Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and resin

Abstract

The present invention provides a curable resin composition, a cured film formed by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, and a semiconductor device comprising the cured film or the laminate, and provides a novel resin comprising a specific structure, wherein the curable resin composition comprises a resin comprising a repeating unit represented by the following formula (1-1) and at least one repeating unit selected from the repeating unit represented by the following formula (2-1), the repeating unit represented by the following formula (2-2), the repeating unit represented by the following formula (2-3), and the repeating unit represented by the following formula (2-4), and a solvent. #imgabs0#

Description

Technical Field

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

[0002] Since polyimide has excellent heat resistance and insulation properties, it is suitable for various uses. The above uses are not particularly limited. If a semiconductor device for actual installation is taken as an example, it can be used as an insulating film or a sealing material or a protective film. In addition, it can also be used as a base film or cover film (COVERLAY) of a flexible substrate.

[0003] For example, in the above applications, polyimide may be used as a curable resin composition containing polyimide or as a curable resin composition containing a polyimide precursor, etc. The precursor is a resin that cyclizes by heating or the like to become a polyimide.

[0004] These curable resin compositions can be applied to substrates or the like by known coating methods and the like, and therefore can be said to have excellent adaptability in production, and for example, the degree of freedom in designing the shape, size, application position, etc. of the curable resin composition to be applied is high.

[0005] In addition to the high performance of resins such as polyimides, the industrial application development of curable resin compositions containing polyimides or polyimide precursors is increasingly expected from the viewpoint of excellent adaptability in production.

[0006] For example, Patent Document 1 describes a photosensitive resin composition including: a polyamic acid having a specific structure; a photopolymerizable compound; and a photopolymerization initiator.

[0007] Previous technical literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application No. 2004-285129 Summary of the invention

[0010] Technical issues to be solved by the invention

[0011] It is desirable to provide a curable resin composition containing a polyimide, the obtained cured film of which has excellent chemical resistance.

[0012] An object of one embodiment of the present invention is to provide a curable resin composition having excellent chemical resistance of the obtained cured film, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate.

[0013] Furthermore, another embodiment of the present invention aims to provide a novel resin.

[0014] Means for solving technical problems

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

[0016] <1> A curable resin composition comprising: a resin comprising a repeating unit represented by the following formula (1-1) and at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (2-1), a repeating unit represented by the following formula (2-2), a repeating unit represented by the following formula (2-3), and a repeating unit represented by the following formula (2-4); and

[0017] Solvents,

[0018] [Chemical formula 1]

[0019]

[0020]

[0021] In formula (1-1), Y 1 Represents a divalent linking group, Ar 1 represents an aromatic hydrocarbon group which may have a substituent or a condensed ring structure, Y 2 represents a single bond or a divalent connecting group;

[0022] In formula (2-1), X 1 Represents a 4-valent linking group, A 1 and A 2 Each independently represents an oxygen atom or -NR N -, R 1 and R 2 Each independently represents a monovalent organic group, R N represents a hydrogen atom or a hydrocarbon group;

[0023] In formula (2-2), X 2 represents a 4-valent linking group;

[0024] In formula (2-3), X 3 represents a trivalent linking group;

[0025] In formula (2-4), X 4 Represents a trivalent linking group, A4 Represents oxygen atom or -NR N -, R 4 represents a monovalent organic group, R N represents a hydrogen atom or a hydrocarbon group.

[0026] <2> The curable resin composition according to <1>, wherein the resin comprises at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), a repeating unit represented by the following formula (3-3), and a repeating unit represented by the following formula (3-4),

[0027] [Chemical formula 2]

[0028]

[0029]

[0030] In formula (3-1), X 5 represents a 4-valent linking group, R 3 and R 4 Each independently represents a monovalent organic group, Z 1 Represents a divalent linking group, R 3 , R 4 and Z 1 At least one of the comprises a polymerizable group;

[0031] In formula (3-2), X 6 represents a 4-valent linking group, Z 2 represents a divalent linking group having a polymerizable group;

[0032] In formula (3-3), X 7 and X 8 Each independently represents a trivalent linking group, Z 3 and Z 4 Each independently represents a divalent linking group, Z 3 and Z 4 At least one of represents a divalent linking group having a polymerizable group;

[0033] In formula (3-4), X 7 and X 8 Each independently represents a trivalent linking group, Z 3 and Z 4 Each independently represents a divalent linking group, R 5 and R 6 Each independently represents a monovalent organic group, Z 3 and Z 4 At least one of them represents a divalent linking group having a polymerizable group, R 5 , R 6, Z 3 and Z 4 At least one of the compounds comprises a polymerizable group.

[0034] <3> The curable resin composition according to <2>, wherein the polymerizable group contained in the repeating unit represented by the above formula (3-1) or the polymerizable group contained in the repeating unit represented by the above formula (3-2) is a group containing an ethylenically unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group.

[0035] <4> The curable resin composition according to any one of <1> to <3>, wherein the content of the repeating unit represented by the formula (1-1) is 0.1% by mass to 60% by mass based on the total mass of the resin.

[0036] <5> The curable resin composition according to any one of <1> to <4>, comprising a polymerizable compound.

[0037] <6> The curable resin composition according to any one of <1> to <5>, which is used for forming an interlayer insulating film for a redistribution layer.

[0038] <7> A cured film obtained by curing the curable resin composition according to any one of <1> to <6>.

[0039] <8> A laminated body comprising two or more layers of the cured films according to <7>, and comprising a metal layer between any of the cured films.

[0040] <9> A method for producing a cured film, comprising a film forming step of applying the curable resin composition according to any one of <1> to <6> on a substrate to form a film.

[0041] <10> The method for producing a cured film according to <9>, comprising the step of heating the film at 50 to 450°C.

[0042] <11> A semiconductor device comprising the cured film according to <7> or the laminated body according to <8>.

[0043] <12> A resin comprising a repeating unit represented by the following formula (1-1) and at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), a repeating unit represented by the following formula (3-3), and a repeating unit represented by the following formula (3-4);

[0044] [Chemical formula 3]

[0045]

[0046] In formula (1-1), Y 1 Represents a divalent linking group, Ar 1 represents an aromatic hydrocarbon group which may have a substituent or a condensed ring structure, Y 2 represents a single bond or a divalent connecting group;

[0047] In formula (3-1), X 5 represents a 4-valent linking group, R 3 and R 4 Each independently represents a monovalent organic group, Z 1 Represents a divalent linking group, R 3 , R 4 and Z 1 At least one of the comprises a polymerizable group;

[0048] In formula (3-2), X 6 Represents a 4-valent group, Z 2 represents a divalent linking group having a polymerizable group;

[0049] In formula (3-3), X 7 and X 8 Each independently represents a trivalent linking group, Z 3 and Z 4 Each independently represents a divalent linking group, Z 3 and Z 4 At least one of represents a divalent linking group having a polymerizable group;

[0050] In formula (3-4), X 7 and X 8 Each independently represents a trivalent linking group, Z 3 and Z 4 Each independently represents a divalent linking group, R 5 and R 6 Each independently represents a monovalent organic group, Z 3 and Z 4 At least one of them represents a divalent linking group having a polymerizable group, R 5 , R 6 , Z 3 and Z 4 At least one of the compounds comprises a polymerizable group.

[0051] Effects of the Invention

[0052] According to one embodiment of the present invention, there are provided a curable resin composition having excellent chemical resistance of the obtained cured film, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate.

[0053] Furthermore, according to another embodiment of the present invention, a novel resin is provided. DETAILED DESCRIPTION

[0054] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described above.

[0055] In the present specification, a numerical range expressed by the symbol “to” indicates a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit, respectively.

[0056] In the present specification, the term "step" refers not only to an independent step but also to a step that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.

[0057] Regarding the marking of groups (atomic groups) in this specification, the marking not indicating substitution and unsubstituted includes both groups (atomic groups) without substitution and groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0058] In the present specification, when simply described as "aliphatic group", "aliphatic hydrocarbon group", "saturated aliphatic hydrocarbon group", "alkyl group", "alkylene group", etc., unless otherwise specified, these groups may have at least one of a branched structure and a cyclic structure. For example, unless otherwise specified, "alkyl group" includes a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an alkyl group represented by a combination of these.

[0059] In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include active rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.

[0060] In this specification, “(meth)acrylate” means both “acrylate” and “methacrylate” or either one of them, “(meth)acrylic acid” means both “acrylic acid” and “methacrylic acid” or either one of them, and “(meth)acryloyl” means both “acryloyl” and “methacryloyl” or either one of them.

[0061] In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0062] In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent. In addition, in this specification, the solid content concentration is the mass percentage of the other components excluding the solvent relative to the total mass of the composition.

[0063] In this specification, unless otherwise stated, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene conversion values ​​according to gel permeation chromatography (GPC determination). In this specification, about weight average molecular weight (Mw) and number average molecular weight (Mn), for example, HLC-8220GPC (TOSOH CORPORATION manufactures) can be used, and protective column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel SuperHZ2000 (TOSOH CORPORATION manufactures) are used as column to obtain. Unless otherwise stated, these molecular weights are measured using THF (tetrahydrofuran) as eluent. And, unless otherwise stated, the detection in GPC determination uses a wavelength 254nm detector of UV line (ultraviolet rays).

[0064] In this specification, about the positional relationship of each layer constituting the laminate, when it is recorded as "up" or "down", as long as there are other layers on the upper side or lower side of the layer that becomes the benchmark in the multilayer concerned. That is, it is also possible to also be separated by the third layer or the third element between the layer that becomes the benchmark and the above-mentioned other layers, and the layer that becomes the benchmark does not need to contact the above-mentioned other layers. And, unless otherwise stated, the direction of the overlapping layer on the substrate is referred to as "up", or in the case of the presence of a curable resin composition layer, the direction from the substrate toward the curable resin composition layer is referred to as "up", and its opposite direction is referred to as "down". In addition, the setting of this up and down direction is for the convenience of explaining this specification, and in actual mode, the "up" direction in this specification can also be different from the vertical upward direction.

[0065] In this specification, unless otherwise specified, as each component contained in the composition, the composition may also contain two or more compounds corresponding to the component. And, unless otherwise specified, the content of each component in the composition represents the total content of all compounds corresponding to the component.

[0066] In this specification, unless otherwise specified, the temperature is 23° C., the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

[0067] In the present specification, a combination of preferred embodiments is a more preferred embodiment.

[0068] (Curable resin composition)

[0069] The curable resin composition of the present invention (hereinafter, also simply referred to as "the composition of the present invention") includes a resin and a solvent containing a repeating unit represented by formula (1-1) and containing at least one repeating unit selected from the repeating unit represented by formula (2-1), a repeating unit represented by formula (2-2), a repeating unit represented by the following formula (2-3) and a repeating unit represented by the following formula (2-4).

[0070] Hereinafter, a resin comprising a repeating unit represented by formula (1-1) and at least one repeating unit selected from a repeating unit represented by formula (2-1), a repeating unit represented by formula (2-2), a repeating unit represented by formula (2-3) and a repeating unit represented by the following formula (2-4) is also referred to as a "specific resin".

[0071] [Chemical formula 4]

[0072]

[0073]

[0074] In formula (1-1), Y 1 Represents a divalent linking group, Ar 1 represents an aromatic hydrocarbon group which may have a substituent or a condensed ring structure, Y 2 represents a single bond or a divalent connecting group;

[0075] In formula (2-1), X 1 Represents a 4-valent linking group, A 1 and A 2 Each independently represents an oxygen atom or -NR N -, R 1 and R 2 Each independently represents a monovalent organic group, R N represents a hydrogen atom or a hydrocarbon group;

[0076] In formula (2-2), X 2 represents a 4-valent linking group;

[0077] In formula (2-3), X 3 represents a trivalent linking group;

[0078] In formula (2-4), X 4 Represents a trivalent linking group, A 4 Represents oxygen atom or -NR N -, R 4 represents a monovalent organic group, R N represents a hydrogen atom or a hydrocarbon group.

[0079] The curable resin composition of the present invention is preferably a negative curable resin composition.

[0080] The negative curable resin composition refers to a composition in which, when a layer formed of the curable resin composition is exposed to light, an unexposed portion (non-exposed portion) is removed by a developer.

[0081] A cured film obtained from the curable resin composition of the present invention has excellent chemical resistance.

[0082] The mechanism by which the above-mentioned effects can be obtained is not clear, but is presumed to be as follows.

[0083] The curable resin composition of the present invention contains a specific resin.

[0084] However, unlike the polyimide resin or polyimide precursor used in the related art, the specific resin contains a repeating unit represented by formula (1-1).

[0085] The repeating unit represented by formula (1-1) includes a condensed ring structure formed by condensation of an aromatic hydrocarbon ring and an oxazole ring. The solvent solubility of the above-mentioned condensed ring structure is low, so it is estimated that the cured film obtained from the curable resin composition including the specific resin containing the repeating unit represented by formula (1-1) has excellent chemical resistance.

[0086] Furthermore, in formula (2-1), R 1 and R 2 Each independently is a monovalent organic group.

[0087] Think with R 1 or R 2 Compared with the case of hydrogen atoms, R 1 and R 2 The structure of a monovalent organic group has low solubility in polar solvents, alkaline aqueous solutions and other chemicals, and thus has excellent chemical resistance. Therefore, it is presumed that even if R remains in the obtained cured film, 1 and R 2 Even when at least one of the above is present, a cured film having excellent chemical resistance can be obtained.

[0088] It is considered that since the cured film has excellent chemical resistance, for example, when a laminate is prepared by applying another curable resin composition containing a solvent to a cured film formed by curing the curable resin composition of the present invention and curing it, even if the cured film comes into contact with a developer or other curable resin composition, dissolution of the cured film is suppressed.

[0089] It is believed that according to the present invention, a cured film can be obtained, the solubility of which is suppressed in polar solvents such as dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP), alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution, or mixed solutions of the above polar solvents and the above alkaline aqueous solutions, and the cured film has excellent chemical resistance.

[0090] However, in Patent Document 1, there is no description or suggestion of a resin containing a repeating unit represented by formula (1-1) and at least one repeating unit selected from the repeating unit represented by formula (2-1), the repeating unit represented by formula (2-2), the repeating unit represented by formula (2-3), and the repeating unit represented by formula (2-4). In addition, in the curable resin composition in Patent Document 1, there is a problem that the chemical resistance of the obtained cured film is low.

[0091] <Specified resin>

[0092] The curable resin composition of the present invention contains a specific resin.

[0093] The specific resin contains a repeating unit represented by formula (1-1) and contains at least one repeating unit selected from the repeating unit represented by formula (2-1), the repeating unit represented by formula (2-2), the repeating unit represented by formula (2-3) and the repeating unit represented by formula (2-4).

[0094] The specific resin may have the repeating unit represented by the formula (1-1) in the side chain, but preferably has the repeating unit in the main chain.

[0095] Furthermore, the specific resin may have at least one repeating unit selected from the repeating unit represented by formula (2-1), the repeating unit represented by formula (2-2), the repeating unit represented by formula (2-3) and the repeating unit represented by formula (2-4) on the side chain, but preferably has the above-mentioned repeating unit on the main chain.

[0096] In the present specification, the “main chain” refers to the longest bond chain in the molecule of the polymer compound constituting the resin, and the “side chain” refers to other bond chains.

[0097] [Repeating unit represented by formula (1-1)]

[0098] -Ar 1 -

[0099] In formula (1-1), Ar 1 It represents an aromatic hydrocarbon group which may have a substituent or a condensed ring structure.

[0100] The above Ar 1The aromatic hydrocarbon group in is preferably an aromatic hydrocarbon group with 6 to 30 carbon atoms, more preferably a group obtained by removing three hydrogen atoms from a benzene ring or a naphthalene ring, and more preferably a group obtained by removing three hydrogen atoms from a benzene ring.

[0101] Preferably, the nitrogen atom and the oxygen atom in formula (1-1) are both 1 The ring members contained in the aromatic hydrocarbon group in are directly bonded.

[0102] Furthermore, Ar is preferred 1 In the formula (1-1), the bonding site to the nitrogen atom and the bonding site to the oxygen atom are located adjacent to each other.

[0103] In this specification, two bonding sites are located at adjacent positions in a ring structure, which means that the ring member in the ring structure having a certain bonding site and the ring member in the ring structure having another bonding site are adjacent ring members in the ring structure. For example, when the ring structure is a benzene ring structure, the adjacent position is the ortho position.

[0104] As Ar 1 The substituent in can be any known substituent without particular limitation, and examples thereof include an alkyl group, a cyclic alkyl group, an alkoxy group, an aryl group, an aryloxy group, a halogenated alkyl group, a hydroxyl group, a carboxyl group, a sulfonic acid group, and a halogen atom.

[0105] As the formation of Ar 1 The ring structure of the condensed ring structure in can use a known ring structure without particular limitation, and examples thereof include aromatic heterocyclic structures such as pyrrole ring, furan ring, thiophene ring, oxazole ring, imidazole ring, pyrazole ring, isoxazole ring, thiazole ring, and isothiazole ring, and saturated heterocyclic structures such as pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, imidazolidine ring, pyrazolidine ring, oxazolidine ring, isoxazolidine ring, thiazolidine ring, isothiazolidine ring, dioxolane ring, and ditetrahydrothiophene ring.

[0106] Furthermore, in the present invention, Ar 1 The embodiment having no fused ring may be adopted, or the embodiment having no substituent and no fused ring may be adopted.

[0107] -Y 1 -

[0108] In formula (1-1), Y 1 represents a divalent linking group, preferably a hydrocarbon group, a heterocyclic group, or at least one hydrocarbon group or heterocyclic group and a group selected from -O-, -C(=O)-, -S-, -S(=O)2- and -NR N - is a group obtained by bonding at least one structure in the above R, more preferably a hydrocarbon group. N It represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, further preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

[0109] As Y 1 The hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aromatic hydrocarbon group is preferred from the viewpoint of developability.

[0110] The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, and preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 2 to 10 carbon atoms.

[0111] The aliphatic hydrocarbon group may have a known substituent, and examples of the substituent include an aromatic group, an alkoxy group, an aryloxy group, and a halogen atom.

[0112] The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably a group obtained by removing at least two hydrogen atoms from a benzene ring structure.

[0113] The aromatic hydrocarbon group may have a known substituent, and examples of the substituent include an aliphatic hydrocarbon group, an alkoxy group, an aryloxy group, and a halogen atom.

[0114] The heterocyclic group may be any of an aliphatic heterocyclic group and an aromatic heterocyclic group, but an aromatic heterocyclic group is preferred from the viewpoint of developability.

[0115] Examples of the hetero atom in the heterocyclic group include a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, and a silicon atom.

[0116] As the above-mentioned aliphatic heterocyclic group, a 5-membered or 6-membered aliphatic heterocyclic group is preferred, and examples thereof include pyrrolidine ring, pyrazolidine ring, imidazolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, piperidine ring, piperazine ring, tetrahydropyran ring, dioxane ring, thiane ring, dithiane ring, morpholine ring, oxazine ring, thiomorpholine ring and the like.

[0117] Examples of the aromatic heterocyclic group include a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a furan ring, a thiophene ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, and a thiadiazole ring.

[0118] -Y 2 -

[0119] In formula (1-1), Y 2 represents a single bond or a divalent organic group, and is preferably a single bond.

[0120] As Y 2 The divalent linking group in the formula (I) may be any of the above-mentioned Y 1 The same divalent linking group as in has the same preferred embodiment.

[0121] -content-

[0122] The content of the repeating unit represented by the formula (1-1) contained in the specific resin is preferably 0.1 to 60% by mass, more preferably 3 to 30% by mass, based on the total mass of the specific resin.

[0123] Furthermore, the specific resin may contain only one repeating unit represented by formula (1-1), or may contain two or more repeating units represented by formula (1-1) of different structures. When containing two or more repeating units represented by formula (1-1), the total content of the repeating units represented by formula (1-1) is preferably within the above range.

[0124] The molar amount of the structure represented by the following formula (1-1′) is preferably 0.01 to 2 mmol / g, more preferably 0.05 to 1.5 mmol / g, and even more preferably 0.1 to 1 mmol / g, based on 1 g of the specific resin.

[0125] [Chemical formula 5]

[0126]

[0127] In formula (1-1'), Ar 1 With Ar in formula (1-1) 1 The meanings are the same and the preferred aspects are also the same.

[0128] In formula (1-1'), two *s each independently represent a bonding site with another structure.

[0129] [Repeating unit represented by formula (2-1)]

[0130] -X 1 -

[0131] In formula (2-1), X 1 The term "representing a tetravalent linking group" may be exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a single bond or a group obtained by linking two or more of these groups via a linking group. Preferably, it is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a single bond or a group obtained by combining two or more of these groups via a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

[0132] As the above-mentioned connecting group, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, halogenated alkylene, arylene or a connecting group formed by two or more of these are bonded, and -O-, -S-, alkylene, halogenated alkylene, aromatic group or a connecting group formed by two or more of these are more preferred.

[0133] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

[0134] As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferred, a halogenated alkylene group having 1 to 10 carbon atoms is more preferred, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferred. Furthermore, as the halogen atom in the above-mentioned halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be mentioned, and a fluorine atom is preferred. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted by a halogen atom, but preferably all hydrogen atoms are substituted by a halogen atom. As examples of preferred halogenated alkylene groups, (ditrifluoromethyl)methylene and the like can be mentioned.

[0135] The aromatic group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0136] Among them, X 1 A group represented by the following formula (5) or formula (6) is preferred.

[0137] [Chemical formula 6]

[0138]

[0139] In formula (5), preferably R 112 It is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbon atoms which may be substituted by a fluorine atom, a group selected from -O-, -CO-, -S-, -SO2- and NHCO- and a combination of these. It is more preferably a single bond, an alkylene group with 1 to 3 carbon atoms which may be substituted by a fluorine atom, a group selected from -O-, -CO-, -S- and SO2-. It is further preferably a divalent group selected from -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and SO2-.

