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

Abstract

A resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device, the resin composition containing: at least one resin selected from the group consisting of a cyclized resin and a precursor thereof; and a compound A represented by formula (A1-1) (in formula (A1-1), R1 is an organic group having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, R2 is a hydrogen atom or an arbitrary organic group, at least two of R1 and R2 may bond to form a ring structure, n represents an integer of 1-3, m represents an integer of 1 or more, and R3 represents an m-valent organic group.

Description

TECHNICAL FIELD

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

[0002] Nowadays, in various fields, resin materials produced from resin compositions containing resins are being utilized.

[0003] For example, cyclic resins such as polyimides are excellent in heat resistance, insulating properties, and the like, and thus are used for various purposes. As the above purposes, there is no particular limitation, and if a semiconductor device for mounting is exemplified, utilization as a material for an insulating film, a sealing material, or a protective film can be cited. Also, it can be used as a base film, a cover film, or the like of a flexible substrate.

[0004] For example, among the above purposes, cyclic resins such as polyimides are used in the form of a resin composition containing a cyclic resin, or a precursor of a cyclic resin such as a polyimide precursor.

[0005] Such a resin composition is applied to a substrate, for example, by coating or the like to form a photosensitive film, and thereafter, exposure, development, heating, or the like are performed as necessary, whereby a cured product can be formed on the substrate.

[0006] The above precursors of cyclic resins such as polyimide precursors are cyclized, for example, by heating, and become cyclic resins such as polyimides in the cured product.

[0007] A resin composition can be applied by a known coating method or the like, and thus it can be said that the adaptability in production is excellent, for example, in the degree of freedom in design of the shape, size, application position, or the like of the resin composition to be applied at the time of application, and the like. From the viewpoint that the above resin composition is excellent in adaptability in production in addition to the high performance possessed by cyclic resins such as polyimides, the industrial application development of the above resin composition is increasingly expected.

[0008] Also, for such a resin material, excellent adhesion to a substrate is required, and various methods for improving the adhesion to a substrate are being studied.

[0009] For example, in Patent Literature 1, a curable resin composition is described, which contains at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamide-imide precursor, and a photo-base generator having an alkoxysilyl group.

[0010] In Patent Literature 2, a negative photosensitive resin composition is described, which contains the following components: (A) a polyimide precursor; (B) a photopolymerization initiator; (C) a silane coupling agent having a specific structure; and (D) an organic solvent containing at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone.

[0011] Prior Art Documents

[0012] Patent Literature

[0013] Patent Literature 1: International Publication No. 2022 / 050278

[0014] Patent Literature 2: Japanese Patent Application Publication No. 2020-173431 SUMMARY

[0015] Technical Problem to be Solved by the Invention

[0016] With respect to a resin composition containing a cyclized resin or a precursor thereof, it is required to obtain a cured product having excellent adhesion to a substrate.

[0017] An object of the present application is to provide a resin composition from which a cured product having excellent adhesion to a substrate can be obtained, a cured product obtained by curing the above resin composition, a laminate containing the above cured product, a method for producing the above cured product, a method for producing the above laminate, a method for producing a semiconductor device including the method for producing the above cured product, and a semiconductor device containing the above cured product.

[0018] Means for Solving the Technical Problem

[0019] Hereinafter, examples of representative embodiments of the present application will be shown.

[0020] <1> A resin composition comprising:

[0021] a resin selected from at least one of the group consisting of a cyclized resin and a precursor thereof; and

[0022] a compound A represented by Formula (A1-1).

[0023] [Chemical Formula 1]

[0024]

[0025] In Formula (A1-1), R 1 is an organic group having at least one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom, R 1 may be the same or different, R 2 is a hydrogen atom or does not correspond to the above R 1any organic group, R 2 may be the same or different, R 1 may be the same or different, R 2 at least 2 of which can be bonded to form a ring structure, n represents an integer of 1 to 3, m represents an integer of 1 or more, R 3 represents an organic group of m valence.

[0026] <2> The resin composition according to <1>, wherein

[0027] Compound A is a compound represented by the following formula (Al-2).

[0028] [Chemical Formula 2]

[0029]

[0030] In formula (Al-2), R 1 is an organic group having at least one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom, R 1 may be the same or different, R 2 is a hydrogen atom or any organic group other than R 1 may be the same or different, R 2 may be the same or different, R 1 may be the same or different, R 2 at least 2 of which can be bonded to form a ring structure, n represents an integer of 1 to 3, L represents a divalent linking group, R 4 represents a hydrogen atom or a monovalent organic group.

[0031] <3> The resin composition according to <1>, wherein

[0032] at least one of R 1 in the above formula (Al-1) contains an amino group or an ester bond.

[0033] <4> The resin composition according to <1>, wherein

[0034] R 3 in the above formula (Al-1) is a group represented by the following formula (R3-1).

[0035] [Chemical Formula 3]

[0036]

[0037] In formula (R3-1), L 31 each independently represents a divalent linking group, R 31 each independently represents a hydrogen atom, an aromatic hydrocarbon group which can be substituted with a substituent, or a group represented by32 -#indicated group, * indicates a bonding site to the nitrogen atom in formula (R3-1), # indicates a bonding site to L 32 in formula (R3-1), R 32 indicates an organic group, m indicates an integer of 1 or more, L 32 indicates a hydrogen atom or a substituent, L 32 indicates a single bond or a connecting group of m valency, * indicates a bonding site to the silicon atom in formula (A1-1).

[0038] <5> A resin composition comprising:

[0039] a resin selected from at least one of the group consisting of a cyclized resin and a precursor thereof; and

[0040] a compound A represented by formula (A2-1).

[0041] [Chemical Formula 4]

[0042]

[0043] in formula (A2-1), R 21 is an organic group having an HSP value of 17.0 to 27.0 MPa 1 / 2 , R 21 , in the case where a plurality of R 22 are present, can be the same or different, R 21 is a hydrogen atom or an arbitrary organic group other than the above R 22 , in the case where a plurality of R 21 are present, can be the same or different, R 22 , and at least two of R 23 and R 23 may be bonded to form a ring structure, n indicates an integer of 1 to 3, m indicates an integer of 1 or more, R 23 indicates an organic group of m valency.

[0044] <6> The resin composition according to any one of <1> to <5>, wherein

[0045] the above resin is a polyimide or a polyimide precursor.

[0046] <7> The resin composition according to any one of <1> to <6>, wherein

[0047] the above resin is a polyimide.

[0048] <8> The resin composition according to any one of <1> to <7>, further comprising a photopolymerization initiator.

[0049] <9> The resin composition according to <8>, further comprising a sensitizer.

[0050] <10> The resin composition according to any one of <1> to <9>, further comprising a compound having a urea bond.

[0051] <11> The resin composition according to any one of <1> to <10>, further comprising a polymerizable compound having at least one of a urea bond and a urethane bond.

[0052] <12> The resin composition according to any one of <1> to <11>, further comprising a solvent having at least one of an amide bond or a hydroxyl group.

[0053] <13> The resin composition according to any one of <1> to <12>, used for forming an interlayer insulating film for a rewiring layer.

[0054] <14> A cured product obtained by curing the resin composition according to any one of <1> to <13>.

[0055] <15> A laminate comprising two or more layers of the cured product according to <14>, and a metal layer between any of the layers of the cured product.

[0056] <16> A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of <1> to <13> on a substrate to form a film.

[0057] <17> The method for producing a cured product according to <16>, comprising:

[0058] an exposure step of selectively exposing the film; and

[0059] a development step of developing the film using a developing solution to form a pattern.

[0060] <18> The method for producing a cured product according to <16> or <17>, comprising a heating step of heating the film at 50 to 450°C.

[0061] <19> A method for producing a laminate, comprising the method for producing a cured product according to any one of <16> to <18>.

[0062] <20> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of <16> to <18>.

[0063] <21> A semiconductor device comprising the cured product according to <14>.

[0064] Effects of the Invention

[0065] According to the present application, there are provided a resin composition from which a cured product having excellent adhesion to a substrate can be obtained, a cured product obtained by curing the above resin composition, a laminate including the above cured product, a method for producing the above cured product, a method for producing the above laminate, a method for producing a semiconductor device including the above method for producing the cured product, and a semiconductor device including the above cured product. DETAILED DESCRIPTION

[0066] Hereinafter, the main embodiments of the present application will be described. However, the present application is not limited to the illustrated embodiments.

[0067] In the present specification, a numerical range indicated by a symbol "~" means a range including a numerical value recited before the "~" as a lower limit value and a numerical value recited after the "~" as an upper limit value.

[0068] In the present specification, the term "step" means not only a separate step but also a step that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.

[0069] In the present specification, in the notation of a group (radical), the notation of "substituted or unsubstituted" includes a group (radical) having no substituent as well as a group (radical) having a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[0070] In the present specification, unless particularly stated, "exposure" includes not only exposure with light but also exposure with a particle beam such as an electron beam, an ion beam, and the like. Furthermore, as light for exposure, there can be mentioned a bright line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active light rays or radiation rays such as an electron beam.

[0071] In the present specification, "(methyl)acrylate" means both or either of "acrylate" and "methacrylate", "(methyl)acrylic acid" means both or either of "acrylic acid" and "methacrylic acid", and "(methyl)acryloyl" means both or either of "acryloyl" and "methacryloyl".

[0072] In the present specification, Me in a structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0073] In the present specification, the total solid content means the total mass of components excluding a solvent from all components of a composition. Furthermore, in the present specification, the solid content concentration means the mass percentage of components other than a solvent with respect to the total mass of the composition.

[0074] In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by a gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. In the present specification, for example, by using an HLC-8220 GPC (manufactured by TOSOH CORPORATION), a guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) are connected in series to serve as a column, whereby the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as an eluent. Among them, in the case of lower solubility or the like, NMP (N-methyl-2-pyrrolidone) can also be used as an eluent in the case where THF is not suitable as an eluent. Furthermore, unless otherwise specified, the detection in the GPC measurement uses a UV ray (ultraviolet ray) detector at a wavelength of 254 nm.

[0075] In the present specification, in the case where the positional relationship of each layer constituting a laminate is described as "upper" or "lower", as long as there is another layer on the upper side or the lower side of the layer serving as a reference among a plurality of layers of interest. That is, a third layer or element can be further interposed between the layer serving as a reference and the other layer, and the layer serving as a reference and the other layer do not necessarily need to be in contact. Unless otherwise specified, the direction in which the layers of a substrate are stacked is referred to as "up", or in the case where there is a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "up", and the opposite direction thereof is referred to as "down". In addition, such a setting of the up-down direction is for the convenience of explaining the present specification, and in an actual mode, the "up" direction in the present specification can also be different from the vertical upward direction.

[0076] In the present specification, unless otherwise specified, as each component contained in a composition, the composition can contain two or more compounds equivalent to the component. Unless otherwise specified, the content of each component in a composition refers to the total content of all compounds equivalent to the component.

[0077] In the present specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.

[0078] In the present specification, a combination of preferred modes is a more preferred mode.

[0079] (resin composition)

[0080] The resin composition according to the first aspect of the present application (hereinafter, also simply referred to as "the first resin composition") contains at least one resin selected from the group consisting of a cyclized resin and a precursor thereof, and a compound A represented by formula (A1-1).

[0081] The resin composition according to the second aspect of the present application (hereinafter, also simply referred to as "the second resin composition") contains at least one resin selected from the group consisting of a cyclized resin and a precursor thereof, and a compound A represented by formula (A2-1).

[0082] The resin composition according to the second aspect of the present application (hereinafter, also simply referred to as "the second resin composition") contains at least one resin selected from the group consisting of a cyclized resin and a precursor thereof, and a compound A represented by formula (A2-1).

[0083] Hereinafter, the first resin composition and the second resin composition are also simply collectively referred to as "the resin composition".

[0084] Hereinafter, the compound A represented by formula (A1-1) contained in the first resin composition is also referred to as "the first compound A".

[0085] Hereinafter, the compound A represented by formula (A2-1) contained in the second resin composition is also referred to as "the second compound A".

[0086] Hereinafter, the case where it is simply described as "the compound A" refers to both the first compound A and the second compound A.

[0087] The resin composition according to the present application is preferably used for forming a photosensitive film for exposure and development, and preferably for forming a film for exposure and development using a developer containing an organic solvent.

[0088] The resin composition according to the present application can be used, for example, for forming an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like, and is preferably used for forming an interlayer insulating film for a rewiring layer.

[0089] Further, the resin composition according to the present application can be used for forming a photosensitive film for positive development, and can be used for forming a photosensitive film for negative development.

[0090] In the present application, negative development refers to development in which a non-exposed portion is removed by development in exposure and development, and positive development refers to development in which an exposed portion is removed by development.

[0091] As the exposure method, the developer, and the development method described above, for example, the exposure method described in the explanation of the exposure step in the explanation of the production method of a cured product described later, the developer described in the explanation of the development step, and the development method described in the explanation of the development step can be used.

[0092] According to the resin composition according to the present application, a cured product having excellent adhesion to a substrate can be obtained.

[0093] The mechanism by which the above-described effects are obtained is not clear, but is presumed as follows.

[0094] In the past, silane coupling agents have been used in resin compositions for the purpose of improving adhesion to substrates and the like. These silane coupling agents are silane coupling agents having a simple unsubstituted trialkoxysilyl structure such as a trimethoxysilyl group.

[0095] In the first aspect of the present application, in the trialkoxysilyl structure, at least one of the alkoxy groups is substituted with an organic group having at least one or more atoms selected from the group consisting of oxygen atoms, nitrogen atoms, and sulfur atoms. As a result, it was found that the adhesion to the substrate after heat resistance testing of the cured film was improved compared to the case where a conventional product was used. The mechanism by which the above effect is obtained is not clear, but it is presumed as follows.

[0096] It is thought that by introducing a heteroatom having a high polarity into the hydrophobic alkoxysilyl group, the interaction of the silane coupling agent with the substrate such as a metal substrate is improved, and the silane coupling agent is biased toward the vicinity of the substrate at the time of film curing. As a result, it is thought that the sol-gel reaction is effectively carried out on the surface of the substrate compared to the conventional product, and thus the adhesion of the cured film to the substrate is improved.

[0097] Further, in the second aspect of the present application, in the trialkoxysilyl structure, at least one of the alkoxy groups is substituted with an organic group having an HSP value of 17.0 to 27.0 MPa 1 / 2 As a result, it was found that the adhesion to the substrate after heat resistance testing of the cured film was improved compared to the case where a conventional product was used. The mechanism by which the above effect is obtained is not clear, but it is presumed as follows.

[0098] It is thought that by introducing an organic group having a high polarity, i.e., an organic group having an HSP value of 17.0 to 27.0 MPa 1 / 2 to the hydrophobic alkoxysilyl group, the silane coupling agent is biased toward the vicinity of the substrate at the time of film curing as described above. As a result, it is thought that the sol-gel reaction is effectively carried out on the surface of the substrate compared to the conventional product, and thus the adhesion of the cured film to the substrate is improved.

[0099] Here, in Patent Documents 1 and 2, nothing is described about the first compound A and the second compound A.

[0100] Hereinafter, the components contained in the resin composition of the present application will be described in detail.

[0101] <Specific Resin>

[0102] The resin composition of the present application contains at least one resin (specific resin) selected from the group consisting of a cyclized resin and a precursor thereof.

[0103] The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.

[0104] In the present application, "main chain" means the relatively longest bonding chain in a resin molecule, and "side chain" means a bonding chain other than that.

[0105] As the ring-forming resin, polyimide, polybenzoxazole, polyamide-imide, and the like can be given.

[0106] The precursor of the ring-forming resin means a resin that changes its chemical structure to become a ring-forming resin by external stimulation, and preferably a resin that changes its chemical structure to become a ring-forming resin by heat, and more preferably a resin that forms a ring structure by a ring-closing reaction by heat to become a ring-forming resin.

[0107] As the precursor of the ring-forming resin, a polyimide precursor, a polybenzoxazole precursor, a polyamide-imide precursor, and the like can be given.

[0108] That is, the resin composition preferably contains at least one resin selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, a polybenzoxazole precursor, polyamide-imide, and a polyamide-imide precursor as the specific resin.

[0109] The resin composition preferably contains polyimide or a polyimide precursor as the specific resin, and more preferably contains polyimide as the specific resin.

[0110] The specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group.

[0111] In the case where the specific resin has a radical polymerizable group, the resin composition of the present application preferably contains a radical polymerization initiator, and more preferably contains a radical polymerization initiator and a radical crosslinking agent. Furthermore, a sensitizer can be contained as necessary. A negative photosensitive film, for example, is formed from such a resin composition.

[0112] Also, the specific resin can have a polarity-converting group such as an acid-decomposable group.

[0113] In the case where the specific resin has an acid-decomposable group, the resin composition preferably contains a photo-acid generator. A positive photosensitive film or a negative photosensitive film of the chemical amplification type, for example, is formed from such a resin composition.

[0114] [Polyimide precursor]

[0115] The kind of the polyimide precursor used in the present application is not particularly limited, and preferably contains a repeating unit represented by the following formula (2).

[0116] [Chemical Formula 5]

[0117]

[0118] In formula (2), A 1and A 2 each independently represents an oxygen atom or -NR z -, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group, R z represents a hydrogen atom or a monovalent organic group.

[0119] A 1 and A 2 each independently represents an oxygen atom or -NR z -, preferably an oxygen atom.

[0120] R z represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.

[0121] R 111 represents a divalent organic group. As the divalent organic group, a group containing a straight-chain or branched aliphatic group, a cyclic aliphatic group, and an aromatic group can be exemplified, preferably a straight-chain or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group composed of a combination of these, more preferably a group containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the above-mentioned straight-chain or branched aliphatic group can be substituted with a group containing a hetero atom, and the hydrocarbon group of the ring member of the above-mentioned cyclic aliphatic group and aromatic group can be substituted with a group containing a hetero atom. As examples of R 111 in formula (2), a group represented by -Ar- and -Ar-L-Ar- can be given, preferably a group represented by -Ar-L-Ar-. Here, Ar each independently represents an aromatic group, and L is a single bond or a aliphatic hydrocarbon group having 1 to 10 carbon atoms which can be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO- or a group composed of a combination of two or more of the above-mentioned groups. These preferable ranges are as described above.

[0122] R 111 is preferably derived from a diamine. As the diamine used in the production of the polyimide precursor, a straight-chain or branched aliphatic diamine, a cyclic aliphatic diamine, an aromatic diamine, or the like can be given. The diamine can be used singly or two or more kinds can be used.

[0123] Specifically, R 111A diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group composed of a combination of these is preferred, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferred. The hydrocarbon group in the chain of the above linear or branched aliphatic group can be substituted with a group containing a hetero atom, and the hydrocarbon group of the ring member of the above cyclic aliphatic group and aromatic group can be substituted with a group containing a hetero atom. As examples of the group containing an aromatic group, the following groups can be given.

[0124] [Chemical Formula 6]

[0125]

[0126] In the formula, A is a single bond or a divalent linking group, and is preferably a single bond or a group selected from a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms which can be substituted with a fluorine atom, -0-, -C(=0)-, -S-, -SO2-, -NHCO-, or a combination of these, more preferably a single bond or a group selected from an alkylene group having 1 to 3 carbon atoms which can be substituted with a fluorine atom, -0-, -C(=0)-, -S-, or -SO2-, and further preferably -CH2-, -0-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-.

[0127] In the formula, * indicates a bonding site to other structures.

[0128] As the diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, or 1,6-diaminohexane;

[0129] 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophorone diamine;

[0130] m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenyl methane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diamino diphenyl sulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenyl methane, 3,3'-dimethyl-4,4'-diaminodiphenyl methane, 4,4'-diamino octafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-H anthracene, 3,3',4,4'-tetraminobiphenyl, 3,3',4,4'-tetraminodiphenyl ether, 1,4-diamino anthraquinone, 1,5-diamino anthraquinone, 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'-diaminodiphenyl methane, 2,4- and 2,5-diaminoisopropylbenzene, 2,5-dimethyl-p-phenylenediamine, acetylguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobismethylbenzidine, and 4,4'-diaminotetrakisphenyl among at least one diamine.

[0131] Also, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferable.

[0132] Also, the diamines having 2 or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 can also be preferably used.

[0133] From the viewpoint of the softness of the obtained organic film, R 111 is preferably represented by -Ar-L-Ar-. Here, Ar is independently an aromatic group, and L is a carbon number 1 to 10 aliphatic hydrocarbon group which can be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group composed of two or more of the above. Ar is preferably a phenylene group, and L is preferably a carbon number 1 or 2 aliphatic hydrocarbon group which can be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO2-. The aliphatic hydrocarbon group here is preferably an alkylene group.

[0134] Also, from the viewpoint of the i-ray transmittance, R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61). Particularly, from the viewpoint of the i-ray transmittance and the easiness of obtaining, a divalent organic group represented by formula (61) is more preferable.

