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

Abstract

The present application provides a resin composition, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a semiconductor device including the cured product or the laminate, or a novel polyimide precursor and a method for producing the same, the resin composition including a polyimide precursor having a repeating unit represented by the following formula (2) and a structure represented by formula (1-1).

Description

Technical Field

[0001] This invention relates to a resin composition, a cured product, a laminate, a method for manufacturing the cured product, a semiconductor device, and a polyimide precursor and a method for manufacturing the same. Background Technology

[0002] Cyclic resins such as polyimide are suitable for a wide range of applications due to their excellent heat resistance and insulation properties. These applications are not particularly limited; for example, in the case of semiconductor devices used in actual installation, they can be used as insulating films, sealing materials, or protective films. Furthermore, they can be used as base films and cover films for flexible substrates.

[0003] For example, in the above-described uses, cyclized resins such as polyimide are used in the form of a resin composition comprising at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin.

[0004] For example, such resin compositions can be applied to a substrate to form a photosensitive film by coating, and then exposed, developed, heated, etc., as needed, thereby forming a cured product on the substrate.

[0005] The precursors of the aforementioned cyclized resins, such as polyimide precursors, are cyclized in the cured product by heating, thus becoming cyclized resins such as polyimide.

[0006] The resin composition can be applied using known coating methods, thus exhibiting excellent manufacturing adaptability. For example, it offers a high degree of design freedom in terms of the shape, size, and application location of the resin composition. Considering both the high performance of cyclized resins such as polyimide and this excellent manufacturing adaptability, the expansion of industrial applications for the aforementioned resin composition is increasingly promising.

[0007] For example, Patent Document 1 describes a polyamic acid ester resin composition comprising a polyimide precursor with a specific structure, a carboxylic acid compound or its anhydride with a specific structure, and optionally, a polymeric compound other than the aforementioned polyimide precursor, wherein the aforementioned carboxylic acid compound or its anhydride may be chemically bonded to the aforementioned polyimide precursor and / or the polymeric compound other than the aforementioned polyimide precursor.

[0008] Patent document 2 describes a resin composition containing a polyimide precursor having specific repeating units.

[0009] Previous technical documents

[0010] Patent documents

[0011] Patent Document 1: International Publication No. 2020 / 080206

[0012] Patent Document 2: Japanese Patent Application Publication No. 2012-224755 Summary of the Invention

[0013] The technical problem to be solved by the invention

[0014] In a resin composition comprising at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin, it is required that the obtained cured product has excellent moisture resistance.

[0015] The purpose of this invention is to provide a resin composition that can produce a cured product with excellent moisture resistance, a cured product obtained by curing the above resin composition, a laminate containing the above cured product, a method for manufacturing the above cured product, and a semiconductor device containing the above cured product or the above laminate, or a novel polyimide precursor and a method for manufacturing the same.

[0016] means for solving technical problems

[0017] The following are examples of representative embodiments of the present invention.

[0018] <1> A resin composition comprising a polyimide precursor having repeating units represented by formula (2) and a structure represented by formula (1-1),

[0019] [Chemical Formula 1]

[0020]

[0021] In equation (2), A 1 and A 2 Each can be used independently to represent an oxygen atom or -NH-, R 111 R represents a divalent organic group. 115 R represents a tetravalent organic group. 11 3 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group.

[0022] [Chemical Formula 2]

[0023]

[0024] In equation (1-1), A 3 and A 4 Each can be used independently to represent an oxygen atom or -NH-, X 1 R represents a tetravalent organic group. 21 and R 22 Each can independently represent a hydrogen atom or a monovalent organic group, Y 1 Z represents a hydrogen atom or a monovalent organic group. 1 Z represents a monovalent organic group having an aromatic group. 1It does not contain any of the structures represented by equation (Z-1) or equation (Z-2) below, Y 1 With Z 1 It can be bonded; * indicates a bonding site with other structures.

[0025] [Chemical Formula 3]

[0026]

[0027] In equation (Z-1), R 115 R represents any one of the repeating units represented by formula (2) contained in the polyimide precursor. 115 The same group, * indicates a bonding site with other structures.

[0028] In equation (Z-2), R 111 R represents any one of the repeating units represented by formula (2) contained in the polyimide precursor. 111 For identical groups, * indicates the bonding site with other structures.

[0029] <2> The resin composition according to <1> wherein the amine value of the polyimide precursor is less than 0.01 mmol / g.

[0030] <3> The resin composition according to <1> or <2>, wherein the acid value of the polyimide precursor is less than 1 mmol / g.

[0031] <4> The resin composition according to any one of <1> to <3>, wherein Z in the above formula (1-1) 1 The formula size is 160 or higher.

[0032] <5> The resin composition according to any one of <1> to <4>, wherein Z in the above formula (1-1) 1 It has at least one group selected from the group consisting of imide, urea and urethane groups.

[0033] <6> The resin composition according to any one of <1> to <5>, wherein Z in the above formula (1-1) 1 It has two or more aromatic groups.

[0034] <7> The resin composition according to any one of <1> to <6>, wherein Z in the above formula (1-1) 1 For groups represented by the following formula (Z1-1) or formula (Z1-2),

[0035] [Chemical Formula 4]

[0036]

[0037] In equation (Z1-1), Ar 1 L represents an aromatic group. 1 Indicates a single bond or a divalent linkage group, X 1 Indicates imide, urea, or carbamate group, L 2 R represents a single bond or a divalent linkage group. 1 Ar represents a monovalent organic group. 1 With R 1 or L 1 With R 1 They can bond to form a ring structure, where * indicates the bonding site with the nitrogen atom in formula (1-1).

[0038] In equation (Z1-2), Ar 2 and Ar 3 Each of the aromatic groups is represented independently, L 3 Ar represents a single bond or a divalent linkage group. 2 and Ar 3 It can also have L 3 Other than the connecting chain, * indicates the bonding site with the nitrogen atom in formula (1-1).

[0039] <8> The resin composition according to any one of <1> to <7>, wherein R of formula (2) 111 For a group represented by the following formula (R-1),

[0040] [Chemical Formula 5]

[0041]

[0042] In equation (R-1), Ar 1 ~Ar 3 Each aryl group represents an aryl group independently, n represents an integer greater than or equal to 1, and * represents a bonding site with the nitrogen atom in equation (2) independently.

[0043] <9> The resin composition according to any one of <1> to <8> further comprises an alkali generating agent.

[0044] <10> The resin composition according to any one of <1> to <9> further comprises a photoradical polymerization initiator.

[0045] <11> The resin composition according to any one of <1> to <10> is used to form an interlayer insulating film for a rewiring layer.

[0046] <12> A cured product, which is formed by curing any one of the resin compositions described in <1> to <11>.

[0047] <13> A laminate comprising two or more layers made of the cured material described in <12>, wherein any layer made of the cured material contains a metal layer between each other.

[0048] <14> A method for manufacturing a cured material, comprising a film forming step of applying a resin composition as described in any one of <1> to <11> to form a film on a substrate.

[0049] <15> The method for manufacturing the cured material according to <14> includes an exposure step for exposing the film and a development step for developing the film.

[0050] <16> The method for manufacturing the cured material according to <14> or <15> includes a heating step of heating the film at 50 to 450°C.

[0051] <17> A semiconductor device comprising the cured material described in <12> or the laminate described in <13>.

[0052] <18> A polyimide precursor having repeating units represented by the following formula (2) and a structure represented by formula (1-1),

[0053] [Chemical Formula 6]

[0054]

[0055] In equation (2), A 1 and A 2 Each can be used independently to represent an oxygen atom or -NH-, R 111 R represents a divalent organic group. 115 R represents a tetravalent organic group. 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group.

[0056] [Chemical Formula 7]

[0057]

[0058] In equation (1-1), A 3 and A 4 Each can be used independently to represent an oxygen atom or -NH-, X 1 R represents a tetravalent organic group. 21 and R 22 Each can independently represent a hydrogen atom or a monovalent organic group, Y 1 Z represents a hydrogen atom or a monovalent organic group. 1 Z represents a monovalent organic group having an aromatic group. 1It does not contain any of the structures represented by equation (Z-1) or equation (Z-2) below, Y 1 With Z 1 It can be bonded; * indicates a bonding site with other structures.

[0059] [Chemical Formula 8]

[0060]

[0061] In equation (Z-1), R 115 R represents any one of the repeating units represented by formula (2) contained in the polyimide precursor. 115 The same group, * indicates a bonding site with other structures.

[0062] In equation (Z-2), R 111 R represents any one of the repeating units represented by formula (2) contained in the polyimide precursor. 111 For identical groups, * indicates the bonding site with other structures.

[0063] <19> A method for manufacturing a polyimide precursor, comprising:

[0064] The process of reacting a tetracarboxylic dianhydride or its diester with a diamine to obtain the reactant; and

[0065] The process of reacting the reactants with the compound represented by formula (T-1),

[0066] [Chemical Formula 9]

[0067]

[0068] In equation (T-1), Y 1 Z represents a hydrogen atom or a monovalent organic group. 1 Y represents a monovalent organic group having an aromatic group. 1 With Z 1 They can bond.

[0069] Invention Effects

[0070] According to the present invention, a resin composition that can produce a cured product with excellent moisture resistance is provided, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, and a semiconductor device containing the cured product or the laminate, or a novel polyimide precursor and a method for manufacturing the same. Detailed Implementation

[0071] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments described.

[0072] In this specification, the numerical range indicated by the symbol “~” refers to the range including the lower limit and upper limit values ​​recorded before and after “~”, respectively.

[0073] In this specification, the term "process" refers not only to independent processes, but also to processes that cannot be clearly distinguished from other processes, provided that the intended function of the process can be achieved.

[0074] In this specification, the designations of groups (atomic groups) include those without substituted and unsubstituted designations, encompassing both unsubstituted and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

[0075] Unless otherwise specified, "exposure" in this manual includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. Moreover, examples of light used for exposure include the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other active light or radiation.

[0076] In this specification, "(meth)acrylate" means "acrylate" and "methacrylate" or either one; "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" or either one; and "(meth)acryloyl" means "acryloyl" and "methacryloyl" or either one.

[0077] In this specification, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl in the structural formula.

[0078] In this specification, total solids content refers to the total mass of all components of the composition other than the solvent. Furthermore, in this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition.

[0079] Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene conversion values. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification can be determined, for example, using an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. When THF is unsuitable as the eluent due to low solubility, NMP (N-methyl-2-pyrrolidone) can be used. Furthermore, unless otherwise specified, a UV (ultraviolet) detector with a wavelength of 254 nm is used for detection in GPC measurements.

[0080] In this specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower," it is sufficient that there are other layers above or below the reference layer among the layers of interest. That is, a third layer or third element may be further sandwiched between the reference layer and the other layers, and the reference layer does not need to be in contact with the other layers. Moreover, unless otherwise specified, the direction of stacking relative to the substrate layers is referred to as "upper," or when a resin composition layer is present, the direction from the substrate towards the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." Furthermore, these vertical and horizontal directions are set for convenience in this specification, and in practice, the "upper" direction in this specification may differ from the vertical direction.

[0081] Unless otherwise specified, in this specification, each component included in the composition may contain two or more compounds equivalent to that component. Furthermore, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds equivalent to that component.

[0082] Unless otherwise specified, the temperature in this manual is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0083] In this specification, the preferred combination of methods is a more preferred method.

[0084] (Resin Composition)

[0085] The resin composition of the present invention comprises a polyimide precursor having a repeating unit represented by the following formula (2) and a structure represented by formula (1-1).

[0086] Hereinafter, a polyimide precursor having repeating units represented by formula (2) and a structure represented by formula (1-1) will also be referred to as a “specific resin”.

[0087] [Chemical Formula 10]

[0088]

[0089] In equation (2), A 1 and A 2 Each can be used independently to represent an oxygen atom or -NH-, R 111 R represents a divalent organic group. 115 R represents a tetravalent organic group. 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group.

[0090] [Chemical Formula 11]

[0091]

[0092] In equation (1-1), A 3 and A 4 Each can be used independently to represent an oxygen atom or -NH-, X 1 R represents a tetravalent organic group. 21 and R 22 Each can independently represent a hydrogen atom or a monovalent organic group, Y 1 Z represents a hydrogen atom or a monovalent organic group. 1 Z represents a monovalent organic group having an aromatic group. 1 It does not contain any of the structures represented by equation (Z-1) or equation (Z-2) below, Y 1 With Z 1 It can be bonded; * indicates a bonding site with other structures.

[0093] [Chemical Formula 12]

[0094]

[0095] In equation (Z-1), R 115 R represents any one of the repeating units represented by formula (2) contained in the polyimide precursor. 115 The same group, * indicates a bonding site with other structures.

[0096] In equation (Z-2), R 111 R represents any one of the repeating units represented by formula (2) contained in the polyimide precursor.111 For identical groups, * indicates the bonding site with other structures.

[0097] The resin composition of the present invention is preferably used to form photosensitive films for exposure and development, and more preferably to form films for exposure and development using a developer containing an organic solvent.

[0098] The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for rewiring layers.

[0099] Furthermore, the resin composition of the present invention can be used in the formation of a photosensitive film for positive development or in the formation of a photosensitive film for negative development, and is preferably used in the formation of a photosensitive film for negative development.

[0100] In this invention, during exposure and development, negative development refers to development that removes the non-exposed areas, while positive development refers to development that removes the exposed areas.

[0101] As the above-described exposure method, developer, and developing method, for example, the exposure method described in the exposure step of the description of the method for manufacturing cured material described later, and the developer and developing method described in the developing step can be used.

[0102] According to the resin composition of the present invention, a cured product with excellent moisture resistance can be obtained.

[0103] The mechanism by which the above effects are achieved is not yet clear, but it is speculated to be as follows.

[0104] Conventionally, compositions containing cyclized resins or their precursors have been used to obtain cured products.

[0105] The inventors have discovered that, in this invention, by bonding the structure represented by formula (1-1) to a polyimide precursor, the moisture resistance of the obtained cured film is improved.

[0106] It is believed that, as in the past, when the ends of the polyimide precursor are quenched by alcohols such as ethanol or anhydride-treated, carboxylic acids tend to remain at the resin ends in the cured film.

[0107] However, it is believed that by bonding the structure represented by formula (1-1) to the polyimide precursor, the structure represented by formula (1-1) is also imidized in the cured film. This is speculated to be because, in the cured film, compared to a resin containing the carboxylic acid residue at the end as described above, the resin containing the imidized structure represented by formula (1-1) as described above has the effect of making it difficult to form water penetration paths, thereby improving moisture resistance.

[0108] Furthermore, considering that the planarity of the resin is improved by bonding the structure represented by Equation (1-1) to the end and that the resin is less likely to entangle with each other, it is speculated that the elongation at break of the cured film will also be improved.

[0109] Furthermore, in conventional polyimide precursors, structures with polymerizable groups, alcohols such as ethanol, are added to the ends. These are then released and volatilized by thermal curing (imidization), thus causing a corresponding amount of film shrinkage. Moreover, film shrinkage is also easily caused by the polymerization of the structures with polymerizable groups at the ends. It is believed that in the present invention, since the release of terminal alcohols and the polymerization of terminal polymerizable groups are almost non-existent, film shrinkage is suppressed.

[0110] Here, neither Patent Document 1 nor Patent Document 2 describes the use of a polyimide precursor having a structure represented by formula (1-1).

[0111] The components contained in the resin composition of the present invention will be described in detail below.

[0112] <Specific Resins>

[0113] The resin composition of the present invention comprises a polyimide precursor (specific resin) having a repeating unit represented by the following formula (2) and a structure represented by formula (1-1).

[0114] [Chemical Formula 13]

[0115]

[0116] In equation (2), A 1 and A 2 Each can be used independently to represent an oxygen atom or -NH-, R 111 R represents a divalent organic group. 115 R represents a tetravalent organic group. 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group.

[0117] [Chemical Formula 14]

[0118]

[0119] In equation (1-1), A 3 and A 4 Each can be used independently to represent an oxygen atom or -NH-, X 1 R represents a tetravalent organic group. 21 and R 22 Each can independently represent a hydrogen atom or a monovalent organic group, Y 1 Z represents a hydrogen atom or a monovalent organic group. 1Z represents a monovalent organic group having an aromatic group. 1 It does not contain any of the structures represented by equation (Z-1) or equation (Z-2) below, Y 1 With Z 1 It can be bonded; * indicates a bonding site with other structures.

[0120] [Chemical Formula 15]

[0121]

[0122] In equation (Z-1), R 115 R represents any one of the repeating units represented by formula (2) contained in the polyimide precursor. 115 The same group, * indicates a bonding site with other structures.

[0123] In equation (Z-2), R 111 R represents any one of the repeating units represented by formula (2) contained in the polyimide precursor. 111 For identical groups, * indicates the bonding site with other structures.

[0124] [Formula (2)]

[0125] A in equation (2) 1 and A 2 Each can be represented independently as an oxygen atom or -NH-, with oxygen atom being preferred.

[0126] R in equation (2) 111 This indicates a divalent organic group. Examples of divalent organic groups include groups comprising straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, these are straight-chain or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 3 to 20 carbon atoms, or combinations thereof. More preferably, these are groups comprising aromatic groups with 6 to 20 carbon atoms. The hydrocarbon groups in the chains of the aforementioned straight-chain or branched aliphatic groups can be replaced by groups containing heteroatoms, and the hydrocarbon groups in the ring members of the aforementioned cyclic aliphatic groups and aromatic groups can be replaced by groups containing heteroatoms. As a preferred embodiment of the present invention, R is exemplified. 111 Examples of groups represented by -Ar- and -Ar-L-Ar- are provided, with groups represented by -Ar-L-Ar- being particularly preferred. Here, Ar is independently an aromatic group, and L is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the above. The preferred ranges are as described above.

[0127] R 111 The preferred diamine is derived from a diamine. Examples of diamines used in the manufacture of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.

[0128] Specifically, the preferred diamine is a diamine comprising a straight-chain 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 combination thereof; more preferably, a diamine comprising an aromatic group having 6 to 20 carbon atoms. The hydrocarbon groups in the chain of the aforementioned straight-chain or branched aliphatic groups can be replaced by groups containing heteroatoms, and the hydrocarbon groups in the ring members of the aforementioned cyclic aliphatic groups and aromatic groups can be replaced by groups containing heteroatoms. Examples of groups containing aromatic groups include the following groups.

[0129] [Chemical Formula 16]

[0130]

[0131] In the formula, A represents a single bond or a divalent linking group, preferably a single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or combinations thereof, more preferably a single bond or a group selected from alkylene groups with 1 to 3 carbon atoms that can be replaced by fluorine atoms, -O-, -C(=O)-, -S-, or -SO2-, and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-.

[0132] In the formula, * indicates the bonding site with other structures.

[0133] As a diamine, specifically, at least one diamine selected from the following can be cited: 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 isophorone diamine; 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) ... Hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfone, bis(4-amino-3-hydroxyphenyl) sulfone, 4,4'-diamino-p-terphenyl, 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'-diaminodiphenyl sulfone, 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, acetylguanidine, 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, diaminobenzoylaniline, 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)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, [4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl The compounds include 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'-hexafluorobitoluidine, and 4,4'-diaminotetraphenyl.

[0134] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are preferred.

[0135] Furthermore, diamines having two or more alkylene glycol units on the main chain, as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598, may be preferred.

[0136] From the perspective of the flexibility of the obtained organic membrane, R 111 Preferably represented by -Ar-L-Ar-. Wherein, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group composed of two or more of the above. Ar is preferably phenylene, and L is preferably an aliphatic hydrocarbon group with 1 or 2 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, or -SO2-. The aliphatic hydrocarbon group here is preferably alkylene.

[0137] Moreover, from the perspective of i-ray transmittance, R 111 Preferably, it is a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, it is more preferably a divalent organic group represented by formula (61).