[0140] In formula (5) and formula (6), * represents a bonding site with other structures.

[0141] About X 1 Specifically, there can be mentioned a tetracarboxylic acid residue remaining after removing anhydride groups from tetracarboxylic dianhydride, etc. The tetracarboxylic dianhydride may be used alone or in combination of two or more.

[0142] It is preferred that tetracarboxylic dianhydride is represented by the following formula (O).

[0143] [Chemical formula 7]

[0144]

[0145] In formula (O), X 1 represents a 4-valent linking group. 1 With X in formula (2-1) 1 The meanings are the same, and the preferred ranges are also the same.

[0146] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane tetracarboxylic dianhydride, dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms thereof.

[0147] Furthermore, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can also be cited as preferred examples.

[0148] -A 1 , A 2 -

[0149] In formula (2-1), A 1 and A 2 Each independently represents an oxygen atom or -NR N -, preferably an oxygen atom.

[0150] The above RN It represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, further preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

[0151] -R 1 , R 2 -

[0152] In formula (2-1), R 1 and R 2 Each independently represents a monovalent organic group.

[0153] As R 1 and R 2 The monovalent organic group in includes a group containing a polymerizable group or an organic group which may contain a heteroatom. From the viewpoint of chemical resistance, developability, and solvent solubility of the specific resin, a group containing a polyalkyleneoxy group is preferred.

[0154] <<Group containing a polymerizable group>>

[0155] As R 1 and R 2 The polymerizable group contained in the group containing a polymerizable group in the above-mentioned is preferably a group containing an ethylenically unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group (preferably an alkoxymethyl group having 1 to 6 carbon atoms in the alkoxy group), more preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a hydroxymethyl group or an alkoxymethyl group, further preferably a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group.

[0156] The number of polymerizable groups contained in the above-mentioned group containing a polymerizable group is 1 or more, preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.

[0157] As the group containing a polymerizable group, a vinyl group, an allyl group, a (meth)acryloyl group or a group represented by the following formula (III) is also preferred.

[0158] [Chemical formula 8]

[0159]

[0160] In formula (III), R 200 represents a hydrogen atom or a methyl group, preferably a methyl group.

[0161] In formula (III), R 201It represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, or a (poly)alkyleneoxy group having 4 to 30 carbon atoms (the alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 3 carbon atoms; and preferably has a repeating number of 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3). In addition, the (poly)alkyleneoxy group represents an alkyleneoxy group or a polyalkyleneoxy group.

[0162] About the preferred R 201 Examples include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, and -CH2CH(OH)CH2-, with ethylene, propylene, trimethylene, and -CH2CH(OH)CH2- being more preferred.

[0163] R is particularly preferred 200 is methyl, R 201 For ethylene.

[0164] In formula (III), * represents a bonding site with other structures.

[0165] <<Organic groups that may contain heteroatoms>>

[0166] It is preferred that the organic group which may contain a heteroatom does not have a polymerizable group.

[0167] Examples of the hetero atom in the organic group which may contain a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom, and an oxygen atom is preferred.

[0168] Furthermore, it is preferred that the hetero atom is contained as an ether bond (—O—).

[0169] As the organic group which may contain a hetero atom, an organic group having 1 to 30 carbon atoms which may contain a hetero atom is preferred, and an organic group having 2 to 20 carbon atoms which may contain a hetero atom is more preferred.

[0170] <<<Polyalkyleneoxy>>>

[0171] Among them, the organic group which may contain a hetero atom is preferably an organic group having a polyalkyleneoxy group.

[0172] In the present invention, the polyalkyleneoxy group refers to a group obtained by directly bonding two or more alkyleneoxy groups. The alkylene groups in the plurality of alkyleneoxy groups included in the polyalkyleneoxy group may be the same or different.

[0173] When the polyalkyleneoxy group includes a plurality of types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, an arrangement having an alternating pattern, or the like.

[0174] The alkylene group preferably has 2 or more carbon atoms (including the carbon atoms of the substituent when the alkylene group has a substituent), more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, further preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.

[0175] Furthermore, the above-mentioned alkylene group may have a substituent, and preferred substituents include an alkyl group, an aryl group, a halogen atom, and the like.

[0176] The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, further preferably 2 to 5, particularly preferably 2 to 4, and most preferably 2.

[0177] As the polyalkyleneoxy group, from the viewpoint of taking into account both solvent solubility and chemical resistance, preferably polyethyleneoxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy or a group obtained by bonding a plurality of ethyleneoxy groups to a plurality of propyleneoxy groups, more preferably polyethyleneoxy or polypropyleneoxy, further preferably polyethyleneoxy. In the group obtained by bonding a plurality of ethyleneoxy groups to a plurality of propyleneoxy groups, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in alternating patterns. The preferred manner of the number of repetitions of the ethyleneoxy groups and the like in these groups is as described above.

[0178] The organic group having a polyalkyleneoxy group is preferably a group represented by the following formula (PO-1).

[0179] [Chemical formula 9]

[0180]

[0181] In formula (PO-1), R P1 Each independently represents an alkylene group, R P2 represents a monovalent organic group, n represents an integer greater than 2, L P1 represents a single bond or a divalent linking group, and * represents the R 1 or R 2 The bonding site of the bonded oxygen atom.

[0182] In formula (PO-1), R P1 Each independently represents an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, more preferably ethylene (-CH2-CH2-) or propylene (-CH2-CH(CH3)- or -CH(CH3)-CH2-), further preferably ethylene.

[0183] In formula (PO-1), R P2It represents a monovalent organic group, preferably an alkyl group, an aromatic hydrocarbon group, an aralkyl group or a group containing a polymerizable group, and more preferably an alkyl group.

[0184] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 2 to 4 carbon atoms, and still more preferably an ethyl group.

[0185] The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and still more preferably a phenyl group.

[0186] The aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms, more preferably an aralkyl group having 7 to 20 carbon atoms, and still more preferably a benzyl group.

[0187] As the polymerizable group contained in the above-mentioned group containing a polymerizable group, a group containing an ethylenically unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group (preferably an alkoxymethyl group having 1 to 6 carbon atoms in the alkoxy group), more preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a hydroxymethyl group or an alkoxymethyl group, further preferably a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group.

[0188] The group containing a polymerizable group is preferably a group represented by the formula (P-1) described later, and more preferably a group represented by the formula (P-2) or the formula (P-3) described later.

[0189] In the formula (PO-1), n ​​is preferably an integer of 2 to 20, more preferably an integer of 2 to 10, further preferably an integer of 2 to 5, particularly preferably an integer of 2 to 4, and most preferably 2.

[0190] In formula (PO-1), L P1 represents a single bond or a divalent linking group, and a single bond is preferred.

[0191] As the divalent linking group, a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group obtained by bonding two or more of these groups, more preferably a hydrocarbon group, -O-, -C(=O)-, -NR N - or a group obtained by bonding two or more of these, more preferably a hydrocarbon group, an ester bond, an amide bond, a urethane bond, a urea bond or a group obtained by combining two or more of these.

[0192] In the present specification, when simply described as "ester bond (-C(=O)O-)", "urethane bond (-OC(=O)NR-)", "amide bond (-C(=O)NR-)", etc., the directions of these bonds are not limited. The above R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, further preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and particularly preferably a hydrogen atom.

[0193] The above R N It represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, further preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

[0194] As the above L P1 The hydrocarbon group in is preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group represented by a combination of these, and more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a group obtained by removing two or more hydrogen atoms from a benzene ring, or a group represented by a bond of these.

[0195] <<<Halogen-substituted hydrocarbon group>>>

[0196] Furthermore, from the viewpoint of solvent solubility and film strength, the organic group which may contain a heteroatom may be a hydrocarbon group substituted with a halogen atom.

[0197] Examples of the halogen atom in the halogen atom-substituted hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferred.

[0198] As the above-mentioned hydrocarbon group, an alkyl group or an aromatic hydrocarbon group is preferred, and an alkyl group is more preferred.

[0199] The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 2 to 4 carbon atoms.

[0200] The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably a phenyl group.

[0201] That is, the hydrocarbon group substituted with a halogen atom is preferably an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.

[0202] By including a hydrocarbon group substituted with a halogen atom as R 1 or R 2 , the film strength of the obtained cured film is improved.

[0203] <<Other Substituents>>

[0204] R1 and R 2 Other substituents are possible.

[0205] Examples of other substituents include hydrocarbon groups having an acid group, etc. Examples of hydrocarbon groups having an acid group include alkyl groups having an acid group, aromatic hydrocarbon groups having an acid group, and aralkyl groups having an acid group.

[0206] As the alkyl group in the alkyl group having an acid group, an alkyl group having 1 to 30 carbon atoms is preferred, an alkyl group having 1 to 20 carbon atoms is more preferred, and an alkyl group having 1 to 10 carbon atoms is further preferred.

[0207] Examples of the acid group in the alkyl group having an acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group, and a carboxyl group is preferred.

[0208] As the aromatic hydrocarbon group in the aromatic hydrocarbon group having an acid group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferred, a phenyl group or a naphthyl group is more preferred, and a phenyl group is further preferred.

[0209] As the aralkyl group having an acid group, an aralkyl group having 7 to 30 carbon atoms is preferred, an aralkyl group having 7 to 20 carbon atoms is more preferred, and a benzyl group is further preferred.

[0210] Examples of the acid group in the aromatic hydrocarbon group having an acid group or the aralkyl group having an acid group include phenolic hydroxyl group, carboxyl group, sulfonic acid group, phosphoric acid group, phosphonic acid group and the like. A phenolic hydroxyl group or a carboxyl group is preferred, and a phenolic hydroxyl group is more preferred.

[0211] Among them, an aromatic hydrocarbon group having an acid group or an aralkyl group having an acid group is preferred, an aromatic hydrocarbon group having a phenolic hydroxyl group or an aralkyl group having a phenolic hydroxyl group is more preferred, and a phenyl group having a phenolic hydroxyl group or a benzyl group having a phenolic hydroxyl group is further preferred.

[0212] From the viewpoint of film strength and chemical resistance, R as a substituent containing an ethylenically unsaturated bond is preferably 1 and R 2 The molar amount of R in all repeating units represented by the formula (2-1) contained in the specific resin is 1 and R 2 The ratio of the total molar amount is 0 to 30%.

[0213] From the viewpoint of film strength, the above ratio is preferably 0 to 10%, more preferably 0 to 5%, and even more preferably 0 to 3%.

[0214] From the viewpoint of chemical resistance, the above ratio is preferably 10 to 30%, more preferably 15 to 30%.

[0215] From the viewpoint of film strength, chemical resistance, and solvent solubility of the specific resin, R is preferably an organic group having 1 to 30 carbon atoms and optionally containing a heteroatom. 1 and R 2 The molar amount of R in all the repeating units represented by the above formula (2-1) contained in the above resin is 1 and R 2 The ratio of the total molar amount is 20 to 100%.

[0216] From the viewpoint of film strength, the lower limit of the above ratio is preferably 30% or more, more preferably 40% or more, further preferably 50% or more, particularly preferably 60% or more, and most preferably 70% or more.

[0217] From the viewpoint of chemical resistance, the upper limit of the above ratio is preferably 95% or less, more preferably 90% or less, further preferably 85% or less, particularly preferably 80% or less, and most preferably 70% or less.

[0218] -content-

[0219] When the specific resin contains the repeating unit represented by formula (2-1), the content of the repeating unit represented by formula (2-1) is preferably 0.1 to 80% by mass, more preferably 20 to 60% by mass, based on the total mass of the specific resin.

[0220] Furthermore, the specific resin may contain only one repeating unit represented by formula (2-1), or may contain two or more repeating units represented by formula (2-1) of different structures. When containing two or more repeating units represented by formula (2-1), the total content of the repeating units represented by formula (2-1) is preferably within the above range.

[0221] [Repeating unit represented by formula (2-2)]

[0222] In formula (2-2), X 2 represents a 4-valent linking group.

[0223] In formula (2-2), X 2 With X in formula (2-1) 1 The meanings are the same and the preferred aspects are also the same.

[0224] Furthermore, when the specific resin contains a repeating unit represented by formula (2-2), the imidization rate (ring closure rate) of the specific resin is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0225] The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

[0226] The imidization ratio is measured, for example, by the following method.

[0227] The infrared absorption spectrum of the specific resin was measured, and the absorption peak at 1377 cm-1 derived from the imide structure was determined. -1 Next, after the specific resin was heat treated at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P1 at 1377 cm -1 The imidization ratio of the specific resin can be determined from the following formula using the obtained peak intensities P1 and P2.

[0228] Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0229] -content-

[0230] When the specific resin contains the repeating unit represented by formula (2-2), the content of the repeating unit represented by formula (2-2) is preferably 0.1 to 80% by mass, more preferably 20 to 60% by mass, based on the total mass of the specific resin.

[0231] Furthermore, the specific resin may contain only one repeating unit represented by formula (2-2), or may contain two or more repeating units represented by formula (2-2) of different structures. When containing two or more repeating units represented by formula (2-2), the total content of the repeating units represented by formula (2-2) is preferably within the above range.

[0232] [Repeating unit represented by formula (2-3)]

[0233] In formula (2-3), X 3 represents a trivalent linking group.

[0234] X 3 Examples include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group obtained by connecting two or more of these groups via a single bond or via a linking group. Preferably, it is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups via a single bond or via a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or via a linking group. Further preferably, it is an aromatic group having 6 to 20 carbon atoms. Particularly preferably, it is a group obtained by removing three hydrogen atoms from a benzene ring.

[0235] As the above-mentioned connecting group, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, halogenated alkylene, arylene or a connecting group formed by two or more of these are bonded, and -O-, -S-, alkylene, halogenated alkylene, aromatic group or a connecting group formed by two or more of these are more preferred.

[0236] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

[0237] As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferred, a halogenated alkylene group having 1 to 10 carbon atoms is more preferred, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferred. Furthermore, as the halogen atom in the above-mentioned halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be mentioned, and a fluorine atom is preferred. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted by a halogen atom, but preferably all hydrogen atoms are substituted by a halogen atom. As examples of preferred halogenated alkylene groups, (ditrifluoromethyl)methylene and the like can be mentioned.

[0238] The aromatic group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0239] And, preferably X 3 It is derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As the halogenation, chlorination is preferred.

[0240] In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound.

[0241] Two of the three carboxyl groups of the above tricarboxylic acid compound may be converted to anhydride.

[0242] Examples of the tricarboxylic acid compound which may be halogenated and is used in the production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds.

[0243] These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0244] Specifically, as the tricarboxylic acid compound, a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups via a single bond or a linking group is preferred, and a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group is more preferred.

[0245] In addition, specific examples of tricarboxylic acid compounds include compounds in which 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid are linked by a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2- or a phenylene group.

[0246] These compounds may be compounds in which two carboxyl groups are anhydrided (for example, trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (for example, trimellitic anhydride).

[0247] Furthermore, when the specific resin contains a repeating unit represented by formula (2-3), the imidization rate (ring closure rate) of the specific resin is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0248] The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

[0249] -content-

[0250] When the specific resin contains the repeating unit represented by formula (2-3), the content of the repeating unit represented by formula (2-3) is preferably 0.1 to 80% by mass, more preferably 20 to 60% by mass, based on the total mass of the specific resin.

[0251] Furthermore, the specific resin may contain only one repeating unit represented by formula (2-3), or may contain two or more repeating units represented by formula (2-3) of different structures. When containing two or more repeating units represented by formula (2-3), the total content of the repeating units represented by formula (2-3) is preferably within the above range.

[0252] [Repeating unit represented by formula (2-4)]

[0253] In formula (2-4), X 4 and X in formula (2-3) 3 The meanings are the same and the preferred aspects are also the same.

[0254] In formula (2-4), A 4 With A in formula (2-1) 1 The meanings are the same and the preferred aspects are also the same.

[0255] In formula (2-4), R 4 With R in formula (2-1) 1 The meanings are the same and the preferred aspects are also the same.

[0256] -content-

[0257] When the specific resin contains the repeating unit represented by formula (2-4), the content of the repeating unit represented by formula (2-4) is preferably 0.1 to 80% by mass, more preferably 20 to 60% by mass, based on the total mass of the specific resin.

[0258] Furthermore, the specific resin may contain only one repeating unit represented by formula (2-4), or may contain two or more repeating units represented by formula (2-4) of different structures. When containing two or more repeating units represented by formula (2-4), the total content of the repeating units represented by formula (2-4) is preferably within the above range.

[0259] [Repeating unit represented by formula (3-1), formula (3-2), formula (3-3) or formula (3-4)]

[0260] The specific resin preferably contains at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), a repeating unit represented by the following formula (3-3), and a repeating unit represented by the following formula (3-4).

[0261] These repeating units contain polymerizable groups in their structures. Therefore, it is considered that a crosslinked structure based on polymerizability is formed in the cured film, and thus the chemical resistance of the obtained cured film is further improved.

[0262] Preferably, the polymerizable group contained in the repeating unit represented by the above formula (3-1), the polymerizable group contained in the repeating unit represented by the above formula (3-2), the polymerizable group contained in the repeating unit represented by the above formula (3-3), and the polymerizable group contained in the repeating unit represented by the above formula (3-4) include a group containing an ethylenically unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group (preferably an alkoxymethyl group having 1 to 6 carbon atoms in the alkoxy group), more preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a hydroxymethyl group or an alkoxymethyl group, and further preferably a (meth)acryloyloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group.

[0263] When the specific resin includes a repeating unit represented by the formula (2-1), the specific resin preferably includes a repeating unit represented by the formula (3-1).

[0264] The repeating unit represented by the formula (3-1) is a repeating unit including the repeating unit represented by the formula (2-1) in its structure.

[0265] When the specific resin includes a repeating unit represented by the formula (2-2), the specific resin preferably includes a repeating unit represented by the formula (3-2).

[0266] The repeating unit represented by the formula (3-2) is a repeating unit including the repeating unit represented by the formula (2-2) in its structure.

[0267] When the specific resin includes a repeating unit represented by the formula (2-3), the specific resin preferably includes a repeating unit represented by the formula (3-3).

[0268] The repeating unit represented by the formula (3-3) is a repeating unit including two repeating units represented by the formula (2-3) in its structure.

[0269] When the specific resin includes a repeating unit represented by the formula (2-4), the specific resin preferably includes a repeating unit represented by the formula (3-4).

[0270] The repeating unit represented by the formula (3-4) is a repeating unit including two repeating units represented by the formula (2-4) in its structure.

[0271] The repeating unit represented by any one of the formulae (4-1) to (4-4) described later does not correspond to the repeating unit represented by any one of the formulae (3-1) to (3-4).

[0272] [Chemical formula 10]

[0273]

[0274]

[0275] In formula (3-1), X 5 represents a 4-valent linking group, R 3 and R 4 Each independently represents a monovalent organic group, Z 1 Represents a divalent linking group, R 3 , R 4 and Z 1 At least one of the comprises a polymerizable group;

[0276] In formula (3-2), X 6 represents a 4-valent linking group, Z 2 It represents a divalent linking group having a polymerizable group.

[0277] In formula (3-3), X 7 and X 8 Each independently represents a trivalent linking group, Z 3 and Z 4 Each independently represents a divalent linking group, Z 3 and Z4 At least one of represents a divalent linking group having a polymerizable group;

[0278] In formula (3-4), X 7 and X 8 Each independently represents a trivalent linking group, Z 3 and Z 4 Each independently represents a divalent linking group, R 5 and R 6 Each independently represents a monovalent organic group, Z 3 and Z 4 At least one of them represents a divalent linking group having a polymerizable group, R 5 , R 6 , Z 3 and Z 4 At least one of the compounds comprises a polymerizable group.

[0279] [Repeating unit represented by formula (3-1)]

[0280] -R 3 , R 4 , X 5 -

[0281] In formula (3-1), R 3 and R 4 are independently connected to R in formula (2-1) 1 and R 2 The meanings are the same and the preferred aspects are also the same.

[0282] In formula (3-1), X 5 With X in formula (2-1) 1 The meanings are the same and the preferred aspects are also the same.

[0283] -Z 1 -

[0284] In formula (3-1), Z 1 It is a divalent linking group.

[0285] Preferred Z 1 It is a divalent linking group having a polymerizable group.

[0286] In Z 1 When Z is a divalent linking group having no polymerizable group, 1 and Z in the following formula (6-1) 5 The meanings are the same and the preferred aspects are also the same.

[0287] In Z 1 In the case of a divalent linking group having no polymerizable group, R 3 and R 4At least one of the groups is a group having a polymerizable group.

[0288] As Z 1 The polymerizable group in the above-mentioned compound preferably includes a group containing an ethylenically unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group (preferably an alkoxymethyl group having 1 to 6 carbon atoms in the alkoxy group), more preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a hydroxymethyl group or an alkoxymethyl group, and further preferably a (meth)acryloyloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group.

[0289] Z 1 The number of polymerizable groups contained in is 1 or more, preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.

[0290] Furthermore, from the viewpoint of developability, Z 1 The group is a group containing an aromatic hydrocarbon group, more preferably a group containing an aromatic hydrocarbon group having 6 to 30 carbon atoms, further preferably a group containing a benzene ring structure or a naphthalene ring structure, and particularly preferably a group containing a benzene ring structure.

[0291] <<Formula (Z-1)>>

[0292] Among them, Z is preferred 1 It is a group represented by the following formula (Z-1).

[0293] [Chemical formula 11]

[0294]

[0295] In formula (Z-1), Q 1 represents an organic group having 1 to 30 carbon atoms, A 1 represents a group including a polymerizable group, n1 represents an integer greater than or equal to 1, and * represents a bonding site to other structures.

[0296] < 1 >>

[0297] Optimize Q 1 It is an n2+2 valent group containing an aromatic hydrocarbon group.