[0135] Formula (51)

[0136] [Chemical Formula 7]

[0137]

[0138] In formula (51), R 50 ~R 57 each independently represents a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R 50 ~R 57 is a fluorine atom, a methyl group, or a trifluoromethyl group, and each independently indicates a bonding site to a nitrogen atom in formula (2).

[0139] As the monovalent organic group of R 50 ~R 57 , an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably, an alkyl group having 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably, a fluorinated alkyl group having 1 to 6 carbon atoms), and the like can be given.

[0140] [Chemical Formula 8]

[0141]

[0142] In formula (61), R 58 and R 59 each independently represents a fluorine atom, a methyl group, or a trifluoromethyl group, and each independently indicates a bonding site to a nitrogen atom in formula (2).

[0143] As the diamine imparting the structure of formula (51) or formula (61), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like can be given. These can be used alone or in combination with two or more kinds.

[0144] Also, R 111 is preferably a group represented by the following formula (71). In the above mode, R 111 is more preferably a group represented by the following formula (72).

[0145] [Chemical Formula 9]

[0146]

[0147] In formula (71), A 1 ~A 3 each independently represents a single bond or a divalent linking group, and indicates a bonding site to a nitrogen atom in formula (2), and the hydrogen atoms of the four benzene rings described in formula (71) can be substituted with a substituent.

[0148] In the present specification, a bond intersecting with a side of a ring structure means that any one of the hydrogen atoms in the ring structure thereof is replaced.

[0149] In the formula (72), * indicates a bonding site with the nitrogen atom in the formula (2).

[0150] In the formula (71), A 1 ~ A 3 Preferably, it is a C1-10aliphatic hydrocarbon group which can be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O)2-, -NHC(=O)-, or a group composed of two or more of these, more preferably, it is a C1-10aliphatic hydrocarbon group which can be substituted with a fluorine atom, -O-, -C(=O)-, or a group composed of two or more of these, and further preferably, it is a C1-10aliphatic hydrocarbon group which can be substituted with a fluorine atom or -O-.

[0151] In particular, A 1 and A 3 Preferably, it is -O-.

[0152] In particular, A 2 Preferably, it is a C1-10aliphatic hydrocarbon group which can be substituted with a fluorine atom.

[0153] Among these, A 1 and A 3 is -O- and A 2 is -C(CH3)2- is one of the preferred modes of the present application.

[0154] The number of carbon atoms of the C1-10aliphatic hydrocarbon group which can be substituted with a fluorine atom is not particularly limited, and is preferably 1-6, and more preferably 1-4.

[0155] As a specific example of the C1-10aliphatic hydrocarbon group which can be substituted with a fluorine atom, there can be mentioned -CH2-, -C(CH3)2-, -C(CF3)2-, and the like, of which -C(CH3)2- is preferred.

[0156] As the substituents of the four benzene rings described in the formula (71), there can be mentioned a fluorine atom, a C1-10hydrocarbon group whose hydrogen atom can be substituted with a fluorine atom, and the like.

[0157] Also, the mode in which all of the four benzene rings described in the formula (71) are unsubstituted is one of the preferred modes of the present application.

[0158] Preferably, it is also a group represented by the following formula (81). In the above mode, R 111 More preferably, it is a group represented by the following formula (82). 111 More preferably, it is a group represented by the following formula (82).

[0159] [Chemical Formula 10]

[0160]

[0161] In formula (81), A 1 and A 2 are each independently a single bond or a divalent linking group, and * indicates a bonding site to the nitrogen atom in formula (2). The hydrogen atoms of the three benzene rings described in formula (81) can each be substituted with a substituent.

[0162] In formula (82), * indicates a bonding site to the nitrogen atom in formula (2).

[0163] In formula (81), A 1 and A 2 are each independently preferably a C1-10aliphatic hydrocarbon group which can be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O)2-, -NHC(=O)-, or a group composed of two or more of these, more preferably a C1-10aliphatic hydrocarbon group which can be substituted with a fluorine atom, -O-, -C(=O)-, or a group composed of two or more of these, further preferably a C1-10aliphatic hydrocarbon group which can be substituted with a fluorine atom or -O-, and particularly preferably -C(CH3)2-.

[0164] R 115 in formula (2) indicates a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by formula (5) or formula (6) described below is more preferred.

[0165] In formula (5) or formula (6), * indicates a bonding site to another structure, respectively.

[0166] [Chemical Formula 11]

[0167]

[0168] In formula (5), R 112 is a single bond or a divalent linking group, and is preferably a single bond or a group selected from a C1-10aliphatic hydrocarbon group which can be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, and -NHCO-, and combinations of these, more preferably a single bond or a group selected from a C1-3alkylene group which can be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO2-, and further preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S-, and -SO2-.

[0169] and R115 Also preferred is a group represented by the following formula (7). In the above mode, R 115 More preferred is a group represented by the following formula (7-2).

[0170] [Chemical Formula 12]

[0171]

[0172] In formula (7), A 1 ~A 3 are each independently a single bond or a divalent linking group, * indicates a bonding site to the carbonyl group in formula (2), and the hydrogen atoms of the four benzene rings described in formula (7) can be substituted with a substituent.

[0173] In formula (7-2), * indicates a bonding site to the carbonyl group in formula (2).

[0174] In formula (7), A 1 ~A 3 and the preferred modes of the substituents in the benzene rings are the same as those of A 1 ~A 3 and the preferred modes of the substituents in the benzene rings in formula (7-1) described above.

[0175] As R 115 , specifically, a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride, and the like can be given. The polyimide precursor can contain only one kind of tetracarboxylic dianhydride residue as the structure corresponding to R 115 , or two or more kinds.

[0176] The tetracarboxylic dianhydride is preferably represented by the following formula (O).

[0177] [Chemical Formula 13]

[0178]

[0179] In formula (O), R 115 represents a tetravalent organic group. The preferred range of R 115 has the same meaning as that of R 115 in formula (2), and the preferred range is also the same.

[0180] As specific examples of the tetracarboxylic dianhydride, there can be mentioned pyromellitic dianhydride (PMDA), 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide 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'-diphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalene tetracarboxylic dianhydride, 2,2',3,3'-diphenyl tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzene tetracarboxylic dianhydride, and alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms of these.

[0181] Also, as the tetracarboxylic dianhydride, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can also be mentioned as preferable examples.

[0182] In formula (2), R 111 and at least one of R 115 may also have an OH group. More specifically, as R 111 , the residue of a bisaminophenol derivative can be mentioned.

[0183] In formula (2), R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group. As the monovalent organic group, a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxide group is preferable. Also, it is preferable that at least one of R 113 and R 114 contain a polymerizable group, and more preferably both contain a polymerizable group. It is also preferable that R 113 and R 114at least one of the groups represented by R1to R4in the formula (I) contains two or more polymerizable groups. As the polymerizable group, a group capable of undergoing crosslinking reaction by the action of heat, radicals, or the like is preferable, and a radical polymerizable group is more preferable. As specific examples of the polymerizable group, a group having an ethylenic unsaturated bond, an alkoxy methyl group, a hydroxyl methyl group, an acyloxy methyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group can be given. As the radical polymerizable group possessed by the polyimide precursor, a group having an ethylenic unsaturated bond is preferable.

[0184] As the group having an ethylenic unsaturated bond, a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group, etc.), a (meth)acrylamide group, a (meth)acryloxy group, a group represented by the following formula (III), and the like can be given, and a group represented by the following formula (III) is preferable.

[0185] [Chemical Formula 14]

[0186]

[0187] In the formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group, or a hydroxymethyl group, and a hydrogen atom or a methyl group is preferable.

[0188] In the formula (III), * represents a bonding site to other structures.

[0189] In the formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkylene oxide group.

[0190] Examples of the preferable R 201 can be given, and an alkylene group, -CH2CH(OH)CH2-, a cycloalkyl group, or a polyalkylene oxide group is preferable, and an alkylene group or a polyalkylene oxide group is further preferable.

[0191] In the present application, the polyalkylene oxide group refers to a group in which two or more alkylene oxide groups are directly bonded. The alkylene groups in the plurality of alkylene oxide groups included in the polyalkylene oxide group can be the same or different.

[0192] In the case where the polyalkylene oxide group contains a plurality of alkylene oxide groups different in alkylene group, the arrangement of the alkylene oxide groups in the polyalkylene oxide group can be a random arrangement, can be an arrangement having blocks, or can be an arrangement having a pattern of alternation or the like.

[0193] The number of carbon atoms of the above-mentioned alkylene group (in the case where the alkylene group has a substituent, the number of carbon atoms including the substituent) is preferably 2 or more, more preferably 2 to 10, further more preferably 2 to 6, further preferably 2 to 5, further more preferably 2 to 4, still further more preferably 2 or 3, and particularly preferably 2.

[0194] Further, the above-mentioned alkylene group can have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, and the like can be mentioned.

[0195] Further, the number of alkylene oxide groups contained in the polyalkylene oxide group (the number of repetitions of the polyalkylene oxide group) is preferably 2 to 20, more preferably 2 to 10, and further preferably 2 to 6.

[0196] As the polyalkylene oxide group, from the viewpoints of solvent solubility and solvent resistance, a polyethylene oxide group, a polypropylene oxide group, a polytrimethylene oxide group, a polytetramethylene oxide group, or a group formed by bonding a plurality of ethylene oxide groups and a plurality of propylene oxide groups, is preferable, a polyethylene oxide group or a polypropylene oxide group is more preferable, and a polyethylene oxide group is further preferable. In the group formed by bonding a plurality of ethylene oxide groups and a plurality of propylene oxide groups, the ethylene oxide groups and the propylene oxide groups can be arranged randomly, can be arranged in blocks, or can be arranged in an alternating or the like pattern. The preferable number of repetitions of the ethylene oxide groups and the like in these groups is as described above.

[0197] In formula (2), at least one of R 113 and R 114 is a hydrogen atom, the polyimide precursor can form a counter salt with a tertiary amine compound having an ethylenic unsaturated bond. As an example of such a tertiary amine compound having an ethylenic unsaturated bond, N,N-dimethylaminopropyl methacrylate can be mentioned.

[0198] In formula (2), at least one of R 113 and R 114 may be a polar conversion group such as an acid-decomposable group. As the acid-decomposable group, there is no particular limitation as long as it is a group that is decomposed under the action of an acid to generate a phenolic hydroxyl group, a carboxyl group, or the like, which is alkali-soluble, and an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, or the like is preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.

[0199] As specific examples of the acid-decomposable group, a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, and the like can be mentioned. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

[0200] The polyimide precursor is also preferably provided with a fluorine atom in the structure. The content of the fluorine atom in the polyimide precursor is preferably 10% by mass or greater, and is preferably 20% by mass or less.

[0201] Also, in order to improve adhesion to a substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine, a mode of using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like can be given.

[0202] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present application is preferably a precursor having a repeating unit represented by formula (2-A). By the polyimide precursor containing a repeating unit represented by formula (2-A), the width of the exposure latitude can be further expanded.

[0203] Formula (2-A)

[0204] [Chemical Formula 15]

[0205]

[0206] In formula (2-A), A 1 and A 2 represent an oxygen atom, R 111 and R 112 each independently represent a divalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, R 113 and R 114 at least one of which is a group containing a polymerizable group, and preferably both are groups containing a polymerizable group.

[0207] A 1 , A 2 , R 111 , R 113 , and R 114 each independently have the same meaning and the same preferable range as A 1 , A 2 , R 111 , R 113 , and R 114 in formula (2). R 112 has the same meaning and the same preferable range as R 112 in formula (5).

[0208] The polyimide precursor can contain one kind of the repeating unit represented by formula (2), or two or more kinds thereof. Also, structural isomers of the repeating unit represented by formula (2) can be contained. The polyimide precursor can contain other kinds of repeating units in addition to the repeating unit represented by formula (2) described above.

[0209] As an embodiment of the polyimide precursor in the present application, a mode in which the content of the repeating unit represented by formula (2) is 50 mol% or more of all the repeating units can be given. The total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the terminal polyimide precursor can be the repeating unit represented by formula (2).

[0210] The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. The number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and further preferably 4,000 to 20,000.

[0211] The dispersity of the molecular weight of the polyimide precursor described above is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0212] In the present specification, the dispersity of the molecular weight is a value calculated from the weight average molecular weight / number average molecular weight.

[0213] In the case where the resin composition contains a plurality of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the dispersity of at least one of the polyimide precursors are within the ranges described above. Also, it is preferable that the weight average molecular weight, the number average molecular weight, and the dispersity of the plurality of polyimide precursors calculated as one resin are within the ranges described above, respectively.

[0214] 〔Polyimide〕

[0215] The polyimide used in the present application can be an alkali-soluble polyimide, or a polyimide which is soluble in a developer mainly composed of an organic solvent.

[0216] In the present specification, the alkali-soluble polyimide means that 0.1 g or more of the polyimide is dissolved with respect to 100 g of a 2.38 mass% aqueous tetramethylammonium solution at 23°C, and from the viewpoint of pattern formability, it is preferable that 0.5 g or more of the polyimide is dissolved, and further preferable that 1.0 g or more of the polyimide is dissolved. The upper limit of the above-mentioned dissolution amount is not particularly limited, and it is preferable that it is 100 g or less.

[0217] From the viewpoint of the film strength and the insulating property of the obtained organic film, the polyimide preferably has a plurality of imide structures in the main chain.

[0218] - fluorine atom -

[0219] From the viewpoint of the film strength of the obtained organic film, the polyimide is also preferably one having a fluorine atom.

[0220] The fluorine atom is, for example, preferably contained in R 132 in the repeating unit represented by the formula (4) described later, or R 131 in the repeating unit represented by the formula (4) described later, and more preferably contained in R 132 in the repeating unit represented by the formula (4) described later, or R 131 in the repeating unit represented by the formula (4) described later.

[0221] The amount of the fluorine atom is preferably 5 mass% or more and, preferably, 20 mass% or less with respect to the total mass of the polyimide.

[0222] - silicon atom -

[0223] From the viewpoint of the film strength of the obtained organic film, the polyimide is also preferably one having a silicon atom.

[0224] The silicon atom is, for example, preferably contained in R 131 in the repeating unit represented by the formula (4) described later, and more preferably contained in R 131 in the repeating unit represented by the formula (4) described later as an organic-modified (poly)siloxane structure described later.

[0225] The above-mentioned silicon atom or the above-mentioned organic-modified (poly)siloxane structure can also be contained in the side chain of the polyimide, and is preferably contained in the main chain of the polyimide.

[0226] The amount of the silicon atom is preferably 1 mass% or more and, preferably, 20 mass% or less with respect to the total mass of the polyimide.

[0227] - ethylenic unsaturated bond -

[0228] From the viewpoint of the film strength of the obtained organic film, the polyimide is preferably one having an ethylenic unsaturated bond.

[0229] The polyimide can have an ethylenic unsaturated bond at the end of the main chain, or in the side chain, but preferably has an ethylenic unsaturated bond in the side chain.

[0230] The above ethylenic unsaturated bond is preferably radical-polymerizable.

[0231] The ethylenic unsaturated bond is preferably included in R 132 or R 131 , more preferably is included in R 132 or R 131 as a group having an ethylenic unsaturated bond.

[0232] Among these, the ethylenic unsaturated bond is preferably included in R 131 , more preferably is included in R 131 as a group having an ethylenic unsaturated bond.

[0233] As the group having an ethylenic unsaturated bond, there can be mentioned a group directly bonded to an aromatic ring and having a vinyl group which can be substituted, such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloxy group, a group represented by the following formula (IV), and the like.

[0234] [Chemical Formula 16]

[0235]

[0236] In formula (IV), R 20 represents a hydrogen atom, a methyl group, an ethyl group, or a hydroxymethyl group, and preferably is a hydrogen atom or a methyl group.

[0237] In formula (IV), R 21 represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms of the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3, and the number of repetitions of the alkyleneoxy group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group in which two or more of these are combined.

[0238] As the alkylene group having 2 to 12 carbon atoms, any one of a linear, branched, cyclic, or combination thereof can be used.

[0239] As the alkylene group having 2 to 12 carbon atoms, an alkylene group having 2 to 8 carbon atoms is preferable, and an alkylene group having 2 to 4 carbon atoms is more preferable.

[0240] Among these, R21 Preferably, the group represented by any one of the following formulae (R1) to (R3) is used, and more preferably, the group represented by formula (R1) is used.

[0241] [Chemical Formula 17]

[0242]

[0243] In formulae (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkylene oxide group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded, X represents an oxygen atom or a sulfur atom, * represents a bonding site to another structure, and ● represents a bonding site to R 21 the oxygen atom to be bonded.

[0244] In formulae (R1) to (R3), the preferable mode of the alkylene group having 2 to 12 carbon atoms or the (poly)alkylene oxide group having 2 to 30 carbon atoms as L is the same as the preferable mode of the alkylene group having 2 to 12 carbon atoms or the (poly)alkylene oxide group having 2 to 30 carbon atoms as R 21 in formula (IV).

[0245] In formula (R1), X is preferably an oxygen atom.

[0246] In formulae (R1) to (R3), the meaning of * is the same as that of * in formula (IV), and the preferable mode is also the same.

[0247] The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate or the like).

[0248] The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate or the like).

[0249] The structure represented by formula (R3) is obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate or the like).

[0250] In formula (IV), * represents a bonding site to another structure, and is preferably a bonding site to the main chain of a polyimide.

[0251] The amount of the ethylenically unsaturated bond is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g, with respect to the total mass of the polyimide.

[0252] - a polymerizable group other than a group having an ethylenic unsaturated bond

[0253] The polyimide can have a polymerizable group other than a group having an ethylenic unsaturated bond.

[0254] As the polymerizable group other than a group having an ethylenic unsaturated bond, there can be mentioned an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, a hydroxymethyl group, and the like.

[0255] The polymerizable group other than a group having an ethylenic unsaturated bond is preferably, for example, R 131 .

[0256] The amount of the polymerizable group other than a group having an ethylenic unsaturated bond is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g, with respect to the total mass of the polyimide.

[0257] - a polarity conversion group -

[0258] The polyimide can have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R 113 and R 114 in the above-described formula (2), and the preferable modes are also the same.

[0259] The polarity conversion group is, for example, contained in R 131 , R 132 , a terminal of the polyimide, and the like in the repeat unit represented by formula (4) described later.

[0260] - acid value -

[0261] In the case where the polyimide is supplied to alkali development, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more, from the viewpoint of improving developability.

[0262] The above-described acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and further preferably 200 mgKOH / g or less.

[0263] In the case where the polyimide is supplied to development using a developer in which an organic solvent is a main component (for example, "solvent development"), the acid value of the polyimide is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and further preferably 5 to 20 mgKOH / g.

[0264] The acid value is measured by a known method, for example, the method described in JIS K 0070: 1992.

[0265] As the acid group contained in the polyimide, from the viewpoint of both storage stability and developability, an acid group having a pKa of 0 to 10 is preferred, and an acid group having a pKa of 3 to 8 is more preferred.

[0266] The pKa is a value that considers a dissociation reaction in which a hydrogen ion is released from an acid and expresses an equilibrium constant Ka thereof by a negative common logarithm pKa. In the present specification, the pKa is set to a calculated value based on ACD / ChemSketch (registered trademark) unless otherwise specified. The pKa can be referred to the value published in "Shinsei 5han The Chemical Society of Japan, Henkaku 5han Kagaku Benran Kiban" edited by The Chemical Society of Japan.

[0267] In the case where the acid group is a polyprotic acid such as phosphoric acid, the above pKa is the first dissociation constant.

[0268] As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0269] - Phenolic hydroxyl group -

[0270] From the viewpoint of making the developing speed based on an alkali developer appropriate, the polyimide preferably has a phenolic hydroxyl group.

[0271] The polyimide can have a phenolic hydroxyl group at the end of the main chain, or can have a phenolic hydroxyl group in a side chain.

[0272] The phenolic hydroxyl group is, for example, preferably contained in R 132 or R 131 in the repeating unit represented by the following formula (4).

[0273] The amount of the phenolic hydroxyl group is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g, with respect to the total mass of the polyimide.

[0274] As the polyimide used in the present application, there is no particular limitation as long as it is a high molecular compound having an imide structure, and preferably contains a repeating unit represented by the following formula (4).

[0275] [Chemical Formula 18]

[0276]

[0277] In formula (4), R 131 represents a divalent organic group, and R 132 represents a tetravalent organic group.

[0278] In the case of having a polymerizable group, the polymerizable group can be located on at least one of R 131 and R 132 , as shown in the following Formula (4-1) or Formula (4-2), or at the terminal of the polyimide.

[0279] Formula (4-1)

[0280] [Chemical Formula 19]

[0281]

[0282] In Formula (4-1), R 133 is a polymerizable group, and the meanings of the other groups are the same as those of Formula (4).

[0283] Formula (4-2)

[0284] [Chemical Formula 20]

[0285]

[0286] In Formula (4-2), at least one of R 134 and R 135 is a polymerizable group, and is an organic group when not a polymerizable group, and the meanings of the other groups are the same as those of Formula (4).

