking group L2-1 or the above-mentioned linking group L2-2, the structure bonded to the side opposite to the linking group L2-1 or the linking group L2-2 of the amide group is not particularly limited, and is preferably a hydrocarbon group, a free radical polymerizable group, or a group represented by a combination of these. 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 a bond of these 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 crosslinking agent U. 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 also be bonded to the linking group L2-1 or the linking group L2-2.

[0589] Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferred that the crosslinking agent U has a hydroxyl group.

[0590] From the viewpoint of compatibility with the specific resin, etc., the crosslinking agent U preferably contains an aromatic group.

[0591] The aromatic group is preferably directly bonded to the urea bond or urethane bond contained in the crosslinking agent U. When the crosslinking agent U 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.

[0592] The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may be a structure in which these groups form a condensed ring, but is preferably an aromatic hydrocarbon group.

[0593] 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.

[0594] 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 aromatic heterocyclic groups, pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. can be mentioned. These rings can be further condensed with other rings, such as indole and benzimidazole.

[0595] As the hetero atom contained in the above aromatic heterocyclic group, a nitrogen atom, an oxygen atom or a sulfur atom is preferred.

[0596] The above-mentioned aromatic group is preferably contained in a linking group that is linked to two or more free radical polymerizable groups and contains a urea bond or a urethane bond, or a linking group that links at least one selected from the above-mentioned hydroxyl group, alkyleneoxy group, amide group and cyano group and at least one free radical polymerizable group contained in the crosslinking agent U.

[0597] The number of atoms (linked chain length) between the urea bond or urethane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2-20, and even more preferably 2-10.

[0598] When the crosslinking agent U contains a total of more than two urea bonds or carbamate bonds, in the case of containing more than two free radical polymerizable groups, or in the case of containing more than two urea bonds or carbamate bonds and containing more than two free radical polymerizable groups, the minimum number of atoms among the number of atoms (linked chain length) of the urea bond or carbamate bond and the free radical polymerizable group may be within the above range.

[0599] In this specification, "the number of atoms (chain length) between a urea bond or a urethane bond and a polymerizable group" refers to the shortest (smallest number of atoms) atomic chain connecting the two atoms or groups of atoms of the connecting object. For example, in the structure represented by the following formula, the number of atoms (chain length) between the urea bond and the free radical polymerizable group (methacryloyloxy group) is 2.

[0600] [Chemical formula 33]

[0601]

[0602] 〔Axis of symmetry〕

[0603] The crosslinking agent U is also preferably a compound having a structure without an axis of symmetry.

[0604] The crosslinking agent U does not have an axis of symmetry 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 the crosslinking agent U is marked on paper, the crosslinking agent U does not have an axis of symmetry means that the structural formula of the crosslinking agent U cannot be marked as having an axis of symmetry.

[0605] Since the cross-linking agent U has no symmetry axis, it is considered that aggregation of the cross-linking agents U in the composition film is suppressed.

[0606] 〔Molecular weight〕

[0607] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and more preferably 200 to 900.

[0608] The method for producing the crosslinking agent U is not particularly limited, and the crosslinking agent U can be obtained, for example, by reacting a compound having a radical polymerizable compound and an isocyanate group with a compound having at least one of a hydroxyl group and an amino group.

[0609] The following are specific examples of the crosslinking agent U, but the crosslinking agent U is not limited to these.

[0610] [Chemical formula 34]

[0611]

[0612] [Chemical formula 35]

[0613]

[0614] [Chemical formula 36]

[0615]

[0616] From the viewpoint of pattern resolution and film stretchability, it is preferred to use a bifunctional methacrylate or acrylate in the resin composition.

[0617] 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, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol Dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloxypropyl methacrylate, EO-modified diacrylate of isocyanuric acid, dimethacrylate of isocyanuric acid, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates having urethane bonds. These can be used in combination of two or more as needed.

[0618] For example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a polyethylene glycol chain with a formula weight of about 200.

[0619] 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, mono(meth)acrylate polypropylene glycol (meth)acrylate and other (meth)acrylic acid derivatives, N-vinyl pyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, allyl glycidyl ether can be preferably used. As a monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, it is also preferred to have a boiling point of more than 100°C at normal pressure.

[0620] Examples of the bifunctional or higher-functional radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0621] 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.

[0622] The radical crosslinking agent may be used alone or in combination of two or more. When two or more radical crosslinking agents are used simultaneously, the total amount thereof is preferably within the above range.

[0623] <Other crosslinking agents>

[0624] The resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.

[0625] The other crosslinking agent refers to a crosslinking agent other than the above-mentioned free radical crosslinking agent, and is preferably a compound having a plurality of groups in the molecule that promote the reaction (form a covalent bond with other compounds in the composition or their reaction products) by the photosensitization of the above-mentioned photoacid generator or photobase generator, and more preferably a compound having a plurality of groups in the molecule that promote the reaction (form a covalent bond with other compounds in the composition or their reaction products) by the action of an acid or a base.

[0626] The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.

[0627] As other cross-linking agents, compounds having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred.

[0628] As other crosslinking agents, for example, compounds having the following structure can be cited: a structure in which an amino-containing compound such as melamine, acetylene carbamide, urea, alkylene urea, benzoguanamine, etc. is reacted with formaldehyde, or formaldehyde is reacted with an alcohol, and the hydrogen atom of the amino group is substituted with an acyloxymethyl group, a hydroxymethyl group, a hydroxyethyl group, or an alkoxymethyl group. The production method of these compounds is not particularly limited, as long as the compounds have the same structure as the compounds produced by the above methods. These compounds may be oligomers formed by self-condensation of the hydroxymethyl groups of these compounds.

[0629] As the above-mentioned amino-containing compound, a crosslinking agent using melamine is referred to as a melamine-based crosslinking agent, a crosslinking agent using acetylene urea, urea or alkylene urea is referred to as a urea-based crosslinking agent, a crosslinking agent using alkylene urea is referred to as an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is referred to as a benzoguanamine-based crosslinking agent.

[0630] Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of acetylene urea-based crosslinking agents and melamine-based crosslinking agents described below.

[0631] Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group, a nitrogen atom of a urea structure described below, or a triazine.

[0632] The alkoxymethyl group or acyloxymethyl group in the above-mentioned compound preferably has 2 to 5 carbon atoms, preferably has 2 or 3 carbon atoms, and more preferably has 2 carbon atoms.

[0633] The total number of the alkoxymethyl groups and acyloxymethyl groups in the above-mentioned compound is preferably 1 to 10, more preferably 2 to 8, particularly preferably 3 to 6.

[0634] The molecular weight of the compound is preferably 1,500 or less, more preferably 180 to 1,200.

[0635] [Chemical formula 37]

[0636]

[0637] R 100 represents an alkyl group or an acyl group.

[0638] R 101 and R 102 Each independently represents a monovalent organic group, and may be bonded to each other to form a ring.

[0639] Examples of the compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds of the following general formula.

[0640] [Chemical formula 38]

[0641]

[0642] In the formula, X represents a single bond or a divalent organic group, and each R 104 Each independently represents an alkyl group or an acyl group, R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that leaves by the action of an acid, a group consisting of -C(R 4 )2COOR 5 The group (R 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 It represents a group that leaves by the action of an acid.

[0643] R 105 Each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.

[0644] Regarding the group that decomposes by the action of an acid to generate an alkali-soluble group, the group that leaves by the action of an acid, and the group consisting of -C(R 4 )2COOR 5 R in the group represented by 5 For example, -C(R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 )、-C(R 01 )(R 02 )(OR 39 )wait.

[0645] In the formula, R 36 ~R 39 Each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. 36 With R 37 They may be bonded to each other to form a ring.

[0646] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

[0647] The above-mentioned alkyl group may be either linear or branched.

[0648] The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.

[0649] The cycloalkyl group may be a monocyclic structure or a polycyclic structure such as a condensed ring.

[0650] The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.

[0651] The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an alkyl group having 7 to 16 carbon atoms.

[0652] The above-mentioned aralkyl group means an aryl group substituted by an alkyl group, and preferred embodiments of these alkyl groups and aryl groups are the same as the preferred embodiments of the above-mentioned alkyl groups and aryl groups.

[0653] The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.

[0654] These groups may further have a known substituent.

[0655] R 01 and R 02 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0656] As the group that decomposes by the action of an acid to generate an alkali-soluble group or the group that leaves by the action of an acid, a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. are preferred. A tertiary alkyl ester group and an acetal group are more preferred.

[0657] Furthermore, as the compound having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl, a compound having at least one group selected from the group consisting of urea bond and urethane bond is also preferred. A preferred embodiment of the above compound is the same as the preferred embodiment of the crosslinking agent U except that the polymerizable group is at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, hydroxyethyl and alkoxymethyl instead of the free radical polymerizable group.

[0658] As a compound having at least one group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group and a hydroxyethyl group, specifically, the following structures can be cited. As a compound having an acyloxymethyl group, a compound in which the alkoxymethyl group of the following compound is changed to an acyloxymethyl group can be cited. As a compound having an alkoxymethyl group or an acyloxymethyl group in the molecule, the following compounds can be cited, but are not limited to these.

[0659] [Chemical formula 39]

[0660]

[0661] [Chemical formula 40]

[0662]

[0663] [Chemical formula 41]

[0664]

[0665] As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available product may be used, or a compound synthesized by a known method may be used.

[0666] From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

[0667] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0668] Specific examples of the urea-based crosslinking agent include monomethylolated acetylene urea, dimethylolated acetylene urea, trimethylolated acetylene urea, tetramethylolated acetylene urea, monomethoxymethylated acetylene urea, dimethoxymethylated acetylene urea, trimethoxymethylated acetylene urea, tetramethoxymethylated acetylene urea, monoethoxymethylated acetylene urea, diethoxymethylated acetylene urea, triethoxymethylated acetylene urea, tetraethoxymethylated acetylene urea, monopropoxymethylated acetylene urea, dipropoxymethylated acetylene urea, tripropoxymethylated acetylene urea, tetrapropoxymethylated acetylene urea, monobutoxymethylated acetylene urea, dibutoxymethylated acetylene urea, tributoxymethylated acetylene urea, tetrabutoxymethylated acetylene urea, and the like.