[0298] Optimize Q 1 The aromatic hydrocarbon group in is an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, further preferably a group obtained by removing two or more hydrogen atoms from a benzene ring, and particularly preferably a group obtained by removing three or more hydrogen atoms from a benzene ring. ​

[0299] In formula (Z-1), Q is preferably 1 The bonding sites of the two * in formula (Z-1) are both aromatic hydrocarbon groups. That is, it is preferred that the two nitrogen atoms in formula (3-1) and Q 1 The aromatic hydrocarbon ring structure contained therein is directly bonded.

[0300] Furthermore, in formula (Z-1), Q is preferably 1 in and A 1 The bonding sites of are all aromatic hydrocarbon groups. That is, preferably A 1 With Q 1 The aromatic hydrocarbon ring structure contained therein is directly bonded.

[0301] Optimize Q 1 It contains at least one structure selected from the structures represented by the following formula (A2-1) to (A2-5), and more preferably contains at least one structure selected from the structures represented by the formula (A2-1) to (A2-5).

[0302] [Chemical formula 12]

[0303]

[0304] In formulas (A2-1) to (A2-5), R A211 ~R A214 , R A221 ~R A224 , R A231 ~R A238 , R A241 ~R A248 and R A251 ~R A258 Each independently represents a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group or a halogen atom, and L A231 and L A241 Each independently represents a single bond, a carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a heteroatom, a heterocyclic group or a halogenated alkylene group, and R A211 ~R A214 At least one of R A221 ~R A224 At least one of R A231 ~R A238 At least one of R A241 ~R A248 At least one of R A251 ~R A258 At least one of them may be the same as A in the above formula (Z-1) 1 , and * independently represents the bonding site with other structures.

[0305] Among them, from the viewpoint of solvent solubility, Q 1 The structure represented by any one of Formula (A2-1) to Formula (A2-4) is contained, and the structure represented by Formula (A2-1) is more preferably contained.

[0306] In formula (A2-1), R is preferably A211 ~R A214 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom. From the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms is more preferred, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferred.

[0307] As the above R A211 ~R A214 The halogen atom in the above-mentioned halogenated alkyl group or the above-mentioned halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom or a bromine atom is preferred.

[0308] Furthermore, it is preferred that the above R A211 ~R A214 At least one of them is the same as A in formula (Z-1) 1 The bonding site is preferably R A213 For the above A 1 bonding part.

[0309] In formula (A2-2), R A221 ~R A224 Respectively with R in formula (A2-1) A211 ~R A214 The meanings are the same and the preferred aspects are also the same.

[0310] Furthermore, it is preferred that the above R A211 ~R A214 At least one of them is the same as A in formula (Z-1) 1 More preferably, one or two of the bonding sites are 2 bonding part.

[0311] In formula (A2-3), R A231 ~R A238 Respectively with R in formula (A2-1) A211 ~R A214 The meanings are the same and the preferred aspects are also the same.

[0312] In formula (A2-3), preferably L A231represents a single bond, a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, a divalent unsaturated hydrocarbon group having 5 to 24 carbon atoms, -O-, -S-, -NR N -, a heterocyclic group or a halogenated alkylene group having 1 to 6 carbon atoms, preferably represents a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, -O- or a heterocyclic group, and more preferably represents a single bond or -O-. N As described above, the preferred aspects are also the same.

[0313] Furthermore, it is preferred that the above R A231 ~R A238 At least one of them is the same as A in formula (Z-1) 1 More preferably, one or two of the bonding sites are 2 The bonding site is preferably R A231 ~R A234 One of the A235 ~R A238 One of the above A 1 bonding part.

[0314] In formula (A2-4), R A241 ~R A248 and L A241 Respectively with R in formula (A2-3) A231 ~R A238 and L A231 The meanings are the same and the preferred aspects are also the same.

[0315] Furthermore, it is preferred that the above R A241 ~R A248 At least one of them is the same as A in formula (Z-1) 1 More preferably, one or two of the bonding sites are 2 The bonding site is preferably R A241 ~R A244 One of the A245 ~R A248 One of the above A 2 bonding part.

[0316] In formula (A2-5), R A251 ~R A258 Respectively with R in formula (A2-1) A211 ~R A214 The meanings are the same and the preferred aspects are also the same.

[0317] Furthermore, it is preferred that the above R A251 ~R A258 At least one of them is the same as A in formula (Z-1) 1 More preferably, one or two of the bonding sites are 1The bonding site is preferably R A251 ~R A254 One of the A255 ~R A258 One of the above A 1 bonding part.

[0318] < 1 >>

[0319] In formula (Z-1), A 1 It represents a group containing a polymerizable group.

[0320] As the polymerizable group, a group containing an ethylenically unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group (preferably an alkoxymethyl group having 1 to 6 carbon atoms in the alkoxy group) is preferred, and a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group or a hydroxymethyl group is more preferred, and a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group is further preferred.

[0321] A 2 The number of polymerizable groups contained in is 1 or more, preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.

[0322] And, preferably A 1 It is a group represented by the following formula (P-1).

[0323] [Chemical formula 13]

[0324]

[0325] In formula (P-1), L 1 represents a single bond or an m+1 valent connecting group, A 2 represents a polymerizable group, m represents an integer greater than 1, and * represents 1 bonding part.

[0326] In formula (P-1), preferably L 1 is a single bond or a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N - or a group obtained by bonding two or more of these, more preferably a single bond or a hydrocarbon group, -O-, -C(=O)-, -NR N - or a group obtained by bonding two or more of these.

[0327] The above R N ​It represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, further preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

[0328] As the above L 1 The hydrocarbon group in is preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group represented by a combination of these, and more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a group obtained by removing two or more hydrogen atoms from a benzene ring, or a group represented by these bonds.

[0329] In formula (P-1), preferably A 2 It is a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a hydroxymethyl group or an alkoxymethyl group, and more preferably a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group.

[0330] In formula (P-1), m is preferably an integer of 1 to 15, more preferably an integer of 1 to 10, further preferably an integer of 1 to 5, particularly preferably 1 or 2, and most preferably 1.

[0331] And, preferably A 1 It is a group represented by the following formula (P-2) or formula (P-3).

[0332] [Chemical formula 14]

[0333] *-A 2 (P-2)*-Z 1 -L 2 -A 2 (P-3)

[0334] In formula (P-2), A 2 Represents a polymerizable group, * represents the 1 bonding part.

[0335] In formula (P-2), A 2 With A in formula (P-1) 2 The meanings are the same and the preferred aspects are also the same.

[0336] In formula (P-3), A 2 Represents a polymerizable group, L 2 represents a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O)2-, a carbonate bond, -NR N - or a group obtained by bonding two or more of these groups, Z 1 represents an ether bond, ester bond, urethane bond, urea bond, carbonate bond or amide bond, and * represents the bond with Y 1 The bonding site.N As mentioned above.

[0337] In formula (P-3), A 2 With A in formula (P-1) 2 The meanings are the same and the preferred aspects are also the same.

[0338] In formula (P-3), preferably L 2 It is a hydrocarbon group, a (poly)alkyleneoxy group or a group represented by a combination of these, and a hydrocarbon group is more preferable.

[0339] In this specification, (poly) alkyleneoxy means alkyleneoxy or polyalkyleneoxy. And, in the present invention, polyalkyleneoxy refers to a group obtained by directly bonding two or more alkyleneoxy groups. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. In the case where the polyalkyleneoxy group contains multiple alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement with blocks, or an arrangement with alternating patterns.

[0340] As the hydrocarbon group, an alkylene group, a divalent aromatic hydrocarbon group or a group represented by a combination thereof is preferred, and an alkylene group is more preferred.

[0341] The alkylene group is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, and still more preferably an alkylene group having 1 to 10 carbon atoms.

[0342] In the present invention, when simply described as "aliphatic hydrocarbon group", "saturated aliphatic hydrocarbon group", "alkyl group", "alkylene group", etc., unless otherwise specified, these groups may have at least one of a branched structure and a cyclic structure. For example, unless otherwise specified, "alkyl group" includes a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an alkyl group represented by a combination of these.

[0343] The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, further preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group.

[0344] The alkylene group in the (poly)alkyleneoxy group is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group or a propylene group, and still more preferably an ethylene group.

[0345] Furthermore, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, further preferably 2 to 5, and particularly preferably 2 to 4.

[0346] In formula (P-3), Z 1It represents an ether bond, an ester bond, a urethane bond, a urea bond or an amide bond, and preferably an ester bond, a urethane bond, a urea bond or an amide bond.

[0347] In formula (P-3), * represents 1 bonding part.

[0348] Furthermore, from the viewpoint of chemical resistance, A is preferred. 1 The distance between the polymerizable group contained in the specific resin and the main chain is 0 to 15, more preferably 0 to 10.

[0349] Among them, A 1 The distance between the polymerizable group contained in and the main chain of a specific resin refers to the smallest number of atoms contained between the atoms contained in the main chain of the polyimide and the polymerizable group. For example, in the resin represented by formula (PZ-3) in the examples described later, the distance between the methacryloyloxy group and the main chain is 4.

[0350] That is, when the polyimide has a ring structure inside the main chain, "atoms contained in the main chain of the polyimide" include ring members of the ring structure.

[0351] And, in A 1 When containing multiple polymerizable groups, it is preferred that A 1 The distance between the polymerizable group closest to the main chain among the polymerizable groups contained in A and the main chain of the polyimide is 0 to 15, more preferably 0 to 10. 1 When a plurality of polymerizable groups are included, it is more preferred that A 1 The distance between all polymerizable groups contained in the polyimide and the main chain is 0 to 15, and particularly preferably 0 to 10.

[0352] < <n1>>

[0353] In formula (Z-1), n1 represents an integer of 1 or greater, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, further preferably an integer of 1 to 4, particularly preferably 1 or 2, and most preferably 1.

[0354] Furthermore, when n1 is an integer greater than 2, n1 A 1 They can be the same or different.

[0355] -content-

[0356] When the specific resin contains the repeating unit represented by formula (3-1), the content of the repeating unit represented by formula (3-1) is preferably 0.1 to 80% by mass, more preferably 20 to 60% by mass, based on the total mass of the specific resin.

[0357] Furthermore, the specific resin may contain only one repeating unit represented by formula (3-1), or may contain two or more repeating units represented by formula (3-1) of different structures. When containing two or more repeating units represented by formula (3-1), the total content of the repeating units represented by formula (3-1) is preferably within the above range.

[0358] [Repeating unit represented by formula (3-2)]

[0359] -X 6 -

[0360] In formula (3-1), X 6 and X in formula (2-2) 2 The meanings are the same and the preferred aspects are also the same.

[0361] -Z 2 -

[0362] In formula (3-2), Z 2 and Z in formula (3-1) 1 The meanings are the same and the preferred aspects are also the same.

[0363] -content-

[0364] When the specific resin contains the repeating unit represented by formula (3-2), the content of the repeating unit represented by formula (3-2) is preferably 0.1 to 80% by mass, more preferably 20 to 60% by mass, based on the total mass of the specific resin.

[0365] Furthermore, the specific resin may contain only one repeating unit represented by formula (3-2), or may contain two or more repeating units represented by formula (3-2) of different structures. When containing two or more repeating units represented by formula (3-2), the total content of the repeating units represented by formula (3-2) is preferably within the above range.

[0366] [Repeating unit represented by formula (3-3)]

[0367] In formula (3-3), X 7 and X 8 Independently with X in formula (2-3) 3 The meanings are the same and the preferred aspects are also the same.

[0368] In formula (3-3), Z 3 and Z 4 At least one of them represents a divalent linking group having a polymerizable group, preferably Z 3 and Z 4 All of them are divalent linking groups having a polymerizable group.

[0369] In Z 3 When Z is a divalent linking group having a polymerizable group, 3 and Z in formula (3-1) 1 The meanings are the same and the preferred aspects are also the same.

[0370] In Z 4 When Z is a divalent linking group having a polymerizable group, 4 and Z in formula (3-1) 1 The meanings are the same and the preferred aspects are also the same.

[0371] In Z 3 When Z is a divalent linking group having no polymerizable group, 3 and Z in the following formula (6-1) 5 The meanings are the same and the preferred aspects are also the same.

[0372] In Z 4 When Z is a divalent linking group having no polymerizable group, 4 and Z in the following formula (6-1) 5 The meanings are the same and the preferred aspects are also the same.

[0373] -content-

[0374] When the specific resin contains the repeating unit represented by formula (3-3), the content of the repeating unit represented by formula (3-3) is preferably 0.1 to 80% by mass, more preferably 20 to 60% by mass, based on the total mass of the specific resin.

[0375] Furthermore, the specific resin may contain only one repeating unit represented by formula (3-3), or may contain two or more repeating units represented by formula (3-3) of different structures. When containing two or more repeating units represented by formula (3-3), the total content of the repeating units represented by formula (3-3) is preferably within the above range.

[0376] [Repeating unit represented by formula (3-4)]

[0377] In formula (3-4), X 7 and X 8 Independently with X in formula (2-4) 4 The meanings are the same and the preferred aspects are also the same.

[0378] In formula (3-4), Z is preferably 3 and Z 4 At least one of Z represents a divalent linking group having a polymerizable group, and Z is more preferably 3 and Z 4 All of them are divalent linking groups having a polymerizable group.

[0379] In Z 3 When Z is a divalent linking group having a polymerizable group, 3 and Z in formula (3-1) 1 The meanings are the same and the preferred aspects are also the same.

[0380] In Z 4 When Z is a divalent linking group having a polymerizable group, 4 and Z in formula (3-1) 1 The meanings are the same and the preferred aspects are also the same.

[0381] In Z 3 When Z is a divalent linking group having no polymerizable group, 3 and Z in the following formula (6-1) 5 The meanings are the same and the preferred aspects are also the same.

[0382] In Z 4 When Z is a divalent linking group having no polymerizable group, 4 and Z in the following formula (6-1) 5 The meanings are the same and the preferred aspects are also the same.

[0383] In formula (3-4), R 5 and R 6 Respectively with R in formula (3-1) 3 and R 4 The meanings are the same and the preferred aspects are also the same.

[0384] -content-

[0385] When the specific resin contains the repeating unit represented by formula (3-4), the content of the repeating unit represented by formula (3-4) is preferably 0.1 to 80% by mass, more preferably 20 to 60% by mass, based on the total mass of the specific resin.

[0386] Furthermore, the specific resin may contain only one repeating unit represented by formula (3-4), or may contain two or more repeating units represented by formula (3-4) of different structures. When containing two or more repeating units represented by formula (3-4), the total content of the repeating units represented by formula (3-4) is preferably within the above range.

[0387] [Formula (4-1), Formula (4-2), Formula (4-3), Formula (4-4)]

[0388] The specific resin preferably contains at least one repeating unit selected from the group consisting of a repeating unit represented by formula (4-1), a repeating unit represented by formula (4-2), and a repeating unit represented by formula (4-3).

[0389] When the specific resin includes a repeating unit represented by the formula (2-1), the specific resin preferably includes a repeating unit represented by the formula (4-1).

[0390] The repeating unit represented by the formula (4-1) is a repeating unit including the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (2-1).

[0391] When the specific resin includes a repeating unit represented by the formula (2-2), the specific resin preferably includes a repeating unit represented by the formula (4-2).

[0392] The repeating unit represented by the formula (4-2) is a repeating unit including the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (2-2).

[0393] When the specific resin includes a repeating unit represented by the formula (2-3), the specific resin preferably includes a repeating unit represented by the formula (4-3).

[0394] The repeating unit represented by the formula (4-3) is a repeating unit including the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (2-3).

[0395] When the specific resin contains the repeating unit represented by the formula (2-4), the specific resin preferably contains the repeating unit represented by the formula (4-4).

[0396] The repeating unit represented by the formula (4-4) is a repeating unit including the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (2-4).

[0397] [Chemical formula 15]

[0398]

[0399] In formula (4-1), X 5 Represents a 4-valent organic group, R 3 and R 4 Each independently represents a monovalent organic group, L 41 It is a structure represented by the following formula (L-1).

[0400] In formula (4-1), X 5 , R 3 and R 4 Respectively with X in formula (3-1) 5 , R 3 and R 4 The meanings are the same and the preferred aspects are also the same.

[0401] In formula (4-2), X 6 Represents a 4-valent group, L 42 It is a structure represented by the following formula (L-1).

[0402] In formula (4-2), X 6 and X in formula (3-2) 6 The meanings are the same and the preferred aspects are also the same.

[0403] In formula (4-3), X 7 and X 8 Each independently represents a trivalent linking group, L 44 represents a divalent linking group, L 43 It is a structure represented by the following formula (L-1).

[0404] In formula (4-3), X 7 and X 8 Respectively with X in formula (3-3) 7 and X 8 The meanings are the same and the preferred aspects are also the same.

[0405] In formula (4-3), L 44 represents a divalent linking group, preferably Z in formula (3-3) 3 The divalent linking group having a polymerizable group or the divalent linking group not having a polymerizable group is the same group, and more preferably Z in formula (3-3) 3 The divalent linking group having a polymerizable group in is the same group.

[0406] In formula (4-4), X 7 and X 8 Each independently represents a trivalent linking group, L 46 represents a divalent linking group, L 45 It is a structure represented by the following formula (L-1).

[0407] In formula (4-4), X 7 and X 8 Respectively with X in formula (3-4) 7 and X 8 The meanings are the same and the preferred aspects are also the same.

[0408] In formula (4-4), R 5 and R 6 Respectively with R in formula (3-4) 5 and R 6 The meanings are the same and the preferred aspects are also the same.

[0409] In formula (4-4), L 46 represents a divalent linking group, preferably Z in formula (3-4) 3 The divalent linking group having a polymerizable group or the divalent linking group not having a polymerizable group is the same group, and more preferably Z in formula (3-4) 3 The divalent linking group having a polymerizable group in is the same group.

[0410] [Chemical formula 16]

[0411]

[0412] In formula (L-1), Y 1 Represents a divalent linking group, Ar 1 represents an aromatic hydrocarbon group which may have a substituent or a condensed ring structure, Y 2 represents a single bond or a divalent linking group, and * represents a bonding site with other structures.

[0413] Y in formula (L-1) 1 ,Ar 1 and Y 2 Respectively with Y in formula (1-1) 1 ,Ar 1 and Y 2 The meanings are the same and the preferred aspects are also the same.

[0414] When the specific resin contains the repeating unit represented by formula (4-1), the content of the repeating unit represented by formula (4-1) is preferably 0.1 to 80% by mass, more preferably 20 to 60% by mass, based on the total mass of the specific resin.

[0415] Furthermore, the specific resin may contain only one repeating unit represented by formula (4-1), or may contain two or more repeating units represented by formula (4-1) of different structures. When containing two or more repeating units represented by formula (4-1), the total content of the repeating units represented by formula (4-1) is preferably within the above range.

[0416] When the specific resin contains the repeating unit represented by formula (4-2), the content of the repeating unit represented by formula (4-2) is preferably 0.1 to 80% by mass, more preferably 20 to 60% by mass, based on the total mass of the specific resin.

[0417] Furthermore, the specific resin may contain only one repeating unit represented by formula (4-2), or may contain two or more repeating units represented by formula (4-2) of different structures. When containing two or more repeating units represented by formula (4-2), the total content of the repeating units represented by formula (4-2) is preferably within the above range.

[0418] When the specific resin contains the repeating unit represented by formula (4-3), the content of the repeating unit represented by formula (4-3) is preferably 0.1 to 80% by mass, more preferably 20 to 60% by mass, based on the total mass of the specific resin.

[0419] Furthermore, the specific resin may contain only one repeating unit represented by formula (4-3), or may contain two or more repeating units represented by formula (4-3) of different structures. When containing two or more repeating units represented by formula (4-3), the total content of the repeating units represented by formula (4-3) is preferably within the above range.

[0420] When the specific resin contains the repeating unit represented by formula (4-4), the content of the repeating unit represented by formula (4-4) is preferably 0.1 to 80% by mass, more preferably 20 to 60% by mass, based on the total mass of the specific resin.

[0421] Furthermore, the specific resin may contain only one repeating unit represented by formula (4-4), or may contain two or more repeating units represented by formula (4-4) of different structures. In the case of containing two or more repeating units represented by formula (4-3), the total content of the repeating units represented by formula (4-4) is preferably within the above range.

[0422] [Formula (5-1)]

[0423] The specific resin also preferably contains a repeating unit represented by formula (5-1).

[0424] The repeating unit represented by the formula (5-1) is a group including the repeating unit represented by the formula (1-1).

[0425] The specific resin preferably contains a repeating unit represented by formula (5-1) and at least one repeating unit selected from the repeating unit represented by formula (3-1), the repeating unit represented by formula (3-2), the repeating unit represented by formula (3-3) and the repeating unit represented by formula (3-4), and more preferably contains a repeating unit represented by formula (5-1) and a repeating unit represented by formula (3-1) or contains a repeating unit represented by formula (5-1) and a repeating unit represented by formula (3-4).

[0426] [Chemical formula 17]

[0427]

[0428] In formula (5-1), L 51 is the structure represented by the above formula (L-1), L 52 It represents a divalent organic group.

[0429] In formula (5-1), L 52 and Z in formula (3-1) 1 The meanings are the same and the preferred aspects are also the same.

[0430] When the specific resin contains the repeating unit represented by formula (5-1), the content of the repeating unit represented by formula (5-1) is preferably 0.1 to 80% by mass, more preferably 10 to 50% by mass, based on the total mass of the specific resin.

[0431] The specific resin may contain only one repeating unit represented by formula (5-1), or may contain two or more repeating units represented by formula (5-1) of different structures. When containing two or more repeating units represented by formula (5-1), the total content of the repeating units represented by formula (5-1) is preferably within the above range.

[0432] [Other repeating units]

[0433] Certain resins may also contain other repeating units.

[0434] Examples of other repeating units include repeating units represented by any one of formula (6-1) to formula (6-4).

[0435] The repeating unit corresponding to any one of the above formulae (3-1) to (3-4), (4-1) to (4-4) and (5-1) does not correspond to the repeating unit represented by any one of formulae (6-1) to (6-4).