[0287] As the polymerizable group, the above group containing an ethylenically unsaturated bond or the above crosslinkable group other than the group having an ethylenically unsaturated bond can be cited.

[0288] R 131 represents a divalent organic group. As the divalent organic group, the same groups as R 111 in Formula (2) can be cited, and the preferable range is also the same.

[0289] As R 131 , a diamine residue remaining after the amino group of a diamine is cited. As the diamine, aliphatic, cyclic aliphatic, or aromatic diamine, etc. can be cited. As specific examples, examples of R 111 in Formula (2) of the polyimide precursor can be cited.

[0290] From the viewpoint of more effectively suppressing warping at the time of calcination, R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain. More preferably, a diamine residue containing two or more of either or both of ethylene glycol chains and propylene glycol chains in one molecule, and further preferably a diamine residue of the above diamine and not containing an aromatic ring.

[0291] As the diamine which collectively contains 2 or more of either or both of ethylene glycol chains, propylene glycol chains in one molecule, JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (product names above, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, and the like can be given, but are not limited to these.

[0292] R 132 represents a tetravalent organic group. As the tetravalent organic group, the same group as R 115 in formula (2) can be given, and the preferable range is also the same.

[0293] For example, as R 115 , a tetravalent organic group exemplified above is bonded to four -C(=O)- moieties in formula (4) to form a condensed ring.

[0294] R 132 can be given. As a specific example, the example of R 115 in formula (2) of a polyimide precursor can be given. From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

[0295] It is also preferable that at least one of R 131 and R 132 has an OH group. More specifically, as R 131 , 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, (DA-1) to (DA-18) described above can be given as preferable examples, and as R 132 , (DAA-1) to (DAA-5) described above can be given as more preferable examples.

[0296] It is also preferable that the polyimide has a fluorine atom in the structure. The content of the fluorine atom in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0297] In order to improve adhesion to a substrate, the polyimide can be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like can be given.

[0298] In order to improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide are capped with a capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochloroformic compound, a monoactive ester compound, or the like. Among these, it is more preferable to use a monoamine, and as the preferable compound of the 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-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminophenylthiol, 3-aminophenylthiol, 4-aminophenylthiol, and the like can be given. Two or more of these can be used, or a plurality of different end groups can be introduced by reacting a plurality of capping agents.

[0299] -Imidization rate (ring closure rate)-

[0300] From the viewpoint of the film strength, insulating properties, and the like of the obtained organic film, the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or greater, more preferably 80% or greater, and further preferably 90% or greater.

[0301] The upper limit of the above imidization rate is not particularly limited, and is preferably 100% or less.

[0302] The above imidization rate is measured, for example, by the following method.

[0303] The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 of the peak at 1377 cm -1 near which is derived from the imide structure is obtained. Next, after the polyimide is heat-treated at 350°C for 1 hour, the infrared absorption spectrum is measured again, and the peak intensity P2 of the peak at 1377 cm -1 near which is derived from the imide structure is obtained. Using the obtained peak intensities P1, P2, the imidization rate of the polyimide can be obtained according to the following formula.

[0304] Imidification rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0305] Polyimide can contain all the R of the repeating unit. 131 and R 132 The repeating unit represented by the same formula (4) above can also contain R. 131 and R 132 The combination contains two or more different repeating units represented by the above formula (4). In addition to the repeating units represented by the above formula (4), polyimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by the above formula (2).

[0306] Polyimides can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine (partially replaced by a monoamine end-capping agent) at low temperature; by reacting a tetracarboxylic dianhydride (partially replaced by an anhydride, monoacyl chloride, or monoreactive ester compound end-capping agent) with a diamine at low temperature; by obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting it with a diamine (partially replaced by a monoamine end-capping agent) in the presence of a condensing agent; by obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acyl-chlorinating the remaining dicarboxylic acid and reacting it with a diamine (partially replaced by a monoamine end-capping agent); and by completely imidizing it using a known imidization reaction method; or by stopping the imidization reaction midway and introducing a partial imide structure; and by introducing a partial imide structure by mixing a fully imidized polymer with the polyimide precursor. Furthermore, other known methods for synthesizing polyimides can also be applied.

[0307] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the flexural strength of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), the weight-average molecular weight is particularly preferably 15,000 or more.

[0308] The number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.

[0309] The dispersity of the molecular weight of the above polyimide is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the dispersity of the molecular weight of the polyimide is not particularly limited, and is preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.

[0310] In the case where the resin composition contains a plurality of polyimides as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the dispersity of at least one of the polyimides are within the above ranges. It is also preferable that the weight average molecular weight, the number average molecular weight, and the dispersity of the plurality of polyimides as one resin are within the above ranges, respectively.

[0311] [Polybenzoxazole precursor]

[0312] As the polybenzoxazole precursor, the compounds described in paragraphs 0073 to 0095 of International Publication No. 2022 / 145355 can be given. The above description is incorporated into the present specification.

[0313] [Polybenzoxazole]

[0314] As the polybenzoxazole, the compounds described in paragraphs 0096 to 0103 of International Publication No. 2022 / 145355 can be given. The above description is incorporated into the present specification.

[0315] [Polyamide-imide precursor]

[0316] As the polyamide-imide precursor, the compounds described in paragraphs 0104 to 0119 of International Publication No. 2022 / 145355 can be given. The above description is incorporated into the present specification.

[0317] [Polyamide-imide]

[0318] As the polyamide-imide, the compounds described in paragraphs 0120 to 0133 of International Publication No. 2022 / 145355 can be given. The above description is incorporated into the present specification.

[0319] [Method for producing polyimide precursor and the like]

[0320] The polyimide precursor and the like are produced, for example, by the method described in paragraphs 0134 to 0136 of International Publication No. 2022 / 145355. The above description is incorporated into the present specification.

[0321] [Content]

[0322] The content of the specific resin in the resin composition of the present application is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and still further preferably 50% by mass or more, relative to the total solid content of the resin composition. Also, the content of the resin in the resin composition of the present application is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, still further preferably 97% by mass or less, and yet further preferably 95% by mass or less, relative to the total solid content of the resin composition.

[0323] The resin composition of the present application can contain only one kind of the specific resin, or can contain two or more kinds thereof. In the case of containing two or more kinds, the total amount is preferably within the above range.

[0324] The resin composition of the present application preferably contains at least two kinds of resins.

[0325] Specifically, the resin composition of the present application can contain two or more kinds of the specific resin and other resins described later, can contain two or more kinds of the specific resin, and preferably contains two or more kinds of the specific resin.

[0326] In the case where the resin composition of the present application contains two or more kinds of the specific resin, for example, two or more kinds of polyimide precursors are preferred, which are polyimide precursors containing a structure derived from a dianhydride (R 115 ) different from each other in the above formula (2).

[0327] <Other Resins>

[0328] The resin composition of the present application can contain the above specific resin and other resins (hereinafter, also simply referred to as "other resins") different from the specific resin.

[0329] As the other resins, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane resin, butyral resin, styrene resin, polyether resin, polyester resin, and the like can be given.

[0330] For example, by further adding a (meth)acrylic resin, a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.

[0331] For example, by adding a (meth)acrylic resin having a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, the contained mole amount of the polymerizable group in 1 g of the resin is 1 x 10 -3or more).

[0332] When the resin composition of the present application 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, still further preferably 2% by mass or more, yet further preferably 5% by mass or more, and yet still further preferably 10% by mass or more, relative to the total solid content of the resin composition.

[0333] When the resin composition of the present application contains other resins, the content of the other resins is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, still further preferably 60% by mass or less, yet further preferably 50% by mass or less, relative to the total solid content of the resin composition.

[0334] As a preferred mode of the resin composition of the present application, a mode in which the content of the other resins is low can also be set. In the above mode, the content of the other resins is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, still further preferably 5% by mass or less, and yet further preferably 1% by mass or less, relative to the total solid content of the resin composition. The lower limit of the above content is not particularly limited, and is 0% by mass or more.

[0335] The resin composition of the present application can contain only one kind of other resins, or can contain two or more kinds. When two or more kinds are contained, the total content is preferably within the above range.

[0336] <Compound A>

[0337] The first resin composition of the present application contains a first compound A.

[0338] The first compound A is a compound represented by formula (Al-1).

[0339] [Chemical Formula 21]

[0340]

[0341] In formula (Al-1), R 1 is an organic group having at least one or more atoms selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, R 1 may be the same or different when a plurality of R 2 is a hydrogen atom or an arbitrary organic group other than the above R 1 , R 2 may be the same or different when a plurality of R 1 and R 2at least 2 of the R groups can be bonded to form a ring structure, n represents an integer of 1 to 3, m represents an integer of 1 or more, R 3 represents an m-valent organic group.

[0342] In formula (A1-1), R 1 is preferably an organic group having at least one or more atoms selected from an oxygen atom and a nitrogen atom. Here, R 1 having an oxygen atom and a nitrogen atom is one of the preferred modes of the present application.

[0343] In formula (A1-1), R 1 is preferably an amino group or an ester bond.

[0344] In formula (A1-1), R 1 is preferably one or more hydrocarbon groups in which a hydrogen atom can be substituted with a substituent, and at least one group selected from the group consisting of a carboxyl group, an ester bond (-C(=O)O-), a urea bond (-NR N -C(=O)NR N -) and a substituted amino group.

[0345] The above R N represents a hydrogen atom or a hydrocarbon group in which a hydrogen atom can be substituted with a substituent. As the above substituent, a hydroxyl group, an alkoxy group, a halogen atom, etc. can be mentioned, and a hydroxyl group is preferred.

[0346] As the above hydrocarbon group, a saturated aliphatic hydrocarbon group in which a hydrogen atom can be substituted with a substituent or an aromatic hydrocarbon group in which a hydrogen atom can be substituted with a substituent is preferred.

[0347] As the above saturated aliphatic hydrocarbon group, a hydrocarbon group having 2 to 10 carbon atoms is preferred, and a hydrocarbon group having 2 to 4 carbon atoms is more preferred. As the substituent when a hydrogen atom of the saturated aliphatic hydrocarbon group is substituted, a hydroxyl group, an alkoxy group, a halogen atom, a polymerizable group, etc. can be mentioned, and a hydroxyl group is preferred. As the polymerizable group, a (meth)acryloyloxy group, a (meth)acrylamido group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, etc. can be mentioned.

[0348] As the above aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferred, and an aromatic hydrocarbon group having 6 carbon atoms is more preferred. As the substituent when a hydrogen atom of the aromatic hydrocarbon group is substituted, an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a polymerizable group, etc. can be mentioned, and a hydroxyl group is preferred. As the polymerizable group, a vinyl group, a (meth)acryloyloxy group, a (meth)acrylamido group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, etc. can be mentioned.

[0349] The orientation of the above ester bond is not particularly limited, and the silicon atom side in formula (A1-1) is preferably the orientation in which the carbon atom included in the ester bond.

[0350] As the substituent group of the above-mentioned substituted amino group, an alkyl group whose hydrogen atom can be substituted with a substituent group or an aromatic group whose hydrogen atom can be substituted with a substituent group can be mentioned. As the substituent group when the hydrogen atom of the above-mentioned alkyl group is substituted, a hydroxyl group, an alkoxy group, a halogen atom, and the like can be mentioned, and a hydroxyl group is preferred. As the substituent group when the hydrogen atom of the above-mentioned aromatic group can be substituted, a hydroxyl group, an alkoxy group, a halogen atom, and the like can be mentioned.

[0351] R 1 A group represented by the following formula (R-1), formula (R-2) or formula (R-3) is preferred.

[0352] [Chemical Formula 22]

[0353]

[0354] In formula (R-1), L R1 represents a hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O-, R R1 and R R2 each independently represents a hydrocarbon group whose hydrogen atom can be substituted with a substituent group, and * indicates a bonding site with the oxygen atom in formula (A1-1).

[0355] In formula (R-2), L R1 represents a hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O-, R R3 represents a hydrogen atom or a hydrocarbon group whose hydrogen atom can be substituted with a substituent group, and * indicates a bonding site with the oxygen atom in formula (A1-1).

[0356] In formula (R-3), L R1 represents a hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O-, R R4 and R R5 represents a hydrogen atom or a hydrocarbon group whose hydrogen atom can be substituted with a substituent group, R R6 represents a hydrocarbon group whose hydrogen atom can be substituted with a substituent group, and * indicates a bonding site with the oxygen atom in formula (A1-1).

[0357] In formula (R-1), L R1 An alkylene group or an alkoxyalkylenealkylene group is preferred, and an alkylene group is more preferred. L R1 The number of carbon atoms of the hydrocarbon group (preferably an alkylene group) in L

[0358] In formula (R-1), R R1 and R R2 each independently preferably represents an alkyl group whose hydrogen atom can be substituted with a substituent group, or an aromatic hydrocarbon group whose hydrogen atom can be substituted with a substituent group.

[0359] As the above alkyl group, an alkyl group having 2 to 10 carbon atoms is preferable, and an alkyl group having 2 to 4 carbon atoms is more preferable. As the substituent for the hydrogen atom of the alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, and the like can be given, and a hydroxyl group is preferable. As the polymerizable group, a vinyl group, a (meth) acryloyloxy group, a (meth) acrylamido group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, and the like can be given.

[0360] As the above aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, and a phenyl group is more preferable. As the substituent for the hydrogen atom of the aromatic hydrocarbon group, an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a polymerizable group, and the like can be given, and a hydroxyl group is preferable. As the polymerizable group, a vinyl group, a (meth) acryloyloxy group, a (meth) acrylamido group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, and the like can be given.

[0361] In the formula (R-1), R R1 is a hydroxyl group, and R R2 is an aromatic hydrocarbon group is one of the preferable modes of the present application. For example, R R1 is a hydroxyethyl group, and R R2 is a phenyl group is preferable.

[0362] In the formula (R-2), L R1 is the same as the preferable mode of L R1 in the above formula (R-1).

[0363] In the formula (R-2), R R3 is the same as the preferable mode of R R1 in the above formula (R-1).

[0364] In the formula (R-2), L R1 is an alkylene group, and R R3 is a hydrogen atom or an unsubstituted alkyl group is one of the preferable modes of the present application. For example, it is preferable that L R1 is a trimethylene group, and R R3 is a hydrogen atom, a methyl group, or an ethyl group.

[0365] In the formula (R-3), L R1 is the same as the preferable mode of L R1 in the above formula (R-1).

[0366] In the formula (R-3), R R4 and R R5 are preferably a hydrogen atom or an alkyl group whose hydrogen atom can be substituted with a substituent.

[0367] The number of carbon atoms of the above alkyl group is preferably from 1 to 10, more preferably from 2 to 4. As a substituent for the hydrogen atom of the alkyl group when substituted, a hydroxyl group, an alkoxy group, a halogen atom, or the like can be given, with a hydroxyl group being preferred. As the polymerizable group, a vinyl group, a (meth)acryloyloxy group, a (meth)acrylamido group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, or the like can be given.

[0368] In formula (R-3), L R6 is preferably an alkyl group which can be substituted with a substituent for a hydrogen atom.

[0369] The number of carbon atoms of the above alkyl group is preferably from 1 to 10, more preferably from 2 to 4. As a substituent for the hydrogen atom of the alkyl group when substituted, a hydroxyl group, an alkoxy group, a halogen atom, or the like can be given, with a hydroxyl group being preferred. As the polymerizable group, a vinyl group, a (meth)acryloyloxy group, a (meth)acrylamido group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, or the like can be given.

[0370] In formula (R-3), L R1 is an alkylene group or an alkyloxyalkylene group, R R4 is a hydrogen atom or a hydroxyalkyl group, R 5 is a hydrogen atom, R 6 is an alkyl group substituted with a polymerizable group for a hydrogen atom is also one of the preferred modes of the present application. For example, L R1 is an ethylene group or an ethyloxyethylene group, R R4 is a hydrogen atom or a hydroxyethyl group, R 5 is a hydrogen atom, R 6 is a (meth)acryloyloxyethyl group is also one of the preferred modes of the present application.

[0371] As the specific examples of R 1 in formula (A1-1), the following are given, but the present application is not limited to these. In the following formulas, * indicates the bonding site to the oxygen atom in formula (A1-1). Also, in the following specific examples, the HSP value (the value of the total HSP described later when * is substituted with a hydrogen atom) is described as HSP.

[0372] [Chemical Formula 23]

[0373]

[0374] In formula (A1-1), R 2 is preferably an alkyl group, preferably an alkyl group having from 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, or an isopropyl group, further preferably a methyl group or an ethyl group.

[0375] Here, the HSP value (the value of the total HSP described later when * is replaced with a hydrogen atom) is 16.9 for a methyl group, 14.8 for an ethyl group, and 15.0 for a hexyl group.

[0376] In formula (A1-1), R 1 and R 2 preferably form a ring structure that contains a nitrogen atom as a ring member.

[0377] Specifically, a ring structure that contains a structure represented by formula (R-4) or formula (R-5) described below is preferable.

[0378] [Chemical Formula 24]

[0379]

[0380] In formula (R-4), L R2 and L R3 each independently represent a hydrocarbon group in which a hydrogen atom can be substituted with a substituent, R R7 represents a hydrocarbon group in which a hydrogen atom can be substituted with a substituent, and * each represents a bonding site to an oxygen atom in formula (A1-1).

[0381] In formula (R-5), L R4 and L R5 each independently represent a hydrocarbon group in which a hydrogen atom can be substituted with a substituent, R R8 represents a hydrogen atom or a hydrocarbon group in which a hydrogen atom can be substituted with a substituent, R R9 represents a hydrocarbon group in which a hydrogen atom can be substituted with a substituent, and * each represents a bonding site to an oxygen atom in formula (A1-1).

[0382] In formula (R-4), L R2 and L R3 each independently preferably represent an alkylene group. As the alkylene group, an alkylene group having 2 to 10 carbon atoms is preferable, an alkylene group having 2 to 4 carbon atoms is more preferable, and an ethylene group is further preferable.

[0383] In formula (R-4), R R7 preferable modes of R R1 in formula (R-1) are the same.

[0384] In formula (R-4), * each preferably bonds to an oxygen atom in formula (A1-1) with a single bond without a linking group.

[0385] In formula (R-5), L R4 and L R5 preferable modes of L R2 and L R3The preferable mode is the same as that of R

[0386] In formula (R-5), R R8 The preferable mode is the same as that of R R5 The preferable mode is the same as that of R

[0387] In formula (R-5), R R9 The preferable mode is the same as that of R R6 The preferable mode is the same as that of R

[0388] In formula (R-5), it is preferable that each of the oxygen atoms in formula (A1-1) is bonded with a single bond without a linking group.

[0389] The following shows examples of the structure included in the ring structure formed when at least two of R 1 and R 2 in formula (A1-1) are bonded to form a ring structure, but the present application is not limited to these. Each of the oxygen atoms in formula (A1-1) is bonded with a single bond without a linking group. Also, in the following specific examples, the HSP value (the value of the total HSP described later when the substituent is a hydrogen atom) described later is recorded as HSP.

[0390] [Chemical Formula 25]

[0391]

[0392] In formula (A1-1), n is preferably 1 or 2. Also, the mode where n is 1 is one of the preferable modes of the present application.

[0393] In formula (A1-1), m is preferably an integer of 1 to 3, more preferably 1 or 2. Also, the mode where m is 1 is one of the preferable modes of the present application.

[0394] In formula (A1-1), R 3 represents an m-valent organic group.

[0395] In formula (A1-1), R 3 preferably contains 1 or more hydrocarbon groups in which a hydrogen atom can be substituted with a substituent and at least one group selected from the group including an amide bond (-C(=0)NR N -) and an imino group (-NR N -).

[0396] The above R N represents a hydrogen atom or a hydrocarbon group in which a hydrogen atom can be substituted with a substituent, and is preferably a hydrogen atom. As the above substituent, a hydroxyl group, an alkoxy group, a halogen atom, and the like can be given.

[0397] As the above hydrocarbon group, a saturated aliphatic hydrocarbon group whose hydrogen atom can be substituted with a substituent or an aromatic hydrocarbon group whose hydrogen atom can be substituted with a substituent is preferable.

[0398] As the above saturated aliphatic hydrocarbon group, a hydrocarbon group having 2 to 10 carbon atoms is preferable, and a hydrocarbon group having 2 to 4 carbon atoms is more preferable. As the substituent when the hydrogen atom of the saturated aliphatic hydrocarbon group is substituted, a hydroxyl group, an alkoxy group, a halogen atom, a polymerizable group, and the like can be given. As the polymerizable group, a vinyl group, a (meth)acryloyloxy group, a (meth)acrylamide group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, and the like can be given.

[0399] As the above aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, and an aromatic hydrocarbon group having 6 carbon atoms is more preferable. As the substituent when the hydrogen atom of the aromatic hydrocarbon group is substituted, a carboxyl group, an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a polymerizable group, and the like can be given. As the polymerizable group, a vinyl group, a (meth)acryloyloxy group, a (meth)acrylamide group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, and the like can be given.