[0138] Equation (51)

[0139] [Chemical Formula 17]

[0140]

[0141] In equation (51), R 50 ~R 57 Each can be 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 * represents the bonding site with the nitrogen atom in formula (2) independently.

[0142] As R 50 ~R 57 Examples of monovalent organic groups include unsubstituted alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0143] [Chemical Formula 18]

[0144]

[0145] In equation (61), R 58 and R 59 Each of the above can be independently represented by a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents the bonding site with the nitrogen atom in formula (2).

[0146] Examples of diamines that impart 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. One or more of these may be used.

[0147] Furthermore, from the viewpoint of the moisture resistance and chemical resistance of the obtained cured film, R 111 Preferably, it is a group represented by the following formula (R-1).

[0148] [Chemical Formula 19]

[0149]

[0150] In equation (R-1), Ar 1 ~Ar 3 Each aryl group represents an aryl group independently, n represents an integer greater than or equal to 1, and * represents a bonding site with the nitrogen atom in equation (2) independently.

[0151] In equation (R-1), Ar 1 and Ar 3 Each group is preferably an aromatic hydrocarbon group, more preferably a phenylene group, and even more preferably a 1,4-phenylene group. 1 and Ar 3 Each of these can be an aromatic heterocycle independently. Examples of heteroatoms included in an aromatic heterocycle include oxygen, sulfur, and nitrogen atoms. Moreover, the aforementioned aromatic heterocycle is preferably a 5-membered or 6-membered ring.

[0152] In equation (R-1), Ar 2 Preferably, it is a group represented by the following formula (AR2-1).

[0153] [Chemical Formula 20]

[0154]

[0155] In formula (AR2-1), * represents the bonding sites with oxygen atoms in formula (R-1).

[0156] In addition, Ar 2 It can be compared with the above Ar 1 Same group.

[0157] In formula (R-1), n ​​is preferably an integer from 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0158] R in equation (2) 115 This indicates a tetravalent organic group. As a tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred.

[0159] In equation (5) or equation (6), * independently represents the bonding site with other structures.

[0160] [Chemical Formula 21]

[0161]

[0162] In equation (5), R 112It is a single bond or a divalent linker, preferably a single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S-, -SO2- and -NHCO-, and combinations thereof, more preferably a single bond, a group selected from alkylene groups with 1 to 3 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S- and -SO2-, and even more preferably a divalent group selected from the group including -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2-.

[0163] Specifically, R 115 Examples include the tetracarboxylic acid residue remaining after removing the anhydride group from a tetracarboxylic dianhydride. As equivalent to R... 115 The structure of the polyimide precursor can contain only one type of tetracarboxylic acid dianhydride residue or more than two types.

[0164] Tetracarboxylic dianhydride is preferably represented by the following formula (O).

[0165] [Chemical Formula 22]

[0166]

[0167] In equation (O), R 115 R represents a tetravalent organic group. 115 R in equation (2) 115 They have the same meaning and the same preferred range.

[0168] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxophthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride. 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl and alkoxy derivatives thereof having 1 to 6 carbon atoms.

[0169] Furthermore, as a preferred example, one could cite tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598.

[0170] In equation (2), R 111 and R 115 At least one of them can also have an OH group. More specifically, as R 111 Examples of residues from diaminophenol derivatives can be cited.

[0171] R in equation (2) 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferred to include straight-chain or branched alkyl groups, cyclic alkyl groups, aromatic groups, or polyalkoxide groups. Furthermore, R is preferred. 113 and R 114 At least one of them contains a polymeric group, more preferably both contain polymeric groups. R is also preferred. 113 and R 114At least one of them contains two or more polymerizable groups. The polymerizable group is a group capable of cross-linking reactions by heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having olefinic unsaturated bonds, alkoxymethyl, hydroxymethyl, acyloxymethyl, epoxy, oxetyl, benzoxazolyl, terminal isocyanate, and amino groups. As a free radical polymerizable group in a polyimide precursor, a group having olefinic unsaturated bonds is preferred.

[0172] Examples of groups having olefinic unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamido, (meth)acryloyloxy, groups represented by formula (III) below, etc.

[0173] [Chemical Formula 23]

[0174]

[0175] In equation (III), R 200 It represents a hydrogen atom, methyl, ethyl or hydroxymethyl, preferably a hydrogen atom or methyl.

[0176] In equation (III), * indicates the bonding site with other structures.

[0177] In equation (III), R 201 It indicates an alkylene group with 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkoxy group.

[0178] R 201 Preferred examples include alkylene compounds such as vinyl, propenyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH2CH(OH)CH2-, and polyalkoxide compounds; more preferably, alkylene compounds such as vinyl and propenyl, -CH2CH(OH)CH2-, cyclohexyl, and polyalkoxide compounds; and even more preferably, alkylene compounds such as vinyl and propenyl or polyalkoxide compounds.

[0179] In this invention, polyalkoxide refers to a group formed by the direct bonding of two or more alkoxide groups. The alkylene groups in the multiple alkoxide groups contained in the polyalkoxide group may be the same or different.

[0180] When a polyalkoxide contains multiple alkoxides with different alkylene groups, the arrangement of the alkoxides in the polyalkoxide can be random, block-shaped, or alternating.

[0181] The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent when the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.

[0182] Furthermore, the aforementioned alkylene groups may have substituents. Preferred substituents include alkyl, aryl, and halogen atoms.

[0183] Furthermore, the number of alkoxides contained in the polyalkoxide (the number of repeats of the polyalkoxide) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0184] From the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethoxy, or groups formed by the bonding of multiple ethyleneoxy groups and multiple propyleneoxy groups are preferred as polyvinyloxy or polypropyleneoxy groups, and polyvinyloxy groups are even more preferred. In the aforementioned groups formed by the bonding of multiple ethyleneoxy and multiple propyleneoxy groups, the ethyleneoxy and propyleneoxy groups can be arranged randomly, form blocks, or be arranged in alternating patterns. The preferred manner for the repetition of the ethyleneoxy groups, etc., in these groups is as described above.

[0185] In equation (2), in R 113 For the case of hydrogen atoms or R 114 In the case of hydrogen atoms, polyimide precursors can form conjugated salts with tertiary amine compounds having olefinically unsaturated bonds. N,N-dimethylaminopropyl methacrylate is an example of such tertiary amine compounds having olefinically unsaturated bonds.

[0186] In equation (2), R 113 and R 114 At least one of them can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, it is not particularly limited as long as it is decomposed by the action of acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups. It is preferred to use acetal groups, ketal groups, silyl groups, silyl ether groups, tertiary alkyl ester groups, etc. From the point of view of exposure sensitivity, acetal groups or ketal groups are more preferred.

[0187] Specific examples of acid-degrading groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0188] Furthermore, the polyimide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0189] Furthermore, to improve adhesion to the substrate, the polyimide precursor can be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0190] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in this invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, the range of exposure latitude can be further increased.

[0191] Equation (2-A)

[0192] [Chemical Formula 24]

[0193]

[0194] In equation (2-A), A 1 and A 2 R represents an oxygen atom. 111 and R 112 Each independently represents a divalent organic group, R 113 and R 114 Each can independently represent 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, preferably both of them are groups containing polymerizable groups.

[0195] A 1 A 2 R 111 R 11 3 and R 114 Independently with A in equation (2) 1 A 2 R 111 R 113 and R 114 They have the same meaning and the same preferred range.

[0196] R 112 R in equation (5) 112 They have the same meaning and the same preferred range.

[0197] The polyimide precursor may contain one repeating unit represented by formula (2), or two or more repeating units. Moreover, it may contain structural isomers of the repeating unit represented by formula (2). Furthermore, in addition to the repeating unit of formula (2) above, the polyimide precursor may obviously also contain other types of repeating units.

[0198] As one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units. The above 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 total content is not particularly limited, and all repeating units in the polyimide precursor except for the end units can be repeating units represented by formula (2).

[0199] [Equation (1-1)]

[0200] In equation (1-1), A 3 and A 4 Oxygen atoms are preferred.

[0201] In equation (1-1), X 1 R in equation (2) above 115 The meanings are the same, and the preferred selection methods are also the same.

[0202] Moreover, X 1 Preferably, it is any one of the repeating units represented by formula (2) contained in the polyimide precursor, R. 115 Same group.

[0203] In equation (1-1), R 21 and R 22 The preferred methods are respectively related to R in equation (2). 114 and R 113 The preferred method is the same.

[0204] Moreover, R 21 and R 22 Preferably, it is any one of the repeating units represented by formula (2) contained in the polyimide precursor, R. 114 and R 113 Same group.

[0205] In equation (1-1), Y 1 Hydrogen atoms are preferred.

[0206] In equation (1-1), in Y 1 When Y is a monovalent organic group, 1 Examples include alkyl, aryl, or Z groups in formula (1-1).1 Same group.

[0207] In equation (1-1), Z 1 It represents a monovalent organic group that has an aromatic group.

[0208] Z 1 The aromatic group can be an aromatic hydrocarbon group or an aromatic heterocyclic group, preferably an aromatic hydrocarbon group.

[0209] As the aforementioned aromatic hydrocarbon group, an aromatic hydrocarbon group with 6 to 30 carbon atoms is preferred, an aromatic hydrocarbon group with 6 to 20 carbon atoms is more preferred, and a benzene ring group is even more preferred.

[0210] Examples of heteroatoms in the aforementioned aromatic heterocyclic groups include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0211] As the above-mentioned aromatic heterocyclic group, it is preferably a 5-membered ring structure, a 6-membered ring structure, or a heterocyclic structure selected from the group consisting of at least two ring structures including 5-membered ring structures and 6-membered ring structures.

[0212] Z 1 It is acceptable to contain one or more aromatic groups, but it is preferred to contain two or more aromatic groups.

[0213] Moreover, Z 1 The aromatic group is preferably located at the bonding site with the nitrogen atom in formula (1-1). That is, Z is preferred. 1 At least one of the aromatic groups in the formula is directly bonded to the nitrogen atom in formula (1-1).

[0214] It is believed that through Z 1 At least one of the aromatic groups in the formula is directly bonded to the nitrogen atom in formula (1-1). The imide ring structure formed after ring closure is directly bonded to the aromatic ring structure. Therefore, the moisture resistance is further improved by increasing the interaction between polymers.

[0215] Moreover, Z in equation (1-1) 1 Preferably, it has at least one group selected from the group consisting of imide, urea and urethane groups, and more preferably, it has at least one group selected from the group consisting of urea and urethane groups.

[0216] In this invention, the imide group refers to -C(=O)NR N The group represented by C(=O)-, the urea group refers to -NR. N C(=O)NR N -, the urethane group refers to -OC (=O)NR N -. The above R NEach group can be independently represented by a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group, or an aryl group, even more preferably a hydrogen atom or an alkyl group, and especially preferably a hydrogen atom. Moreover, the orientation of these groups is not particularly limited.

[0217] These groups can be directly bonded to aromatic groups, or they can have alkylene groups or other linking groups between them and the aromatic groups.

[0218] It is believed that, considering reasons such as the formation of hydrogen bonds between these groups or between these groups and other structures, the moisture resistance is further improved by including these groups, which increases the interaction between specific resins or between specific resins and other components.

[0219] Z in equation (1-1) 1 The formula weight is preferably 160 or more, more preferably 170 to 500, and even more preferably 180 to 300.

[0220] Wherein, Z in equation (1-1) 1 Preferably, the group is represented by the following formula (Z1-1) or the following formula (Z1-2).

[0221] [Chemical Formula 25]

[0222]

[0223] In equation (Z1-1), Ar 1 L represents an aromatic group. 1 Indicates a single bond or a divalent linkage group, X 1 Indicates imide, urea, or carbamate group, L 2 R represents a single bond or a divalent linkage group. 1 Ar represents a monovalent organic group. 1 With R 1 or L 1 With R 1 They can bond to form a ring structure, where * indicates the bonding site with the nitrogen atom in formula (1-1).

[0224] In equation (Z1-2), Ar 2 and Ar 3 Each of the aromatic groups is represented independently, L 3 Ar represents a single bond or a divalent linkage group. 2 and Ar 3 It can also have L 3 Other than the connecting chain, * indicates the bonding site with the nitrogen atom in formula (1-1).

[0225] In equation (Z1-1), Ar 1The aromatic group can be an aromatic hydrocarbon group or an aromatic heterocyclic group, preferably an aromatic hydrocarbon group.

[0226] As the aforementioned aromatic hydrocarbon group, an aromatic hydrocarbon group with 6 to 30 carbon atoms is preferred, an aromatic hydrocarbon group with 6 to 20 carbon atoms is more preferred, and a benzene ring group is even more preferred.

[0227] Examples of heteroatoms in the aforementioned aromatic heterocyclic groups include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0228] As the above-mentioned aromatic heterocyclic group, it is preferably a 5-membered ring structure, a 6-membered ring structure, or a heterocyclic structure selected from the group consisting of at least two ring structures including 5-membered ring structures and 6-membered ring structures.

[0229] In equation (Z1-1), L 1 This represents a single bond or a divalent linker, preferably a single bond, a hydrocarbon group, or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N A group represented by a combination of at least one group from the group - is more preferably a single bond or a hydrocarbon group, and even more preferably a single bond.

[0230] The above R N As stated above.

[0231] The aforementioned hydrocarbon group can be any one of aliphatic hydrocarbon groups or aromatic hydrocarbon groups, preferably a group represented by a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group or a combination thereof, and more preferably a saturated aliphatic hydrocarbon group.

[0232] Moreover, L 1 In and X 1 The preferred bonding site is a hydrocarbon group.

[0233] In equation (Z1-1), X 1 Preferably, it contains urea or carbamate groups.

[0234] In equation (Z1-1), L 2 It indicates a single bond or a divalent linker, preferably a single bond.

[0235] In L 2 In the case of a divalent linker, L 2 Preferably, the radicals are hydrocarbon, -O-, -C(=O)-, -S-, -S(=O)2-, or -NR. N - or a combination of two or more of these groups. The above R N As stated above.

[0236] In equation (Z1-1), R 1 It represents a monovalent organic group, preferably alkyl or aryl.

[0237] As an aryl group, it can be a monovalent aromatic hydrocarbon group or a monovalent aromatic heterocyclic group, preferably a monovalent aromatic hydrocarbon group, and more preferably a phenyl group.

[0238] Examples of heteroatoms in monovalent aromatic heterocyclic groups include oxygen, sulfur, and nitrogen atoms.

[0239] As a monovalent aromatic heterocyclic group, it is preferably a 5-membered ring structure, a 6-membered ring structure, or a heterocyclic structure selected from the group consisting of at least two ring structures including 5-membered ring structures and 6-membered ring structures.

[0240] In equation (Z1-1), Ar 1 With R 1 They can bond together to form ring structures. Examples of the ring structures formed include imide ring structures.

[0241] In equation (Z1-1), L 1 With R 1 They can bond together to form ring structures. Examples of the formed ring structures include imide ring structures. In L... 1 With R 1 In the case of bonding to form a ring structure, L is preferred. 1 Contains an aromatic ring, and L 1 In R 1 The bonding site is the aromatic ring.

[0242] As in Ar 1 With R 1 In the case of bonding to form a ring structure, the group represented by formula (Z1-1), or L 1 With R 1 Specific examples of the way in which the group represented by formula (Z1-1) forms a ring structure by bonding can be given by the following structures, but are not limited thereto. In the following formula, L represents a single bond or a divalent linking group, preferably a single bond, a hydrocarbon group, or a hydrocarbon group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR. N A group represented by a combination of at least one group from the group - is more preferably a single bond or a hydrocarbon group.

[0243] [Chemical Formula 26]

[0244]

[0245] In equation (Z1-2), Ar 2 The preferred method is the Ar in equation (Z1-1) 1 The preferred method is the same.

[0246] In equation (Z1-2), Ar 3The preferred method is the Ar in equation (Z1-1) 1 The preferred method is the same.

[0247] In equation (Z1-2), Ar 2 and Ar 3 It can also have L 3 Other links. As Ar 2 and Ar 3 It also has L 3 Ar in the case of other link chains 2 and Ar 3 Multiple Ar examples can be cited. 2 The structure formed by connecting each other through the aforementioned links, multiple Ar 3 The structure is formed by connecting the components together via the aforementioned connecting chain. Preferably, the connecting chain is L in formula (Z1-2). 3 Same group.

[0248] As a specific example of a group represented by formula (Z1-2) with such a connecting chain, the following structures can be given, but are not limited to.

[0249] [Chemical Formula 27]

[0250]

[0251] In formula (Z1-2), L 3 This indicates a single bond or a divalent linked group, preferably a single bond or a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O)2-, or -NR. N - or a combination of two or more of these groups, more preferably a single bond, -O-, or -C(=O)-. The above R N As stated above.

[0252] The following shows Z in equation (1-1) 1 These are specific examples, but the present invention is not limited thereto.

[0253] [Chemical Formula 28]

[0254]

[0255] In formula (1-1), * denotes the bonding site with other structures, preferably with R in any repeating unit represented by formula (2) contained in the polyimide precursor. 111 The bonding sites.

[0256] A portion of the structure represented by equation (1-1) can be closed loop as represented by equation (1-1-1) or equation (1-1-2) below.

[0257] Furthermore, the structure represented by formula (1-1) is preferably heated to become the structure represented by formula (1-1-1) or formula (1-1-2) below, and more preferably the structure represented by formula (1-1-2).

[0258] The cured product obtained by curing the resin composition of the present invention preferably contains a structure represented by the following formula (1-1-1) or formula (1-1-2), more preferably a structure represented by formula (1-1-2).

[0259] [Chemical Formula 29]

[0260]

[0261] In equations (1-1-1) and (1-1-2), X 1 Z 1 R 21 and A 3 respectively with X in equation (1-1) 1 Z 1 R 21 and A 3 The meanings are the same, and the preferred selection methods are also the same.

[0262] The polyimide precursor may have at least one structure represented by formula (1-1), preferably one or two.

[0263] Specifically, among the repeating units represented by equation (2), preferably at least one of the repeating units represented by equation (2) at the end is bonded to equation (1-1). If there are two repeating units represented by equation (2) at the end, preferably one or two of them are bonded to equation (1-1).

[0264] Moreover, if there are more than three repeating units represented by equation (2) at the end, one of them can be bonded to equation (1-1), or all of them can be bonded to equation (1-1).

[0265] The amine value of the polyimide precursor is preferably below 0.01 mmol / g, more preferably 0.001 to 0.0099 mmol / g, and even more preferably 0 to 0.0009 mmol / g.

[0266] The amine value was measured as follows: Approximately 0.5 g of polyimide precursor was accurately weighed, dissolved in 50 mL of acetic acid, and measured using an automatic potentiometric titration apparatus (AT-710M; manufactured by KYOTOELECTRONICS MANUFACTURING CO.,LTD.) with 0.1 mol / L perchloric acid-acetic acid solution. A blank test was performed using the same method for calibration.

[0267] Amine value = a × 5.611 / c

[0268] a: Consumption of 0.1 mol / L perchloric acid (mL)

[0269] c: Amount of sample (g)

[0270] The acid value of the polyimide precursor is preferably below 1 mmol / g, more preferably 0.2 to 0.99 mmol / g, and even more preferably 0 to 0.19 mmol / g.

[0271] The acid values ​​mentioned above were measured in accordance with the JIS (Japanese Industrial Standards) K 0070:1992.

[0272] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. Furthermore, the number-average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0273] The molecular weight dispersion of the aforementioned polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyimide precursor; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

[0274] In this specification, the molecular weight dispersion is a value calculated by weight-average molecular weight / number-average molecular weight.

[0275] Furthermore, when the resin composition includes multiple polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the aforementioned ranges. Moreover, it is even more preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the multiple polyimide precursors as a single resin are each within the aforementioned ranges.