[0669] Urea crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea,

[0670] Ethylene urea crosslinking agents such as monomethylolated ethylene urea or dimethylolated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea,

[0671] Acrylene urea crosslinking agents such as monomethylolated propylene urea, dimethylolated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea,

[0672] 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

[0673] Specific examples of the benzoguanamine-based crosslinking agent include monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, tetramethylolated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0674] Furthermore, as the compound having at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used.

[0675] Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenylhydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)diphenyl Benzophenone, methoxymethylbenzoic acid methoxymethylbenzene, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4"-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

[0676] As other crosslinking agents, commercially available products can be used. Preferred commercially available products include 46DMOC, 46DMOEP (all manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, and DMOM- PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, hereinafter the same) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (all manufactured by SANWA CHEMICAL CO., LTD.), etc.

[0677] The resin composition of the present invention also preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another crosslinking agent.

[0678] -Epoxy compounds (compounds having epoxy groups)-

[0679] As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a cross-linking reaction below 200°C and does not cause a dehydration reaction due to cross-linking, so it is not easy to cause film shrinkage. Therefore, by containing an epoxy compound, low-temperature curing and warping of the resin composition can be effectively suppressed.

[0680] The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and can suppress warping. The polyethylene oxide group represents a group having 2 or more repeating units of ethylene oxide, and preferably has 2 to 15 repeating units.

[0681] Examples of epoxy compounds include bisphenol A epoxy resins; bisphenol F epoxy resins; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, pentaerythritol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy group-containing silicones such as polymethyl (glycidoxypropyl) siloxane, etc., but are not limited to these. Specific examples include EPICLON (registered trademark, the same shall apply hereinafter) 850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON HP-4770, EPICLON EXA-830LVP, EPICLON EXA-8183, EPICLON EXA-8169, EPICLON N-660, EPICLON N-665-EXP-S, and EPICLON N-740 (these are trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark, the same shall apply hereinafter) BEO-20E, RIKARESIN BE0-60E, RIKARESIN HBE-100, RIKARESIN DME-100, and RIKARESIN L-200 (these are trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (these are trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark, the same below) 2021P, CELLOXIDE 2081, CELLOXIDE 2000, EHPE3150, EPOLEAD (registered trademark, the same below) GT401, EPOLEAD PB4700, EPOLEAD PB3600 (these are trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are trade names, Nippon Kayaku Co., Ltd.), etc. In addition, the following compounds can also be preferably used.

[0682] [Chemical formula 42]

[0683]

[0684] In the formula, n is an integer of 1-5, and m is an integer of 1-20.

[0685] In the above structure, from the viewpoint of achieving both heat resistance and improvement in elongation, it is preferred that n is 1 to 2 and m is 3 to 7.

[0686] -Oxetane compound (compound having an oxetane group)-

[0687] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

[0688] -Benzoxazine compound (compound having a benzoxazolyl group)-

[0689] Benzoxazine compounds are preferred because they do not generate outgassing during curing due to a crosslinking reaction caused by a ring-opening addition reaction and also reduce thermal shrinkage to suppress the generation of warping.

[0690] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (these are trade names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

[0691] The content of other crosslinking agents 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 particularly preferably 1.0 to 10% by mass relative to the total solid content of the resin composition. Other crosslinking agents may contain only one or more. When containing two or more other thermal crosslinking agents, it is preferred that the total amount thereof is within the above range.

[0692] <(C) Photopolymerization Initiator>

[0693] The resin composition of the present invention contains (C) a photopolymerization initiator (also simply referred to as a “photopolymerization initiator”).

[0694] The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. In addition, an activator that acts with a photoexcited sensitizer to generate active free radicals may also be used.

[0695] 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 the 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 ethyl acetate as a solvent at a concentration of 0.01 g / L.

[0696] 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, hexaarylbisimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur 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, the compounds described in paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, Japanese Patent Publication No. 6301489, 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 can be cited, and these contents are incorporated into this specification.

[0697] 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.

[0698] In one embodiment of the present invention, as the photo-radical 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.

[0699] 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.

[0700] As the α-aminoketone-based 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.

[0701] 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. This content is incorporated into the present specification.

[0702] As the photo-radical polymerization initiator, an oxime compound can be more preferably used. By using an oxime compound, the exposure latitude can be further effectively improved. Oxime compounds have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator, so they are particularly preferred.

[0703] 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. The compounds described in Technology (1995, pp. 202-232), the compounds described in Japanese Patent Application Publication No. 2000-066385, the compounds described in Japanese Patent Publication No. 2004-534797, the compounds described in Japanese Patent Publication No. 2017-019766, the compounds described in Japanese Patent No. 6065596, the compounds described in International Publication No. 2015 / 152153, the compounds described in International Publication No. 2017 / 051680, the compounds described in Japanese Patent Publication No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, the compounds described in International Publication No. 2013 / 167515, etc., the contents of which are incorporated into the present specification.

[0704] 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.

[0705] [Chemical formula 43]

[0706]

[0707] Commercially available products of oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in JP-A-2012-014052), TR-PBG-304, 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 DaitoChemix Corporation), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). In addition, oxime compounds of the following structures can also be used.

[0708] [Chemical formula 44]

[0709]

[0710] 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.

[0711] 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.

[0712] 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, heterocyclic oxygen group, alkenyl, alkylsulfanyl, arylsulfanyl, acyl or amino is preferred. An alkyl, alkoxy, aryl, aryloxy, heterocyclic oxygen group, alkylsulfanyl, arylsulfanyl or amino is more preferred. An alkoxy, alkylsulfanyl or amino is further preferred.

[0713] 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).

[0714] [Chemical formula 45]

[0715]

[0716] 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,

[0717] 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,

[0718] R X3 ~R X14 Each independently represents a hydrogen atom or a substituent.

[0719] Among them, R X10 ~R X14 At least one of them is an electron withdrawing group.

[0720] In the above formula, preferably R X12 is an electron-withdrawing group and R X10 , R X11 , R X13 , R X14 A hydrogen atom.

[0721] 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.

[0722] 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.

[0723] 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, triaryl imidazole 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.

[0724] 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.

[0725] 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.

[0726] 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.

[0727] The content of the photopolymerization initiator in the resin composition of the present invention 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.

[0728] 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.

[0729] The resin composition of the present invention may contain a thermal polymerization initiator.

[0730] 〔Sensitizer〕

[0731] 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 undergo chemical changes and decompose, and generate free radicals, acids, or bases.

[0732] As sensitizers that can be used, compounds such as benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo can be used.

[0733] 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, and p-dimethylaminoindanone. Benzyl indanone, 2-(p-dimethylaminophenyl biphenylene)-benzothiazole, 2-(p-dimethylaminophenyl vinylene)benzothiazole, 2-(p-dimethylaminophenyl vinylene) isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl -7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylamino isopentyl benzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminophenylvinyl)benzoxazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, and the like.

[0734] Furthermore, other sensitizing pigments may also be used.

[0735] 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.

[0736] 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.

[0737] 〔Chain transfer agent〕

[0738] 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.

[0739] 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.

[0740] 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.

[0741] 〔Photoacid generator〕

[0742] The resin composition of the present invention may contain a photoacid generator.

[0743] The photoacid generator refers to a compound that generates at least one of a Bronsted acid and a Lewis acid by irradiation with light of 200 nm to 900 nm. The irradiated light is preferably light of a wavelength of 300 nm to 450 nm, more preferably light of 330 nm to 420 nm. When the photoacid generator is used alone or together with a sensitizer, the photoacid generator is preferably one that can generate an acid by photosensitization.

[0744] Preferred examples of the acid to be generated include hydrogen halide, carboxylic acid, sulfonic acid, sulfinic acid, thiosulfinic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxide, and sulfonic acid amide.

[0745] Examples of the photoacid generator include quinonediazide compounds, oximesulfonate compounds, organic halogen compounds, organic borate compounds, disulfonic acid compounds, and onium salt compounds.

[0746] From the viewpoint of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds and onium salt compounds are preferred, and from the viewpoint of mechanical properties of the film to be formed, oxime esters are preferred.

[0747] As quinonediazide compounds, there can be mentioned compounds obtained by bonding sulfonic acid esters of quinonediazide to monovalent or polyvalent hydroxy compounds, compounds obtained by bonding sulfonic acid of quinonediazide to monovalent or polyvalent amine compounds via sulfonamide, compounds obtained by bonding sulfonic acid of quinonediazide to polyhydroxypolyamino compounds via ester bonds and / or sulfonamide, etc. All functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may not be substituted with quinonediazide, but it is preferred that 40 mol% or more of the functional groups as a whole are substituted with quinonediazide on average. By containing such quinonediazide compounds, a resin composition that is sensitive to i-rays (wavelength 365nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) of a mercury lamp, which are common ultraviolet rays, can be obtained.

[0748] Specific examples of the hydroxy compound include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, tert-butyl alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS- 26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are product names, Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are product names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), novolac resin, etc., but are not limited to these.

[0749] Specific examples of the amino compound include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl ether, but are not limited thereto.

[0750] Furthermore, specific examples of the polyhydroxypolyamino compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3′-dihydroxybenzidine, but are not limited thereto.

[0751] Among these, it is preferable to contain a phenol compound and an ester with 4-naphthoquinonediazidesulfonyl group as the quinonediazide compound. This can achieve higher sensitivity and higher resolution to i-ray exposure.

[0752] The content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the resin. By setting the content of the quinonediazide compound within this range, a contrast between the exposed portion and the unexposed portion can be obtained, thereby achieving higher sensitivity, which is preferred. In addition, a sensitizer or the like may be added as needed.

[0753] The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as an "oxime sulfonate compound").