[0400] In formula (A1-1), R 3 A group represented by the following formula (R3-1) is preferable.

[0401] [Chemical Formula 26]

[0402]

[0403] In formula (R3-1), L 31 Each independently represents a divalent linking group, R 31 Each independently represents a divalent linking group, m represents an integer of 1 or more, and L 32 represents a hydrogen atom or a substituent, and L 32 represents an m-valent linking group, and * represents a bonding site to the silicon atom in formula (A1-1).

[0404] In formula (R3-1), L 31 A substituted alkylene group is preferable. The number of carbon atoms of the above alkylene group is preferably 2 to 10, and further preferably 2 to 4. Also, an alkylene group which is not substituted is one of the preferable modes of the present application.

[0405] R 31 A hydrocarbon group or a group represented by *-C(=O)R 32 is preferable.

[0406] As R 31The hydrocarbon group represented by the above, more preferably an aromatic hydrocarbon group in which a hydrogen atom can be substituted with a substituent, or an aliphatic unsaturated hydrocarbon group in which a hydrogen atom can be substituted with a substituent, more preferably an aromatic hydrocarbon group in which a hydrogen atom can be substituted with a substituent.

[0407] As the aromatic hydrocarbon group in which a hydrogen atom can be substituted with a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms in which a hydrogen atom can be substituted with a substituent is preferable, and a phenylene group in which a hydrogen atom can be substituted with a substituent is more preferable. As the substituent in the aromatic hydrocarbon group in which a hydrogen atom can be substituted with a substituent, a carboxyl group, a hydroxyl group, an alkyl group, an alkoxy group, a halogen atom, and the like can be given, and a carboxyl group is preferable.

[0408] As the aliphatic unsaturated hydrocarbon group in which a hydrogen atom can be substituted with a substituent, an ethylene group and the like can be given.

[0409] In R 31 The group represented by *-C(=O)R 32 In the group represented by *-C(=O)R 32 , * represents a bonding site to the nitrogen atom in the formula (R3-1), and # represents a bonding site to L 32 in the formula (R3-1). The above R 31 represents an organic group, and an aromatic hydrocarbon group in which a hydrogen atom can be substituted with a substituent is preferable. The preferable mode of the aromatic hydrocarbon group in which a hydrogen atom can be substituted with a substituent is the same as that of the above R 31 when the above R

[0410] m is the same number as m in the formula (A1-1).

[0411] When m is 1, L 32 represents a hydrogen atom or a substituent, and a hydrogen atom or a carboxyl group is preferable. In addition, a publicly known substituent can be used within a range where the effects of the present application can be obtained.

[0412] When m is 2 or more, L 32 represents a single bond or a connecting group having m valences, and a hydrocarbon group in which a hydrogen atom can be substituted with a substituent, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N , or a group in which two or more of these are bonded. In particular, when m is 2, L 32 is more preferably -CH2-, -O-, -C(=O)-, -C(CF3)2-, or -C(CH3)2-, and further preferably -C(=O)-.

[0413] As the specific examples of R 3 in the formula (A1-1), the following are described, but the present application is not limited to these. In the following formulae, * represents a bonding site to the silicon atom in the formula (A1-1).

[0414] [Chemical Formula 27]

[0415]

[0416] The first compound A is preferably a compound represented by the following formula (A1-2).

[0417] [Chemical Formula 28]

[0418]

[0419] In formula (A1-2), R 1 is an organic group having at least one or more atoms selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, R 1 may be the same or different when a plurality of R 2 is a hydrogen atom or an arbitrary organic group other than R 1 described above, R 2 may be the same or different when a plurality of R 1 and R 2 may be bonded to form a ring structure, n represents an integer of 1 to 3, L represents a divalent linking group, and R 4 represents a hydrogen atom or a monovalent organic group.

[0420] In formula (A1-2), R 1 , R 2 , and n are preferably the same as R 1 , R 2 , and n in formula (A1-1) described above.

[0421] In formula (A1-2), L is preferably an alkylene group from which a hydrogen atom can be substituted. The number of carbon atoms in the alkylene group is preferably 2 to 10, and further preferably 2 to 4. Also, it is one of the preferred modes of the present application that the alkylene group is an unsubstituted alkylene group.

[0422] In formula (A1-2), R 4 is preferably a hydrocarbon group or a group represented by *-C(=O)R 33 .

[0423] In formula (A1-2), as the hydrocarbon group represented by R 4 , more preferably, it is an aromatic hydrocarbon group from which a hydrogen atom can be substituted or an aliphatic unsaturated hydrocarbon group from which a hydrogen atom can be substituted, and more preferably, it is an aromatic hydrocarbon group from which a hydrogen atom can be substituted.

[0424] As the aromatic hydrocarbon group of which the hydrogen atom can be substituted with a substituent, a carbon number 6 to 20 aromatic hydrocarbon group of which the hydrogen atom can be substituted with a substituent is preferable, and a phenylene group of which the hydrogen atom can be substituted with a substituent is more preferable. As the substituent of the aromatic hydrocarbon group of which the hydrogen atom can be substituted with a substituent, a carboxyl group, a hydroxyl group, an alkyl group, an alkoxy group, a halogen atom, and the like can be given, and a carboxyl group is preferable.

[0425] As the aliphatic unsaturated hydrocarbon group of which the hydrogen atom can be substituted with a substituent, an ethylene group and the like can be given.

[0426] In R 31 denotes a group represented by *-C(=O)R 33 denotes a group represented by *-C(=O)R 33 denotes an organic group, and a aromatic hydrocarbon group of which the hydrogen atom can be substituted with a substituent is preferable. The preferable mode of the aromatic hydrocarbon group of which the hydrogen atom can be substituted with a substituent is the same as that of the above R 4 denotes an organic group, and a aromatic hydrocarbon group of which the hydrogen atom can be substituted with a substituent is preferable. The preferable mode of the aromatic hydrocarbon group of which the hydrogen atom can be substituted with a substituent is the same as that of the above R

[0427] The second resin composition of the present application contains a second compound A.

[0428] The second compound A is a compound represented by formula (A2-1).

[0429] [Chemical Formula 29]

[0430]

[0431] In formula (A2-1), R 21 denotes an organic group having an HSP value of 17.0 to 27.0 MPa 1 / 2 denotes an organic group having an HSP value of 17.0 to 27.0 MPa 21 may be the same or different, R 22 denotes a hydrogen atom or any organic group other than the above R 21 denotes a hydrogen atom or any organic group other than the above R 22 may be the same or different, R 21 and at least two of R 22 may be bonded to form a ring structure, n denotes an integer of 1 to 3, m denotes an integer of 1 or more, and R 23 denotes an organic group of m valence.

[0432] In formula (A2-1), R 21 denotes an organic group having an HSP value of 17.0 to 27.0 MPa 1 / 2 denotes an organic group having an HSP value of 17.0 to 27.0 MPa 1 / 2 denotes an organic group having an HSP value of 17.0 to 27.0 MPa

[0433] In the present specification, R 21 and R 22 described later, the SP value is the total HSP calculated by the following formula, using the calculation software HSPiP (version 4.1.07) for a structure in which the bond of R 21 or R 22 with oxygen is replaced with hydrogen, with 3 components (dD, dP, dH) being calculated.

[0434] total HSP (MPa 1 / 2 ) = (dD 2 + dP 2 + dH 2 ) 1 / 2

[0435] In formula (A2-1), the preferable mode of the structure of R 21 is the same as the preferable mode of the structure of R 1 in formula (A1-1) described above.

[0436] In formula (A2-1), R 22 is a hydrogen atom or any organic group other than R 21 described above, and is preferably any organic group other than R 21 described above.

[0437] Any organic group other than R 21 described above means an organic group having an HSP value of less than 17.0 MPa 1 / 2 , or an HSP value of more than 27.0 MPa 1 / 2 , and is preferably an organic group having an HSP value of less than 17.0 MPa 1 / 2 .

[0438] In formula (A2-1), the preferable mode of the structure of R 22 is the same as the preferable mode of the structure of R 23 in formula (A1-1) described above.

[0439] In formula (A2-1), the preferable mode of n, m and the structure of R 23 is the same as the preferable mode of n, m and the structure of R 3 in formula (A1-1) described above.

[0440] The second compound A is preferably a compound represented by the following formula (A2-2).

[0441] [Chemical Formula 30]

[0442]

[0443] In formula (A2-2), R 21The HSP value is 17.0–27.0 MPa. 1 / 2 organic groups, R 21 R is an organic group having at least one atom selected from oxygen, nitrogen, and sulfur atoms. 21 When multiple instances exist, they can be the same or different, R 22 It is a hydrogen atom or not equivalent to the above R. 21 Any organic group, R 22 When multiple instances exist, they can be the same or different, R 21 and R 22 At least two of them can bond to form a ring structure, where n represents an integer from 1 to 3, L represents a divalent linking group, and R 24 It represents a hydrogen atom or an organic group with a valence of 1.

[0444] In equation (A2-2), R 21 and R 22 The preferred method is the same as R in equation (1-2) 21 and R 22 The preferred method is the same.

[0445] In equation (A2-2), n, L, and R 24 The preferred method is the same as n, L and R in equation (1-2). 24 The preferred method is the same.

[0446] [Molecular weight]

[0447] The molecular weight of compound A is preferably 300 to 1500, more preferably 320 to 1000, and even more preferably 350 to 800.

[0448] [Synthesis Method]

[0449] Compound A can be synthesized, for example, by reacting a trialkoxysilyl compound with its corresponding alcohol compound under anhydrous conditions and in the presence of a strong acid such as hydrochloric acid to carry out an alkoxy exchange reaction. Alternatively, other known synthetic methods can be used, and the synthetic method is not particularly limited.

[0450] [Specific example]

[0451] As a specific example of compound A, there is no particular limitation, and any compound used in the examples described below can be cited.

[0452] 〔content〕

[0453] The content of the compound A of the present application is preferably 0.02 to 10 mass% relative to the total solid content of the resin composition. The lower limit is more preferably 0.05 mass% or more, further preferably 0.10 mass% or more, and particularly preferably 0.20 mass% or more. The upper limit is more preferably 8 mass% or less, further preferably 4 mass% or less, and particularly preferably 2 mass% or less. Also, a mode of 0.5 mass% or less is one of the preferred modes of the present application.

[0454] The compound A can be used singly in one kind, or two or more kinds can be used in combination. In the case of using two or more kinds in combination, the total amount thereof is preferably within the above range.

[0455] <Compound X1>

[0456] The resin composition of the present application can contain the compound X1.

[0457] The compound X1 is a compound having a structure selected from at least one of a 1,3-dicarbonyl structure and a β-hydroxycarbonyl structure, and having a molecular weight of 1,000 or less.

[0458] Here, the 1,3-dicarbonyl structure means the structure represented by the following formula (DC-1), and the β-hydroxycarbonyl structure means the structure represented by the following formula (HC-1).

[0459] [Chemical Formula 31]

[0460]

[0461] In the formula (DC-1) or the formula (HC-1), * and # each represent a bonding site with another structure. Here, * is preferably a bonding site with a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. Also, # is preferably a bonding site with a hydrogen atom or a carbon atom.

[0462] Here, the structure represented by the above (DC-1) can be an enol type like the following formula (DC-2).

[0463] Also, the structure represented by the above (HC-1) can be an enol type like the following formula (HC-2).

[0464] [Chemical Formula 32]

[0465]

[0466] In the formula (DC-2) or the formula (HC-2), * and # each represent a bonding site with another structure. * is preferably a bonding site with a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. Also, # is preferably a bonding site with a hydrogen atom or a carbon atom.

[0467] Compound X1 preferably does not contain a metal atom in the structure. The metal atom mentioned herein is set to not include a quasi-metal atom such as silicon dioxide.

[0468] Also, compound X1 is preferably not coordinated to a metal atom in the resin composition.

[0469] 〔Molecular weight〕

[0470] The molecular weight of compound X1 is 1,000 or less, preferably 100 to 500, more preferably 100 to 400, further preferably 100 to 350, particularly preferably 100 to 300, and more further preferably 100 to 250.

[0471] 〔Specific examples〕

[0472] As specific examples of compound X1, there are no particular limitations, and compounds of the following structures can be given.

[0473] [Chemical formula 33]

[0474]

[0475] 〔Content〕

[0476] The content of compound X1 with respect to the total solid content of the resin composition of the present application is preferably 0.01 to 30 mass%. The lower limit is more preferably 0.02 mass% or more, further preferably 0.05 mass% or more, and particularly preferably 0.10 mass% or more. The upper limit is more preferably 20 mass% or less, further preferably 10 mass% or less, and particularly preferably 5 mass% or less. Also, 1 mass% or less is one of the preferred modes of the present application.

[0477] Compound X1 can be used alone or in combination with two or more. In the case of combination with two or more, the total amount is preferably within the above range.

[0478] <Compound X2>

[0479] The resin composition of the present application preferably contains compound X2.

[0480] Compound X2 is a compound represented by the following formula (B-1).

[0481] [Chemical formula 34]

[0482]

[0483] In formula (B-1), R B1 represents a tertiary alkyl group, and R B2 each independently represents a hydrogen atom or an organic group.

[0484] In formula (B-1), RB1 represents a tertiary alkyl group, preferably a group represented by the following formula (B1-1), more preferably a tert-butyl group.

[0485] [Chemical Formula 35]

[0486]

[0487] In formula (B1-1), R B3 each independently represents an alkyl group, and * represents a bonding site to the benzene ring in formula (B-1).

[0488] In formula (B1-1), R B3 each independently is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Furthermore, the above alkyl group is preferably a linear alkyl group.

[0489] In formula (B-1), R B2 In the case where R B2 is preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and a ring structure. As the hydrocarbon group, it is preferable to be an aliphatic saturated hydrocarbon group, or a group represented by a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. As the ring structure, it can be any one of an aromatic ring structure, an aliphatic ring structure, preferably an aliphatic ring structure, and more preferably an isocyanuric ring structure.

[0490] The molecular weight of the compound X2 is preferably 100 to 2000, more preferably 150 to 1000, and further preferably 200 to 800.

[0491] As specific examples of the compound represented by formula (B-1), 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, 4,4',4"-(1-methylpropyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene-m-cresol, 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tert-butylhydroquinone, di-tert-butyl-p-cresol, 4,4-thio-bis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and the like can be given.

[0492] The content of the compound X2 in the present resin composition is preferably 0.1 to 5% by mass relative to the total solid content of the resin composition. The lower limit is more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more. The upper limit is more preferably 3% by mass or less, and further preferably 1% by mass or less.

[0493] The compound X2 can be used alone or in combination of two or more. In the case of combination of two or more, the total amount is preferably within the above range.

[0494] <Compound X3>

[0495] The present resin composition preferably contains a compound represented by the following formula (X-3) from the viewpoint of improving developability and the like.

[0496] [Chemical Formula 36]

[0497]

[0498] In formula (X-3), R X1represents a hydrogen atom or an alkyl group, and n is an integer of 1 to 10.

[0499] In formula (X-3), R X1 Preferably, it is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, further preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom, a methyl group or an ethyl group.

[0500] As specific examples of the compound X3, 4-hydroxybutyric acid, 4-hydroxybutyric acid methyl ester, 4-hydroxybutyric acid ethyl ester, 4-hydroxybutyric acid propyl ester, 4-hydroxybutyric acid isopropyl ester, 4-hydroxybutyric acid butyl ester, 4-hydroxybutyric acid pentyl ester, 4-hydroxybutyric acid hexyl ester, 4-hydroxybutyric acid heptyl ester, 4-hydroxybutyric acid octyl ester, 4-hydroxybutyric acid nonyl ester, 4-hydroxybutyric acid decyl ester, and the like can be given.

[0501] The content of the compound X3 is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the specific resin.

[0502] <Compound containing a Group 4 element>

[0503] From the viewpoint of chemical resistance, the resin composition of the present application can contain a compound containing a Group 4 element.

[0504] The compound containing a Group 4 element preferably contains a compound of titanium, zirconium or hafnium, and more preferably a compound of titanium.

[0505] Further, the compound containing a Group 4 element is preferably an organometallic complex, and more preferably an organotitanium complex.

[0506] Specific examples of the compound containing titanium are shown in the following I) to VII).

[0507] I) Titanium chelate compound: Among them, from the viewpoint of the storage stability and good pattern of the negative photosensitive resin composition, more preferably a titanium chelate having two or more alkoxy groups, and specific examples are bis(triethanolamine) titanium diisopropylate, bis(n-butanol) titanium bis(2,4-pentanedione), titanium diisopropylate bis(2,4-pentanedione), bis(tetramethylheptanedione) titanium diisopropoxide, bis(acetylacetate) titanium diisopropoxide, and the like.

[0508] II) Tetraalkoxy titanium compound: For example, tetra(n-butoxy) titanium, tetraethoxy titanium, tetra(2-ethylhexyloxy) titanium, tetraisobutoxy titanium, tetraisopropoxy titanium, tetramethoxy titanium, tetramethoxypropoxy titanium, tetramethylphenoxy titanium, tetra(n-nonyloxy) titanium, tetra(n-propoxy) titanium, tetra-stearyloxy titanium, tetra[bis{2,2-(allyloxymethyl) butyloxy}] titanium, and the like.

[0509] III) Titanium cyclopentadienyl compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1 H-pyrrol-1 -yl)phenyl) titanium, and the like. 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1 H-pyrrol-1-yl)phenyl) titanium, and the like.

[0510] IV) Titanium monoalkoxide compounds: for example, tris(dioctyl phosphate) isopropoxy titanium, tris(dodecyl benzene sulfonate) isopropoxy titanium, and the like.

[0511] V) Titanium oxide compounds: for example, bis(pentanedionate) titanium oxide, bis(tetramethylheptanedionate) titanium oxide, phthalocyanine titanium oxide, and the like.

[0512] VI) Titanium acetylacetonate compounds: for example, titanium acetylacetonate, and the like.

[0513] VII) Titanate coupling agents: for example, isopropyl tridodecyl benzene sulfonyl titanate, and the like.

[0514] In the above I) to VII), from the viewpoint of exerting more excellent chemical resistance, it is preferable that the compound containing titanium be at least one compound selected from the group consisting of the above I) titanium chelate compound, II) tetraalkoxy titanium compound, and III) titanium cyclopentadienyl compound. In particular, it is preferable that the compound containing titanium be diisopropoxy bis(ethyl acetoacetate) titanium, tetra(n-butoxy) titanium, and bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1 H-pyrrol-1-yl)phenyl) titanium.

[0515] In the case where the resin composition contains the compound containing the Group IV element, the content is preferably 0.05 parts by mass to 10 parts by mass, and more preferably 0.1 parts by mass to 2 parts by mass, with respect to 100 parts by mass of the specific resin. In the case where the above content is 0.05 parts by mass or more, heat resistance and chemical resistance are improved, and in the case where the content is 10 parts by mass or less, storage stability is improved.

[0516] <Polymehzable Compound>

[0517] The resin composition of the present application preferably contains a polymerizable compound.

[0518] In particular, the resin composition of the present application preferably further contains a polymerizable compound having at least one of a urea bond and a urethane bond. The resin composition of the present application, as the polymerizable compound having at least one of a urea bond and a urethane bond, preferably further contains a radical crosslinking agent having at least one of a urea bond and a urethane bond described later.

[0519] As the polymerizable compound, a radical crosslinking agent or other crosslinking agent can be mentioned.

[0520] 〔Radical crosslinking agent〕

[0521] The resin composition of the present application preferably contains a radical crosslinking agent.

[0522] The radical crosslinking agent is a compound having a radical polymerizable group. As the radical polymerizable group, a group containing an ethylenic unsaturated bond is preferred. As the group containing an ethylenic unsaturated bond, a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, a (meth)acrylamide group, and the like can be given.

[0523] Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and a (meth)acryloyl group is more preferred from the viewpoint of reactivity.

[0524] The radical crosslinking agent is preferably a compound having one or more ethylenic unsaturated bonds, and more preferably a compound having two or more ethylenic unsaturated bonds. The radical crosslinking agent can have three or more ethylenic unsaturated bonds.

[0525] As the compound having two or more ethylenic unsaturated bonds, a compound having two to fifteen ethylenic unsaturated bonds is preferred, a compound having two to ten ethylenic unsaturated bonds is more preferred, and a compound having two to six ethylenic unsaturated bonds is further preferred.

[0526] From the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present application preferably also contains a compound having two ethylenic unsaturated bonds and a compound having three or more of the above ethylenic unsaturated bonds.