[0276] [Manufacturing method of specific resins]

[0277] The method for manufacturing a particular resin of the present invention preferably includes the following steps: a step of reacting a tetracarboxylic dianhydride or its diester with a diamine to obtain a reactant; and a step of reacting the reactant with a compound represented by formula (T-1).

[0278] [Chemical Formula 30]

[0279]

[0280] In equation (T-1), Y 1 Z represents a hydrogen atom or a monovalent organic group. 1 Y represents a monovalent organic group having an aromatic group. 1 With Z 1 They can bond.

[0281] For example, as a process for obtaining a reactant by reacting a tetracarboxylic dianhydride or its diester with a diamine, examples include: a method for reacting a tetracarboxylic dianhydride with a diamine at low temperature; a method for obtaining a polyamic acid by reacting a tetracarboxylic dianhydride with a diamine at low temperature and then esterifying it with a condensing agent or an alkylating agent; a method for obtaining a diester from a tetracarboxylic dianhydride and an alcohol and then reacting it with a diamine in the presence of a diamine and a condensing agent; and a method for obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine. Of the above manufacturing methods, a method for obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine is more preferred.

[0282] Examples of condensing agents mentioned above include dicyclohexanediimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.

[0283] Examples of alkylating agents include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.

[0284] Examples of halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphoryl chloride.

[0285] Furthermore, in order to form a reaction site with the compound represented by formula (T-1), it is preferable that the molar amount of tetracarboxylic dianhydride or its diester is greater than the molar amount of diamine.

[0286] Specifically, the molar ratio of the diamine to the tetracarboxylic dianhydride or its diester is preferably 45-50%, more preferably 35-45%.

[0287] In methods for manufacturing polyimide precursors, organic solvents are preferably used during the reaction. One or more organic solvents may be used.

[0288] As an organic solvent, it can be appropriately determined according to the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc.

[0289] In methods for manufacturing polyimide precursors, a basic compound is preferably added during the reaction. The basic compound can be one type or two or more types.

[0290] Basic compounds can be appropriately determined based on the raw materials, and examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-aminopyridine, etc.

[0291] The reaction conditions in the process of reacting the above reactants with the compound represented by formula (T-1) can be determined with reference to the reaction conditions when using a known capping agent in a polyimide precursor.

[0292] In equation (T-1), Y 1 and Z 1 Each of the above equations (1-1) contains Y. 1 and Z 1 The meanings are the same, and the preferred selection methods are also the same.

[0293] Furthermore, the method for manufacturing the polyimide precursor of the present invention may also include a step of capping the ends of the polyimide precursor with other capping agents.

[0294] Other end-capping agents can be used in conjunction with the compound represented by formula (T-1) above, or the ends can be further end-capped after the step of reacting the above reactants with the compound represented by formula (T-1).

[0295] Other end-capping agents include monohydric alcohols, phenols, thiols, benzenethiophenols, and monoamines. Monohydric alcohols, phenols, or monoamines are preferred in terms of reactivity and film stability. Preferred monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecyl alcohol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, etc. (primary alcohols), isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, etc. (secondary alcohols), tert-butanol, adamantanol, etc. (tertiary alcohols). Preferred phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, etc. Furthermore, preferred compounds as 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-carboxyl-7-aminonaphthalene, 1-carboxyl-6-aminonaphthalene, and 1-carboxyl-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-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, or multiple different end groups can be introduced by reacting various end-capping agents.

[0296] Furthermore, when blocking the amino groups at the resin terminus, compounds having functional groups that can react with the amino group can be used for blocking. Preferred end-blocking agents for the amino group include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being more preferred. Preferred compounds for carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Preferred compounds for carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, neopentyl chloride, cyclohexaneformyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantaneformyl chloride, heptafluorobutyryl chloride, stearoyl chloride, and benzoyl chloride.

[0297] -Solid precipitation-

[0298] The manufacture of polyimide precursors may include a solid precipitation process. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, and the polymer component is precipitated, thereby precipitating it as a solid and drying it to obtain the polyimide precursor. To improve the purification degree, the polyimide precursor may be repeatedly subjected to operations such as re-dissolving, re-precipitating, and drying. A further step may be included to remove ionic impurities using an ion exchange resin.

[0299] 〔content〕

[0300] The content of a specific resin in the resin composition of the present invention, relative to the total solids content of the resin composition, is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more. Furthermore, the content of the resin in the resin composition of the present invention, relative to the total solids content of the resin composition, is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and still even more preferably 95% by mass or less.

[0301] The resin composition of the present invention may contain only one specific resin or may contain two or more resins. When containing two or more resins, the total amount is preferably within the above-mentioned range.

[0302] Furthermore, the resin composition of the present invention preferably contains at least two resins.

[0303] Specifically, the resin composition of the present invention may contain two or more specific resins and other resins described below, or may contain two or more specific resins, preferably two or more specific resins.

[0304] When the resin composition of the present invention contains two or more specific resins, it is preferable, for example, to contain a structure derived from dianhydride (R in formula (2) above). 115 Two or more different polyimide precursors.

[0305] <Other Resins>

[0306] The resin composition of the present invention may include the specific resin described above and other resins different from the specific resin (hereinafter also referred to as "other resins").

[0307] Other resins that differ from specific resins include polyimide precursors such as phenolic resins, polyamides, epoxy resins, polycrystalline siloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyraldehyde resins, styrene resins, polyether resins, and polyester resins.

[0308] As a polyimide precursor that differs from a particular resin, examples include resins that contain repeating units represented by formula (2) but do not contain structures represented by formula (1-1).

[0309] For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can also be obtained.

[0310] For example, by replacing the polymerizable compound described later in the resin composition or by adding a polymerizable group with a weight average molecular weight of less than 20,000 and a high polymerizable group value (e.g., the molar content of polymerizable groups in 1g of resin is 1×10⁻⁶) in addition to the polymerizable compound described later in the resin composition. -3 (Meth)acrylic resins with a molar ratio of 100 mol / g or higher can improve the coatability of resin compositions, the solvent resistance of patterns (cured products), etc.

[0311] When the resin composition of the present invention contains other resins, the content of the other resins relative to the total solid content of the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more.

[0312] Furthermore, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solid content of the resin composition.

[0313] Furthermore, as a preferred embodiment of the resin composition of the present invention, it is also possible to configure it with a low content of other resins. In the above embodiment, the content of other resins relative to the total solids content of the resin composition is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the above content is not particularly limited, and 0% by mass or more is acceptable.

[0314] The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, the total amount is preferably within the above-mentioned range.

[0315] <Polymerizing compounds>

[0316] The resin composition of the present invention preferably contains a polymerizable compound.

[0317] Examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0318] [Free radical cross-linking agent]

[0319] The resin composition of the present invention preferably contains a free radical crosslinking agent.

[0320] A free radical crosslinking agent is a compound having a free radical polymerizable group. Preferably, the free radical polymerizable group contains an olefinically unsaturated bond. Examples of such olefinically unsaturated groups include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acrylamido groups.

[0321] Among these, (meth)acryloyl, (meth)acrylamido, and vinylphenyl are preferred groups containing olefinic unsaturated bonds, and (meth)acryloyl is more preferred from the viewpoint of reactivity.

[0322] The free radical crosslinking agent is preferably a compound having one or more olefinic unsaturated bonds, more preferably a compound having two or more olefinic unsaturated bonds. The free radical crosslinking agent may have three or more olefinic unsaturated bonds.

[0323] As for the above-mentioned compounds having two or more olefinic unsaturated bonds, compounds having 2 to 15 olefinic unsaturated bonds are preferred, compounds having 2 to 10 olefinic unsaturated bonds are more preferred, and compounds having 2 to 6 olefinic unsaturated bonds are even more preferred.

[0324] Furthermore, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains compounds having two olefinic unsaturated bonds and compounds having three or more of the above-mentioned olefinic unsaturated bonds.

[0325] The molecular weight of the free radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the free radical crosslinking agent is preferably 100 or more.

[0326] Specific examples of free radical polymerizable compounds include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyols, and amides of unsaturated carboxylic acids and polyamines. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, or thioalkyl groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids are also preferred. Moreover, addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred. Substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or toluenesulfonyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are even more preferred. Furthermore, as other examples, compounds that replace the aforementioned unsaturated carboxylic acids with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc., can be used. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0327] Furthermore, the free radical crosslinking agent is preferably a compound with a boiling point of 100°C or higher at normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerol, or trimethylolethane, which are added to polyfunctional alcohols with ethylene oxide or propylene oxide followed by (meth)acrylate addition. Esterified compounds, urethane (meth)acrylates described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, epoxy acrylates as products of the reaction of epoxy resin and (meth)acrylic acid, and other polyfunctional acrylates or methacrylates; and mixtures thereof. Furthermore, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are preferred. Moreover, polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds having cyclic ether groups and olefinic unsaturated bonds, such as glycidyl (meth)acrylate, can also be cited.

[0328] Furthermore, as a preferred free radical crosslinking agent other than those mentioned above, compounds having a fluorene ring and having two or more groups having olefinic unsaturated bonds, as described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, and Japanese Patent No. 4364216, as well as cardo resins, can also be used.

[0329] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, and vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493, etc., can also be used. Moreover, compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. Furthermore, compounds described as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0330] In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 are also preferred to be used, and these contents are incorporated in this specification.

[0331] Furthermore, the compounds described in Japanese Patent Application Publication No. 10-062986 as formulas (1) and (2) along with their specific examples can also be used as free radical crosslinking agents. These compounds are obtained by esterification of (meth)acrylates after the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol.

[0332] Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Publication No. 2015-187211 can also be used as free radical crosslinking agents, and this information is incorporated into this specification.

[0333] As free radical crosslinking agents, preferred products include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (Nippon Kayaku Co., Ltd.)), A-TMMT (Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (Nippon Kayaku Co., Ltd.)), A-DPH (Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol or propylene glycol residues. Oligomer types can also be used.

[0334] Commercially available free radical crosslinking agents include, for example, SR-494 (a tetrafunctional acrylate with four vinyl groups) and SR-209, 231, and 239 (difunctional methacrylates with four vinyl groups) manufactured by Sartomer Company, Inc.; DPCA-60 (a hexafunctional acrylate with six pentylene groups) and TPA-330 (a trifunctional acrylate with three isobutyrite groups) manufactured by Nippon Kayaku Co., Ltd.; urethane oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.); NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300; UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.); and DPHA-40H (manufactured by Nippon Kayaku). (manufactured by Kyoisha Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), etc.

[0335] As free radical crosslinking agents, urethane acrylates described in Japanese Patent Publication Nos. 48-041708, 51-037193, 02-032293, and 02-016765, and urethane compounds having an ethylene oxide backbone described in Japanese Patent Publication Nos. 58-049860, 56-017654, 62-039417, and 62-039418 are also preferred. Furthermore, compounds having an amino or thioether structure within the molecule as described in Japanese Patent Publication Nos. 63-277653, 63-260909, and 01-105238 can also be used as free radical crosslinking agents.

[0336] The free radical crosslinking agent can be a free radical crosslinking agent having acid groups such as carboxyl groups or phosphate groups. The free radical crosslinking agent with acid groups is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably a free radical crosslinking agent that reacts the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to give it acid groups. Particularly preferred are compounds in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol in the free radical crosslinking agent that reacts the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to give it acid groups. Commercially available examples include, for instance, polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO.,LTD.

[0337] The preferred acid value of the free radical crosslinking agent containing acid groups is 0.1–300 mg KOH / g, and particularly preferably 1–100 mg KOH / g. When the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent manufacturability and, consequently, excellent developability. Furthermore, it demonstrates good polymerizability. The above acid values ​​were measured according to the description in JIS K 0070:1992.

[0338] From the viewpoint of pattern resolution and film elasticity, the resin composition preferably uses difunctional methacrylates or acrylates.

[0339] 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-pentylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, etc. Dimethacrylates, including dimethylol-tricyclodecane dimethacrylates, dimethylol-tricyclodecane dimethacrylates, ethylene oxide (EO) adduct dimethacrylates of bisphenol A, EO adduct dimethacrylates of bisphenol A, PO adduct dimethacrylates of bisphenol A, PO adduct dimethacrylates of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylates, EO-modified dimethacrylates of isocyanuric acid, isocyanuric acid-modified dimethacrylates, other difunctional acrylates with urethane bonds, and difunctional methacrylates with urethane bonds. Two or more of these can be mixed as needed.

[0340] In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a molecular weight of about 200 for the polyethylene glycol chain.

[0341] From the viewpoint of suppressing warping caused by controlling the elastic modulus of the accompanying pattern (cured product), the resin composition of the present invention preferably uses a monofunctional free radical crosslinking agent as the free radical crosslinking agent. As a monofunctional free radical crosslinking agent, preferred materials include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylate derivatives, N-vinylpyrrolidone, N-vinyl caprolactam, and allyl glycidyl ether. As a monofunctional free radical crosslinking agent, compounds with a boiling point of 100°C or higher at ambient pressure are also preferred to suppress volatilization before exposure.

[0342] In addition, examples of allyl compounds, such as diallyl phthalate and triallyl trimellitate, can be cited as free radical crosslinking agents with two or more functions.

[0343] When a free radical crosslinking agent is included, its content relative to the total solids content of the resin composition of the present invention is preferably more than 0% by mass and less than 60% by mass. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0344] Free radical crosslinking agents can be used alone or in combination of two or more. When using two or more, their combined dosage is preferably within the range mentioned above.

[0345] [Other crosslinking agents]

[0346] The resin composition of the present invention preferably also contains other crosslinking agents different from the free radical crosslinking agents described above.

[0347] In this invention, other crosslinking agents refer to crosslinking agents other than the aforementioned free radical crosslinking agents. Preferably, they are compounds having multiple groups within the molecule that promote the formation of covalent bonds between the compounds and their reaction products in the composition by photosensitization by the aforementioned photoacid generators or photobase generators, etc. More preferably, they are compounds having multiple groups within the molecule that promote the formation of covalent bonds between the compounds and their reaction products in the composition by the action of acids or bases.

[0348] The acid or base mentioned above is preferably an acid or base generated from a photoacid generator or a photoalkali generator during the exposure process.

[0349] As other crosslinking agents, it is preferable to have compounds having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl and alkoxymethyl, and more preferably compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom.

[0350] Other crosslinking agents include, for example, compounds having the following structure: obtained by reacting amino-containing compounds such as melamine, acetylacetonate, urea, alkylene urea, and benzoguanidine with formaldehyde or formaldehyde and an alcohol, thereby replacing the hydrogen atoms of the aforementioned amino groups with acyloxymethyl, hydroxymethyl, or alkoxymethyl groups. The method of manufacturing these compounds is not particularly limited, as long as the compound has the same structure as the compound manufactured by the above method. Furthermore, these compounds can be oligomers formed by the self-condensation of the hydroxymethyl groups of these compounds.

[0351] As for the aforementioned amino-containing compounds, crosslinking agents using melamine are called melamine-based crosslinking agents, crosslinking agents using acetylenide, urea, or alkylene urea are called urea-based crosslinking agents, crosslinking agents using alkylene urea are called alkylene urea-based crosslinking agents, and crosslinking agents using benzoguanidine are called benzoguanidine-based crosslinking agents.

[0352] 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 later.

[0353] As a compound containing at least one of alkoxymethyl and acylmethyl groups in this invention, examples of compounds in which the alkoxymethyl or acylmethyl group is directly substituted on an aromatic group, a nitrogen atom of a urea structure described below, or a triazine are provided.

[0354] Regarding the alkoxymethyl or acylmethyl groups present in the above-mentioned compounds, it is preferred that the number of carbon atoms is 2 to 5, more preferably 2 or 3, and even more preferably 2.

[0355] The total number of alkoxymethyl and acylmethyl groups in the above-mentioned compounds is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[0356] The molecular weight of the above-mentioned compound is preferably below 1500, and more preferably between 180 and 1200.

[0357] [Chemical Formula 31]

[0358]

[0359] R 100 Indicates alkyl or acyl groups.

[0360] R 101 and R 102 Each of these groups independently represents a monovalent organic group and can bond with each other to form a ring.

[0361] Compounds in which alkoxymethyl or acylmethyl groups are directly substituted on aromatic groups include, for example, compounds of the following general formula.

[0362] [Chemical Formula 32]

[0363]

[0364] In the formula, X represents a single bond or a divalent organic group, and each R 104 Each can be independently represented by an alkyl or acyl group, R 103 This refers to a group consisting of a hydrogen atom, alkyl, alkenyl, aryl, aralkyl, or a group that decomposes under the action of an acid to form a base-soluble group (e.g., a group that is released by the action of an acid, or a group formed by -C(R)). 4 )2COOR 5 The group represented (R) 4 R represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively. 5 This indicates a group that is released by the action of an acid.

[0365] R 105 Each can independently represent an alkyl or alkenyl group, where a, b, and c are each 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.

[0366] Regarding groups that decompose under the action of acid to form alkali-soluble groups, groups that are released under the action of acid, and groups derived from -C(R) 4 )2COOR 5 The R in the indicated group 5 For example, one can cite -C(R) 36 (R) 37 (R) 38 ), -C(R 36 (R) 37 (OR) 39 ), -C(R 01 (R) 02 (OR) 39 )wait.

[0367] In the formula, R 36 ~R 39 Each can be independently represented as alkyl, cycloalkyl, aryl, aralkyl, or alkenyl. R 36 With R 37 They can bond together to form a ring.

[0368] 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.

[0369] The aforementioned alkyl groups can be either straight-chain or branched.

[0370] As the aforementioned cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferred, and a cycloalkyl group having 3 to 8 carbon atoms is more preferred.

[0371] The aforementioned cycloalkyl groups can be monocyclic or polycyclic structures such as fused rings.

[0372] The aryl group is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, and more preferably a phenyl group.

[0373] As the aforementioned aralkyl group, aralkyl groups with 7 to 20 carbon atoms are preferred, and alkyl groups with 7 to 16 carbon atoms are more preferred.

[0374] The aryl group mentioned above refers to an aryl group that has been substituted with an alkyl group. The preferred methods for these alkyl and aryl groups are the same as those for the alkyl and aryl groups mentioned above.

[0375] The alkenyl group mentioned above is preferably an alkenyl group with 3 to 20 carbon atoms, and more preferably an alkenyl group with 3 to 16 carbon atoms.

[0376] Moreover, these groups can further have known substituents within the scope of achieving the effects of the present invention.

[0377] R 01 and R 02 Each can be independently represented by a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group.

[0378] The preferred groups, such as tertiary alkyl esters, acetals, cumyl esters, and enols, are those that decompose under acidic action to form alkali-soluble groups or are released under acidic action. Tertiary alkyl esters and acetals are more preferred.

[0379] As compounds having an alkoxymethyl group, specific examples include the following structures. Compounds having an acylmethyl group include those in which the alkoxymethyl group of the following compounds is replaced with an acylmethyl group. As compounds having an alkoxymethyl group or an acylmethyl group intramolecularly, the following compounds can be cited, but are not limited to these.

[0380] [Chemical Formula 33]

[0381]

[0382] [Chemical Formula 34]

[0383]

[0384] Compounds containing at least one of alkoxymethyl and acylmethyl groups can be commercially available or synthesized by known methods.

[0385] From the viewpoint of heat resistance, compounds in which alkoxymethyl or acylmethyl groups are directly substituted on the aromatic ring or triazine ring are preferred.