[0754] The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably a compound represented by the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105).

[0755] [Chemical formula 46]

[0756]

[0757] In formula (OS-1), X 3 represents an alkyl group, an alkoxy group or a halogen atom. 3 In the case of , they may be the same or different. 3 The alkyl group and the alkoxy group in the group may have a substituent. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom is preferably a chlorine atom or a fluorine atom.

[0758] Preferably, m3 represents an integer of 0 to 3, 0 or 1. When m3 is 2 or 3, multiple X 3 Can be the same or different.

[0759] R 34 W represents an alkyl group or an aryl group, and is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthracenyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

[0760] In the formula (OS-1), it is particularly preferred that m3 is 3, X 3 Methyl, X 3 The substitution position is ortho, R 34 A compound which is a straight-chain alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorbornylmethyl or p-tolyl group.

[0761] Specific examples of the oxime sulfonate compound represented by formula (0S-1) include the following compounds described in paragraphs 0064 to 0068 of JP-A-2011-209692 and paragraphs 0158 to 0167 of JP-A-2015-194674, and these contents are incorporated into the present specification.

[0762] [Chemical formula 47]

[0763]

[0764] In formula (OS-103) to formula (OS-105), R s1 represents an alkyl group, an aryl group or a heteroaryl group, and sometimes there are multiple R s2 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and a plurality of R may exist. s6 Each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer of 0-6.

[0765] R sl The alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms) or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by the above-mentioned group may have a substituent.

[0766] R s2 Preferably, it is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), and more preferably a hydrogen atom or an alkyl group. s2 Preferably, one or two of them are alkyl groups, aryl groups or halogen atoms, more preferably, one is alkyl groups, aryl groups or halogen atoms, and particularly preferably, one is alkyl groups and the rest are hydrogen atoms. s2 The alkyl group or aryl group represented may have a substituent.

[0767] Xs preferably represents O or S, O. In the above formula (OS-103) to (OS-105), the ring containing Xs as a ring atom is a 5-membered ring or a 6-membered ring.

[0768] ns represents 1 or 2. When Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2.

[0769] R s6 The alkyl group (preferably having 1 to 30 carbon atoms) and alkoxy group (preferably having 1 to 30 carbon atoms) represented by the above-mentioned group may have a substituent.

[0770] ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0771] The compound represented by formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the compound represented by formula (OS-104) is preferably a compound represented by the following formula (OS-107), and the compound represented by formula (OS-105) is preferably a compound represented by the following formula (OS-108) or formula (OS-109).

[0772] [Chemical formula 48]

[0773]

[0774] In formula (OS-106) to formula (OS-111), R t1 represents an alkyl group, an aryl group or a heteroaryl group, R t7 represents a hydrogen atom or a bromine atom, R t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, and R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R t2 represents a hydrogen atom or a methyl group.

[0775] R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

[0776] R t8 It represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, and is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0777] R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.

[0778] R t2 It represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

[0779] Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z) of the oxime may be any one or a mixture.

[0780] Specific examples of the oxime sulfonate compounds represented by formula (OS-103) to (OS-105) include compounds described in paragraphs 0088 to 0095 of JP-A-2011-209692 and paragraphs 0168 to 0194 of JP-A-2015-194674, and these contents are incorporated into the present specification.

[0781] As another preferred embodiment of the compound containing at least one oxime sulfonate group, compounds represented by the following formula (OS-101) and formula (OS-102) can be mentioned.

[0782] [Chemical formula 49]

[0783]

[0784] In formula (OS-101) and formula (OS-102), R u9 R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group or a heteroaryl group. u9 It is preferably a cyano group or an aryl group, and more preferably a cyano group, a phenyl group or a naphthyl group.

[0785] R u2a represents an alkyl group or an aryl group.

[0786] Xu represents -O-, -S-, -NH-, -NR u5 -、-CH2-、-CR u6 H- or CR u6 Ru 7 -, R u5 ~R u7 Each independently represents an alkyl group or an aryl group.

[0787] R u1 ~R u4 R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfone group, a cyano group or an aryl group. u1 ~R u4 The two of R can be bonded to each other to form a ring. In this case, the ring can be condensed to form a condensed ring together with the benzene ring. u1 ~R u4 Preferably, it is a hydrogen atom, a halogen atom or an alkyl group. u1 ~R u4 At least two of them may be bonded to each other to form an aryl group. u1 ~R u4 The above-mentioned substituents may further have a substituent.

[0788] The compound containing at least one oxime sulfonate group is preferably a compound represented by the formula (OS-102).

[0789] Furthermore, in the oxime sulfonate compound, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring may be any one or a mixture.

[0790] Specific examples of the compound represented by formula (OS-101) include compounds described in paragraphs 0102 to 0106 of JP-A-2011-209692 and paragraphs 0195 to 0207 of JP-A-2015-194674, and the contents thereof are incorporated herein.

[0791] Among the above compounds, the following b-9, b-16, b-31 and b-33 are preferred.

[0792] [Chemical formula 50]

[0793]

[0794] Examples of commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Corporation), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

[0795] Furthermore, the compounds represented by the following structural formula can also be mentioned as preferred examples.

[0796] [Chemical formula 51]

[0797]

[0798] Examples of the organic halogenated compound include compounds described in paragraphs 0042 to 0043 of JP-A-2015-087409, which are incorporated herein.

[0799] The content of the photoacid generator is preferably 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, further preferably 0.5 to 10% by mass, further preferably 0.5 to 3% by mass, further preferably 0.5 to 1.2% by mass, based on the total solid content of the resin composition.

[0800] The photoacid generator may be used alone or in combination of two or more. When two or more photoacid generators are used in combination, the total amount thereof is preferably within the above range.

[0801] Furthermore, in order to impart photosensitivity to a desired light source, it is also preferably used together with a sensitizer.

[0802] <Alkali Generator>

[0803] The resin composition of the present invention may contain a base generator. 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.

[0804] In particular, when the resin composition contains a precursor of a cyclized resin, it is preferred that the resin composition contains a base generator. When the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be promoted by heating, thereby obtaining a cured product having good mechanical properties or chemical resistance, for example, the performance as an interlayer insulating film for a redistribution layer contained in a semiconductor package becomes good.

[0805] 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.

[0806] 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.

[0807] Specific examples of the nonionic base generating agent include compounds represented by formula (B1), formula (B2) or formula (B3).

[0808] [Chemical formula 52]

[0809]

[0810] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 Each independently represents an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom. 1 and Rb 2 will not become a hydrogen atom at the same time. 1 , Rb 2 and Rb 3In addition, in this specification, the tertiary amine structure refers to a structure in which the three bonds of the trivalent nitrogen atom are covalently bonded to the carbon atom of the hydrocarbon group. Therefore, when the carbon atom bonded to the trivalent nitrogen atom is a carbon atom constituting a carbonyl group, that is, when an amide group is formed with the nitrogen atom, it is not a tertiary amine structure.

[0811] In formula (B1) and (B2), Rb is preferably 1 , Rb 2 and Rb 3 At least one of the rings contains a cyclic structure, and more preferably at least two of the rings contain a cyclic structure. As the cyclic structure, it can be any one of a monocyclic ring and a condensed ring, preferably a monocyclic ring or a condensed ring formed by condensing two monocyclic rings. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.

[0812] More specifically, Rb 1 and Rb 2 Preferably, it is a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12). These groups may have a substituent. Rb 1 With Rb 2 They may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. 1 and Rb 2 Preferably, it is a linear, branched or cyclic alkyl group which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), more preferably a cycloalkyl group which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), and further preferably a cyclohexyl group which may have a substituent.

[0813] As Rb 3Examples of the group include alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and more preferably 3 to 12 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and more preferably 6 to 10 carbon atoms), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 12, and more preferably 2 to 6 carbon atoms), aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and more preferably 7 to 12 carbon atoms), arylalkenyl groups (preferably having 8 to 24 carbon atoms, more preferably 8 to 20, and more preferably 8 to 16 carbon atoms), alkoxy groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and more preferably 3 to 12 carbon atoms), aryloxy groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and more preferably 6 to 12 carbon atoms), and arylalkoxy groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and more preferably 7 to 12 carbon atoms). Among these, cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), arylalkenyl groups, and arylalkoxy groups are preferred. R 3 It may further have a substituent.

[0814] The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

[0815] [Chemical formula 53]

[0816]

[0817] In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 Respectively with Rb in formula (B1) 1 and Rb 2 same.

[0818] R 13 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), and may have a substituent. 13 Aralkyl groups are preferred.

[0819] R 33 and Rb 34Each of them independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), and is preferably a hydrogen atom.

[0820] R 35 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), and an aryl group is preferred.

[0821] The compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a).

[0822] [Chemical formula 54]

[0823]

[0824] R 11 and Rb 12 The meaning is the same as Rb in formula (B1-1) 11 and Rb 12 have the same meaning.

[0825] R 15 and Rb 16 It is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), and preferably a hydrogen atom or a methyl group.

[0826] R 17 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), and an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), among which an aryl group is preferred.

[0827] [Chemical formula 55]

[0828]

[0829] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the linking chain connecting adjacent oxygen atoms and carbon atoms and having 3 or more atoms on the linking chain. N1 and R N2 Each independently represents a monovalent organic group.

[0830] In this specification, "linking chain" refers to a chain connecting two atoms or groups of atoms as linking objects in a path that connects these linking objects with the shortest (smallest number of atoms) path. For example, in a compound represented by the following formula, L is composed of phenylene ethylene and has ethylene as a saturated hydrocarbon group, the linking chain is composed of 4 carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "linking chain length") is 4.

[0831] [Chemical formula 56]

[0832]

[0833] The number of carbon atoms in L in formula (B3) (including carbon atoms other than carbon atoms in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly carrying out the above-mentioned intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. As specific preferred compounds of the alkali generator, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002 can also be cited.

[0834] Furthermore, the base generating agent also preferably contains a compound represented by the following formula (N1).