[0527] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0528] As specific examples of the radical crosslinking agent, mention can be made of unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, amides thereof, preferably esters of unsaturated carboxylic acids with polyhydric alcohol compounds and amides of unsaturated carboxylic acids with polyamine compounds. Also, it is possible to preferably use, as the addition reactant, unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, an amino group, a sulfanyl group, etc. with a monofunctional or polyfunctional isocyanate or an epoxy compound, as the dehydrative condensation reactant, a monofunctional or polyfunctional carboxylic acid, etc. Also, it is possible to preferably use, as the addition reactant, unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, mercaptan, and as the substitution reactant, unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogeno group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine, mercaptan. Also, as another example, it is possible to use, instead of the above-mentioned unsaturated carboxylic acid, a compound group of unsaturated phosphonic acid, styrene, etc. vinylbenzene derivative, vinyl ether, allyl ether, etc. As specific examples, reference can be made to the description of paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, which is incorporated into the present specification.

[0529] The radical crosslinking agent is also preferably a compound having a boiling point of 100°C or higher at normal pressure. As the compound having a boiling point of 100°C or higher at normal pressure, mention can be made of the compounds described in paragraph 0203 of International Publication No. 2021 / 112189, etc. The content is incorporated into the present specification.

[0530] As the preferred radical crosslinking agent other than the above, mention can be made of the radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021 / 112189, etc. The content is incorporated into the present specification.

[0531] As the radical crosslinking agent, di-pentaerythritol triacrylate (commercially available product: KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), di-pentaerythritol tetraacrylate (commercially available products: KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.)), di-pentaerythritol penta(meth)acrylate (commercially available product: KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), di-pentaerythritol hexa(meth)acrylate (commercially available products: 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. Oligomer types of these can also be used.

[0532] As commercially available products of the radical crosslinking agent, for example, 4-functional acrylate SR-494 having 4 ethyleneoxy chains, 2-functional methacrylate SR-209, 231, 239 having 4 ethyleneoxy chains (manufactured by Sartomer Company, Inc.), 6-functional acrylate DPCA-60 having 6 pentyleneoxy chains, 3-functional acrylate TPA-330 having 3 isobutyleneoxy chains (manufactured by Nippon Kayaku Co., Ltd.), urethane oligomer UAS-10, 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.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), and the like can be given.

[0533] As the radical crosslinking agent, it is also preferable to use urethane acrylate compounds described in Japanese Patent Application Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Application Publication No. 02-032293, Japanese Patent Application Publication No. 02-016765, urethane compounds having an oxirane skeleton described in Japanese Patent Application Publication No. 58-049860, Japanese Patent Application Publication No. 56-017654, Japanese Patent Application Publication No. 62-039417, Japanese Patent Application Publication No. 62-039418. As the radical crosslinking agent, it is also possible to use compounds having an amino structure and a thioether structure in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, Japanese Patent Application Laid-Open No. 01-105238.

[0534] The radical crosslinking agent can be a radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydric compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent having an acid group obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydric compound. It is particularly preferable that, among the radical crosslinking agents having an acid group obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydric compound, the aliphatic polyhydric compound is a compound of pentaerythritol or dipentaerythritol. As a commercially available product, for example, polyacid-modified acrylic acid oligomer M-510, M-520, and the like manufactured by TOAGOSEI CO., LTD. can be mentioned.

[0535] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and more preferably 1 to 100 mgKOH / g. The acid value of the radical crosslinking agent is excellent in terms of workability in production and development, and is excellent in terms of development. Furthermore, the polymerizability is good. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0536] As the radical crosslinking agent, it is also preferable to use a radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond (hereinafter, also referred to as "crosslinking agent U").

[0537] In the present application, the urea bond is a bond represented by *-NR N -C(=O)-NR N a bond represented by *, R N each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site to a carbon atom.

[0538] In the present application, the urethane bond is a bond represented by *-O-C(=O)-NR N a bond represented by *, R Nrepresents a hydrogen atom or a monovalent organic group, and * represents a bonding site to a carbon atom, respectively.

[0539] By the resin composition containing the crosslinking agent U, the chemical resistance, the resolution, and the like are sometimes improved.

[0540] The mechanism by which the above effects are obtained is not clear, but it is considered that, for example, when curing is performed by heating or the like, a part of the crosslinking agent U thermally decomposes, thereby generating an amine or the like, and the above amine or the like promotes the cyclization of the precursor of the polyimide.

[0541] The crosslinking agent U can have only one urea bond or one urethane bond, can have one or more urea bonds and one or more urethane bonds, can have two or more urea bonds without having a urethane bond, or can have two or more urethane bonds without having a urea bond.

[0542] The total number of the urea bonds and the urethane bonds in the crosslinking agent U is one or more, preferably one to 10, more preferably one to 4, and further preferably one or two.

[0543] In the case where the crosslinking agent U does not have a urethane bond, the number of the urea bonds in the crosslinking agent U is one or more, preferably one to 10, more preferably one to 4, and further preferably one or two.

[0544] In the case where the crosslinking agent U does not have a urea bond, the number of the urethane bonds in the crosslinking agent U is one or more, preferably one to 10, more preferably one to 4, and further preferably one or two.

[0545] The radical polymerizable group in the crosslinking agent U is not particularly limited, but examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acrylamide group, a vinylphenyl group, a maleimide group, and the like, preferably a (meth)acryloyloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group, and more preferably a (meth)acryloyloxy group.

[0546] In the case where the crosslinking agent U has two or more radical polymerizable groups, the structures of the respective radical polymerizable groups can be the same or different.

[0547] The number of the radical polymerizable groups in the crosslinking agent U can be one, or can be two or more, preferably one to 10, further preferably one to 6, and particularly preferably one to 4.

[0548] The radical polymerizable group value (mass of the compound per 1 mole of the radical polymerizable group) in the crosslinking agent U is preferably 150 to 400 g / mol.

[0549] From the viewpoint of the chemical resistance of the cured product, the lower limit of the value of the radical polymerizable group is more preferably 200 g / mol or greater, further preferably 210 g / mol or greater, still further preferably 220 g / mol or greater, yet further preferably 230 g / mol or greater, yet further preferably 240 g / mol or greater, and particularly preferably 250 g / mol or greater.

[0550] From the viewpoint of the development property, the upper limit of the value of the radical polymerizable group is more preferably 350 g / mol or less, further preferably 330 g / mol or less, and particularly preferably 300 g / mol or less.

[0551] The value of the polymerizable group of the crosslinking agent U is preferably 210 to 400 g / mol, and more preferably 220 to 400 g / mol.

[0552] The crosslinking agent U is preferably, for example, a structure represented by the following formula (U-1).

[0553] [Chemical Formula 37]

[0554]

[0555] In formula (U-1), R U1 is a hydrogen atom or a monovalent organic group, A is -O- or -NR N , R N is a hydrogen atom or a monovalent organic group, Z U1 is an m-valent organic group, Z U2 is an n+1-valent organic group, X is a radical polymerizable group, n is an integer of 1 or greater, and m is an integer of 1 or greater.

[0556] R U1 is preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group, and more preferably a hydrogen atom.

[0557] R N is preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group, and more preferably a hydrogen atom.

[0558] Z U1 is preferably a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N , or a group in which two or more of these are bonded, and more preferably a hydrocarbon group or a group in which a hydrocarbon group and at least one kind of group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O)2-, and -NR N are bonded.

[0559] As the above hydrocarbon group, a hydrocarbon group having 20 or less carbon atoms is preferable, a hydrocarbon group having 18 or less carbon atoms is more preferable, and a hydrocarbon group having 16 or less carbon atoms is further preferable. As the above hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond of these, etc. can be given. R N represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or a methyl group.

[0560] Z U2 is preferably a hydrocarbon group, -0-, -C(=0)-, -S-, -S(=0)2-, -NR N or a group in which two or more of these are bonded, and is more preferably a hydrocarbon group or a group in which a hydrocarbon group and at least one group selected from the group consisting of -0-, -C(=0)-, -S-, -S(=0)2-, and -NR N are bonded.

[0561] As the above hydrocarbon group, the same hydrocarbon group as given in Z U1 is preferable, and the same preferable mode is also preferable.

[0562] X is not particularly limited, but a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acrylamido group, a vinylphenyl group, a maleimido group, etc. can be given, and is preferably a (meth)acryloyloxy group, a (meth)acrylamido group, a vinylphenyl group, or a maleimido group, and more preferably a (meth)acryloyloxy group.

[0563] n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1.

[0564] m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and further preferably 1 or 2.

[0565] The crosslinking agent U also preferably has at least one of a hydroxyl group, an alkyleneoxy group, an amido group, and a cyano group.

[0566] From the viewpoint of the chemical resistance of the obtained cured film, the hydroxyl group can be an alcoholic hydroxyl group or a phenolic hydroxyl group, and is preferably an alcoholic hydroxyl group.

[0567] From the viewpoint of the chemical resistance of the obtained cured film, as the alkyleneoxy group, a hydrocarbon group having 2 to 20 carbon atoms is preferable, a hydrocarbon group having 2 to 10 carbon atoms is more preferable, a hydrocarbon group having 2 to 4 carbon atoms is further preferable, and an ethyleneoxy group or a propyleneoxy group is more further preferable, and an ethylene group is particularly preferable.

[0568] The alkyleneoxy group can be included in the crosslinking agent U as a polyalkyleneoxy group. The number of repetitions of the alkyleneoxy group at this time is preferably 2 to 10, and more preferably 2 to 6.

[0569] Amido group means -C(=0)-NR N - the bond represented by N R is as described above. In the case where the crosslinking agent U has an amido group, the crosslinking agent U can contain, for example, R-C(=0)-NR N - the group represented by * or -C(=0)-NR N - the group represented by R. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group.

[0570] The crosslinking agent U can have two or more structures selected from the group consisting of a hydroxyl group, an alkyleneoxy group (in the case of constituting a polyalkyleneoxy group, a polyalkyleneoxy group), an amido group, and a cyano group within the molecule, but a mode in which only one is present within the molecule is also preferable.

[0571] The above-described hydroxyl group, alkyleneoxy group, amido group, and cyano group can be present at any position of the crosslinking agent U, but from the viewpoint of chemical resistance, with respect to the crosslinking agent U, it is also preferable that at least one selected from the group consisting of the above-described hydroxyl group, alkyleneoxy group, amido group, and cyano group be connected to at least one radical-polymerizable group contained in the crosslinking agent U via a linking group containing a urea bond or a urethane bond (hereinafter, also referred to as "linking group L2-1").

[0572] In particular, in the case where the crosslinking agent U contains only one radical-polymerizable group, it is preferable that the radical-polymerizable group contained in the crosslinking agent U be connected to at least one selected from the group consisting of a hydroxyl group, an alkyleneoxy group (in the case of constituting a polyalkyleneoxy group, a polyalkyleneoxy group), an amido group, and a cyano group via a linking group containing a urea bond or a urethane bond (hereinafter, also referred to as "linking group L2-2").

[0573] In the case where the crosslinking agent U contains an alkyleneoxy group (in the case of constituting a polyalkyleneoxy group, a polyalkyleneoxy group) and has the above-described linking group L2-1 or the above-described linking group L2-2, the structure bonded to the side opposite to the linking group L2-1 or the linking group L2-2 of the alkyleneoxy group (in the case of constituting a polyalkyleneoxy group, a polyalkyleneoxy group) is not particularly limited, and is preferably a hydrocarbon group, a radical-polymerizable group, or a group represented by a combination of these. As the above-described hydrocarbon group, a hydrocarbon group having 20 or fewer carbon atoms is preferable, a hydrocarbon group having 18 or fewer carbon atoms is more preferable, and a hydrocarbon group having 16 or fewer carbon atoms is further preferable. As the above-described hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond of these can be mentioned. Furthermore, the preferable mode of the radical-polymerizable group is the same as the preferable mode of the radical-polymerizable group in the above-described crosslinking agent U.

[0574] In the case where the crosslinking agent U contains an amide group and has the above-mentioned linking group L2-1 or the above-mentioned linking group L2-2, the structure bonded to the side opposite to the linking group L2-1 or the linking group L2-2 of the amide group is not particularly limited, and is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination of these. As the above-mentioned hydrocarbon group, a hydrocarbon group having 20 or less carbon atoms is preferable, a hydrocarbon group having 18 or less carbon atoms is more preferable, and a hydrocarbon group having 16 or less carbon atoms is further preferable. Also, as the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond of these, etc. can be given. The preferable mode of the radically polymerizable group is the same as the preferable mode of the radically polymerizable group in the above-mentioned crosslinking agent U. Also, in the above-mentioned mode, the carbon atom side of the amide group can be bonded to the linking group L2-1 or the linking group L2-2, or the nitrogen atom side of the amide group can be bonded to the linking group L2-1 or the linking group L2-2.

[0575] Of these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, the crosslinking agent U is preferably one having a hydroxyl group.

[0576] From the viewpoint of compatibility with a specific resin, etc., the crosslinking agent U is preferably one containing an aromatic group.

[0577] The above-mentioned aromatic group is preferably directly bonded to the urea bond or the carbamate bond contained in the crosslinking agent U. In the case where the crosslinking agent U contains two or more urea bonds or carbamate bonds, one of the urea bonds or the carbamate bonds is preferably directly bonded to the aromatic group.

[0578] The aromatic group can be an aromatic hydrocarbon group or an aromatic heterocyclic group, or can be a structure in which these form a condensed ring, and is preferably an aromatic hydrocarbon group.

[0579] As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, and a group in which two or more hydrogen atoms are removed from a benzene ring structure is further preferable.

[0580] As the above-mentioned aromatic heterocyclic group, an aromatic heterocyclic group having a 5-membered ring or a 6-membered ring is preferable. As the aromatic heterocycle in such an aromatic heterocyclic group, a pyrrole, an imidazole, a triazole, a tetrazole, a pyrazole, a furan, a thiophene, an oxazole, an isoxazole, a thiazole, a pyridine, a pyrazine, a pyrimidine, a pyridazine, a triazine, etc. can be given. These rings can be condensed with other rings further, such as an indole, a benzimidazole.

[0581] As the heteroatom contained in the above-mentioned aromatic heterocyclic group, a nitrogen atom, an oxygen atom, or a sulfur atom is preferable.

[0582] The above aromatic group is preferably included in, for example, a linking group that links two or more radical polymerizable groups and includes a urea bond or a urethane bond, or a linking group that links at least one selected from the group consisting of the above hydroxyl group, alkyleneoxy group, amido group, and cyano group to at least one radical polymerizable group included in the crosslinking agent U.

[0583] The number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, and is preferably 30 or less, more preferably 2 to 20, and further preferably 2 to 10.

[0584] In the case where the crosslinking agent U includes two or more urea bonds or urethane bonds in total, includes two or more radical polymerizable groups, or includes two or more urea bonds or urethane bonds and includes two or more radical polymerizable groups, the smallest number of atoms (linking chain length) among the number of atoms between the urea bond or urethane bond and the radical polymerizable group can be within the above range.

[0585] In the present specification, the "number of atoms (linking chain length) between the urea bond or urethane bond and the polymerizable group" means the shortest (smallest number of atoms) atom chain in the path connecting two atoms or atom groups as connection objects. For example, in the structure represented by the following formula, the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.

[0586] [Chemical Formula 38]

[0587]

[0588] 〔Symmetry axis〕

[0589] The crosslinking agent U is also preferably a compound having no structure with a symmetry axis.

[0590] The crosslinking agent U having no symmetry axis means a compound that is not left-right symmetric, and has no axis that, when the compound as a whole is rotated, produces a molecule identical to the original molecule. Also, in the case where the structural formula of the crosslinking agent U is marked on paper, the crosslinking agent U having no symmetry axis means that the structural formula of the crosslinking agent U cannot be marked in a form having a symmetry axis.

[0591] It is considered that, because the crosslinking agent U has no symmetry axis, the aggregation between the crosslinking agents U is suppressed in the composition film.

[0592] 〔Molecular weight〕

[0593] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1500, and further preferably 200 to 900.

[0594] The production method of the crosslinking agent U is not particularly limited, but for example, it can be obtained by reacting a compound having a radical polymerizable compound and an isocyanate group with a compound having at least one of a hydroxyl group or an amino group.

[0595] The following shows specific examples of the crosslinking agent U, but the crosslinking agent U is not limited thereto.

[0596] [Chemical Formula 39]

[0597]

[0598] [Chemical Formula 40]

[0599]

[0600] [Chemical Formula 41]

[0601]

[0602] From the viewpoint of resolution of a pattern and stretchability of a film, the resin composition is preferably one using a 2-functional methacrylate or acrylate.

[0603] As a specific compound, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct of bisphenol A diacrylate, EO adduct of bisphenol A dimethacrylate, PO (propylene oxide) adduct of bisphenol A diacrylate, PO adduct of bisphenol A dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, EO-modified isocyanuric acid dimethacrylate, other 2-functional acrylates having a urethane bond, 2-functional methacrylates having a urethane bond can be used. Two or more of these can be used in mixture as needed.

[0604] In addition, for example, PEG 200 diacrylate refers to a polyethylene glycol diacrylate in which the formula weight of the polyethylene glycol chain is about 200.

[0605] From the viewpoint of suppressing warping of the resist pattern (cured product), the resin composition of the present application can preferably use a monofunctional radical crosslinking agent as the radical crosslinking agent. As the monofunctional radical crosslinking agent, it is possible to preferably use n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitorl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and the like (meth)acrylic acid derivatives, N-vinylpyrrolidone, N-vinylcaprolactam, and the like N-vinyl compounds, allyl glycidyl ether, and the like. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, it is also preferable to use a compound having a boiling point of 100°C or higher at normal pressure.

[0606] Further, as the 2 or more functional radical crosslinking agent, it is possible to cite diallyl phthalate, triallyl trimellitate, and the like allyl compounds.

[0607] In the case of containing the radical crosslinking agent, the content of the radical crosslinking agent with respect to the total solid content of the resin composition is preferably more than 0 mass% and 60 mass% or less. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 50 mass% or less, and further preferably 30 mass% or less.

[0608] The radical crosslinking agent can be used singly in one kind, or two or more kinds can be used in combination. In the case of using two or more kinds in combination, the total amount thereof is preferably within the above range.

[0609] [Other Crosslinking Agents]

[0610] The resin composition of the present application also preferably contains other crosslinking agents different from the above-described radical crosslinking agent.

[0611] The other crosslinking agent refers to a crosslinking agent other than the above-described radical crosslinking agent, and is preferably a compound having a plurality of groups that promote the formation of a covalent bond between the other compound in the composition or a reaction product thereof through the action of an acid or a base in the molecule, and is preferably a compound having a plurality of groups that promote the formation of a covalent bond between the other compound in the composition or a reaction product thereof through the action of an acid or a base in the molecule.

[0612] The above-described acid or base is preferably an acid or a base generated from the photoacid generator or the photobase generator in the exposure process.

[0613] As other crosslinking agents, compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355 can be mentioned. The above description is incorporated into the present specification.

[0614] 〔Polymerization initiator〕

[0615] The resin composition of the present application preferably contains a polymerization initiator.

[0616] The polymerization initiator can be either a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator is particularly preferred.

[0617] The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation as to the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, it is preferred that the photoradical polymerization initiator be photosensitive to light rays in the ultraviolet region to the visible region. Also, it can be an activator that acts on a sensitizer excited by light and generates active radicals.

[0618] The photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L·mol -1 ·cm -1 in the range of a wavelength of about 240 to 800 nm (preferably, 330 to 500 nm). The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferred that the measurement be performed at a concentration of 0.01 g / L using ethyl acetate solvent by ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian).

[0619] As the photoradical polymerization initiator, a publicly known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, and the like), acylphosphine compounds such as acyloxyphosphine, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminophenylacetophenone, α-hydroxy ketone compounds such as hydroxyphenylacetophenone, azo-based compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, and the like can be exemplified. As to details of these, reference can be made to the description of paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357, paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, which are incorporated into the present specification. Further, compounds described in paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313, which are incorporated into the present specification, can be exemplified.

[0620] As the ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, which is incorporated into the present specification, can be exemplified. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

[0621] In one embodiment of the present application, as the photoradical polymerization initiator, a hydroxyphenylacetophenone compound, an aminophenylacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, the aminophenylacetophenone-based initiators described in Japanese Patent Application Publication No. H10-291969 and the acyloxyphosphine-based initiators described in Japanese Patent No. 4225898, which are incorporated into the present specification, can be used.

[0622] As the α-hydroxy ketone-based initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (all manufactured by BASF) can be used.

[0623] As the α-amino ketone-based initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0624] As the aminophenylacetophenone-based initiator, acylphosphine oxide-based initiator, metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be preferably used. This content is incorporated into the present specification.

[0625] As the photoradical polymerization initiator, an oxime compound can be more preferably cited. By using an oxime compound, the exposure latitude can be further effectively improved. The exposure latitude (exposure margin) of an oxime compound is wide and also functions as a photocuring accelerator, and thus is particularly preferable.