[0386] Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

[0387] Specific examples of urea-based crosslinking agents include monohydroxymethylated acetylenoid, dihydroxymethylated acetylenoid, trihydroxymethylated acetylenoid, tetrahydroxymethylated acetylenoid, monomethoxymethylated acetylenoid, dimethoxymethylated acetylenoid, trimethoxymethylated acetylenoid, tetramethoxymethylated acetylenoid, monoethoxymethylated acetylenoid, diethoxymethylated acetylenoid, triethoxymethylated acetylenoid, tetraethoxymethylated acetylenoid, monopropoxymethylated acetylenoid, dipropoxymethylated acetylenoid, tripropoxymethylated acetylenoid, tetrapropoxymethylated acetylenoid, monobutoxymethylated acetylenoid, dibutoxymethylated acetylenoid, tributoxymethylated acetylenoid, or tetrabutoxymethylated acetylenoid, etc.

[0388] Urea crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea.

[0389] Monohydroxymethylated vinylurea or dihydroxymethylated vinylurea, monomethoxymethylated vinylurea, dimethoxymethylated vinylurea, monoethoxymethylated vinylurea, diethoxymethylated vinylurea, monopropoxymethylated vinylurea, dipropoxymethylated vinylurea, monobutoxymethylated vinylurea or dibutoxymethylated vinylurea, etc., are vinylurea-based crosslinking agents.

[0390] Acrylurea crosslinking agents such as monohydroxymethylated acrylate, dihydroxymethylated acrylate, monomethoxymethylated acrylate, dimethoxymethylated acrylate, monoethoxymethylated acrylate, diethoxymethylated acrylate, monopropoxymethylated acrylate, dipropoxymethylated acrylate, monobutoxymethylated acrylate, or dibutoxymethylated acrylate.

[0391] 1,3-Di(methoxymethyl)-4,5-dihydroxy-2-imidazolinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolinone, etc.

[0392] Specific examples of benzoguanidine-based crosslinking agents include, for instance, monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, monoethoxymethylated benzoguanidine, diethoxymethylated benzoguanidine, triethoxymethylated benzoguanidine, tetraethoxymethylated benzoguanidine, monopropoxymethylated benzoguanidine, dipropoxymethylated benzoguanidine, tripropoxymethylated benzoguanidine, tetrapropoxymethylated benzoguanidine, monobutoxymethylated benzoguanidine, dibutoxymethylated benzoguanidine, tributoxymethylated benzoguanidine, and tetrabutoxymethylated benzoguanidine.

[0393] Furthermore, as a compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl, it is also preferable to use a compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl directly bonded to an aromatic ring (preferably a benzene ring).

[0394] Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzoic acid hydroxymethylbenzene, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, and bis(methoxymethyl)diphenylbenzene. Methyl ketone, methoxymethylbenzoic acid, 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'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

[0395] Other crosslinking agents can be commercially available products. Preferred commercially available products include 46DMOC, 46DMOEP (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, same below) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALACMW-100LM, NIKALAC MX-750LM (all manufactured by SANWA CHEMICAL CO.,LTD), etc.

[0396] Furthermore, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds and benzoxazine compounds as other crosslinking agents.

[0397] -Epoxy compounds (compounds containing epoxy groups)-

[0398] As an epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy groups undergo cross-linking reactions below 200°C and do not trigger dehydration reactions due to cross-linking, thus minimizing film shrinkage. Therefore, by containing an epoxy compound, low-temperature curing and warping of the resin composition of the present invention can be effectively suppressed.

[0399] The epoxy compound preferably contains polyethylene oxide. This further reduces the elastic modulus and suppresses warping. Polyethylene oxide refers to a group in which ethylene oxide has two or more repeating units, preferably 2 to 15.

[0400] Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol 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; and silicones containing epoxy groups such as polymethyl(epoxypropoxypropyl)siloxane, but these are not limited to these.Specifically, examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, and EPICLON (registered trademark) N-740 (these are product names, DIC). (Manufactured by Corporation), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are trade names, manufactured by ADEKACORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are trade names, manufactured by Daicel). The following compounds are manufactured by Nippon Kayaku Co., Ltd.: 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 (trade names, manufactured by Nippon Kayaku Co., Ltd.). Furthermore, the following compounds are also preferred.

[0401] [Chemical Formula 35]

[0402]

[0403] In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

[0404] In the above structure, considering both heat resistance and improved elongation, n is preferably 1 to 2 and m is preferably 3 to 7.

[0405] -Oxycyclic butane compounds (compounds containing an oxycyclic butyl group)-

[0406] Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetane-butyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetane-butyl)methyl] ester. As specific examples, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO.,LTD. is preferred; these can be used alone or in mixtures of two or more.

[0407] -Benzoxazine compounds (compounds containing a benzoxazole group)-

[0408] Benzooxazine compounds are preferred because they do not undergo degassing during curing due to the crosslinking reaction caused by the ring-opening addition reaction, thereby reducing thermal shrinkage and inhibiting warping.

[0409] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (trade names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and dihydrobenzoxazine compounds of phenolic varnish type. These can be used alone or in combination of two or more.

[0410] The content of other crosslinking agents relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. Other crosslinking agents may be present in only one type or in two or more types. When two or more other thermal crosslinking agents are present, their total content is preferably within the above-mentioned range.

[0411] [Polymerization initiator]

[0412] The resin composition of the present invention preferably contains a polymerization initiator, and more preferably a free radical polymerization initiator. The free radical polymerization initiator preferably includes a free radical polymerization initiator capable of initiating polymerization by light and / or heat. Particularly preferred is a photoradical polymerization initiator.

[0413] There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, photoradical polymerization initiators that are sensitive to light in the ultraviolet to visible regions are preferred. Moreover, it can be an active agent that interacts with the photoexcited sensitizer and generates active free radicals.

[0414] The photoradical polymerization initiator preferably contains at least one initiator having a wavelength of at least about 50 L·mol⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). -1 ·cm -1 The molar absorptivity of a compound. The molar absorptivity of a compound can be measured using known methods. For example, it is preferred to use a UV-Vis spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0415] As photoradical polymerization initiators, any known compounds can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, hexaaryl diimidazoles, 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, azido compounds, metallocene compounds, organoboron compounds, and iron aromatic hydrocarbon complexes. For detailed information on these, please refer to paragraphs 0165-0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, 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 Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313, all of which are incorporated herein by reference.

[0416] As ketone compounds, examples include those described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferred.

[0417] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, as these contents are incorporated herein by reference.

[0418] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

[0419] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

[0420] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Application Publication No. 2009-191179, which match the maximum absorption wavelength to a light source of wavelengths such as 365 nm or 405 nm, can also be used, and these contents are incorporated in this specification.

[0421] Examples of acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Furthermore, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, and IRGACURE-TPO (trade names: all manufactured by BASF) can also be used.

[0422] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem Co., Ltd.).

[0423] Oxime compounds are more preferably selected as photoradical polymerization initiators. By using oxime compounds, exposure latitude can be further improved more effectively. Oxime compounds are particularly preferred because they offer a wide exposure latitude and also act as photocuring accelerators.

[0424] Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 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 the Journal of Photopolymer Science and... The compounds described in Technology (1995, pp. 202-232), Japanese Patent Application Publication No. 2000-066385, Japanese Patent Application Publication No. 2004-534797, Japanese Patent Application Publication No. 2017-019766, Japanese Patent No. 6065596, International Publication No. 2015 / 152153, International Publication No. 2017 / 051680, Japanese Patent Application Publication No. 2017-198865, International Publication No. 2017 / 164127 (paragraphs 0025-0038), and International Publication No. 2013 / 167515 are included in this specification.

[0425] Preferred oxime compounds include, for example, compounds with the following structures: 3-(benzoyloxy(imino))but-2-one, 3-(acetoxy(imino))but-2-one, 3-(propionyloxy(imino))but-2-one, 2-(acetoxy(imino))pent-3-one, 2-(acetoxy(imino))-1-phenylprop-1-one, 2-(benzoyloxy(imino))-1-phenylprop-1-one, 3-((4-toluenesulfonyloxy(imino))but-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylprop-1-one. In the resin compositions of the present invention, oxime compounds (oxime-based photoradical polymerization initiators) are preferably used, particularly as photoradical polymerization initiators. Oxime-based photoradical polymerization initiators have an intramolecular linking group >C=NOC(=O)-.

[0426] [Chemical Formula 36]

[0427]

[0428] Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), and ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 as described in Japanese Patent Application Publication No. 2012-014052) are also preferred. Furthermore, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), ADEKAARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. Additionally, DFI-091 (manufactured by Daito Chemix Corporation) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can also be used. Moreover, oxime compounds with the following structures can also be used.

[0429] [Chemical Formula 37]

[0430]

[0431] Oxime compounds having a fluorene ring can also be used as photoradical polymerization initiators. Specific examples of oxime compounds having a fluorene ring include the compounds described in Japanese Patent Application Publication No. 2014-137466 and the compounds described in Japanese Patent No. 06636081, which are incorporated herein by reference.

[0432] As photoradical polymerization initiators, oxime compounds with at least one benzene ring having a carbazole ring as the backbone of a naphthalene ring can also be used. Specific examples of such oxime compounds include the compounds described in International Publication No. 2013 / 083505, the contents of which are incorporated herein by reference.

[0433] Oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Application Publication No. 2013-164471, which are incorporated herein by reference.

[0434] Nitro-containing oxime compounds can be used as photopolymerization initiators. Nitro-containing oxime compounds are preferably dimers. Specific examples of nitro-containing oxime compounds include compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Application Publication No. 2014-137466, and paragraphs 0007 to 0025 of Japanese Patent Application Publication No. 4223071, the contents of which are incorporated herein by reference. Furthermore, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION) is another example of a nitro-containing oxime compound.

[0435] Oxime compounds having a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75 as described in International Publication No. 2015 / 036910.

[0436] As photoradical polymerization initiators, oxime compounds with hydroxyl substituents bonded to the carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019 / 088055, which are incorporated herein by reference.

[0437] As a photopolymerization initiator, Ar aromatic cyclic groups obtained by introducing electron-withdrawing groups into the aromatic ring can also be used. OX1 Oxime compounds (hereinafter also referred to as oxime compounds OX). As the above aromatic cyclic group Ar... OX1Examples of electron-withdrawing groups include acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano, with acyl and nitro being preferred. Acyl is more preferred for the ease of forming a film with excellent lightfastness, and benzoyl is even more preferred. The benzoyl group may have substituents. Preferred substituents are halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkylthioalkyl, arylthioalkyl, acyl, or amino, with alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkylthioalkyl, or amino being more preferred, and alkoxy, alkylthioalkyl, or amino being even more preferred.

[0438] The oxime compound OX is preferably selected from at least one of the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compounds represented by formula (OX2).

[0439] [Chemical Formula 38]

[0440]

[0441] In the formula, R X1 This indicates alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthioalkyl, arylthioalkyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphonyl, carbamoyl, or aminosulfonyl.

[0442] R X2 This indicates alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylthioalkyl, arylthioalkyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyloxy, or amino.

[0443] R X3 ~R X14 Each can be used to represent a hydrogen atom or a substituent independently.

[0444] Among them, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0445] In the above formula, R is preferred. X12 R is an electron-withdrawing group. X10 R X11 R X13 R X14 It is a hydrogen atom.

[0446] Specific examples of oxime compounds OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, which are incorporated herein by reference.

[0447] Examples of preferred oxime compounds include those with specific substituents shown in Japanese Patent Application Publication No. 2007-269779 and those with thioaryl groups shown in Japanese Patent Application Publication No. 2009-191061, which are incorporated herein by reference.

[0448] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethane triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0449] More preferably, the photoradical polymerization initiator is a trihalomethane triazine compound, an α-amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazolium dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound. More preferably, it is a compound selected from at least one compound including trihalomethane triazine compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, and benzophenone compounds. Even more preferably, it is a metallocene compound or an oxime compound.

[0450] Furthermore, photoradical polymerization initiators can also include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), and other N,N'-tetraalkyl-4,4'-diaminobenzophenone; aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1; quinones formed by cyclization of aromatic rings with alkyl anthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkylbenzoin; and benzyl derivatives such as benzyl dimethyl ketal. Moreover, compounds represented by the following formula (I) can also be used.

[0451] [Chemical Formula 39]

[0452]

[0453] In equation (I), R I00The alkyl group having 1 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, the alkoxy group having 1 to 12 carbon atoms, the phenyl group, or the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 12 carbon atoms, the halogen atom, the cyclopentyl group, the cyclohexyl group, the alkenyl group having 2 to 12 carbon atoms, the alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and the alkyl group having 1 to 4 carbon atoms, are substituted with at least one phenyl or biphenyl group. I01 For groups represented by formula (II) or with R I00 The same group, R I02 ~R I04 Each is independently an alkyl group, an alkoxy group, or a halogen atom, having 1 to 12 carbon atoms.

[0454] [Chemical Formula 40]

[0455]

[0456] In the formula, R I05 ~R I07 R in equation (I) above I02 ~R I04 same.

[0457] Furthermore, the photoradical polymerization initiator can also use compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469, which are incorporated in this specification.

[0458] As photoradical polymerization initiators, photoradical polymerization initiators with two or more functionalities can be used. By using such photoradical polymerization initiators, two or more free radicals are generated from one molecule of the initiator, thus achieving good sensitivity. Moreover, when using compounds with asymmetric structures, crystallinity decreases while solubility in solvents increases, making them less prone to precipitation over time, thereby improving the long-term stability of the resin composition. Specific examples of photoradical polymerization initiators with two or more functionalities include dimers of oxime compounds described in Japanese Patent Application Publication Nos. 2010-527339, 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680; and compounds (E) and compounds described in Japanese Patent Application Publication No. 2013-522445. (G) Cmpd1 to 7 as described in International Publication No. 2016 / 034963, oxime ester photoinitiators as described in paragraph 0007 of Japanese Patent Application Publication No. 2017-523465, photoinitiators as described in paragraphs 0020 to 0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators as described in paragraphs 0017 to 0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators as described in Japanese Patent Application Publication No. 6469669 are included in this specification.

[0459] When a photoradical polymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are included, the total amount is preferably within the above-mentioned range.

[0460] In addition, photopolymerization initiators can sometimes also act as thermal polymerization initiators. Therefore, heating with ovens, heating plates, etc., can sometimes further promote crosslinking based on photopolymerization initiators.

[0461] [Sensitizer]

[0462] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., resulting in electron transfer, energy transfer, and heating. As a result, the thermal free radical polymerization initiator and photofree radical polymerization initiator undergo chemical changes and decompose, generating free radicals, acids, or bases.

[0463] As usable sensitizers, compounds such as benzophenone, mifepristone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenothiazine, pyrrolopyrazole azomethyl, xanthones, phthalocyanines, benzopyrans, and indigo compounds can be used.

[0464] Examples of sensitizers include mifepristone, 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-dimethylaminophenylenepropyl dihydroindone, and p-dimethylaminophenylenepropyl dihydroindone. Aminophenylmethylene dihydroindone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethyl 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-toluenediethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, Isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphthalene(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzoylaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc.

[0465] Furthermore, other sensitizing pigments can also be used.

[0466] For details regarding the sensitizing pigments, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which are incorporated herein by reference.

[0467] When the resin composition contains a sensitizer, the content of the sensitizer relative to the total solids content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass. A single sensitizer may be used alone, or two or more may be used in combination.

[0468] [Chain transfer agent]

[0469] 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. Examples of chain transfer agents include compounds having intramolecularly -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, and xanthate compounds having thiocarbonyl thio groups used in RAFT (Reversible Addition Fragmentation chain Transfer) polymerization. These generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. In particular, thiols are preferred.

[0470] Furthermore, the chain transfer agent can also use compounds described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which are incorporated herein by reference.

[0471] When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solids of the resin composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. The chain transfer agent may be only one type or may be two or more types. When there are two or more chain transfer agents, their total amount is preferably within the above-mentioned range.

[0472] <Alkali generating agent>

[0473] The resin composition of the present invention may contain an alkali-generating agent. Here, an alkali-generating agent refers to a compound capable of generating alkali through physical or chemical action. Preferred alkali-generating agents for the resin composition of the present invention include thermal alkali-generating agents and photo-alkali-generating agents.

[0474] In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains an alkali-generating agent. By containing a thermal alkali-generating agent in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, resulting in improved mechanical properties and chemical resistance of the cured product, and, for example, improved performance of the interlayer insulating film used as a rewiring layer in semiconductor packaging.

[0475] As a base-generating agent, it can be either an ionic or a nonionic base-generating agent. Examples of bases generated from the base-generating agent include, for example, secondary and tertiary amines.

[0476] The alkali generating agent of the present invention is not particularly limited, and known alkali generating agents can be used. Examples of known alkali 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, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimide compounds, phthalimide derivative compounds, and acyloxyimide compounds.

[0477] Specific compounds that can be cited as nonionic base generating agents include those represented by formula (B1), formula (B2), or formula (B3).

[0478] [Chemical Formula 41]

[0479]

[0480] In equations (B1) and (B2), Rb 1 、Rb 2 and Rb 3 Each of these can be an organic group, a halogen atom, or a hydrogen atom that does not possess a tertiary amine structure. Specifically, Rb... 1 and Rb 2 It will not simultaneously become a hydrogen atom. Furthermore, Rb 1 、Rb 2 and Rb 3 None of them contain a carboxyl group. Furthermore, in this specification, a tertiary amine structure refers to a structure in which all three bonds of the trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, it is not limited to this definition when the bonded carbon atoms are carbon atoms forming a carbonyl group, i.e., when they form an amide group together with the nitrogen atom.

[0481] In equations (B1) and (B2), Rb is preferred. 1 、Rb 2 and Rb 3At least one of the rings contains a cyclic structure, more preferably at least two rings. The cyclic structure can be either a monocyclic ring or a fused ring, preferably a monocyclic ring or a fused ring formed by the condensation of two monocyclic rings. The monocyclic ring is preferably a 5-membered or 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, more preferably a cyclohexane ring.

[0482] More specifically, Rb 1 and Rb 2 Preferably, the groups are hydrogen atoms, alkyl groups (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), alkenyl groups (preferably 2-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryl groups (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-10), or aralkyl groups (preferably 7-25 carbon atoms, more preferably 7-19, and even more preferably 7-12). These groups may have substituents within the range that allows the effects of the invention to be achieved. Rb 1 With Rb 2 They can bond together to form rings. Preferably, the formed rings are nitrogen-containing heterocycles with 4 to 7 members. Rb 1 and Rb 2 In particular, it is preferred to have a straight-chain, branched or cyclic alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12) that may have substituents, more preferably a cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12) that may have substituents, and even more preferably a cyclohexyl group that may have substituents.

[0483] As Rb 3 Examples of such compounds include alkyl groups (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryl groups (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-10), alkenyl groups (preferably 2-24 carbon atoms, more preferably 2-12, and even more preferably 2-6), aralkyl groups (preferably 7-23 carbon atoms, more preferably 7-19, and even more preferably 7-12), aryl-alkenyl groups (preferably 8-24 carbon atoms, more preferably 8-20, and even more preferably 8-16), alkoxy groups (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryloxy groups (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-12), or arylalkoxy groups (preferably 7-23 carbon atoms, more preferably 7-19, and even more preferably 7-12). Among them, cycloalkyl (preferably 3-24 carbon atoms, more preferably 3-18, and even more preferably 3-12), aryl, and arylalkoxy are preferred. Rb 3 The invention may further contain substituents within the scope of achieving the effects of the invention.

[0484] The compound represented by formula (B1) is preferably a compound represented by formula (B1-1) or formula (B1-2) below.

[0485] [Chemical Formula 42]

[0486]

[0487] In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 respectively with Rb in equation (B1) 1 and Rb 2 They have the same meaning.