[0436] [Chemical formula 18]

[0437]

[0438] In formula (6-1), X 5 represents a 4-valent linking group, R 3 and R 4 Each independently represents a monovalent organic group having no polymerizable group, and Z 1 represents a divalent linking group having no polymerizable group and any one of the structures represented by the above formula (L-1);

[0439] In formula (6-2), X 6 represents a 4-valent linking group, Z 6 represents a divalent linking group having no polymerizable group and any one of the structures represented by the above formula (L-1);

[0440] In formula (6-3), X 7 and X 8 Each independently represents a trivalent linking group, Z 7 and Z 8 Each independently represents a divalent linking group having no polymerizable group and no structure represented by the above formula (L-1).

[0441] In formula (6-4), X 7 and X 8 Each independently represents a trivalent linking group, R 5 and R 6 Each independently represents a monovalent organic group having no polymerizable group, and Z 7 and Z 8 Each independently represents a divalent linking group having no polymerizable group and no structure represented by the above formula (L-1).

[0442] In formula (6-1), X 5 and X in formula (3-1) 5 The meanings are the same and the preferred aspects are also the same.

[0443] In formula (6-1), preferably R 3 and R 4 are independently R in formula (2-1) 1 and R 2 The substituent having a heteroatom in the formula (2-1) is a substituent having no polymerizable group. 1 and R 2 The preferred embodiment of the substituent having no polymerizable group among the substituent having a heteroatom in is the same.

[0444] In formula (6-1), Z is preferably 5 is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or at least one of these groups and -O-, -C(=O)-, -S-, -S(=O)2- and -NR N - is a group obtained by bonding at least one of N As mentioned above.

[0445] The aliphatic hydrocarbon group is preferably an aliphatic saturated hydrocarbon group having 2 to 30 carbon atoms, and more preferably an aliphatic saturated hydrocarbon group having 2 to 10 carbon atoms.

[0446] Furthermore, the aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon ring group having 6 to 20 ring members.

[0447] The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably an aromatic hydrocarbon group having 6 carbon atoms.

[0448] Among them, Z is preferred from the viewpoint of solvent solubility. 5 It is a group containing an aliphatic hydrocarbon ring group or an aromatic hydrocarbon ring group, and is more preferably a group containing an aromatic hydrocarbon ring group.

[0449] Furthermore, from the viewpoint of the flexibility of the obtained cured film, it is preferred that Z in formula (6-1) 5 by-Ar 0 -L 0 -Ar 0 - means. 0 Each independently represents an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), and is preferably a phenylene group. 0 and L in the above formula (A2-3) A231 The meanings are the same and the preferred aspects are also the same.

[0450] From the viewpoint of i-ray transmittance, Z in formula (6-1) is preferably 5 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, a divalent organic group represented by formula (61) is more preferred.

[0451] [Chemical formula 19]

[0452]

[0453] In formula (51), R 50 ~R 57 are independently a hydrogen atom, a fluorine atom or a monovalent organic group, R 50 ~R 57 At least one of them is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group, and * each independently represents a bonding site to other structures.

[0454] As R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0455] [Chemical formula 20]

[0456]

[0457] In formula (61), R 58 and R 59 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

[0458] Preferably, Z in formula (6-1) 5 It is a structure derived from diamine.

[0459] Examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane or isophoronediamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3-aminophenylenediamine. ,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone or 3,3-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide or 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, bis(4-amino-3-carboxyphenyl)methane, 2,2-bis(4-aminophenyl ) propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis( 4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-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-(3',5'-diaminobenzoyloxy)ethyl methacrylate, 2,4-diaminocumene or 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl- m-phenylenediamine, 4,6-dihydroxy-1,3-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, diaminobenzoic acid, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenyl) At least one of the following diamines: 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotoluidine and 4,4'-diaminoquaternary biphenyl.

[0460] Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0461] A diamine having two or more alkylene glycol units described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 in the main chain can also be preferably used.

[0462] Furthermore, examples of the diamine that imparts the structure of the above formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One of these may be used alone, or two or more may be used in combination.

[0463] Furthermore, the following diamines can also be preferably used.

[0464] [Chemical formula 21]

[0465]

[0466] Furthermore, in order to improve the adhesion to the substrate, as the diamine component, a diamine having a siloxane structure such as bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane can be used.

[0467] In formula (6-2), X 6 and X in formula (3-2) 6 The meanings are the same and the preferred aspects are also the same.

[0468] In formula (6-2), Z 6 and Z in formula (6-1) 5 The meanings are the same and the preferred aspects are also the same.

[0469] In formula (6-3), X 7 and X 8 and X in formula (3-3) 7 and X 8 The meanings are the same and the preferred aspects are also the same.

[0470] In formula (6-3), Z 7 and Z 8 Independently with Z in formula (6-1) 5 The meanings are the same and the preferred aspects are also the same.

[0471] In formula (6-4), X 7 and X 8 and X in formula (3-4) 7 and X 8 The meanings are the same and the preferred aspects are also the same.

[0472] In formula (6-4), Z 7 and Z 8 Independently with Z in formula (6-1) 5 The meanings are the same and the preferred aspects are also the same.

[0473] In formula (6-4), R 5 and R 6 Independently with R in formula (6-1) 3 and R 4 The meanings are the same and the preferred aspects are also the same.

[0474] Furthermore, as another repeating unit, a repeating unit represented by the following formula (PAI-1) may be contained.

[0475] The repeating unit corresponding to the above formula (5-1) does not correspond to the repeating unit represented by the formula (PAI-1).

[0476] [Chemical formula 22]

[0477]

[0478] In the formula (PAI-1), R 116 Represents a divalent organic group, R 111 It represents a divalent organic group.

[0479] In the formula (PAI-1), R 116 Examples include a linear or branched aliphatic group, a cyclic aliphatic group and an aromatic group, a heteroaromatic group, or a group obtained by connecting two or more of these groups via a single bond or a linking group. Preferably, it is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups via a single bond or a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

[0480] As the above-mentioned linking group, preferred are -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, halogenated alkylene, arylene or a linking group formed by two or more of these bonds, and more preferred are -O-, -S-, alkylene, halogenated alkylene, arylene or a linking group formed by two or more of these bonds.

[0481] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

[0482] As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferred, a halogenated alkylene group having 1 to 10 carbon atoms is more preferred, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferred. Furthermore, as the halogen atom in the above-mentioned halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be mentioned, and a fluorine atom is preferred. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted by a halogen atom, but preferably all hydrogen atoms are substituted by a halogen atom. As examples of preferred halogenated alkylene groups, (ditrifluoromethyl)methylene and the like can be mentioned.

[0483] As the arylene group, a phenylene group or a naphthylene group is preferred, a phenylene group is more preferred, and a 1,3-phenylene group or a 1,4-phenylene group is further preferred.

[0484] And, preferably R 116 Derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide.

[0485] In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide.

[0486] The carboxyl group in the dicarboxylic acid dihalide may be halogenated, and is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide is preferably a dicarboxylic acid dichloride compound.

[0487] Examples of the dicarboxylic acid compound or dicarboxylic acid dihalide which may be halogenated and is used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides.

[0488] These dicarboxylic acid compounds or dicarboxylic acid dihalides may be used alone or in combination of two or more.

[0489] Specifically, as the dicarboxylic acid compound or dicarboxylic acid dihalide, a dicarboxylic acid compound or dicarboxylic acid dihalide containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups via a single bond or a linking group is preferred, and a dicarboxylic acid compound or dicarboxylic acid dihalide containing an aromatic group having 6 to 20 carbon atoms or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group is more preferred.

[0490] Specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecanoic acid, and 2,6-difluorohexane. Sebacatedioic acid, 1,9-azeladic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, dohenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, Heptadecanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxyl diphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc.

[0491] Specific examples of the dicarboxylic acid dihalide include compounds having a structure in which two carboxyl groups in the above-mentioned specific examples of the dicarboxylic acid compound are halogenated.

[0492] In the formula (PAI-1), R 111 With Z in the above formula (3-1) 1 The meanings are the same and the preferred aspects are also the same.

[0493] When the specific resin contains other repeating units, the content of the other repeating units is preferably 0.1 to 40% by mass, more preferably 5 to 30% by mass, based on the total mass of the specific resin.

[0494] Furthermore, the specific resin can also be set to a mode that substantially does not contain other repeating units. In the above-mentioned mode, it is preferred that the content of other repeating units is 20% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less relative to the total mass of the specific resin. The lower limit of the above-mentioned content is not particularly limited and can be 0% by mass.

[0495] Furthermore, the specific resin may contain only one type of other repeating unit, or may contain two or more other repeating units having different structures. When containing two or more other repeating units, it is preferred that the total content of the other repeating units is within the above range.

[0496] -Preferred Embodiments of Specific Resins-

[0497] The specific resin is preferably any one of the following aspects (1) to (5).

[0498] (2) Contains a repeating unit represented by the formula (3-2) and a repeating unit represented by the formula (4-2).

[0499] (2) Contains a repeating unit represented by the formula (3-2) and a repeating unit represented by the formula (4-2).

[0500] (2) Contains a repeating unit represented by the formula (3-2) and a repeating unit represented by the formula (4-2).

[0501] (2) Contains a repeating unit represented by the formula (3-2) and a repeating unit represented by the formula (4-2).

[0502] (5) contains at least one repeating unit selected from the repeating unit represented by formula (3-1), the repeating unit represented by formula (3-2), the repeating unit represented by formula (3-3) and the repeating unit represented by formula (3-4) and the repeating unit represented by formula (5-1).

[0503] In the above (1), the specific resin may further contain other repeating units.

[0504] For example, in the above (1), the specific resin may further include a repeating unit represented by the formula (5-1).

[0505] In the above (1), the total content of the repeating unit represented by the formula (3-1) and the repeating unit represented by the formula (4-1) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more relative to the total mass of the specific resin. The upper limit of the above total content is not particularly limited and can be 100% by mass.

[0506] In the above (2), the specific resin may further contain other repeating units.

[0507] For example, in the above (2), the specific resin may further include at least one selected from the repeating unit represented by the formula (3-1) and the repeating unit represented by the formula (4-1).

[0508] Furthermore, for example, in the above (2), the specific resin may further include a repeating unit represented by the formula (5-1).

[0509] In the above (2), the total content of the repeating unit represented by the formula (3-2) and the repeating unit represented by the formula (4-2) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more relative to the total mass of the specific resin. The upper limit of the above total content is not particularly limited and can be 100% by mass.

[0510] In the above (3), the specific resin may further contain other repeating units.

[0511] For example, in the above (3), the specific resin may further include at least one selected from the repeating unit represented by the formula (3-4) and the repeating unit represented by the formula (4-4).

[0512] In the above (3), the specific resin may further contain a repeating unit represented by formula (5-1).

[0513] In the above (3), the total content of the repeating unit represented by the formula (3-3) and the repeating unit represented by the formula (4-3) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more relative to the total mass of the specific resin. The upper limit of the above total content is not particularly limited and can be 100% by mass.

[0514] In the above (4), the specific resin may further contain other repeating units.

[0515] For example, in the above (4), the specific resin may further include a repeating unit represented by the formula (5-1).

[0516] In the above (4), the total content of the repeating unit represented by the formula (3-4) and the repeating unit represented by the formula (4-4) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more relative to the total mass of the specific resin. The upper limit of the above total content is not particularly limited and can be 100% by mass.

[0517] In the above (5), the specific resin may further contain other repeating units.

[0518] In the above (5), the total content of the repeating unit represented by the formula (3-1), the repeating unit represented by the formula (3-2), the repeating unit represented by the formula (3-3), the repeating unit represented by the formula (3-4) and the repeating unit represented by the formula (5-1) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more relative to the total mass of the specific resin. The upper limit of the above total content is not particularly limited and can be 100% by mass.

[0519] -Terminal structure-

[0520] The terminal structure of the specific resin is not particularly limited, but in order to improve the storage stability of the composition, it can be sealed with end-capping agents such as monoamine, acid anhydride, monocarboxylic acid, monoacyl chloride compound, and monoactive ester compound. Among these end-capping agents, monoamine is preferably used. As monoamine, 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, 1-carboxyl-5-aminonaphthalene, 2-carboxyl-7-aminonaphthalene, Naphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 4-aminostyrene, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

[0521] [content]

[0522] From the viewpoint of increasing the elongation at break of the obtained cured film, the content of the specific resin in the curable resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more, based on the total solid content of the curable resin composition.

[0523] The upper limit of the above content is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, further preferably 97% by mass or less, further preferably 95% by mass or less, from the viewpoint of improving the resolution of the curable resin composition.

[0524] [Physical properties of specific resins]

[0525] -Molecular weight-

[0526] The weight average molecular weight (Mw) of the specific resin is preferably 2,000 to 500,000, more preferably 5,000 to 200,000, and further preferably 10,000 to 100,000.

[0527] The number average molecular weight (Mn) of the specific resin is preferably 800 to 250,000, more preferably 2,000 to 100,000, and further preferably 4,000 to 50,000.

[0528] The molecular weight dispersion of the specific resin is preferably 1.5 to 3.5, more preferably 2 to 3.

[0529] In the present specification, the molecular weight dispersion refers to a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).

[0530] -Acid value-

[0531] The acid value of the specific resin is preferably 0 to 2.0 mmol / g, more preferably 0 to 1.5 mmol / g, and even more preferably 0 to 1.0 mmol / g.

[0532] When the curable resin composition is used for alkali development described below, the acid value of the specific resin is preferably 1.2 to 7 mmol / g, more preferably 1.5 to 6 mmol / g, and further preferably 2 to 5 mmol / g.

[0533] In the present invention, the acid value refers to the amount (mmol) of acid groups contained in 1 g of a specific resin.

[0534] The acid group refers to a group that is neutralized by a base (such as sodium hydroxide) at a pH of 12 or higher. The acid group is preferably a group having a pKa of 10 or less.

[0535] The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0536] Examples of the acid group include a phenolic hydroxyl group, a carboxyl group, and a sulfonic acid group, and a carboxyl group is preferred.

[0537] [Polymerization Group Value]

[0538] The molar amount of the polymerizable group contained in 1 g of the specific resin (polymerizable group value, unit: mmol / g) is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g.

[0539] When the specific resin contains an ethylenically unsaturated bond as a polymerizable group, the molar amount of the ethylenically unsaturated bond contained in 1 g of the specific resin is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g.

[0540] When the specific resin contains polymerizable groups such as cyclic ether groups, methylol groups, and alkoxymethyl groups, the molar amount of the polymerizable groups contained in 1 g of the specific resin is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g.

[0541] [Specific example]

[0542] Specific examples of the specific resin include specific resins used in Examples described later.

[0543] [Production method (production method of a specific resin comprising a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-1) or a specific resin comprising a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-4))]

[0544] When the specific resin contains a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-1) or contains a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-4), the specific resin is synthesized, for example, by the synthesis method shown in the synthesis example in the examples described later.

[0545] Furthermore, it is preferred that the method for producing the specific resin includes a step of reacting a diamine, a tetravalent carboxylic acid compound or a derivative thereof, and a compound having an oxazoline ring structure formed by condensing with an aromatic ring (precursor production step).

[0546] -Precursor manufacturing steps-

[0547] As a diamine used in the said precursor production process, the diamine represented by following formula (DA-1) is mentioned.

[0548] [Chemical formula 23]

[0549] H2N-L 21 -NH2 (DA-1)

[0550] In formula (DA-1), L 21 and Z in formula (3-1) 1 The meanings are the same and the preferred aspects are also the same.

[0551] The tetravalent carboxylic acid oxide compound used in the above-mentioned precursor production step may be a carboxylic acid dianhydride or a compound having a structure in which two of the four carboxyl groups are modified by esterification, halogenation, etc. Preferably, among the carboxylic acid dianhydride represented by the formula (DC-1) described later or the carboxylic acid dianhydride represented by the above-mentioned formula (O), a compound in which two of the four carboxyl groups after hydrolysis are esterified can be cited.

[0552] It is preferred that R in the above formula (2-1) is introduced by the above esterification. 1 and R 2 .

[0553] Furthermore, it is preferred that the compound in which two of the four carboxyl groups are esterified is halogenated using a halogenating agent and then reacted with a diamine.

[0554] In addition, the reaction conditions in the precursor production step can be appropriately determined with reference to known esterification conditions.

[0555] Examples of the compound containing an oxazoline ring structure condensed with an aromatic ring used in the precursor production step include a diamine containing an oxazoline ring structure condensed with an aromatic ring or a dicarboxylic acid containing an oxazoline ring structure condensed with an aromatic ring.

[0556] The carboxyl group in the dicarboxylic acid having an oxazoline ring structure formed by condensation with an aromatic ring may be a carboxylic acid modified with a halide or the like.

[0557] Examples of the diamine containing an oxazoline ring structure formed by condensation with an aromatic ring include compounds represented by the following formula (ODA-1).

[0558] Examples of the dicarboxylic acid containing an oxazoline ring structure formed by condensation with an aromatic ring include compounds represented by the following formula (ODC-1).

[0559] [Chemical formula 24]

[0560]

[0561] In formula (ODA-1) or formula (ODC-1), Y 1 ,Ar 1 , Y 2 Respectively with Y in formula (1-1) 1 ,Ar 1 , Y 2 The meanings are the same and the preferred aspects are also the same.

[0562] In formula (ODC-1), R represents -OH or a substituent, preferably -OH or a halogen atom. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom, and preferably a chlorine atom.

[0563] By using a diamine having an oxazoline ring structure formed by condensation with an aromatic ring, a repeating unit represented by formula (4-1) is introduced into the specific resin.

[0564] By using a dicarboxylic acid having an oxazoline ring structure formed by condensation with an aromatic ring, a repeating unit represented by formula (5-1) is introduced into the specific resin.

[0565] Furthermore, in the precursor production step, it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one kind or two or more kinds.

[0566] The organic solvent can be appropriately selected according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone.

[0567] The precursor production step preferably includes a step of precipitating a solid. Specifically, the specific resin in the reaction solution is precipitated in water and dissolved in a solvent such as tetrahydrofuran that can dissolve the polyimide precursor, thereby precipitating a solid.

[0568] -Diamine production process-

[0569] The method for producing a specific resin may include the following step (diamine production step), namely, reacting a compound A having two nitro groups, at least one reactive group and an aromatic hydrocarbon group with a compound B having a group that can form a bond with the reactive group and a polymerizable group, and after obtaining a compound C in which compound A and compound B are bonded, reducing the nitro group in the compound C to obtain a diamine.

[0570] The diamine obtained in the diamine production step is used as the diamine in the precursor production step.

[0571] The reactive group in the compound A is not particularly limited, and examples thereof include an amino group, a hydroxyl group, and a carboxyl group.

[0572] The compound A preferably has a structure in which two nitro groups and at least one reactive group are directly bonded to an aromatic hydrocarbon group.

[0573] The group that can form a bond with the reactive group in the compound B is not particularly limited, and examples thereof include a hydroxyl group, a carboxyl group, a carboxylic acid halide group, an epoxy group, and an isocyanate group.

[0574] Examples of the polymerizable group in compound B include Z in the above formula (3-1): 1 The groups exemplified as the groups included in .

[0575] Compound C is a group obtained by reaction of compound A and compound B, and is a compound having two nitro groups and a group including at least one polymerizable group.

[0576] By reducing the nitro group in compound C, a diamine compound is obtained.

[0577] As the reduction method, known methods such as Bechamp reduction, hydrogenation reaction using a metal catalyst such as palladium, platinum, nickel and a hydrogen source such as hydrogen gas or ammonium formate, and reduction method using a metal hydride as a reducing agent can be used.

[0578] For example, the synthesis of the dinitro compound (A-1) in the examples described below is a reaction in which 3,5-dinitrobenzoyl chloride as compound A and 2-hydroxyethyl methacrylate as compound B are reacted to obtain the dinitro compound (A-1) as compound C.

[0579] The synthesis of diamine (AA-1) in the examples described below is a reaction in which two nitro groups in the dinitro form (A-1) as compound C are reduced to obtain diamine (AA-1).

[0580] -Carboxylic acid dianhydride production process-

[0581] The method for producing a specific resin may include a step of reacting a diamine compound with a compound having one carboxylic acid anhydride group and one carboxyl group to obtain a carboxylic acid dianhydride having two or more amide bonds (carboxylic acid dianhydride production step).

[0582] The one carboxyl group may be a carboxylic acid halide group.

[0583] The details of the above reaction may be determined by referring to a known amidation method.

[0584] For example, the synthesis of anhydride (MA-1) in the examples described below is a reaction in which AA-1 as a diamine compound reacts with trimellitic anhydride chloride as a compound having one carboxylic anhydride group and one carboxylic acid halide group to obtain anhydride (MA-1) having two amide bonds.

[0585] Examples of the obtained carboxylic dianhydride include compounds represented by the following formula (DC-1).

[0586] [Chemical formula 25]

[0587]

[0588] In formula (DC-1), X 7 , X 8 and Z 3 Respectively with X in formula (3-3) 7 , X 8 and Z 3 The meanings are the same and the preferred aspects are also the same.

[0589] [Production method (production method of a specific resin comprising a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-2) or a specific resin comprising a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-3))]

[0590] A specific resin (hereinafter also referred to as a closed-ring specific resin) comprising a repeating unit represented by formula (1-1) and at least one repeating unit selected from the repeating unit represented by formula (2-2) and the repeating unit represented by formula (2-3) can be synthesized, for example, by the synthesis method shown in the synthesis example in the examples described later.

[0591] Furthermore, the method for producing a closed-ring specific resin may include an imidization step of imidizing a specific resin comprising a repeating unit represented by the above-mentioned formula (1-1) and a repeating unit represented by the formula (2-1) or a specific resin comprising a repeating unit represented by the formula (1-1) and a repeating unit represented by the formula (2-4).