[0626] As specific examples of the oxime compound, there can be mentioned the compounds described in Japanese Patent Application Publication No. 2001-233842, the compounds described in Japanese Patent Application Publication No. 2000-080068, the compounds described in Japanese Patent Application Publication No. 2006-342166, the compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), the compounds described in J.C.S. Perkin II (1979, pp. 156-162), the compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), the compounds described in Japanese Patent Application Publication No. 2000-066385, the compounds described in Japanese Patent Application Laid-Open No. 2004-534797, the compounds described in Japanese Patent Application Publication No. 2017-019766, the compounds described in Japanese Patent No. 6065596, the compounds described in International Publication No. 2015 / 152153, the compounds described in International Publication No. 2017 / 051680, the compounds described in Japanese Patent Application Publication No. 2017-198865, the compounds described in International Publication No. 2017 / 164127, pp. 0025-0038, the compounds described in International Publication No. 2013 / 167515, and the like, which are incorporated into the present specification.

[0627] As a preferred oxime compound, for example, there can be mentioned the compounds of the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetyloxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetyloxy(imino))pentan-3-one, 2-(acetyloxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, and the like. In the resin composition, it is particularly preferred that an oxime compound be used as a photoradical polymerization initiator. The oxime compound as the photoradical polymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

[0628] [Chemical Formula 42]

[0629]

[0630] As a commercial product of the oxime compound, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in Japanese Patent Application Publication No. 2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemix Corporation), SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be given. Also, an oxime compound having the following structure can be used.

[0631] [Chemical Formula 43]

[0632]

[0633] As the photoradical polymerization initiator, for example, an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of International Publication No. 2021 / 112189, an oxime compound having at least one benzene ring of a carbazole ring as a skeleton of a naphthalene ring, an oxime compound having a fluorine atom can be used.

[0634] Also, an oxime compound having a nitro group described in paragraphs 0208 to 0210 of International Publication No. 2021 / 020359, an oxime compound having a benzofuran skeleton, an oxime compound having a substituent having a hydroxyl group bonded to a carbazole skeleton can be used. These contents are incorporated into the present specification.

[0635] As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar OX1 having an electron-withdrawing group introduced on an aromatic ring (hereinafter, also referred to as oxime compound OX) can be used. As the above aromatic ring group Ar OX1As the electron-withdrawing group, acyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, cyano, preferably acyl and nitro, more preferably acyl, further preferably benzoyl can be given, from the viewpoint of easily forming a film excellent in light resistance. The benzoyl group can have a substituent. As the substituent, halogen atom, cyano, nitro, hydroxy, alkyl, alkoxy, aryl, aryloxy, heterocyclic group, heterocyclic-oxy group, alkenyl, alkylsulfanyl, arylsulfanyl, acyl or amino, more preferably alkyl, alkoxy, aryl, aryloxy, heterocyclic-oxy group, alkylsulfanyl, arylsulfanyl or amino, further preferably alkoxy, alkylsulfanyl or amino are preferred.

[0636] The oxime compound OX is preferably at least one selected from the group consisting of a compound represented by formula (OX1) and a compound represented by formula (OX2), more preferably a compound represented by formula (OX2).

[0637] [Chemical Formula 44]

[0638]

[0639] In the formula, R X1 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic group, heterocyclic-oxy group, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphinyl, carbamoyl or sulfamoyl,

[0640] R X2 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic group, heterocyclic-oxy group, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyloxy or amino,

[0641] R X3 ~R X14 each independently represents a hydrogen atom or a substituent.

[0642] wherein at least one of R X10 ~R X14 is an electron-withdrawing group.

[0643] In the above formula, it is preferred that R X12 be an electron-withdrawing group and R X10 , R X11 , R X13 , R X14 be a hydrogen atom.

[0644] As specific examples of the oxime compound OX, the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 can be given, the content of which is incorporated into the present specification.

[0645] As particularly preferred oxime compounds, the oxime compounds having specific substituents shown in Japanese Patent Application Publication No. 2007-269779, the oxime compounds having a sulfur aryl group shown in Japanese Patent Application Publication No. 2009-191061, and the like can be given, the content of which is incorporated into the present specification.

[0646] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, an onium salt compound, a benzothiazole compound, a benzophenone compound, a phenylethanone compound and derivatives thereof, a cyclopentadiene-benzene-iron complex and salts thereof, a halomethyl oxadiazole compound, a 3-aryl-substituted coumarin compound.

[0647] Further, the photoradical polymerization initiator is a trihalomethyltriazine compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, an onium salt compound, a benzophenone compound, a phenylethanone compound, more preferably at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-amino ketone compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, a benzophenone compound, and further preferably a metallocene compound or an oxime compound.

[0648] As the photoradical polymerization initiator, the compounds described in paragraphs 0175 to 0179 of International Publication No. 2021 / 020359, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used, the content of which is incorporated into the present specification.

[0649] As the photoradical polymerization initiator, a 2-functional or 3-functional or more photoradical polymerization initiator can be used. By using such a photoradical polymerization initiator, since 2 or more radicals are generated from 1 molecule of the photoradical polymerization initiator, good sensitivity can be obtained. Also, in the case of using a compound having an asymmetric structure, the crystallinity decreases and the solubility in a solvent or the like is improved, so precipitation over time is difficult, and thus the stability over time of the resin composition can be improved. As specific examples of the 2-functional or 3-functional or more photoradical polymerization initiator, the dimer of the oxime compound described in Japanese Patent Application Publication No. 2010-527339, Japanese Patent Application Publication No. 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407 to 0412 of Japanese Patent Application Publication No. 2016-532675, International Publication No. 2017 / 033680, paragraphs 0039 to 0055, the compounds (E) and (G) described in Japanese Patent Application Publication No. 2013-522445, Cmpd1 to 7 described in International Publication No. 2016 / 034963, the oxime ester-based photoinitiator described in Japanese Patent Application Publication No. 2017-523465, paragraph 0007, the photoinitiator described in Japanese Patent Application Publication No. 2017-167399, paragraphs 0020 to 0033, the photopolymerization initiator (A) described in Japanese Patent Application Publication No. 2017-151342, paragraphs 0017 to 0026, the oxime ester photoinitiator described in Japanese Patent No. 6469669, and the like can be given, which are incorporated into the present specification.

[0650] In the case where the resin composition contains a photopolymerization initiator, the content thereof with respect to the total solid content of the resin composition 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 more further preferably 1.0 to 10% by mass. The photopolymerization initiator can contain only one kind, or two or more kinds. When two or more kinds of photopolymerization initiators are contained, the total amount thereof is preferably within the above range.

[0651] In addition, since the photopolymerization initiator sometimes also functions as a thermal polymerization initiator, crosslinking using the photopolymerization initiator is sometimes further performed by heating with an oven, a hot plate, or the like.

[0652] 〔Sensitizer〕

[0653] The resin composition can contain a sensitizer. The sensitizer absorbs a specific active light to become an electronically excited state. The sensitizer in the electronically excited state contacts a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like to generate an electron transfer, an energy transfer, heat generation, or the like. Thereby, the thermal radical polymerization initiator, the photoradical polymerization initiator undergoes a chemical change to decompose, and a radical, an acid, or a base is generated.

[0654] As the sensitizer which can be used, compounds such as benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole methine azo-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based, and the like can be used.

[0655] As the sensitizer, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminobenzalacetophenone, p-dimethylaminobenzalacetophenone, 2-(p-dimethylaminophenyl)ethylene)-benzothiazole, 2-(p-dimethylaminophenyl)vinyl)benzothiazole, 2-(p-dimethylaminophenyl)vinyl)iso-benzothiazole, 1,3-bis(4'-dimethylaminobenzylidene)propanone, 1,3-bis(4'-diethylaminobenzylidene)propanone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyl-diethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isopentyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzophenylamine, N-methylacetanilide, 3',4'-dimethylacetanilide, and the like can be mentioned.

[0656] Also, other sensitizing dyes can be used.

[0657] For details of the sensitizing dye, reference can be made to the description of paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated into the present specification.

[0658] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and further preferably 0.5 to 10% by mass, relative to the total solid content of the resin composition. One kind of sensitizer can be used alone, or two or more kinds of sensitizers can be used in combination.

[0659] 〔Chain transfer agent〕

[0660] The resin composition of the present application can contain a chain transfer agent. The chain transfer agent is defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005), pages 683-684. As the chain transfer agent, for example, a compound group having -S-S-, -SO2-S-, -N-O-, SH, PH, SiH, and GeH in the molecule, a dithiobenzoate having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation chain Transfer) polymerization, a trithiocarbonate, a dithio carbamate, a xanthate compound, and the like can be used. These supply hydrogen to a low-activity radical to generate a radical, or after oxidation, a radical can be generated by deprotonation. In particular, a mercaptan compound can be preferably used.

[0661] Also, the chain transfer agent can use the compound described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219, which is incorporated into the present specification.

[0662] When the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition. The chain transfer agent can be only one kind, or two or more kinds. When the chain transfer agent is two or more kinds, the total amount of the two or more kinds is preferably within the above range.

[0663] Also, it is one of the preferred modes of the present application that the resin composition of the present application contains two or more kinds of polymerization initiators as the polymerization initiator.

[0664] Specifically, the resin composition of the present application preferably contains a photopolymerization initiator and a thermal polymerization initiator described later, or contains the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.

[0665] By containing the photopolymerization initiator and the thermal polymerization initiator described later, it is sometimes possible to perform pattern formation using exposure, and when curing is performed using the heating process described later, it is easy to perform radical polymerization and improve properties such as chemical resistance.

[0666] As the content ratio when the photopolymerization initiator and the thermal polymerization initiator described later are contained, the content of the thermal polymerization initiator is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0667] By containing the photoradical polymerization initiator and the photoacid generator, the performance such as resolution is sometimes improved.

[0668] As the content ratio when the photopolymerization initiator and the photoacid generator are contained, the content of the photoacid generator is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the photoacid generator.

[0669] [Thermal polymerization initiator]

[0670] As the thermal polymerization initiator, for example, a thermal radical polymerization initiator can be given. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes the polymerization reaction of a compound having polymerizability. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also be performed, and thus the solvent resistance can be further improved.

[0671] As the thermal radical polymerization initiator, specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554 can be given, which are incorporated into the present specification.

[0672] In the case where the resin composition contains the thermal polymerization initiator, the content thereof relative to the total solid content of the resin composition is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further preferably 0.5 to 15% by mass. The resin composition can contain only one kind of thermal polymerization initiator, or can contain two or more kinds of thermal polymerization initiators. In the case where two or more kinds of thermal polymerization initiators are contained, the total content is preferably within the above range.

[0673] <Alkali generating agent>

[0674] The resin composition of the present application can contain an alkali generating agent. Here, the alkali generating agent refers to a compound that can generate an alkali by physical action or chemical action. As the preferred alkali generating agent, a thermal alkali generating agent and a photoalkali generating agent can be given.

[0675] In particular, in the case where the resin composition contains a precursor of a polyimide, the resin composition preferably contains an alkali generating agent. By containing the thermal alkali generating agent in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and thus the mechanical properties or chemical resistance of the cured product can be made good, and the performance as an interlayer insulating film for a rewiring layer contained in a semiconductor package can be made good, for example.

[0676] As the base generating agent, an ionic base generating agent or a nonionic base generating agent can be used. As the base generated from the base generating agent, for example, a secondary amine, a tertiary amine can be given.

[0677] The base generating agent is not particularly limited, and a publicly known base generating agent can be used. As the publicly known base generating agent, for example, a carbamoyl oxime compound, a carbamoyl hydroxyl amine compound, a carbamic acid compound, a formamide compound, an acetamide compound, a carbamate compound, a benzyl carbamate compound, a nitrobenzyl carbamate compound, a sulfonamide compound, an imidazole derivative compound, an amic acid imide compound, a pyridine derivative compound, an α-aminoacetophenone derivative compound, a quaternary ammonium salt derivative compound, an imine salt, a pyridinium salt, an α-lactone ring derivative compound, an amic acid imide compound, a phthalimide derivative compound, an acyloxy imine compound, and the like can be given.

[0678] As specific examples of the nonionic base generating agent, the compounds described in paragraphs 0249 to 0275 of International Publication No. 2022 / 145355 can be given. The above description is incorporated into the present specification.

[0679] As the base generating agent, the following compounds can be given, but are not limited thereto.

[0680] [Chemical Formula 45]

[0681]

[0682] The molecular weight of the nonionic base generating agent is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

[0683] As specific preferred compounds of the ionic base generating agent, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002 can be given.

[0684] As specific examples of the ammonium salt, the following compounds can be given, but are not limited thereto.

[0685] [Chemical Formula 46]

[0686]

[0687] As specific examples of the imine salt, the following compounds can be given, but are not limited thereto.

[0688] [Chemical Formula 47]

[0689]

[0690] Further, from the viewpoint of storage stability and generation of a base by deprotection at the time of curing, as the base generator, an amine whose amino group is protected with a tert-butyloxycarbonyl group is preferred.

[0691] As the amine compound whose amino group is protected with a tert-butyloxycarbonyl group, for example, ethanolamine, 3-amino-l-propanol, l-amino-2-propanol, 2-amino-l-propanol, 4-amino-l-butanol, 2-amino-l-butanol, l-amino-2-butanol, 3-amino-2,2-dimethyl-l-propanol, 4-amino-2-methyl-l-butanol, valinol, 3-amino-l,2-propanediol, 2-amino-l,3-propanediol, tyramine, norephedrine, 2-amino-l-phenyl-l,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-l-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzene methanol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidinyl)-2-propanol, 1,4-butanediol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxatridecane, or an amino acid and a derivative thereof whose amino group is protected with a tert-butyloxycarbonyl group can be mentioned, but are not limited to these.

[0692] In the case where the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass, relative to 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less, and still further preferably 10 parts by mass or less, and more further preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.

[0693] One or two or more kinds of base generators can be used. In the case where two or more kinds are used, the total amount is preferably within the above range.

[0694] < Solvent >

[0695] The resin composition of the present application preferably contains a solvent.

[0696] The resin composition of the present application preferably contains a solvent having at least one of an amide bond or a hydroxyl group as a solvent. Such a solvent is excellent in solubility of the compounds A, and is capable of inhibiting agglomeration of these compounds.

[0697] The solvent can be used arbitrarily using a known solvent. The solvent is preferably an organic solvent. As the organic solvent, compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, alcohols, and the like can be given.

[0698] As the esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and the like)), 3-alkyl alkoxylpropionates (e.g., methyl 3-alkoxylpropionate, ethyl 3-alkoxylpropionate, and the like (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and the like)), 2-alkyl alkoxylpropionates (e.g., methyl 2-alkoxylpropionate, ethyl 2-alkoxylpropionate, propyl 2-alkoxylpropionate, and the like (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy-2-methylpropionates (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, and the like), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, and the like can be given as preferable examples.

[0699] As the ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, and the like can be given as preferable examples.

[0700] As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone, and the like can be given as preferred examples.

[0701] As cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, and the like, cyclic terpenes such as limonene, and the like can be given as preferred examples.

[0702] As sulfoxides, for example, dimethyl sulfoxide can be given as a preferred example.

[0703] As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N-formylmorpholine, N-acetylmorpholine, and the like can be given as preferred examples.

[0704] As ureas, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolinone, and the like can be given as preferred examples.

[0705] As alcohols, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylbenzyl alcohol, n-pentanol, methylpentanol, diacetone alcohol, and the like can be given as preferred examples.

[0706] As to the solvent, from the viewpoint of improvement in the properties of the coated surface, it is also preferred to mix two or more of the forms.

[0707] In the present application, it is preferable that the solvent be one kind selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropanamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucosan, and dihydrolevoglucosan, or a mixed solvent composed of two or more kinds. Particularly preferable is a combination of dimethyl sulfoxide and γ-butyrolactone, a combination of dimethyl sulfoxide and γ-valerolactone, a combination of 3-methoxy-N,N-dimethylpropanamide and γ-butyrolactone, a combination of 3-methoxy-N,N-dimethylpropanamide and γ-butyrolactone and dimethyl sulfoxide, or a combination of N-methyl-2-pyrrolidone and ethyl lactate. Also, one of the preferable modes of the present application is a mode in which toluene is further added to the solvent in which these are combined, in an amount of about 1 to 10 mass% relative to the total mass of the solvent.

[0708] In particular, from the viewpoint of storage stability and the like of the resin composition, a mode in which γ-valerolactone is contained as the solvent is one of the preferable modes of the present application. In this mode, the content of γ-valerolactone is preferably 50 mass% or more, more preferably 60 mass% or more, and further preferably 70 mass% or more, relative to the total mass of the solvent. Also, the upper limit of the above content is not particularly limited, and can be 100 mass%. The above content can be determined taking into consideration the solubility and the like of the specific resin and the like contained in the resin composition.

[0709] Also, in the case of a combination of dimethyl sulfoxide and γ-valerolactone, it is preferable to contain 60 to 90 mass% of γ-valerolactone and 10 to 40 mass% of dimethyl sulfoxide, more preferably 70 to 90 mass% of γ-valerolactone and 10 to 30 mass% of dimethyl sulfoxide, and further preferably 75 to 85 mass% of γ-valerolactone and 15 to 25 mass% of dimethyl sulfoxide, relative to the total mass of the solvent.

[0710] From the viewpoint of coatability, the content of the solvent is preferably set to an amount in which the total solid content concentration of the resin composition of the present application reaches 5 to 80 mass%, more preferably to an amount in which it reaches 5 to 75 mass%, further preferably to an amount in which it reaches 10 to 70 mass%, and more further preferably to an amount in which it reaches 20 to 70 mass%. As for the solvent content, it can be adjusted in accordance with the intended thickness of the coating film and the coating method. In the case where two or more kinds of solvents are contained, it is preferable that the total amount thereof be within the above range.

[0711] < Metal adhesion improver >

[0712] From the viewpoint of improving adhesion to metal materials used in electrodes or wiring and the like, the resin composition of the present application preferably contains a metal adhesion improver. As the metal adhesion improver, there can be mentioned silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-keto ester compounds, amino compounds, and the like.

[0713] Among them, the compound corresponding to the above-mentioned compound A is set to not correspond to the metal adhesion improver and the silane coupling agent mentioned here.

[0714] [Silane Coupling Agent]

[0715] As the silane coupling agent, for example, there can be mentioned the compounds described in paragraph 0316 of International Publication No. 2021 / 112189, the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 2018-173573, which are incorporated into the present specification. Also, it is preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358. It is also preferable to use the following compounds as the silane coupling agent. In the following formulae, Me represents a methyl group, and Et represents an ethyl group. Also, the following R can be mentioned as a structure derived from a blocking agent for a blocked isocyanate group. As the blocking agent, there can be mentioned alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, active methylene compounds, and the like, as long as they are selected according to the temperature at which the blocking is released. For example, from the viewpoint of desiring to set the temperature at which the blocking is released to 160 to 180°C, it is preferable to be a caprolactam or the like. As a commercial product of such a compound, there can be mentioned X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

[0716] [Chemical Formula 48]

[0717]

[0718] As other silane coupling agents, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(l,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used alone or in combination of two or more.

[0719] Also, as the silane coupling agent, an oligomer type compound having a plurality of alkoxysilyl groups can be used.

[0720] As such an oligomer type compound, a compound containing a repeating unit represented by the following formula (S-1) or the like can be mentioned.

[0721] [Chemical Formula 49]

[0722]

[0723] In formula (S-1), R S1 represents a monovalent organic group, R S2 represents a hydrogen atom, a hydroxyl group or an alkoxy group, and n represents an integer of 0 to 2.

[0724] R S1The structure preferably contains a polymerizable group. As the polymerizable group, a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, an amino group, or the like can be given. As the group having an ethylenically unsaturated bond, a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group, or the like), a (meth)acrylamide group, a (meth)acryloyloxy group, or the like can be given, and a vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is preferred, a vinylphenyl group or a (meth)acryloyloxy group is more preferred, and a (meth)acryloyloxy group is further preferred.

[0725] R S2 An alkyl group is preferred, and a methyl group or an ethyl group is more preferred.

[0726] n represents an integer of 0 to 2, and 1 is preferred.

[0727] Here, the structures of the plurality of repeating units represented by formula (S-1) contained in the oligomer type compound can be the same, respectively.

[0728] Here, in the plurality of repeating units represented by formula (S-1) contained in the oligomer type compound, n is preferably 1 or 2 in at least one of them, n is more preferably 1 or 2 in at least two of them, and n is further preferably 1 in at least two of them.

[0729] As such an oligomer type compound, a commercially available product can be used, and as the commercially available product, for example, KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be given.

[0730] 〔Aluminum-based adhesion aid〕

[0731] As the aluminum-based adhesion aid, for example, aluminum tris(acetylacetonate), aluminum tris(acetylacetoacetate), aluminum acetylacetonate diisopropylate, or the like can be given.

[0732] As the other metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186, the sulfide-based compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935, or the like can also be used, and these contents are incorporated into the present specification.