[0488] Rb 13 The groups are alkyl (preferably 1-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), alkenyl (preferably 2-24 carbon atoms, more preferably 2-18, and even more preferably 3-12), aryl (preferably 6-22 carbon atoms, more preferably 6-18, and even more preferably 6-12), or aralkyl (preferably 7-23 carbon atoms, more preferably 7-19, and even more preferably 7-12), and may have substituents within the range that allows the effects of the present invention to be achieved. Rb 13 Preferably, it is an aryl alkyl group.

[0489] Rb 33 and Rb 34 Each of the following is independently composed of hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 8, and even more preferably 2 to 3), aryl groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), aralkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and preferably hydrogen atoms.

[0490] Rb 35 The carbon atoms are alkyl (preferably 1-24, more preferably 1-12, and even more preferably 3-8), alkenyl (preferably 2-12, more preferably 2-10, and even more preferably 3-8), aryl (preferably 6-22, more preferably 6-18, and even more preferably 6-12), aralkyl (preferably 7-23, more preferably 7-19, and even more preferably 7-12), and preferably aryl.

[0491] The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a).

[0492] [Chemical Formula 43]

[0493]

[0494] Rb 11 and Rb 12 With Rb in equation (B1-1) 11 and Rb 12 They have the same meaning.

[0495] Rb 15 and Rb 16 The atom is a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11), and preferably a hydrogen atom or a methyl group.

[0496] Rb 17 The carbon atoms are alkyl (preferably 1-24, more preferably 1-12, and even more preferably 3-8), alkenyl (preferably 2-12, more preferably 2-10, and even more preferably 3-8), aryl (preferably 6-22, more preferably 6-18, and even more preferably 6-12), or aralkyl (preferably 7-23, more preferably 7-19, and even more preferably 7-12), with aryl being the most preferred.

[0497] [Chemical Formula 44]

[0498]

[0499] In formula (B3), L represents a divalent hydrocarbon group with a saturated hydrocarbon group in the path of the linking chain connecting adjacent oxygen and carbon atoms, indicating a hydrocarbon group with 3 or more atoms in the linking chain path. Furthermore, R... N1 and R N2 Each can be used to represent a monovalent organic group independently.

[0500] In this specification, a "linking chain" refers to an atomic chain along a path connecting two atoms or groups of atoms of the linked objects, where these linked objects are connected by the shortest (minimum number of atoms) distance. For example, in a compound represented by the following formula, L is composed of styrene, has vinyl as a saturated hydrocarbon group, the linking chain consists of 4 carbon atoms, and the number of atoms along the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length" or "linking chain length") is 4.

[0501] [Chemical Formula 45]

[0502]

[0503] The number of carbon atoms in L of formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of enabling the above-mentioned intramolecular cyclization reaction to proceed rapidly, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific examples of preferred compounds as base generating agents include, 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.

[0504] Furthermore, the alkali generating agent preferably comprises a compound represented by the following formula (N1).

[0505] [Chemical Formula 46]

[0506]

[0507] In equation (N1), R N1 and R N2 Each independently represents a monovalent organic group, R C1 The symbol represents a hydrogen atom or a protecting group, and L represents a divalent linker.

[0508] 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 even more preferably 5 or less. The linking chain length refers to the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

[0509] In equation (N1), R N1 and R N2 Each group independently represents a monovalent organic group (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), preferably a hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10). Specifically, examples include aliphatic hydrocarbon groups (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10) or aromatic hydrocarbon groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), preferably aliphatic hydrocarbon groups. As R N1 and R N2If an aliphatic hydrocarbon group is used, the resulting base will have high basicity, which is preferred. Furthermore, the aliphatic and aromatic hydrocarbon groups can have substituents, and the aliphatic and aromatic hydrocarbon groups can also have oxygen atoms in the aliphatic hydrocarbon chain, the aromatic ring, or the substituents. In particular, examples can be given of aliphatic hydrocarbon groups having oxygen atoms in the hydrocarbon chain.

[0510] As a component of R N1 and R N2 The aliphatic hydrocarbon group can be exemplified by straight-chain or branched chain alkyl groups, cyclic alkyl groups, combinations of chain alkyl and cyclic alkyl groups, and alkyl groups having oxygen atoms in the chain. The number of carbon atoms in the straight-chain or branched chain alkyl group is preferably 1 to 24, more preferably 2 to 18, and even more preferably 3 to 12. Examples of straight-chain or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl.

[0511] The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0512] The number of carbon atoms in the group involved in the combination of chain alkyl and cyclic alkyl is preferably 4 to 24, more preferably 4 to 18, and even more preferably 4 to 12. Examples of the groups involved in the combination of chain alkyl and cyclic alkyl include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl.

[0513] The alkyl group having oxygen atoms in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched.

[0514] From the perspective of increasing the boiling point of the alkali produced by the subsequent decomposition, R N1 and R N2 Preferably, the alkyl group has 5 to 12 carbon atoms. In formulations where adhesion to metal (e.g., copper) layers is important, the alkyl group having cyclic alkyl groups and 1 to 8 carbon atoms is preferred.

[0515] R N1 and R N2 They can link together to form a ring structure. When forming a ring structure, oxygen atoms, etc., can be present in the chain. Furthermore, R... N1 and R N2The formed ring structure can be a monocyclic ring or a fused ring, preferably a monocyclic ring. The formed ring structure is preferably a 5-membered or 6-membered ring containing a nitrogen atom from formula (N1), such as pyrrole rings, imidazole rings, pyrazole rings, pyrrolidine rings, imidazoleidine rings, piperidine rings, piperazine rings, morpholine rings, etc., with pyrroleline rings, pyrrolidine rings, piperidine rings, piperazine rings, and morpholine rings being the most preferred.

[0516] R C1 This indicates a hydrogen atom or a protecting group, preferably a hydrogen atom.

[0517] As a protecting group, a protecting group that decomposes by the action of an acid or base is preferred, and a protecting group that decomposes by an acid is a preferred example.

[0518] Specific examples of protecting groups include chain-like or cyclic alkyl groups or chain-like or cyclic alkyl groups having oxygen atoms in the chain. Examples of chain-like or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl. Examples of chain-like alkyl groups having oxygen atoms in the chain include alkoxyalkyl groups, and more specifically, methoxymethyl (MOM) and ethoxyethyl (EE). Examples of cyclic alkyl groups having oxygen atoms in the chain include epoxy, glycidyl, oxacyclobutyl, tetrahydrofuranyl, and tetrahydropyranyl (THP)yl.

[0519] The divalent linking group constituting L is not particularly limited, but a hydrocarbon group is preferred, and an aliphatic hydrocarbon group is more preferred. The hydrocarbon group may have substituents, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linking group that may have an oxygen atom in the chain is preferred, more preferably a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group that may have an oxygen atom in the chain, and even more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. These groups preferably do not have an oxygen atom.

[0520] The number of carbon atoms in the divalent hydrocarbon linking group is preferably 1 to 24, more preferably 2 to 12, and even more preferably 2 to 6. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. The number of carbon atoms in the group (e.g., arylene alkyl) involved in the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group is preferably 7 to 22, more preferably 7 to 18, and even more preferably 7 to 10.

[0521] As the linking group L, specifically, preferably a linear or branched alkylene group, a cyclic alkylene group, a combination of linear and cyclic alkylene groups, an alkylene group having an oxygen atom in the chain, a linear or branched alkenyl group, a cyclic alkenyl group, an aryl group, or an aryl alkylene group.

[0522] The linear or branched alkylene groups preferably have 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4.

[0523] The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6.

[0524] The number of carbon atoms in the groups involved in the combination of chain alkylene and cyclic alkylene is preferably 4 to 24, more preferably 4 to 12, and even more preferably 4 to 6.

[0525] The alkylene group containing oxygen atoms in the chain can be chain-like or cyclic, and can be straight-chain or branched. The number of carbon atoms in the alkylene group containing oxygen atoms in the chain is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.

[0526] The number of carbon atoms in the linear or branched chain-like alkenyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 3. The number of C=C bonds in the linear or branched chain-like alkenyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0527] The cyclic alkenyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenyl group preferably has 1 to 6 C=C bonds, more preferably 1 to 4, and even more preferably 1 to 2.

[0528] The number of carbon atoms in the arylene group is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10.

[0529] The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11.

[0530] Preferably, the compounds are chain-like alkylene, cyclic alkylene, alkylene with oxygen atoms in the chain, chain-like alkenyl, arylene, and arylene alkylene; more preferably, 1,2-vinyl, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis-vinylene), phenylene (1,2-phenylene), phenylenemethylene (especially 1,2-phenylenemethylene), and vinyloxyvinyl (especially 1,2-vinyloxy-1,2-vinyl).

[0531] Examples of alkali-generating agents can be given below, but the present invention should not be interpreted as limiting thereto.

[0532] [Chemical Formula 47]

[0533]

[0534] The molecular weight of the nonionic alkali generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. As a lower limit, it is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0535] Specific examples of preferred compounds as ionic base generators include, for instance, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0536] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these.

[0537] [Chemical Formula 48]

[0538]

[0539] Specific examples of imine salts include the following compounds, but the present invention is not limited to these.

[0540] [Chemical Formula 49]

[0541]

[0542] When the resin composition of the present invention contains an alkali-generating agent, the content of the alkali-generating agent relative to 100 parts by weight of the resin in the resin composition of the present invention is preferably 0.1 to 50 parts by weight. The lower limit is more preferably 0.3 parts by weight or more, and even more preferably 0.5 parts by weight or more. The upper limit is more preferably 30 parts by weight or less, even more preferably 20 parts by weight or less, and even more preferably 10 parts by weight or less, but can be 5 parts by weight or less, or 4 parts by weight or less.

[0543] One or more alkali-generating agents can be used. When two or more are used, the total dosage is preferably within the range mentioned above.

[0544] <Solvent>

[0545] The resin composition of the present invention preferably contains a solvent.

[0546] Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0547] Examples of esters preferably 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 alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionate esters (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.)). Alkyl propionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

[0548] Examples of ethers include, 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 acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0549] Examples of ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0550] Examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0551] As a sulfoxide, dimethyl sulfoxide is a preferred example.

[0552] Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0553] Examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolinone.

[0554] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylbenzyl alcohol, n-pentanol, methylpentanol, and diacetone alcohol.

[0555] Regarding solvents, from the perspective of improving the properties of the coating surface, it is preferable to use a mixture of two or more solvents.

[0556] In this invention, a solvent preferably selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellolytic acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, L-glucanone, and dihydroL-glucanone, or a mixture of two or more solvents, is preferred. Particularly preferred are the combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate.

[0557] Regarding the solvent content, from the viewpoint of coatability, it is preferable to set the total solids concentration of the resin composition of the present invention to be 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the required coating thickness and coating method.

[0558] The resin composition of the present invention may contain only one solvent or two or more solvents. When containing two or more solvents, their total amount is preferably within the above-mentioned range.

[0559] <Metal Adhesion Modifier>

[0560] The resin composition of the present invention preferably contains a metal adhesion modifier for improving adhesion to metal materials used in electrodes or wiring, etc. Examples of metal adhesion modifiers include silane coupling agents having alkoxysilane groups, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having sulfonamide structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-keto ester compounds, and amino compounds.

[0561] [Silane coupling agent]

[0562] Examples of silane coupling agents include, for example, compounds described in paragraph 0167 of International Publication No. 2015 / 199219, compounds described in paragraphs 0062-0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063-0071 of International Publication No. 2011 / 080992, compounds described in paragraphs 0060-0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045-0052 of Japanese Patent Application Publication No. 2014-041264, compounds described in paragraph 0055 of International Publication No. 2014 / 097594, and compounds described in paragraphs 0067-0078 of Japanese Patent Application Publication No. 2018-173573, all of which are incorporated herein by reference. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358, it is preferable to use two or more different silane coupling agents. Moreover, the following compounds are preferred as silane coupling agents. In the following formulas, Me represents methyl and Et represents ethyl.

[0563] [Chemical Formula 50]

[0564]

[0565] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimeth ... Propyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureapropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0566] [Aluminum-based adhesive additives]

[0567] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and diisopropyl ethyl acetoacetate aluminum.

[0568] Furthermore, as other metal adhesion modifiers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 can also be used, and these contents are included in this specification.

[0569] The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably in the range of 0.1 to 30 parts by weight, more preferably in the range of 0.1 to 10 parts by weight, and even more preferably in the range of 0.5 to 5 parts by weight. By setting it to the lower limit or above, the adhesion between the pattern and the metal layer becomes better; by setting it to the upper limit or below, the heat resistance and mechanical properties of the pattern become better. The metal adhesion modifier can be only one type or two or more types. When two or more types are used, their total content is preferably within the above range.

[0570] <Migration Inhibitor>

[0571] The resin composition of the present invention preferably further comprises a migration inhibitor. By including a migration inhibitor, the migration of metal ions originating from the metal layer (metal wiring) into the membrane can be effectively suppressed.

[0572] There are no particular limitations on the migration inhibitors, and examples include compounds with heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), thioureas and compounds with thioalkyl groups, hindered phenolic compounds, salicylic acid derivatives, and hydrazide derivatives. 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 tetrazolium compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

[0573] Alternatively, ion trapping agents that capture anions such as halide ions can be used.

[0574] Other migration inhibitors include rust inhibitors described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are included in this specification.

[0575] The following compounds can be cited as specific examples of migration inhibitors.

[0576] [Chemical Formula 51]

[0577]

[0578] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the resin composition of the present invention 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.

[0579] There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, their total number is preferably within the range mentioned above.

[0580] <Polymerization Inhibitor>

[0581] The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0582] Preferred compounds as polymerization inhibitors include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, and 1-nitroso-2-naphthyl Phenol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy radical, 2,2,6,6-tetramethylpiperidine 1-oxy radical, phenothiazine, phenazine, 1,1-diphenyl-2-picrylhydrazine, copper(II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. Furthermore, it is possible to use the polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Patent Application Publication No. 2015 / 125469, which are incorporated herein by reference.

[0583] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solids content of the resin composition of the present invention is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.

[0584] There may be only one polymerization inhibitor or two or more. When there are two or more polymerization inhibitors, their total number is preferably within the range mentioned above.

[0585] <Other Additives>

[0586] The resin composition of the present invention can be incorporated with various additives as needed within the range of achieving the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anticoagulants, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.). By appropriately containing these components, the film properties and other properties can be adjusted. Regarding these components, for example, reference can be made to the descriptions after paragraph 0183 of Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, the contents of which are incorporated herein by reference. When these additives are incorporated, their total amount is preferably set to 3% by mass or less of the solid content of the resin composition of the present invention.

[0587] [surfactants]

[0588] As surfactants, various types of surfactants can be used, including fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants. Surfactants can be nonionic, cationic, or anionic.

[0589] By including a surfactant in the resin composition of the present invention, the liquid properties (especially flowability) when preparing the coating liquid can be further improved, and the uniformity of the coating thickness and the liquid-saving properties can be further improved. That is, when a film is formed using a coating liquid containing a surfactant composition, the interfacial tension between the coated surface and the coating liquid decreases, thereby improving the wettability of the coated surface and improving the coating properties of the coated surface. Therefore, it is possible to form a film with less thickness variation and greater uniformity.

[0590] Examples of fluorinated surfactants include, for example, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (all manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, Novec FC4432 (all manufactured by 3M Japan Limited), Surflon S-382, and Surflon... SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (all manufactured by ASAHI GLASS CO.,LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVASolutions Inc.), etc. Fluorinated surfactants can also use compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503, which are included in this specification. As a fluorinated surfactant, block polymers can also be used. For example, compounds described in Japanese Patent Application Publication No. 2011-89090 can be cited, and these contents are incorporated into this specification.

[0591] Fluorinated surfactants may also preferably use fluorinated polymers (comprising repeating units derived from (meth)acrylate compounds having fluorine atoms and repeating units derived from (meth)acrylate compounds having two or more (preferably five or more) alkeneoxy groups (preferably ethoxy or propyleneoxy groups), and the following compounds may also be cited as fluorinated surfactants used in this invention.

[0592] [Chemical Formula 52]

[0593]

[0594] The weight-average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

[0595] Regarding fluorinated surfactants, fluorinated polymers with olefinically unsaturated groups on their side chains can also be used as fluorinated surfactants. Specific examples include compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Furthermore, commercially available products include, for example, MEGAFACE RS-101, RS-102, and RS-718K manufactured by DICCOporation.

[0596] The fluorine content in fluorinated surfactants is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass. Fluorinated surfactants with fluorine content in this range are effective in terms of uniform coating thickness, liquid-saving properties, and good solubility in the composition.

[0597] Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow CorningToray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, and BYK330 (manufactured by BYK Chemie GmbH).

[0598] Examples of hydrocarbon-based surfactants include PIONIN A-76, NEWKALGEN FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, and PIONIN P-4050-T (all manufactured by TAKEMOTO OIL & FATCO., LTD).

[0599] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, etc. Commercially available products include PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL&FATCO.,LTD), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry CO.,Ltd.), etc.

[0600] As cationic surfactants, examples include organosiloxane polymers such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers such as POLYFLOW No.75, No.77, No.90, and No.95 (manufactured by Kyoisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0601] As anionic surfactants, examples include WO04, WO05, WO17 (Yusho Co., Ltd.), and SANDET BL (manufactured by SANYO KASEI Co., Ltd.).

[0602] Surfactants can be used in single-agent or in combination of two or more.

[0603] The surfactant content relative to the total solids content of the composition is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass.

[0604] [Higher fatty acid derivatives]

[0605] To prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanoamide can be added to the resin composition of the present invention so that they are biased towards the surface of the resin composition of the present invention during the drying process after coating.

[0606] Furthermore, the higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which are incorporated herein by reference.

[0607] When the resin composition of the present invention contains higher fatty acid derivatives, the content of the higher fatty acid derivatives relative to the total solid content of the resin composition of the present invention is preferably 0.1 to 10% by mass. There may be only one type of higher fatty acid derivative, or there may be two or more types. When there are two or more types of higher fatty acid derivatives, their total content is preferably within the above-mentioned range.

[0608] [Thermal polymerization initiator]

[0609] The resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals through thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be carried out, thereby further improving solvent resistance. Furthermore, the aforementioned photopolymerization initiators sometimes also have the function of initiating polymerization by heat, and can sometimes be added as thermal polymerization initiators.

[0610] Specifically, compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, which are incorporated herein by reference, can be cited as thermal free radical polymerization initiators.

[0611] When a thermal polymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass. The thermal polymerization initiator may contain only one type or two or more types. When two or more thermal polymerization initiators are included, the total amount is preferably within the above-mentioned range.

[0612] [Inorganic particles]

[0613] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

[0614] The average particle size of the aforementioned inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and especially preferably 0.04 to 0.5 μm.

[0615] The above-mentioned average particle size of inorganic particles is the primary particle size and the volume average particle size. The volume average particle size can be measured by dynamic light scattering based on the Nanotrac WAVE II EX-150 (manufactured by NIKKISOCO.,LTD.).

[0616] When the above measurements are difficult to perform, measurements can also be taken using centrifugal sedimentation transmission method, X-ray transmission method, and laser diffraction / scattering method.

[0617] [Ultraviolet absorber]

[0618] The compositions of the present invention may contain ultraviolet absorbers. As ultraviolet absorbers, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and other ultraviolet absorbers can be used.

[0619] Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Furthermore, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0620] Examples of acrylonitrile-based ultraviolet absorbers that can be replaced include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triazine-based ultraviolet absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecoxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecoxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; and 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine. Bis(hydroxyphenyl)triazine compounds such as 4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octoxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, etc.

[0621] In this invention, the various ultraviolet absorbers mentioned above can be used individually or in combination of two or more.

[0622] The composition of the present invention may or may not contain an ultraviolet absorber, but when it does contain an ultraviolet absorber, the content of the ultraviolet absorber relative to the total solid content of the composition of the present invention is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.1% by mass or less.