[0592] In the imidization step, the specific resin obtained in the above-mentioned precursor production step, etc., which contains a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-1), or the specific resin containing a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-4) is imidized, thereby obtaining a closed-ring specific resin.

[0593] The imidization step may be any of thermal imidization (eg, imidization by heating), chemical imidization (eg, imidization using a catalyst), or imidization based on a combination thereof, and may be performed, for example, by heating in the presence of a catalyst such as an amine compound.

[0594] Furthermore, in the imidization step, for example, a dehydrating agent may be used. Examples of the dehydrating agent include carboxylic anhydrides such as acetic anhydride.

[0595] In addition, about the detail of imidization, it can be carried out by a well-known method.

[0596] -Other manufacturing methods-

[0597] Furthermore, the method for producing the ring-closed specific resin may be a method in which the carboxylic dianhydride and the diamine compound are heated at a high temperature to dehydrate them during the reaction, thereby synthesizing the resin in one step.

[0598] Examples of the carboxylic dianhydride include carboxylic dianhydride represented by the above formula (O) and carboxylic dianhydride represented by the above formula (DC-1).

[0599] As the diamine compound, a diamine compound represented by the above formula (DA-1) can be used.

[0600] Furthermore, the method for producing the resin used in the present invention may be a method in which the carboxylic dianhydride and the diisocyanate compound are reacted and then decarboxylated at a high temperature to synthesize the resin in one step.

[0601] Examples of the carboxylic acid dianhydride include carboxylic acid dianhydride represented by the above formula (DC-1). The above carboxylic acid dianhydride is preferably a compound obtained in the above tetravalent carboxylic acid production step.

[0602] Examples of the diisocyanate compound include compounds in which two amino groups in the compound represented by the above formula (DA-1) are each replaced with an isocyanate group.

[0603] For details of these production methods, reference can be made to known methods for synthesizing polyimide.

[0604] <Solvent>

[0605] The curable resin composition of the present invention contains a solvent.

[0606] Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0607] Examples of the 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 alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) 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), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, and the like.

[0608] As the ethers, for example, preferably there can be mentioned diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate and the like.

[0609] Preferred examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosanone, and dihydroglucosanone.

[0610] Preferred examples of the aromatic hydrocarbons include toluene, xylene, anisole, and limonene.

[0611] As the sulfoxides, for example, dimethyl sulfoxide is preferably used.

[0612] Preferred examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0613] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0614] Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monopropylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethylene glycol monobenzyl ether, ethylene glycol monoethylene glycol monophenyl ether, methyl phenyl carbinol, n-pentanol, methyl pentanol and diacetone alcohol.

[0615] Regarding the solvent, a mixture of two or more kinds is also preferred from the viewpoint of improving the properties of the coating surface.

[0616] In the present invention, preferably selected from 3-ethoxy propionic acid methyl ester, 3-ethoxy propionic acid ethyl ester, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxy propionic acid methyl ester, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, or a mixed solvent consisting of two or more. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone simultaneously. In addition, the combination of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and γ-butyrolactone is also preferred.

[0617] From the viewpoint of coating properties, the content of the solvent is preferably set to an amount of 5 to 80% by mass, more preferably 5 to 75% by mass, further preferably 10 to 70% by mass, and further preferably 40 to 70% by mass, so that the total solid content of the curable resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, further preferably 10 to 70% by mass, and further preferably 40 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating and the coating method.

[0618] The solvent may be contained in one kind or in two or more kinds. When two or more kinds of solvents are contained, the total amount is preferably within the above range.

[0619] <Photosensitizer>

[0620] The curable resin composition of the present invention preferably contains a photosensitizer. As the photosensitizer, preferably, a photopolymerization initiator is used.

[0621] [Photopolymerization initiator]

[0622] The curable resin composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer.

[0623] The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. In addition, an activator that generates active free radicals by reacting with a photoexcited sensitizer may also be used.

[0624] Preferably, the photo-radical polymerization initiator contains at least one having a wavelength of at least about 50 L / mol in the range of about 300 to 800 nm (preferably 330 to 500 nm). -1 / cm -1 The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferably measured by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) using an ethyl acetate solvent at a concentration of 0.01 g / L.

[0625] As a photo-radical polymerization initiator, known compounds can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, compounds with a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbisimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azides, metallocene compounds, organic boron compounds, iron aromatic complexes, etc. can be cited. For these details, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Publication No. 2016-027357, and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, and the content is incorporated into this specification.

[0626] Examples of the ketone compound include compounds described in paragraph 0087 of JP-A-2015-087611, and the contents are incorporated herein. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

[0627] In one embodiment of the present invention, as the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can be preferably used. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used.

[0628] As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127, and IRGACURE 727 (product names: all manufactured by BASF) can be used.

[0629] As the aminoacetophenone-based initiator, commercially available products such as IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all manufactured by BASF Corporation) can be used.

[0630] As the aminoacetophenone-based initiator, a compound described in Japanese Patent Application Laid-Open No. 2009-191179, which has an absorption maximum wavelength that matches a light source having a wavelength of 365 nm or 405 nm, can also be used.

[0631] Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. Commercially available products such as IRGACURE-819 and IRGACURE-TPO (product names: both manufactured by BASF Corporation) can also be used.

[0632] Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF Corporation) and the like.

[0633] As the photo-radical polymerization initiator, an oxime compound can be more preferably used. By using an oxime compound, the exposure latitude can be more effectively improved. Oxime compounds have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator, so they are particularly preferred.

[0634] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, and compounds described in JP-A-2006-342166.

[0635] Preferred oxime compounds include, for example, compounds of the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the curable resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of >C=NOC(=O)- in the molecule.

[0636] [Chemical formula 26]

[0637]

[0638] Among the commercial products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used. In addition, oxime compounds of the following structures can also be used.

[0639] [Chemical formula 27]

[0640]

[0641] As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466 and compounds described in Japanese Patent No. 06636081.

[0642] As the photopolymerization initiator, an oxime compound having a carbazole ring and a skeleton in which at least one benzene ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013 / 083505.

[0643] In addition, oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of JP-A-2014-500852, and compound (C-3) described in paragraph 0101 of JP-A-2013-164471.

[0644] As the most preferable oxime compound, there can be mentioned an oxime compound having a specific substituent as disclosed in JP-A-2007-269779 or an oxime compound having a thioaryl group as disclosed in JP-A-2009-191061.

[0645] From the viewpoint of exposure sensitivity, the preferred photoradical polymerization initiator is a compound selected from trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0646] Further preferred photoradical polymerization initiators are further preferably trihalomethyl triazine compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds, and are at least one compound selected from trihalomethyl triazine compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds. It is further preferred to use metallocene compounds or oxime compounds, and oxime compounds are further preferred.

[0647] In addition, the photoradical polymerization initiator may also include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), 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 ring condensation of an aromatic ring with an alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin, benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, compounds represented by the following formula (I) may also be used.

[0648] [Chemical formula 28]

[0649]

[0650] In formula (I), R I00 is phenyl or biphenyl substituted with at least one of an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, R I01 is a group represented by formula (II) or is I00 The same group, R I02 ~R I04 Each of them is independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[0651] [Chemical formula 29]

[0652]

[0653] In the formula, R I05 ~R I07 R of the above formula (I) I02 ~R I04 same.

[0654] Furthermore, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used.

[0655] When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and further preferably 1.0 to 10% by mass relative to the total solid content of the curable resin composition of the present invention. The photopolymerization initiator may contain only one or more than one. When containing two or more photopolymerization initiators, the total amount is preferably within the above range.

[0656] [Photoacid generator]

[0657] Furthermore, the curable resin composition of the present invention may contain a photoacid generator as a photosensitizer.

[0658] The photoacid generator is not particularly limited as long as it generates an acid upon exposure, and examples thereof include quinonediazide compounds, onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts, and sulfonate compounds such as imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzylsulfonate.

[0659] Examples of the quinonediazide compound include a quinonediazide sulfonic acid ester bonded to a polyhydroxy compound, a quinonediazide sulfonic acid sulfonamide bonded to a polyamino compound, a quinonediazide sulfonic acid bonded to a polyhydroxypolyamino compound via at least one of an ester bond and a sulfonamide bond, etc. In the present invention, for example, preferably 50 mol% or more of the entire functional group of these polyhydroxy compounds or polyamino compounds is substituted with quinonediazide.

[0660] In the present invention, as quinonediazide, at least one of 5-naphthoquinonediazidesulfonyl and 4-naphthoquinonediazidesulfonyl can be preferably used. 4-naphthoquinonediazidesulfonyl ester compound has absorption in the i-ray region of mercury lamp and is suitable for i-ray exposure. The absorption of 5-naphthoquinonediazidesulfonyl ester compound extends to the g-ray region of mercury lamp and is suitable for g-ray exposure. In the present invention, it is preferred to select 4-naphthoquinonediazidesulfonyl ester compound and 5-naphthoquinonediazidesulfonyl ester compound according to the exposure wavelength. In addition, the same molecule may contain a naphthoquinonediazidesulfonyl ester compound having a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group, or may contain a 4-naphthoquinonediazidesulfonyl ester compound and a 5-naphthoquinonediazidesulfonyl ester compound.

[0661] The naphthoquinonediazide compounds can be synthesized by an esterification reaction of a compound having a phenolic hydroxyl group and a quinonediazidesulfonyl compound, or by a known method. By using these naphthoquinonediazide compounds, the resolution, sensitivity, and residual film rate can be further improved.

[0662] Examples of the naphthoquinonediazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds thereof.

[0663] Examples of the onium salt compound or the sulfonate compound include compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.

[0664] In addition, commercial products can be used as the photoacid generator, and examples of commercial products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638, and WPAG-699 (all manufactured by FFUJIFILM Wako Pure Chemical Corporation).

[0665] When a photoacid generator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 2 to 15% by mass relative to the total solid content of the curable resin composition of the present invention. The photoacid generator may contain only one type or two or more types. When two or more photoacid generators are contained, the total amount is preferably within the above range.

[0666] <Thermal polymerization initiator>

[0667] The curable resin composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, a polymerization reaction of a specific resin and a polymerizable compound can also be carried out in the heating step described later, thereby further improving chemical resistance.

[0668] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

[0669] When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 5 to 15% by mass relative to the total solid content of the curable resin composition of the present invention. The thermal polymerization initiator may contain only one or more than one. When containing two or more thermal polymerization initiators, the total amount is preferably within the above range.

[0670] <Thermal Acid Generator>

[0671] The curable resin composition of the present invention may contain a thermal acid generator as a polymerization initiator.

[0672] The thermal acid generator has the effect of generating an acid by heating and promoting a crosslinking reaction of at least one compound selected from compounds having a methylol group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound, or a methylol group contained in a specific resin.

[0673] Furthermore, when the curable resin composition of the present invention contains a thermal acid generator, it is preferred that the specific resin contains a methylol group or an alkoxymethyl group as a polymerizable group.

[0674] The thermal decomposition starting temperature of the thermal acid generator is preferably 50° C. to 270° C., more preferably 50° C. to 250° C. Furthermore, it is preferred to select a thermal acid generator that does not generate acid when the curable resin composition is applied to a substrate and then dried (pre-baking: about 70 to 140° C.), but generates acid when finally heated (curing: about 100 to 400° C.) after patterning in subsequent exposure and development, because it is possible to suppress a decrease in sensitivity during development.

[0675] The thermal decomposition start temperature was determined as the peak temperature of the lowest exothermic peak when the thermal acid generator was heated to 500° C. at 5° C. / min in a pressure-resistant capsule.

[0676] Examples of the instrument used when measuring the thermal decomposition starting temperature include Q2000 (manufactured by TA Instruments).

[0677] The acid generated from the thermal acid generator is preferably a strong acid, for example, aromatic sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or haloalkanesulfonic acids such as trifluoromethanesulfonic acid, etc. Examples of such thermal acid generators include those described in paragraph 0055 of JP-A-2013-072935.

[0678] Among them, from the viewpoint of less residue in the cured film and less deterioration of the physical properties of the cured film, it is more preferable to generate an alkanesulfonic acid having 1 to 4 carbon atoms or a haloalkanesulfonic acid having 1 to 4 carbon atoms. As the thermal acid generator, methanesulfonic acid (4-hydroxyphenyl) dimethyl sulfonium salt, methanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl) dimethyl sulfonium salt, methanesulfonic acid benzyl (4-hydroxyphenyl) methyl sulfonium salt, methanesulfonic acid benzyl (4-((methoxycarbonyl)oxy)phenyl) methyl sulfonium salt, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium salt, trifluoromethanesulfonic acid (4 trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)methylsulfonium salt, trifluoromethanesulfonic acid benzyl(4-hydroxyphenyl)methylsulfonium salt, trifluoromethanesulfonic acid benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium salt, trifluoromethanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium salt, trifluoromethanesulfonic acid, 3-(5-(((propanesulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl)propionitrile, 2,2-bis(3-(methylsulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

[0679] Furthermore, as the thermal acid generator, the compounds described in paragraph 0059 of JP-A-2013-167742 are also preferred.

[0680] The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the specific resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, so the mechanical properties and chemical resistance of the cured film can be further improved. In addition, from the viewpoint of the electrical insulation of the cured film, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less.

[0681] <Polymerizable compounds>

[0682] The curable resin composition of the present invention preferably contains a polymerizable compound.

[0683] In this specification, the compound corresponding to the above-mentioned specific resin is assumed not to correspond to the polymerizable compound.

[0684] As the polymerizable compound, a polyfunctional polymerizable compound is preferred. In the present specification, a polyfunctional polymerizable compound refers to a compound having two or more polymerizable groups.

[0685] Furthermore, as the polymerizable compound, a radical polymerizable compound is preferred, and a compound having two or more radical polymerizable groups is more preferred.

[0686] [Radical polymerizable compound]

[0687] As the polymerizable compound, a free radical polymerizable compound can be used. The free radical polymerizable compound is a compound having a free radical polymerizable group. As the free radical polymerizable group, groups having ethylenically unsaturated bonds such as vinyl, allyl, vinylphenyl, and (meth)acryloyl can be cited. Preferably, the free radical polymerizable group is (meth)acryloyl, and from the viewpoint of reactivity, (meth)acryloyloxy is more preferred.

[0688] The number of radical polymerizable groups possessed by the radical polymerizable compound may be 1 or 2 or more, preferably the radical polymerizable compound has 2 or more radical polymerizable groups, more preferably 3 or more. The upper limit is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

[0689] The molecular weight of the radical polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical polymerizable compound is preferably 100 or more.

[0690] From the viewpoint of developability, the curable resin composition of the present invention preferably contains at least one free radical polymerizable compound having two or more functional groups, more preferably at least one free radical polymerizable compound having three or more functional groups. In addition, it may be a mixture of a free radical polymerizable compound having two or more functional groups and a free radical polymerizable compound having three or more functional groups. For example, the number of functional groups of a polymerizable monomer having two or more functional groups means that the number of free radical polymerizable groups in one molecule is two or more.

[0691] As specific examples of free radical polymerizable compounds, unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides can be cited, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides with affinity substituents such as hydroxyl or amino, thiol and monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids can also be preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides with dissociable substituents such as halogen or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, the unsaturated carboxylic acid may be replaced by a compound group consisting of unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. As a specific example, reference may be made to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, and these contents are incorporated into this specification.

[0692] Furthermore, the radical polymerizable compound is preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trimethylolpropane tri(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, glycerol or trimethylolethane, etc., which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the obtained compound. Compounds obtained by esterification, such as (meth) acrylate urethanes described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193, polyester acrylates described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 52-030490, epoxy acrylates as reaction products of epoxy resin and (meth) acrylic acid, and multifunctional acrylates or methacrylates and mixtures thereof. In addition, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. In addition, multifunctional (meth) acrylates obtained by reacting compounds having a cyclic ether group and an ethylenically unsaturated bond such as (meth) acrylate with a multifunctional carboxylic acid can also be cited.

[0693] Furthermore, as preferred radical polymerizable compounds other than the above, compounds having a fluorene ring and having two or more groups containing ethylenically unsaturated bonds, or cardo resins described in JP-A-2010-160418, JP-A-2010-129825, and JP-4364216 may be used.

[0694] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, or vinylphosphonic acid compounds described in Japanese Patent Publication No. 02-025493 can also be cited. In addition, compounds containing perfluoroalkyl groups described in Japanese Patent Publication No. 61-022048 can also be used. Furthermore, those introduced 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.

[0695] In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and compounds described in paragraphs 0087 to 0131 of WO-2015 / 199219 can also be preferably used, and the contents thereof are incorporated into the present specification.

[0696] In Japanese Patent Application Laid-Open No. 10-062986, compounds described as formula (1) and formula (2) together with specific examples thereof can also be used as radical polymerizable compounds. These compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then subjecting it to (meth)acrylic esterification.

[0697] Furthermore, compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as other radical polymerizable compounds, and these contents are incorporated into the present specification.

[0698] As the radical polymerizable compound, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

[0699] Examples of commercially available radical polymerizable compounds include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer Company, Inc., SR-209, 231, and 239, a bifunctional methyl acrylate having four vinyloxy chains, manufactured by Sartomer Company, Inc., DPCA-60, a hexafunctional acrylate having six pentyloxy chains, manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having three isobutyloxy chains, 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.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and NK ester 4G (manufactured by NK ester M-9300 and NK ester A-9300). Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOFCORPORATION), etc.

[0700] As free radical polymerizable compounds, urethane acrylates described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418 are also preferred. Furthermore, as the radical polymerizable compound, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 can also be used.

[0701] The radical polymerizable compound may be a radical polymerizable compound having an acid group such as a carboxyl group or a phosphoric acid group. Preferably, the radical polymerizable compound having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably, a radical polymerizable compound having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. It is particularly preferred that among the radical polymerizable compounds having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is a compound of pentaerythritol or dipentaerythritol. As commercially available products, for example, as polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd., M-510, M-520, etc. can be cited.

[0702] The preferred acid value of the radical polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. As long as the acid value of the radical polymerizable compound is within the above range, the operability in manufacturing is excellent, and further the developability is excellent. In addition, the polymerizability is good. In addition, from the viewpoint of the developing speed during alkaline development, the preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. The above acid value is measured according to the description of JIS K 0070:1992.

[0703] Regarding the curable resin composition of the present invention, from the viewpoint of suppressing warpage with the control of the elastic modulus of the cured film, monofunctional free radical polymerizable compounds can be preferably used as free radical polymerizable compounds. As monofunctional free radical polymerizable compounds, preferably 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, (meth) acrylate glycidyl, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and other (meth) acrylic acid derivatives, N-vinyl pyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, allyl glycidyl ether, diallyl phthalate, trimellitic acid triallyl ester and other allyl compounds are used. The monofunctional radical polymerizable compound is preferably a compound having a boiling point of 100° C. or higher at normal pressure in order to suppress volatilization before exposure. In addition, from the viewpoint of pattern resolution and film stretchability, it is also preferable to use a bifunctional methacrylate or acrylate.

[0704] As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, etc. can be used. Alkene acid ester, dimethylol tricyclodecane diacrylate, dimethylol tricyclodecane dimethacrylate, the EO (ethylene oxide) adduct diacrylate of bisphenol A, the EO adduct dimethacrylate of bisphenol A, the PO (propylene oxide) adduct diacrylate of bisphenol A, the PO adduct dimethacrylate of bisphenol A, 2 hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, 2 functional acrylates with other urethane bonds, 2 functional methacrylates with urethane bonds. These can be mixed and used in two or more according to needs. In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate and the formula weight of polyethylene glycol chain is about 200.

[0705] [Polymerizable compounds other than the above-mentioned radically polymerizable compounds]

[0706] The curable resin composition of the present invention may further contain polymerizable compounds other than the above-mentioned free radical polymerizable compounds. Examples of polymerizable compounds other than the above-mentioned free radical polymerizable compounds include compounds having a methylol group, an alkoxymethyl group or an acyloxymethyl group; epoxy compounds; oxetane compounds; and benzoxazine compounds.

[0707] -Compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group-

[0708] As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), formula (AM4) or formula (AM5) is preferred.

[0709] [Chemical formula 30]

[0710]

[0711] (wherein, t represents an integer from 1 to 20, R 104 represents a t-valent organic group having 1 to 200 carbon atoms, R 105 Indicates -OR 106 or-OCO-R 107 The group represented by R 106 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, R 107 It represents an organic group having 1 to 10 carbon atoms.

[0712] [Chemical formula 31]

[0713]

[0714] (Where R 404 represents a divalent organic group having 1 to 200 carbon atoms, R 405 Indicates -OR 406 or-OCO-R 407 The group represented by R 406 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, R 407 It represents an organic group having 1 to 10 carbon atoms.

[0715] [Chemical formula 32]

[0716]

[0717] (wherein, u represents an integer from 3 to 8, R 504 represents a u-valent organic group having 1 to 200 carbon atoms, R 505 Indicates -OR 506 or-OCO-R 507 The group represented by R 506 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, R 507 It represents an organic group having 1 to 10 carbon atoms.

[0718] Specific examples of the compound represented by formula (AM4) include 46DMOC, 46DMOEP (these are product names, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (these are product names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (product name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol (2,6-dimethoxymethyl-4-tert-butylphenol), 2,6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacetoxymethyl-p-cresol (2,6-diacetoxymethyl-p-cresol), etc.

[0719] Specific examples of the compound represented by formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (product name, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALACMW-100LM (the above are product names, manufactured by Sanwa Chemical Co., Ltd.).

[0720] -Epoxy compounds (compounds having epoxy groups)-

[0721] As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a crosslinking reaction below 200°C and does not produce a dehydration reaction caused by crosslinking, so it is not easy to cause film shrinkage. Therefore, containing an epoxy compound is effective in suppressing low-temperature curing and warping of the curable resin composition.

[0722] The epoxy compound preferably contains a polyethylene oxide group. Therefore, the elastic modulus is further reduced and warping can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and preferably the number of repeating units is 2 to 15.