[0835] [Chemical formula 57]

[0836]

[0837] In formula (N1), R N1 and R N2 Each independently represents a monovalent organic group, R C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0838] L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. As an upper limit, it is preferably 12 or less, more preferably 8 or less, and further preferably 5 or less. The linking chain length refers to the number of atoms present in the atomic arrangement, and the atomic arrangement becomes the shortest distance between the two carbonyl groups in the formula.

[0839] In formula (N1), R N1 and R N2 Each independently represents a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 1 to 10), and specifically, an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 1 to 10) or an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), preferably an aliphatic hydrocarbon group. When an aliphatic hydrocarbon group is used as R N1 and R N2 , the basicity of the generated base is high, so it is preferred. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain or in the aromatic ring or in the substituent. In particular, the aliphatic hydrocarbon group can be exemplified as having an oxygen atom in the hydrocarbon chain.

[0840] As a component of R N1 and R N2 The aliphatic hydrocarbon group includes a linear or branched chain alkyl group, a cyclic alkyl group, a group including a combination of a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The number of carbon atoms in the linear or branched chain alkyl group is preferably 1 to 24, more preferably 2 to 18, and further preferably 3 to 12. Examples of the linear or branched chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, and the like.

[0841] The number of carbon atoms in the cyclic alkyl group is preferably 3 to 12, more preferably 3 to 6. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0842] The number of carbon atoms of the group comprising a combination of a chain alkyl group and a cyclic alkyl group is preferably 4 to 24, more preferably 4 to 18, and further preferably 4 to 12. Examples of the group comprising a combination of a chain alkyl group and a cyclic alkyl group include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl.

[0843] The number of carbon atoms in the alkyl group having an oxygen atom in the chain is preferably 2 to 12, more preferably 2 to 6, and further preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be chain-like, cyclic, linear or branched.

[0844] However, from the viewpoint of increasing the boiling point of the base generated by decomposition described later, R N1 and R N2 An alkyl group having 5 to 12 carbon atoms is preferred. However, in a formulation where adhesion to a metal (eg, copper) layer is important, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

[0845] R N1 and R N2 The ring structure may have oxygen atoms in the chain. N1 and R N2 The formed cyclic structure can be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. As the formed cyclic structure, a 5-membered ring or a 6-membered ring containing a nitrogen atom in formula (N1) is preferred, for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc. can be cited, and preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring can be cited.

[0846] R C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

[0847] As the protecting group, a protecting group that is decomposed by the action of an acid or a base is preferred, and a protecting group that is decomposed by an acid is preferably used.

[0848] As a specific example of the protecting group, a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain can be cited. As chain or cyclic alkyl groups, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, etc. can be cited. As chain alkyl groups having an oxygen atom in the chain, alkoxyalkyl groups can be cited, preferably methoxymethyl (MOM) groups, ethoxyethyl (EE) groups, etc. can be cited. As cyclic alkyl groups having an oxygen atom in the chain, epoxy groups, glycidyl groups, oxetanyl groups, tetrahydrofuranyl groups, tetrahydropyranyl (THP) groups, etc. can be cited.

[0849] In formula (N1), the divalent linking group constituting L is not particularly limited, and is preferably a hydrocarbon group, and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may also have atoms other than carbon atoms in the hydrocarbon chain. The divalent linking group is more preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, and further preferably a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a group comprising a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group that may have an oxygen atom in the chain, and further preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. These groups may not have an oxygen atom.

[0850] The number of carbon atoms of the divalent hydrocarbon linking group is preferably 1 to 24, more preferably 2 to 12, and further preferably 2 to 6. The number of carbon atoms of the divalent aliphatic hydrocarbon group is preferably 1 to 12, more preferably 2 to 6, and further preferably 2 to 4. The number of carbon atoms of the divalent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 18, and further preferably 6 to 10. The number of carbon atoms of the group comprising a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (e.g., aralkylene group) is preferably 7 to 22, more preferably 7 to 18, and further preferably 7 to 10.

[0851] Specifically, the linking group L is preferably a linear or branched chain alkylene group, a cyclic alkylene group, a group comprising a combination of a linear alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, or an arylene alkylene group.

[0852] The linear or branched alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.

[0853] The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.

[0854] The number of carbon atoms of the group consisting of a combination of a linear alkylene group and a cyclic alkylene group is preferably 4 to 24, more preferably 4 to 12, and even more preferably 4 to 6.

[0855] The alkylene group having an oxygen atom in its chain may be chain or cyclic, and may be linear or branched. The number of carbon atoms in the alkylene group having an oxygen atom in its chain is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.

[0856] The number of carbon atoms in the linear or branched alkenylene group is preferably 2 to 12, more preferably 2 to 6, and further preferably 2 to 3. The number of C═C bonds in the linear or branched alkenylene group is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 3.

[0857] The number of carbon atoms in the cyclic alkenylene group is preferably 3 to 12, more preferably 3 to 6. The number of C═C bonds in the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.

[0858] The arylene group has preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms.

[0859] The arylenealkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 11 carbon atoms.

[0860] Among them, preferred are chain alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, chain alkenylene groups, arylene groups, and arylene alkylene groups; more preferred are 1,2-ethylene, propylene (particularly 1,3-propylene), cyclohexanediyl (particularly 1,2-cyclohexanediyl), vinylene (particularly cis-vinylene), phenylene (1,2-phenylene), phenylene methylene (particularly 1,2-phenylene methylene), and ethyleneoxyethylene (particularly 1,2-ethyleneoxy-1,2-ethylene).

[0861] Examples of the base generating agent include the following compounds, but the base generating agent is not limited to these compounds.

[0862] [Chemical formula 58]

[0863]

[0864] 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.

[0865] 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.

[0866] Specific examples of the ammonium salt include the following compounds, but are not limited to these.

[0867] [Chemical formula 59]

[0868]

[0869] Specific examples of the imide salt include the following compounds, but are not limited to these.

[0870] [Chemical formula 60]

[0871]

[0872] 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.

[0873] 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.

[0874] <(D) Radical Inhibitor>

[0875] The resin composition of the present invention contains (D) a radical polymerization inhibitor. The (D) radical polymerization inhibitor is at least one compound selected from (D-1) a compound having a radical in the molecule and (D-2) a compound having no radical in the molecule and having a molecular weight of 270 or more.

[0876] As the (D) radical polymerization inhibitor, it is preferred to contain at least (D-1) a compound having a radical in the molecule.

[0877] [(D-1) Compounds having free radicals in their molecules]

[0878] (D-1) The compound having a radical in the molecule (also referred to as "compound (D-1)") is a compound having a radical in the molecule and functioning as a radical polymerization inhibitor.

[0879] The compound (D-1) is preferably a compound having an oxygen radical (*-O·) in the molecule. * indicates a bonding position to another structure.

[0880] The compound (D-1) is preferably a compound having an N-oxyl radical (a group represented by the following formula (n1)) in the molecule. In the following formula (n1), * represents a bonding position to another structure.

[0881] [Chemical formula 61]

[0882]

[0883] The compound (D-1) is further preferably a compound represented by the following formula (n2).

[0884] [Chemical formula 62]

[0885]

[0886] In formula (n2), Q1 to Q8 each independently represent a hydrogen atom or a substituent. p represents an integer of 1 to 5. When there are multiple Q3 and Q4, they may be different or the same. At least two of Q1 to Q8 may be bonded to form a ring. At least one of -CQ1Q2-, -CQ3Q4-, -CQ5Q6-, and -CQ7Q8- may be substituted by at least one of -O- and -C(=O)-.

[0887] The substituent represented by Q1 to Q8 is not particularly limited, but examples thereof include organic groups, sulfonamide groups, halogen atoms, hydroxyl groups, sulfo groups, amino groups, thiol groups, cyano groups, carboxyl groups, epoxy groups, glycidyl groups, (meth)acryloyl groups, (meth)acryloyloxy groups, (meth)acrylamide groups, nitro groups, isocyanate groups, isothiocyanate groups, (trialkoxysilyl)alkoxy groups, (trialkoxysilyl)alkylamide groups, etc. There are no particular limitations on the organic group, and examples thereof include the following organic group W.

[0888] (Organic Group W)

[0889] Examples of the organic group W include alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heterocyclic, aralkyl, cyano, alkoxy, aryloxy, heterocyclicoxy, acyl (alkylcarbonyl or arylcarbonyl), acyloxy (alkylcarbonyloxy or arylcarbonyloxy), carbamoyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkylthio, arylthio, heterocyclicthio, alkyl or arylsulfinyl, alkyl or arylsulfonyl, arylcarbonyloxy, aryloxycarbonyloxy, aryl or heterocyclic azo, acylamino, sulfonamide, imide, acylamino, carbamoyl, and lactone.

[0890] Furthermore, each of the above groups may further have a substituent if possible. For example, an alkyl group which may have a substituent is also included as one form of the organic group W. The above substituent is not particularly limited, but examples thereof include one or more of the groups shown as the organic group W, a halogen atom, a nitro group, a primary to a tertiary amine group, a phosphine group, a phosphine group, a phosphineoxy group, a phosphineamino group, a phosphono group, a silyl group, a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like (hereinafter referred to as "substituent T").

[0891] Furthermore, the number of carbon atoms in the organic group W is, for example, 1 to 30.

[0892] Furthermore, the number of atoms other than hydrogen atoms contained in the organic group W is, for example, 1 to 50.

[0893] Furthermore, the number of carbon atoms of the alkyl group exemplified in the organic group W is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.

[0894] The alkyl group may be either linear or branched.

[0895] Examples of the alkyl group include linear or branched alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, and n-hexyl group.

[0896] In the alkyl group which may have a substituent, the substituent which the alkyl group may have is not particularly limited, and examples thereof include the groups exemplified in the substituent T described above.