[0623] [Organotitanium compounds]

[0624] The resin composition of this embodiment may contain an organotitanium compound. By containing an organotitanium compound, the resin composition can form a resin layer with excellent chemical resistance even when cured at low temperatures.

[0625] Examples of usable organotitanium compounds include compounds in which organic groups are bonded to titanium atoms via covalent or ionic bonds.

[0626] Specific examples of organotitanium compounds are shown in I) to VII) below.

[0627] I) Chelated titanium compounds: Among these, chelated titanium compounds having two or more alkoxy groups are more preferred, considering the excellent storage stability of the resin composition and the ability to obtain a good cured pattern. Specific examples include bis(triethanolamine)diisopropoxy titanium, bis(n-butoxy)bis(2,4-glutarate) titanium, diisopropoxybis(2,4-glutarate) titanium, diisopropoxybis(tetramethylheptanediate) titanium, and diisopropoxybis(ethyl acetoacetate) titanium.

[0628] II) Tetraalkoxy titanium compounds: such as tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearoxytitanium, tetra[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc.

[0629] III) Dioctenoid compounds: such as pentamethylcyclopentadienetrimethoxytitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc.

[0630] IV) Monoalkoxy titanium compounds: such as tris(dioctyl phosphate) isopropoxy titanium, tris(dodecyl benzenesulfonate) isopropoxy titanium, etc.

[0631] V) Titanium oxide compounds: such as bis(glutarate) titanium oxide, bis(tetramethylheptane) titanium oxide, phthalocyanine titanium oxide, etc.

[0632] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0633] VII) Titanate coupling agents: such as isopropyltris(2-dodecylbenzenesulfonyl)titanate, etc.

[0634] Of these, from the viewpoint of exhibiting better drug resistance, at least one compound selected from the group consisting of I) chelated titanium compounds, II) tetraalkoxy titanium compounds and III) dicarboxylated titanium compounds is preferred as the organotitanium compound. Particularly preferred are diisopropoxybis(ethyl acetoacetate)titanium, tetra(n-butoxy)titanium, and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium.

[0635] When an organotitanium compound is incorporated, the amount incorporated is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of a specific resin. When the amount incorporated is 0.05 parts by weight or more, the cured pattern obtained more effectively exhibits good heat resistance and chemical resistance; on the other hand, when it is 10 parts by weight or less, the composition exhibits better storage stability.

[0636] [Antioxidants]

[0637] The compositions of the present invention may contain antioxidants. By including antioxidants as additives, the tensile properties and adhesion to metal materials of the cured film can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. As a phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, hindered phenolic compounds are examples. Compounds having substituents at the site adjacent to the phenolic hydroxyl group (ortho position) are preferred. As the above-mentioned substituents, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, the antioxidant is also preferably a compound having a phenolic group and a phosphite group in the same molecule. Moreover, phosphorus-based antioxidants are also preferred. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxophosphahepta-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxophosphahepta-2-yl)oxy]ethyl]amine, and bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite. Commercially available antioxidants include, for example, ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, and ADEKA STAB AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, the antioxidants can also be compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, which are incorporated herein by reference. Moreover, the compositions of the present invention may contain potential antioxidants as needed. Compounds that function as potential antioxidants include those whose antioxidant sites are protected by a protecting group, and whose protecting group is removed by heating at 100–250°C or at 80–200°C in the presence of an acid / base catalyst, thereby enabling them to function as antioxidants. Compounds described in International Publication Nos. 2014 / 021023, 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219 are examples of potential antioxidants, and these are incorporated herein by reference. Commercially available products that are potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION).

[0638] Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and compounds represented by formula (3).

[0639] [Chemical Formula 53]

[0640]

[0641] In general formula (3), R 5 R represents an alkyl group having 2 or more hydrogen atoms or carbon atoms (preferably 2 to 10 carbon atoms). 6 R represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). 7 It represents a 1- to 4-valent organic group containing at least one of an alkylene group, an oxygen atom, and a nitrogen atom with 2 or more carbon atoms (preferably 2 to 10 carbon atoms). k represents an integer from 1 to 4.

[0642] The compound represented by formula (3) inhibits the oxidative degradation of the aliphatic groups and phenolic hydroxyl groups present in the resin. Moreover, it can inhibit metal oxidation by preventing rust on metallic materials.

[0643] In order to be effective on both resin and metal materials simultaneously, k is more preferably an integer from 2 to 4. As R 7 Examples of suitable groups include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and combinations thereof, and may further include substituents. From the viewpoint of solubility in the developer and metal adhesion, alkyl ethers and -NH- are preferred, while -NH- is more preferred from the viewpoint of metal adhesion resulting from interaction with the resin and the formation of metal complexes.

[0644] Examples of compounds represented by general formula (3) include the following compounds, but are not limited to the following structures.

[0645] [Chemical Formula 54]

[0646]

[0647] [Chemical Formula 55]

[0648]

[0649] [Chemical Formula 56]

[0650]

[0651] [Chemical Formula 57]

[0652]

[0653] The amount of antioxidant added relative to 100 parts by weight of a specific resin is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight. By setting the amount added to 0.1 parts by weight or more, it is easy to obtain improved tensile properties and adhesion to metal materials even under high temperature and high humidity environments. Moreover, by setting it to 10 parts by weight or less, for example, the sensitivity of the resin composition is improved through interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, their sum and dosage are preferably within the above-mentioned range.

[0654] [Anticoagulant]

[0655] The resin composition of this embodiment may contain an anti-coagulant as needed. Examples of anti-coagulants include sodium polyacrylate.

[0656] In this invention, one type of anti-coagulation agent can be used alone, or two or more types can be used in combination.

[0657] The composition of the present invention may or may not contain an anti-coagulant, but when it is contained, the content of the anti-coagulant relative to the total solid content of the composition of the present invention is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 5% by mass or less.

[0658] [Phenolic compounds]

[0659] The resin composition of this embodiment may contain phenolic compounds as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (trade names, manufactured by ASAHI YUKIZAI CORPORATION).

[0660] In this invention, phenolic compounds can be used alone or in combination of two or more.

[0661] The compositions of the present invention may or may not contain phenolic compounds, but when they are contained, the content of phenolic compounds relative to the total solid content of the compositions of the present invention is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less.

[0662] [Other polymers]

[0663] Other examples of polymeric compounds include siloxane resins, (meth)acrylic acid polymers copolymerized with (meth)acrylic acid, phenolic varnish resins, methyl phenolic resins, polyhydroxystyrene resins, and copolymers thereof. Other polymeric compounds may be modifiers incorporating crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

[0664] In this invention, other polymer compounds can be used alone or in combination of two or more.

[0665] The composition of the present invention may or may not contain other polymeric compounds, but when it does contain other polymeric compounds, the content of other polymeric compounds relative to the total solid content of the composition of the present invention is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less.

[0666] <Characteristics of the Resin Composition>

[0667] The viscosity of the resin composition of the present invention can be adjusted by the concentration of the solid components of the resin composition. From the viewpoint of coating film thickness, 1,000 mm is preferred. 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 remains within the above range, a highly uniform coating film can be easily obtained. For example, 1,000 mm. 2 At speeds above 12,000 mm, it is easy to apply the required film thickness for use as an insulating film for rewiring. 2 When the speed is below a certain value, a coating film with excellent surface finish can be obtained.

[0668] <Restrictions on substances contained in resin compositions>

[0669] The moisture content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. When it is less than 2.0%, the storage stability of the resin composition is improved.

[0670] Methods for maintaining moisture content include adjusting humidity in storage conditions and reducing the porosity of the storage container.

[0671] From the viewpoint of insulation, it is preferable that the metal content of the resin composition of the present invention is less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excluding 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-mentioned range.

[0672] Furthermore, as a method to reduce metal impurities accidentally included in the resin composition of the present invention, the following methods can be cited: selecting raw materials with 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 with a filter, lining the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

[0673] Regarding the resin composition of the present invention, considering its use as a semiconductor material, from the viewpoint of wiring corrosion resistance, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass. The amount present as halide ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. The total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is preferably within the above-mentioned ranges.

[0674] As a method for adjusting the content of halogen atoms, ion exchange treatment is a preferred example.

[0675] As a container for the resin composition of the present invention, conventionally known containers can be used. Furthermore, for the purpose of preventing impurities from contaminating the raw materials or the resin composition of the present invention, multi-layered bottles with an inner wall composed of six types of six-layered resins, or bottles with a seven-layered structure formed by six types of resins, are preferred. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0676] <Cureds of Resin Compositions>

[0677] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.

[0678] The cured product of the present invention is a cured product formed by curing the resin composition of the present invention.

[0679] The curing of the resin composition is preferably carried out by heating, with the heating temperature more preferably in the range of 120°C to 400°C, further preferably in the range of 140°C to 380°C, and particularly preferably in the range of 170°C to 350°C. The morphology of the cured resin composition is not particularly limited, and it can be selected as film, rod, sphere, granule, etc., depending on the application. In this invention, the cured product is preferably in the form of a film. Furthermore, by patterning the resin composition, the shape of the cured product can be selected according to applications such as forming a protective film on the wall surface, forming conductive through-holes, adjusting impedance, electrostatic capacitance or internal stress, or imparting heat dissipation function. The film thickness of the cured product (the film composed of the cured product) is preferably 0.5 μm or more and 150 μm or less.

[0680] The shrinkage rate of the resin composition of the present invention during curing is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, which can be calculated according to the following formula.

[0681] Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) × 100

[0682] <Characteristics of cured resin compositions>

[0683] The imidization reaction rate of the cured 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, it may sometimes result in a cured product with excellent mechanical properties.

[0684] The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

[0685] The glass transition temperature (Tg) of the cured 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.

[0686] <Preparation of Resin Compositions>

[0687] The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be carried out using conventionally known methods.

[0688] Mixing can be carried out by stirring blades, by ball milling, or by rotating the tank itself.

[0689] The temperature during mixing is preferably 10–30°C, more preferably 15–25°C.

[0690] Furthermore, for the purpose of removing foreign matter such as dust or particles from the resin composition of the present invention, filtration is preferably performed using a filter. Regarding the filter pore size, for example, a pore size of 5 μm or less is preferred, 1 μm or less is more preferred, 0.5 μm or less is more preferred, and 0.1 μm or less is even more preferred. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferred. The filter can be a filter that has been pre-cleaned with an organic solvent. In the filtration process, multiple filters can be connected in series or in parallel. When using multiple filters, filters with different pore sizes or materials can be used in combination. As a connection method, for example, an HDPE filter with a pore size of 1 μm can be used as the first stage, and an HDPE filter with a pore size of 0.2 μm can be used as the second stage, and the two can be connected in series. Furthermore, various materials can be filtered multiple times. When filtering multiple times, it can be a circulating filtration. Furthermore, pressure filtration can be performed. When performing pressure filtration, for example, the applied pressure can be 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.

[0691] Besides using filters for filtration, adsorption materials can also be used for impurity removal. Furthermore, filtration and impurity removal using adsorption materials can be combined. Known adsorption materials can be used as adsorption materials. Examples include inorganic adsorption materials such as silica gel and zeolite, and organic adsorption materials such as activated carbon.

[0692] After filtration, a further step can be performed whereby the resin composition filled in the bottle is placed under reduced pressure for degassing.

[0693] (Method for manufacturing solidified products)

[0694] The method for manufacturing the cured product of the present invention preferably includes a film forming step in which a resin composition is applied to a substrate to form a film.

[0695] Furthermore, the method for manufacturing the cured product of the present invention more preferably includes the above-described film forming step, an exposure step for selectively exposing the film formed by the film forming step, and a developing step for developing the film exposed by the exposure step using a developing solution to form a pattern.

[0696] The method for manufacturing the cured product of the present invention preferably includes at least one of the above-described film forming step, the above-described exposure step, the above-described developing step, a heating step for heating the pattern obtained by the developing step, and a post-developing exposure step for exposing the pattern obtained by the developing step.

[0697] Furthermore, the manufacturing method of the present invention preferably includes the above-described film formation step and the step of heating the above-described film.

[0698] The following is a detailed explanation of each process.

[0699] <Membrane Formation Process>

[0700] The resin composition of the present invention can be used in a film forming process suitable for forming a film on a substrate.

[0701] The method for manufacturing the cured product of the present invention preferably includes a film forming step in which a resin composition is applied to a substrate to form a film.

[0702] [Substrate]

[0703] The type of substrate can be appropriately determined according to the application. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; vapor-deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe (e.g., any substrate formed of metal or substrates with metal layers formed by plating, vapor deposition, etc.); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; molded substrates; and electrode plates for plasma display panels (PDPs). There are no particular limitations. In this invention, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred.

[0704] Furthermore, layers such as an adhesion layer and an oxide layer formed of hexamethyldisilazane (HMDS) can be provided on the surface of these substrates.

[0705] Furthermore, the shape of the substrate is not particularly limited; it can be circular or rectangular.

[0706] For the size of the substrate, when it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. When it is rectangular, the length of the shorter side is, for example, 100 to 1000 mm, preferably 200 to 700 mm.

[0707] Furthermore, as a substrate, a plate-like material can be used, with a panel-like substrate (substrate) being preferred.

[0708] Furthermore, when a resin composition is applied to the surface of a resin layer (e.g., a layer composed of cured material) or a metal layer to form a film, the resin layer and the metal layer become substrates.

[0709] As a method for applying the resin composition of the present invention to a substrate, coating is preferred.

[0710] Specifically, applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slot coating, and inkjet coating. From the viewpoint of film thickness uniformity, spin coating, slot coating, spray coating, or inkjet coating are more preferred. From both the viewpoint of film thickness uniformity and productivity, spin coating and slot coating are preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating are preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be applied for approximately 10 seconds to 3 minutes.

[0711] Furthermore, it is also possible to apply a method for transferring a coating film formed by pre-applying it to a dummy support using the above-described application method onto a substrate.

[0712] Regarding the transfer method, the manufacturing method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 is also preferred in this invention.

[0713] Furthermore, it can also perform a process to remove excess film from the ends of the substrate. Examples of such processes include edge bead rinse (EBR) and back-side rinse.

[0714] Furthermore, the following pre-wetting process can also be used: before coating the resin composition onto the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

[0715] <Drying Process>

[0716] The above-mentioned membrane can be dried after the membrane formation process (layer formation process) to remove the solvent.

[0717] That is, the method for manufacturing the cured product of the present invention may include a drying step of drying the film formed by the film forming step.

[0718] Furthermore, the aforementioned drying process is preferably performed after the film formation process and before the exposure process.

[0719] The drying temperature of the membrane in the drying process is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Furthermore, drying can be carried out under reduced pressure. Examples of drying times include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

[0720] <Exposure Process>

[0721] The above-mentioned film can undergo an exposure process that selectively exposes the film.

[0722] That is, the method for manufacturing the cured product of the present invention may include an exposure step of selectively exposing the film formed by the film forming step.

[0723] Selective exposure refers to exposing only a portion of a film. Furthermore, by performing selective exposure, exposed areas (exposed regions) and unexposed areas (non-exposed regions) are formed on the film.

[0724] Regarding the exposure amount, there is no particular limitation as long as it is sufficient to cure the resin composition of the present invention. For example, based on the exposure energy at a wavelength of 365 nm, it is preferably 50 to 10,000 mJ / cm. 2 More preferably 200–8,000 mJ / cm 2 .

[0725] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[0726] Regarding the exposure wavelength, in relation to the light source, examples include (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, gamma rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), broadband (three wavelengths of gamma, 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; EUV (wavelength 13.6nm), (6) electron beams, (7) second harmonic 532nm and third harmonic 355nm of YAG lasers, etc. For the resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is even more preferred. This results in particularly high exposure sensitivity.

[0727] Moreover, the exposure method is not particularly limited, as long as at least a portion of the film composed of the resin composition of the present invention is exposed, such as exposure using a photomask or exposure based on direct laser imaging.

[0728] <Post-exposure heating process>

[0729] The above-mentioned film can undergo a heating process after exposure (post-exposure heating process).

[0730] That is, the method for manufacturing the cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.

[0731] The post-exposure heating process can be performed after the exposure process and before the development process.

[0732] The heating temperature in the post-exposure heating process is preferably 50℃~140℃, more preferably 60℃~120℃.

[0733] The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.

[0734] Regarding the heating rate in the post-exposure heating process, it is preferably 1 to 12°C / minute from the initial heating temperature to the maximum heating temperature, more preferably 2 to 10°C / minute, and even more preferably 3 to 10°C / minute.

[0735] Furthermore, the heating rate can be adjusted appropriately during the heating process.

[0736] There are no particular limitations on the heating method used in the post-exposure heating process; known heating plates, ovens, infrared heaters, etc., can be used.

[0737] Furthermore, heating is preferably carried out in an atmosphere with low oxygen concentration by circulating inert gases such as nitrogen, helium, or argon.

[0738] <Developing Process>

[0739] The exposed film can be developed using a developing solution to form a pattern.

[0740] That is, the method for manufacturing the cured product of the present invention may include a developing step of developing a film exposed by an exposure step using a developing solution to form a pattern. By developing, one of the exposed and unexposed portions of the film is removed to form a pattern.

[0741] Here, the development process that removes the non-exposed parts of the film is called negative development, and the development process that removes the exposed parts of the film is called positive development.

[0742] [Developing solution]

[0743] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[0744] When the developer is an alkaline aqueous solution, examples include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. More preferably, TMAH is preferred. For example, when using TMAH, the content of alkaline compounds in the developer is preferably 0.01 to 10% by mass of the total amount of developer, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

[0745] When the developer contains an organic solvent, esters are preferably included, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionate esters (e.g., 3-alkyl...). Methyl hydroxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., 2-methoxy-2-methylpropionate) Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., etc. Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; examples of preferred cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; examples of preferred sulfoxides include dimethyl sulfoxide; examples of preferred alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, and triethylene glycol; and examples of preferred amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0746] Furthermore, when the developer contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used. In this invention, a developer containing at least one type selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred; a developer containing at least one type selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred; and a developer containing cyclopentanone is most preferred.

[0747] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Furthermore, the above content can also be 100% by mass.

[0748] Developer may also contain other ingredients.

[0749] Other components include, for example, well-known surfactants and well-known defoamers.

[0750] [Method for supplying developer]

[0751] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the developer. Methods include: immersing the substrate with the film formed in the developer; swirling immersion development using a nozzle to supply the developer to the film formed on the substrate; or continuous supply of developer. There are no particular restrictions on the type of nozzle; examples include direct-flow nozzles, spray nozzles, and atomizing nozzles.

[0752] From the viewpoints of developer penetration, non-image area removal, and manufacturing efficiency, it is preferable to supply the developer using a direct current nozzle or a continuous supply method using a spray nozzle. From the viewpoint of developer penetration into the image area, a spray nozzle supply method is more preferred.

[0753] Furthermore, the following process can be adopted: after continuously supplying developer with a DC nozzle, rotating the substrate to remove developer from the substrate, rotating and drying, and then continuously supplying developer with a DC nozzle again, rotating the substrate to remove developer from the substrate, or repeating this process multiple times.

[0754] Furthermore, as a method for supplying developer in the developing process, one can employ a process of continuously supplying developer to the substrate, a process of keeping the developer on the substrate in a substantially static state, a process of vibrating the developer on the substrate using ultrasound or the like, and a process combining these methods.

[0755] The preferred development time is 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution is not particularly limited, but it is preferably performed at 10 to 45°C, and more preferably at 18 to 30°C.

[0756] During the developing process, the pattern can be further cleaned (rinsed) with a rinsing solution after treatment with the developing solution. Furthermore, methods such as supplying the rinsing solution before the developing solution in contact with the pattern has completely dried can also be employed.