[0723] Examples of epoxy compounds include bisphenol A epoxy resins; bisphenol F epoxy resins; alkylene glycol epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol epoxy resins such as polypropylene glycol diglycidyl ether; epoxy-containing polysiloxanes such as polymethyl (glycidyloxypropyl) siloxanes, epoxy resins of isocyanuric acid derivatives such as glycidyl isocyanurate, and epoxy resins of glycoluril derivatives such as N,N',N",N"'-tetraglycidyl glycoluril, but are not limited to these. In addition, from the viewpoint of chemical resistance, the above-mentioned isocyanuric acid derivatives or glycoluril derivatives are preferred. It is speculated that this is because aprotic and highly polar structures such as ring structures such as isocyanuric acid ring structures and glycoluril structures are effective for chemical resistance.

[0724] Specifically, there can be mentioned 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) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA- 4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, 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, EPICLON (registered trademark) N-740, RIKARESIN (registered trademark) BEO-20E (the above are product names, DIC CORPORATION), RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (product names, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, manufactured by ADEKA CORPORATION), TG-G, MA-DGIC, DA-MGIC (the above are product names, manufactured by SHIKOKU CHEMICALS CORPORATION), etc. Among them, epoxy resins containing a polyethylene oxide group are preferred from the viewpoint of suppressing warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E are preferred because they contain a polyethylene oxide group.

[0725] -Oxetane compound (compound having an oxetane group)-

[0726] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As specific examples, ARON OXETANE series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

[0727] -Benzoxazine compound (compound having a polybenzoxazolyl group)-

[0728] The benzoxazine compound is preferred because it causes a cross-linking reaction by a ring-opening addition reaction and does not produce outgassing during curing, thereby further reducing thermal shrinkage and suppressing the occurrence of warpage.

[0729] Preferred examples of benzoxazine compounds include Ba-type benzoxazine, Bm-type benzoxazine, Pd-type benzoxazine, Fa-type benzoxazine (these are product names, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

[0730] The content of the polymerizable compound is preferably greater than 0% by mass and less than 60% by mass relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.

[0731] The polymerizable compound may be used alone or in combination of two or more. When two or more are used simultaneously, the total amount is preferably within the above range.

[0732] <Other resins>

[0733] The curable resin composition of the present invention may contain other resins (hereinafter, also simply referred to as “other resins”) different from the above-mentioned specific resin.

[0734] Examples of the other resins include polyimides of a different type from the specific resin, polyimide precursors of a different type from the specific resin, polysiloxane, resins containing a siloxane structure, epoxy resins, and acrylic resins.

[0735] For example, by further adding an acrylic resin, a composition having excellent coating properties can be obtained, and a cured film having excellent chemical resistance can be obtained.

[0736] For example, by adding an acrylic resin having a high polymerizable group value and a weight average molecular weight of 20,000 or less to the composition instead of or in addition to the polymerizable compound described below, the coating properties of the composition and the chemical resistance of the cured film can be improved.

[0737] [Polyimide (other resins)]

[0738] From the viewpoint of the film strength of the obtained cured film, the polyimide as the other resin preferably contains a repeating unit represented by the above formula (4).

[0739] In the polyimide, the repeating unit represented by the formula (4) may be one type or two or more types. In addition to the repeating unit of the formula (4), the polyimide may contain other types of repeating units.

[0740] One embodiment of the polyimide of the present invention is a polyimide precursor in which 50 mol % or more, further 70 mol % or more, and particularly 90 mol % or more of the total repeating units are repeating units represented by formula (4). The upper limit is practically 100 mol % or less.

[0741] The weight average molecular weight (Mw) of the polyimide is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

[0742] The molecular weight dispersion of the polyimide is preferably 1.5 to 3.5, more preferably 2 to 3.

[0743] The polyimide can be obtained by cyclizing a polyimide precursor as another resin described later by heating or the like.

[0744] [Polyimide precursor (other resins)]

[0745] From the viewpoint of the film strength of the obtained cured film, it is preferred that the polyimide precursor contains a repeating unit represented by the above formula (1).

[0746] In the polyimide precursor, the repeating unit represented by formula (1) may be one or more. Furthermore, the structural isomers of the repeating unit represented by formula (1) may also be included. Furthermore, in addition to the repeating unit of the above formula (1), the polyimide precursor may also include other types of repeating units.

[0747] One embodiment of the polyimide precursor in the present invention includes a polyimide precursor in which 50 mol % or more, further 70 mol % or more, and particularly 90 mol % or more of the total repeating units are repeating units represented by formula (1). The upper limit is practically 100 mol % or less.

[0748] The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

[0749] The molecular weight dispersion of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

[0750] The polyimide precursor is obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with diamine, and is preferably obtained by halogenating dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting the halogenated dicarboxylic acid or a dicarboxylic acid derivative with diamine.

[0751] In the method for producing a polyimide precursor, it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one kind or two or more kinds.

[0752] The organic solvent can be appropriately selected according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

[0753] It is preferred that a step of precipitating a solid is included when producing a polyimide precursor. Specifically, a solid can be precipitated by precipitating the polyimide precursor in the reaction solution in water and dissolving the polyimide precursor in a solvent such as tetrahydrofuran that can dissolve the polyimide precursor.

[0754] When the curable resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more, relative to the total solid content of the curable resin composition.

[0755] Furthermore, the content of other resins in the curable resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less, relative to the total solid content of the curable resin composition.

[0756] In addition, as a preferred embodiment of the curable resin composition of the present invention, the content of other resins can also be set to a low content. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less relative to the total solid content of the curable resin composition. The lower limit of the above content is not particularly limited as long as it is 0% by mass or more.

[0757] The curable resin composition of the present invention may contain only one type of other resin or two or more types. When containing two or more types, the total amount is preferably within the above range.

[0758] <Onium salt>

[0759] The curable resin composition of the present invention preferably contains an onium salt.

[0760] In particular, when the curable resin composition includes a resin including a repeating unit represented by formula (2-1) or a repeating unit represented by formula (2-4) as the specific resin, the curable resin composition preferably includes a thermal base generator.

[0761] The type of the onium salt is not particularly limited, and preferred examples include ammonium salts, iminium salts, sulfonium salts, iodonium salts, and phosphonium salts.

[0762] Among them, ammonium salts or imide salts are preferred from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts or phosphonium salts are preferred from the viewpoint of compatibility with the polymer.

[0763] Furthermore, the onium salt is a salt of a cation having an onium structure and an anion, and the cation and the anion may be bonded via a covalent bond or may not be bonded via a covalent bond.

[0764] That is, the onium salt may be an intramolecular salt having a cationic part and an anionic part in the same molecular structure, or an intermolecular salt in which a cationic molecule and an anionic molecule, which are different molecules, are ionically bonded, preferably an intermolecular salt. In addition, in the curable resin composition of the present invention, the cationic part or cationic molecule and the anionic part or anionic molecule may be bonded by an ionic bond or may be dissociated.

[0765] The cation in the onium salt is preferably an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation, and more preferably at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation.

[0766] The onium salt used in the present invention may be a thermal base generator.

[0767] The thermal base generator is a compound that generates a base by heating, and examples thereof include acidic compounds that generate a base when heated to 40° C. or higher.

[0768] [Ammonium salt]

[0769] In the present invention, the ammonium salt means a salt of an ammonium cation and an anion.

[0770] -Ammonium cation-

[0771] As the ammonium cation, a quaternary ammonium cation is preferred.

[0772] Furthermore, as the ammonium cation, a cation represented by the following formula (101) is preferred.

[0773] [Chemical formula 33]

[0774]

[0775] In formula (101), R 1 ~R 4 Each independently represents a hydrogen atom or a hydrocarbon group, R 1 ~R 4 At least two of them may be bonded to form a ring.

[0776] In formula (101), preferably R 1 ~R 4 Each of R is independently a hydrocarbon group, more preferably an alkyl group or an aryl group, and further preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. 1 ~R 4 It may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group.

[0777] In R 1 ~R 4 When at least two of the above are bonded to form a ring, the above ring may also contain a hetero atom. Examples of the above hetero atom include a nitrogen atom.

[0778] The ammonium cation is preferably represented by any one of the following formulas (Y1-1) and (Y1-2).

[0779] [Chemical formula 34]

[0780]

[0781] In formula (Y1-1) and (Y1-2), R 101 represents an n-valent organic group, R 1 With R in formula (101) 1 The meaning is the same as Ar 101 and Ar 102 Each independently represents an aryl group, and n represents an integer of 1 or greater.

[0782] In formula (Y1-1), preferably R 101 It is a group obtained by removing n hydrogen atoms from an aliphatic hydrocarbon, an aromatic hydrocarbon, or a structure formed by bonding these, and more preferably a group obtained by removing n hydrogen atoms from a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene, or naphthalene.

[0783] In formula (Y1-1), n ​​is preferably 1 to 4, more preferably 1 or 2, and further preferably 1.

[0784] In formula (Y1-2), Ar is preferably 101 and Ar 102 Each is independently phenyl or naphthyl, more preferably phenyl.

[0785] -Anions-

[0786] As the anion in the ammonium salt, it is preferably selected from one of a carboxylate anion, a phenol anion, a phosphate anion and a sulfate anion, and a carboxylate anion is more preferred because both the stability and thermal decomposition of the salt can be taken into account. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.

[0787] Preferably, the carboxylate anion is an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this embodiment, the stability, curability and developability of the curable resin composition can be further improved. In particular, by using an anion of a divalent carboxylic acid, the stability, curability and developability of the curable resin composition can be further improved.

[0788] The carboxylate anion is preferably represented by the following formula (X1).

[0789] [Chemical formula 35]

[0790]

[0791] In formula (X1), EWG represents an electron withdrawing group.

[0792] In this embodiment, the electron-withdrawing group indicates that the Hammett substituent constant σm represents a positive value. σm is described in detail in Tsuyoshi Tsunoh, Journal of Synthetic Organic Chemistry, Japan, Vol. 23, No. 8 (1965) p. 631-642. In addition, the electron-withdrawing group in this embodiment is not limited to the substituents described in the above literature.

[0793] Examples of substituents in which σm represents a positive value include CF3 group (σm=0.43), CF3C (=O) group (σm=0.63), HC≡C group (σm=0.21), CH2=CH group (σm=0.06), Ac group (σm=0.38), MeOC (=O) group (σm=0.37), MeC (=O)CH=CH group (σm=0.21), PhC (=O) group (σm=0.34), H2NC (=O)CH2 group (σm=0.06), etc. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same).

[0794] It is preferred that EWG is a group represented by the following formulae (EWG-1) to (EWG-6).

[0795] [Chemical formula 36]

[0796]

[0797] In formulas (EWG-1) to (EWG-6), R x1 ~R x3 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group.

[0798] In the present invention, it is preferred that the carboxylate anion is represented by the following formula (XA).

[0799] [Chemical formula 37]

[0800]

[0801] In formula (XA), L 10 represents a single bond or is selected from an alkylene group, an alkenyl group, an aromatic group, -NR X - and the divalent linking group in these combinations, R X represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

[0802] Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetate anion, and an oxalate anion.

[0803] From the viewpoint that the specific resin is easy to cyclize at low temperature and the storage stability of the curable resin composition is easy to improve, the onium salt in the present invention preferably contains an ammonium cation as a cation, and the above-mentioned onium salt contains an anion having a pKa (pKaH) of a conjugate acid of 2.5 or less as an anion, and more preferably contains an anion having a pKa (pKaH) of 1.8 or less.

[0804] The lower limit of the pKa is not particularly limited, but is preferably -3 or more, more preferably -2 or more, from the viewpoint of making it difficult for the generated base to be neutralized and improving the cyclization efficiency of a specific resin or the like.

[0805] As the above-mentioned pKa, the values ​​described in Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Edited by: Braude, EA, Nachod, FC; Academic Press, New York, 1955) or Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 1959) can be referred to. For compounds not described in these documents, the values ​​calculated from the structural formula using the software ACD / pKa (manufactured by ACD / Labs) were used.

[0806] Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto.

[0807] [Chemical formula 38]

[0808]

[0809] [Imine salt]

[0810] In the present invention, the iminium salt means a salt of an iminium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and the preferred embodiments are also the same.

[0811] -Iminium cation-

[0812] As the iminium cation, a pyridinium cation is preferred.

[0813] Furthermore, as the iminium cation, a cation represented by the following formula (102) is also preferred.

[0814] [Chemical formula 39]

[0815]

[0816] In formula (102), R 5 and R 6 Each independently represents a hydrogen atom or a hydrocarbon group, R 7 Represents a hydrocarbon group, R 5 ~R 7 At least two of them may be bonded to form a ring.

[0817] In formula (102), R 5 and R 6 With R in the above formula (101) 1 ~R 4 The meanings are the same and the preferred aspects are also the same.

[0818] In formula (102), preferably R 7 With R 5 and R 6 At least one of them is bonded to form a ring. The above ring may also contain a heteroatom. As the above heteroatom, a nitrogen atom can be mentioned. And, as the above ring, a pyridine ring is preferred.

[0819] The iminium cation is preferably represented by any one of the following formulas (Y1-3) to (Y1-5).

[0820] [Chemical formula 40]

[0821]

[0822] In formulas (Y1-3) to (Y1-5), R 101 represents an n-valent organic group, R 5 With R in formula (102) 5 has the same meaning, R 7 With R in formula (102) 7 , n represents an integer greater than 1, and m represents an integer greater than 0.

[0823] In formula (Y1-3), preferably R 101 It is a group obtained by removing n hydrogen atoms from an aliphatic hydrocarbon, an aromatic hydrocarbon, or a structure formed by bonding these, and more preferably a group obtained by removing n hydrogen atoms from a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene, or naphthalene.

[0824] In formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and further preferably 1.

[0825] In formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and even more preferably 1.

[0826] Specific examples of the imide salt include the following compounds, but the present invention is not limited thereto.

[0827] [Chemical formula 41]

[0828]

[0829] [Sulfonium salt]

[0830] In the present invention, the sulfonium salt refers to a salt of a sulfonium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and preferred embodiments are also the same.

[0831] -Sulfonium cation-

[0832] As the sulfonium cation, a tertiary sulfonium cation is preferred, and a triarylsulfonium cation is more preferred.

[0833] Furthermore, as the sulfonium cation, a cation represented by the following formula (103) is preferred.

[0834] [Chemical formula 42]

[0835]

[0836] In formula (103), R 8 ~R 10 Each independently represents a hydrocarbon group.

[0837] Preferred R 8 ~R 10 Each independently represents an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and further preferably a phenyl group.

[0838] R 8 ~R 10 It may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc. Among them, as a substituent, it is preferred to have an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and further preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0839] R 8 ~R 10 The groups may be the same or different, but are preferably the same from the viewpoint of synthetic suitability.

[0840] [Iodine salt]

[0841] In the present invention, the iodonium salt means a salt of an iodonium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and the preferred embodiments are also the same.

[0842] -Ion cation-

[0843] As the iodonium cation, a diaryliodonium cation is preferred.

[0844] Furthermore, as the iodonium cation, a cation represented by the following formula (104) is preferred.

[0845] [Chemical formula 43]

[0846]

[0847] In formula (104), R 11 and R 12 Each independently represents a hydrocarbon group.

[0848] Preferred R 11 and R 12 Each independently represents an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and further preferably a phenyl group.

[0849] R 11 and R 12 It may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc. Among them, as a substituent, it is preferred to have an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and further preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0850] R 11 and R 12 The groups may be the same or different, but are preferably the same from the viewpoint of synthetic suitability.

[0851] [Phosphonium salts]

[0852] In the present invention, the phosphonium salt means a salt of a phosphonium cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and preferred embodiments are also the same.

[0853] -Phosphonium cation-

[0854] As the phosphonium cation, a quaternary phosphonium cation is preferred, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation.

[0855] Furthermore, as the phosphonium cation, a cation represented by the following formula (105) is preferred.

[0856] [Chemical formula 44]

[0857]

[0858] In formula (105), R 13 ~R 16 Each independently represents a hydrogen atom or a hydrocarbon group.

[0859] Preferred R 13 ~R 16 Each independently represents an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and further preferably a phenyl group.

[0860] R 13 ~R 16 It may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc. Among them, as a substituent, it is preferred to have an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and further preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0861] R 13 ~R 16 The groups may be the same or different, but are preferably the same from the viewpoint of synthetic suitability.

[0862] When the curable resin composition of the present invention includes an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, and can be 5% by mass or less, or 4% by mass or less.

[0863] The onium salt can be used alone or in combination of two or more. When two or more are used, the total amount is preferably within the above range.

[0864] <Thermal alkali generator>

[0865] The curable resin composition of the present invention may contain a thermal base generator.

[0866] In particular, when the curable resin composition includes a resin including a repeating unit represented by formula (2-1) or a repeating unit represented by formula (2-4) as the specific resin, the curable resin composition preferably includes a thermal base generator.

[0867] The thermal base generator may be a compound corresponding to the above-mentioned onium salt, or may be another thermal base generator other than the above-mentioned onium salt.

[0868] As other thermal base generating agents, nonionic thermal base generating agents can be mentioned.

[0869] Examples of the nonionic thermal base generator include compounds represented by formula (B1) or formula (B2).

[0870] [Chemical formula 45]

[0871]

[0872] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 are independently an organic group without a tertiary amine structure, a halogen atom or a hydrogen atom. 1 and Rb 2 will not become a hydrogen atom at the same time. 1 , Rb 2 and Rb 3 In addition, in this specification, the tertiary amine structure refers to a structure in which the three bonds of the trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, when the carbon atom to which the bond is formed is a carbon atom that forms a carbonyl group, that is, when an amide group is formed together with the nitrogen atom, it is not limited to this.

[0873] In formula (B1) and formula (B2), Rb is preferably 1 , Rb 2 and Rb 3 At least one of the rings contains a cyclic structure, and more preferably at least two of the rings contain a cyclic structure. As the cyclic structure, it can be any one of a monocyclic ring and a condensed ring, preferably a monocyclic ring or a condensed ring formed by condensing two monocyclic rings. Preferably, the monocyclic ring is a 5-membered ring or a 6-membered ring, preferably a 6-membered ring. Preferably, the monocyclic ring is a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.

[0874] More specifically, Rb is preferably 1 and Rb 2 It is a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12). These groups may have a substituent within the range in which the effect of the present invention is exerted. Rb 1 With Rb 2 They may be bonded to each other to form a ring. As the ring formed, a 4- to 7-membered nitrogen-containing heterocyclic ring is preferred. In particular, Rb is preferred 1 and Rb 2 It is a linear, branched or cyclic alkyl group which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), more preferably a cycloalkyl group which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), and further preferably a cyclohexyl group which may have a substituent.

[0875] As Rb 3 , examples include alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 12, and further preferably 2 to 6), aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), aralkenyl groups (preferably having 8 to 24 carbon atoms, more preferably 8 to 20, and further preferably 8 to 16), alkoxy groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), aryloxy groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), and aralkyloxy groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12). Among these, cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18, and further preferably 3 to 12), aralkenyl groups, and aralkyloxy groups are preferred. Rb 3 The compound may further have a substituent within a range where the effects of the present invention are exhibited.

[0876] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

[0877] [Chemical formula 46]

[0878]

[0879] In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 Respectively with Rb in formula (B1) 1 and Rb 2 same.

[0880] R 13 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and further preferably 3 to 12), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), and may have a substituent within the range in which the effects of the present invention are exerted. Among them, Rb is preferred 13 It is an aralkyl group.

[0881] R 33 and Rb 34 Each of them independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), and is preferably a hydrogen atom.

[0882] R 35 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), and an aryl group is preferred.

[0883] Furthermore, it is also preferred that the compound represented by formula (B1-1) is a compound represented by formula (B1-1a).

[0884] [Chemical formula 47]

[0885]

[0886] R 11 and Rb 12 With Rb in formula (B1-1) 11 and Rb 12 have the same meaning.

[0887] R 15 and Rb 16 It is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and further preferably 2 to 3), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11), and preferably a hydrogen atom or a methyl group.

[0888] R 17 It is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 3 to 8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10, and further preferably 3 to 8), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 12), and an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 12), among which an aryl group is preferred.

[0889] The molecular weight of the nonionic thermal base generator is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

[0890] Among the above-mentioned onium salts, specific examples of the compound as a thermal base generator and specific examples of other thermal base generators include the following compounds.

[0891] [Chemical formula 48]

[0892]

[0893] [Chemical formula 49]

[0894]

[0895] [Chemical formula 50]

[0896]

[0897] The content of the thermal base generator is preferably 0.1 to 50% by mass relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. The thermal base generator can be used alone or in combination. When two or more types are used, the total amount is preferably within the above range.

[0898] <Compounds having a sulfonamide structure, compounds having a thiourea structure>

[0899] From the viewpoint of improving the adhesion of the obtained pattern (cured film) to the substrate, the photosensitive resin composition of the present invention preferably further contains at least one compound selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure.

[0900] In particular, when the curable resin composition includes a specific resin containing at least one repeating unit selected from the repeating unit represented by formula (2-2) and the repeating unit represented by formula (2-3) as the specific resin, it is preferred to further contain at least one compound selected from the compound having a sulfonamide structure and the compound having a thiourea structure.

[0901] [Compounds having a sulfonamide structure]

[0902] The sulfonamide structure is a structure represented by the following formula (S-1).

[0903] [Chemical formula 51]

[0904]

[0905] In formula (S-1), R represents a hydrogen atom or an organic group, and R may be bonded to other structures to form a ring structure, and * each independently represents a bonding site to other structures.

[0906] Preferably, the above R is the same as R in the following formula (S-2): 2 Same group.

[0907] The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but is preferably a compound having one sulfonamide structure.

[0908] The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).

[0909] [Chemical formula 52]

[0910]

[0911] In formula (S-2), R 1 , R 2 and R 3 Each independently represents a hydrogen atom or a monovalent organic group, R 1 , R 2 and R 3 Two or more of them may be bonded to each other to form a ring structure.