[0733] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By being equal to or greater than the lower limit of the above range, the adhesion of the pattern to the metal layer becomes good, and by being equal to or less than the upper limit of the above range, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver can be only one kind, or two or more kinds. In the case of two or more kinds, the total amount is preferably within the above range.

[0734] <Migration inhibitor>

[0735] The resin composition of the present application preferably further contains a migration inhibitor. By containing a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions from the metal layer (or metal wiring) into the film can be effectively inhibited.

[0736] The migration inhibitor mentioned here is not equivalent to the compound X1 or the compound X2 mentioned above.

[0737] As the migration inhibitor, there is no particular limitation, and a compound having a heterocycle (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, and 6H-pyran ring, triazine ring), a compound having thioureum and sulfanyl, a hindered phenol-based compound, a salicylic acid derivative-based compound, a hydrazide derivative-based compound can be mentioned. In particular, a triazole-based compound such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, a tetrazole-based compound such as 1H-tetrazole, 5-phenyltetrazole, 5-amino-1H-tetrazole, and the like can be preferably used.

[0738] As the migration inhibitor, an ion capturing agent that captures anions such as halide ions can also be used.

[0739] As other migration inhibitors, the rust preventive agent described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Publication No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015 / 199219, and the like can be used, and the contents thereof are incorporated into the present specification.

[0740] As specific examples of the migration inhibitor, the following compounds can be mentioned.

[0741] [Chemical Formula 50]

[0742]

[0743] 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, relative to the total solid content of the resin composition, in the case where the resin composition of the present application has the migration inhibitor.

[0744] The migration inhibitor can be only one or two or more. In the case where the migration inhibitor is two or more, the total amount thereof is preferably within the above range.

[0745] <Polymerization Inhibitor>

[0746] The resin composition of the present application preferably contains a polymerization inhibitor. As the polymerization inhibitor, there can be mentioned phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl radical-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, metal compounds, and the like.

[0747] The polymerization inhibitor mentioned here is provided not to correspond to the above-mentioned compound X1 or compound X2.

[0748] As the specific compound of the polymerization inhibitor, there can be mentioned the compounds described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, and the like. The content is incorporated into the present specification.

[0749] The content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and further preferably 0.05 to 10% by mass, relative to the total solid content of the resin composition, in the case where the resin composition of the present application has the polymerization inhibitor.

[0750] The polymerization inhibitor can be only one or two or more. In the case where the polymerization inhibitor is two or more, the total amount thereof is preferably within the above range.

[0751] [Compound of Urea, Compound of Carbodiimide, Compound of Isourea]

[0752] The resin composition of the present application can contain at least one compound selected from the group consisting of a compound having a urea bond (urea compound), a compound having a carbodiimide structure (carbodiimide compound), and a compound having an isourea bond (isourea compound) (hereinafter, also referred to as "urea compound or the like") from the viewpoint of the elongation at break and the adhesion to a metal or a resin layer.

[0753] Among these, the resin composition of the present application preferably further contains a compound having a urea bond.

[0754] Among the urea compound or the like mentioned here, the aforementioned compound A, the aforementioned polymerizable compound, and a compound corresponding to a silane coupling agent are not included.

[0755] As the urea compound, a compound represented by the following formula (UR-1) can be given, as the carbodiimide compound, a compound represented by the following formula (UR-2) can be given, and as the isourea compound, a compound represented by the following formula (UR-3) can be given.

[0756] [Chemical Formula 51]

[0757]

[0758] In formula (UR-1), formula (UR-2), or formula (UR-3), R 11 and R 12 independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which can have a substituent, R 21 and R 22 independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which can have a substituent, R 31 and R 32 independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which can have a substituent, R 33 represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which can have a substituent.

[0759] In formula (UR-1), formula (UR-2), or formula (UR-3), R 11 and R 12 independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which can have a substituent, R

[0760] As R 11 and R 12The unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms is preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms, and even more preferably ethyl, isopropyl, tert-butyl or cyclohexyl.

[0761] In formula (UR-1), R 11 and R 12 It can be an aliphatic hydrocarbon group with 2 to 7 carbon atoms, each independently having at least one substituent selected from the group consisting of hydroxyl, alkoxy, thiol and alkylthio groups.

[0762] The aliphatic hydrocarbon group having 2 to 7 carbon atoms may have 2 or more of the above-mentioned substituents, but preferably only 1 of the above-mentioned substituents.

[0763] In formula (UR-2), R 21 and R 22 Each can be independently represented as an aliphatic hydrocarbon group with 1 to 7 carbon atoms that can have substituents.

[0764] In formula (UR-2), R 21 and R 22 Preferably, it is an unsubstituted aliphatic hydrocarbon group with 1 to 7 carbon atoms, or an aliphatic hydrocarbon group with 1 to 7 carbon atoms having an amino or quaternary ammonium group as a substituent, more preferably an unsubstituted aliphatic hydrocarbon group with 1 to 7 carbon atoms.

[0765] In formula (UR-2), R 21 and R 22 The preferred embodiments of the above-mentioned unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms or aliphatic hydrocarbon groups having 1 to 7 carbon atoms with the above-mentioned substituents are respectively related to R. 11 and R 12 The same as shown in the description.

[0766] In formula (UR-3), R 31 and R 32 Preferably, it is an unsubstituted aliphatic hydrocarbon group with 1 to 7 carbon atoms, or an aliphatic hydrocarbon group with 1 to 7 carbon atoms having an amino or quaternary ammonium group as a substituent, more preferably an unsubstituted aliphatic hydrocarbon group with 1 to 7 carbon atoms.

[0767] In formula (UR-3), R 31 and R 32 The preferred embodiments of the above-mentioned unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms or aliphatic hydrocarbon groups having 1 to 7 carbon atoms with the above-mentioned substituents are respectively related to R. 11 and R 12 The same as shown in the description.

[0768] In formula (UR-3), R33 represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which can have a substituent, preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, further preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[0769] In formula (UR-3), R 33 , preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a tert-butyl group, more preferably an ethyl group.

[0770] As specific examples of the urea compound and the like, mention can be made of dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, diisopropylisourea, and the like, but the present application is not limited thereto.

[0771] The total content of the urea compound and the like is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 8.0 parts by mass, and further preferably 1.0 to 6.0 parts by mass, with respect to 100 parts by mass of the specific resin.

[0772] The urea compound and the like can be used alone or in combination of two or more. In the case where two or more kinds of bases are combined in the treatment liquid containing a base, the total content of these is preferably within the above range.

[0773] <Light Absorber>

[0774] The resin composition of the present application also preferably contains a compound (light absorber) whose absorbance at the exposure wavelength decreases due to exposure.

[0775] As the light absorber, mention can be made of the compounds described in paragraphs 0159 to 0183 of International Publication No. 2022 / 202647, the compounds described in paragraphs 0088 to 0108 of Japanese Patent Application Publication No. 2019-206689, and the like. These contents are incorporated into the present specification.

[0776] The content of the light absorber with respect to the total solid content of the resin composition of the present application is not particularly limited, and is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and further preferably 1 to 5 mass%.

[0777] <Other Additives>

[0778] The resin composition of the present application can contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, photo-acid generators, anti-coagulation agents, phenol-based compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), and the like, as needed within a range where the effects of the present application are obtained. By appropriately containing these components, the properties of the film, such as the physical properties, can be adjusted. As for these components, for example, the description of paragraphs 0183 and thereafter of Japanese Patent Application Publication No. 2012-003225 (corresponding to the description of paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), the description of paragraphs 0101 to 0104 and 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, and the like, are incorporated into the present specification. In the case where these additives are incorporated, the total content thereof is preferably 3% by mass or less of the solid content of the resin composition of the present application.

[0779] As these other additives, the compounds described in paragraphs 0316 to 0358 of International Publication No. 2022 / 145355 can be mentioned. The above description is incorporated into the present specification.

[0780] <Properties of the resin composition>

[0781] The viscosity of the resin composition of the present application can be adjusted using the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, it is preferably 1,000 mm 2 / s to 12,000 mm 2 / s, more preferably 2,000 mm 2 / s to 10,000 mm 2 / s, further preferably 2,500 mm 2 / s to 8,000 mm 2 / s. If it is within the above range, a coating film with high uniformity is easily obtained. If it is 1,000 mm 2 / s or more, it is easy to coat, for example, with a film thickness required as an insulating film for a re-wiring, and if it is 12,000 mm 2 / s or less, a coating film with excellent coating surface properties is obtained.

[0782] <Restriction on the contained substances of the resin composition>

[0783] The water content of the resin composition of the present application is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and further preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved.

[0784] As a method of adjusting the content of moisture, there can be mentioned adjusting the humidity under storage, reducing the void fraction of the storage container at the time of storage, and the like.

[0785] From the viewpoint of insulation, the metal content of the resin composition of the present application is preferably less than 5 parts per million (ppm) by mass, more preferably less than 1 ppm by mass, and further preferably less than 0.5 ppm by mass. As the metal, there can be mentioned sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, and the like, but the metal contained in the form of a complex with an organic compound is excluded. In the case where a plurality of metals are contained, the total of these metals is preferably within the above range.

[0786] Further, as a method of reducing metal impurities that are unexpectedly contained in the resin composition of the present application, there can be mentioned a method of selecting a raw material having a small metal content as a raw material constituting the resin composition of the present application, filtering the raw material constituting the resin composition of the present application with a filter, distilling under conditions in which contamination is as much as possible suppressed by lining the inside of the apparatus with polytetrafluoroethylene or the like, and the like.

[0787] With respect to the resin composition of the present application, if the use as a semiconductor material is considered, from the viewpoint of wiring corrosion, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and further preferably less than 200 ppm by mass. Of these, the amount present in the form of a halide ion is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and further preferably less than 0.5 ppm by mass. As the halogen atom, there can be mentioned a chlorine atom and a bromine atom. The total of the chlorine atom and the bromine atom or the total of the chloride ion and the bromide ion is preferably within the above range, respectively.

[0788] As a method of adjusting the content of halogen atoms, there can be preferably mentioned ion exchange treatment and the like.

[0789] As the storage container of the resin composition of the present application, a storage container conventionally known can be used. As the storage container, in order to suppress the mixing of impurities into the raw material or the resin composition of the present application, a multilayer bottle in which the inner wall of the container is composed of six kinds of six-layer resins, a bottle in which a seven-layer structure is formed with six kinds of resins is also preferably used. As such a container, there can be mentioned, for example, the container described in Japanese Patent Application Publication No. 2015-123351.

[0790]

[0791] By curing the resin composition of the present application, a cured product of the resin composition can be obtained.

[0792] The cured product of the present application is a cured product obtained by curing a resin composition.

[0793] ​The curing of the resin composition is preferably performed by heating, more preferably at a temperature of 120°C to 400°C, further preferably at a temperature of 140°C to 380°C, and particularly preferably at a temperature of 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited and can be selected as a film, a rod, a sphere, a particle, or the like according to the use. In the present application, the cured product is preferably in the form of a film. The shape of the cured product can also be selected according to the use, such as forming a protective film on a wall surface, forming a through-hole for conduction, adjusting the impedance, electrostatic capacity, or internal stress, imparting a heat dissipation function, or the like, by patterning the resin composition. The film thickness of the cured product (film composed of the cured product) is preferably 0.5 μm or more and 150 μm or less.

[0794] The shrinkage rate when the resin composition of the present application is cured is preferably 50% or less, more preferably 45% or less, and further preferably 40% or less. Here, the shrinkage rate refers to the percentage of the change in volume of the resin composition before and after curing and can be calculated by the following equation.

[0795] Shrinkage rate (%) = 100 - (volume after curing ÷ volume before curing) x 100

[0796] <Properties of the cured product of the resin composition>

[0797] The imidization reaction rate of the cured product of the resin composition of the present application is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. If it is 70% or more, it sometimes becomes a cured product having excellent mechanical properties.

[0798] The elongation at break of the cured product of the resin composition of the present application is preferably 30% or more, more preferably 40% or more, and further preferably 50% or more.

[0799] The glass transition temperature (Tg) of the cured product of the resin composition of the present application is preferably 180°C or more, more preferably 210°C or more, and further preferably 230°C or more.

[0800] <Preparation of the resin composition>

[0801] The resin composition of the present application can be prepared by mixing the above-described components.

[0802] As a method for preparing the resin composition, for example, the method described in paragraphs 0283 to 0284 of International Publication No. 2022 / 210532 can be used. These descriptions are incorporated into the present specification.

[0803] (Method for producing the cured product)

[0804] The method for producing the cured product of the present application preferably includes a film forming step of applying the resin composition to a substrate to form a film.

[0805] The method for producing a cured product more preferably includes the film forming step described above, an exposure step of selectively exposing the film formed by the film forming step, and a development step of developing the film exposed by the exposure step using a developing solution to form a pattern.

[0806] The method for producing a cured product particularly preferably includes the film forming step described above, the exposure step described above, the development step described above, and at least one of a heating step of heating the pattern obtained by the development step and a post-development exposure step of exposing the pattern obtained by the development step.

[0807] Also, the method for producing a cured product preferably includes the film forming step described above and a step of heating the film (heating step).

[0808] The heating step described above is preferably a heating step of heating the film at 50 to 450°C.

[0809] Also, the method for producing a cured product of the present application can further include a drying step, a post-exposure heating step, a post-development exposure step, a metal layer forming step, and the like, the steps described in International Publication No. 2022 / 210532.

[0810] The steps in the method for producing a cured product of the present application can be performed, for example, by the same methods as the steps described in paragraphs 0285 to 0325 of International Publication No. 2022 / 210532. These descriptions are incorporated into the present application specification.

[0811] <Usage>

[0812] As the field to which the method for producing a cured product of the present application or the cured product of the present application can be applied, insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, and the like can be given. In addition to these, sealing films, substrate materials (base films or cover films for flexible printed boards, interlayer insulating films), or cases where a pattern is formed on an insulating film for mounting purposes such as the above by etching can be given. With respect to these uses, for example, reference can be made to Science & Technology Co., Ltd. "High Functioning and Application Technology of Polyimides" April 2008, Akira Kakiuchi / Supervision, CMC Technical Library "Fundamentals and Development of Polyimide Materials" November 2011, Japan Polyimide-Aromatic High Molecular Research Association / Editor "Latest Polyimide Fundamentals and Applications" NTS, August 2010, and the like.

[0813] The method for producing a cured product of the present application or the cured product of the present application can also be used for the production of printing plates such as offset plates or screen plates, the use of etching for molded parts, the production of protective lacquers and dielectric layers in electronics, particularly microelectronics, and the like.

[0814] (Laminate and method for producing a laminate)

[0815] The laminate of the present application refers to a structure having a plurality of layers composed of the cured product of the present application.

[0816] The laminate is a laminate comprising 2 or more layers composed of the cured product, and can be a laminate laminated with 3 or more layers.

[0817] Of the 2 or more layers composed of the cured product contained in the above laminate, at least one layer is a layer composed of the cured product of the present application, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product accompanying the above shrinkage, etc., it is also preferable that all the layers composed of the cured product in the above laminate are composed of the cured product of the present application.

[0818] That is, the production method of the laminate of the present application preferably comprises the production method of the cured product of the present application, and more preferably comprises the production method of the cured product of the present application repeated a plurality of times.

[0819] The laminate of the present application preferably comprises 2 or more layers composed of the cured product, and comprises a metal layer between any of the layers composed of the cured product. The above metal layer is preferably formed by the above metal layer forming step.

[0820] That is, the production method of the laminate of the present application preferably further comprises a metal layer forming step of forming a metal layer on a layer composed of the cured product between the production methods of the cured product performed a plurality of times. The preferable mode of the metal layer forming step is as described above.

[0821] As the above laminate, for example, a laminate comprising a layer structure in which 3 layers of a layer composed of a first cured product, a metal layer, and a layer composed of a second cured product are sequentially laminated can be cited as a preferable example.

[0822] The above layer composed of a first cured product and the above layer composed of a second cured product are preferably both layers composed of the cured product of the present application. The resin composition of the present application used for forming the above layer composed of a first cured product and the resin composition of the present application used for forming the above layer composed of a second cured product can be a composition having the same composition, or can be a composition having a different composition. The metal layer in the laminate of the present application can be preferably used as a metal wiring such as a rewiring layer.

[0823] <Layering Step>

[0824] The production method of the laminate of the present application preferably comprises a layering step.

[0825] The lamination process is a series of processes including, on the surface of a pattern (resin layer) or a metal layer, sequentially performing at least one of (a) a film forming process (layer forming process), (b) an exposure process, (c) a development process, (d) a heating process, and a post-development exposure process. Of these, it can be a manner in which (a) the film forming process, (d) the heating process, and the post-development exposure process are repeated. Further, (e) a metal layer forming process can be included after at least one of (d) the heating process and the post-development exposure process. Of course, the above-described drying process and the like can be further appropriately included in the lamination process.

[0826] In the case where the lamination process is further performed after the lamination process, a surface activation treatment process can be further performed after the above-described exposure process, after the above-described heating process, or after the above-described metal layer forming process. As the surface activation treatment, a plasma treatment is exemplified. Details of the surface activation treatment will be described later.

[0827] The above-described lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.

[0828] For example, like a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, it is preferable that the resin layer be provided in a structure of 2 or more layers and 20 or less layers, and it is further preferable that the resin layer be provided in a structure of 2 or more layers and 9 or less layers.

[0829] The composition, shape, film thickness, and the like of each layer can be the same or different.

[0830] In the present application, in particular, it is preferable that, after the metal layer is provided, a cured product (resin layer) of the above-described resin composition of the present application be further formed so as to cover the metal layer. Specifically, a manner in which (a) the film forming process, (b) the exposure process, (c) the development process, (d) the heating process, and the post-development exposure process, and (e) the metal layer forming process are sequentially repeated, or a manner in which (a) the film forming process, (d) the heating process, and the post-development exposure process, and (e) the metal layer forming process are sequentially repeated can be exemplified. By alternately performing the lamination process of the resin composition layer (resin layer) of the present application and the metal layer forming process, the resin composition layer (resin layer) of the present application and the metal layer can be alternately laminated.

[0831] (Surface activation treatment process)

[0832] The method for manufacturing the laminate of the present application preferably includes a surface activation treatment process of performing a surface activation treatment on at least a part of the metal layer and the resin composition layer.

[0833] The surface activation treatment process is usually performed after the metal layer formation process, but can also be performed after the above-described development process (preferably after at least one of the heating process and the post-development exposure process), after the surface activation treatment process is performed on the resin composition layer.

[0834] The surface activation treatment can be performed on at least a part of the metal layer, on at least a part of the resin composition layer after exposure, or on at least a part of each of the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a part of the metal layer, and preferably on a part or all of the region of the metal layer on which the 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 to the resin composition layer (film) provided on the surface thereof can be improved.

[0835] The surface activation treatment is preferably also performed on a part or all of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, the adhesion to the metal layer or the resin layer provided on the surface subjected to the surface activation treatment can be improved. In particular, in the case where the resin composition layer is cured, such as in the case where negative development is performed, the resin composition layer is less likely to be damaged by the surface treatment, and the adhesion is easily improved.

[0836] The surface activation treatment can be performed, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. The contents are incorporated into the present specification.

[0837] (Semiconductor device and method for manufacturing the same)

[0838] The present application also discloses a semiconductor device including the cured product or the laminate of the present application.

[0839] Further, the present application also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured product or a method for manufacturing a laminate of the present application.

[0840] As a specific example of a semiconductor device in which the resin composition of the present application is used to form an interlayer insulating film for a rewiring layer, reference can be made to the description in paragraphs 0213 to 0218 and the description of FIG. 1 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated into the present specification.

[0841] Examples

[0842] The present application will be further specifically described below by citing examples. The materials, amounts, proportions, processing contents, processing sequences, etc. shown in the following examples can be appropriately changed without departing from the gist of the present application. Therefore, the scope of the present application is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0843] <Method for producing a precursor of a cyclized resin>

[0844] [Synthesis Example 1: Synthesis of a precursor of a cyclized resin (Resin 1)]

[0845] Into a separable flask, 4,4'-oxydiphthalic dianhydride (ODPA) 23.48 g and bisphthalic dianhydride (BPDA) 22.27 g were charged, and 2-hydroxyethyl methacrylate (HEMA) 39.69 g and tetrahydrofuran 136.83 g were added, and stirred at room temperature (25°C), and pyridine 24.66 g was added while stirring, to obtain a reaction mixture. After the reaction exotherm was completed, the reaction mixture was allowed to cool to room temperature, and left to stand for 16 hours.

[0846] Next, a solution of dicyclohexyl carbodiimide (DCC) 62.46 g dissolved in tetrahydrofuran 61.57 g was added to the reaction mixture while stirring under ice cooling over 40 minutes, and then 4,4'-diamino diphenyl ether (DADPE) 27.42 g was suspended in tetrahydrofuran 119.73 g, and added while stirring over 60 minutes. Further, after stirring at room temperature for 2 hours, ethanol 7.17 g was added and stirred for 1 hour, and then tetrahydrofuran 136.83 g was added. The precipitate generated in the reaction mixture was removed by filtration, to obtain a reaction solution.