[0757] [Rinse solution]

[0758] When the developer is an alkaline aqueous solution, water can be used as the rinsing solution, for example. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, or an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0759] When the rinsing solution contains an organic solvent, preferred organic solvents include, for example, esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., 3-alkoxy...). Methyl propionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-alkoxy-2-methylpropionate) Methyl acetoacetate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., etc. Examples of preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; examples of preferred cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; examples of preferred sulfoxides include dimethyl sulfoxide; examples of preferred alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, and triethylene glycol; and examples of preferred amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0760] When the rinsing solution contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used. In this invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are even more preferred.

[0761] When the rinsing solution contains an organic solvent, it is preferable that the rinsing solution contains at least 50% by mass of an organic solvent, more preferably at least 70% by mass, and even more preferably at least 90% by mass. Moreover, the rinsing solution may contain 100% by mass of an organic solvent.

[0762] The rinsing solution may also contain other ingredients.

[0763] Other components include, for example, well-known surfactants and well-known defoamers.

[0764] [Method for supplying flushing fluid]

[0765] As long as the desired pattern can be formed, there are no particular restrictions on the method of supplying the rinsing liquid. The following methods are available: immersing the substrate in the rinsing liquid, supplying the rinsing liquid to the substrate by swirling and immersion, supplying the rinsing liquid to the substrate by spraying a nozzle, and continuously supplying the rinsing liquid to the substrate by a direct current nozzle.

[0766] From the perspectives of the penetrability of the rinsing fluid, the removal of non-image areas, and manufacturing efficiency, methods for supplying rinsing fluid include spray nozzles, direct current nozzles, and mist nozzles. A continuous supply method using a mist nozzle is preferred. From the perspective of the penetrability of the rinsing fluid to the image area, a mist nozzle supply method is even more preferred. There are no particular limitations on the type of nozzle; examples include direct current nozzles, spray nozzles, and mist nozzles.

[0767] That is, the rinsing process is preferably a process of supplying or continuously supplying rinsing liquid to the exposed film via a DC nozzle, and more preferably a process of supplying rinsing liquid via a spray nozzle.

[0768] Furthermore, as a method for supplying rinsing fluid in the rinsing process, one can employ a process of continuously supplying rinsing fluid to the substrate, a process of keeping the rinsing fluid on the substrate in a substantially static state, a process of vibrating the rinsing fluid on the substrate using ultrasound or the like, and a process combining these methods.

[0769] The preferred rinsing time is 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution is not particularly limited, but it is preferably performed at 10 to 45°C, more preferably at 18 to 30°C.

[0770] <Heating Process>

[0771] The pattern obtained through the developing process (or the washed pattern if a washing process is performed) can be subjected to a heating process that heats the pattern obtained through the developing process.

[0772] That is, the method for manufacturing the cured product of the present invention may include a heating step of heating the pattern obtained by the developing step.

[0773] Furthermore, the method for manufacturing the cured product of the present invention may include a heating step of heating a pattern obtained by other methods without a developing step or a film obtained by a film forming step.

[0774] During the heating process, resins such as polyimide precursors cyclize into resins such as polyimide.

[0775] Furthermore, it also involves crosslinking unreacted crosslinking groups in specific resins or crosslinking agents other than specific resins.

[0776] The heating temperature (maximum heating temperature) in the heating process is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, and even more preferably 160 to 250°C, especially preferably 160 to 230°C.

[0777] The heating process is preferably a process in which the cyclization reaction of the polyimide precursor is promoted within the pattern by means of the alkali or the like generated from the alkali generating agent through heating.

[0778] Regarding the heating process, the heating is preferably performed at a rate of 1 to 12°C / minute from the initial temperature to the maximum heating temperature. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. By setting the heating rate to 1°C / minute or more, productivity can be ensured while preventing excessive evaporation of acid or solvent; by setting the heating rate to 12°C / minute or less, residual stress in the cured product can be mitigated.

[0779] Furthermore, in the case of an oven capable of rapid heating, the heating rate from the initial temperature to the maximum heating temperature is preferably 1 to 8°C / second, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0780] The initial heating temperature is preferably 20–150°C, more preferably 20–130°C, and even more preferably 25–120°C. The initial heating temperature refers to the temperature at which the process begins when the material is heated to the maximum heating temperature. For example, in the case of applying the resin composition of the present invention to a substrate and then drying it, the temperature of the dried film (layer) is preferred; for example, it is preferably started at a temperature 30–200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

[0781] The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0782] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and especially preferably 120°C or higher.

[0783] The upper limit of the above temperature is preferably below 350°C, more preferably below 250°C, and even more preferably below 240°C.

[0784] Heating can be performed in stages. For example, the following steps can be performed: heating from 25°C to 120°C at a rate of 3°C / min and holding at 120°C for 60 minutes, then heating from 120°C to 180°C at a rate of 2°C / min and holding at 180°C for 120 minutes. Furthermore, it is preferable to perform the treatment while irradiating with ultraviolet light, as described in U.S. Patent No. 9,159,547. Such pretreatment steps can improve the properties of the membrane. The pretreatment steps are preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment can be a two-stage or more process; for example, the first stage of the pretreatment step can be performed in the range of 100–150°C, and then the second stage of the pretreatment step can be performed in the range of 150–200°C.

[0785] Furthermore, cooling can be performed after heating, and the preferred cooling rate at this time is 1 to 5°C / minute.

[0786] Regarding the heating process, to prevent the decomposition of specific resins, it is preferable to carry it under reduced pressure using inert gases such as nitrogen, helium, or argon, thereby creating an atmosphere with a low oxygen concentration. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

[0787] There are no particular limitations on the heating method used in the heating process; examples include heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0788] <Post-development exposure process>

[0789] The pattern obtained through the developing process (or the washed pattern in the case of a washing process) can replace the heating process described above, or, in addition to the heating process described above, be exposed to the pattern after the developing process via a post-developing exposure process.

[0790] That is, the method for manufacturing the cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for manufacturing the cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.

[0791] In the post-development exposure process, reactions such as cyclization of polyimide precursors by exposure to photoalkali generating agents and removal of acid-degrading groups by exposure to photoacid generating agents can be promoted.

[0792] In the post-development exposure process, at least a portion of the pattern obtained in the development process needs to be exposed, preferably all of the pattern is exposed.

[0793] Based on the exposure energy conversion at the wavelength where the photosensitive compound has sensitivity, the exposure amount in the post-development exposure process is preferably 50–20,000 mJ / cm². 2 More preferably 100–15,000 mJ / cm 2 .

[0794] Regarding the post-development exposure process, for example, the light source used in the above-mentioned exposure process can be used, and broadband light is preferred.

[0795] <Metal Layer Formation Process>

[0796] The pattern obtained through the development process (preferably at least one of the heating process and the post-development exposure process) can be used for a metal layer forming process to form a metal layer on the pattern.

[0797] That is, the method for manufacturing the cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on a pattern obtained by a developing step (preferably at least one of a heating step and a post-developing exposure step).

[0798] There are no particular limitations on the metal layer; any existing metal can be used, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are preferred, and copper is even more preferred.

[0799] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, patterning methods combining sputtering, photolithography, and etching, and patterning methods combining photolithography and electroplating can be cited. As a preferred method of plating, electroplating using copper sulfate plating solution and copper cyanide plating solution can be cited.

[0800] The thickness of the metal layer, measured in the thickest part, is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm.

[0801] <Uses>

[0802] Examples of applications applicable to the manufacturing method of the cured product of the present invention or to the cured product of the present invention include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, and stress-relief films. Other examples include sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), or patterns formed on insulating films used in practical mounting applications of the above types by etching. For these applications, references can be made to Science & Technology Co., Ltd., “High Functionalization and Application Technology of Polyimides,” April 2008, supervised by Masaaki Kakimoto; CMC Technology Library, “Fundamentals and Development of Polyimide Materials,” November 2011; and the Japan Polyimide & Aromatic Polymer Research Association, ed., “Latest Polyimide Fundamentals and Applications,” NTS, August 2010.

[0803] Furthermore, the method for manufacturing the cured product of the present invention or the cured product of the present invention can also be used in the manufacture of offset printing plates or screen printing plates, the use of forming parts in etching, and the manufacture of protective coatings and dielectric layers in electronics, especially microelectronics.

[0804] (Laminated bodies and methods for manufacturing laminated bodies)

[0805] The laminate of the present invention refers to a structure having multiple layers composed of the cured product of the present invention.

[0806] The laminate of the present invention is a laminate comprising two or more layers composed of a cured material, or it may be a laminate consisting of three or more layers.

[0807] Of the two or more layers composed of the above-mentioned cured material included in the laminate, at least one layer is composed of the cured material of the present invention. From the viewpoint of suppressing the shrinkage of the cured material or the deformation of the cured material that accompanies the shrinkage, it is even more preferable that all the layers composed of the cured material included in the laminate are composed of the cured material of the present invention.

[0808] That is, the method for manufacturing the laminate of the present invention preferably includes the method for manufacturing the cured product of the present invention, and more preferably includes the steps of repeating the method for manufacturing the cured product of the present invention multiple times.

[0809] The laminate of the present invention comprises two or more layers made of cured material, preferably in which any layer made of the cured material contains a metal layer between them. The metal layer is preferably formed by the metal layer forming process described above.

[0810] That is, the method for manufacturing the laminate of the present invention preferably includes a metal layer forming step between multiple methods for manufacturing cured products, wherein a metal layer is formed on the layer composed of the cured product. The preferred embodiment of the metal layer forming step is as described above.

[0811] As an example of the aforementioned laminate, a laminate structure comprising at least three layers sequentially stacked together, namely a layer composed of a first cured material, a metal layer, and a layer composed of a second cured material, is preferably provided.

[0812] Both the layer composed of the first cured product and the layer composed of the second cured product are preferably layers composed of the cured product of the present invention. The resin composition of the present invention used to form the layer composed of the first cured product and the resin composition of the present invention used to form the layer composed of the second cured product may be the same composition or different compositions. The metal layer in the laminate of the present invention can preferably be used as a rewiring layer or other metal wiring.

[0813] <Layering Process>

[0814] The manufacturing method of the laminate of the present invention preferably includes a lamination process.

[0815] The lamination process includes a series of steps on the surface of a pattern (resin layer) or metal layer, sequentially performing at least one of the following steps: (a) film formation (layer formation step), (b) exposure step, (c) development step, (d) heating step, and post-development exposure step. This can be achieved by repeating at least one of (a) film formation step, (d) heating step, and post-development exposure step. Furthermore, (e) metal layer formation step can be included after at least one of (d) heating step and post-development exposure step. The lamination process can obviously be further appropriately included with steps such as the aforementioned drying step.

[0816] When performing a further lamination process after the lamination process, a surface activation treatment process can be performed after the aforementioned exposure process, the aforementioned heating process, or the aforementioned metal layer formation process. Plasma treatment is an example of a surface activation treatment. Details regarding surface activation treatment will be explained later.

[0817] The above-mentioned layering process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.

[0818] For example, a structure with 2 or more but less than 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure with 2 or more but less than 9 layers is even more preferred.

[0819] The composition, shape, and film thickness of the above layers can be the same or different.

[0820] In this invention, it is preferable to further form a cured resin composition (resin layer) of the present invention to cover the metal layer, particularly after the metal layer is formed. Specifically, examples include repeating at least one of (a) film formation step, (b) exposure step, (c) development step, (d) heating step and post-development exposure step, and (e) metal layer formation step in that order, or repeating at least one of (a) film formation step, (d) heating step and post-development exposure step, and (e) metal layer formation step in that order. By alternately performing the lamination step of the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately laminated.

[0821] (Surface activation treatment process)

[0822] The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a portion of the above-mentioned metal layer and resin composition layer.

[0823] The surface activation treatment process is usually performed after the metal layer formation process, but it can also be performed after the development process (preferably after at least one of the heating process and the post-development exposure process) or after the surface activation treatment process of the resin composition layer.

[0824] The surface activation treatment can be performed on at least a portion of the metal layer, on at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. Preferably, the surface activation treatment is performed on at least a portion of the metal layer, and more preferably on a portion or all of the area on the surface of the metal layer where the resin composition layer is formed. Thus, by performing a surface activation treatment on the surface of the metal layer, the adhesion to the resin composition layer (film) disposed on its surface can be improved.

[0825] Furthermore, the surface activation treatment is preferably performed on part or all of the exposed resin composition layer (resin layer). In this way, by performing surface activation treatment on the surface of the resin composition layer, the adhesion to the metal layer and resin layer disposed on the surface-activated surface can be improved. Especially in cases such as negative development, where the resin composition layer has been cured, it is less likely to be damaged by surface treatment, thus easily improving adhesion.

[0826] As a surface activation treatment, specifically, options include plasma treatment with various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixtures, argon / oxygen mixtures, etc.), corona discharge treatment, etching treatment based on CF4 / O2, NF3 / O2, SF6, NF3, NF3 / O2, surface treatment based on ultraviolet (UV) ozone, treatment after removing the oxide film by immersion in an aqueous hydrochloric acid solution followed by immersion in an organic surface treatment agent containing at least one of amino and thiol groups, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J / m. 2 More preferably, it is 1000 to 100,000 J / m 2 The optimal value is 10,000 to 50,000 J / m 2 .

[0827] (Semiconductor devices and their manufacturing methods)

[0828] The present invention also discloses a semiconductor device comprising the cured product of the present invention or the laminate of the present invention.

[0829] Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured product of the present invention or a method for manufacturing a laminate of the present invention. Specific examples of semiconductor devices in which the resin composition of the present invention is used to form an interlayer insulating film for a rewiring layer can be found in paragraphs 0213 to 0218 of Japanese Patent Application Publication No. 2016-027357 and in Figure 1, the contents of which are incorporated herein by reference.

[0830] (Polyimide precursor)

[0831] The polyimide precursor of the present invention comprises repeating units represented by the following formula (2) and a structure represented by formula (1-1).

[0832] The preferred embodiment of the polyimide precursor of the present invention is the same as the preferred embodiment of the specific resin contained in the resin composition of the present invention described above.

[0833] [Chemical Formula 58]

[0834]

[0835] In equation (2), A 1 and A 2 Each can be used independently to represent an oxygen atom or -NH-, R 111 R represents a divalent organic group. 115 R represents a tetravalent organic group. 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group.

[0836] [Chemical Formula 59]

[0837]

[0838] In equation (1-1), A 3 and A 4 Each can be used independently to represent an oxygen atom or -NH-, X 1 R represents a tetravalent organic group. 21 and R 22 Each can independently represent a hydrogen atom or a monovalent organic group, Y 1 Z represents a hydrogen atom or a monovalent organic group. 1 Z represents a monovalent organic group having an aromatic group. 1 It does not contain any of the structures represented by equation (Z-1) or equation (Z-2) below, Y 1 With Z 1 It can be bonded; * indicates a bonding site with other structures.

[0839] [Chemical Formula 60]

[0840]

[0841] In equation (Z-1), R 115 R represents any one of the repeating units represented by formula (2) contained in the polyimide precursor. 115 The same group, * indicates a bonding site with other structures.

[0842] In equation (Z-2), R 111R represents any one of the repeating units represented by formula (2) contained in the polyimide precursor. 111 For identical groups, * indicates the bonding site with other structures.

[0843] (Method for manufacturing polyimide precursors)

[0844] The method for manufacturing the polyimide precursor of the present invention includes the following steps: a step of reacting a tetracarboxylic dianhydride or its diester with a diamine to obtain a reactant; and a step of reacting the reactant with a compound represented by formula (T-1).

[0845] The preferred method for manufacturing the polyimide precursor of the present invention is the same as the preferred method for manufacturing the specific resin contained in the resin composition of the present invention described above.

[0846] [Chemical Formula 61]

[0847]

[0848] In equation (T-1), Y 1 Z represents a hydrogen atom or a monovalent organic group. 1 Y represents a monovalent organic group having an aromatic group. 1 With Z 1 They can bond.

[0849] Example

[0850] The present invention will be further described in detail below with examples. The materials, amounts, proportions, processing methods, and processing order shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass measurements.

[0851] <Synthesis of Polymer End-Capping Agent AN-1>

[0852] In a flask equipped with a stirrer and a condenser, 15.2 g (100 mmol) of 2-methyl-4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.01 g of Neostan U-600 (manufactured by NITTO KASEI CO,.LTD.) were dissolved in 150 mL of tetrahydrofuran, and the mixture was stirred at 25 °C. Then, 11.9 g (100 mmol) of p-tolyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour, followed by heating to 50 °C and stirring for 4 hours. Next, the mixture was added to a mixed solvent of 200 mL of ethyl acetate and 400 mL of hexane, filtered, and the precipitate was recovered. The filtrate was dried under vacuum at 40 °C for 20 hours to obtain the nitro compound (ANN-1).

[0853] Next, 27.9 g (500 mmol) of reduced iron (manufactured by FUJIFILM Wako Pure Chemical Corporation), 5.9 g (110 mmol) of ammonium chloride (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 3.0 g (50 mmol) of acetic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation) were weighed into a flask equipped with a stirrer and a condenser. 200 mL of isopropanol and 30 mL of pure water were added and the mixture was stirred. Then, 19.9 g (70 mmol) of the dried nitrocellulose (ANN-1) was added little by little over 1 hour, with stirring for 30 minutes. The mixture was then heated to 85°C and stirred for 2 hours. After cooling to below 25°C, it was filtered using Celite (registered trademark). The filtrate was concentrated using a rotary evaporator and dissolved in 800 mL of ethyl acetate. The sample was transferred to a separatory funnel and washed twice with 300 mL of saturated sodium bicarbonate solution, followed by washing with 300 mL of water and then 300 mL of saturated saline solution. After separation and washing, the sample was dried with 30 g of magnesium sulfate, then concentrated using a distiller and dried under vacuum to obtain 16 g of AN-1.

[0854] according to 1 H-NMR spectroscopy confirmed it to be AN-1. It is speculated that the structure of AN-1 is represented by the following formula (AN-1).

[0855] [Chemical Formula 62]

[0856]

[0857] <Synthesis of Polymer End-Capping Agents AN-2 to AN-4>

[0858] Polymer end-capping agents AN-2 to AN-4 were synthesized using the same method as AN-1 described above. It is speculated that the structures of AN-2 to AN-4 are represented by the following formulas (AN-2) to (AN-4), respectively.

[0859] [Chemical Formula 63]

[0860]

[0861] <Synthetic Example A-1: ​​Synthesis of Polyimide Precursor (A-1)>

[0862] 21.2 g (68.1 mmol) of 4,4'-oxophthalic dianhydride, 17.8 g (137 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 22.8 g (289 mmol) of pyridine, and 85 g of diethylene glycol dimethyl ether were mixed and stirred at 60 °C for 6 hours to prepare a diester of 4,4'-oxophthalic acid and 2-hydroxyethyl methacrylate. Next, the mixture was cooled to -20 °C, and 16.7 g (140 mmol) of thionyl chloride was added dropwise over 90 minutes, followed by stirring for 2 hours to obtain a white precipitate of pyridinium hydrochloride. Next, a solution obtained by dissolving 20.8 g (56.5 mmol) of 4,4'-bis(4-aminophenoxy)biphenyl and 2.40 g (11.6 mmol) of polymer end-capping agent AN-3 (the above-mentioned synthetic product) in 100 mL of NMP was added dropwise over 1 hour. Then, 10.0 g (217 mmol) of ethanol was added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 L of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 L of water for 30 minutes, and filtered again. Finally, the obtained polyimide precursor resin was dried under reduced pressure at 45 °C for 2 days to obtain the polyimide precursor (A-1). The obtained polyimide precursor A-1 has a weight-average molecular weight of 19,900 and a number-average molecular weight of 8,100.

[0863] It is speculated that the polyimide precursor (A-1) is a compound having a repeating unit and a terminal structure represented by the following formula (A-1). The acid value is 0.095 mmol / g, and the amine value is 0.004 mmol / g.