[0912] Preferred R 1 , R 2 and R 3 Each independently is a monovalent organic group.

[0913] As R 1 , R 2 and R 3 Examples of the group include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group obtained by combining two or more of these groups.

[0914] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl.

[0915] The cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0916] The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group.

[0917] The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, and more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.

[0918] The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl.

[0919] Examples of the heterocyclic group include a group obtained by removing a hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyranyl ring, a triazine ring, and the like.

[0920] Among them, R is preferred 1 is an aromatic group and R 2 and R 3 A compound wherein each is independently a hydrogen atom or an alkyl group.

[0921] Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1-sulfonamide, naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethanesulfonamide.

[0922] [Compounds having a thiourea structure]

[0923] The thiourea structure is a structure represented by the following formula (T-1).

[0924] [Chemical formula 53]

[0925]

[0926] In formula (T-1), R 4 and R 5 Each independently represents a hydrogen atom or a monovalent organic group, R 4 and R 5 Can bond to form a ring structure, R 4 It can bond with other structures bonded by * to form a ring structure, R 5 It may bond with other structures bonded with * to form a ring structure, and * each independently represents a bonding site with other structures.

[0927] Preferred R 4 and R 5 are each independently a hydrogen atom.

[0928] As R 4 and R 5 Examples of the group include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group obtained by combining two or more of these groups.

[0929] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl.

[0930] The cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0931] The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group.

[0932] The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, and more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.

[0933] The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl.

[0934] Examples of the heterocyclic group include a group obtained by removing a hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperidine ring, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyranyl ring, a triazine ring, and the like.

[0935] The compound having a thiourea structure may be a compound having two or more thiourea structures, but is preferably a compound having one thiourea structure.

[0936] The compound having a thiourea structure is preferably a compound represented by the following formula (T-2).

[0937] [Chemical formula 54]

[0938]

[0939] In formula (T-2), R 4 ~R 7 Each independently represents a hydrogen atom or a monovalent organic group, R 4 ~R 7 At least two of the may be bonded to each other to form a ring structure.

[0940] In formula (T-2), R 4 and R 5 With R in formula (T-1) 4 and R 5 The meanings are the same and the preferred aspects are also the same.

[0941] In formula (T-2), preferably R 6 and R 7 Each independently is a monovalent organic group.

[0942] In formula (T-2), R 6 and R 7 The preferred embodiment of the monovalent organic group in formula (T-1) is the same as R 4 and R 5 The preferred embodiment of the monovalent organic group in is the same as that in the above examples.

[0943] Examples of the compound having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1-adamantylthiourea, N-benzoylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea, N,N-diphenylthiourea, ethylenethiourea (2-imidazolinethione), carbimazole, and 1,3-dimethyl-2-thiohydantoin.

[0944] The total content of the compound having a sulfonamide structure and the compound having a thiourea structure is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.2 to 3% by mass based on the total mass of the photosensitive resin composition of the present invention.

[0945] The photosensitive resin composition of the present invention may contain only one compound selected from compounds having a sulfonamide structure and compounds having a thiourea structure, or may contain two or more compounds. When only one compound is contained, the content of the compound is within the above range, and when two or more compounds are contained, the total amount thereof is preferably within the above range.

[0946] <Migration inhibitor>

[0947] The curable resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, it is possible to effectively suppress the migration of metal ions originating from the metal layer (metal wiring) into the curable resin composition layer.

[0948] The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds having thiourea and sulfhydryl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 5-methylbenzotriazole, and 4-methylbenzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

[0949] Alternatively, an ion capture agent that captures anions such as halogen ions may also be used.

[0950] As other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Laid-Open No. 2011-059656, the compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015 / 199219, etc. can be used.

[0951] Specific examples of the migration inhibitor include the following compounds.

[0952] [Chemical formula 55]

[0953]

[0954] When the curable resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and further preferably 0.1 to 1.0% by mass based on the total solid content of the curable resin composition.

[0955] The migration inhibitor may be one kind or two or more kinds. When there are two or more kinds of migration inhibitors, the total amount is preferably within the above range.

[0956] <Polymerization inhibitor>

[0957] The curable resin composition of the present invention preferably contains a polymerization inhibitor.

[0958] As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, 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-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminotetraacetic acid, 1,2-cyclohexanediaminotetraacetic acid, glycol ether diaminotetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, Phenol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N-nitrosophenylhydroxylamine first cerium salt, 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-tetramethylpiperidinium 1-oxyl free radical, phenothiazine, 1,1-diphenyl-2-pyrrolehydrazine, dibutyl dithiocarbonate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. Furthermore, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO 2015 / 125469 can also be used.

[0959] Furthermore, the following compounds (Me is methyl group) can be used.

[0960] [Chemical formula 56]

[0961]

[0962] When the curable resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 20.0% by mass, preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and further preferably 0.05 to 2.5% by mass, relative to the total solid content of the curable resin composition of the present invention.

[0963] The polymerization inhibitor may be one kind or two or more kinds. When there are two or more kinds of polymerization inhibitors, the total amount is preferably within the above range.

[0964] <Metal Adhesion Improver>

[0965] The curable resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes or wiring, etc. Examples of the metal adhesion improver include silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having thiourea, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0966] Examples of silane coupling agents include compounds described in paragraph 0167 of International Publication No. 2015 / 199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication No. 2011 / 080992, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, and compounds described in paragraph 0055 of International Publication No. 2014 / 097594. It is also preferred to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358. Furthermore, it is also preferable to use the following compounds as the silane coupling agent: In the following formula, Et represents an ethyl group.

[0967] [Chemical formula 57]

[0968]

[0969] Furthermore, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used. Examples of other silane coupling agents include vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, 3-glycidoxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl Trimethoxysilane, N-2-(aminoethyl)-3-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-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0970] Examples of the aluminum-based adhesion promoter include aluminum tris(ethyl acetoacetate), aluminum tris(acetylacetonate), and aluminum tris(ethyl acetoacetonate diisopropylate.

[0971] The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the specific resin, more preferably in the range of 0.5 to 15 parts by mass, and further preferably in the range of 0.5 to 5 parts by mass. By setting it to above the above lower limit, the adhesion between the cured film and the metal layer after the curing step becomes good, and by setting it to below the above upper limit, the heat resistance and mechanical properties of the cured film after the curing step become good. The metal adhesion improver can be only one or more than two. When using two or more, the total amount is preferably within the above range.

[0972] <Other additives>

[0973] The curable resin composition of the present invention can be formulated with various additives as needed, such as sensitizers such as N-phenyldiethanolamine, photobase generators, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. When these additives are formulated, the total amount is preferably set to 3% by mass or less of the solid content of the curable resin composition.

[0974] [Sensitizer]

[0975] The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in an electronically excited state contacts with a thermal curing accelerator, a thermal free radical polymerization initiator, a photo-free radical polymerization initiator, etc., thereby generating electron transfer, energy transfer, heat generation, etc. Therefore, the thermal curing accelerator, the thermal free radical polymerization initiator, and the photo-free radical polymerization initiator cause chemical changes and decompose, and generate free radicals, acids, or bases.

[0976] Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine.

[0977] Furthermore, a sensitizing dye may be used as the sensitizer.

[0978] For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and the contents are incorporated into this specification.

[0979] When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and further preferably 0.5 to 10% by mass relative to the total solid content of the curable resin composition of the present invention. The sensitizer may be used alone or in combination of two or more.

[0980] [Chain transfer agent]

[0981] The curable resin composition of the present invention may have a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Society of Polymer Science, Japan, 2005) pages 683-684. As chain transfer agents, for example, a compound group having SH, PH, SiH and GeH in the molecule is used. These can generate free radicals by supplying hydrogen to low-activity free radicals or can generate free radicals by deprotonation after being oxidized. In particular, thiol compounds can be preferably used.

[0982] Furthermore, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219 can also be used.

[0983] When the curable resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and further preferably 1 to 5 parts by mass relative to 100 parts by mass of the total solid content of the curable resin composition of the present invention. The chain transfer agent may be only one or more than two. When there are two or more chain transfer agents, the total amount is preferably within the above range.

[0984] [Surfactant]

[0985] From the viewpoint of further improving the coating property, various surfactants can be added to the curable resin composition of the present invention. As surfactants, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and polysilicone-based surfactants can be used. In addition, the following surfactants are also preferred. In the following formula, the brackets representing the repeating units of the main chain represent the content (mol %) of each repeating unit, and the brackets representing the repeating units of the side chains represent the number of repetitions of each repeating unit.

[0986] [Chemical formula 58]

[0987]

[0988] Furthermore, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International Publication No. 2015 / 199219 can also be used.

[0989] Examples of the fluorine-based surfactant include 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, Novell FC4430, Novell FC4432 (all manufactured by 3M Japan Limited), Surflon S-382, 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 OMNOVA Solutions Inc.), etc. The fluorine-based surfactant can also use the compounds described in paragraphs 0015 to 0158 of Japanese Unexamined Patent Publication No. 2015-117327 and the compounds described in paragraphs 0117 to 0132 of Japanese Unexamined Patent Publication No. 2011-132503. A block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-089090.

[0990] The fluorine-based surfactant can also preferably be a fluorine-containing polymer compound comprising a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy groups).

[0991] Fluorine-based surfactants can also be used as fluorine-containing polymers having ethylenically unsaturated groups on the side chains. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Publication No. 2010-164965, such as MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC CORPORATION.

[0992] The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. In terms of uniformity of the thickness of the coating film or liquid saving, a fluorine-based surfactant having a fluorine content within this range is effective and has good solubility in the composition.

[0993] Examples of the silicone surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive performance Materials Inc.), KP341, KF6001, and KF6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, and BYK330 (all manufactured by BYK Chemie GmbH).

[0994] Examples of the hydrocarbon-based surfactant 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 & FAT CO., LTD.).

[0995] Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic 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 Limited.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

[0996] Specific examples of the cationic surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by KYOEISHA CHEMICAL Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0997] Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured by Sanyo Kasei Co., Ltd.).

[0998] When the curable resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass % relative to the total solid content of the curable resin composition of the present invention, and more preferably 0.005 to 1.0 mass %. The surfactant may be only one or more than two. When there are two or more surfactants, the total amount is preferably within the above range.

[0999] [Higher fatty acid derivatives]

[1000] In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the curable resin composition of the present invention so as to localize on the surface of the curable resin composition during the drying process after coating.

[1001] Furthermore, as the higher fatty acid derivatives, compounds described in paragraph 0155 of International Publication No. 2015 / 199219 can also be used.

[1002] When the curable resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the curable resin composition of the present invention. The higher fatty acid derivative may be only one or more than two. When there are two or more higher fatty acid derivatives, the total amount is preferably within the above range.

[1003] [Inorganic particles]

[1004] 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, and the like.

[1005] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm.

[1006] When the average particle diameter of the inorganic particles is large, the mechanical properties of the cured film may be deteriorated. Also, when the average particle diameter of the inorganic particles exceeds 2.0 μm, the resolution may be reduced due to scattering of exposure light.

[1007] [Ultraviolet light absorber]

[1008] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, or other ultraviolet absorber may be used.

[1009] Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Examples of the benzotriazole ultraviolet absorber 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'-t-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.

[1010] Examples of the substituted acrylonitrile-based ultraviolet absorber 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-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; Bis(hydroxyphenyl)triazine compounds such as 2,4-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-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine; and the like.

[1011] In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.

[1012] The composition of the present invention may or may not contain a UV absorber, but when contained, the content of the UV absorber is preferably 0.001% by mass to 1% by mass, more preferably 0.01% by mass to 0.1% by mass, relative to the total solid content of the composition of the present invention.

[1013] [Organotitanium compounds]

[1014] The resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains the organic titanium compound, a resin layer having excellent chemical resistance can be formed even when the resin composition is cured at a low temperature.

[1015] Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.

[1016] Specific examples of the organic titanium compound are shown in the following I) to VII):

[1017] I) Titanium chelate compounds: Among them, titanium chelate compounds having two or more alkoxy groups are more preferred because the storage stability of the negative photosensitive resin composition is excellent and a good cured pattern can be obtained. Specific examples include diisopropyl bis(triethanolamine)titanium, di(n-butyl alcohol)bis(2,4-pentanedionetitanium), diisopropyl bis(2,4-pentanedione)titanium, diisopropyl bis(tetramethylheptanedione)titanium, diisopropyl bis(ethyl acetoacetate)titanium, and the like.

[1018] II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonoxide), titanium tetra(n-propoxide), titanium tetrastearylate, titanium tetra[bis{2,2-(allyloxymethyl)butoxide}], and the like.

[1019] III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc.

[1020] IV) Monoalkoxy titanium compound: for example, tris(dioctyl phosphate)titanium isopropoxide, tris(dodecylphenyl sulfonate)titanium isopropoxide, and the like.

[1021] V) Titanium oxide compound: for example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), titanium phthalocyanine oxide, and the like.

[1022] VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate.

[1023] VII) Titanate coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[1024] Among them, as the organic titanium compound, it is preferred to select at least one compound selected from the above-mentioned I) titanium chelate compound, II) tetraalkoxy titanium compound and III) titanocene compound from the viewpoint of exerting better chemical resistance. In particular, diisopropyl bis(ethyl acetoacetate) titanium, tetra(n-butoxide) titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium are preferred.

[1025] When an organic titanium compound is added, the amount thereof is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the precursor of the cyclized resin. When the amount is 0.05 parts by mass or more, the obtained cured pattern exhibits good heat resistance and chemical resistance, while when the amount is 10 parts by mass or less, the storage stability of the composition is excellent.

[1026] [Antioxidant]

[1027] The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the elongation characteristics of the cured film and the adhesion to the metal material can be improved. As the antioxidant, phenol compounds, phosphite compounds and thioether compounds can be mentioned. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. As a preferred phenol compound, a hindered phenol compound can be mentioned. Preferably, a compound has a substituent at a position adjacent to the phenolic hydroxyl group (ortho position). As the substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, it is also preferred that the antioxidant is a compound having a phenol group and a phosphite group in the same molecule. In addition, the antioxidant can also preferably use a phosphorus-based antioxidant. Examples of the phosphorus-based antioxidant include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl)phosphite. Commercially available antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80, and Adekastab AO-330 (all manufactured by ADEKA CORPORATION). In addition, antioxidants may also include compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967. In addition, the composition of the present invention may contain a latent antioxidant as required. As a latent antioxidant, a compound in which a portion that functions as an antioxidant is protected by a protecting group and a compound that functions as an antioxidant by heating at 100 to 250° C. or heating at 80 to 200° C. in the presence of an acid / base catalyst to remove the protecting group and function as an antioxidant can be cited. As a latent antioxidant, compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Publication No. 2017-008219 can be cited. As a commercially available product of a latent antioxidant, ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION) can be cited. As an example of a preferred antioxidant, 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and a compound represented by the general formula (3) can be cited.

[1028] [Chemical formula 59]

[1029]

[1030] In the general formula (3), R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, R6 represents an alkylene group having 2 or more carbon atoms, R7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms, an O atom, and a N atom, and k represents an integer of 1 to 4.

[1031] The compound represented by the general formula (3) can suppress oxidative degradation of aliphatic groups and phenolic hydroxyl groups of resins and can suppress metal oxidation by its rust-proofing effect on metal materials.

[1032] It can act on both the resin and the metal material, so it is more preferable that k is an integer of 2 to 4. As R7, alkyl, cycloalkyl, alkoxy, alkyl ether, alkyl silyl, alkoxy silyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and combinations thereof can be cited, and it may also have a substituent. Among them, from the viewpoint of solubility in the developer and metal adhesion, it is preferred to have alkyl ether and -NH-, and from the viewpoint of interaction with the resin and metal adhesion when the metal complex is formed, -NH- is more preferred.

[1033] Examples of the compound represented by the following general formula (3) include the following, but the compound is not limited to the following structure.

[1034] [Chemical formula 60]

[1035]

[1036] [Chemical formula 61]

[1037]

[1038] [Chemical formula 62]

[1039]

[1040] [Chemical formula 63]

[1041]

[1042] The amount of the antioxidant added is preferably 0.1 to 10 parts by mass relative to the resin, more preferably 0.5 to 5 parts by mass. When the amount added is less than 0.1 parts by mass, it is not easy to obtain the effect of improving the elongation characteristics after reliability and the adhesion to the metal material, and when the amount added is more than 10 parts by mass, there is a concern that the sensitivity of the resin composition decreases due to the interaction with the photosensitizer. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, the total amount of these is preferably within the above range.

[1043] <Regulation on other contained substances>

[1044] From the viewpoint of the coating surface properties, the water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and further preferably less than 0.6% by mass. As a method for maintaining the water content, the humidity in the storage conditions and the porosity of the storage container can be exemplified.

[1045] From the viewpoint of insulation, the metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel, etc. When a plurality of metals are included, the total amount of these metals is preferably within the above range.

[1046] Furthermore, as a method for reducing metal impurities accidentally contained in the curable resin composition of the present invention, the following methods can be cited: selecting a raw material with a low metal content as a raw material constituting the curable resin composition of the present invention; filtering the raw material constituting the curable resin composition of the present invention through a filter; lining a device with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination.

[1047] If the curable resin composition of the present invention is used as a semiconductor material, from the viewpoint of wiring corrosion, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and further preferably less than 200 mass ppm. Among them, it is preferred that the content in the form of halogen ions is less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be cited. Preferably, the total of chlorine atoms and bromine atoms or chlorine ions and bromide ions is respectively within the above range. As a method for adjusting the content of halogen atoms, ion exchange treatment can be preferably cited.

[1048] As the storage container of the curable resin composition of the present invention, a conventionally known storage container can be used. In addition, as the storage container, in order to suppress the mixing of impurities into the raw materials or the curable resin composition, it is also preferred to use a multilayer bottle having an inner wall of the container composed of six types of six layers of resins, or a bottle having a seven-layer structure of six types of resins. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

[1049] <Preparation of curable resin composition>

[1050] The curable resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and the mixing can be carried out by a conventionally known method.

[1051] Furthermore, in order to remove foreign matter such as dust or particles in the curable resin composition, it is preferred to filter using a filter. Preferably, the filter pore size is 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, it is preferably 5 μm or less, more preferably 3 μm or less, and further preferably 1 μm or less. The material of the preferred filter is polytetrafluoroethylene, polyethylene or nylon. The filter can use a filter pre-cleaned with an organic solvent. In the filtering step of the filter, multiple filters can also be connected in series or in parallel for use. When using multiple filters, filters with different pore sizes or materials can be used in combination. Furthermore, various materials can be filtered multiple times. When filtering multiple times, it can be a circulation filter. Furthermore, filtering can also be performed after pressurization. When filtering after pressurization, the pressure of pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, it is preferably 0.01 MPa to 1.0 MPa, more preferably 0.03 MPa to 0.9 MPa, and even more preferably 0.05 MPa to 0.7 MPa.

[1052] In addition to filtering using a filter, an impurity removal treatment using an adsorbent may be performed. Filter filtering and impurity removal treatment using an adsorbent may also be combined. As the adsorbent, a known adsorbent may be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be cited.

[1053] <Application of curable resin composition>

[1054] The curable resin composition of the present invention is preferably used to form an interlayer insulating film for a redistribution layer.

[1055] Furthermore, the present invention can also be used for forming an insulating film or a stress buffer film of a semiconductor device.

[1056] (Cured film, laminated body, semiconductor device, and method for producing the same)

[1057] Next, a cured film, a laminated body, a semiconductor device, and methods for producing these will be described.

[1058] The cured film of the present invention is formed by curing the curable resin composition of the present invention. The film thickness of the cured film of the present invention can be set to 0.5 μm or more, or 1 μm or more, and the upper limit can be set to 100 μm or less, or 30 μm or less.

[1059] The cured film of the present invention can be stacked in two or more layers, and further stacked in 3 to 7 layers to form a laminate. Preferably, the laminate of the present invention is a laminate having two or more cured films and a metal layer between the cured films. In addition, the laminate of the present invention includes two or more cured films, preferably including a metal layer between any of the above-mentioned cured films. For example, a laminate having a layer structure including at least three layers of a first cured film, a metal layer, and a second cured film can be preferably cited. The first cured film and the second cured film are both cured films of the present invention, for example, the first cured film and the second cured film are both films formed by curing the curable resin composition of the present invention. The curable resin composition of the present invention used to form the first cured film and the curable resin composition of the present invention used to form the second cured film may be a composition of the same composition or a composition of different composition, but from the viewpoint of manufacturing adaptability, a composition of the same composition is preferred. Such a metal layer can be preferably used as a metal wiring such as a redistribution layer.

[1060] As the fields to which the cured film of the present invention can be applied, there can be cited insulating films of semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc. In addition, there can be cited sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), or the case where patterns are formed by etching insulating films for actual installation purposes as described above. For these uses, for example, reference can be made to Science & Technology Co., Ltd. "High Functionalization and Application Technology of Polyimides" April 2008, supervised by Masaaki Kakimoto, CMC Technical Library "Basics and Development of Polyimide Materials" November 2011, Japan Polyimide / Aromatic Polymer Research Society / Editor "Latest Polyimide Basics and Applications" NTS, August 2010, etc.

[1061] Furthermore, the cured film of the present invention can also be used in the production of offset printing plates, screen printing plates and other plates, the use of etching molded components, and the production of protective varnishes and dielectric layers in electronics, especially microelectronics.

[1062] The method for producing a cured film of the present invention (hereinafter, also simply referred to as “the production method of the present invention”) preferably includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film.

[1063] Furthermore, it is more preferable that the method for producing a cured film of the present invention includes the film forming step, and further includes an exposure step of exposing the film and a development step of developing the film (performing a development treatment on the film).

[1064] Furthermore, it is more preferable that the method for producing a cured film of the present invention includes the film forming step (and the developing step as necessary) and further includes a heating step of heating the film at 50 to 450°C.