[0897] As the alkyl moiety in the alkoxy group (including the alkoxy moiety in the substituent group containing an alkoxy group (for example, alkoxycarbonyloxy group)), the alkyl moiety in the aralkyl group, the alkyl moiety in the alkylcarbonyl group, the alkyl moiety in the alkylcarbonyloxy group, the alkyl moiety in the alkylthio group, the alkyl moiety in the alkylsulfinyl group, and the alkyl moiety in the alkylsulfonyl group exemplified in the organic group W, the above-mentioned alkyl groups are preferred. In addition, in the alkoxy group which may have a substituent, the aralkyl group which may have a substituent, the alkylcarbonyloxy group which may have a substituent, the alkylthio group which may have a substituent, the alkylsulfinyl group which may have a substituent, and the alkylsulfonyl group which may have a substituent, the same substituent as the substituent in the alkyl group which may have a substituent can be mentioned.

[0898] Examples of the cycloalkyl group in the organic group W include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. The number of carbon atoms in the cycloalkyl group is preferably 5 to 20, more preferably 5 to 15. In the cycloalkyl group which may have a substituent, the substituents which the cycloalkyl group may have may be the same as the substituents in the alkyl group which may have a substituent.

[0899] The alkenyl group exemplified in the organic group W may be linear or branched. The number of carbon atoms of the alkenyl group is preferably 2 to 20. The substituents that the alkenyl group may have include the same examples as the substituents in the alkyl group that may have a substituent.

[0900] The number of carbon atoms of the cycloalkenyl group exemplified in the organic group W is preferably 5 to 20. In the cycloalkenyl group which may have a substituent, the substituent which may be possessed by the cycloalkenyl group may be the same as the substituent in the alkyl group which may have a substituent.

[0901] The alkynyl group exemplified in the organic group W may be either linear or branched. The number of carbon atoms in the alkynyl group is preferably 2 to 20. In the alkynyl group which may have a substituent, the substituent which the alkynyl group may have may be the same as the substituent in the alkyl group which may have a substituent.

[0902] The number of carbon atoms of the cycloalkynyl group exemplified in the organic group W is preferably 5 to 20. In the cycloalkynyl group which may have a substituent, the substituent which may have the cycloalkynyl group may be exemplified by the same substituent as in the alkyl group which may have a substituent.

[0903] Unless otherwise specified, the aryl group exemplified in the organic group W may be a monocyclic group or a polycyclic group (eg, 2 to 6 rings).

[0904] The number of ring atoms of the aryl group is preferably 6-15, more preferably 6-10.

[0905] The aryl group is preferably a phenyl group, a naphthyl group, or an anthracenyl group, and more preferably a phenyl group.

[0906] In the aryl group which may have a substituent, examples of the substituent which the aryl group may have include the same examples as the substituents in the alkyl group which may have a substituent.

[0907] Furthermore, regarding the aryl moiety in the aryl-containing substituent (for example, aryloxy group) among the groups exemplified in the organic group W, the same examples as those exemplified in the above-mentioned organic group W can also be given.

[0908] The heterocyclic group exemplified in the organic group W may be any of an aromatic heterocyclic group (heteroaryl group) and an aliphatic heterocyclic group, and may be any of a monocyclic ring and a polycyclic ring (for example, 2 to 6 rings).

[0909] The number of heteroatoms contained in the heterocyclic group as ring-constituting atoms is, for example, 1 to 10. Examples of the heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon and boron atoms.

[0910] The number of ring atoms of the heterocyclic group is preferably 5 to 15.

[0911] In the heterocyclic group which may have a substituent, examples of the substituent which the heterocyclic group may have include the same examples as the substituents in the alkyl group which may have a substituent.

[0912] The heterocyclic ring of the heterocyclic oxy group, heterocyclic thio group and heterocyclic azo group exemplified in the organic group W refers to a ring containing a heteroatom as a ring-constituting atom, and unless otherwise specified, may be any of an aromatic heterocyclic ring and an aliphatic heterocyclic ring, and may be any of a monocyclic ring and a polycyclic ring (e.g., 2 to 6 rings).

[0913] The number of hetero atoms contained in the hetero ring as ring-constituting atoms is, for example, 1 to 10. Examples of the hetero atom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom.

[0914] The number of ring atoms of the heterocyclic ring is preferably 5 to 15.

[0915] In the heterocyclic ring which may have a substituent, examples of the substituent which the heterocyclic ring may have include the same examples as the substituents in the alkyl group which may have a substituent.

[0916] As the lactone group exemplified in the organic group W, a 5- to 7-membered lactone group is preferred, and a 5- to 7-membered lactone ring in which another ring structure is condensed to form a bicyclic structure or a spiro structure is more preferred.

[0917] In the lactone group which may have a substituent, examples of the substituent which the lactone group may have include the same examples as the substituents in the alkyl group which may have a substituent.

[0918] Preferably, at least one of Q1 to Q8 is a polar group. Examples of the polar group include alkoxy, acyl, acyloxy, amido, carbamoyl, hydroxyl, cyano, carboxyl, amine, thiol, epoxy, glycidyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamide, and nitro. Particularly preferred are alkoxy, acyl, acyloxy, amido, carbamoyl, hydroxyl, cyano, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamide, and nitro.

[0919] Also preferred is an embodiment in which at least one of -CQ1Q2-, -CQ3Q4-, -CQ5Q6-, and -CQ7Q8- may be substituted with at least one of -O- and -C(=O)-.

[0920] p represents an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

[0921] The compound (D-1) is particularly preferably a compound represented by the following formula (n3).

[0922] [Chemical formula 63]

[0923]

[0924] In the formula (n3), Q9 represents a hydrogen atom or a substituent.

[0925] Q9 preferably represents a substituent, and more preferably represents a polar group. The polar group is the same as described above.

[0926] The molecular weight of the compound (D-1) is preferably 140 or more, more preferably 160 or more, and further preferably 170 or more. The upper limit of the molecular weight of the compound (D-1) is not particularly limited, but may be, for example, 3000 or less, or 1000 or less. Furthermore, the compound (D-1) may be a polymer, in which case the weight average molecular weight may be 3000 to 30000.

[0927] [(D-2) A compound having no free radical in the molecule and having a molecular weight of 270 or more]

[0928] (D-2) The compound having no radical in the molecule and a molecular weight of 270 or more (also referred to as "compound (D-2)") is a compound having no radical in the molecule, a molecular weight of 270 or more, and acting as a radical polymerization inhibitor.

[0929] The molecular weight of the compound (D-2) is preferably 500 or more, more preferably 700 or more. The upper limit of the molecular weight of the compound (D-2) is not particularly limited, but may be, for example, 3000 or less, or 2000 or less. Furthermore, the compound (D-2) may be a polymer, in which case the weight average molecular weight may be 3000 to 30000.

[0930] The compound (D-2) is preferably at least one selected from phenolic compounds, quinone compounds, amino compounds, thiol compounds, phosphorus compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds and metal compounds.

[0931] A phenolic compound is a compound formed by replacing one or more hydroxyl groups on an aromatic ring, more preferably a compound formed by replacing one or more hydroxyl groups on an aromatic hydrocarbon ring, further preferably a compound formed by replacing one or more hydroxyl groups on an aromatic hydrocarbon ring having 6 to 20 carbon atoms, and particularly preferably a compound formed by replacing one or more hydroxyl groups on a benzene ring or a naphthalene ring. The number of hydroxyl groups substituted on one aromatic ring of a phenolic compound is preferably 1 or more and 4 or less. As a phenolic compound, a compound represented by the following formula (m1) is preferred.

[0932] As the quinone-based compound, a compound represented by the following formula (m2) is preferred.

[0933] As the amine-based compound, an aromatic amine compound is preferred, and at least one selected from the group consisting of a compound represented by the following formula (m3) and a compound represented by the following formula (m4) is preferred.

[0934] [Chemical formula 64]

[0935]

[0936] In formula (m1), R C1 and R C2 Each independently represents a hydrogen atom or an organic group. C1 and R C2 At least one of R represents an organic group. C3 represents a substituent. r1 represents an integer from 0 to 3.C3 In the case of multiple R C3 Can be the same or different. C3 They may be bonded to each other to form a ring.

[0937] In formula (m2), R C4 and R C5 R each independently represents a hydrogen atom or a substituent. C6 represents a substituent. r2 represents an integer from 0 to 4. C6 In the case of multiple R C6 Can be the same or different. C4 and R C5 Can be bonded to form a ring. C6 They may be bonded to each other to form a ring.

[0938] In formula (m3), R C7 and R C8 Each independently represents a substituent. r3 and r4 each independently represent an integer of 0 to 5. C7 In the case of multiple R C7 Can be the same or different. C7 They can bond to each other to form a ring. C8 In the case of multiple R C8 Can be the same or different. C8 They may be bonded to each other to form a ring.

[0939] In formula (m4), R C9 and R C10 Each independently represents a substituent. r5 and r6 each independently represent an integer of 0 to 4. C9 In the case of multiple R C9 Can be the same or different. C9 They can bond to each other to form a ring. C10 In the case of multiple R C10 Can be the same or different. C10 They may bond to each other to form a ring. C1 represents a single bond or a divalent linking group.

[0940] In formula (m1), as R C1 and R C2 The at least one organic group represented by includes the organic group W mentioned above, preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably a tert-butyl group.

[0941] In R C3In the case of an organic group, an organic group having 1 to 100 carbon atoms is preferred, and an organic group having 1 to 50 carbon atoms is more preferred. Examples of the organic group include the organic group W described above.

[0942] In formula (m2), as R C4 ~R C6 The substituent represented is not particularly limited, but examples thereof include organic groups, sulfonamide groups, halogen atoms, hydroxyl groups, sulfo groups, amino groups, thiol groups, cyano groups, carboxyl groups, epoxy groups, glycidyl groups, (meth)acryloyl groups, (meth)acryloyloxy groups, (meth)acrylamide groups, nitro groups, etc. As the organic group, the organic group W mentioned above can be listed.