[0847] The obtained reaction solution was added to 716.21 g of ethanol to generate a precipitate composed of a crude polymer. The generated crude polymer was filtered and dissolved in tetrahydrofuran 403.49 g, to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water, and the polymer was precipitated, and the obtained precipitate was filtered and vacuum-dried, to obtain 80.3 g of resin 1 in powder form. The molecular weight of the resin 1 was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 20,000. The structure of the resin 1 was confirmed by H-NMR to be the structure represented by the following formula (P-1). Further, by appropriately adjusting the equivalent of 4,4'-diamino diphenyl ether, resin 1 having Mw of 5,000, 10,000, 30,000, 13,000, 14,000, 16,000, and 17,000 was also synthesized, respectively. 1 The structure of the resin 1 was confirmed by H-NMR to be the structure represented by the following formula (P-1). Further, by appropriately adjusting the equivalent of 4,4'-diamino diphenyl ether, resin 1 having Mw of 5,000, 10,000, 30,000, 13,000, 14,000, 16,000, and 17,000 was also synthesized, respectively.

[0848] [Synthetic Example 2A: Synthesis of the precursor of the cyclized resin (resin 2A)]

[0849] A diester of 4,4'-oxophthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diethylene glycol dimethyl ether was synthesized by mixing at 60 °C for 4 hours. The reaction mixture was then cooled to -10 °C, and 17.0 g of thionyl chloride was added over 60 minutes while maintaining the temperature at -10 ± 5 °C. After dilution with 50 mL of N-methylpyrrolidone, a solution obtained by dissolving 12.6 g of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 60 minutes at -10 ± 5 °C. The mixture was stirred at room temperature for 2 hours. Then, 10.0 g of ethanol was added, and the mixture was stirred at room temperature for 1 hour.

[0850] Next, 6000g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was filtered and dissolved in 500g of tetrahydrofuran. 6000g of water (a poor solvent) was added to the obtained solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was filtered again and dried under reduced pressure at 45°C for 3 days.

[0851] 46.6 g of dried powder was dissolved in 419.6 g of tetrahydrofuran, followed by the addition of 2.3 g of triethylamine, and stirred at room temperature for 35 minutes. Then, 3000 g of ethanol was added, and the precipitate was filtered off. The resulting precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTec) were added, and the mixture was stirred for 4 hours. Subsequently, the ion exchange resin was removed by filtration, and the resulting polymer solution was added to 5600 g of water to obtain a precipitate. The precipitate was filtered off and dried under reduced pressure at 45°C for 24 hours, thereby obtaining 45.1 g of resin 2A.

[0852] pass 1 H-NMR confirmed that the structure of resin 2A is represented by the following formula (P-2). The molecular weight of resin 2A was determined by gel permeation chromatography (converted to standard polystyrene), and the weight-average molecular weight (Mw) was 20,000.

[0853] [Synthetic Example 2B: Synthesis of the precursor of the cyclized resin (resin 2B)]

[0854] The resin 2B having a structure represented by the following formula (P-2) was synthesized by the same method as in Synthesis Example 1, except that the compound used was appropriately changed. 1 The structure of the resin 2B was confirmed by H-NMR to be represented by the following formula (P-2).

[0855] The Mw of the resin 2B was 20,000.

[0856] 〔Synthesis Examples 3 to 9, 12 to 15: Synthesis of precursors of cyclized resins (resins 3 to 9, resins 12 to 15)〕

[0857] The resins 3 to 9, resins 12 to 15 having a structure represented by any one of the following formulas (P-3) to (P-9), (P-12) to (P-15) were synthesized by the same method as in Synthesis Example 1, except that the compound used was appropriately changed.

[0858] The Mw of the resin 3 was 20,000, the Mw of the resin 4 was 20,000, the Mw of the resin 5 was 20,000, the Mw of the resin 6 was 20,000, the Mw of the resin 7 was 20,000, the Mw of the resin 8 was 20,000, the Mw of the resin 9 was 20,000, the Mw of the resin 12 was 20,000, the Mw of the resin 13 was 20,000, the Mw of the resin 14 was 20,000, and the Mw of the resin 15 was 20,000. The structures of the resins 3 to 9, resins 12 to 15 were confirmed by H-NMR to be represented by the following formulas (P-3) to (P-9), (P-12) to (P-15), respectively. 1 The structures of the resins 3 to 9, resins 12 to 15 were confirmed by H-NMR to be represented by the following formulas (P-3) to (P-9), (P-12) to (P-15), respectively.

[0859] 〔Synthesis Example 10: Synthesis of polyimide (resin 10)〕

[0860] In a flask equipped with a condenser and a stirrer, 18.0 g (40.5 millimoles) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in N-methylpyrrolidone (NMP) 80.0 g while removing moisture. Next, 7.95 g (39.7 millimoles) of 4,4'-oxydianiline (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirred at 25°C for 3 hours, and further stirred at 45°C for 3 hours. Next, 12.8 g (160 millimoles) of pyridine, 10.3 g (101 millimoles) of acetic anhydride, and 40.0 g of N-methylpyrrolidone (NMP) were added, and stirred at 80°C for 3 hours, and diluted with 50 g of N-methylpyrrolidone (NMP).

[0861] The reaction solution was precipitated in 1 liter of methanol and stirred at 3000 rpm for 15 minutes. The resin was filtered, stirred in 1 liter of methanol for 30 minutes again and filtered again. The obtained resin was dried under reduced pressure at 40°C for 1 day to obtain resin 10. As a result of measurement of the molecular weight of resin 10 by gel permeation chromatography (conversion to standard polystyrene), the weight average molecular weight (Mw) was 20,000. The structure of resin 10 was confirmed by H-NMR to be the structure represented by the following formula (P-10). 1 The structure of resin 10 was confirmed by H-NMR to be the structure represented by the following formula (P-10).

[0862] [Synthesis Examples 11, 16 to 18: Synthesis of polyimides (resins 11, 16 to 18)]

[0863] Resins 11 represented by the structures of the following formulas (P-11), (P-16) to (P-18) were synthesized by the same method as Synthesis Example 10, with appropriate modification of the compounds used, except for the following. The molecular weight of each of resins 11, 16 to 18 was measured by gel permeation chromatography (conversion to standard polystyrene), and the weight average molecular weight (Mw) was 20,000. 1 The structure of resin 11, 16 to 18 was confirmed by H-NMR to be the structure represented by the following formulas (P-11), (P-16) to (P-18).

[0864] The Mw of each of resins 11, 16 to 18 was 20,000.

[0865] [Chemical Formula 52]

[0866]

[0867] [Chemical Formula 53]

[0868]

[0869] [Chemical Formula 54]

[0870]

[0871] <Example and Comparative Example>

[0872] In each of the examples, each of the resin compositions was obtained by mixing the components described in the following table. Also, in the comparative example, the comparative composition was obtained by mixing the components described in the following table.

[0873] Specifically, the content (amount of blending) of each of the components described in the table other than the solvent was set to the amount (mass parts) described in the column of "mass parts" of each column of the table.

[0874] The content (amount of blending) of the solvent was set to the value (mass %) of the solid component concentration of the composition to be "solid component concentration" in the table, and the ratio (mass ratio) of the content of each solvent with respect to the total mass of the solvent was set to the ratio described in the column of "ratio" in the table.

[0875] The obtained resin compositions and comparative compositions were subjected to pressure filtration using a polytetrafluoroethylene filter having a pore width of 0.8 μm.

[0876] Also, in the tables, the notation of "-" indicates that the composition does not contain the corresponding ingredient.

[0877] [Table 1]

[0878]

[0879] [Table 2]

[0880]

[0881] [Table 3]

[0882]

[0883] [Table 4]

[0884]

[0885] [Table 5]

[0886]

[0887] [Table 6]

[0888]

[0889] [Table 7]

[0890]

[0891] [Table 8]

[0892]

[0893] [Table 9]

[0894]

[0895] The details of each ingredient described in the tables are as follows.

[0896] [Resin]

[0897] • Resin 1 to Resin 15: Resin 1 to Resin 15 obtained by the above Synthesis Examples

[0898] [Monomer (Polymerizable Compound)]

[0899] • M-1 to M-4: Compounds having the following structures

[0900] [Chemical Formula 55]

[0901]

[0902] • DPHA: Dipentaerythritol Hexaacrylate

[0903] 〔Polymerization initiator or photo-acid generator〕

[0904] • I-1 to I-9: Compounds of the following structure

[0905] [Chemical Formula 56]

[0906]

[0907] 〔Thermal base generator〕

[0908] A-1 to A-5: Compounds of the following structure

[0909] [Chemical Formula 57]

[0910]

[0911] 〔Polymerization inhibitor〕

[0912] • E-9: Compound of the following structure

[0913] [Chemical Formula 58]

[0914]

[0915] • B-1 to B-4: Compounds of the following structure, B-4 and B-5 are compounds corresponding to Compound X2.

[0916] [Chemical Formula 59]

[0917]

[0918] 〔Compound A or silane coupling agent (metal adhesion improving agent)〕

[0919] • C-1 to C-23: Compounds of the following structure. C-1 to C-23 are compounds corresponding to Compound A (in the structural formula, Me represents methyl group and Et represents ethyl group).

[0920] • CR-1: Compound of the following structure, CR-1 is a compound not corresponding to Compound A (in the structural formula, Et represents ethyl group).

[0921] • CX-1 to CX-4: Compounds of the following structure, CX-1 to CX-4 are compounds not corresponding to Compound A (in the structural formula, Me represents methyl group and Et represents ethyl group).

[0922] [Chemical Formula 60]

[0923]

[0924] [Chemical Formula 61]

[0925]

[0926] [Chemical Formula 62]

[0927]

[0928] 〔Migration inhibitor〕

[0929] • D-1 to D-3: Compounds of the following structures

[0930] [Chemical Formula 63]

[0931]

[0932] 〔Additive〕

[0933] • E-1 to E-6, E-9, E-11 to E-19: Compounds of the following structures

[0934] [Chemical Formula 64]

[0935]

[0936] • E-7: 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol ester with 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid

[0937] • E-8: The following synthetic product

[0938] <Additive: Synthesis of diazonaphthoquinone compound E-8>

[0939] To a flask was added 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylenyl)bisphenol (manufactured by Honshu Chemical Industry Co., Ltd.: Tris-PA) 29.72 g (70 mmol). Next, 1,2-naphthoquinonediazide-5-sulfonic acid chloride 46.93 g (174.9 mmol), triethylamine 17.9 g were stirred and dissolved in acetone 300 g, and this was added dropwise to the flask over 30 minutes using a dropping funnel, and stirring was performed at an internal temperature of 30°C for 30 minutes. Next, hydrochloric acid was added dropwise, and stirring was performed for 30 minutes. Next, a solution of purified water 1640 g and hydrochloric acid 30 g was prepared in a beaker, and the filtrate obtained by filtering the hydrochloride salt from the reaction liquid was added dropwise to this, and the precipitate was filtered, washed with water, and dried at 40°C under vacuum for 50 hours, to obtain diazonaphthoquinone compound E-8.

[0940] 〔Solvent〕

[0941] • NMP: N-methyl-2-pyrrolidone

[0942] • EL: Ethyl lactate

[0943] • DMSO: Dimethyl sulfoxide

[0944] • GBL: γ-Butyrolactone

[0945] • GVL: γ-Valerolactone

[0946] • MDMPA: 3-Methoxy-N,N-dimethylpropionamide

[0947] • toluene: Toluene

[0948] <Evaluation>

[0949] 〔Evaluation of substrate adhesion〕

[0950] The resin composition layer or comparative composition layer was formed by spin coating the resin composition or comparative composition prepared in each of the examples and comparative examples on a copper substrate in a layer form. The copper substrate on which the resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes, and a resin composition layer or comparative composition layer having a film thickness and a uniform thickness as described in the "Film thickness (μm)" column of the table was formed on the copper substrate.

[0951] In the examples described as "M" in the "Exposure condition" column, a stepper was used as a light source, and the resin composition layer or comparative composition layer on the copper substrate was exposed to light having an exposure energy of 500 mJ / cm 2 In the examples described as "CP" in the "Developing solution" column of the table, a photomask having a non-masked portion in the form of a 100 μm square square was used, and in the examples described as "T" in the "Developing solution" column of the table, a photomask having a masked portion in the form of a 100 μm square square was used, and the resin composition layer or comparative composition layer on the copper substrate was exposed to light having an exposure wavelength (nm) described in the "Exposure wavelength (nm)" column of the table.

[0952] In the examples described as "D" in the "Exposure condition" column, a direct exposure device (ADTEC DE-6UH III) was used as a light source, and the resin composition layer or comparative composition layer on the copper substrate was exposed to light having an exposure energy of 500 mJ / cm 2 In the examples described as "D" in the "Exposure condition" column, a direct exposure device (ADTEC DE-6UH III) was used as a light source, and the resin composition layer or comparative composition layer on the copper substrate was exposed to light having an exposure energy of 500 mJ / cm

[0953] Then, the resin layer was obtained by developing for 60 seconds with a developing solution described in the column of "Developing solution" of the table. The description of "CP" in the table means cyclopentanone, and the description of "T" in the table means a 2.38 mass% aqueous solution of tetramethylammonium hydroxide.

[0954] Further, in the examples in which a numerical value is described in the column of "Curing temperature", the resin film obtained in each example was warmed at a temperature increasing rate of 10°C / min under a nitrogen atmosphere, and after the temperature described in the column of "Curing temperature (°C)" of the table was reached, the temperature was maintained for the time described in the column of "Curing time (min)" of the table, and a cured product was obtained.

[0955] In the examples in which "IR" is described in the column of "Curing temperature (°C)", an infrared lamp heating device (manufactured by ADVANCE RIKO, Inc., RTP-6) was used to warm the resin film obtained in each example at a temperature increasing rate of 10°C / min under a nitrogen atmosphere, and after 230°C was reached, the temperature was maintained for the time described in the column of "Curing time (min)" of the table, and a cured product was obtained.

[0956] The shear force was measured for the cured product on the copper substrate using a joint strength testing machine (manufactured by XYZTEC, Condor Sigma) under an environment of 25°C and 65% relative humidity (RH), and evaluation was performed according to the following evaluation criteria. The evaluation results are described in the column of "Substrate adhesion" of the table. It can be said that the greater the shear force, the more excellent the adhesion of the cured film.

[0957] Evaluation Criteria

[0958] A: The shear force exceeds 30 gf.

[0959] B: The shear force exceeds 25 gf and is 30 gf or less.

[0960] C: The shear force exceeds 20 gf and is 25 gf or less.

[0961] D: The shear force is 20 gf or less.

[0962] Further, 1 gf is 0.00980665 N.

[0963] Evaluation of Substrate Adhesion after Heat Resistance Test

[0964] The copper substrate with the cured product obtained was left in a tank in the atmosphere at a temperature of 175°C for 192 hours, and evaluation was performed using a joint strength testing machine, and evaluation of the substrate adhesion after the heat resistance test was performed by the same method and evaluation criteria as the above-described evaluation of the substrate adhesion. The evaluation results are described in the column of "Substrate adhesion after heat resistance test" of the table. It can be said that the greater the shear force, the more excellent the adhesion of the cured film after the heat resistance test.

[0965] From the above results, it was found that the cured product formed from the resin composition of the present application is excellent in the substrate adhesion after the high-temperature storage test by containing the compound corresponding to Compound A.

[0966] The comparative composition relating to Comparative Example 1 does not contain the compound corresponding to Compound A. With respect to the cured product formed from this comparative composition, it was found that the substrate adhesion after the high-temperature storage test was poor.

[0967] Example 201

[0968] After the photosensitive film having a film thickness of 20 μm was formed by applying the resin composition used in Example 1 to the surface of the copper thin layer of the resin substrate on which the copper thin layer was formed in a layer shape, drying at 100°C for 5 minutes, and then performing exposure using a stepper (manufactured by Nikon Corporation, NSR1505 i6), exposure was performed through a mask (a binary mask having a pattern of 1:1 line and space, and a line width of 10 μm) at a wavelength of 365 nm. After the above exposure, development was performed using cyclopentanone for 2 minutes, and then the layer was rinsed with PGMEA for 30 seconds to obtain a pattern of the layer.

[0969] Subsequently, the temperature was increased at a rate of 10°C / minute in a nitrogen atmosphere, and after reaching 230°C, the temperature was maintained at 230°C for 180 minutes to form an interlayer insulating film for a rewiring layer. The interlayer insulating film for a rewiring layer was excellent in insulating properties.

[0970] Further, as a result of manufacturing a semiconductor device using the interlayer insulating film for a rewiring layer, it was confirmed that the device was normally operated.

Claims

1. A resin composition comprising: a resin selected from at least one of the group consisting of a cyclized resin and a precursor thereof; and a compound A represented by formula (Al-1), [Chemical Formula 1] In equation (A1-1), R 1 R is an organic group having at least one atom selected from oxygen, nitrogen, and sulfur atoms. 1 When multiple instances exist, they can be the same or different, R 2 It is a hydrogen atom or not equivalent to the R mentioned above. 1 Any organic group, R 2 When multiple instances exist, they can be the same or different, R 1 and R 2 At least two of them can bond together to form a ring structure, where n represents an integer from 1 to 3, m represents an integer greater than 1, and R 3 This represents an organic group with an m-valence.

2. The resin composition according to claim 1, wherein the compound A is a compound represented by the following formula (Al-2), [Chemical Formula 2] In formula (A1-2), R 1 is an organic group having at least one or more atoms selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, R 1 may be the same or different when a plurality of R 2 is an organic group other than R 1 , R 2 may be the same or different when a plurality of R 1 and R 2 may be bonded to form a ring structure, n represents an integer of 1 to 3, L represents a divalent linking group, and R 4 represents a hydrogen atom or a monovalent organic group.

3. The resin composition according to claim 1, wherein at least one of R in the formula (A1-1) 1 contains an amino group or an ester bond.

4. The resin composition according to claim 1, wherein R in the formula (A1-1) is a group represented by the following formula (R3-1) 3 R3-1 [Chemical Formula 3] In formula (R3-1), L 31 each independently represents a divalent linking group, R 31 each independently represents a hydrogen atom, an aromatic hydrocarbon group which can be substituted by a substituent, or a group represented by 32 -#, * represents a bonding site to the nitrogen atom in formula (R3-1), and # represents a bonding site to L 32 in formula (R3-1), R 32 represents an organic group, and m represents an integer of 1 or more, L 32 represents a hydrogen atom or a substituent, and m represents an integer of 2 or more, L 32 represents a single bond or a linking group of m valence, and * represents a bonding site to the silicon atom in formula (A1-1).

5. A resin composition comprising: a resin selected from at least one of the group consisting of a cyclized resin and a precursor thereof; and a compound A represented by formula (A2-1), [Chemical Formula 4] In equation (A2-1), R 21 The HSP value is 17.0–27.0 MPa. 1 / 2 organic groups, R 21 When multiple instances exist, they can be the same or different, R 22 It is a hydrogen atom or not equivalent to the R mentioned above. 21 Any organic group, R 22 When multiple instances exist, they can be the same or different, R 21 and R 22 At least two of them can bond together to form a ring structure, where n represents an integer from 1 to 3, m represents an integer greater than 1, and R 23 This represents an organic group with an m-valence.

6. The resin composition according to any one of claims 1 to 5, wherein the resin is a polyimide or a polyimide precursor.

7. The resin composition according to any one of claims 1 to 5, wherein the resin is a polyimide.

8. The resin composition according to any one of claims 1 to 5, further comprising a photopolymerization initiator.

9. The resin composition according to claim 8, further comprising a sensitizer.

10. The resin composition according to any one of claims 1 to 5, further comprising a compound having a urea bond.

11. The resin composition according to any one of claims 1 to 5, further comprising a polymerizable compound having at least one of a urea bond and a urethane bond.

12. The resin composition according to any one of claims 1 to 5, further comprising a solvent having at least one of an amide bond or a hydroxyl group.

13. The resin composition according to any one of claims 1 to 5, used for forming an interlayer insulating film for a rewiring layer.

14. A cured product obtained by curing the resin composition according to any one of claims 1 to 5.

15. A laminate comprising two or more layers of the cured product according to claim 14, and a metal layer between any of the layers of the cured product.

16. A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of claims 1 to 5 on a substrate to form a film.

17. The method for producing a cured product according to claim 16, comprising: an exposure step of selectively exposing the film; and a development step of developing the film using a developing solution to form a pattern.

18. The method for producing a cured product according to claim 16, comprising a heating step of heating the film at 50 to 450°C.

19. A method for producing a laminate, comprising the method for producing a cured product according to claim 16.

20. A method for producing a semiconductor device, comprising the method for producing a cured product according to claim 16.

21. A semiconductor device comprising the cured product according to claim 14. ​

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