[1065] Specifically, it is also preferable to include the following steps (a) to (d).

[1066] (a) Film formation step of applying a curable resin composition to a substrate to form a film (curable resin composition layer)

[1067] (b) After the film forming step, an exposure step of exposing the film to light

[1068] (c) a developing step of developing the exposed film

[1069] (d) a heating step of heating the developed film at 50 to 450° C.

[1070] By heating in the heating step, the developed curable resin composition layer can be further cured. In the heating step, for example, the thermal base generator is decomposed, so that sufficient curability can be obtained.

[1071] The method for manufacturing a laminated body according to a preferred embodiment of the present invention includes a method for manufacturing a cured film according to the present invention. Regarding the method for manufacturing a laminated body according to the present embodiment, after forming a cured film according to the method for manufacturing a cured film, step (a) or steps (a) to (c) or steps (a) to (d) are performed again. In particular, each of the above steps is performed in sequence multiple times, for example, preferably 2 to 5 times (i.e., 3 to 6 times in total). By stacking the cured films in this way, a laminated body can be formed. In the present invention, it is preferred that a metal layer is provided, especially on a portion where a cured film is provided or between the cured films or at these two locations. In addition, in the manufacture of the laminated body, it is not necessary to repeat all steps (a) to (d), and a laminated body of a cured film can be obtained by performing at least (a), preferably (a) to (c) or (a) to (d) multiple times as described above.

[1072] <Film forming step (layer forming step)>

[1073] The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) of applying a curable resin composition to a substrate to form a film (layer).

[1074] The type of substrate can be appropriately set according to the purpose, but there is no particular limitation, and examples thereof include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, amorphous silicon, quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, electrode plates of plasma display panels (PDP), etc. In addition, a layer such as a bonding layer or an oxide layer may be provided on the surface of these substrates. In the present invention, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.

[1075] Furthermore, as the base material, for example, a plate-shaped base material (substrate) is used.

[1076] The shape of the substrate is not particularly limited, and may be circular or rectangular, but is preferably rectangular.

[1077] On the surface of these substrates, a layer such as an adhesion layer and an oxide layer made of hexamethyldisilazane (HMDS) or the like may be provided.

[1078] The size of the substrate is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in diameter, in the case of a circular shape, and 100 to 1000 mm in length, preferably 200 to 700 mm in length, in the case of a rectangular shape.

[1079] Furthermore, when a curable resin composition layer is formed on the surface of a resin layer such as a curable resin composition layer or on the surface of a metal layer, the resin layer or the metal layer serves as a substrate.

[1080] As a method of applying the curable resin composition to a substrate, coating is preferred.

[1081] Specifically, as the applicable method, dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating and inkjet can be exemplified. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, spin coating, slit coating, spray coating and inkjet are more preferred. By adjusting the appropriate solid content concentration or coating conditions according to the method, a resin layer of the desired thickness can be obtained. In addition, the coating method can also be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred. If it is a rectangular substrate, slit coating, spray coating, inkjet, etc. are preferred. In the case of using the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm (revolutions per minute: revolutions per minute) for about 10 seconds to 1 minute. Depending on the viscosity of the resin composition and the desired film thickness, it is also preferred to apply the coating at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. In order to obtain uniform film thickness, a combination of multiple rotation speeds may be used for coating.

[1082] Furthermore, a method of transferring a coating film formed by previously applying the coating film to a temporary support by the above-mentioned applying method to a substrate can also be applied.

[1083] Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably adopted in the present invention.

[1084] Furthermore, a step of removing the remaining film at the end of the substrate may be performed. Examples of such a step include edge bead rinsing (EBR), air knife, back rinse, etc. A pre-wetting step may also be adopted in which various solvents are applied to the substrate to improve the wettability of the substrate before the resin composition is applied to the substrate, and then the resin composition is applied.

[1085] <Drying Step>

[1086] The manufacturing method of the present invention may also include a step of drying to remove the solvent after the film forming step (layer forming step) after forming the above-mentioned film (curable resin composition layer). The preferred drying temperature is 50 to 150° C., more preferably 70 to 130° C., and further preferably 90 to 110° C. The drying time may be 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

[1087] <Exposure steps>

[1088] The manufacturing method of the present invention may also include an exposure step of exposing the film (curable resin composition layer). The exposure amount is not particularly limited as long as the curable resin composition can be cured, but for example, it is preferably irradiated with 100 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. 2 , more preferably irradiation 200 to 8,000 mJ / cm 2 .

[1089] The exposure wavelength can be appropriately set within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[1090] Regarding the exposure wavelength, if it is explained in relation to the light source, examples include (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), broadband (3 wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beams, (7) second harmonics of YAG lasers at 532 nm and third harmonics at 355 nm, etc. Regarding the curable resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is particularly preferred. Therefore, particularly high exposure sensitivity can be obtained. From the viewpoint of handling and productivity, a broad (three wavelengths of g, h, and i rays) light source such as a high-pressure mercury lamp or a semiconductor laser 405 nm is also preferred.

[1091] <Development Step>

[1092] The manufacturing method of the present invention may also include a developing step of developing the exposed film (curable resin composition layer). By developing, the unexposed portion (non-exposed portion) is removed. As long as the desired pattern can be formed, the developing method is not particularly limited, for example, spitting the developer from the nozzle, spraying with a sprayer, and immersing the substrate in the developer, etc., preferably using the spitting from the nozzle. In the developing step, it is possible to adopt a step of continuously supplying the developer to the substrate, a step of keeping the developer in a substantially stationary state on the substrate, a step of vibrating the developer using ultrasound, etc., and a step combining these.

[1093] Development is performed using a developer. If the curable resin composition is a negative curable resin composition, a developer that removes the unexposed portion (non-exposed portion) of the curable resin composition layer can be used without particular restrictions, and if the curable resin composition of the present invention is a positive curable resin composition, a developer that removes the exposed portion (exposed portion) can be used without particular restrictions.

[1094] In the present invention, the case where an alkali developer is used as a developer is referred to as alkaline development, and the case where a developer containing 50% by mass or more of an organic solvent is used as a developer is referred to as solvent development.

[1095] In alkaline development, the content of the organic solvent in the developer is preferably 10 mass % or less, more preferably 5 mass % or less, further preferably 1 mass % or less, based on the total mass of the developer. It is particularly preferred that the developer contains no organic solvent.

[1096] More preferably, the developer in the alkaline development is an aqueous solution having a pH of 9 to 14.

[1097] As the alkaline compound contained in the developer in the alkaline development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, ammonia or amines can be cited. As amines, for example, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc. Among them, alkaline compounds that do not contain metals are preferred, and ammonium compounds are more preferred.

[1098] The basic compound may be one or more. For example, when TMAH is used, the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.3 to 3% by mass based on the total mass of the developer.

[1099] In solvent development, it is more preferred that the developer contains 90% or more of an organic solvent. In the present invention, it is preferred that the developer contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained by inputting a structural formula into ChemBioDraw as a calculated value.

[1100] As for the organic solvent, examples of esters preferably include 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 alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), )), 3-alkoxy propionic acid alkyl esters (e.g., 3-alkoxy propionic acid methyl ester, 3-alkoxy propionic acid ethyl ester, etc. (e.g., 3-methoxy propionic acid methyl ester, 3-methoxy propionic acid ethyl ester, 3-ethoxy propionic acid methyl ester, 3-ethoxy propionic acid ethyl ester, etc.)), 2-alkoxy propionic acid alkyl esters (e.g., 2-alkoxy propionic acid methyl ester, 2-alkoxy propionic acid ethyl ester, 2-alkoxy propionic acid propyl ester, etc. (e.g., 2-methoxy propionic acid methyl ester, 2-methoxy propionic acid ethyl ester, 2-methoxy propionic acid propyl ester, 2-ethoxy propionic acid methyl ester, 2-ethoxy propionic acid propyl ester, etc.) ethyl propionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, 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, and the like, and ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl As the ketones, for example, preferably there can be mentioned methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., as the aromatic hydrocarbons, for example, preferably there can be mentioned toluene, xylene, anisole, limonene, etc., and as the sulfoxides, for example, preferably there can be mentioned dimethyl sulfoxide.

[1101] In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. When the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more.

[1102] The developer may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[1103] Preferably, 50% by mass or more of the developer is an organic solvent, more preferably 70% by mass or more, and even more preferably 90% by mass or more. Furthermore, 100% by mass of the developer may be an organic solvent.

[1104] [Developer Supply Method]

[1105] There is no particular limitation on the method of supplying the developer as long as the desired pattern can be formed, and there are methods of immersing the substrate in the developer, supplying the developer onto the substrate using a nozzle to perform immersion development, or continuously supplying the developer. There is no particular limitation on the type of nozzle, and examples include a straight nozzle, a shower nozzle, a spray nozzle, and the like.

[1106] From the viewpoint of the permeability of the developer, the removability of the non-image area, and the manufacturing efficiency, it is preferred to use a method of supplying the developer using a straight nozzle or a method of continuously supplying the developer using a spray nozzle. From the viewpoint of the permeability of the developer to the image area, it is more preferred to use a method of supplying the developer using a spray nozzle.

[1107] Furthermore, the step of continuously supplying developer using a straight nozzle, rotating the substrate to remove the developer from the substrate, continuously supplying developer again using a straight nozzle after spin drying, and then rotating the substrate to remove the developer from the substrate can be adopted, and this step can also be repeated multiple times.

[1108] Furthermore, as a method for supplying the developer in the development step, a step of continuously supplying the developer to the substrate, a step of keeping the developer in a roughly static state on the substrate, a step of vibrating the developer on the substrate using ultrasound, etc., and a combination of these steps can be adopted.

[1109] The development time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but can be generally 10 to 45°C, preferably 20 to 40°C.

[1110] After the treatment with the developer, rinsing may be further performed. Also, a method such as supplying a rinsing liquid before the developer in contact with the pattern is completely dried may be adopted.

[1111] When solvent development is performed, it is preferred to use an organic solvent different from the developer for rinsing. Examples of the rinsing solution in solvent development include PGMEA (propylene glycol monomethyl ether acetate) and IPA (isopropyl alcohol), and PGMEA is preferred.

[1112] In the case of alkaline development, it is preferable to perform rinsing with pure water.

[1113] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and further preferably 5 seconds to 1 minute. The temperature of the rinsing liquid during rinsing is not particularly limited, and can be preferably 10 to 45°C, more preferably 18 to 30°C.

[1114] When the rinsing liquid contains an organic solvent, the organic solvent may be preferably 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 alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., 3-alkoxypropionic acid alkyl esters) 2-alkoxypropionic acid methyl esters, 3-alkoxypropionic acid ethyl esters, etc. (for example, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, etc.)), 2-alkoxy propionic acid alkyl esters (for example, 2-alkoxypropionic acid methyl ester, 2-alkoxypropionic acid ethyl ester, 2-alkoxypropionic acid propyl esters, etc. (for example, 2-methoxypropionic acid methyl ester, 2-methoxypropionic acid ethyl ester, 2-methoxypropionic acid propyl ester, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester)), 2-alkoxy-2-methylpropionic acid methyl esters and 2-alkoxy-2-methylpropionic acid ethyl esters (for example, 2-methoxy-2-methyl The ethers include, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate. etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc., and as sulfoxides, dimethyl sulfoxide, and as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc., can be preferably mentioned.

[1115] When the rinse liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present 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 further preferred.

[1116] When the rinse liquid contains an organic solvent, preferably 50% by mass or more of the rinse liquid is an organic solvent, more preferably 70% by mass or more of the rinse liquid is an organic solvent, and further preferably 90% by mass or more of the rinse liquid is an organic solvent. Alternatively, 100% by mass of the rinse liquid may be an organic solvent.

[1117] The rinse may also contain other ingredients.

[1118] As other components, a well-known surfactant, a well-known defoaming agent, etc. are mentioned, for example.

[1119] [Method of supplying flushing liquid]

[1120] There are no particular restrictions on the method of supplying the rinsing liquid as long as the desired pattern can be formed, and there are methods of immersing the substrate in the rinsing liquid, performing spin immersion development on the substrate, supplying the rinsing liquid to the substrate in a spraying form, and continuously supplying the developer to the substrate through a mechanism such as a vertical nozzle.

[1121] From the perspective of the permeability of the rinse liquid, the removal of the non-image part, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., preferably a method of continuously supplying using a spray nozzle, and from the perspective of the permeability of the rinse liquid to the image part, a method of supplying using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc.

[1122] That is, the rinsing step is preferably a step of supplying or continuously supplying a rinsing liquid to the film after exposure through a straight nozzle, and more preferably a step of supplying the rinsing liquid through a spray nozzle.

[1123] Furthermore, as a method for supplying the rinsing liquid in the rinsing step, there can be adopted a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid in a substantially static state on the substrate, a step of vibrating the rinsing liquid on the substrate using ultrasound or the like, and a step combining these.

[1124] <Heating steps>

[1125] The production method of the present invention preferably includes a step of heating the developed film at 50 to 450° C. (heating step).

[1126] It is preferable to include a heating step after the film forming step (layer forming step), the drying step, and the developing step.

[1127] The curable resin composition of the present invention contains polymerizable compounds other than the specific resin. However, in this step, unreacted polymerizable compounds other than the specific resin can be subjected to a curing reaction, and unreacted polymerizable groups in the specific resin can be subjected to a curing reaction.

[1128] Furthermore, when the specific resin is a polyimide precursor and the curable resin composition contains a thermal base generator, in the heating step, for example, the thermal base generator decomposes to generate a base, thereby causing a cyclization reaction of the polyimide precursor.

[1129] The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50° C. or higher, more preferably 80° C. or higher, further preferably 140° C. or higher, particularly preferably 150° C. or higher, further preferably 160° C. or higher, and most preferably 170° C. or higher. The upper limit is preferably 450° C. or lower, more preferably 350° C. or lower, further preferably 250° C. or lower, and particularly preferably 220° C. or lower.

[1130] Regarding heating, it is preferred to carry out the heating from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 12°C / minute, more preferably 2 to 10°C / minute, and further preferably 3 to 10°C / minute. By setting the heating rate to be 1°C / minute or more, productivity can be ensured and excessive volatilization of amines can be prevented. By setting the heating rate to be 12°C / minute or less, the residual stress of the cured film can be relaxed. In addition, in the case of an oven capable of rapid heating, it is preferred to carry out the heating from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8°C / second, more preferably 2 to 7°C / second, and further preferably 3 to 6°C / second.

[1131] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and further preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when the curable resin composition is applied to a substrate and then dried, it is the temperature of the dried film (layer), and it is preferably gradually heated from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the curable resin composition.

[1132] The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.

[1133] In particular, when forming a multilayer laminate, it is preferred to heat at a heating temperature of 180° C. to 320° C., more preferably 180° C. to 260° C., from the viewpoint of the adhesion between the layers of the cured film. The reason for this is not clear, but it is believed that this is because the polymerizable groups in the specific resin between the layers undergo a cross-linking reaction.

[1134] Heating can be carried out in stages. As an example, the following pretreatment step can be performed, that is, the temperature is increased from 25°C to 180°C at 3°C / min and maintained at 180°C for 60 minutes, and the temperature is increased from 180°C to 200°C at 2°C / min and maintained at 200°C for 120 minutes. The heating temperature as the pretreatment step is preferably 100-200°C, more preferably 110-190°C, and further preferably 120-185°C. In this pretreatment step, it is also preferred to treat while irradiating ultraviolet rays as described in the specification of U.S. Patent No. 9159547. Through these pretreatment steps, the properties of the film can be improved. The pretreatment step can be carried out in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment can be a step of more than two stages, for example, pretreatment step 1 can be carried out in the range of 100-150°C, and then pretreatment step 2 can be carried out in the range of 150-200°C.

[1135] Furthermore, the heating may be followed by cooling, and the cooling rate at this time is preferably 1 to 5° C. / min.

[1136] In order to prevent the specific resin from decomposing, it is preferably carried out in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon during the heating step. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

[1137] The heating means is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric oven, and a hot air oven.

[1138] <Metal layer formation step>

[1139] The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the film (curable resin composition layer) after the development treatment.

[1140] The metal layer is not particularly limited, and any conventional metal can be used. Examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, and alloys containing these metals. Copper and aluminum are more preferred, and copper is further preferred.

[1141] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, and Japanese Patent Application Publication No. 2004-101850 can be used. For example, photolithography, stripping, electrolytic plating, electroless plating, etching, printing, and methods combining these methods can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be cited.

[1142] The thickness of the metal layer may be, for example, 0.01 to 100 μm at the thickest portion, preferably 0.1 to 50 μm, and more preferably 1 to 10 μm.

[1143] <Lamination steps>

[1144] The production method of the present invention preferably further includes a lamination step.

[1145] The lamination step is a series of steps including performing (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step again in sequence on the surface of a cured film (resin layer) or a metal layer. Among them, it can be a method in which only the film forming step (a) is repeated. In addition, it can also be a method in which the heating step (d) is performed at the end or in the middle of the lamination. That is, it can also be set as follows, that is, the steps (a) to (c) are repeated a specified number of times, and then the heating (d) is performed, so that the stacked curable resin composition layer is cured together. In addition, the metal layer forming step (e) can also be included after the (c) development step, and the heating (d) can also be performed each time, or the heating (d) can be performed together after the specified number of laminations. It is beyond doubt that the above-mentioned drying step and heating step can be further appropriately included in the lamination step.

[1146] When the lamination step is further performed after the lamination step, a surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer forming step. As the surface activation treatment, plasma treatment can be exemplified.

[1147] The lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times. In the lamination step, the layers may be the same in composition, shape, film thickness, etc., or different in composition, shape, film thickness, etc.

[1148] For example, a structure in which the resin layers are more than 2 layers and less than 20 layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, can be cited as an example. A structure in which the resin layers are more than 3 layers and less than 7 layers is preferred, and a structure in which the resin layers are more than 3 layers and less than 5 layers is further preferred.

[1149] <Surface activation treatment steps>

[1150] The method for producing a cured film of the present invention may include a surface activation treatment step of performing surface activation treatment on at least a portion of the metal layer and the photosensitive resin composition layer.

[1151] The surface activation treatment step is usually performed after the metal layer forming step. However, the metal layer forming step may be performed after the above-mentioned exposure and development step by subjecting the photosensitive resin composition layer to the surface activation treatment step.

[1152] The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the photosensitive resin composition layer after exposure, or on at least a portion of both the metal layer and the photosensitive resin composition layer after exposure. Preferably, the surface activation treatment is performed on at least a portion of the metal layer, and preferably, the surface activation treatment is performed on a portion or all of the region of the metal layer where the photosensitive resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin layer disposed on the surface thereof can be improved.

[1153] Furthermore, it is preferred that a part or all of the exposed photosensitive resin composition layer (resin layer) is also subjected to surface activation treatment. Thus, by subjecting the surface of the photosensitive resin composition layer to ...

Claims

1. A curable resin composition comprising: A resin comprising a repeating unit represented by the following formula (1-1) and at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3-2), a repeating unit represented by the following formula (3-3), and a repeating unit represented by the following formula (3-4); and Solvents, In formula (1-1), Y 1 Represents a divalent linking group, Ar 1 represents an aromatic hydrocarbon group optionally having a substituent or a condensed ring structure, Y 2 represents a single bond or a divalent connecting group; In formula (3-2), X 6 represents a 4-valent linking group, Z 2 represents a divalent linking group having a group containing an ethylenically unsaturated bond; In formula (3-3), X 7 and X 8 Each independently represents a trivalent linking group, Z 3 and Z 4 Each independently represents a divalent linking group, Z 3 and Z 4 At least one of represents a divalent linking group having a polymerizable group; In formula (3-4), X 7 and X 8 Each independently represents a trivalent linking group, Z 3 and Z 4 Each independently represents a divalent linking group, R 5 and R 6 Each independently represents a monovalent organic group, Z 3 and Z 4 At least one of them represents a divalent linking group having a polymerizable group, R 5 , R 6 , Z 3 and Z 4 At least one of the compounds comprises a polymerizable group.

2. The curable resin composition according to claim 1, wherein The content of the repeating unit represented by the formula (1-1) is 0.1% by mass to 60% by mass based on the total mass of the resin. The curable resin composition according to claim 1 or 2, comprising a polymerizable compound. 4 . The curable resin composition according to claim 1 , which is used for forming an interlayer insulating film for a redistribution layer. 5 . A cured film obtained by curing the curable resin composition according to claim 1 . 6 . A laminate comprising two or more layers of the cured film according to claim 5 , and comprising a metal layer between any of the cured films. 7 . A method for producing a cured film, comprising a film forming step of applying the curable resin composition according to claim 1 to a substrate to form a film. 8 . The method for producing a cured film according to claim 7 , comprising the step of heating the film at 50° C. to 450° C. 9 . A semiconductor device comprising the cured film according to claim 5 .

10. A resin comprising a repeating unit represented by the following formula (1-1) and at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3-2), a repeating unit represented by the following formula (3-3), and a repeating unit represented by the following formula (3-4); In formula (1-1), Y 1 Represents a divalent linking group, Ar 1 represents an aromatic hydrocarbon group optionally having a substituent or a condensed ring structure, Y 2 represents a single bond or a divalent connecting group; In formula (3-2), X 6 represents a 4-valent linking group, Z 2 represents a divalent linking group having a group containing an ethylenically unsaturated bond; In formula (3-3), X 7 and X 8 Each independently represents a trivalent linking group, Z 3 and Z 4 Each independently represents a divalent linking group, Z 3 and Z 4 At least one of represents a divalent linking group having a polymerizable group; In formula (3-4), X 7 and X 8 Each independently represents a trivalent linking group, Z 3 and Z 4 Each independently represents a divalent linking group, R 5 and R 6 Each independently represents a monovalent organic group, Z 3 and Z 4 At least one of them represents a divalent linking group having a polymerizable group, R 5 , R 6 , Z 3 and Z 4 At least one of the compounds comprises a polymerizable group.

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