[0943] In formula (m3) and formula (m4), R C7 ~R C10 The substituent represented is not particularly limited, and examples thereof include organic groups, hydroxyl groups, halogen atoms, amino groups (the amino group may have a substituent, and the substituent may include the organic group W described above), etc. As the organic group, the organic group W described above may be mentioned.

[0944] As L C1 The divalent linking group represented by is not particularly limited, but preferably alkylene, -S-, -O-, -SO-, -SO2-, -CO-, -NR C11 -, or a linking group formed by combining two or more of these. C11 represents a hydrogen atom or an organic group. Examples of the organic group include the organic group W described above.

[0945] As the thiol compound, an aromatic thiol compound is preferred. The aromatic thiol compound is preferably a compound in which a thiol group and an aromatic group are bonded, and examples of the aromatic group include aryl groups and heteroaryl groups, and examples of the aryl groups and heteroaryl groups include the aryl groups and heteroaryl groups exemplified in the organic group W.

[0946] As the phosphorus compound, a phosphite compound is preferred, and an aromatic phosphite compound is more preferred. As the aromatic group contained in the aromatic phosphite compound, an aryl group and a heteroaryl group can be listed, and as the aryl group and the heteroaryl group, the aryl group and the heteroaryl group exemplified in the organic group W can be listed.

[0947] As the nitro compound and the nitroso compound, an aromatic nitro compound and an aromatic nitroso compound are preferred. The aromatic ring contained in the aromatic nitro compound and the aromatic nitroso compound is preferably an aromatic hydrocarbon ring. The number of carbon atoms forming the aromatic ring is preferably 6 to 20, more preferably 6 to 15. The aromatic ring may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, a hydroxyl group, and the like.

[0948] (D) The content of the radical polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 10% by mass, and even more preferably 0.05 to 5% by mass, based on the total solid content of the resin composition.

[0949] (D) The radical polymerization inhibitor can be used alone or in combination of two or more. When two or more radical polymerization inhibitors are used, the total amount is preferably within the above range.

[0950] <Other inhibitors>

[0951] The resin composition of the present invention may contain other polymerization inhibitors (polymerization inhibitors other than the above-mentioned (D) free radical polymerization inhibitor). Other polymerization inhibitors are compounds having no free radicals in the molecule and a molecular weight of less than 270, and examples thereof include phenolic compounds, quinone compounds, amino compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0952] Specific examples of other polymerization inhibitors include compounds described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, phenoxazine, and the like. This content is incorporated into the present specification.

[0953] When the resin composition of the present invention contains other polymerization inhibitors, the content of the other polymerization inhibitors is preferably 0.01 to 20% by mass, more preferably 0.02 to 10% by mass, and further preferably 0.05 to 5% by mass based on the total solid content of the resin composition.

[0954] The other polymerization inhibitor may be used alone or in combination of two or more. When the other polymerization inhibitor is used in combination of two or more, the total amount thereof is preferably within the above range.

[0955] <(E) Solvent>

[0956] The resin composition of the present invention contains (E) a solvent (also simply referred to as a "solvent").

[0957] 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.

[0958] 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, 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.

[0959] 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.

[0960] Examples of the ketones preferably include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0961] 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.

[0962] As the sulfoxides, for example, dimethyl sulfoxide can be mentioned as a preferred sulfoxide.

[0963] As 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.

[0964] As the urea, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferred.

[0965] 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.

[0966] 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.

[0967] In the present invention, preferably, it is a solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celulose 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, dimethyl sulfoxide and γ-valerolactone, 3-methoxy-N, N-dimethylpropionamide and γ-butyrolactone, 3-methoxy-N, N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or N-methyl-2-pyrrolidone and ethyl lactate simultaneously. It is also one of the preferred embodiments of the present invention to further add 1 to 10% by mass of toluene to the total mass of the solvent to these solvents used simultaneously.

[0968] Especially, from the viewpoint of the storage stability of resin combination etc., the mode comprising γ-valerolactone as solvent is also one of preferred modes of the present invention.In such mode, the content of γ-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 included in resin combination etc. to determine.

[0969] Furthermore, when dimethyl sulfoxide and γ-valerolactone are used simultaneously, it is preferred that the total mass of the solvent 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.

[0970] The solid content concentration of the resin composition of the present invention is not particularly limited and can be set to, for example, 1 to 80% by mass. However, when applied by a slit coating method, it is preferably 40% by mass or less, more preferably 5 to 35% by mass, and particularly preferably 10 to 33% by mass.

[0971] The content of the solvent is preferably such that the solid content concentration of the resin composition of the present invention is within the above range. When two or more solvents are contained, the total of the solvents is preferably within the above range.

[0972] <Acid Capture Agent>

[0973] In order to reduce the performance change caused by time from exposure to heating, the resin combination of the present invention preferably contains an acid capture agent. Here, the acid capture agent refers to a compound that can capture acid by being present in the system, preferably a compound with low acidity and high pKa. As the acid capture agent, it is preferably a compound with amino, preferably a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, etc., preferably a primary amine, a secondary amine, a tertiary amine, an ammonium salt, more preferably a secondary amine, a tertiary amine, an ammonium salt.

[0974] As the acid scavenger, preferably, there can be mentioned compounds having an imidazole structure, a diazabicyclic structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, etc. When having an onium structure, the acid scavenger is preferably selected from ammonium, diazo, iodine, sulfonium, A salt of a cation such as pyridinium and an anion of an acid having lower acidity than the acid generated by the acid generator.

[0975] Examples of the acid scavenger having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of the acid scavenger having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of the acid scavenger having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group. Specifically, examples include triphenylsulfonium hydroxide, tri(tert-butylphenyl)sulfonium hydroxide, bis(tert-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. As acid scavengers having a trialkylamine structure, tri(n-butyl)amine, tri(n-octyl)amine, etc. can be cited. As acid scavengers having an aniline structure, 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, N,N-dihexylaniline, etc. can be cited. As acid scavengers having a pyridine structure, pyridine, 4-methylpyridine, etc. can be cited. As alkylamine derivatives having a hydroxyl group and / or an ether bond, ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tri(methoxyethoxyethyl)amine, etc. can be cited. As aniline derivatives having a hydroxyl group and / or an ether bond, N,N-bis(hydroxyethyl)aniline, etc. can be cited.

[0976] Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methyl Hexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-diphenylamineethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, etc.

[0977] The acid scavenger may be used alone or in combination of two or more. The composition of the present invention may contain an acid scavenger, but when contained, the content of the acid scavenger is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the composition.

[0978] The ratio of the acid generator to the acid trapping agent is preferably acid generator / acid trapping agent (molar ratio) = 2.5 to 300. That is, from the viewpoint of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing the decrease in resolution caused by the coarsening of the relief pattern over time before the post-exposure heat treatment, it is preferably 300 or less. The acid generator / acid trapping agent (molar ratio) is preferably 5.0 to 200, and more preferably 7.0 to 150.

[0979] [Urea compounds, carbodiimide compounds, isourea compounds]

[0980] From the viewpoint of elongation at break and adhesion to a metal or resin layer, the resin composition of the present invention may contain at least one compound selected from urea compounds, carbodiimide compounds and isourea compounds (hereinafter also referred to as “urea compounds etc.”).

[0981] Examples of the urea compound include compounds represented by the following formula (UR-1), examples of the carbodiimide compound include compounds represented by the following formula (UR-2), and examples of the isourea compound include compounds represented by the following formula (UR-3).

[0982] [Chemical formula 65]

[0983]

[0984] 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.

[0985] In formula (UR-1), R 11 and R 12Each 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 at least one substituent selected from a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, a tertiary amine salt structure and a quaternary ammonium as a substituent, and is more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.

[0986] 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.

[0987] In formula (UR-1), R 11 and R 12 Each of the 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.

[0988] The aliphatic hydrocarbon group having 2 to 7 carbon atoms may have two or more substituents, but preferably has only one substituent.

[0989] 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.

[0990] In formula (UR-2), preferably R 21 and R 22 It is 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, and it is more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.

[0991] In formula (UR-2), R 21 and R 22 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 substituent are the same as the preferred embodiments described in the description of R11 and R12, respectively.

[0992] In formula (UR-3), preferably R 31 and R 32 It is 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, and it is more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.

[0993] In formula (UR-3), R 31 and R 32Preferred 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 substituent are the same as the preferred embodiments described in the description of R11 and R12, respectively.

[0994] 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.

[0995] In formula (UR-3), R 33 , preferably methyl, ethyl, propyl, isopropyl, butyl or tert-butyl, more preferably ethyl.

[0996] Specific examples of the urea compound include dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, diisopropylisourea, and the like, but are not limited thereto.

[0997] The total content of the urea compound and the like is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 8.0 parts by mass, and even more preferably 1.0 to 6.0 parts by mass, based on 100 parts by mass of the specific resin.

[0998] The urea compound or the like may be used alone or in combination of two or more thereof. When two or more alkalis are used in combination in the alkali-containing treatment liquid, the total content of these alkalis is preferably within the above range.

[0999] <Characteristics of Resin Composition>

[1000] 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, further 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 with excellent coating surface shape can be obtained.

[1001] <Regarding Restrictions on Substances Contained in Resin Compositions>

[1002] 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.

[1003] 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.

[1004] 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.

[1005] In addition, as a method for reducing metal impurities unintentionally 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.

[1006] 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.

[1007] As a method for adjusting the content of halogen atoms, ion exchange treatment or the like is preferably mentioned.

[1008] 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, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

[1009] <Cured product of resin composition>

[1010] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[1011] The cured product of the present invention is a cured product obtained by curing the resin composition.

[1012] 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.

[1013] 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.

[1014] Shrinkage rate [%] = 100-(volume after curing ÷ volume before curing) × 100

[1015] <Characteristics of Cured Product of Resin Composition>

[1016] 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.

[1017] 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.

[1018] 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.

[1019] <Metal Adhesion Improver>

[1020] 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.

[1021] 〔Silane coupling agent〕

[1022] As the 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 Application 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 Application 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 Ft represents an ethyl group.