[0864] [Chemical Formula 64]

[0865]

[0866] <Synthetic Examples A-2 to A-7: Synthesis of Polyimide Precursors (A-2) to (A-7)>

[0867] In Synthesis Example A-1, the polymer end-capping agent (AN-3), dianhydride (4,4'-oxydiphthalic dianhydride), and diamine (4,4'-bis(4-aminophenoxy)biphenyl) were changed. Otherwise, polyimide precursors (A-2) to (A-7) were synthesized by the same method.

[0868] It is speculated that the polyimide precursors (A-2) to (A-7) are compounds having repeating units and terminal structures represented by the following formulas (A-2) to (A-7), respectively. Furthermore, the weight-average molecular weight (Mw), number-average molecular weight (Mn), acid value, and amine value of the polyimide precursors (A-2) to (A-7) are shown in the table below. In the following formulas, the subscripts in parentheses indicate the proportion (molar ratio) of each repeating unit.

[0869] [Chemical Formula 65]

[0870]

[0871] [Chemical Formula 66]

[0872]

[0873] [Chemical Formula 67]

[0874]

[0875] <Synthetic Example A-8: Synthesis of Polyimide Precursor (A-8)>

[0876] 77.5 g of 4,4'-oxyphthalic dianhydride (ODPA) was placed in a separating flask, and 65.0 g of 2-hydroxyethyl methacrylate (HEMA) and 200 ml of γ-butyrolactone were added. While stirring at room temperature, 40.0 g of pyridine was added, thus obtaining the reaction mixture. After the exothermic reaction was complete, the mixture was cooled to room temperature and then allowed to stand for 16 hours.

[0877] Next, while under ice-cold conditions, a solution of 103.2 g of dicyclohexylcarbodiimide (DCC) dissolved in 100 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Then, a suspension of 77.0 g of 4,4'-diaminodiphenyl ether was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 9.3 g of 4-phenoxyaniline was added and stirred for 1 hour. Then, 200 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was obtained by filtration, yielding the reaction solution.

[0878] The obtained reaction solution was added to 2 liters of ethanol, generating a precipitate composed of crude polymer. The crude polymer was filtered off and dissolved in 1 liter of tetrahydrofuran to obtain a crude polymer solution. This crude polymer solution was added dropwise to 10 liters of water to precipitate the polymer. The precipitate was filtered off and then vacuum dried to obtain powdered polymer A-8. The weight-average molecular weight (Mw) of polymer A-8 was measured to be 21,200, and the number-average molecular weight was 8,000.

[0879] [Chemical Formula 68]

[0880]

[0881] <Synthetic Examples A-9 to A-10: Synthesis of Polyimide Precursors (A-9) to (A-10)>

[0882] In synthesis example A-8, the polymer end-capping agent (AN-3) and 2-hydroxyethyl methacrylate (HEMA) were changed. Otherwise, polyimide precursors (A-9) to (A-10) were synthesized by the same method.

[0883] It is speculated that the polyimide precursors (A-9) to (A-10) are compounds having repeating units and terminal structures represented by the following formulas (A-9) to (A-10), respectively. Furthermore, the weight-average molecular weight (Mw), number-average molecular weight (Mn), acid value, and amine value of the polyimide precursors (A-9) to (A-10) are shown in the table below.

[0884] [Chemical Formula 69]

[0885]

[0886] <Comparative Synthesis of Compound Cmp-1>

[0887] 77.5 g of 4,4'-oxyphthalic dianhydride (ODPA) and 73.5 g of 4,4'-biphenyl dianhydride were added to a separating flask, along with 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone. 79.1 g of pyridine was added while stirring at room temperature to obtain the reaction mixture. After the reaction-induced exothermic reaction was complete, the mixture was cooled to room temperature and allowed to stand for 16 hours.

[0888] Next, while under ice-cold conditions, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Then, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether suspended in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirring continued for 1 hour. Finally, 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration, thus obtaining the reaction solution.

[0889] The obtained reaction solution was added to 3 liters of ethanol, generating a precipitate composed of crude polymer. The crude polymer was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer. The precipitate was filtered off and then vacuum dried to obtain polymer-1 in powder form. The weight-average molecular weight (Mw) of polymer Cmp-1 was measured and found to be 22,600.

[0890] [Chemical Formula 70]

[0891]

[0892] [Table 1]

[0893] A-2 18900 7200 0.105 0.0057 A-3 25600 10500 0.083 0.0061 A-4 28300 11200 0.096 0.0021 A-5 21000 8900 0.112 0.0037 A-6 22500 9300 0.085 0.0035 A-7 20100 8300 0.099 0.0041 A-8 21200 8000 0.101 0.0056 A-9 30400 13500 0.098 0.0075 A-10 20900 8500 0.112 0.0055 Cmp-1 22600 8900 0.413 0.0351

[0894] <Examples and Comparative Examples>

[0895] In each embodiment, the components listed in the table below were mixed to obtain each resin composition. Furthermore, in each comparative example, the components listed in the table below were mixed to obtain each comparative composition.

[0896] Specifically, the content of each component recorded in the table is set to the amount (parts by mass) recorded in the "Amount Added" column of each column in the table.

[0897] The obtained resin composition and the comparative composition were pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.5 μm.

[0898] Furthermore, in the table, a "-" indicates that the composition does not contain the corresponding ingredient.

[0899] [Table 2]

[0900]

[0901] [Table 3]

[0902]

[0903] The detailed information of each component recorded in the table is as follows.

[0904] [Resin]

[0905] • A-1 to A-10: A-1 to A-10 synthesized above. • Cmp-1: The above-described synthesized products (comparative example).

[0906] [Polymerization initiators (all trade names)]

[0907] • OXE-01: IRGACURE OXE 01 (manufactured by BASF)

[0908] •OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[0909] [Alkali-generating agent]

[0910] • D-1~D-2: Compounds with the following structures

[0911] ·D-3: WPBG-027 (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0912] [Chemical Formula 71]

[0913]

[0914] [Polymerization initiators (all trade names)]

[0915] • OXE-01: IRGACURE OXE 01 (manufactured by BASF)

[0916] •OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[0917] [Polymerizing compounds (all trade names)]

[0918] ·SR-209: SR-209 (manufactured by Sartomer Company, Inc.)

[0919] ·SR-231: SR-231 (manufactured by Sartomer Company, Inc.)

[0920] • ADPH: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) [Migration inhibitor]

[0921] •E-1~E-6: Compounds with the following structures

[0922] [Chemical Formula 72]

[0923]

[0924] [Metal adhesion modifier]

[0925] • F-1~F-3: Compounds with the following structures

[0926] [Chemical Formula 73]

[0927]

[0928] [Polymerization inhibitor]

[0929] G-1: 1,4-Benzoquinone

[0930] G-2: 4-Methoxyphenol

[0931] G-3: 1,4-Dihydroxybenzene

[0932] • G-4: Compounds with the following structures

[0933] [Chemical Formula 74]

[0934]

[0935] [Other additives]

[0936] H-1: N-Phenylenediethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0937] [Solvent]

[0938] DMSO: Dimethyl sulfoxide

[0939] GBL: γ-Butyrolactone

[0940] NMP: N-methylpyrrolidone

[0941] The table indicates that the solvent used was a mixture of DMSO and GBL at a mass ratio of 80:20.

[0942] <Evaluation>

[0943] [Evaluation of elongation at break]

[0944] In each embodiment and comparative example, a resin composition layer was formed by spin-coating a resin composition or a comparative composition onto a silicon wafer. The silicon wafer with the obtained resin composition layer applied was dried on a hot plate at 100°C for 5 minutes, resulting in a uniform resin composition layer with a thickness of approximately 15 μm on the silicon wafer.

[0945] Using a stepper motor (Nikon NSR 2005 i9C), at 500mJ / cm 2 The obtained resin composition layer was subjected to i-ray exposure at the specified exposure energy.

[0946] The exposed resin composition layer (resin layer) was heated under a nitrogen atmosphere at a rate of 10°C / min until it reached the temperature listed in the "Temperature" column of the "Curing Conditions" section of the table, and then heated for 3 hours. The cured resin layer (cured film) was then immersed in a 4.9% (w / w) hydrofluoric acid aqueous solution and peeled off from the silicon wafer. The peeled cured film was then punched to produce test pieces with a width of 3 mm and a length of 30 mm. The obtained test pieces were measured using a tensile testing machine (TENSILON) at a crosshead speed of 300 mm / min, at 25°C and 65% RH (relative humidity), according to JIS-K6251. Each test was performed five times, and the arithmetic mean of the elongation at break (elongation at break) was used as the index value.

[0947] Evaluate the above index values ​​according to the evaluation criteria below, and record the evaluation results in the "Elongation at Break" column of the table. It can be said that the higher the above index value, the better the film strength (elongation at break) of the cured film.

[0948] -Evaluation Criteria-

[0949] A: The above indicator value is above 70%.

[0950] B: The above indicator value is above 60% and below 70%.

[0951] C: The above indicator value is above 50% and below 60%.

[0952] D: The above indicator value is less than 50%.

[0953] [Evaluation of curing shrinkage]

[0954] In each embodiment and comparative example, a resin composition layer was formed by spin-coating a resin composition or a comparative composition onto a silicon wafer. The silicon wafer with the obtained resin composition layer applied was dried on a hot plate at 100°C for 5 minutes, resulting in a uniform curable resin composition layer with a thickness of approximately 15 μm. The film thickness of the curable resin composition layer was measured using a reflective spectrophotometer (FE-3000 OTSUKA ELECTRONICS CO.,LTD), and this value is designated as "film thickness A".

[0955] Next, using a stepper motor (Nikon NSR 2005 i9C), the entire surface of the obtained curable resin composition layer was cured at 500 mJ / cm². 2 The exposure energy was used for i-ray exposure.

[0956] The exposed curable resin composition layer (resin layer) was heated in a nitrogen atmosphere at a heating rate of 10°C / min. After reaching the temperature recorded in the "Temperature" column of the "Curing Conditions" section of the table, it was heated for 3 hours and then cooled to 25°C to obtain the cured product.

[0957] The film thickness of the cured material was measured using a reflective spectrophotometer (manufactured by FE-3000OTSUKA ELECTRONICS CO.,LTD), and this value was designated as "film thickness B".

[0958] The membrane shrinkage rate is calculated using the following formula.

[0959] Calculation formula: Shrinkage rate (%) = 100 - (film thickness B ÷ film thickness A × 100)

[0960] The evaluation should be conducted according to the following criteria, and the results should be recorded in the "Cure Shrinkage" column of the table. The smaller the shrinkage rate value, the better the cure shrinkage of the obtained composition layer.

[0961] -Evaluation Criteria-

[0962] A: Membrane shrinkage rate is less than 20%.

[0963] B: The membrane shrinkage rate is greater than 20% and less than 25%.

[0964] C: The membrane shrinkage rate is greater than 25% and less than 30%.

[0965] D: The membrane shrinkage rate is over 30%.

[0966] [Evaluation of moisture resistance]

[0967] Resin compositions or comparative compositions prepared in the various examples and comparative examples were applied to silicon wafers using spin coating, thereby forming resin composition layers. The silicon wafers with the applied resin composition layers were dried on a hot plate at 100°C for 5 minutes, forming a uniform resin composition layer with a thickness of approximately 15 μm on the silicon wafers. A stepper (Nikon NSR 2005i9C) was used with a flow rate of 500 mJ / cm². 2The resin composition layer on the silicon wafer was exposed to the exposure energy. The exposed resin composition layer (resin layer) was heated in a nitrogen atmosphere at a heating rate of 10°C / min. The temperature was then set at the temperature listed in the "Temperature" column of the "Curing Conditions" section of the table for 180 minutes to obtain the cured resin composition layer (resin layer).

[0968] The obtained cured layer was immersed in a high-temperature and high-humidity bath at 121°C and 100% humidity for 250 hours. The film loss was measured before and after immersion in the following solution under the following conditions.

[0969] Solution: A mixture of dimethyl sulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution in a 90:10 ratio.

[0970] Evaluation conditions: The resin layer was immersed in the chemical solution at 75°C for 15 minutes, and the film thickness before and after immersion was compared to calculate the film loss (%). The film thickness was measured at 10 points on the coated surface using an ellipsometry (Foothill KT-22), and the arithmetic mean was calculated as the film thickness.

[0971] The evaluation should be conducted according to the following criteria, and the results should be recorded in the "Moisture Resistance" column of the table. The smaller the difference (%) in membrane weight loss before and after immersion in the high-temperature, high-humidity bath, the better the moisture resistance.

[0972] The difference in membrane shrinkage before and after high temperature and high humidity input = AB

[0973] A: The thickness of the cured layer before immersion in the high-temperature and high-humidity bath, after immersion in the above-mentioned solution under the above conditions / the film thickness before immersion × 100

[0974] B: The thickness of the cured layer after immersion in the high-temperature and high-humidity bath, after being impregnated with the above-mentioned solution under the above conditions / the film thickness before impregnation × 100

[0975] -Evaluation Criteria-

[0976] A: The difference in membrane shrinkage before and after high temperature and high humidity is less than 5%.

[0977] B: The difference in membrane shrinkage before and after high temperature and high humidity is more than 5% but less than 10%.

[0978] C: The difference in membrane shrinkage before and after high temperature and high humidity is more than 10% but less than 20%.

[0979] D: The difference in membrane reduction before and after high temperature and high humidity is more than 20%.

[0980] The results above show that the cured film made of the resin composition of the present invention has excellent moisture resistance.

[0981] The resins contained in the comparative compositions of Comparative Examples 1-2 do not include the structure represented by formula (1-1).

[0982] It can be seen that the cured film made from this comparative composition has poor moisture resistance.

[0983] <Example 101>

[0984] The resin composition used in Example 1 was applied in a layered manner to the surface of a resin substrate with a copper thin layer formed thereon using spin coating. After drying at 100°C for 4 minutes to form a resin composition layer with a film thickness of 20 μm, it was exposed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-space pattern and a linewidth of 10 μm). After exposure, the layer was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain the layer pattern.

[0985] Next, under a nitrogen atmosphere, the temperature was increased at a rate of 10°C / min until it reached 230°C, and then maintained at 230°C for 3 hours to form an interlayer insulating film for the rewiring layer. This interlayer insulating film for the rewiring layer exhibits excellent insulation properties.

[0986] Furthermore, semiconductor devices were fabricated using this rewiring layer with an interlayer insulating film, and they were confirmed to be functioning normally.

Claims

1. A resin composition comprising a polyimide precursor having repeating units represented by formula (2) and a structure represented by formula (1-1), In equation (2), A 1 and A 2 Each oxygen atom is represented independently, R 111 R represents a divalent organic group. 115 R represents a tetravalent organic group. 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group. In equation (1-1), A 3 and A 4 Each oxygen atom is represented independently, X 1 R represents a tetravalent organic group. 21 and R 22 Each can independently represent a hydrogen atom or a monovalent organic group, Y 1 Z represents a hydrogen atom or a monovalent organic group. 1 Z represents a monovalent organic group having an aromatic group. 1 It does not contain any of the structures represented by the following formula (Z-1) or formula (Z-2), Z 1 Having at least one group selected from the group consisting of imide, urea, and carbamate, Z 1 At least one of the aromatic groups in Y is directly bonded to the nitrogen atom in formula (1-1), 1 With Z 1 Optional bonding; * indicates bonding sites with other structures. In equation (Z-1), R 115 The term R represents any one of the repeating units represented by formula (2) contained in the polyimide precursor. 115 The same group, * indicates a bonding site with other structures. In equation (Z-2), R 111 The term R represents any one of the repeating units represented by formula (2) contained in the polyimide precursor. 111 For identical groups, * indicates the bonding site with other structures.

2. The resin composition according to claim 1, wherein, The amine value of the polyimide precursor is less than 0.01 mmol / g.

3. The resin composition according to claim 1 or 2, wherein, The acid value of the polyimide precursor is less than 1 mmol / g.

4. The resin composition according to claim 1 or 2, wherein, Z in equation (1-1) 1 The formula size is 160 or higher.

5. The resin composition according to claim 1 or 2, wherein, Z in equation (1-1) 1 It has two or more aromatic groups.

6. The resin composition according to claim 1 or 2, wherein, Z in equation (1-1) 1 For groups represented by the following formula (Z1-1), In equation (Z1-1), Ar 1 L represents an aromatic group. 1 Indicates a single bond or a divalent linkage group, X 1 Indicates imide, urea, or carbamate group, L 2 R represents a single bond or a divalent linkage group. 1 Ar represents a monovalent organic group. 1 With R 1 or L 1 With R 1 The ring structure is formed by optional bonding, and * indicates the bonding site with the nitrogen atom in formula (1-1).

7. The resin composition according to claim 1 or 2, wherein, R in equation (2) 111 For a group represented by the following formula (R-1), In equation (R-1), Ar 1 ~Ar 3 Each aryl group represents an aryl group independently, n represents an integer greater than or equal to 1, and * represents a bonding site with the nitrogen atom in equation (2) independently.

8. The resin composition according to claim 1 or 2, further comprising an alkali-generating agent.

9. The resin composition according to claim 1 or 2, further comprising a photoradical polymerization initiator.

10. The resin composition according to claim 1 or 2, used to form an interlayer insulating film for a rewiring layer.

11. A cured product formed by curing the resin composition according to any one of claims 1 to 10.

12. A laminate comprising two or more layers formed from the cured material of claim 11, wherein any layer formed from the cured material comprises a metal layer between each other.

13. A method for manufacturing a cured product, comprising a film forming step of applying the resin composition of any one of claims 1 to 10 to form a film on a substrate.

14. The method for manufacturing a cured material according to claim 13, comprising an exposure step of exposing the film to light and a development step of developing the film to light it.

15. The method for manufacturing a cured material according to claim 13, comprising a heating step of heating the film at 50°C to 450°C.

16. A semiconductor device comprising the cured material of claim 11.

17. A polyimide precursor having repeating units represented by formula (2) and a structure represented by formula (1-1), In equation (2), A 1 and A 2 Each oxygen atom is represented independently, R 111 R represents a divalent organic group. 115 R represents a tetravalent organic group. 113 and R 114 Each can independently represent a hydrogen atom or a monovalent organic group. In equation (1-1), A 3 and A 4 Each oxygen atom is represented independently, X 1 R represents a tetravalent organic group. 21 and R 22 Each can independently represent a hydrogen atom or a monovalent organic group, Y 1 Z represents a hydrogen atom or a monovalent organic group. 1 Z represents a monovalent organic group having an aromatic group. 1 It does not contain any of the structures represented by the following formula (Z-1) or formula (Z-2), Z 1 Having at least one group selected from the group consisting of imide, urea, and carbamate, Z 1 At least one of the aromatic groups in Y is directly bonded to the nitrogen atom in formula (1-1), 1 With Z 1 Optional bonding; * indicates bonding sites with other structures. In equation (Z-1), R 115 The term R represents any one of the repeating units represented by formula (2) contained in the polyimide precursor. 115 The same group, * indicates a bonding site with other structures. In equation (Z-2), R 111 The term R represents any one of the repeating units represented by formula (2) contained in the polyimide precursor. 111 For identical groups, * indicates the bonding site with other structures.

18. A method for manufacturing a polyimide precursor, comprising: The process of reacting a tetracarboxylic acid dianhydride or its diester with a diamine to obtain the reaction product; and The process of reacting the reaction product with the compound represented by formula (T-1), In equation (T-1), Y 1 Z represents a hydrogen atom or a monovalent organic group. 1 Z represents a monovalent organic group having an aromatic group. 1 Having at least one group selected from the group consisting of imide, urea, and carbamate, Z 1 At least one of the aromatic groups in Y is directly bonded to the nitrogen atom in formula (T-1), Y 1 With Z 1 Optional bonding.

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