[1023] [Chemical formula 66]

[1024]

[1025] 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.

[1026] 〔Aluminum-based adhesive additive〕

[1027] Examples of the aluminum-based adhesion promoter include tris(ethyl acetoacetate)aluminum, tris(acetylacetonate)aluminum, and diisopropyl ethyl acetoacetate aluminum.

[1028] 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.

[1029] 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 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.

[1030] <Migration Inhibitor>

[1031] 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.

[1032] 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, and a triazine ring), compounds having a thiourea or a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[1033] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions may also be used.

[1034] As other migration inhibitors, for example, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication 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.

[1035] Specific examples of the migration inhibitor include the following compounds.

[1036] [Chemical formula 67]

[1037]

[1038] 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.

[1039] 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.

[1040] <Organometallic Complex>

[1041] From the viewpoint of chemical resistance, the resin composition of the present invention may contain an organic metal complex.

[1042] The organometallic complex is not particularly limited as long as it is an organic complex compound containing a metal atom, but is preferably a complex compound containing a metal atom and an organic group, more preferably a compound in which an organic group is coordinated to a metal atom, and still more preferably a metallocene compound.

[1043] The metallocene compound refers to an organic metal complex containing two cyclopentadienyl anion derivatives which may have substituents as η5-ligands.

[1044] The organic group is not particularly limited, but is preferably a hydrocarbon group or a group consisting of a hydrocarbon group and a hetero atom. The hetero atom is preferably an oxygen atom, a sulfur atom, or a nitrogen atom.

[1045] It is preferred that at least one of the above organic groups is a cyclic group, and it is more preferred that at least two of the organic groups are cyclic groups.

[1046] The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably a 5-membered cyclic group.

[1047] The cyclic group may be a hydrocarbon ring or a heterocyclic ring, and is preferably a hydrocarbon ring.

[1048] The 5-membered cyclic group is preferably a cyclopentadienyl group.

[1049] The organic metal complex preferably contains 2 to 4 cyclic groups in one molecule.

[1050] The metal contained in the organometallic complex is not particularly limited, but is preferably a metal corresponding to a Group 4 element, more preferably at least one metal selected from titanium, zirconium and hafnium, further preferably at least one metal selected from titanium and zirconium, and particularly preferably titanium.

[1051] The organometallic complex may contain two or more metal atoms or only one metal atom, but preferably contains only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one metal atom or two or more metal atoms.

[1052] The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound or a hafnocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, further preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.

[1053] An embodiment in which the organic metal complex has a photoradical polymerization initiation capability is preferred.

[1054] In the present invention, having the ability to initiate photo-radical polymerization means being able to generate free radicals capable of initiating free radical polymerization by irradiation with light. For example, when a composition comprising a free radical crosslinking agent and an organic metal complex is irradiated with light in a wavelength region where the organic metal complex absorbs light and the free radical crosslinking agent does not absorb light, the presence or absence of the ability to initiate photo-radical polymerization can be confirmed by confirming whether the free radical crosslinking agent disappears. In order to confirm whether there is disappearance, an appropriate method can be selected according to the type of the free radical crosslinking agent, for example, it can be confirmed by IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography).

[1055] When the organometallic complex has the ability to initiate photoradical polymerization, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, further preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.

[1056] When the organometallic complex does not have the ability to initiate photoradical polymerization, the organometallic complex is preferably at least one compound selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, acylated titanium compounds, chelated titanium compounds, zirconocene compounds and hafnocene compounds, more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds and hafnocene compounds, further preferably at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds, and particularly preferably a titanocene compound.

[1057] The molecular weight of the organic metal complex is preferably 50 to 2,000, more preferably 100 to 1,000.

[1058] Preferred examples of the organic metal complex include compounds represented by the following formula (P).

[1059] [Chemical formula 68]

[1060]

[1061] In formula (P), M is a metal atom, and R is each independently a substituent.

[1062] It is preferred that R is each independently selected from an aromatic group, an alkyl group, a halogen atom and an alkylsulfonyloxy group.

[1063] The metal atom represented by M in formula (P) is preferably an iron atom, a titanium atom, a zirconium atom or a hafnium atom, more preferably a titanium atom, a zirconium atom or a hafnium atom, further preferably a titanium atom or a zirconium atom, and particularly preferably a titanium atom.

[1064] Examples of the aromatic group in R in the formula (P) include aromatic groups having 6 to 20 carbon atoms, preferably aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as phenyl, 1-naphthyl or 2-naphthyl.

[1065] The alkyl group in R in formula (P) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, propyl, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, and cyclopentyl.

[1066] Examples of the halogen atom in the above R include F, Cl, Br and I.

[1067] The alkyl group constituting the alkylsulfonyloxy group in the above R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, propyl, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, and cyclopentyl.

[1068] The above R may further have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, and a diarylamino group.

[1069] Specific examples of organic metal complexes are not particularly limited, but include tetraisopropoxytitanium, tetra(2-ethylhexyloxy)titanium, diisopropoxybis(ethyl acetoacetate)titanium, diisopropoxybis(acetylacetonate)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, pentamethylcyclopentadienyltrimethoxytitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium and the following compounds.

[1070] [Chemical formula 69]

[1071]

[1072] In addition, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018 / 025738 can also be mentioned, and the contents are incorporated into the present specification.

[1073] The content of the organic metal complex is preferably 0.1 to 30% by mass relative to the total solid content of the resin composition. The lower limit is more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, particularly preferably 3.0% by mass or more, and the upper limit is more preferably 25% by mass or less.

[1074] The organic metal complex can be used alone or in combination. When two or more organic metal complexes are used, the total amount is preferably within the above range.

[1075] The resin composition may contain a compound whose absorbance at an exposure wavelength decreases due to exposure (hereinafter, also referred to as “compound AA”).

[1076] It can be inferred that since the resin composition contains compound AA whose absorbance at the exposure wavelength becomes smaller due to exposure, when the layer composed of the resin composition is exposed, compound AA absorbs the exposure light, so that photosensitizers such as photopolymerization initiators are not easily photosensitized in areas with a small exposure amount (for example, areas around the area actually to be exposed), and in areas with a large exposure amount, photosensitizers such as photopolymerization initiators become easily photosensitized due to the decolorization of compound AA (the absorbance at the exposure wavelength becomes smaller due to exposure).

[1077] Furthermore, it is considered that the decomposition product (for example, the decomposition product of the naphthoquinonediazide compound) generated by the decolorization of the compound AA is also incorporated into the crosslinking of the resin etc., and the crosslinking density is further increased, thereby improving the chemical resistance of the cured product.

[1078] In particular, when the resin composition contains a specific resin as the resin and a naphthoquinonebisazide compound as the compound AA, the resin and the decomposition product of the naphthoquinonebisazide compound may form a crosslinked structure, and the chemical resistance may be significantly improved.

[1079] Whether or not the compound a contained in the resin composition is the compound AA (that is, whether or not the absorbance at the exposure wavelength decreases due to exposure) can be determined by the following method.

[1080] 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 referred to as "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, the solvent is used when the resin composition contains a solvent, and N-methyl-2-pyrrolidone is used when the resin composition does not contain a solvent.

[1081] Next, the solution of the compound a was irradiated with exposure light at a cumulative exposure dose of 500 mJ per mol of the compound a.

[1082] Then, the molar absorption coefficient (mol -1 ·L·cm -1 , also known as the "molar absorption coefficient 2". ).

[1083] 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 5% or more, compound a is judged to be a compound whose absorbance at the exposure wavelength decreases due to exposure (i.e., compound AA).

[1084] Attenuation rate (%) = (1-molar absorption coefficient 2 / molar absorption coefficient 1) × 100

[1085] The attenuation rate is preferably 10% or more, and more preferably 20% or more. The upper limit of the attenuation rate is not particularly limited, and may be 100%.

[1086] 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.

[1087] Furthermore, when the resin composition contains a photopolymerization initiator as a compound different from compound AA, the wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator is sensitive. The photopolymerization initiator is sensitive to a certain wavelength, which means that polymerization initiating species are generated when the photopolymerization initiator is exposed to light at a certain wavelength.

[1088] As for the wavelength of the above-mentioned exposure light, in relation to the light source, there are (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.

[1089] The wavelength of the exposure light may be any wavelength to which the photopolymerization initiator is sensitive, and h-rays (wavelength 405 nm) or i-rays (wavelength 365 nm) are preferred, and i-rays (wavelength 365 nm) are more preferred.

[1090] Compound AA 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.

[1091] Whether or not compound AA is a compound that generates a radical polymerization initiating species upon exposure can be determined by the following method.

[1092] A solution containing the same concentration of compound AA and a radical crosslinking agent as that contained in the resin composition is prepared. When the resin composition contains a radical crosslinking agent, as the radical crosslinking agent in the above solution, the same compound as that contained in the resin composition is used at the same concentration. When the resin composition does not contain a radical crosslinking agent, methyl methacrylate is used at a concentration 5 times that of compound AA.

[1093] Thereafter, exposure light was irradiated, and the accumulated exposure amount was set to 500 mJ.

[1094] After exposure, polymerization of the polymerizable compound is determined by, for example, high performance liquid chromatography. When the ratio of the molar amount of the polymerizable compound polymerized to the total molar amount of the polymerizable compound is 10% or less, compound AA is determined to be a compound that does not generate radical polymerization initiating species by exposure.

[1095] 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%.

[1096] 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.

[1097] The wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition has sensitivity.

[1098] As the compound generating free radical polymerization initiating species by exposure, the same compounds as the photo radical polymerization initiator can be cited. When the composition contains the photo radical polymerization initiator as compound AA, the compound with the lowest polymerization initiating ability of the generated free radical species is used as compound AA, and the others are used as photo polymerization initiators.

[1099] Examples of the compound that does not generate a radical polymerization initiating species by exposure include, in addition to a photoacid generator and a photobase generator, a pigment whose absorption wavelength changes by exposure.

[1100] Among them, the compound AA is preferably a naphthoquinonediazide compound or a dye whose absorbance changes upon exposure, and more preferably a naphthoquinonediazide compound.

[1101] Furthermore, as compound AA, for example, a photoacid generator or a photobase generator can be used in combination with a compound whose absorbance at an exposure wavelength decreases depending on pH.

[1102] 〔Naphthoquinone diazide〕

[1103] Examples of the naphthoquinonediazide compound include compounds that generate indenecarboxylic acid upon exposure and whose absorbance at the exposure wavelength decreases, and compounds having a 1,2-naphthoquinonediazide structure are preferred.

[1104] As the naphthoquinonediazide compound, naphthoquinonediazidesulfonic acid esters of hydroxy compounds are preferred.

[1105] Examples of the hydroxy compound include compounds described in paragraphs 0092 to 0107 of JP-A-2019-206689, and the contents are incorporated into the present specification.

[1106] Furthermore, a compound represented by the following formula (H6) is also preferred.

[1107] [Chemical formula 70]

[1108]

[1109] 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.

[1110] In formula (H6), R 46 and R 47 Each of them independently is preferably an alkyl group, an alkoxy group or an aryl group, and more preferably an alkyl group.

[1111] In formula (H6), n16 and n17 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

[1112] In formula (H6), m11 and m12 are each independently preferably an integer of 1 to 3, and more preferably 2 or 3.

[1113] Examples of the compound represented by formula (H6) include the following compounds.

[1114] [Chemical formula 71]

[1115]

[1116] 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;

[1117] Polyhydroxyphenyl alkyl ketones such as 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyvalerophenone, 2,3,4-trihydroxyhexanophenone,

[1118] 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,

[1119] Polyhydroxybenzoic acid esters such as propyl 3,4,5-trihydroxybenzoate, phenyl 2,3,4-trihydroxybenzoate, phenyl 3,4,5-trihydroxybenzoate,

[1120] 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,

[1121] Alkylene-bis(polyhydroxybenzoates) such as ethylene glycol-bis(3,5-dihydroxybenzoate) and ethylene glycol-bis(3,4,5-trihydroxybenzoate),

[1122] 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,

[1123] 4,4'-thiobis(1,3-dihydroxy)benzene and other bis(polyhydroxy)sulfides,

[1124] 2,2',4,4'-Tetrahydroxydiphenyl ether and other bis(polyhydroxyphenyl) ethers,

[1125] 2,2',4,4'-Tetrahydroxydiphenyl sulfoxide and other bis(polyhydroxyphenyl) sulfoxides,

[1126] 2,2',4,4'-diphenyl sulfone and other bis(polyhydroxyphenyl) sulfones,

[1127] 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,

[1128] Polyhydroxy spirobis-indanes such as 3,3,3',3'-tetramethyl-1,1'-spirobis-indanes-5,6,5',6'-tetraol, 3,3,3',3'-tetramethyl-1,1'-spirobis-indanes-5,6,7,5',6',7'-hexaol, 3,3,3',3'-tetramethyl-1,1'-spirobis-indanes-4,5,6,4',5',6'-hexaol, 3,3,3',3'-tetramethyl-1,1'-spirobis-indanes-4,5,6,5',6',7'-hexaol, and polyhydroxy spirobis-indanes such as 2,4,4-trimethyl-2',4',7'-trihydroxyflavanes,

[1129] Polyhydroxyphthalides such as 3,3-bis(3,4-dihydroxyphenyl)phthalide, 3,3-bis(2,3,4-trihydroxyphenyl)phthalide, 3',4',5',6'-tetrahydroxybis[phthalide-3,9'-xanthen], flavonoid pigments such as morin, quercetin, and rutin,

[1130] 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-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 1-[α-methyl-α-(4'-hydroxyphenyl)ethyl]-4-[α,α'-bis(4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(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-[ polyhydroxy compounds described in Japanese Patent Application Laid-Open No. 4-253058, such as α',α'-bis(4"-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(2',4'-dihydroxyphenyl)ethyl]-3-[α',α'-bis(4"-hydroxyphenyl)ethyl]benzene, polyhydroxy compounds described in Japanese Patent Application Laid-Open No. 5-224410, such as α,α,α',α',α",α"-hexa-(4-hydroxyphenyl)-1,3,5-triethylbenzene, polyhydroxy compounds described in Japanese Patent Application Laid-Open No. 5-303200, EP-530148, such as 1,2,2,3-tetra(p-hydroxyphenyl)propane and 1,3,3,5-tetra(p-hydroxyphenyl)pentane,

[1131] 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,

[1132] 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, [(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'-spirobis(1H-indene)-5,5',6,6',7,7'hexanol, bis(4-hydroxy-3,5-dimethylphenyl)methyl-(4-hydroxy-3-methoxyphenyl)methane, and the like.

[1133] Fur...

Claims

1. A method for producing a film, comprising: containing (A) resin; (C) a photopolymerization initiator; (D) a radical polymerization inhibitor which is at least one compound selected from (D-1) a compound having a free radical in the molecule and (D-2) a compound having no free radical in the molecule and having a molecular weight of 270 or more; and (E) After the photosensitive resin composition containing a solvent is applied on a substrate, The drying process is performed at a pressure of 5000 Pa or less.

2. A method for producing a film, comprising: containing (A) resin; (C) a photopolymerization initiator; (D) a radical polymerization inhibitor which is at least one compound selected from (D-1) a compound having a free radical in the molecule and (D-2) a compound having no free radical in the molecule and having a molecular weight of 270 or more; and (E) After the photosensitive resin composition containing a solvent is applied on a substrate, A step of drying at a first temperature; and A step of drying at a second temperature higher than the first temperature at a pressure within a range of ±10% of the pressure in the step of drying at the first temperature.

3. A method for producing a film, comprising only: containing (A) resin; (C) a photopolymerization initiator; (D) a radical polymerization inhibitor which is at least one compound selected from (D-1) a compound having a free radical in the molecule and (D-2) a compound having no free radical in the molecule and having a molecular weight of 270 or more; and (E) After the photosensitive resin composition containing a solvent is applied on a substrate, The drying step is a step of drying at 90° C. or higher for more than five minutes.

4. The method for producing a film according to any one of claims 1 to 3, wherein: The photosensitive resin composition satisfies at least one of the following (i) and (ii), (i) Containing (B-1) a radical polymerizable compound (ii) The (A) contains a radical polymerizable site.

5. The method for producing a film according to any one of claims 1 to 3, wherein: The (A) is at least one resin selected from the group consisting of polyimide and a polyimide precursor.

6. The method for producing a film according to any one of claims 1 to 3, wherein: The (A) contains a repeating unit represented by the following formula (2): In formula (2), A 1 and A 2 Each independently represents an oxygen atom or -NH-, R 111 Represents a divalent organic group, R 115 Represents a 4-valent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, wherein R 113 and R 114 At least one of them has a group represented by the following formula (III), In formula (III), R 200 represents a hydrogen atom, methyl, ethyl or hydroxymethyl, * represents the bonding position with other structures, R 201 It represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group or a polyalkyleneoxy group.

7. The method for producing a film according to any one of claims 1 to 3, wherein: The molecular weight of (D-2) is 700 or more.

8. The method for producing a film according to any one of claims 1 to 3, wherein: The molecular weight of (D-1) is 160 or more.

9. The method for producing a film according to any one of claims 1 to 3, wherein: The photosensitive resin composition has a solid content concentration of 35% by mass or less.

10. The method for producing a film according to any one of claims 1 to 3, wherein: Cu is contained on the surface of the substrate.

11. The method for producing a film according to claim 1, wherein: The temperature in the step of drying under the pressure of 5000 Pa or less is 35° C. or more and 80° C. or less.

12. A photosensitive resin composition comprising: (A) resin; (C) a photopolymerization initiator; (D) a radical polymerization inhibitor which is at least one compound selected from (D-1) a compound having a free radical in the molecule and (D-2) a compound having no free radical in the molecule and having a molecular weight of 270 or more; and (E) Solvent.

13. The photosensitive resin composition according to claim 12, wherein The photosensitive resin composition satisfies at least one of the following (i) and (ii), (i) Containing (B-1) a radical polymerizable compound (ii) The (A) contains a radical polymerizable site.

14. The photosensitive resin composition according to claim 12, wherein The (A) is at least one resin selected from the group consisting of polyimide and a polyimide precursor.

15. The photosensitive resin composition according to claim 12, wherein The (A) contains a repeating unit represented by the following formula (2): In formula (2), A 1 and A 2 Each independently represents an oxygen atom or -NH-, R 111 Represents a divalent organic group, R 115 Represents a 4-valent organic group, R 113 and R 114 Each independently represents a hydrogen atom or a monovalent organic group, wherein R 113 and R 114 At least one of them has a group represented by the following formula (III), In formula (III), R 200 represents a hydrogen atom, methyl, ethyl or hydroxymethyl, * represents the bonding position with other structures, R 201 It represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group or a polyalkyleneoxy group.

16. The photosensitive resin composition according to claim 12, wherein The molecular weight of (D-2) is 700 or more.

17. The photosensitive resin composition according to claim 12, wherein The molecular weight of (D-1) is 160 or more.

18. The photosensitive resin composition according to claim 12, wherein The photosensitive resin composition has a solid content concentration of 35% by mass or less. 19 . The photosensitive resin composition according to claim 12 , which is used for forming an interlayer insulating film for a redistribution layer.

20. A method for producing a solidified product, comprising: A step of applying the photosensitive resin composition according to any one of claims 12 to 18 on a substrate and drying it under reduced pressure to form a film; An exposure step of selectively exposing the film; and, In the development step, the film exposed in the exposure step is developed using a developer to form a pattern. 21 . A cured product obtained by curing the photosensitive resin composition according to claim 12 . 22 . A laminate comprising two or more layers consisting of the cured product according to claim 21 , wherein a metal layer is provided between any of the layers consisting of the cured product.

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